JP4080364B2 - Radical generator and photosensitive resin composition - Google Patents

Description

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立して水素原子又は置換基であり、互いに結合した環構造であってもよい。化学構造Ｘはｎ価の直鎖、及び／又は分岐、及び／又は環状の飽和、不飽和の多価アルキル基、アリール基、アリル基から選ばれる有機基であって、且つ、その内部に単結合、エステル結合、エーテル結合、チオエーテル結合、アミノ結合、アミド結合、ウレタン結合、ウレア結合、チオカルバメート結合、カルボジイミド結合、カーボネート結合の結合を１つ以上有しても良い。ｎは２以上の整数である。）で表されるナフタルイミド構造含有基を２つ以上有する化合物（ａ）からなることを特徴とする。
【００２７】
（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ独立して水素原子又は置換基であり、互いに結合した環構造であってもよい。）
で表されるナフタルイミド構造含有基を２つ以上有する化合物（ａ）からなることを特徴とする。
【００２８】
ナフタルイミド構造含有基によるラジカル発生機構は、ナフタルイミド構造が電磁波や放射線等の光を吸収することによってラジカルを発生させるものと推定される。
【００２９】
本発明に係るラジカル発生剤は、上記ナフタルイミド構造含有基が水素引き抜き型のラジカル発生部位として機能し、放射線等を照射して励起させることによりラジカル反応を起こしたり、ラジカル重合を開始したり、高分子を架橋することもできる。ナフタルイミド構造含有基は、自己開裂型よりも安定性が高い水素引き抜き型であり、しかも耐熱性が良好なナフタレン骨格を有するため、耐熱性、安定性、保存性が高いラジカル発生剤を得ることができる。
【００３０】
さらに、π結合が多く連結していることから吸収波長がマレイミドよりも長波長化している為、高圧水銀灯の主要な発光波長である３６５ｎｍの波長に対し吸収を持ちやすく、感度が良好である。
【００３１】
また、本発明に係るラジカル発生剤は、エチレン性不飽和結合だけでなく芳香環等種々の化合物とも反応可能であり、エチレン性不飽和結合を有さない樹脂組成物であっても、高分子を架橋したり或いはラジカル反応をすることができる。従って、本発明に係るラジカル発生剤は、一般的な光ラジカル重合開始剤として用いられるほか、例えば芳香族ポリマーを含有する樹脂組成物の架橋剤として用いて硬化後の耐溶剤性を向上させることが可能である。
【００３２】
また、本発明に係るラジカル発生剤は、ラジカル発生部位として機能するナフタルイミド構造含有基を一分子内に２つ以上有するため、一分子内に含まれる複数のナフタルイミド構造含有基のうち、どこか１箇所でもラジカルを発生させて重合体等反応物と結合を形成していれば、当該分子に含まれる未反応のラジカル発生部位も全て重合体等反応物の化学構造の一部となる。ラジカル発生剤が重合体等反応物の化学構造の一部となるため、ラジカル発生剤の分子内に未反応部位が残っても、重合体等反応物中に個々の未反応部位は遊離の形で残存せず、ポストベーク時に揮発しない。しかも、化合物（ａ）は未反応のまま残存しても、ラジカル発生部位が耐熱性の高いナフタルイミド構造を有しているので、揮発性の分解物が生成しない。
【００３３】
従って、作業安全性の問題や、耐光性の悪化や、着色や退色、塗膜のはがれやクラックの発生等、最終製品の信頼性を低下させる問題や、薬液寿命を短くする問題や、臭気が発生する問題も全て解決することができる。
【００３４】
さらに、マレイミド構造を形成する反応は、加熱や触媒等により脱水縮合反応をしないと形成されず、そのため合成上様々な問題があったが、ナフタルイミド構造を形成する反応は脱水縮合反応が進行しやすく、マレイミド構造に比べて合成が非常に簡便であり、溶媒溶解性も良好なことから、合成上有利である。そのため、収率、反応速度、管理面、コスト面を含めて生産性が上がる。
【００３５】
前記式（２）において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ独立して水素原子、ハロゲン原子、水酸基、メルカプト基、アミノ基、シアノ基、シリル基、シラノール基、アルコキシ基、ニトロ基、カルボキシル基、アセチル基、アセトキシ基、スルホン基、置換基を有していてもよい有機基、又はそれらが互いに結合した環構造であることが、原料調達の容易性、合成の簡便性の点から好ましい。
【００３６】
実用的な感度を得るために、露光光源のいずれかの発光波長における前記化合物（ａ）のモル吸光係数は、０．１以上であることが好ましい。
【００３７】
また、前記化合物（ａ）の最大モル吸光係数ε_ＭＡＸは、２０００以上であることが好ましい。ナフタルイミド部位のラジカル発生メカニズムは、π−π^＊遷移が重要であると推測されるが、一般に最大モル吸光係数ε_ＭＡＸが２０００以上の場合にはπ−π^＊遷移が起こっていることが多い。
【００３８】
前記化合物（ａ）は、少なくとも１５７ｎｍ、１９３ｎｍ、２４８ｎｍ、３６５ｎｍ、４０５ｎｍ、４３６ｎｍのいずれかの波長に吸収を有することが、照射光源の発光波長と重なり、露光波長として利用するのに便利であることから好ましい。
【００３９】
前記化合物（ａ）の９０％熱分解温度は、５０℃以上であることが、樹脂組成物の保存安定性の点から好ましい。
【００４０】
前記化合物（ａ）は、モノマー等の重合成分に対する溶解性が高いほど開始剤としての作用が向上し、感度が高くなるので、化合物（ａ）の２０℃におけるアクリル酸メチルに対する飽和濃度が、０．０１ｍｏｌ／Ｌ以上であることが好ましい。
【００４１】
上記課題を解決するための本発明に係る感光性樹脂組成物は、１分子中に下記式（２）
【００４２】
【化４】

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立して水素原子又は置換基であり、互いに結合した環構造であってもよい。化学構造Ｘはｎ価の直鎖、及び／又は分岐、及び／又は環状の飽和、不飽和の多価アルキル基、アリール基、アリル基から選ばれる有機基であって、且つ、その内部に単結合、エステル結合、エーテル結合、チオエーテル結合、アミノ結合、アミド結合、ウレタン結合、ウレア結合、チオカルバメート結合、カルボジイミド結合、カーボネート結合の結合を１つ以上有しても良い。ｎは２以上の整数である。）で表されるナフタルイミド構造含有基を２つ以上有する化合物（ａ）と、エチレン性不飽和結合を有する化合物及び芳香族化合物から選ばれる少なくとも１種類の硬化反応性化合物とを必須成分として含有することを特徴とする。
【００４３】
（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ独立して水素原子、置換基であり、互いに結合して閉環していてもよい。）
で表されるナフタルイミド構造含有基を２つ以上有する化合物（ａ）を必須成分として含有することを特徴とする。
【００４４】
本発明に係る感光性樹脂組成物は、上記本発明に係るラジカル発生剤を含有しており、化合物（ａ）のナフタルイミド構造含有基が水素引き抜き型のラジカル発生部位として機能し、光を照射して励起させることによりラジカル化し、感光性樹脂組成物中でラジカル反応を起こさせる。感光性樹脂組成物中のラジカル反応性化合物は、当該化合物の種類によってラジカル重合や、ラジカル発生剤である化合物（ａ）とのラジカル二量化反応や、ラジカル性架橋反応等、さまざまなラジカル反応を引き起こし、感光性樹脂組成物を硬化させたり、溶解性を変化させたりする。
【００４５】
本発明に係る感光性樹脂組成物において、ナフタルイミド構造含有基によって発生したラジカルは、エチレン性不飽和結合だけでなく芳香環等種々の化合物とも反応可能なため、エチレン性不飽和結合を有さない感光性樹脂組成物であっても、高分子を架橋したりラジカル反応をすることができ、必須成分の化合物（ａ）を含有すれば、エチレン性不飽和結合を有さない感光性樹脂組成物であっても、硬化及び／又は溶解性の変化を引き起こすことができる。さらに、２つ以上有するナフタルイミド構造含有基のうちどこか１箇所に発生したラジカルが感光性樹脂組成物と結合することにより、感光性樹脂組成物の化学構造の一部となる。そのため、ラジカル発生剤が感光性樹脂組成物中に遊離の形で残存することがない。その結果、最終製品の信頼性を低下させる問題も解決する。
【００４６】
さらに、ラジカル発生剤として機能する化合物（ａ）が、マレイミド構造に比べて合成が非常に簡便であり、合成上有利であるため、収率、反応速度、管理面、コスト面を含めて生産性が上がる。
【００４７】
本発明に係る感光性樹脂組成物は、硬化反応性化合物としてエチレン性不飽和結合を有する化合物（ｂ）を含んでもよい。該化合物（ｂ）は、ラジカル重合可能な硬化反応性化合物として従来から広く利用されており、応用範囲が広い。
【００４８】
ラジカルの発生効率を向上させて感度を高めるために、本発明の樹脂組成物には水素供与体を更に配合することが好ましい。
【００４９】
本発明に係る感光性樹脂組成物にエチレン性不飽和結合を有する化合物（ｂ）を配合する場合には、化合物（ａ）の量を感光性樹脂組成物の固形分全体の０．１重量％以上の割合とすることが、光照射による樹脂組成物の硬化速度が遅くなったり、発生するラジカルの量が少ないため架橋密度が低くなり、塗膜の強度や塗膜のガラス転移温度が低下することを防ぐ点から好ましい。
【００５０】
前記感光性樹脂組成物に含有される前記化合物（ａ）以外の成分は、照射光源の発光波長と前記化合物（ａ）の吸収波長が重なる波長領域における透過率が２０％以上であることが、前記化合物（ａ）に充分な光を到達させて感度を上げる点から好ましい。
【００５１】
前記感光性樹脂組成物を、パターン形成材料（レジスト）、塗料又は印刷インキ、或いは、カラーフィルター、電子部品、層間絶縁膜、配線被覆膜、光学部材、光回路、光回路部品、反射防止膜、ホログラム又は建築材料の形成材料として用いることは、製品や膜の高耐熱性、高安定性の点から好ましい。また、露光時の臭気の発生がない為、作業環境が向上する。
【００５２】
上記課題を解決するための本発明に係る印刷物、カラーフィルター、電子部品、層間絶縁膜、配線被覆膜、光学部材、光回路、光回路部品、反射防止膜、ホログラム又は建築材料は、前記感光性樹脂組成物の硬化物により少なくとも一部分が形成されていることを特徴とする。
【００５３】
本発明に係る印刷物、カラーフィルター、電子部品、層間絶縁膜、配線被覆膜、光学部材、光回路、光回路部品、反射防止膜、ホログラム又は建築材料は、高耐熱性、高安定性の感光性樹脂組成物の硬化物により少なくとも一部分が形成されているため、製品や膜としても高耐熱性、高安定性であり、そのため生産の歩留まりも高いというメリットがある。
【００５４】
【発明の実施の形態】
以下において本発明を詳しく説明する。なお本発明において光には、感光性化合物のラジカル発生部位をラジカル化し又は感光性樹脂組成物にラジカル反応を引き起こさせることが可能な可視及び非可視領域の波長の電磁波だけでなく、電子線のような粒子線、及び、電磁波と粒子線を総称する放射線又は電離放射線が含まれる。樹脂組成物の光硬化には、主に、紫外線、可視光、電子線、電離放射線等が使用される。
【００５５】
先ず、本発明に係るラジカル発生剤について説明する。本発明に係るラジカル発生剤は、１分子中に下記式（１）
【００５６】
【化５】

【００５７】
（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ独立して水素原子又は置換基であり、互いに結合した環構造であってもよい。）
で表されるナフタルイミド構造含有基を２つ以上有する化合物（ａ）からなることを特徴とする。
【００５８】
上記化合物（ａ）は、一分子内にあるナフタルイミド構造が同一のものでも良いし、２種以上のナフタルイミド構造が一分子内に混在していても良い。
【００５９】
ナフタルイミド構造含有基によるラジカル発生機構は、ナフタルイミド構造が電磁波や放射線等の光を吸収することによってラジカルを発生させるものと推定される。
【００６０】
本発明に係るラジカル発生剤は、上記ナフタルイミド構造含有基が水素引き抜き型のラジカル発生部位として機能し、光を照射して励起させることによりラジカル反応を起こしたり、ラジカル重合を開始したり、高分子を架橋することもできる。
【００６１】
上記式（１）で表されるナフタルイミド構造含有基のうち、式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ独立して水素原子又は置換基であり、互いに結合した環構造であってもよい。
【００６２】
上記置換基としては、例えば、ハロゲン原子、水酸基、メルカプト基、アミノ基、シアノ基、シリル基、シラノール基、アルコキシ基、ニトロ基、カルボキシル基、アセチル基、アセトキシ基、スルホン基、置換基を有していてもよい有機基、又はそれらが互いに結合した環構造が挙げられ、置換基を有していてもよい有機基としては、例えば、飽和又は不飽和アルキル基、飽和又は不飽和ハロゲン化アルキル基、又はフェニル基、ナフチル基等の芳香族基、アリル基、等が挙げられる。
【００６３】
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶が、水酸基又は上記例示の置換基である場合には、原料調達の容易性、合成の簡便性の点から好ましい。
【００６４】
また、上記の互いに結合した環構造であってもよいとは、シクロヘキシル基等の脂肪族性の環構造だけでなく、例えば、Ｒ¹、Ｒ²に芳香環が結合してアントラセン構造をとるものや、Ｒ²、Ｒ³に芳香環が結合してフェナントレン構造をとるものや、同様にしてピレン構造をとるものやペリレン構造をとるもの等、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶においてナフタレン環に結合してナフタレンより大きい縮合環炭化水素となっているものも、イミド環が６員環構造になっていれば、本発明のナフタルイミド構造含有基に含まれる。また、環構造は芳香族性の縮合環であっても、脂肪族性の環構造であっても良く、さらに環構成原子としてＣ以外の異種原子を含んでいても良い。
【００６５】
感光性樹脂組成物に配合する時の溶解性を向上させる点から、化合物（ａ）に導入される置換基としては、炭素数１〜１５の飽和及び不飽和アルキル基、アルコキシ基、ブロモ基、クロロ基、フルオロ基等が好ましい。
【００６６】
上記化合物（ａ）において２つ以上のナフタルイミド構造含有基のＮが結合する部分をＸで表すと、化合物（ａ）は下記式（２）で表すことができる。
【００６７】
【化６】

【００６８】
（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は式（１）と同じであり、Ｘはｎ価の化学構造、ｎは２以上の整数である）
上記式（１）に含まれる化学構造Ｘは２価以上のいかなる化学構造を持つものでも良いが、代表的には有機基である。有機基としては、例えば、直鎖、及び／又は分岐、及び／又は環状の飽和、不飽和の多価アルキル基、アリール基、アリル基、等が挙げられ、その内部に単結合、エステル結合、エーテル結合、チオエーテル結合、アミノ結合、アミド結合、ウレタン結合、ウレア結合、チオカルバメート結合、カルボジイミド結合、カーボネート結合等の結合を１つ以上有しても良い。
【００６９】
２価以上の化学構造であって有機基以外のものとしては、例えば、シロキサン、シラン、ボラジン等が挙げられる。
【００７０】
特に、価格や入手のしやすさ、合成の簡便さ、溶解性の観点からは、直鎖、又は分岐の多価アルキル基が好ましく、その内部にエステル結合、エーテル結合、アミド結合、ウレタン結合、ウレア結合を含むものがさらに好ましい。また、耐熱性の観点からは、飽和または不飽和の環状構造を有するような直鎖、又は分岐の多価アルキル基が好ましく、その内部にエステル結合、エーテル結合、アミド結合、ウレタン結合、ウレア結合を含むものがさらに好ましい。
【００７１】
本発明に係るラジカル発生剤は、ナフタルイミド構造含有基を２つ以上有するが、ラジカル重合性化合物又はラジカル重合以外のラジカル反応性化合物を３次元架橋する点からは３つ以上が好ましく、さらにラジカル発生剤がポリマー骨格に式（１）のナフタルイミド構造含有基をペンダント状に複数有する構造であって、感光性樹脂組成物中でメインポリマーとして用いられる場合には、達成したい重合度と同程度量のナフタルイミド構造を有することが好ましいが、用いる材料系や最終塗膜の物性等を考慮し、適宜、最適値を選択できる。
【００７２】
上記ラジカル発生剤は、π結合が多く連結していることから吸収波長がマレイミドよりも長波長化している為、高圧水銀灯の主要な発光波長である３６５ｎｍの波長に対し吸収を持ちやすく、感度が良好である。
【００７３】
感度を向上させるためには、化合物（ａ）の構造中に含まれるナフタルイミド骨格が放射線によって励起し、ラジカルを発生させ易い化学構造となるように置換基Ｒ¹乃至Ｒ⁶及び中心構造Ｘを選定することが有効と考えられる。
【００７４】
実用的な感度を得るためには、上記式（１）のＲ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶の置換基を組み合わせ、化合物（ａ）の吸収波長の一部が、プロセスにおける露光光源（照射光源）に含まれるいずれかの波長の発光波長と重なる様にするのが好ましく、特に、化合物（ａ）の吸収極大が、該吸収極大に最も近い発光波長の値の±２０％以内に入ることが好ましく、±１０％以内に入ることがさらに好ましい。
【００７５】
同じく感度の点から、プロセスにおける露光光源（照射光源）の発光のいずれかの波長において、化合物（ａ）のモル吸光係数が０．１以上であることが好ましい。ここでモル吸光係数εとは、Ｌａｍｂｅｒｔ−Ｂｅｅｒの法則から導き出される関係で、以下の式で表される。
【００７６】
Ａ＝εｃｂ
Ａ＝吸光度
ｂ＝試料中の光路長（ｃｍ）
ｃ＝溶質の濃度（ｍｏｌ／Ｌ）
通常、同じ濃度の溶液を用い、同じ光路長のセルによって、入射波長を変化させながら吸光度の変化を記録すると、波長によって吸光度が変化し、測定対象とされる化合物に固有の波長において最大モル吸光係数ε_ＭＡＸを示す。上記露光波長における前記化合物（ａ）のモル吸光係数が０．１以上とは、当該化合物（ａ）を用いて露光を行う際に採用する波長のいずれかで測定した時のモル吸光係数が０．１以上と言う意味であり、最大モル吸光係数ε_ＭＡＸが０．１以上と言う意味ではない。
【００７７】
また、ナフタルイミド化合物の最大モル吸光係数の点から考えると、ナフタルイミド化合物の励起状態は、π−π^＊遷移によるものと考えられる。この励起状態を経る事で、ラジカルが発生していると考えられるので、ナフタルイミドが、π−π^＊遷移を起こすことが重要である。有機化合物のスペクトルによる同定法第５版（R.M.Silverstein 1993）によれば、π−π^＊遷移は、１０，０００以上のモル吸光係数によって特徴付けられるとあるが、実際は、フェノールの様にモル吸光係数が数千程度でもπ−π^＊遷移を起こすものもあるので、ナフタルイミドの最大モル吸光係数が２，０００以上であれば、ラジカルの発生や架橋反応をしやすいと考えられる。従って、化合物（ａ）の最大モル吸光係数ε_ＭＡＸは２０００以上であることが好ましい。
【００７８】
一般的な高圧水銀ランプの場合、３６５ｎｍ（ｉ線）、４０５ｎｍ（ｈ線）、４３６ｎｍ（ｇ線）の３つの大きな発光があるが、実際は、３３３ｎｍ等にも発光があるため、これらの波長付近に化合物（ａ）の吸収極大があれば良い。また、Ｆ２エキシマレーザー（１５７ｎｍ）、ＡｒＦエキシマレーザー（１９３ｎｍ）、ＫｒＦエキシマレーザー（２４８ｎｍ）等で照射を行なう場合には、これらの波長付近に吸収を有していればよい。具体的には、３６５ｎｍ付近の吸収極大は３６５±７３ｎｍの範囲に入るのが好ましく、３６５±３７ｎｍの範囲に入るのがさらに好ましい。
【００７９】
上記した汎用性の高い露光光源の主要な発光波長である１５７ｎｍ、１９３ｎｍ、２４８ｎｍ、３６５ｎｍ、４０５ｎｍ、４３６ｎｍのいずれかの波長の少なくとも一つと重なる領域に吸収波長が重なる場合には、露光波長として利用するのに便利であり、その波長におけるモル吸光係数が０．１以上であることが特に好ましい。
【００８０】
所望の波長に対して吸収波長をシフトさせる為に、どのような置換基を導入したら良いかという指針として、Interpretation of the Ultraviolet Spectra of Natural Products （A.I.Scott 1964）や、有機化合物のスペクトルによる同定法 第５版（R.M.Silverstein 1993）に記載の表を参考にすることができる。
【００８１】
本発明のラジカル発生剤は、水素引き抜き型であることから、ただ加熱しただけではラジカルを発生させにくく、また、基本骨格がナフタルイミド骨格であることから加熱による分解を起こしにくい。従って、耐熱性に優れており、感光性樹脂組成物に配合した時に該樹脂組成物の保存安定性が良好であり、最終的に得られる硬化膜の安定性も向上し、塗膜の耐光性悪化、着色や退色、塗膜の剥がれやクラックを防止することができる。
【００８２】
耐熱性の点から、本発明に係るラジカル発生剤は、前記化合物（ａ）の９０％熱分解温度が５０℃以上であることが好ましく、１００℃以上であることが更に好ましい。
【００８３】
ここで、９０％熱分解温度とは、後述の本発明の実施例と同様の手法で、熱重量分析装置を用いて重量減少を測定した時に、サンプルの重量が初期の重量の９０％になった温度のことを言う。同様に９５％熱分解温度とはサンプル重量が初期重量の９５％になった時の温度である。
【００８４】
上記化合物（ａ）は、塗布適性、硬化後の透明性、露光時の感度等を向上させる点から、感光性樹脂組成物に配合する時の溶解性が高いことが好ましい。
【００８５】
塗布時の塗工適性の点からは、化合物（ａ）は溶剤に対する溶解性が高いことが好ましく、具体的には、使用する溶剤、特に後述する汎用溶剤のいずれかに対する化合物（ａ）の溶解性が０．１重量％以上であることが好ましい。
【００８６】
また、溶剤を用いて透明に溶解した感光性樹脂組成物であっても、その中に含有される固形分同士の相溶性が低い場合には、塗工時に溶剤が揮発すると乾燥中の塗膜内で析出物が生じ、充分な透明性が得られない。そのため、光学部材のように透明性が高い塗膜又は成形体が要求される場合には、感光性樹脂組成物中の他の固形成分、特に後述する化合物（ｂ）のような重合性化合物、その中でもモノマー成分との相溶性が高い化合物（ａ）を用いることが好ましい。高い透明性が求められる場合には、感光性樹脂組成物を硬化させて形成した塗膜の膜厚が１０μｍの時に、全光線透過率（ＪＩＳ Ｋ７１０５）が９０％以上であることが好ましく、９５％以上であることが更に好ましい。
【００８７】
化合物（ａ）の重合性化合物に対する溶解性が高い場合には、開始剤としての作用が向上するので、露光時の感度にも優れる。この点から、モノマー成分の代表としてアクリル酸メチルを用いて溶解性を評価したときに、化合物（ａ）の２０℃におけるアクリル酸メチルに対する飽和濃度が、０．０１ｍｏｌ／Ｌ以上であることが好ましい。
【００８８】
化合物（ａ）の溶解性又は相溶性は、ナフタルイミド環に置換基を導入することによって向上させることができる。この観点からは、ナフタルイミド環の置換基として、炭素数１〜１５の飽和又は不飽和アルキル基、アルコキシ基、ブロモ基、クロロ基、フルオロ基等が好ましい。また、上記式（２）のＸの構造を変更するか又はＸに置換基を導入することでも、化合物（ａ）の溶解性又は相溶性を向上させることができる。化合物（ａ）のナフタルイミド環又はＸ部分に導入される置換基又は施される構造変更は、溶解させたい溶剤又は相溶させたい他の固形成分によって種々選択される。例えば、置換基としてカルボキシル基を選択した場合には、水や有機極性溶剤に溶解し易くなり、エステルを導入した場合には、エステル結合を有する溶剤や化合物への溶解性が向上する。
【００８９】
上記式（１）のような１，８−ナフタルイミド化合物は、一般にナフタレンの１位と８位に置換基を有し、それらが無水物となって結合している１，８−ナフタル酸無水物から合成される。イミド結合は、まず無水物とアミンが付加反応し、アミド酸が形成された後、加熱や触媒等により脱水縮合反応をすることで形成されるのが一般的である。フタル酸無水物やマレイン酸無水物の様に酸無水物が５員環構造を有する場合は、上記のような２段階で反応が進行し、加熱や触媒等により脱水縮合反応をしないとイミドが形成されず、そのため合成上様々な問題がある。これに対して、１，８−ナフタル酸無水物は、６員環の無水物構造を有しているため、１級のアミンと付加反応をすると脱水反応が進行しやすい。６員環構造は５員環構造よりもゆがみが少なくエネルギー的に安定であり、６員環構造の場合、アミド酸よりもイミドの方が安定である為と考えられる。これらの事から、ナフタルイミド構造はマレイミド構造に比べ合成が非常に簡便であり、合成上有利である。従って、化合物（ａ）からなる光ラジカル発生剤は、収率、反応速度、管理面、コスト面を含めて生産性も高い。
【００９０】
本発明におけるナフタルイミド構造含有基を２つ以上有する化合物（ａ）は、公知の種々の手法を用いて合成することができる。具体的に例示すると、ナフタル酸無水物とジアミン、トリアミン、テトラアミン等、複数のアミノ基を有する化合物とを反応させる手法や、ナフタル酸無水物にアミノアルコールを反応させて、Ｎ−ヒドロキシアルキル（アリル）ナフタルイミドを合成した後、多価カルボン酸と脱水縮合させる手法や、Ｎ−ヒドロキシアルキル（アリル）ナフタルイミドを合成した後、多価カルボン酸クロライドと反応させる手法や、ナフタル酸無水物とアミノ酸を反応させ、Ｎ―カルボキシアルキル（アリル）ナフタルイミドを合成し、その後塩化チオニル等で処理し酸クロライド化した後に、多価アミンや多価アルコールと反応させる手法等が挙げられるが、特に限定されない。
【００９１】
上記合成方法における原料としては、１，８−ナフタル酸無水物、４−ブロモ−１，８−ナフタル酸無水物等の酸無水物の他に、その誘導体を用いても良い。ナフタル酸無水物の誘導体としては、最終的に得たい化合物（ａ）の置換基Ｒ¹乃至Ｒ⁶がすでに導入されたものを用いてもよい。また、式（１）の置換基Ｒ^１〜Ｒ^６は、イミド化反応を行う前に導入しても良いし、イミド化反応後に導入しても良い。
【００９２】
ナフタルイミド構造含有基を２つ有する化合物（ａ）を合成する手法をこれより具体的に例示するが、本発明の合成方法として特に限定されるものではない。また、類似の手法や公知の手法を用いてナフタルイミド構造含有基を２つ以上有する化合物を合成することが出来る。
【００９３】
先ず、１，８−ナフタル酸無水物をＮ，Ｎ，−ジメチルホルムアミドに投入し攪拌する。そこへ１，１２−ジアミノドデカンをナフタル酸無水物と１／２モル滴下し、室温で１〜１５時間程度、攪拌する。この時、用いる反応溶媒は、ジメチルホルムアミドに限定されず、２種以上の溶媒を混合して用いても良い。反応溶媒としては、有機極性溶媒等、最終生成物が溶解する溶媒が好ましい。ナフタル酸無水物は溶解性に乏しく一般の溶媒には、溶解し難いので、アミンと反応することで溶解するようになる場合が多い。
【００９４】
１，８−ナフタル酸無水物は、室温でアミンと混合し攪拌するのみでイミド結合を形成する場合がある。さらに反応を加速させるために、室温〜２００℃までの範囲で温度を加えても良い。また、反応の際に発生する水を除去するために、トルエン等の共沸溶媒を混合させて用いても良い。
【００９５】
このように、数時間攪拌された反応液の溶媒を留去、または、水等に投入することで除去し、固体を取り出す。これを、所望の溶媒にて再結晶を行なうことで、Ｎ−置換ナフタルイミド化合物、すなわち、この場合は式（１）で表されるナフタルイミド構造含有基を２つ有する化合物（ａ）を得ることができる。精製の方法は、再結晶に限定されず、昇華精製やカラムクロマトグライフィー等、公知のあらゆる方法が用いることが可能であるが、コストの観点から再結晶が好ましい。
【００９６】
ここで用いる酸無水物は１，８−ナフタル酸無水物だけでなく、目的に応じて４位にブロモ基を有した４−ブロモ−１，８−ナフタル酸無水物のように予め置換基が導入されたものを用いても良い。
【００９７】
また、ここで用いるアミノ化合物は、化合物（ａ）に導入すべきナフタルイミド構造含有基の数に応じて、アミノ化合物が有するアミノ基（−ＮＨ₂）の数を選択すれば良い。
【００９８】
ナフタルイミド構造含有基を２つ有する化合物の場合には、ジアミノ化合物を用いることができる。具体的には、３，５−ジアミノ安息香酸、４，４’−ジヒドロキシ−３，３’−ジアミノビフェニル、３，４−ジアミノ安息香酸、３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル、２，３−ジアミノ−４−ヒドロキシピリジン、２，２−ビス（４−ヒドロキシ−３−アミノフェニル）ヘキサフルオロプロパン、２，４−ジアミノフェノール、２，４−ジアミノ安息香酸、３−カルボキシ−４，４’−ジアミノジフェニルエ−テル、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルエ−テル、３−カルボキシ−４，４’−ジアミノジフェニルメタン、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルメタン、３，３’−ジカルボキシ−４，４’−ジアミノビフェニル、３，３’，５，５’−テトラカルボキシ−４，４’−ジアミノビフェニル、３−カルボキシ−４，４’−ジアミノジフェニルスルホン、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルスルホン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（３−カルボキシ−４−アミノフェニル）プロパン、４，４’−（又は３，４’−、３，３’−、２，４’−、２，２’−）ジアミノジフェニルエーテル、４，４’−（又は３，４’−、３，３’−、２，４’−、２，２’−）ジアミノジフェニルメタン、４，４’−（又は３，４’−、３，３’−、２，４’−、２，２’−）ジアミノジフェニルスルホン、４，４’−（又は３，４’−、３，３’−、２，４’−、２，２’−）ジアミノジフェニルスルフィド、パラフェニレンジアミン、メタフェニレンジアミン、ｐ−キシリレンジアミン、ｍ−キシリレンジアミン、ｏ−トリジン，ｏ−トリジンスルホン、４，４’−メチレン−ビス−（２，６−ジエチルアニリン）、４，４’−メチレン−ビス−（２，６−ジイソプロピルアニリン）、２，４−ジアミノメシチレン、１，５−ジアミノナフタレン、４，４’−ベンゾフェノンジアミン、ビス−｛４−（４’−アミノフェノキシ）フェニル｝スルホン、１，１，１，３，３，３−ヘキサフルオロ−２，２−ビス（４−アミノフェニル）プロパン、２，２−ビス｛４−（４’−アミノフェノキシ）フェニル｝プロパン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、３，３’，５，５’−テトラメチル−４，４’−ジアミノジフェニルメタン、ビス｛４−（３’−アミノフェノキシ）フェニル｝スルホン、２，２−ビス（４−アミノフェニル）プロパン、エチレンジアミン、ジエチレントリアミン、１，３−ジアミノプロパン、１，２−ジアミノプロパン、２，２−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノペンタン、１，６−ジアミノへキサン、１，４−ジアミノシクロヘキサン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，１２−ジアミノドデカン、２−（２−アミノエトキシ）エチルアミン等が挙げられるが特に限定されない。
【００９９】
ナフタルイミド構造含有基を３つ有する化合物（ａ）の場合には、トリアミノ化合物、ナフタルイミド構造含有基を４つ有する化合物（ａ）の場合には、テトラアミノ化合物を用いて、ナフタルイミドを２つ有する化合物の場合と同様にして、化合物（ａ）を合成できる。また、合成時のナフタル酸無水物とアミノ化合物の仕込み比を変化させることで、アミノ化合物のアミノ基の数よりナフタルイミド基の導入量が少ない化合物（ａ）を合成することも出来る。
【０１００】
上記の手法以外の合成手法として、ナフタル酸無水物にアミノアルコールを反応させて、Ｎ−ヒドロキシアルキル（アリル）ナフタルイミドを合成した後、多価カルボン酸と脱水縮合させる手法を具体的に例示するが、本発明の合成方法として特に限定されるものではない。
【０１０１】
先ず、１，８−ナフタル酸無水物をＮ，Ｎ，−ジメチルホルムアミドに投入し攪拌する。そこへ２−アミノエタノールをナフタル酸無水物と等モル滴下し、室温で１〜１５時間程度、攪拌する。この時、用いる反応溶媒は、ジメチルホルムアミドに限定されず、有機極性溶媒等、最終生成物が溶解する溶媒であればよく、それらは単独で用いても２種以上を混合させても良い。ナフタル酸無水物は溶解性に乏しく一般の溶媒には、溶解し難いので、アミンと反応することで溶解するようになる場合が多い。
【０１０２】
１，８−ナフタル酸無水物は、室温でアミンと混合し攪拌するのみでイミド結合を形成する場合がある。さらに反応を加速させるために、室温〜２００℃までの範囲で温度を加えても良い。また、反応の際に発生する水を除去するために、トルエン等の共沸溶媒を混合させて用いても良い。
【０１０３】
１，８−ナフタル酸無水物に２−アミノエタノールを反応させて合成した、Ｎ−２―ヒドロキシエチルナフタルイミドは、種々の方法で化合物（ａ）とすることができる。以下に代表例を示すが本発明はこれに限定されない。
【０１０４】
Ｎ−２―ヒドロキシエチルナフタルイミドと、１．２モル等量の４−ジメチルアミノピリジンを、脱水したトルエン等の溶媒に溶解させる。そこに、０．６モル等量のサクシニルクロライドを徐々に滴下し、１〜１５時間室温で攪拌する。分液ろうとで、１ＮＨＣｌで処理し、４−ジメチルアミノピリジンを水層に移動させる。水層と油層に分離した後、油層を、さらに、飽和ＮａＨＣＯ₃溶液を用い処理し、未反応のサクシニルクロライド由来のコハク酸を水層に移動させ、油層と水層を分離する。このようにして、得られた油層を硫酸マグネシウム等の適当な脱水剤で脱水し、ろ過を行なう。このろ液から溶媒を留去した物を再結晶して目的物を得る。
【０１０５】
以上の操作の他に、酸触媒によるジカルボン酸との脱水縮合による方法でも同様の化合物を得ることができる。
【０１０６】
また、特開平５−１９５０５号公報に開示されているようなＮ−カルボキシアルキルナフタルイミドを用いて、公知の方法でアミドや、エステル、ウレアを合成しても、化合物（ａ）を得ることが出来る。
【０１０７】
先に述べた様に、ここで用いる酸無水物は１，８−ナフタル酸無水物だけでなく、目的に応じて４位にブロモ基を有した４−ブロモ−１，８−ナフタル酸無水物のように予め置換基が導入されたものを用いても良い。
【０１０８】
また、ここで用いるアミン化合物も２−アミノエタノールに限定されず目的に応じて、種々のアミン化合物を用いることができる。例えば、プロパノールアミン、ヘキサノールアミン等のオキシアルキルアミン、エトキシエタノールアミン、プロポキシプロパノールアミン、２−（２−アミノエトキシ）エタノール等の置換オキシアルキルアミン等、が挙げられる。
【０１０９】
このようにして得られる本発明に係るラジカル発生剤は、上記ナフタルイミド構造含有基が水素引き抜き型のラジカル発生部位として機能し、電磁波や放射線等の光を照射して励起させることによりラジカル反応を起こすことができる。ナフタルイミド構造含有基は、自己開裂型ではなく水素引き抜き型であり、しかも耐熱性が良好なナフタレン骨格を有するため、耐熱性、安定性、保存性が高い光ラジカル発生剤を得ることができる。
【０１１０】
また、ナフタルイミド構造含有基によって発生したラジカルは水素引抜きのメカニズムを経るため、エチレン性不飽和結合等の一般的なラジカル重合性基だけでなく、芳香環等種々の化合物とも反応可能なため、例えばキシレンのような低分子量の芳香族化合物と反応したり或いはＰＥＴのような芳香族部位を有する高分子を架橋することができる。また、ラジカル発生部位として機能するナフタルイミド構造含有基を２つ以上有するため、一分子内の２つ以上のナフタルイミド含有基が他の分子と結合して３次元架橋構造を形成することもできる。従って、化合物（ａ）であるラジカル発生剤は、一般的な光ラジカル重合開始剤として用いられるほか、例えば芳香族ポリマーを含有する樹脂組成物の架橋剤として用いて硬化後の耐溶剤性を向上させることが可能である。
【０１１１】
また、ラジカル発生剤の一分子内に含まれる複数のナフタルイミド構造含有基（ラジカル発生部位）のうち、どこか１箇所でもラジカルを発生させて重合体等反応物と結合を形成していれば、当該分子に含まれる未反応のラジカル発生部位も全て重合体等反応物の化学構造の一部となる。そのため、ラジカル発生剤の分子内に未反応部位が残っても、個々の未反応部位は重合体等反応物中に遊離の形で残存せず、ポストベーク時に揮発しない。しかも、ラジカル発生部位は未反応のまま残存しても水素引き抜き型であると共に、耐熱性の高いナフタルイミド構造を有しているから、硬化後の塗膜中で揮発性の分解物を生成することがない。そのため、本発明のラジカル発生剤由来の残存物は、塗膜の変質を引き起こしにくい。このように、本発明のラジカル発生剤由来の残存物は、感光性樹脂組成物の硬化塗膜中においてマトリックスと結合し、且つ、化学的に安定した形で存在し、耐熱性、耐候性、安定性を損なわない。
【０１１２】
従って、本発明の光ラジカル重合開始剤由来の残存物は、作業安全性の問題や、耐光性の悪化、着色や退色の発生、塗膜のはがれやクラックの発生等の最終製品の信頼性を低下させる問題や、薬液寿命を短くする問題や、臭気が発生する問題を引き起こさない。
【０１１３】
また、マレイミド構造を形成する反応は、加熱や触媒等により脱水縮合反応を促進させないと形成されず、そのため合成上様々な問題があったが、ナフタルイミド構造を形成する反応ではマレイミドに比べて脱水縮合反応が速やかに進行し、合成が非常に簡便であり、合成上有利である。そのため、収率、反応速度、管理面、コスト面を含めて生産性が上がる。
【０１１４】
次に、本発明に係る感光性樹脂組成物について説明する。
【０１１５】
本発明に係る感光性樹脂組成物は、上述した式（１）で表されるナフタルイミド構造含有基を２つ以上有する化合物（ａ）を必須成分として含有することを特徴とし、必要に応じてラジカル反応性化合物又はその他の硬化反応性化合物、高分子量のバインダー成分、水素供与体、化合物（ａ）以外のラジカル発生剤、又は、その他の成分を含有してもよい。
【０１１６】
本発明に係る感光性樹脂組成物（以下、単に、樹脂組成物とする。）は、上記化合物（ａ）からなるラジカル発生剤のナフタルイミド構造含有基が水素引き抜き型のラジカル発生部位として機能し、電磁波や放射線等の光を照射して励起させることによりラジカル化し、樹脂組成物中でラジカル反応を起こさせる。樹脂組成物中のラジカル反応性化合物は、当該化合物の種類によってラジカル重合や、ラジカル発生剤である化合物（ａ）とのラジカル二量化反応や、ラジカル性架橋反応等、さまざまなラジカル反応を引き起こし、樹脂組成物を硬化させたり、溶解性を変化させたりする。
【０１１７】
ここで、架橋とは、架橋結合を生成することをいい、架橋結合とは、鎖状に結合した原子からなる分子のうちの任意の２原子間に橋をかけるようにして形成された結合をいい、この場合の結合は、同一分子内でも他分子間でも良い（化学辞典 東京化学同人 ｐ．１０８２）。
【０１１８】
エチレン性不飽和結合を有する化合物（ｂ）は、ラジカル重合可能な硬化反応性化合物として従来から広く利用されており、応用範囲が広いことから、本発明においても好適に用いられる。エチレン性不飽和結合を有する化合物（ｂ）としては、エチレン性不飽和結合を１つ又は２つ以上有する化合物、及び、少なくとも１つのエチレン性不飽和結合と共に他の官能基を有する化合物を用いることができ、例えば、アミド系モノマー、（メタ）アクリレートモノマー、ウレタン（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー、エポキシ（メタ）アクリレート、及びヒドロキシル基含有（メタ）アクリレート、スチレン等の芳香族ビニル化合物を挙げることができる。
【０１１９】
アミド系モノマーとしては、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、アクリロイルモルホリン等のアミド化合物がある。
【０１２０】
（メタ）アクリレートモノマーとしては、ヘキサヒドロフタルイミドエチルアクリレート、コハクイミドエチルアクリレート等のイミドアクリレート類；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、２−ヒドロキシ−３−フェニルプロピルアクリレート等のヒドロキシアルキル（メタ）アクリレート類；フェノキシエチル（メタ）アクリレート等のフェノールのアルキレンオキシド付加物のアクリレート類及びそのハロゲン核置換体；エチレングリコールのモノまたはジ（メタ）アクリレート、メトキシエチレングリコールのモノ（メタ）アクリレート、テトラエチレングリコールのモノまたはジ（メタ）アクリレート、トリプロピレングリコールのモノまたはジ（メタ）アクリレート等の、グリコールのモノまたはジ（メタ）アクリレート類；トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートおよびペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサアクリレート等のポリオールおよびそのアルキレンオキサイドの（メタ）アクリル酸エステル化物、イソシアヌール酸ＥＯ変性ジまたはトリ（メタ）アクリレート等が挙げられる。
【０１２１】
ウレタン（メタ）アクリレートオリゴマーとしては、ポリオールと有機ポリイソシアネートの反応物に対して、さらにヒドロキシル基含有（メタ）アクリレートを反応させた反応物等が挙げられる。
【０１２２】
ここで、ポリオールとしては、低分子量ポリオール、ポリエチレングリコール及びポリエステルポリオール等があり、低分子量ポリオールとしては、エチレングリコール、プロピレングリコール、シクロヘキサンジメタノール及び３−メチル−１，５−ペンタンジオール等が挙げられ、ポリエーテルポリオールとしては、ポリエチレングリコール及びポリプロピレングリコール等が挙げられ、ポリエステルポリオールとしては、これら低分子量ポリオール及び／又はポリエーテルポリオールと、アジピン酸、コハク酸、フタル酸、ヘキサヒドロフタル酸及びテレフタル酸等の二塩基酸又はその無水物等の酸成分との反応物が挙げられる。
【０１２３】
また、上記ポリオールと反応させる有機ポリイソシアネートとしては、トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、ヘキサメチレンジイソシアネート及びイソホロンジイソシアネート等が挙げられる。
【０１２４】
ポリエステル（メタ）アクリレートオリゴマーとしては、ポリエステルポリオールと（メタ）アクリル酸との脱水縮合物が挙げられる。ポリエステルポリオールとしては、エチレングリコール、ポリエチレングリコール、シクロヘキサンジメタノール、３−メチル−１，５−ペンタンジオール、プロピレングリコール、ポリプロピレングリコール、１，６−ヘキサンジオール及びトリメチロールプロパン等の低分子量ポリオール、並びにこれらのアルキレンオキシド付加物等のポリオールと、アジピン酸、コハク酸、フタル酸、ヘキサヒドロフタル酸及びテレフタル酸等の二塩基酸又はその無水物等の酸成分とからの反応物等が挙げられる。
【０１２５】
エポキシ（メタ）アクリレートは、エポキシ樹脂に（メタ）アクリル酸等の不飽和カルボン酸を付加反応させたもので、ビスフェノールＡ型エポキシ樹脂のエポキシ（メタ）アクリレート、フェノールあるいはクレゾールノボラック型エポキシ樹脂のエポキシ（メタ）アクリレート、ポリエーテルのジグリシジルエーテルの（メタ）アクリル酸付加反応体等が挙げられる。
【０１２６】
化合物（ｂ）は、ラジカル重合性化合物又はラジカル重合以外のラジカル反応性化合物を３次元架橋する点からはエチレン性不飽和結合を２個以上、特に３個以上有することが好ましい。
【０１２７】
また、感光性樹脂組成物を、電子部材やカラーフィルター等の用途で露光によりパターンを形成するレジストとして用いる場合には、感光性樹脂組成物のアルカリ現像性を向上させる為に、化合物（ｂ）としてカルボキシル基やフェノール性水酸基、スルホン酸基、水酸基等のアルカリ可溶性や、親水性の官能基を有すものを用いても良い。
【０１２８】
本発明の感光性樹脂組成物には、当該組成物の未硬化状態での成膜性及び硬化後の塗膜物性を調節するために、バインダー成分として高分子化合物を配合しても良い。高分子化合物としては、公知のあらゆる高分子化合物を用いることができる。例えば、トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、ヘキサメチレンジイソシアネート及びイソホロンジイソシアネート等の有機ポリイソシアネート；酢酸ビニル、塩化ビニル、アクリル酸エステル、メタクリル酸エステル等のアクリル又はビニル化合物の重合体及び共重合体；ポリスチレン等のスチレン系樹脂；ホルマール樹脂やブチラール樹脂等のアセタール樹脂；シリコーン樹脂；フェノキシ樹脂；ビスフェノールＡ型エポキシ樹脂等に代表されるエポキシ樹脂；ポリウレタン等のウレタン樹脂；フェノール樹脂；ケトン樹脂；キシレン樹脂；ポリアミド樹脂；ポリイミド樹脂；ポリエーテル樹脂；ポリフェニレンエーテル樹脂；ポリベンゾオキサゾール樹脂；環状ポリオレフィン樹脂；ポリカーボネート樹脂；ポリエステル樹脂；ポリアリレート樹脂；ポリスチレン樹脂；ノボラック樹脂；ポリカルボジイミド、ポリベンゾイミダゾール、ポリノルボルネン等の脂環式高分子；シロキサン系高分子等の公知のあらゆる高分子化合物が挙げられるが、これらに限定されない。
【０１２９】
必須成分である化合物（ａ）が有するナフタルイミド構造含有基によって発生したラジカルは、エチレン性不飽和結合だけでなく、芳香環等種々の化合物の反応も進行するため、エチレン性不飽和結合を有する化合物が存在しない系でも、硬化、及び／または溶解性の変化を引き起こすことができる。従って化合物（ａ）は、エチレン性不飽和結合を有する化合物を含有する感光性樹脂組成物を通常のラジカル重合反応により硬化させるだけでなく、例えば、ポリスチレンやポリエチレンテレフタレート（ＰＥＴ）等の一般的には非重合性の芳香族ポリマーを含有する感光性樹脂組成物を架橋反応により硬化させて、耐溶剤性、耐熱性、硬度、強度、密着性等の膜物性を向上させることができる。
【０１３０】
そのため、感光性樹脂組成物を調製するために化合物（ａ）と混合する高分子量の硬化反応性バインダー成分としては、エチレン性不飽和結合を有する化合物等の一般的なラジカル重合性化合物ばかりでなく、公知のあらゆる高分子化合物を用いることができる。
【０１３１】
また、化合物（ａ）自体がラジカル反応性化合物として機能する場合には、ラジカル反応性化合物を混合しなくても感光性樹脂組成物を調製することができる。従って、この場合には、高分子量の非反応性バインダー成分を用いることも可能であり、バインダー成分を全く用いなくてもよい。
【０１３２】
これらの高分子化合物は、単独で用いても、２種以上を組合わせて用いても良い。バインダー成分である高分子化合物は、感光性樹脂組成物の用途にもよるが重量平均分子量が通常、１０，０００，０００以下であることが好ましい。分子量が大きすぎると、溶解性や加工特性の悪化を招く。
【０１３３】
本発明に係る樹脂組成物中における化合物（ａ）の量は、感光性樹脂組成物の固形分全体の０．１重量％以上であることが、光照射による樹脂組成物の硬化速度が遅くなったり、発生するラジカルの量が少ないため架橋密度が低くなり、塗膜の強度や塗膜のガラス転移温度が低下することを防ぐ点から好ましく、感度や塗膜の物性の点から、１重量％以上であることが更に好ましい。この場合、目的に応じて諸物性を考慮の上、化合物（ｂ）及び／又は上記高分子化合物に対する化合物（ａ）の混合割合は適宜選択できる。なお、感光性樹脂組成物の固形分とは溶剤以外の全成分であり、液状のモノマー成分も固形分に含まれる。
【０１３４】
また、硬化反応性化合物として、化合物（ｂ）と共に他のラジカル反応性化合物を組み合わせて用いる場合には、組み合わせるラジカル反応性化合物の種類及び量に応じて化合物（ａ）の量を適宜調節する。
【０１３５】
本発明の感光性樹脂組成物が化合物（ｂ）を含む場合、充分な光硬化性を得るために化合物（ｂ）は、感光性樹脂組成物の固形分全体の１重量％以上であることが好ましい。感光性樹脂組成物は、化合物（ｂ）以外の高分子量のバインダー成分を含んでいても良く、その場合には用途に応じて、樹脂組成物全体の固形分の１重量％以上９７重量％以下が好ましい。エチレン性不飽和結合を含まない高分子量バインダー成分が９７重量％よりも多い場合は、光による硬化性が低下しやすい。
【０１３６】
また、化合物（ａ）は水素引き抜き型のラジカル発生剤であるので、よりラジカルの発生効率が向上し感度が良くなる点から、本発明の樹脂組成物中に水素供与体が含まれていることが好ましい。水素供与体の水素供与性基としては、アルキル基のように炭素に直接水素がついている官能基や、一般に水素供与性基として用いられているアミン、チオール、水酸基又はエーテル結合を有する有機基等が挙げられる。特に、水素を供与しやすいチオール、アミン、水酸基、及び、エーテル結合を有する有機基が感度の点から好ましい。エーテル結合は、該エーテル結合の隣りの炭化水素構造（アルカン、アルケン）の水素が引き抜かれ易いと言われている。従って、エーテル結合を含む水素供与基は、そのような水素を有する構造であることが好ましい。
【０１３７】
水素供与体に含まれる水素供与性基の配合割合は、感度の点からは、樹脂組成物に含まれているナフタルイミド部位のモル数と同じかそれ以上が好ましいが、感度と最終的に得られる塗膜の物性との関係により、適宜、適正な値を選択できる。
【０１３８】
本発明の感光性樹脂組成物を光により硬化させる際には、ラジカル反応を促進するために、必要に応じて化合物（ａ）と共に、その他の光ラジカル発生剤を使用しても良い。化合物（ａ）と共に他の光ラジカル発生剤を併用する場合には、該他の光ラジカル発生剤が分解物を生じさせ、硬化膜の変色や物性、分解物の揮発、感光性樹脂組成物の安定性、保存性等の問題を起こす可能性がある。しかしながら、化合物（ａ）の併用によって他の光ラジカル発生剤の使用量を少なくすることができるので、他の光ラジカル発生剤しか用いない場合と比べて、上記諸問題は発生し難く、仮に発生したとしても程度が軽いので、充分なラジカル反応性を引き出しながらも、光ラジカル発生剤による問題を実用的に許容できる程度に抑えることができる。
【０１３９】
その他の光ラジカル発生剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル及びベンゾインイソプロピルエーテル等のベンゾインとそのアルキルエーテル；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン、１−ヒドロキシアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン及び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−オン等のアセトフェノン；２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリ−ブチルアントラキノン、１−クロロアントラキノン及び２−アミルアントラキノン等のアントラキノン；２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン及び２，４−ジイソピルチオキサントン等のチオキサントン；アセトフェノンジメチルケタール及びベンジルジメチルケタール等のケタール；２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド等のモノアシルホスフィンオキシドあるいはビスアシルホスフィンオキシド；ベンゾフェノン等のベンゾフェノン類；並びにキサントン類等が挙げられる。
【０１４０】
これらの光ラジカル発生剤は単独で使用することも、安息香酸系、アミン系等の光重合開始促進剤と組み合わせて使用することもできる。これら光ラジカル発生剤の好ましい配合割合は、樹脂組成物全体に対して０．１重量％以上３５重量％以下で、より好ましくは、１重量％以上１０重量％以下である。
【０１４１】
本発明に係る感光性樹脂組成物に加工特性や各種機能性を付与するために、その他に様々な有機又は無機の低分子又は高分子化合物を配合してもよい。例えば、染料、界面活性剤、レベリング剤、可塑剤、微粒子、増感剤等を用いることができる。微粒子には、ポリスチレン、ポリテトラフルオロエチレン等の有機微粒子、コロイダルシリカ、カーボン、層状珪酸塩等の無機微粒子等が含まれ、その機能又は形態としては顔料、フィラー、繊維等がある。
【０１４２】
これら任意成分の配合割合は、樹脂組成物の固形分全体に対し、０．１重量％〜９５重量％の範囲が好ましい。０．１重量%未満だと、添加物を添加した効果が発揮されにくく、９５重量％を越えると、樹脂組成物量が少なく樹脂組成物の特性が最終生成物に反映されにくい。
【０１４３】
照射光源の発光を吸収してしまうような成分を感光性樹脂組成物中に多量に配合する場合には、化合物（ａ）に光が充分到達しなくなり、感度が低下する。そのため、樹脂組成物の感度を重視する点から、露光光源の発光波長と樹脂組成物に混合されている化合物（ａ）の吸収波長が重なる波長領域における、化合物（ａ）以外の成分の透過率が２０％以上であることが好ましい。
【０１４４】
また、本発明に係る感光性樹脂組成物は、溶剤を用いて適切な濃度に希釈しても良い。溶剤としては各種の汎用溶剤、例えば、ジエチルエーテル、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル等のエーテル類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のグリコールモノエーテル類(いわゆるセロソルブ類)；メチルエチルケトン、アセトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノンなどのケトン類；酢酸エチル、酢酸ブチル、酢酸ｎ−プロピル、酢酸ｉ−プロピル、酢酸ｎ−ブチル、酢酸ｉ−ブチル、前記グリコールモノエーテル類の酢酸エステル（例えば、メチルセロソルブアセテート、エチルセロソルブアセテート）、メトキシプロピルアセテート、エトキシプロピルアセテート、修酸ジメチル、乳酸メチル、乳酸エチル等のエステル類；エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、ジエチレングリコール、グリセリン等のアルコール類；塩化メチレン、１，１−ジクロロエタン、１，２−ジクロロエチレン、１−クロロプロパン、１−クロロブタン、１−クロロペンタン、クロロベンゼン、ブロムベンゼン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン等のハロゲン化炭化水素類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類；Ｎ−メチルピロリドンなどのピロリドン類；γ−ブチロラクトン等のラクトン類；ジメチルスルホキシドなどのスルホキシド類、その他の有機極性溶媒類等が挙げられ、更には、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、及び、その他の有機非極性溶媒類等も挙げられる。また、反応性希釈剤として、常温で液体のエチレン性不飽和化合物等、反応性基を構造中に有するような化合物を溶剤として用いても良い。これらの溶媒は単独もしくは組み合わせて用いられる。また、これら溶剤は、通常例えば孔径０．０５μｍ〜０．２μｍ程度のフィルター等、既知の種々の方法で不純物を濾過して用いても良い。
【０１４５】
樹脂組成物は、必須成分である化合物（ａ）に、必要に応じて化合物（ｂ）等の硬化反応性化合物、高分子量のバインダー成分等の任意成分を場合や用途に応じて攪拌等して混合することにより調製できる。
【０１４６】
このようにして得られる本発明に係る感光性樹脂組成物は、パターン形成材料（レジスト）、コーティング材、印刷インキ、接着剤、充填剤、成形材料、３次元造形等、光の照射によって硬化したり又は溶解性が変化する材料が用いられている公知の全ての分野・製品に利用できるが、特に、耐熱性が必要で高度の信頼性を要求される、塗料、印刷インキ、カラーフィルター、電子部品、層間絶縁膜、配線被覆膜、光学部材、光回路、光回路部品、反射防止膜、ホログラム又は建築材料を形成するのに適している。
【０１４７】
例えば、カラーフィルターの場合には、画素部、当該画素部の境界に設けられる遮光部（ブラックマトリックス）、保護膜、セルギャップを維持するためのスペーサーを上記感光性樹脂組成物の硬化物により形成することができる。
【０１４８】
電子部品の場合には、例えば、半導体装置のアンダーフィル剤、封止剤、等が例示できる。
【０１４９】
層間絶縁膜としては、耐熱性、絶縁信頼性が要求されるビルドアップ基板用の層間絶縁膜や燃料電池における層間絶縁膜、自動車部品や家電製品の絶縁コーティング、等を上記感光性樹脂組成物の硬化物により形成することができる。
【０１５０】
また、配線保護膜としては、プリント配線板の表面の配線保護層であるソルダーレジストや、電線の表面被覆、等が例示できる。
【０１５１】
光学部材の場合には、各種光学レンズのオーバーコートや、反射防止膜、光導波路、分波装置等の光回路部品、レリーフ型、及び体積型のホログラム、等が例示できる。
【０１５２】
建築材料の場合には、壁紙、壁材、床材その他の揮発成分の少ない表皮材料、接着・粘着材料、インキ等が例示できる。
【０１５３】
本発明に係る印刷物、カラーフィルター、電子部品、層間絶縁膜、配線被覆膜、光学部材、光回路、光回路部品、反射防止膜ホログラム又は建築材料は、高耐熱性、高安定性の感光性樹脂組成物の硬化物により少なくとも一部分が形成されているため、高耐熱性、高安定性であり、そのため生産の歩留まりも高いというメリットがある。
【０１５４】
【実施例】
１．製造例
（製造例１）（ポリ−４−メチルスチレンの合成）
攪拌機を取りつけた５００ｍＬのセパラブルフラスコに酢酸エチル３０ｍＬを入れ、窒素を１００ｍＬ／ｍｉｎで流しながら、６０℃のオイルバスにつけ攪拌した。そこへ、ＡＩＢＮ（２，２'−アゾビスイソブチロニトリル）４００ｍｇを溶かした４−メチルスチレン５０ｇを滴下した。７時間攪拌を続けた後、反応液を酢酸エチルで適当に希釈し、エタノールに滴下することで再沈殿を行ない精製し、４２．３ｇの目的物（高分子１）を得た。
【０１５５】
（製造例２）（４−メチルスチレンとハイドロキシスチレンの共重合体の合成）
製造例１と同様の手法で、原料を４−メチルスチレン４１．３ｇ(0.35mol)と４−アセトキシスチレン２４．３ｇ(0.15mol)の混合系にして重合を行なった。再沈殿精製の後、得られた高分子を、テトラヒドロフランに溶解させ、そこへ、ＮａＯＨ飽和メタノール溶液を適量滴下することで脱保護をし、その後、再沈殿によって精製しアルカリ可溶性高分子１を４２．９ｇ得た。
【０１５６】
（製造例３）（エポキシ基含有アクリルポリマーの合成）
攪拌機を取りつけた５００ｍＬのセパラブルフラスコに、乾燥させた酢酸エチルを１５０ｍｌ入れ、窒素を１００ｍＬ／ｍｉｎで流しながら６０℃のオイルバスに浸漬し攪拌した。そこへ、ＡＩＢＮ（２，２’−アゾビスイソブチロニトリル）２００ｍｇを溶かし込んだメチルメタクリレート（ＭＭＡ）３０．１ｇ（０．３ｍｏｌ）と、グリシジルメタクリレート（ＧＭＡ）１４．２ｇ（０．１ｍｏｌ）の混合溶液を、徐々に滴下した。滴下終了から４時間後に反応を終了し、ｎ−ヘキサンで再沈殿することにより、エポキシ基含有アクリルポリマーを４２．３ｇ得た。ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量は、１５００００であり、ＮＭＲによる共重合比はＧＭＡ：ＭＭＡ＝１：２．６であった。
【０１５７】
（製造例４）
１Ｌのなす型フラスコに、１，８−ナフタル酸無水物１９．８ｇ（0.1mol）とＮ，Ｎ−ジメチルホルムアミド（以下ＤＭＦ）５００ｍＬと触媒量のピリジンを入れ、攪拌した。そこに、２−アミノエタノール６．７ｇ（0.11mol）を滴下し、室温で１５時間攪拌した。ロータリーエバポレーターによって、ＤＭＦを留去し、メタノールによって再結晶をし、Ｎ−２−ヒドロキシエチルナフタルイミドの針状結晶を２２．５ｇ得た（前駆体化合物１）。
【０１５８】
【化７】

【０１５９】
（製造例５）
使用原料の酸無水物を、４−ブロモ−１，８−ナフタル酸無水物に変更した以外は、製造例４と同様の条件で反応を行った。なお、各原料は製造例４と同じモル数で仕込んだ（前駆体化合物２）。
【０１６０】
【化８】

【０１６１】
（製造例６）
１Ｌのなす型フラスコに、１，８−ナフタル酸無水物１９．８ｇ（0.1mol）とＤＭＦ５００ｍＬと触媒量のピリジンを入れ、攪拌した。そこに、β−アラニン８．９ｇ（0.1mol）を添加し、室温で４時間攪拌した後、１３０℃で５時間攪拌した。ロータリーエバポレーターによってＤＭＦを留去し、メタノールによって再結晶をし、Ｎ−２−カルボキシエチルナフタルイミドの結晶を２０．９ｇ得た（前駆体化合物３）。
【０１６２】
【化９】

【０１６３】
（製造例７）
前駆体化合物１（Ｎ−２−ヒドロキシエチルナフタルイミド）９.６ｇ（40mmol）と、４−ジメチルアミノピリジン５．４ｇ（44mmol）を１Ｌの３つ口フラスコに投入し、中央部の口に塩化カルシウム管をつけ、残りの２つはシリコンＷキャップ（商品名：アズワン社製）で、密閉する。そこへ予め脱水されたテトラヒドロフラン（ＴＨＦ）５００ｍｌをシリンジを用い、投入し室温で攪拌する。そこへ、アクリル酸クロライド４．０ｇ（44mmol）を滴下し、室温で１０時間攪拌する。その後、反応液を分液ろうとで、１Ｎ ＨＣｌで処理し、４−ジメチルアミノピリジンを水層に移動させた。水層と油層に分離した後、油層を更に飽和ＮａＨＣＯ₃溶液を用い処理し、未反応のアクリル酸クロライド由来のアクリル酸を水層に移動させ、油層と水層を分離した。このようにして、得られた油層を硫酸マグネシウム等の適当な脱水剤で脱水し、ろ過を行なった。このろ液から溶媒を留去した物をクロロホルム−酢酸エチル混合溶媒で再結晶して目的物を１０．３ｇ得た。（前駆体化合物４）
【０１６４】
【化１０】

【０１６５】
２．ラジカル発生剤の調製
（実施例１）
１Ｌのなす型フラスコに、１，８−ナフタル酸無水物１９．８ｇ（0.1mol）とＮ，Ｎ−ジメチルホルムアミド（以下ＤＭＦ）５００ｍＬと触媒量のピリジンを入れ、攪拌した。そこに、１，１２−ジアミノドデカン１０．２ｇ（0.5mol）を投入し、１３０℃で５時間攪拌した。ロータリーエバポレーターによってＤＭＦを留去し、テトラヒドロフランによって再結晶をし、目的物の針状結晶を２５．５ｇ得た（化合物１）。
【０１６６】
【化１１】

【０１６７】
（実施例２）
使用原料の酸無水物を、４−クロロ−１，８−ナフタル酸無水物に変更した以外は実施例１と同様の条件で反応を行った。なお、各原料は実施例１と同じモル数で仕込んだ。（化合物２）
【０１６８】
【化１２】

【０１６９】
（実施例３）
化合物２ ３．２ｇ（５mmol）を、１Ｌの三つ口フラスコに投入し、乾燥させたイソプロピルアルコール５００ｍＬに溶解させ、室温で攪拌させた。そこへ、乾燥させたイソプロピルアルコール２００ｍＬに１ｇの金属ナトリウムを反応させて得られた、ナトリウムイソプロポキシドのイソプロピルアルコール溶液を、徐々に滴下しながらＴＬＣ（薄層クロマトグラフィー）で反応の経過を追跡し、原料である化合物２のスポットが消失するまで滴下を続け、化合物２のスポットが消失した時点で反応を終了させる。反応液を純水５Ｌに投入し、析出物を乾燥後、カラムクロマトグラフィーで精製し、化合物３を得た。
【０１７０】
【化１３】

【０１７１】
（実施例４）
使用原料の酸無水物を、４−ブロモ−１，８−ナフタル酸無水物に変更した以外は、実施例１と同様の条件で反応を行った。なお、各原料は実施例１と同じモル数で仕込んだ（化合物４）。
【０１７２】
【化１４】

【０１７３】
（実施例５）
使用原料のジアミンを、ジエチレントリアミンに変更し、反応温度を４０℃にした以外は、実施例１及び４と同様の条件で反応を行った。なお、各原料は実施例１と同じモル数で仕込んだ。（化合物５、化合物６）
【０１７４】
【化１５】

【０１７５】
（実施例６）
前駆体化合物１（Ｎ−２−ヒドロキシエチルナフタルイミド）９.６ｇ（40mmol）と、４−ジメチルアミノピリジン５．４ｇ（44mmol）を１Ｌの３つ口フラスコに投入し、中央部の口に塩化カルシウム管をつけ、残りの２つはシリコンＷキャップ（商品名：アズワン社製）で、密閉する。そこへ予め脱水されたテトラヒドロフラン（ＴＨＦ）５００ｍＬをシリンジを用い、投入し室温で攪拌する。そこへ、予め１０ｍＬの脱水されたＴＨＦに溶解してあったコハク酸クロライド（サクシニルクロライド）を３．４ｇ（22mmol）を滴下し、室温で10時間攪拌する。その後、反応液を分液ろうとで、１ＮＨＣｌで処理し、４−ジメチルアミノピリジンを水層に移動させた。水層と油層に分離した後、油層を、さらに、飽和ＮａＨＣＯ₃溶液を用い処理し、未反応のコハク酸クロライド由来のコハク酸を水層に移動させ、油層と水層を分離した。このようにして、得られた油層を硫酸マグネシウム等の適当な脱水剤で脱水し、ろ過を行なった。このろ液から溶媒を留去した物をクロロホルム−酢酸エチル混合溶媒で再結晶して目的物を９．４ｇ得た。（化合物７）
【０１７６】
【化１６】

【０１７７】
（実施例７）
使用原料の化合物を、４−ブロモ−１，８−ナフタル酸無水物由来の前駆体化合物２に変更した以外は、実施例６と同様の条件で反応を行った。なお、各原料は実施例６と同じモル数で仕込んだ。（化合物８）
【０１７８】
【化１７】

【０１７９】
（実施例８）
スチレン−マレイミド共重合体（Ｍｎ＝１６００、共重合比＝１．３：１、アルドリッチ製）１１．７ｇ（上記のモル比による１構成単位あたりの換算値の約50mmol）と前駆体化合物１（Ｎ−２−ヒドロキシエチルナフタルイミド）１２．１ｇ（50mmol）を、３００ｍＬのなすフラスコに入れ、予め乾燥させたテトラヒドロフラン１００ｍＬに溶解させた。そこへ触媒量の濃硫酸を滴下し、６０℃で９６時間撹拌した。その後、反応液をヘキサンに投入して再沈殿を行い、濾過、乾燥し、ナルタルイミド基を導入した目的物２０．３ｇを得た。（化合物９）
【０１８０】
【化１８】

【０１８１】
（実施例９）
実施例８の使用原料である前駆体化合物１を、前駆体化合物２に変更した以外は、実施例８と同様の条件で反応を行った。なお、各原料は実施例８と同じモル数で仕込み、目的物２１．１ｇを得た。（化合物１０）
【０１８２】
【化１９】

【０１８３】
（実施例１０）
前駆体化合物４を３．０ｇ（10mmol）とメタクリル酸メチル３．０ｇ（30mmol）をクロロホルム５０ｍＬに溶解させ攪拌した。反応容器中に１００ｍＬ／ｍｉｎで窒素を流しながらＡＩＢＮ（２，２’−アゾビスブチロニトリル）を２００ｍｇ投入し、５０℃で１４時間攪拌後、ｎ−ヘキサンで再沈殿し、前駆体化合物４とメタクリル酸メチルの共重合体を、５．２ｇ得た（化合物１１）。ゲルパーミエーションクロマトグラフィーによる重量平均分子量はポリスチレン換算で３９０００であり、ＮＭＲによる重合比は、前駆体化合物４：メタクリル酸メチル＝１：３．２であった。
【０１８４】
【化２０】

【０１８５】
（実施例１１）
８．１ｇのエポキシ基含有アクリルポリマー（製造例３）と５．４ｇ（２０ｍｍｏｌ）の前駆体化合物３を、３００ｍｌの乾燥させたジメチルホルムアミド（ＤＭＦ）に溶かし、トリエチルアミン１滴を加えた後、１００℃で２０時間攪拌した。反応液を、ｎ−ヘキサンで再沈殿し、目的の化合物を１２．７ｇ得た（化合物１２）。
【０１８６】
【化２１】

【０１８７】
（比較例１）
上部にディーンスターク菅を取りつけた１Ｌのなす型フラスコに、マレイン酸無水物９．８ｇ（0.1mol）とＮ，Ｎ−ジメチルホルムアミド（以下ＤＭＦ）４００ｍＬとトルエン１００ｍＬと触媒量のピリジンを入れ、攪拌した。そこに、１，１２−ジアミノドデカン１０．２ｇ（0.5mol）を投入し、１３０℃で１５時間、トルエンと共沸して来た水を除去しながら攪拌した。ロータリーエバポレーターによって、ＤＭＦを留去し、テトラヒドロフランによって再結晶をし、目的物を１２．５ｇ得た。（比較化合物１）
【０１８８】
【化２２】

【０１８９】
（比較例２）
実施例８の使用原料である前駆体化合物１を、ドデカノールに変更した以外は、実施例８と同様の条件で反応を行った。なお、各原料は、実施例８と同じモル数で仕込み、目的物を１２．２ｇ得た。（比較化合物２）
【０１９０】
【化２３】

【０１９１】
３．感光性樹脂組成物の調製
（実施例１２〜２３、比較例３〜６）
実施例１〜１１で得られた化合物１〜１２、比較例１、２で得られた比較化合物１、２、及び、光ラジカル発生剤（商品名：イルガキュア９０７、チバスペシャルティケミカルズ製）、及び、ベンゾフェノン（東京化成工業（株）製）の各々と、３官能アクリレート（商品名：Ｍ３０５、東亞合成製）とを、３官能アクリレートのエチレン性二重結合に対して、各化合物の光ラジカル発生部位がモル比（光ラジカル発生部位／エチレン性二重結合）で１／１００になるように混合し、ＴＨＦで溶解して、実施例１２〜２３の感光性樹脂組成物１〜１２及び比較例３〜６の比較組成物１〜４を作製した。
【０１９２】
（実施例２４）
実施例１０で得られた化合物１１と３官能アクリレート（商品名：Ｍ３０５、東亞合成製）を、重量ベースで等量混合し、ＴＨＦで溶解して、感光性樹脂組成物１３を作製した。
【０１９３】
（実施例２５〜３６、比較例７〜９）
上記実施例１２〜２３及び比較例３、４、６で得られた感光性樹脂組成物に、光ラジカル発生部位と等モルのトリエタノールアミンを水素供与体として添加し、実施例２５〜３６の感光性樹脂組成物１４〜２５及び比較例７〜９の比較組成物５〜７を作製した。
【０１９４】
（実施例３７）
上記実施例２４で得られた感光性樹脂組成物１３に、光ラジカル発生部位と等モルのトリエタノールアミンを水素供与体として添加し、実施例３７の感光性樹脂組成物２６を作製した。
【０１９５】
４．評価試験
（１）耐熱性評価１
熱重量分析装置（パーキンエルマー社製ＴＧＡ７）を用いて、１０℃／ｍｉｎ．の昇温条件で化合物１と、比較化合物１の熱分解温度を測定した。測定結果を図１に示す。この結果より、化合物１は２００℃まではほとんど分解せず、３００℃での重量減少が２％程度と非常に熱安定性が高いことがわかる。一方、比較化合物１は２００℃で１２％程度、３００℃で２０％程度重量減少することがわかった。
【０１９６】
（２）耐熱性評価２
差動型示差熱天秤（リガク製ＴＧ８１２０）を用いて窒素雰囲気下１０℃／ｍｉｎの昇温速度で化合物１〜８、比較化合物１及び光ラジカル発生剤（商品名：イルガキュア９０７、チバスペシャルティケミカルズ製）の９０％熱分解温度を測定した。測定結果を表１に示す。この結果より、化合物１〜８は、比較化合物であるマレイミド（比較化合物１）やＩｒｇ９０７に比べ熱分解点が高く、耐熱性が良好であることがわかる。
【０１９７】
【表１】

【０１９８】
（３）ＵＶ吸収評価
化合物１〜４及び７についての1.0×１０^−５mol/Lのアセトニトリル溶液を用い、ＵＶ吸収スペクトルを測定した。測定結果を図２、図３及び表２に示す。
【０１９９】
【表２】

【０２００】
この結果よりナフタルイミドの芳香環部位に置換基を持たない化合物１及び７は溶液中では３３０ｎｍに極大を持ち、その波長でのモル吸光係数から、π―π^＊遷移による励起であることが推察される。
【０２０１】
モル吸光係数によって、その吸収がどの遷移状態に対応する吸収かを見積もることが出来る。一般に、モル吸光係数が大きいほど、光を吸収しやすく、つまり励起されやすく、ラジカルの発生や架橋反応の進行がしやすい、つまり感度の点からは、露光波長におけるモル吸光係数が大きい分子の方が良い。
【０２０２】
また、ナフタルイミド基の４位に臭素を導入した化合物４、及び、塩素を導入した化合物２では、無置換の化合物に比べて極大波長が１０ｎｍほど長波長にシフトしており、高圧水銀灯の発光波長である３６５ｎｍの波長での吸収が大きくなっている。さらに、ナフタルイミドの芳香環への置換基としてイソプロピルエーテル基を導入した化合物３では、吸収極大が３６５ｎｍにあり、高圧水銀灯の発光波長である３６５ｎｍに非常に大きな吸収を持つことがわかる。
【０２０３】
ナフタルイミドによるラジカルの生成は、水素引き抜きによるものと考えられる。一般に、水素引き抜きによるラジカルの生成は、カルボニル基の３重項励起状態によって引き起こされるといわれており、化合物が励起されても蛍光発光や熱失活に吸収したエネルギーを使ってしまう割合が多いと、ラジカルの発生効率が落ちると思われる。
【０２０４】
そのような水素引き抜き以外の失活過程の割合が少ない場合には、露光波長での吸収が大きければ大きいほど、感光性化合物は励起されやすくなる為、ラジカルの発生効率も向上すると考えられるので、化合物２、３及び４は無置換の化合物１及び７と比べて３６５ｎｍの波長に対して感度が向上すると予想される。
【０２０５】
更に、あとに述べる種々の実験から、π−π^*遷移の励起が観測されるような波長の電磁波が照射されている時と、いない時では、照射されている時の方がラジカルの発生効率が良好になっており、ナフタルイミド部位のラジカル発生メカニズムは、π−π^*遷移が重要であると推測される。一般にπ−π^*遷移は、モル吸光係数が２０００以上の場合が多く、この値以上のモル吸光係数を有する化合物であれば、メカニズムから考慮するとラジカルの発生や架橋反応の進行がしやすいと考えられる。
【０２０６】
（４）硬化性評価１
製造例１で合成したポリ−４−メチルスチレン５．９ｇと、化合物１ １．４ｇをクロロホルムに溶解し、ガラス基板上にスピンコートで塗膜を形成した。
【０２０７】
上記塗膜に、手動露光装置（大日本スクリーン株式会社製、ＭＡ−１２００）でｈ線換算で紫外線照射を行い、その後、塗膜が硬化しているか確認した。その際に、３３３ｎｍ、３６５ｎｍ，４０５ｎｍ、４３６ｎｍの波長の光を通すフィルターを用いたものと、フィルターを用いず高圧水銀ランプの発光波長をそのまま用いて露光したものと２種類検討した。硬化性は、露光後の塗膜を２４時間クロロホルム溶液に浸漬した後の塗膜の状態で判断した。
【０２０８】
結果を表３に示す。フィルター無しの場合は１０００ｍＪで、フィルターありの場合は５０００ｍＪで塗膜がクロロホルムに不溶になった。露光により、ポリ−４−メチルスチレンを、化合物１が架橋することで、塗膜の溶解性が低下し硬化したものと考えられる。
【０２０９】
また、フィルターの有無による硬化性の違いは、化合物１の紫外線吸収波長領域が３６０ｎｍ以下である為、その領域の波長の発光が大幅にカットされているフィルターありの方が、感度が低下したものと考えられる。
【０２１０】
つまり、ナフタルイミド化合物の吸収が、露光波長と重なっていればいるほど感度が上がると示唆される。また、この時カットされている波長領域のモル吸光係数が２０００以上であることから、この領域ではπ−π^*遷移が起こっていると考えられ、ラジカルの発生にπ−π^*遷移が大きく関わっていると推測される。一方で、それよりも小さいモル吸光係数をもつｎ−π^＊遷移も起こっており、その吸収が、π−π^＊遷移の大きな吸収によって隠されている可能性もある。
【０２１１】
上記で作製した塗膜にライン／スペース：１ｍｍ／１ｍｍのストライプマスクを通してフィルター無しで１０００ｍJ露光した後、クロロホルムに浸漬することで、上記塗膜の良好なストライプパターンを得ることが出来た。
【０２１２】
また、同様にして、製造例２で重合したアルカリ可溶性高分子６．０ｇと化合物１ １．４ｇを混合して作製した塗膜も上記のマスクを通して露光した。その後、１ＮのＮａＯＨ水溶液に浸漬し未露光部を洗い流した所、良好なストライプパターンを得ることが出来た。
【０２１３】
【表３】

【０２１４】
（５）硬化性評価２
多官能モノマーとして、水酸基含有５官能アクリレート（商品名サートマーＳＲ３９９、日本化薬製）、６官能アクリレート（商品名Ｍ４００、東亞合成（株）製）を用い、化合物１を多官能モノマーの２重結合に対して、モル比で１／２０混合した溶液を作製しガラス基板上にスピンコートした。比較の為に、化合物１を、比較化合物１、光ラジカル発生剤イルガキュア３６９（商品名）（チバスペシャルティケミカルズ製）及び、ベンゾフェノン（東京化成工業（株）製）に置き換えた塗膜も作製した。
【０２１５】
上記塗膜に、手動露光装置（大日本スクリーン株式会社製、ＭＡ−１２００）でｈ線換算で５０００ｍＪ／ｃｍ²照射を行い、その後、塗膜が硬化しているか確認した。硬化の程度は、露光後の塗膜を触指することで判定し、塗膜表面がべとつかず、充分硬い膜となっている場合を○、露光を行っても液状のままであったものを×とした。
【０２１６】
表４に評価結果を示す。化合物１は比較化合物１及びイルガキュア３６９と同様に多官能アクリレートを硬化できることから、ナフタルイミドがラジカル発生剤として機能していることが分かる。
【０２１７】
【表４】

【０２１８】
（６）硬化性評価３
感光性樹脂組成物１〜１３及び比較組成物１〜４の各々を、クロムをスパッタしたガラス基板上にスピンコートし、塗膜を得た。
【０２１９】
上記塗膜にＵＶ露光しながら、赤外分光装置で８１０ｃｍ^-1のピークの減少量を経時的に記録し、２重結合の消失がどの程度進行しているか確認した。測定時のサンプル周囲の雰囲気は窒素置換した。ＵＶ露光装置は、ウシオ電機製ＵＶスポットキュアＳＰ−III型（標準反射鏡タイプ）を用い、ＵＶランプは、ウシオ電機製ＵＳＨ−２５５ＢＹを用いた。また、赤外分光装置は、ＢＩＯ ＲＡＤ製ＦＴ Ｓ６０００を用いた。
【０２２０】
３官能アクリレートＭ３０５との相溶性、露光時の臭気、露光量に対する２重結合の減少量（反応率）、塗膜の着色について観察した結果を表５に示す。
【０２２１】
比較組成物２は、光ラジカル発生部位を持たない比較化合物２を用いているので、２重結合がほとんど反応してない。組成物１〜１３はナフタルイミド部位を持つ化合物を用いており、該化合物がアクリルモノマーであるＭ３０５と相溶するものは反応性が高い。ナフタルイミド基含有化合物がＭ３０５と相溶していることで発生したラジカルの拡散が進行し反応していると考えられる。
【０２２２】
また、比較組成物１は、マレイミド基を持つ比較化合物１を用いており、該比較化合物１はＭ３０５と相溶するものの反応がそれほど進んでいない。また、同じく水素引抜き型のラジカル発生剤であるベンゾフェノンも同様である。市販の光ラジカル発生剤であるＩｒｇ９０７は反応率が高く、反応が良好に進行しているが自己開裂型のラジカル発生剤であるため、塗膜中に不純物が残存する。
【０２２３】
また、露光波長における吸収が大きい化合物３は、置換基の異なる他の類似化合物に比べ、３官能モノマーＭ３０５との相溶性は良好なものの、露光波長への吸収に比べて、反応率は向上しなかった。
【０２２４】
これは、化合物３が蛍光を強く発光することによるものであると推察される。1.0×１０^−５mol/Lのアセトニトリル溶液にて、吸収極大波長で励起を行ない、蛍光の発光強度を測定した所、化合物３は化合物１や化合物２に対して１０倍以上も蛍光の発光強度が強く、吸収したエネルギーの多くを蛍光として外部に放出していることが確認された。このことは吸収した光のエネルギーを充分ラジカル生成へ利用していない事を示していると思われる。その為、時間当りの反応率という観点においては蛍光の発光強度の小さいナフタルイミド化合物の方が好ましい。
【０２２５】
【表５】

【０２２６】
（７）硬化性評価４
製造例１で合成したポリ−４−メチルスチレン５．９ｇと化合物１ １．４ｇをクロロホルムに溶解し、ガラス基板上にスピンコートで塗膜を形成した。（Sample Ａ）
上記塗膜を、ＵＶを露光しながら、赤外分光装置（BIO RAD社製ＦＴＳ6000）で１７２５ｃｍ^-1のピークの増加量を経時で記録し、どの程度架橋反応が進行しているか確認した。
【０２２７】
ＵＶ露光装置はウシオ電機製ＵＶスポットキュアＳＰ-III型（標準反射鏡タイプ）を用い、ＵＶランプは、ＵＳＨ−２５５ＢＹ （ウシオ電機製）を用いた。
【０２２８】
また、ナフタルイミド部位が水素引き抜き型ラジカル発生剤であるか確認するため、ナフタルイミド部位と等モルになるように、Sample Ａの組成に更にｎ−ドデカノールを添加した塗膜も作製し同様の検討を行なった。（Sample Ｂ）
測定結果を図４に示す。この結果より、塗膜中にドデカノールを添加した系の方が約２倍、ピークの増加量が大きい事から、水素供与性基を塗膜中に含有した方が架橋反応がはやく進行していることがわかる。メカニズム的には炭素についた水素も引き抜かれるが、チオールや水酸基、アミノ基の場合、水素がより引き抜かれやすいため、ラジカルの発生効率が上昇し、感度が向上したものと考えられる。
【０２２９】
つまり、ナフタルイミド基は水素供与性基が共存した状態で、露光することで感度を高められると考えられる。
【０２３０】
（８）硬化性評価５
ナフタルイミド部位が水素引き抜き型ラジカル発生剤であることを確認するため、感光性樹脂組成物１４〜２６及び比較組成物５〜７各々を用い、上記の硬化性評価３と同じ手順で、３官能アクリレートＭ３０５との相溶性、露光時の臭気、露光量に対する２重結合の減少量（反応率）、塗膜の着色について観察した。結果を表６に示す。
【０２３１】
一部のサンプルを除き、トリエタノールアミンの添加により反応率が向上した。特に、低露光量での反応率の上昇が見受けられる。つまり、ナフタルイミド基は水素供与性基が共存した状態で、露光することで感度を高められると考えられる。
【０２３２】
【表６】

【０２３３】
（９）モノマー成分に対する溶解性
（メタ）アクリロイル系多官能モノマーを、ナフタルイミドによって光硬化させる場合に、マトリックスに対する溶解性と反応率との関係を確認するために、ナフタルイミド部位の構造が同じでスペーサー部位が異なる構造をもつ化合物１及び７について、上記の硬化性評価を行なった際のマトリックスである３官能モノマーＭ３０５（東亞合成製：商品名）に対する２０℃における飽和濃度を求めた。さらに、溶解性の評価を一般化するために、アクリル酸メチルに対する２０℃における飽和濃度も求めた。その結果を第７表に示す。
【０２３４】
【表７】

【０２３５】
この結果より、溶解性が良好なサンプルほど反応率が良好である事がわかる。つまり、ナフタルイミド部位が同じ構造の場合、イミド結合の窒素原子より伸びる側鎖の構造によってマトリックスへの溶解性が変化し、この溶解性を良好にすることで、低露光量でも高い反応率を得られると思われる。
【０２３６】
（１０）アウトガス評価
上記の感光性組成物１、２、３、７及び比較組成物３を、ガラス基板上にスピンコートし５０℃のホットプレート上で１分間加熱後、手動露光装置（大日本スクリーン株式会社製、MA-1200）で、高圧水銀灯によりｈ線換算で２０００mJ/cm^２の露光を行ない、厚さ２５μmの塗膜を得た。
【０２３７】
その塗膜が形成されたガラス基板を、１ｃｍ×１．５ｃｍの大きさに切り出し、2５０℃で１時間加熱時に発生したガスを、GC-MS（株式会社島津製作所製 QP-5000）を用いて分析した。
【０２３８】
その他の測定条件は以下の通りである。
【０２３９】

その結果、全てのサンプルにおいて、多官能モノマーＭ３０５由来の分解物が検出された。さらに、比較組成物３を用いた塗膜のみ、それ以外の光ラジカル発生剤由来の分解物と思われる芳香族化合物が数種類検出された。
【０２４０】
以上の事より、本発明のナフタルイミド化合物は、加熱によって開始剤由来の分解物をガスとして発生させる事がないことが明らかとなった。
【０２４１】
【発明の効果】
本発明に係るラジカル発生剤は、ナフタルイミド構造含有基が水素引き抜き型のラジカル発生部位として機能し、光を照射して励起させることによりラジカル反応を起こすことができる。ナフタルイミド構造含有基は、自己開裂型よりも安定性が高い水素引き抜き型であり、しかも耐熱性が良好なナフタレン骨格を有するため、耐熱性、安定性、保存性が高い光ラジカル発生剤を得ることができる。
【０２４２】
また、本発明に係るラジカル発生剤は、エチレン性不飽和結合だけでなく芳香環等種々の化合物とも反応可能であり、エチレン性不飽和結合を有さない樹脂組成物であっても、高分子を架橋したり或いはラジカル反応をすることができる。従って、本発明に係る光ラジカル発生剤は、一般的な光ラジカル重合開始剤として用いられるほか、例えば芳香族ポリマーを含有する樹脂組成物の架橋剤として用いて硬化後の耐溶剤性を向上させることが可能である。
【０２４３】
また、本発明に係るラジカル発生剤は、ラジカル発生部位として機能するナフタルイミド構造含有基を一分子内に２つ以上有するため、そのうちどこか１箇所に発生したラジカルが重合体等反応物と結合することにより、重合体等反応物の化学構造の一部となる。ラジカル発生剤が重合体等反応物の化学構造の一部となるため、ラジカル発生剤が未反応で残っても、重合体等反応物中に遊離の形で残存しない。しかも、ラジカル発生部位は未反応のまま残存しても水素引き抜き型であると共に、耐熱性の高いナフタルイミド構造を有しているから、硬化後の塗膜中で揮発性の分解物を生成することがない。そのため、ラジカル発生剤はポストベーク時に揮発せず、従来のように塗膜中に独立して残存することもない。その結果、作業安全性の問題や、耐光性の悪化や、着色や退色、塗膜のはがれやクラックの発生等、最終製品の信頼性を低下させる問題や、薬液寿命を短くする問題や、臭気が発生する問題も全て解決することができる。
【０２４４】
さらに、マレイミド構造を形成する反応は、加熱や触媒等により脱水縮合反応を促進させないと形成されず、そのため合成上様々な問題があったが、ナフタルイミド構造を形成する反応は、マレイミドのような５員環構造のイミドに比べて脱水縮合反応が速やかに進行し、合成が非常に簡便であり、溶媒溶解性も良好なことから、合成上有利である。そのため、収率、反応速度、管理面、コスト面を含めて生産性が上がる。
【０２４５】
本発明に係る感光性樹脂組成物は、上記化合物（ａ）からなる光ラジカル重合開始剤のナフタルイミド構造含有基が水素引き抜き型のラジカル発生部位として機能し、光を照射して励起させることによりラジカル化し、樹脂組成物中でラジカル反応を起こさせる。ナフタルイミド構造含有基によって発生したラジカルは、エチレン性不飽和結合だけでなく芳香環等種々の化合物とも反応可能なため、エチレン性不飽和結合を有さない樹脂組成物であっても、高分子を架橋したりラジカル反応をすることができ、硬化及び／又は溶解性の変化を引き起こすことができる。さらに、２つ以上有するナフタルイミド構造含有基のうちどこか１箇所に発生したラジカルが樹脂組成物と結合することにより樹脂組成物の化学構造の一部となる。そのため、ラジカル発生剤やその分解物が樹脂組成物中に遊離の形で残存することがない。その結果、最終製品の信頼性を低下させる問題も解決する。
【０２４６】
本発明に係る感光性樹脂組成物を、パターン形成材料（レジスト）、塗料又は印刷インキ、或いは、カラーフィルター、電子部品、層間絶縁膜、配線被覆膜、光学部材、光回路、光回路部品、反射防止膜、ホログラム又は建築材料の形成材料として用いる場合には、製品や膜が高耐熱性、高安定性となる効果がある。また、露光時の臭気の発生がない為、作業環境が向上する。
【０２４７】
本発明に係る印刷物、カラーフィルター、電子部品、層間絶縁膜、配線被覆膜、光学部材、光回路、光回路部品、反射防止膜、ホログラム又は建築材料は、高耐熱性、高安定性の感光性樹脂組成物の硬化物により少なくとも一部分が形成されているため、製品や膜としても高耐熱性、高安定性であり、そのため生産の歩留まりも高いというメリットがある。
【図面の簡単な説明】
【図１】熱分解温度の測定結果を示すグラフである。
【図２】ＵＶ吸収スペクトル（化合物１、４、７）の測定結果を示すグラフである。
【図３】ＵＶ吸収スペクトル（化合物１、２、３、４）の測定結果を示すグラフである。
【図４】ＵＶ照射中の１７２５ｃｍ^-1のピークの増加量を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention includes a radical generator, a photosensitive resin composition containing the radical generator, and a printed material, a color filter, an electronic component, an interlayer insulating film, a wiring coating film, produced using the photosensitive resin composition, Regarding optical members, optical circuits, optical circuit components, antireflection films, holograms or building materials, in particular, they have particularly high heat resistance and do not remain as independent components in cured products, and can be synthesized under mild conditions. Radical generator, photosensitive resin composition containing the radical generator, and a printed material and color filter that are at least partly formed of a cured product of the photosensitive resin composition and have high heat resistance and high stability , Electronic components, interlayer insulating films, wiring coating films, optical members, optical circuits, optical circuit components, antireflection films, holograms, or building materials.
[0002]
[Prior art]
Photosensitive resins that cure or change solubility upon irradiation with radiation such as ultraviolet rays are generally those having good solubility in the exposed area (positive type) and those having good solubility in the unexposed area (negative). Type). In the case of the negative type, since the photosensitive resin itself is cured and becomes insoluble by exposure, the photosensitive resin often remains on the substrate and becomes a part of the product as a functional film. Negative photosensitive resins have been used for paints, printing inks, adhesives, printing masters, etc., but in recent years, solder resists for printed wiring board wiring protection, interlayer insulation films, and color filter pixel formation Applications have been extended to resists.
[0003]
One of the commonly used negative photosensitive resins is a compound having one or more ethylenically unsaturated bonds, a photoradical initiator that generates radicals by light irradiation, and developability and coating as required. There is a resin composition in which a polymer compound that imparts film flexibility, an inorganic filler, a pigment, and the like are blended. When this composition is irradiated with radiation, a compound having an ethylenically unsaturated bond is bonded by a radical reaction, and is cured with a large molecular weight. During this curing reaction, the three-dimensional network structure is developed by a crosslinking reaction, whereby the hardness, strength, adhesion, solvent resistance, and heat resistance of the resulting cured product are improved.
[0004]
Photoradical initiators are generally classified into self-cleavage types and hydrogen abstraction types. In the former case, by absorbing light of a specific wavelength (electromagnetic wave or radiation), the bond at the site corresponding to that wavelength is broken, and radicals are generated at each site that was split at that time, from which radical reaction occurs Begins. In the latter case, when light of a specific wavelength is absorbed to be in an excited state, hydrogen is extracted from surrounding hydrogen donors, and radicals are generated in each of the extracted and extracted ones.
[0005]
In general, the self-cleavage type has good sensitivity and radical generation efficiency, but is unstable to heat, and has problems in heat resistance, stability, storage stability, and the like of a photosensitive resin composition containing the self-cleavage type. On the other hand, the hydrogen abstraction type has relatively low sensitivity because the radical generation efficiency is determined by the fact that the hydrogen donor needs to be in the vicinity of the excited initiator and the size of the energy barrier when extracting hydrogen. Since radicals are not generated unless hydrogen is extracted by entering an excited state, the stability and storage stability of the resin composition are high.
[0006]
Solder resists used for the surface coating of printed wiring boards are mixed with organic pigments and fillers to impart heat resistance and flame retardancy, and color filter pixel resists contain color display pigments. Have been mixed. Since these pigments are components that absorb light, in order to increase the sensitivity of the photosensitive resin, a self-cleavage type photoradical initiator is mainly used, and a large amount is expected in anticipation that it is not sufficiently utilized for radical reactions. Mixing. Here, the unreacted initiator that was not cleaved by irradiation and the reaction with the reactants were inhibited due to the reaction in the solid phase even when radicalized by cleavage because the amount was not used for radical reaction. There is something to do.
[0007]
In the cured product after the exposure, a large amount of the residue derived from the initiator exists, and among them, the uncleavable photoradical initiator remains reactive after the exposure, thereby changing the quality of the product. In addition, the uncleaved photoradical initiator and the decomposition product that has been cleaved but deactivated without being consumed by the radical reaction are not bound to the crosslinked structure of the matrix and must be present in the product as independent components. Inhibits membrane properties. Therefore, if the initiator-derived residue is left as it is, it will cause deterioration of light resistance, coloring and fading, peeling of the coating film and generation of cracks, etc., resulting in final products such as interlayer insulation films and solder resists for electronic parts, color There is a problem that the reliability of the filter pixel forming resist is lowered.
[0008]
Since the self-cleaving type photo radical initiator has a strong sublimation property and decomposes by heat, it can be removed from the product by post-baking the product after exposure and development at a temperature of hundreds of degrees C. or more. However, a large amount of the sublimate derived from the initiator adheres to the heating device during post-baking, and it falls on the product obtained by curing, causing a product defect, which is a problem. In addition, there is a problem from the viewpoint of work safety because the decomposition product of the initiator is included in the atmosphere around the heating device.
[0009]
It is possible to remove more radical initiator-derived residues by setting the post-baking conditions at a higher temperature and for a longer time, but because of volatilization from the solid, it is possible to completely remove it. Have difficulty. If conditions are stricter to remove more impurities derived from radical initiators, the conditions may cause product defects.
[0010]
On the other hand, similar processing systems using radiation are used for resists for processing electronic members and dry film resists used as release films. Although the resist for processing is finally peeled off and does not remain in the product, it is an initiator from the resist film in a chemical solution such as ferric chloride or cupric chloride used for processing in processing steps such as copper wiring formation. There was a problem that the residue of the origin was eluted and the life of the chemical solution was shortened.
[0011]
Furthermore, when photosensitive resins are used as protective coatings to protect the wallpaper of buildings and the surface of walls, reduction of solvent components and odor components from the entire building material from the viewpoint of measures against sick house syndrome, etc. However, there is a problem that an odor is generated even after the coating film is cured by using a highly volatile initiator.
[0012]
From these problems, there are radical generators and resin compositions that do not volatilize during post-baking or after photocuring, and that are substantially free of components derived from radical generators that remain independently in the coating film. It is desired.
[0013]
As means for solving these problems, ESACURE KIP 150 (trade name) (manufactured by Nippon Siebel Hegner Co., Ltd.) and the like introduce a photoradical generation site into the side chain of the polymer skeleton. In this way, since the photo radical generator has a plurality of radical generating sites in one molecule, if one of the sites in the molecule is radicalized and bound to the matrix of the coating film, Since some unreacted radical generation sites are also bonded to the matrix through the polymer skeleton, they do not volatilize during post-baking and do not move through the coating film, so that the reliability in the final product is hardly lowered.
[0014]
However, in this case, the photoradical generation site introduced into the side chain is a self-cleavage type, and is easily decomposed by heating to generate radicals. Therefore, the heat resistance of the photosensitive resin composition containing the photoradical There are still problems with stability and storage stability. In addition, the portion of the radical generation site that remains in the polymer skeleton after cleavage is bonded to the matrix structure, but some of the decomposition products cleaved from the polymer skeleton by photoradical reaction and post-baking are not consumed by the radical reaction. Since it is deactivated and remains independently from the matrix, if it is left as it is, it adversely affects the physical properties of the coating film, and it is difficult to completely sublimate and remove it even after post-baking.
[0015]
International publications WO 98/58912 and JP 2002-3559 propose (meth) acrylates having maleimide groups. When maleimide absorbs electromagnetic waves, it reacts with vinyl ether as an electron acceptor to generate radicals. It is also possible to generate radicals by extracting hydrogen (Radical Polymerization Handbook, published by NTS, 1999, page 312). However, since maleimide has an ethylenic double bond, if a monomer having both a maleimide group and a (meth) acryl group is radically polymerized, a crosslinking reaction proceeds and gelation occurs. Therefore, International Publication WO 98/58912 and JP 2002-3559 A introduce a substituent such as a cyclohexyl group into the maleimide group, thereby reducing the reactivity of the maleimide group due to steric hindrance. Overcoming. However, on the other hand, since the reactivity of the maleimide moiety is lowered, there is a problem that the radical reaction initiation efficiency is also lowered. In addition, since the reaction of forming an acid anhydride and amine to form a maleimide group is carried out by a dehydration reaction, a high temperature of 100 ° C. or higher is required for efficient reaction without using a catalyst. When an ethylenically unsaturated bond is directly introduced at the time of formation, there is a synthetic problem that polymerization of the ethylenically unsaturated bond occurs. In addition, although a dehydration reaction can be performed using a dehydration catalyst such as acetic anhydride, there is a problem in the synthesis in any case, which causes an increase in cost and complicated subsequent purification steps.
[0016]
S. Jonsson et al. Described a photoreactive cross-linking agent of a compound having a maleimide group at both ends in Proc. RadTech 96 (North America Nashville 377 pages 1996). This reacts rapidly with vinyl ether, but because of the maleimide group, there was a problem in synthesis as described above.
[0017]
Furthermore, industrial materials July 2002 issue P.I. 107-P. 111 describes the UV absorption spectrum of a compound having a maleimide moiety. According to this, an unsubstituted maleimide compound has no absorption at 350 nm or more. For this reason, there is no absorption at 365 nm, 405 nm, and 436 nm, which are the main emission wavelengths of a high-pressure mercury lamp, which is a commonly used exposure light source, and the maleimide group does not change anything for these lights. Not expected.
[0018]
For this reason, since the maleimide group has no sensitivity to the above-described wavelength, there is a problem that exposure must be performed by a light source having a light emission of 350 nm or less in order to use maleimide for photocuring. In addition, the high-pressure mercury lamp emits light with a wavelength of less than 365 nm, but is usually an area cut by a filter. Even if it is not cut with a filter, the emission intensity is small, so that the exposure time becomes very long when the same lamp is used as compared with a radical generator having absorption at 365 nm.
[0019]
On the other hand, according to 1999 Kubo et al., When an aromatic compound such as N-methyl-1,8-naphthalimide and p-xylene is irradiated with ultraviolet rays in the presence of methanol in an acetonitrile solution, naphthalimide and the aromatic compound are obtained in a high yield. (P.175 Chemistry Letters 1999). Among them, as a mechanism of the reaction, naphthalimide excited by ultraviolet rays forms an exciplex with an aromatic compound, and then a radical is generated by extracting hydrogen, and the reaction of naphthalimide and aromatic compound It is described that a bond is formed between them. However, this document only describes the reaction in solution and only the reaction between naphthalimide and some low molecular weight aromatic compounds.
[0020]
Further, compounds having two naphthalimide moieties are disclosed in WO 9402466 for use in pharmaceuticals, and JP-A-7-160020 and JP-A-2001-117247 for use in electrophotographic photoreceptors. Are disclosed as electron transport materials. However, in the former application, it is used as a pharmaceutical. In the latter application, the invention is a photoconductor, but the naphthalimide compound functions only as a charge transport agent, and generates a charge when irradiated with light. These compounds are blended separately, and the function of the naphthalimide compound as a photo radical initiator and the crosslinking reactivity are not mentioned at all.
[0021]
[Problems to be solved by the invention]
The present invention has been achieved in view of the above-mentioned actual situation, and its first object is to exist in a chemically stable state in a cured coating without remaining independently in the coating, An object of the present invention is to provide a radical generator that has high heat resistance, high stability and high storage stability, can be synthesized under relatively mild conditions, and has high productivity.
[0022]
The second object of the present invention is to use the radical generator according to the present invention, the decomposition product of the initiator is not liberated after radical polymerization, high heat resistance, high sensitivity to practical wavelength, exposure It is an object of the present invention to provide a photosensitive resin composition that does not sometimes generate odor, has high stability and storage stability, and is advantageous in terms of synthesis.
[0023]
The third object of the present invention is to provide a product that is at least partly formed from the cured product of the photosensitive resin composition according to the present invention and has high heat resistance and high stability.
[0024]
The present invention solves at least one of these objects.
[0025]
[Means for Solving the Problems]
  The radical generator according to the present invention for solving the above problems is contained in one molecule.Following formula (2)
[0026]
[Chemical Formula 3]

(Wherein R¹, R², R³, R⁴, R⁵And R⁶Are each independently a hydrogen atom or a substituent, and may be a ring structure bonded to each other.The chemical structure X is an organic group selected from n-valent linear and / or branched and / or cyclic saturated, unsaturated polyvalent alkyl groups, aryl groups, and allyl groups, and has a simple structure inside it. One or more of bonds, ester bonds, ether bonds, thioether bonds, amino bonds, amide bonds, urethane bonds, urea bonds, thiocarbamate bonds, carbodiimide bonds, and carbonate bonds may be included. n is an integer of 2 or more. )It consists of the compound (a) which has two or more naphthalimide structure containing groups represented by these.
[0027]
(Wherein R¹, R², R^Three, R^Four, R^FiveAnd R⁶Are each independently a hydrogen atom or a substituent, and may be a ring structure bonded to each other. )
It consists of the compound (a) which has two or more naphthalimide structure containing groups represented by these.
[0028]
The radical generation mechanism by the naphthalimide structure-containing group is presumed that the naphthalimide structure generates radicals by absorbing light such as electromagnetic waves and radiation.
[0029]
In the radical generator according to the present invention, the above-mentioned naphthalimide structure-containing group functions as a hydrogen abstraction type radical generating site, causes radical reaction by irradiating it with radiation or the like, initiates radical polymerization, Polymers can also be crosslinked. The naphthalimide structure-containing group is a hydrogen abstraction type that is more stable than the self-cleavage type and has a naphthalene skeleton with good heat resistance, so that a radical generator with high heat resistance, stability, and storage stability can be obtained. Can do.
[0030]
Furthermore, since many π bonds are connected, the absorption wavelength is longer than that of maleimide, so that absorption is easily obtained at a wavelength of 365 nm, which is the main emission wavelength of a high-pressure mercury lamp, and the sensitivity is good.
[0031]
In addition, the radical generator according to the present invention can react not only with ethylenically unsaturated bonds but also with various compounds such as aromatic rings, and even a resin composition having no ethylenically unsaturated bonds may be a polymer. Can be crosslinked or radically reacted. Therefore, the radical generator according to the present invention can be used as a general photo-radical polymerization initiator, and can be used, for example, as a crosslinking agent for a resin composition containing an aromatic polymer to improve the solvent resistance after curing. Is possible.
[0032]
In addition, since the radical generator according to the present invention has two or more naphthalimide structure-containing groups that function as radical generating sites in one molecule, it is possible to determine which of the plurality of naphthalimide structure-containing groups contained in one molecule. As long as a radical is generated at one location to form a bond with a reactant such as a polymer, all the unreacted radical generating sites contained in the molecule also become part of the chemical structure of the reactant such as a polymer. Since the radical generator becomes a part of the chemical structure of the reactant such as a polymer, even if an unreacted site remains in the molecule of the radical generator, each unreacted site in the reactant such as a polymer is in a free form. Does not remain and does not evaporate during post-baking. Moreover, even if the compound (a) remains unreacted, the radical generation site has a highly heat-resistant naphthalimide structure, so that a volatile decomposition product is not generated.
[0033]
Therefore, problems such as work safety problems, deterioration of light resistance, coloring and fading, peeling of coatings and occurrence of cracks, and other problems that reduce the reliability of the final product, problems that shorten the life of chemicals, and odors All the problems that occur can be solved.
[0034]
Furthermore, the reaction that forms the maleimide structure is not performed unless a dehydration condensation reaction is performed by heating, a catalyst, or the like. Therefore, there have been various problems in the synthesis, but the reaction that forms the naphthalimide structure proceeds with the dehydration condensation reaction. It is easy to synthesize and is very simple compared to the maleimide structure, and has good solvent solubility, which is advantageous for synthesis. Therefore, productivity is improved including yield, reaction rate, management and cost.
[0035]
  Formula (2)R¹, R², R^Three, R^Four, R^FiveAnd R⁶Each independently represents a hydrogen atom, halogen atom, hydroxyl group, mercapto group, amino group, cyano group, silyl group, silanol group, alkoxy group, nitro group, carboxyl group, acetyl group, acetoxy group, sulfone group, or substituent. An organic group that may be present or a ring structure in which they are bonded to each other is preferable from the viewpoint of ease of raw material procurement and ease of synthesis.
[0036]
In order to obtain practical sensitivity, the molar extinction coefficient of the compound (a) at any emission wavelength of the exposure light source is preferably 0.1 or more.
[0037]
Further, the maximum molar extinction coefficient ε of the compound (a)_MAXIs preferably 2000 or more. The radical generation mechanism of the naphthalimide moiety is π-π^*The transition is assumed to be important, but in general the maximum molar extinction coefficient ε_MAXΠ−π when is over 2000^*Often there are transitions.
[0038]
The compound (a) has absorption at least at any wavelength of 157 nm, 193 nm, 248 nm, 365 nm, 405 nm, and 436 nm, which overlaps with the emission wavelength of the irradiation light source and is convenient for use as an exposure wavelength. To preferred.
[0039]
The 90% thermal decomposition temperature of the compound (a) is preferably 50 ° C. or higher from the viewpoint of storage stability of the resin composition.
[0040]
The higher the solubility of the compound (a) in a polymerization component such as a monomer, the better the action as an initiator and the higher the sensitivity. Therefore, the saturation concentration of the compound (a) with respect to methyl acrylate at 20 ° C. is 0. It is preferable that it is 0.01 mol / L or more.
[0041]
  The photosensitive resin composition according to the present invention for solving the above problems is contained in one molecule.Following formula (2)
[0042]
[Formula 4]

(Wherein R¹, R², R³, R⁴, R⁵And R⁶Are each independently a hydrogen atom or a substituent, and may be a ring structure bonded to each other. The chemical structure X is an organic group selected from n-valent linear and / or branched and / or cyclic saturated, unsaturated polyvalent alkyl groups, aryl groups, and allyl groups, and has a simple structure inside it. One or more of bonds, ester bonds, ether bonds, thioether bonds, amino bonds, amide bonds, urethane bonds, urea bonds, thiocarbamate bonds, carbodiimide bonds, and carbonate bonds may be included. n is an integer of 2 or more. The compound (a) having two or more naphthalimide structure-containing groups represented by the formula (1)) and at least one curing reactive compound selected from a compound having an ethylenically unsaturated bond and an aromatic compound are contained as essential components. It is characterized by doing.
[0043]
(Wherein R¹, R², R^Three, R^Four, R^FiveAnd R⁶Are each independently a hydrogen atom or a substituent, and may be bonded to each other to be closed. )
And a compound (a) having two or more naphthalimide structure-containing groups represented by the formula:
[0044]
The photosensitive resin composition according to the present invention contains the radical generator according to the present invention, and the naphthalimide structure-containing group of the compound (a) functions as a hydrogen abstraction type radical generation site, and is irradiated with light. Then, it is radicalized by being excited to cause a radical reaction in the photosensitive resin composition. The radical-reactive compound in the photosensitive resin composition undergoes various radical reactions such as radical polymerization, radical dimerization reaction with the compound (a), which is a radical generator, and radical crosslinking reaction, depending on the type of the compound. Causing the photosensitive resin composition to cure or change the solubility.
[0045]
In the photosensitive resin composition according to the present invention, the radical generated by the naphthalimide structure-containing group can react with not only an ethylenically unsaturated bond but also various compounds such as an aromatic ring, and thus has an ethylenically unsaturated bond. Photosensitive resin composition having no ethylenically unsaturated bond as long as it contains the essential component compound (a), even if it is a non-photosensitive resin composition. Even objects can cause changes in cure and / or solubility. Further, a radical generated at any one of two or more naphthalimide structure-containing groups is bonded to the photosensitive resin composition, thereby becoming a part of the chemical structure of the photosensitive resin composition. Therefore, the radical generator does not remain in a free form in the photosensitive resin composition. As a result, the problem of reducing the reliability of the final product is solved.
[0046]
Furthermore, the compound (a) that functions as a radical generator is very simple to synthesize compared to the maleimide structure, and is advantageous in terms of synthesis. Therefore, productivity including yield, reaction rate, management, and cost is included. Goes up.
[0047]
The photosensitive resin composition according to the present invention may contain a compound (b) having an ethylenically unsaturated bond as a curing reactive compound. The compound (b) has been widely used as a radically polymerizable curing reactive compound and has a wide range of applications.
[0048]
In order to improve the generation efficiency of radicals and increase sensitivity, it is preferable to further add a hydrogen donor to the resin composition of the present invention.
[0049]
When the compound (b) having an ethylenically unsaturated bond is added to the photosensitive resin composition according to the present invention, the amount of the compound (a) is 0.1% by weight of the total solid content of the photosensitive resin composition. By setting the ratio to the above, the curing rate of the resin composition by light irradiation becomes slow, or the amount of generated radicals is small, so the crosslinking density is lowered, and the coating strength and the glass transition temperature of the coating are lowered. It is preferable from the point which prevents this.
[0050]
Components other than the compound (a) contained in the photosensitive resin composition have a transmittance of 20% or more in a wavelength region where the emission wavelength of the irradiation light source and the absorption wavelength of the compound (a) overlap. It is preferable from the viewpoint of increasing sensitivity by allowing sufficient light to reach the compound (a).
[0051]
The photosensitive resin composition can be used as a pattern forming material (resist), paint or printing ink, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film. It is preferable to use it as a forming material for holograms or building materials from the viewpoint of high heat resistance and high stability of products and films. In addition, since no odor is generated during exposure, the working environment is improved.
[0052]
The printed matter, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film, hologram or building material according to the present invention for solving the above-mentioned problems It is characterized in that at least a part is formed by a cured product of the conductive resin composition.
[0053]
The printed matter, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film, hologram, or building material according to the present invention has high heat resistance and high stability. Since at least a part of the cured resin composition is formed, the product or film has high heat resistance and high stability, and therefore has a merit of high production yield.
[0054]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below. In the present invention, the light includes not only electromagnetic waves having wavelengths in the visible and invisible regions that can radicalize the radical generation site of the photosensitive compound or cause a radical reaction in the photosensitive resin composition, but also an electron beam. Such particle beam, and radiation or ionizing radiation which collectively refers to electromagnetic wave and particle beam are included. For the photocuring of the resin composition, ultraviolet rays, visible light, electron beams, ionizing radiation and the like are mainly used.
[0055]
First, the radical generator according to the present invention will be described. The radical generator according to the present invention has the following formula (1) in one molecule.
[0056]
[Chemical formula 5]

[0057]
(Wherein R¹, R², R^Three, R^Four, R^FiveAnd R⁶Are each independently a hydrogen atom or a substituent, and may be a ring structure bonded to each other. )
It consists of the compound (a) which has two or more naphthalimide structure containing groups represented by these.
[0058]
The compound (a) may have the same naphthalimide structure in one molecule, or two or more naphthalimide structures may be mixed in one molecule.
[0059]
The radical generation mechanism by the naphthalimide structure-containing group is presumed that the naphthalimide structure generates radicals by absorbing light such as electromagnetic waves and radiation.
[0060]
In the radical generator according to the present invention, the naphthalimide structure-containing group functions as a hydrogen abstraction-type radical generating site, and when excited by irradiation with light, causes radical reaction, initiates radical polymerization, It is also possible to crosslink molecules.
[0061]
Of the naphthalimide structure-containing groups represented by the above formula (1), R¹, R², R^Three, R^Four, R^FiveAnd R⁶Are each independently a hydrogen atom or a substituent, and may be a ring structure bonded to each other.
[0062]
Examples of the substituent include halogen atoms, hydroxyl groups, mercapto groups, amino groups, cyano groups, silyl groups, silanol groups, alkoxy groups, nitro groups, carboxyl groups, acetyl groups, acetoxy groups, sulfone groups, and substituents. And an organic group which may have a substituent, and examples of the organic group which may have a substituent include a saturated or unsaturated alkyl group, a saturated or unsaturated alkyl halide, and the like. Group, aromatic group such as phenyl group and naphthyl group, allyl group, and the like.
[0063]
R¹, R², R^Three, R^Four, R^FiveAnd R⁶Is a hydroxyl group or the above-exemplified substituents, it is preferable from the viewpoint of easy procurement of raw materials and simple synthesis.
[0064]
In addition, the ring structure bonded to each other is not limited to an aliphatic ring structure such as a cyclohexyl group,¹, R²Or an anthracene structure bonded with an aromatic ring, R², R^ThreeA ring having an aromatic ring to form a phenanthrene structure, a structure having a pyrene structure in the same manner, a structure having a perylene structure, etc.¹, R², R^Three, R^Four, R^FiveAnd R⁶In the above, those having a condensed ring hydrocarbon larger than naphthalene bonded to the naphthalene ring are also included in the naphthalimide structure-containing group of the present invention if the imide ring has a 6-membered ring structure. Further, the ring structure may be an aromatic condensed ring or an aliphatic ring structure, and may further contain a hetero atom other than C as a ring constituting atom.
[0065]
From the viewpoint of improving the solubility when blended in the photosensitive resin composition, the substituent introduced into the compound (a) is a saturated and unsaturated alkyl group having 1 to 15 carbon atoms, an alkoxy group, a bromo group, A chloro group, a fluoro group and the like are preferable.
[0066]
In the compound (a), when a portion to which N of two or more naphthalimide structure-containing groups is bonded is represented by X, the compound (a) can be represented by the following formula (2).
[0067]
[Chemical 6]

[0068]
(Wherein R¹, R², R^Three, R^Four, R^FiveAnd R⁶Is the same as in formula (1), X is an n-valent chemical structure, and n is an integer of 2 or more)
The chemical structure X contained in the above formula (1) may have any chemical structure having a valence of 2 or more, but is typically an organic group. Examples of the organic group include linear and / or branched and / or cyclic saturated, unsaturated polyvalent alkyl groups, aryl groups, allyl groups, and the like, and a single bond, an ester bond, One or more bonds such as an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, a thiocarbamate bond, a carbodiimide bond, and a carbonate bond may be included.
[0069]
Examples of the divalent or higher chemical structure other than the organic group include siloxane, silane, and borazine.
[0070]
In particular, from the viewpoint of price, availability, ease of synthesis, and solubility, a linear or branched polyvalent alkyl group is preferable, and an ester bond, an ether bond, an amide bond, a urethane bond, Those containing a urea bond are more preferred. Further, from the viewpoint of heat resistance, a linear or branched polyvalent alkyl group having a saturated or unsaturated cyclic structure is preferable, and an ester bond, an ether bond, an amide bond, a urethane bond, a urea bond is contained therein. More preferably, those containing
[0071]
The radical generator according to the present invention has two or more naphthalimide structure-containing groups, but three or more are preferable from the viewpoint of three-dimensionally crosslinking a radical polymerizable compound or a radical reactive compound other than radical polymerization. When the generator has a structure having a plurality of pendant naphthalimide structure-containing groups of the formula (1) in the polymer skeleton and is used as the main polymer in the photosensitive resin composition, the degree of polymerization desired to be achieved It is preferable to have an amount of naphthalimide structure, but an optimum value can be selected as appropriate in consideration of the material system used, physical properties of the final coating film, and the like.
[0072]
Since the radical generator has many π bonds connected, the absorption wavelength is longer than that of maleimide. Therefore, the radical generator is likely to have absorption at a wavelength of 365 nm, which is the main emission wavelength of a high-pressure mercury lamp, and the sensitivity is high. It is good.
[0073]
In order to improve the sensitivity, the substituent R is formed so that the naphthalimide skeleton contained in the structure of the compound (a) is excited by radiation and has a chemical structure that easily generates radicals.¹To R⁶It is considered effective to select the central structure X.
[0074]
In order to obtain practical sensitivity, R in the above formula (1)¹, R², R^Three, R^Four, R^FiveAnd R⁶It is preferable that a part of the absorption wavelength of the compound (a) overlaps with the emission wavelength of one of the wavelengths included in the exposure light source (irradiation light source) in the process. ) Is preferably within ± 20%, more preferably within ± 10% of the value of the emission wavelength closest to the absorption maximum.
[0075]
Similarly, in terms of sensitivity, the molar extinction coefficient of the compound (a) is preferably 0.1 or more at any wavelength of light emitted from the exposure light source (irradiation light source) in the process. Here, the molar extinction coefficient ε is a relationship derived from Lambert-Beer's law and is expressed by the following equation.
[0076]
A = εcb
A = absorbance
b = optical path length in the sample (cm)
c = Concentration of solute (mol / L)
Normally, when the change in absorbance is recorded while changing the incident wavelength with a cell having the same optical path length using the same concentration solution, the absorbance changes depending on the wavelength, and the maximum molar absorption at the wavelength specific to the compound to be measured. Coefficient ε_MAXIndicates. The molar extinction coefficient of the compound (a) at the exposure wavelength is 0.1 or more when the molar extinction coefficient when measured at any of the wavelengths employed when performing exposure using the compound (a) is 0. Means greater than 1 and maximum molar extinction coefficient ε_MAXDoes not mean 0.1 or more.
[0077]
Also, considering the maximum molar extinction coefficient of the naphthalimide compound, the excited state of the naphthalimide compound is π−π^*It is thought to be due to transition. Since it is thought that radicals are generated by passing through this excited state, naphthalimide is π-π^*It is important to make a transition. According to the identification method of organic compounds by spectrum, 5th edition (R.M.Silverstein 1993), π-π^*The transition is said to be characterized by a molar extinction coefficient of 10,000 or more, but in practice, even if the molar extinction coefficient is about several thousand like phenol, π-π^*Some transitions occur, and it is considered that radical generation and a crosslinking reaction are likely to occur if the maximum molar extinction coefficient of naphthalimide is 2,000 or more. Therefore, the maximum molar extinction coefficient ε of compound (a)_MAXIs preferably 2000 or more.
[0078]
In the case of a general high-pressure mercury lamp, there are three large light emissions of 365 nm (i-line), 405 nm (h-line), and 436 nm (g-line). It suffices if the compound (a) has an absorption maximum. In addition, when irradiation is performed with an F2 excimer laser (157 nm), an ArF excimer laser (193 nm), a KrF excimer laser (248 nm), etc., it is only necessary to have absorption near these wavelengths. Specifically, the absorption maximum near 365 nm is preferably in the range of 365 ± 73 nm, and more preferably in the range of 365 ± 37 nm.
[0079]
Used as an exposure wavelength when the absorption wavelength overlaps at least one of the wavelengths 157 nm, 193 nm, 248 nm, 365 nm, 405 nm, and 436 nm, which are the main emission wavelengths of the above versatile exposure light source It is particularly preferable that the molar extinction coefficient at the wavelength is 0.1 or more.
[0080]
Interpretation of the Ultraviolet Spectra of Natural Products (AIScott 1964) and identification methods by spectrum of organic compounds as a guideline on what substituents should be introduced to shift the absorption wavelength relative to the desired wavelength You can refer to the table described in the fifth edition (RMSilverstein 1993).
[0081]
Since the radical generating agent of the present invention is a hydrogen abstraction type, it is difficult to generate radicals only by heating, and since the basic skeleton is a naphthalimide skeleton, it is difficult to decompose by heating. Therefore, it is excellent in heat resistance, and when blended in a photosensitive resin composition, the storage stability of the resin composition is good, the stability of the cured film finally obtained is also improved, and the light resistance of the coating film Deterioration, coloring, fading, peeling and cracking of the coating film can be prevented.
[0082]
From the viewpoint of heat resistance, the radical generator according to the present invention preferably has a 90% thermal decomposition temperature of the compound (a) of 50 ° C. or higher, more preferably 100 ° C. or higher.
[0083]
Here, the 90% pyrolysis temperature is the same method as in the examples of the present invention described later, and when the weight loss is measured using a thermogravimetric analyzer, the weight of the sample becomes 90% of the initial weight. Refers to the temperature. Similarly, the 95% pyrolysis temperature is the temperature at which the sample weight reaches 95% of the initial weight.
[0084]
The compound (a) preferably has high solubility when blended in the photosensitive resin composition from the viewpoint of improving coating suitability, transparency after curing, sensitivity during exposure, and the like.
[0085]
From the viewpoint of coating suitability at the time of coating, the compound (a) is preferably highly soluble in a solvent. Specifically, the compound (a) is dissolved in any of the solvents to be used, particularly general-purpose solvents described later. The property is preferably 0.1% by weight or more.
[0086]
Moreover, even if it is the photosensitive resin composition melt | dissolved transparently using the solvent, when the compatibility of the solid content contained in it is low, when the solvent volatilizes at the time of coating, the coating film in drying A precipitate is formed in the film, and sufficient transparency cannot be obtained. Therefore, when a highly transparent coating film or molded body is required like an optical member, other solid components in the photosensitive resin composition, particularly a polymerizable compound such as the compound (b) described later, Among these, it is preferable to use the compound (a) having high compatibility with the monomer component. When high transparency is required, the total light transmittance (JIS K7105) is preferably 90% or more when the thickness of the coating film formed by curing the photosensitive resin composition is 10 μm. % Or more is more preferable.
[0087]
When the solubility of the compound (a) in the polymerizable compound is high, the action as an initiator is improved, so that the sensitivity at the time of exposure is also excellent. From this point, when the solubility is evaluated using methyl acrylate as a representative monomer component, the saturation concentration of compound (a) with respect to methyl acrylate at 20 ° C. is preferably 0.01 mol / L or more. .
[0088]
The solubility or compatibility of the compound (a) can be improved by introducing a substituent into the naphthalimide ring. From this point of view, a saturated or unsaturated alkyl group having 1 to 15 carbon atoms, an alkoxy group, a bromo group, a chloro group, a fluoro group, or the like is preferable as a substituent of the naphthalimide ring. Moreover, the solubility or compatibility of a compound (a) can also be improved by changing the structure of X of said Formula (2), or introducing a substituent into X. The substituent introduced into the naphthalimide ring or the X moiety of the compound (a) or the structural change to be applied is variously selected depending on the solvent to be dissolved or other solid components to be compatible. For example, when a carboxyl group is selected as a substituent, it becomes easy to dissolve in water or an organic polar solvent, and when an ester is introduced, the solubility in a solvent or compound having an ester bond is improved.
[0089]
A 1,8-naphthalimide compound such as the above formula (1) generally has a substituent at the 1-position and the 8-position of naphthalene, and these are bonded as anhydrides in 1,8-naphthalic anhydride. It is synthesized from things. In general, an imide bond is formed by first performing an addition reaction between an anhydride and an amine to form an amic acid, followed by a dehydration condensation reaction by heating or a catalyst. When the acid anhydride has a five-membered ring structure, such as phthalic anhydride or maleic anhydride, the reaction proceeds in the two steps as described above. It is not formed, so there are various problems in synthesis. On the other hand, since 1,8-naphthalic anhydride has a 6-membered ring anhydride structure, the dehydration reaction easily proceeds when an addition reaction with a primary amine is performed. The 6-membered ring structure is less distorted and more energetically stable than the 5-membered ring structure. In the case of the 6-membered ring structure, the imide is more stable than the amide acid. For these reasons, the naphthalimide structure is very simple to synthesize compared to the maleimide structure, and is advantageous in synthesis. Therefore, the photo radical generator composed of the compound (a) has high productivity including yield, reaction rate, management and cost.
[0090]
The compound (a) having two or more naphthalimide structure-containing groups in the present invention can be synthesized using various known methods. Specifically, a method of reacting naphthalic anhydride with a compound having a plurality of amino groups such as diamine, triamine, and tetraamine, or reacting amino alcohol with naphthalic anhydride to form N-hydroxyalkyl (allyl) ) After synthesizing naphthalimide, dehydrating condensation with polyvalent carboxylic acid, synthesizing N-hydroxyalkyl (allyl) naphthalimide, then reacting with polyvalent carboxylic acid chloride, naphthalic anhydride and amino acid , N-carboxyalkyl (allyl) naphthalimide is synthesized, and then treated with thionyl chloride or the like to acid chloride, and then reacted with a polyvalent amine or polyhydric alcohol, but is not particularly limited. .
[0091]
In addition to acid anhydrides such as 1,8-naphthalic anhydride and 4-bromo-1,8-naphthalic anhydride, derivatives thereof may be used as raw materials in the above synthesis method. As the derivative of naphthalic anhydride, the substituent R of the compound (a) to be finally obtained¹To R⁶May already be used. In addition, substituent R of formula (1)¹~ R⁶May be introduced before the imidization reaction or after the imidation reaction.
[0092]
A method for synthesizing the compound (a) having two naphthalimide structure-containing groups will be specifically illustrated, but is not particularly limited as the synthesis method of the present invention. In addition, a compound having two or more naphthalimide structure-containing groups can be synthesized using a similar method or a known method.
[0093]
First, 1,8-naphthalic anhydride is added to N, N, -dimethylformamide and stirred. Then, 1/2 mole of 1,12-diaminododecane and naphthalic anhydride are added dropwise thereto and stirred at room temperature for about 1 to 15 hours. At this time, the reaction solvent to be used is not limited to dimethylformamide, and two or more kinds of solvents may be mixed and used. The reaction solvent is preferably a solvent in which the final product is dissolved, such as an organic polar solvent. Naphthalic anhydride is poorly soluble and difficult to dissolve in common solvents, so it often dissolves by reacting with amines.
[0094]
1,8-Naphthalic anhydride may form an imide bond only by mixing with an amine and stirring at room temperature. Further, in order to accelerate the reaction, the temperature may be added in the range from room temperature to 200 ° C. Further, in order to remove water generated during the reaction, an azeotropic solvent such as toluene may be mixed and used.
[0095]
In this manner, the solvent of the reaction liquid stirred for several hours is removed by distilling or throwing it into water or the like to remove the solid. This is recrystallized in a desired solvent to obtain an N-substituted naphthalimide compound, that is, in this case, a compound (a) having two naphthalimide structure-containing groups represented by the formula (1). be able to. The purification method is not limited to recrystallization, and any known method such as sublimation purification or column chromatography can be used, but recrystallization is preferable from the viewpoint of cost.
[0096]
The acid anhydride used here is not limited to 1,8-naphthalic anhydride, but has a substituent in advance such as 4-bromo-1,8-naphthalic anhydride having a bromo group at the 4-position depending on the purpose. You may use what was introduced.
[0097]
The amino compound used here is an amino group (—NH) of the amino compound, depending on the number of naphthalimide structure-containing groups to be introduced into the compound (a).₂) Should be selected.
[0098]
In the case of a compound having two naphthalimide structure-containing groups, a diamino compound can be used. Specifically, 3,5-diaminobenzoic acid, 4,4′-dihydroxy-3,3′-diaminobiphenyl, 3,4-diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl 2,3-diamino-4-hydroxypyridine, 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 2,4-diaminophenol, 2,4-diaminobenzoic acid, 3-carboxy- 4,4′-diaminodiphenyl ether, 3,3′-dicarboxy-4,4′-diaminodiphenyl ether, 3-carboxy-4,4′-diaminodiphenylmethane, 3,3′-dicarboxy- 4,4′-diaminodiphenylmethane, 3,3′-dicarboxy-4,4′-diaminobiphenyl, 3,3 ′, 5,5′-tetracarboxy-4, '-Diaminobiphenyl, 3-carboxy-4,4'-diaminodiphenylsulfone, 3,3'-dicarboxy-4,4'-diaminodiphenylsulfone, 1,1,1,3,3,3-hexafluoro- 2,2-bis (3-carboxy-4-aminophenyl) propane, 4,4 ′-(or 3,4′-, 3,3′-, 2,4′-, 2,2 ′-) diaminodiphenyl ether 4,4 '-(or 3,4'-, 3,3'-, 2,4'-, 2,2'-) diaminodiphenylmethane, 4,4'- (or 3,4'-, 3, 3'-, 2,4'-, 2,2 '-) diaminodiphenylsulfone, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'- ) Diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xy Range amine, m-xylylene diamine, o-tolidine, o-tolidine sulfone, 4,4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylene-bis- (2,6- Diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4′-benzophenonediamine, bis- {4- (4′-aminophenoxy) phenyl} sulfone, 1,1,1,3 3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,2-bis {4- (4′-aminophenoxy) phenyl} propane, 3,3′-dimethyl-4,4 ′ -Diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis {4- (3'-aminophenoxy) phenyl} sulfo 2,2-bis (4-aminophenyl) propane, ethylenediamine, diethylenetriamine, 1,3-diaminopropane, 1,2-diaminopropane, 2,2-diaminopropane, 1,4-diaminobutane, 1,5 -Diaminopentane, 1,6-diaminohexane, 1,4-diaminocyclohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,12-diaminododecane, 2- (2-aminoethoxy) ethylamine, etc. There is no particular limitation.
[0099]
In the case of the compound (a) having three naphthalimide structure-containing groups, a triamino compound, and in the case of the compound (a) having four naphthalimide structure-containing groups, a tetraamino compound is used to convert naphthalimide 2 The compound (a) can be synthesized in the same manner as in the case of the compound having two. Moreover, the compound (a) in which the amount of naphthalimide groups introduced is smaller than the number of amino groups in the amino compound can be synthesized by changing the charging ratio of naphthalic anhydride and amino compound during synthesis.
[0100]
As a synthesis method other than the above method, a method of reacting an amino alcohol with naphthalic anhydride to synthesize N-hydroxyalkyl (allyl) naphthalimide and then dehydrating and condensing with a polyvalent carboxylic acid is specifically exemplified. However, the synthesis method of the present invention is not particularly limited.
[0101]
First, 1,8-naphthalic anhydride is added to N, N, -dimethylformamide and stirred. 2-aminoethanol is added dropwise in an equimolar amount with naphthalic anhydride, and the mixture is stirred at room temperature for about 1 to 15 hours. At this time, the reaction solvent to be used is not limited to dimethylformamide, and any solvent that dissolves the final product, such as an organic polar solvent, may be used alone or two or more of them may be mixed. Naphthalic anhydride is poorly soluble and difficult to dissolve in common solvents, so it often dissolves by reacting with amines.
[0102]
1,8-Naphthalic anhydride may form an imide bond only by mixing with an amine and stirring at room temperature. Further, in order to accelerate the reaction, the temperature may be added in the range from room temperature to 200 ° C. Further, in order to remove water generated during the reaction, an azeotropic solvent such as toluene may be mixed and used.
[0103]
N-2-hydroxyethyl naphthalimide synthesized by reacting 1,8-naphthalic anhydride with 2-aminoethanol can be converted to compound (a) by various methods. Representative examples are shown below, but the present invention is not limited thereto.
[0104]
N-2-hydroxyethylnaphthalimide and 1.2 molar equivalents of 4-dimethylaminopyridine are dissolved in a solvent such as dehydrated toluene. Thereto, 0.6 mol equivalent of succinyl chloride is gradually added dropwise and stirred at room temperature for 1 to 15 hours. Treat with 1N HCl in a separatory funnel to transfer 4-dimethylaminopyridine to the aqueous layer. After separation into an aqueous layer and an oil layer, the oil layer is further saturated with NaHCO 3._ThreeThe solution is used for treatment, succinic acid derived from unreacted succinyl chloride is transferred to the aqueous layer, and the oil layer and the aqueous layer are separated. The oil layer thus obtained is dehydrated with a suitable dehydrating agent such as magnesium sulfate, and filtered. A product obtained by evaporating the solvent from the filtrate is recrystallized to obtain a target product.
[0105]
In addition to the above operations, the same compound can be obtained by a method by dehydration condensation with a dicarboxylic acid using an acid catalyst.
[0106]
Further, compound (a) can be obtained by synthesizing an amide, ester or urea by a known method using N-carboxyalkylnaphthalimide as disclosed in JP-A-5-19505. I can do it.
[0107]
As described above, the acid anhydride used here is not only 1,8-naphthalic anhydride but also 4-bromo-1,8-naphthalic anhydride having a bromo group at the 4-position depending on the purpose. Those having a substituent introduced in advance may be used.
[0108]
The amine compound used here is not limited to 2-aminoethanol, and various amine compounds can be used according to the purpose. Examples thereof include oxyalkylamines such as propanolamine and hexanolamine, substituted oxyalkylamines such as ethoxyethanolamine, propoxypropanolamine, and 2- (2-aminoethoxy) ethanol.
[0109]
In the radical generator according to the present invention thus obtained, the naphthalimide structure-containing group functions as a hydrogen abstraction type radical generation site, and the radical reaction is induced by irradiating with light such as electromagnetic waves and radiation. Can wake up. Since the naphthalimide structure-containing group is not a self-cleavable type but a hydrogen abstraction type and has a naphthalene skeleton with good heat resistance, a photoradical generator having high heat resistance, stability and storage stability can be obtained.
[0110]
In addition, since the radical generated by the naphthalimide structure-containing group goes through a hydrogen abstraction mechanism, it can react not only with general radical polymerizable groups such as ethylenically unsaturated bonds but also with various compounds such as aromatic rings. For example, it can react with a low molecular weight aromatic compound such as xylene, or can crosslink a polymer having an aromatic moiety such as PET. Moreover, since it has two or more naphthalimide structure-containing groups that function as radical generating sites, two or more naphthalimide-containing groups in one molecule can be combined with other molecules to form a three-dimensional crosslinked structure. . Therefore, the radical generator which is the compound (a) is used as a general photo radical polymerization initiator, and for example, used as a crosslinking agent for a resin composition containing an aromatic polymer to improve the solvent resistance after curing. It is possible to make it.
[0111]
If a radical is generated at any one of a plurality of naphthalimide structure-containing groups (radical generation sites) contained in one molecule of the radical generator to form a bond with a reactant such as a polymer. All unreacted radical generating sites contained in the molecule are also part of the chemical structure of the reactant such as a polymer. Therefore, even if an unreacted site remains in the molecule of the radical generator, each unreacted site does not remain in a free form in a reaction product such as a polymer and does not volatilize during post-baking. Moreover, even if the radical generation site remains unreacted, it is a hydrogen abstraction type and has a highly heat-resistant naphthalimide structure, so that a volatile decomposition product is generated in the cured coating film. There is nothing. For this reason, the residue derived from the radical generator of the present invention is unlikely to cause alteration of the coating film. As described above, the residue derived from the radical generator of the present invention is bonded to the matrix in the cured coating film of the photosensitive resin composition and exists in a chemically stable form, heat resistance, weather resistance, Does not impair stability.
[0112]
Therefore, the residue derived from the radical photopolymerization initiator of the present invention has a problem of work safety, deterioration of light resistance, occurrence of coloring and fading, peeling of the coating film and occurrence of cracks, and the reliability of the final product. It does not cause the problem of decreasing, the problem of shortening the chemical life, or the problem of generating odor.
[0113]
In addition, the reaction that forms the maleimide structure is not formed unless the dehydration condensation reaction is promoted by heating, a catalyst, etc., and thus there have been various problems in the synthesis. However, the reaction that forms the naphthalimide structure is dehydrated compared to maleimide. The condensation reaction proceeds rapidly, the synthesis is very simple, and it is advantageous in synthesis. Therefore, productivity is improved including yield, reaction rate, management and cost.
[0114]
Next, the photosensitive resin composition according to the present invention will be described.
[0115]
The photosensitive resin composition according to the present invention is characterized by containing a compound (a) having two or more naphthalimide structure-containing groups represented by the above formula (1) as an essential component. A radical reactive compound or other curing reactive compound, a high molecular weight binder component, a hydrogen donor, a radical generator other than the compound (a), or other components may be contained.
[0116]
In the photosensitive resin composition according to the present invention (hereinafter simply referred to as a resin composition), the naphthalimide structure-containing group of the radical generator composed of the compound (a) functions as a hydrogen abstraction type radical generation site. Radicalization occurs when excited by irradiation with light such as electromagnetic waves or radiation, and causes a radical reaction in the resin composition. The radical reactive compound in the resin composition causes various radical reactions such as radical polymerization, radical dimerization reaction with the compound (a) as a radical generator, radical crosslinking reaction, etc. depending on the type of the compound, The resin composition is cured or the solubility is changed.
[0117]
Here, the term “crosslinking” refers to generation of a crosslinking bond, and the term “crosslinking” refers to a bond formed by bridging any two atoms among molecules composed of atoms bonded in a chain. In this case, the bond may be within the same molecule or between other molecules (Chemical Dictionary Tokyo Chemical Doujin p.1082).
[0118]
The compound (b) having an ethylenically unsaturated bond has been widely used as a radically polymerizable curing reactive compound and has a wide range of applications, and is therefore preferably used in the present invention. As the compound (b) having an ethylenically unsaturated bond, a compound having one or more ethylenically unsaturated bonds and a compound having another functional group together with at least one ethylenically unsaturated bond are used. For example, amide monomers, (meth) acrylate monomers, urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, epoxy (meth) acrylates, hydroxyl group-containing (meth) acrylates, aromatic vinyl such as styrene A compound can be mentioned.
[0119]
Examples of amide monomers include amide compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and acryloylmorpholine.
[0120]
Examples of (meth) acrylate monomers include imide acrylates such as hexahydrophthalimidoethyl acrylate and succinimide ethyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenylpropyl Hydroxyalkyl (meth) acrylates such as acrylates; acrylates of alkylene oxide adducts of phenols such as phenoxyethyl (meth) acrylates and their halogen nucleus substitutions; mono- or di (meth) acrylates of ethylene glycol, methoxyethylene glycols Mono (meth) acrylate, tetraethylene glycol mono or di (meth) acrylate, tripropylene glycol mono or di (meth) acrylate, etc. Mono- or di (meth) acrylates of glycols; polyols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate and alkylene oxides thereof ( Examples include meth) acrylic ester, isocyanuric acid EO-modified di- or tri (meth) acrylate.
[0121]
Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a reaction product of a polyol and an organic polyisocyanate.
[0122]
Here, examples of the polyol include a low molecular weight polyol, polyethylene glycol, and polyester polyol, and examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexanedimethanol, and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polyethylene glycol and polypropylene glycol. Examples of the polyester polyol include these low molecular weight polyols and / or polyether polyols, adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid. And a reaction product with an acid component such as a dibasic acid or an anhydride thereof.
[0123]
Examples of the organic polyisocyanate to be reacted with the polyol include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
[0124]
As a polyester (meth) acrylate oligomer, the dehydration condensate of a polyester polyol and (meth) acrylic acid is mentioned. Examples of the polyester polyol include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, and these And a reaction product from a polyol such as an alkylene oxide adduct and an acid component such as a dipic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or an anhydride thereof.
[0125]
Epoxy (meth) acrylate is obtained by addition reaction of unsaturated carboxylic acid such as (meth) acrylic acid to epoxy resin. Epoxy (meth) acrylate of bisphenol A type epoxy resin, epoxy of epoxy or cresol novolac type epoxy resin (Meth) acrylate, (meth) acrylic acid addition reactant of diglycidyl ether of polyether, and the like.
[0126]
The compound (b) preferably has 2 or more, particularly 3 or more ethylenically unsaturated bonds from the viewpoint of three-dimensional crosslinking of a radically polymerizable compound or a radically reactive compound other than radically polymerized.
[0127]
In addition, when the photosensitive resin composition is used as a resist for forming a pattern by exposure in applications such as electronic members and color filters, the compound (b) is used to improve the alkali developability of the photosensitive resin composition. Alternatively, those having an alkali-soluble or hydrophilic functional group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a hydroxyl group may be used.
[0128]
In the photosensitive resin composition of the present invention, a polymer compound may be blended as a binder component in order to adjust the film-forming property in the uncured state of the composition and the physical properties of the coated film after curing. Any known polymer compound can be used as the polymer compound. For example, organic polyisocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate; vinyl acetate, vinyl chloride, acrylate ester, methacrylate ester, etc. Polymers and copolymers of acrylic or vinyl compounds; styrene resins such as polystyrene; acetal resins such as formal resins and butyral resins; silicone resins; phenoxy resins; epoxy resins typified by bisphenol A type epoxy resins; polyurethanes, etc. Urethane resin; phenol resin; ketone resin; xylene resin; polyamide resin; polyimide resin; polyether resin; polyphenylene ether resin; Sol resin; cyclic polyolefin resin; polycarbonate resin; polyester resin; polyarylate resin; polystyrene resin; novolac resin; alicyclic polymer such as polycarbodiimide, polybenzimidazole, polynorbornene; Examples include, but are not limited to, molecular compounds.
[0129]
The radical generated by the naphthalimide structure-containing group of the compound (a), which is an essential component, has not only an ethylenically unsaturated bond, but also a reaction of various compounds such as an aromatic ring, and thus has an ethylenically unsaturated bond. Even in systems where no compound is present, curing and / or solubility changes can be caused. Therefore, the compound (a) not only cures a photosensitive resin composition containing a compound having an ethylenically unsaturated bond by a normal radical polymerization reaction, but generally includes, for example, polystyrene and polyethylene terephthalate (PET). Can cure a photosensitive resin composition containing a non-polymerizable aromatic polymer by a crosslinking reaction to improve film properties such as solvent resistance, heat resistance, hardness, strength, and adhesion.
[0130]
Therefore, the high molecular weight curing reactive binder component mixed with the compound (a) to prepare the photosensitive resin composition includes not only general radical polymerizable compounds such as compounds having an ethylenically unsaturated bond. Any known polymer compound can be used.
[0131]
Moreover, when the compound (a) itself functions as a radical reactive compound, a photosensitive resin composition can be prepared without mixing the radical reactive compound. Therefore, in this case, it is possible to use a high molecular weight non-reactive binder component, and it is not necessary to use a binder component at all.
[0132]
These polymer compounds may be used alone or in combination of two or more. The polymer compound as the binder component preferably has a weight average molecular weight of usually 10,000,000 or less, although it depends on the use of the photosensitive resin composition. If the molecular weight is too large, the solubility and processing characteristics are deteriorated.
[0133]
The amount of the compound (a) in the resin composition according to the present invention is 0.1% by weight or more of the total solid content of the photosensitive resin composition, so that the curing rate of the resin composition by light irradiation becomes slow. The amount of generated radicals is small, so that the crosslinking density is low, which is preferable from the viewpoint of preventing the strength of the coating film and the glass transition temperature of the coating film from being lowered. From the viewpoint of sensitivity and physical properties of the coating film, 1% by weight It is still more preferable that it is above. In this case, the mixing ratio of the compound (a) to the polymer (b) and / or the polymer compound can be appropriately selected in consideration of various physical properties according to the purpose. In addition, solid content of the photosensitive resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.
[0134]
Moreover, when using in combination with another radical reactive compound with a compound (b) as a curing reactive compound, the quantity of a compound (a) is suitably adjusted according to the kind and quantity of a radical reactive compound to combine.
[0135]
When the photosensitive resin composition of the present invention contains the compound (b), the compound (b) may be 1% by weight or more of the total solid content of the photosensitive resin composition in order to obtain sufficient photocurability. preferable. The photosensitive resin composition may contain a high molecular weight binder component other than the compound (b). In that case, the solid content of the resin composition as a whole is 1% by weight or more and 97% by weight or less depending on the application. Is preferred. When the amount of the high molecular weight binder component not containing an ethylenically unsaturated bond is more than 97% by weight, the curability by light tends to decrease.
[0136]
In addition, since the compound (a) is a hydrogen abstraction type radical generator, a hydrogen donor is contained in the resin composition of the present invention because the radical generation efficiency is further improved and the sensitivity is improved. Is preferred. Examples of the hydrogen donor group of the hydrogen donor include a functional group in which hydrogen is directly attached to carbon such as an alkyl group, and an organic group having an amine, thiol, hydroxyl group or ether bond generally used as a hydrogen donor group. Is mentioned. In particular, thiols, amines, hydroxyl groups, and organic groups having an ether bond that easily donate hydrogen are preferable from the viewpoint of sensitivity. The ether bond is said to facilitate the extraction of hydrogen in the hydrocarbon structure (alkane, alkene) next to the ether bond. Therefore, the hydrogen donor group containing an ether bond is preferably a structure having such a hydrogen.
[0137]
From the viewpoint of sensitivity, the blending ratio of the hydrogen-donating group contained in the hydrogen donor is preferably equal to or more than the number of moles of naphthalimide sites contained in the resin composition. An appropriate value can be selected as appropriate depending on the relationship with the physical properties of the coating film to be formed.
[0138]
When the photosensitive resin composition of the present invention is cured by light, other photoradical generators may be used together with the compound (a) as necessary in order to accelerate the radical reaction. When another photoradical generator is used in combination with the compound (a), the other photoradical generator generates a decomposition product, and the discoloration and physical properties of the cured film, the volatilization of the decomposition product, the photosensitive resin composition May cause problems such as stability and storage stability. However, the combined use of compound (a) makes it possible to reduce the amount of other photoradical generators used, so that the above problems are less likely to occur than when only other photoradical generators are used. However, since the degree is light, the problem caused by the photo radical generator can be suppressed to a practically acceptable level while extracting sufficient radical reactivity.
[0139]
Other photo radical generators include, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, etc. Anthraquinone, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylpyroxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine oxide Monoacylphosphine oxides or bisacylphosphine oxides such as benzophenones such as benzophenone, and xanthones.
[0140]
These photo radical generators can be used alone or in combination with a photopolymerization initiation accelerator such as benzoic acid or amine. A preferable blending ratio of these photo radical generators is 0.1% by weight or more and 35% by weight or less, more preferably 1% by weight or more and 10% by weight or less with respect to the entire resin composition.
[0141]
In order to impart processing characteristics and various functionalities to the photosensitive resin composition according to the present invention, various other organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles, sensitizers, and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and the functions or forms include pigments, fillers, fibers, and the like.
[0142]
The blending ratio of these optional components is preferably in the range of 0.1 wt% to 95 wt% with respect to the entire solid content of the resin composition. When the amount is less than 0.1% by weight, the effect of adding the additive is hardly exhibited, and when the amount exceeds 95% by weight, the amount of the resin composition is small and the properties of the resin composition are hardly reflected in the final product.
[0143]
When a large amount of a component that absorbs light emitted from the irradiation light source is added to the photosensitive resin composition, light does not reach the compound (a) sufficiently, and the sensitivity is lowered. Therefore, from the point of emphasizing the sensitivity of the resin composition, the transmittance of components other than the compound (a) in the wavelength region where the emission wavelength of the exposure light source and the absorption wavelength of the compound (a) mixed in the resin composition overlap. Is preferably 20% or more.
[0144]
Moreover, you may dilute the photosensitive resin composition which concerns on this invention to a suitable density | concentration using a solvent. As the solvent, various general-purpose solvents such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and the like; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether (so-called cellosolves); ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; Ethyl acetate, butyl acetate, n-acetate Lopyl, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (eg methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, dimethyl oxalate, lactic acid Esters such as methyl and ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, Halogenated hydrocarbons such as 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; N, N-dimethylformua Amides such as N, N-dimethylacetamide; pyrrolidones such as N-methylpyrrolidone; lactones such as γ-butyrolactone; sulfoxides such as dimethyl sulfoxide; and other organic polar solvents. , Aromatic hydrocarbons such as benzene, toluene and xylene, and other organic nonpolar solvents. Moreover, you may use as a reactive diluent a compound which has a reactive group in a structure, such as an ethylenically unsaturated compound liquid at normal temperature. These solvents are used alone or in combination. These solvents may be used after filtering impurities by various known methods such as a filter having a pore diameter of about 0.05 μm to 0.2 μm.
[0145]
In the resin composition, the compound (a), which is an essential component, is stirred with an optional component such as a curing reactive compound such as the compound (b) or a high molecular weight binder component, if necessary, depending on the case or application. It can be prepared by mixing.
[0146]
The photosensitive resin composition according to the present invention thus obtained is cured by irradiation with light, such as a pattern forming material (resist), a coating material, a printing ink, an adhesive, a filler, a molding material, and a three-dimensional modeling. It can be used for all known fields and products where materials with varying solubility are used, but in particular, paints, printing inks, color filters, electronics, which require heat resistance and require high reliability. Suitable for forming parts, interlayer insulating films, wiring coating films, optical members, optical circuits, optical circuit parts, antireflection films, holograms or building materials.
[0147]
For example, in the case of a color filter, a pixel portion, a light shielding portion (black matrix) provided at the boundary of the pixel portion, a protective film, and a spacer for maintaining a cell gap are formed from a cured product of the photosensitive resin composition. can do.
[0148]
In the case of an electronic component, for example, an underfill agent and a sealant for a semiconductor device can be exemplified.
[0149]
As the interlayer insulating film, an interlayer insulating film for a build-up substrate that requires heat resistance and insulating reliability, an interlayer insulating film for a fuel cell, an insulating coating for automobile parts and household appliances, etc. It can be formed by a cured product.
[0150]
Examples of the wiring protective film include a solder resist that is a wiring protective layer on the surface of the printed wiring board, and a surface coating of the electric wire.
[0151]
In the case of an optical member, examples thereof include overcoats of various optical lenses, optical circuit components such as antireflection films, optical waveguides, and branching devices, relief-type and volume-type holograms, and the like.
[0152]
In the case of building materials, wallpaper materials, wall materials, floor materials, and other skin materials with low volatile components, adhesive / adhesive materials, inks, and the like can be exemplified.
[0153]
The printed matter, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film hologram or building material according to the present invention has high heat resistance and high stability. Since at least a part is formed by the cured product of the resin composition, there is a merit that it has high heat resistance and high stability, and therefore the production yield is also high.
[0154]
【Example】
1. Production example
(Production Example 1) (Synthesis of poly-4-methylstyrene)
In a 500 mL separable flask equipped with a stirrer, 30 mL of ethyl acetate was added, and the mixture was stirred in an oil bath at 60 ° C. while flowing nitrogen at 100 mL / min. Thereto was added dropwise 50 g of 4-methylstyrene in which 400 mg of AIBN (2,2′-azobisisobutyronitrile) was dissolved. After stirring for 7 hours, the reaction solution was appropriately diluted with ethyl acetate and added dropwise to ethanol for reprecipitation and purification to obtain 42.3 g of the desired product (Polymer 1).
[0155]
(Production Example 2) (Synthesis of 4-methylstyrene and hydroxystyrene copolymer)
In the same manner as in Production Example 1, polymerization was carried out using a raw material mixture of 41.3 g (0.35 mol) of 4-methylstyrene and 24.3 g (0.15 mol) of 4-acetoxystyrene. After reprecipitation purification, the obtained polymer is dissolved in tetrahydrofuran, and deprotection is performed by dropping a suitable amount of NaOH saturated methanol solution thereto. Thereafter, the alkali-soluble polymer 1 is purified by reprecipitation. .9 g was obtained.
[0156]
(Production Example 3) (Synthesis of epoxy group-containing acrylic polymer)
A 500 mL separable flask equipped with a stirrer was charged with 150 ml of dried ethyl acetate, and immersed in an oil bath at 60 ° C. while flowing nitrogen at 100 mL / min and stirred. Thereto, 30.1 g (0.3 mol) of methyl methacrylate (MMA) in which 200 mg of AIBN (2,2′-azobisisobutyronitrile) was dissolved, and 14.2 g (0.1 mol) of glycidyl methacrylate (GMA) The mixed solution was gradually added dropwise. The reaction was completed 4 hours after the completion of the dropwise addition, and 42.3 g of an epoxy group-containing acrylic polymer was obtained by reprecipitation with n-hexane. The weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) was 150,000, and the copolymerization ratio by NMR was GMA: MMA = 1: 2.6.
[0157]
(Production Example 4)
Into a 1 L-shaped flask, 19.8 g (0.1 mol) of 1,8-naphthalic anhydride, 500 mL of N, N-dimethylformamide (hereinafter DMF) and a catalytic amount of pyridine were added and stirred. Thereto, 6.7 g (0.11 mol) of 2-aminoethanol was added dropwise and stirred at room temperature for 15 hours. DMF was distilled off with a rotary evaporator and recrystallization was performed with methanol to obtain 22.5 g of needle-shaped crystals of N-2-hydroxyethylnaphthalimide (precursor compound 1).
[0158]
[Chemical 7]

[0159]
(Production Example 5)
The reaction was carried out under the same conditions as in Production Example 4 except that the acid anhydride used was changed to 4-bromo-1,8-naphthalic anhydride. Each raw material was charged in the same number of moles as in Production Example 4 (precursor compound 2).
[0160]
[Chemical 8]

[0161]
(Production Example 6)
Into a 1 L-shaped flask, 19.8 g (0.1 mol) of 1,8-naphthalic anhydride, 500 mL of DMF and a catalytic amount of pyridine were added and stirred. Β-alanine 8.9g (0.1mol) was added there, and after stirring at room temperature for 4 hours, it stirred at 130 degreeC for 5 hours. DMF was distilled off using a rotary evaporator and recrystallization was performed using methanol to obtain 20.9 g of N-2-carboxyethylnaphthalimide crystals (precursor compound 3).
[0162]
[Chemical 9]

[0163]
(Production Example 7)
9.6 g (40 mmol) of precursor compound 1 (N-2-hydroxyethylnaphthalimide) and 5.4 g (44 mmol) of 4-dimethylaminopyridine were put into a 1 L three-necked flask, and chlorinated in the center of the mouth. A calcium tube is attached, and the remaining two are sealed with a silicon W cap (trade name: manufactured by ASONE). Thereto, 500 ml of dehydrated tetrahydrofuran (THF) is added using a syringe and stirred at room temperature. Acrylic acid chloride 4.0g (44mmol) is dripped there, and it stirs at room temperature for 10 hours. Thereafter, the reaction solution was treated with 1N HCl in a separatory funnel to transfer 4-dimethylaminopyridine to the aqueous layer. After separation into an aqueous layer and an oil layer, the oil layer is further saturated with NaHCO 3._ThreeIt processed using the solution, the acrylic acid derived from unreacted acrylic acid chloride was moved to the water layer, and the oil layer and the water layer were separated. Thus, the obtained oil layer was dehydrated with a suitable dehydrating agent such as magnesium sulfate and filtered. A product obtained by evaporating the solvent from the filtrate was recrystallized with a chloroform-ethyl acetate mixed solvent to obtain 10.3 g of the desired product. (Precursor compound 4)
[0164]
[Chemical Formula 10]

[0165]
2. Preparation of radical generator
(Example 1)
Into a 1 L-shaped flask, 19.8 g (0.1 mol) of 1,8-naphthalic anhydride, 500 mL of N, N-dimethylformamide (hereinafter DMF) and a catalytic amount of pyridine were added and stirred. Thereto, 10.2 g (0.5 mol) of 1,12-diaminododecane was added and stirred at 130 ° C. for 5 hours. DMF was distilled off with a rotary evaporator and recrystallized with tetrahydrofuran to obtain 25.5 g of a target needle crystal (Compound 1).
[0166]
Embedded image

[0167]
(Example 2)
The reaction was performed under the same conditions as in Example 1 except that the acid anhydride used was changed to 4-chloro-1,8-naphthalic anhydride. Each raw material was charged in the same number of moles as in Example 1. (Compound 2)
[0168]
Embedded image

[0169]
(Example 3)
Compound 2 (3.2 g, 5 mmol) was charged into a 1 L three-necked flask, dissolved in 500 mL of dried isopropyl alcohol, and stirred at room temperature. To this, 200 g of dried isopropyl alcohol was allowed to react with 1 g of sodium metal, and an isopropyl alcohol solution of sodium isopropoxide was slowly added dropwise, and the progress of the reaction was monitored by TLC (thin layer chromatography). Then, the dropping is continued until the spot of the compound 2 as a raw material disappears, and the reaction is terminated when the spot of the compound 2 disappears. The reaction solution was poured into 5 L of pure water, and the precipitate was dried and purified by column chromatography to obtain Compound 3.
[0170]
Embedded image

[0171]
Example 4
The reaction was carried out under the same conditions as in Example 1 except that the acid anhydride used was changed to 4-bromo-1,8-naphthalic anhydride. Each raw material was charged in the same number of moles as in Example 1 (Compound 4).
[0172]
Embedded image

[0173]
(Example 5)
The reaction was carried out under the same conditions as in Examples 1 and 4 except that the starting diamine was changed to diethylenetriamine and the reaction temperature was 40 ° C. Each raw material was charged in the same number of moles as in Example 1. (Compound 5, Compound 6)
[0174]
Embedded image

[0175]
(Example 6)
9.6 g (40 mmol) of precursor compound 1 (N-2-hydroxyethylnaphthalimide) and 5.4 g (44 mmol) of 4-dimethylaminopyridine were put into a 1 L three-necked flask, and chlorinated in the center of the mouth. A calcium tube is attached, and the remaining two are sealed with a silicon W cap (trade name: manufactured by ASONE). Thereto, 500 mL of tetrahydrofuran (THF) dehydrated in advance is added using a syringe and stirred at room temperature. To this, 3.4 g (22 mmol) of succinic acid chloride (succinyl chloride) previously dissolved in 10 mL of dehydrated THF is added dropwise and stirred at room temperature for 10 hours. Thereafter, the reaction solution was treated with 1N HCl in a separatory funnel to transfer 4-dimethylaminopyridine to the aqueous layer. After separation into an aqueous layer and an oil layer, the oil layer is further saturated with NaHCO 3._ThreeIt processed using the solution, the succinic acid derived from the unreacted succinic acid chloride was moved to the water layer, and the oil layer and the water layer were separated. Thus, the obtained oil layer was dehydrated with a suitable dehydrating agent such as magnesium sulfate and filtered. The product obtained by evaporating the solvent from the filtrate was recrystallized with a chloroform-ethyl acetate mixed solvent to obtain 9.4 g of the desired product. (Compound 7)
[0176]
Embedded image

[0177]
(Example 7)
The reaction was carried out under the same conditions as in Example 6 except that the compound of the raw material used was changed to precursor compound 2 derived from 4-bromo-1,8-naphthalic anhydride. Each raw material was charged in the same number of moles as in Example 6. (Compound 8)
[0178]
Embedded image

[0179]
(Example 8)
Styrene-maleimide copolymer (Mn = 1600, copolymerization ratio = 1.3: 1, manufactured by Aldrich) 11.7 g (about 50 mmol of converted value per unit unit by the above molar ratio) and precursor compound 1 ( 12.1 g (50 mmol) of N-2-hydroxyethylnaphthalimide) was placed in a 300 mL eggplant flask and dissolved in 100 mL of previously dried tetrahydrofuran. A catalytic amount of concentrated sulfuric acid was added dropwise thereto, and the mixture was stirred at 60 ° C. for 96 hours. Thereafter, the reaction solution was poured into hexane for reprecipitation, filtered and dried to obtain 20.3 g of a target product into which a naltalimide group was introduced. (Compound 9)
[0180]
Embedded image

[0181]
Example 9
The reaction was carried out under the same conditions as in Example 8 except that the precursor compound 1 used in Example 8 was changed to the precursor compound 2. Each raw material was charged in the same number of moles as in Example 8 to obtain 21.1 g of the desired product. (Compound 10)
[0182]
Embedded image

[0183]
(Example 10)
Precursor compound 4 (3.0 g, 10 mmol) and methyl methacrylate (3.0 g, 30 mmol) were dissolved in chloroform (50 mL) and stirred. 200 mg of AIBN (2,2′-azobisbutyronitrile) was introduced into the reaction vessel while flowing nitrogen at 100 mL / min, stirred at 50 ° C. for 14 hours, reprecipitated with n-hexane, and precursor compound 4 And 5.2 g of a copolymer of methyl methacrylate were obtained (Compound 11). The weight average molecular weight by gel permeation chromatography was 39000 in terms of polystyrene, and the polymerization ratio by NMR was precursor compound 4: methyl methacrylate = 1: 3.2.
[0184]
Embedded image

[0185]
(Example 11)
8.1 g of epoxy group-containing acrylic polymer (Preparation Example 3) and 5.4 g (20 mmol) of precursor compound 3 were dissolved in 300 ml of dried dimethylformamide (DMF), 1 drop of triethylamine was added, Stir at 20 ° C. for 20 hours. The reaction solution was reprecipitated with n-hexane to obtain 12.7 g of the desired compound (Compound 12).
[0186]
Embedded image

[0187]
(Comparative Example 1)
9.8 g (0.1 mol) of maleic anhydride, 400 mL of N, N-dimethylformamide (hereinafter referred to as DMF), 100 mL of toluene and a catalytic amount of pyridine are added to a 1 L eggplant-shaped flask equipped with a Dean-Stark koji at the top, and stirred. did. Thereto, 10.2 g (0.5 mol) of 1,12-diaminododecane was added and stirred while removing water azeotroped with toluene at 130 ° C. for 15 hours. DMF was distilled off using a rotary evaporator and recrystallization was performed using tetrahydrofuran to obtain 12.5 g of the desired product. (Comparative Compound 1)
[0188]
Embedded image

[0189]
(Comparative Example 2)
The reaction was carried out under the same conditions as in Example 8, except that the precursor compound 1 used in Example 8 was changed to dodecanol. Each raw material was charged in the same number of moles as in Example 8 to obtain 12.2 g of the desired product. (Comparative Compound 2)
[0190]
Embedded image

[0191]
3. Preparation of photosensitive resin composition
(Examples 12 to 23, Comparative Examples 3 to 6)
Compounds 1 to 12 obtained in Examples 1 to 11, Comparative compounds 1 and 2 obtained in Comparative Examples 1 and 2, and a photo radical generator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals), and Each of benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and trifunctional acrylate (trade name: M305, manufactured by Toagosei Co., Ltd.) with respect to the ethylenic double bond of trifunctional acrylate, photoradical generation site of each compound Were mixed so that the molar ratio (photoradical generation site / ethylenic double bond) would be 1/100, and dissolved in THF, photosensitive resin compositions 1-12 of Examples 12-23 and Comparative Example 3 Comparative compositions 1 to 4 were prepared.
[0192]
(Example 24)
Compound 11 obtained in Example 10 and trifunctional acrylate (trade name: M305, manufactured by Toagosei Co., Ltd.) were mixed in an equal amount on a weight basis and dissolved in THF to prepare a photosensitive resin composition 13.
[0193]
(Examples 25-36, Comparative Examples 7-9)
To the photosensitive resin compositions obtained in Examples 12 to 23 and Comparative Examples 3, 4, and 6, equimolar amounts of triethanolamine as the photoradical generation site were added as hydrogen donors. The photosensitive resin compositions 14-25 and the comparative compositions 5-7 of Comparative Examples 7-9 were produced.
[0194]
(Example 37)
To the photosensitive resin composition 13 obtained in Example 24, a photoradical generation site and an equimolar amount of triethanolamine were added as a hydrogen donor to prepare the photosensitive resin composition 26 of Example 37.
[0195]
4). Evaluation test
(1) Heat resistance evaluation 1
Using a thermogravimetric analyzer (Perkin Elmer TGA7), 10 ° C./min. The thermal decomposition temperatures of Compound 1 and Comparative Compound 1 were measured under the following temperature rise conditions. The measurement results are shown in FIG. From this result, it can be seen that Compound 1 hardly decomposes up to 200 ° C., and the weight loss at 300 ° C. is about 2%, which is very high in thermal stability. On the other hand, Comparative Compound 1 was found to lose weight by about 12% at 200 ° C. and by about 20% at 300 ° C.
[0196]
(2) Heat resistance evaluation 2
Using a differential type differential thermal balance (TG8120 manufactured by Rigaku) at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, compounds 1 to 8, comparative compound 1 and a photo radical generator (trade names: Irgacure 907, manufactured by Ciba Specialty Chemicals) ) Was measured. The measurement results are shown in Table 1. From these results, it can be seen that the compounds 1 to 8 have a higher thermal decomposition point and better heat resistance than maleimide (Comparative Compound 1) and Irg907, which are comparative compounds.
[0197]
[Table 1]

[0198]
(3) UV absorption evaluation
1.0 x 10 for compounds 1-4 and 7^-5A UV absorption spectrum was measured using a mol / L acetonitrile solution. The measurement results are shown in FIGS.
[0199]
[Table 2]

[0200]
From this result, compounds 1 and 7 having no substituent at the aromatic ring site of naphthalimide have a maximum at 330 nm in the solution. From the molar extinction coefficient at that wavelength, π−π^*It is inferred that the excitation is caused by transition.
[0201]
With the molar extinction coefficient, it is possible to estimate which transition state the absorption corresponds to. In general, the larger the molar extinction coefficient, the easier it is to absorb light, i.e., more easily excite, and more easily generate radicals or proceed to the cross-linking reaction. Is good.
[0202]
Moreover, in the compound 4 in which bromine is introduced at the 4-position of the naphthalimide group and the compound 2 in which chlorine is introduced, the maximum wavelength is shifted to a long wavelength by about 10 nm as compared with the unsubstituted compound, and light emission of the high pressure mercury lamp Absorption at a wavelength of 365 nm, which is the wavelength, is increased. Furthermore, it can be seen that Compound 3 in which an isopropyl ether group is introduced as a substituent on the aromatic ring of naphthalimide has an absorption maximum at 365 nm and has a very large absorption at 365 nm, which is the emission wavelength of a high-pressure mercury lamp.
[0203]
The generation of radicals by naphthalimide is thought to be due to hydrogen abstraction. In general, the generation of radicals due to hydrogen abstraction is said to be caused by the triplet excited state of the carbonyl group, and even if the compound is excited, there is a large proportion of the energy used for fluorescence emission and thermal deactivation. It seems that the radical generation efficiency is reduced.
[0204]
When the ratio of the deactivation process other than hydrogen abstraction is small, the greater the absorption at the exposure wavelength, the more easily the photosensitive compound is excited, so the radical generation efficiency is also considered to improve. Compounds 2, 3 and 4 are expected to be more sensitive to 365 nm wavelengths than unsubstituted compounds 1 and 7.
[0205]
Furthermore, from various experiments described later, π-π^*The radical generation efficiency of the naphthalimide moiety is better when the electromagnetic wave with the wavelength at which the excitation of the transition is observed is irradiated or not. Is π−π^*The transition is assumed to be important. Generally π-π^*In many cases, the transition has a molar extinction coefficient of 2000 or more, and if it is a compound having a molar extinction coefficient of this value or more, it is considered that the generation of radicals and the progress of the crosslinking reaction are easy to take into account from the mechanism.
[0206]
(4) Curability evaluation 1
5.9 g of poly-4-methylstyrene synthesized in Production Example 1 and 1.4 g of Compound 1 were dissolved in chloroform, and a coating film was formed on a glass substrate by spin coating.
[0207]
The above-mentioned coating film was irradiated with ultraviolet rays in terms of h rays with a manual exposure device (manufactured by Dainippon Screen Co., Ltd., MA-1200), and then it was confirmed whether the coating film was cured. At that time, two types were examined: one using a filter that transmits light having wavelengths of 333 nm, 365 nm, 405 nm, and 436 nm, and one exposed using the emission wavelength of a high-pressure mercury lamp without using a filter. Curability was judged by the state of the coating film after the exposed coating film was immersed in a chloroform solution for 24 hours.
[0208]
The results are shown in Table 3. The film became insoluble in chloroform at 1000 mJ without the filter and at 5000 mJ with the filter. It is considered that the poly-4-methylstyrene is exposed to light and the compound 1 is cross-linked so that the solubility of the coating film is lowered and cured.
[0209]
In addition, the difference in curability depending on the presence or absence of a filter is that the ultraviolet absorption wavelength region of Compound 1 is 360 nm or less, and therefore the sensitivity with the filter with the light emission of that region being significantly cut is reduced. it is conceivable that.
[0210]
That is, it is suggested that the sensitivity increases as the absorption of the naphthalimide compound overlaps with the exposure wavelength. In addition, since the molar extinction coefficient of the wavelength region cut at this time is 2000 or more, in this region, π−π^*The transition is considered to occur, and π-π^*It is estimated that the transition is greatly involved. On the other hand, n-π having a smaller molar extinction coefficient^*Transitions are also taking place and the absorption is π-π^*It may also be hidden by a large absorption of the transition.
[0211]
The coating film prepared above was exposed to 1000 mJ without a filter through a line / space: 1 mm / 1 mm stripe mask, and then immersed in chloroform, whereby a good stripe pattern of the coating film could be obtained.
[0212]
Similarly, a coating film prepared by mixing 6.0 g of the alkali-soluble polymer polymerized in Production Example 2 and 1.4 g of Compound 1 was also exposed through the mask. Thereafter, the strip was immersed in a 1N NaOH aqueous solution to wash away the unexposed portion, and a good stripe pattern was obtained.
[0213]
[Table 3]

[0214]
(5) Curability evaluation 2
As the polyfunctional monomer, a hydroxyl group-containing pentafunctional acrylate (trade name: Sartomer SR399, manufactured by Nippon Kayaku Co., Ltd.) and hexafunctional acrylate (trade name: M400, manufactured by Toagosei Co., Ltd.) are used. On the other hand, a solution in which the molar ratio was 1/20 was prepared and spin-coated on a glass substrate. For comparison, a coating film in which compound 1 was replaced by comparative compound 1, photoradical generator Irgacure 369 (trade name) (manufactured by Ciba Specialty Chemicals) and benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was also prepared.
[0215]
On the above coating film, 5000 mJ / cm in terms of h-line with a manual exposure device (MA-1200, manufactured by Dainippon Screen Co., Ltd.)²Irradiation was performed, and then it was confirmed whether the coating film was cured. The degree of curing is determined by touching the coating after exposure. ○ When the coating surface is not sticky and is a sufficiently hard film, it remains liquid even after exposure. X.
[0216]
Table 4 shows the evaluation results. Since Compound 1 can cure the polyfunctional acrylate similarly to Comparative Compound 1 and Irgacure 369, it can be seen that naphthalimide functions as a radical generator.
[0217]
[Table 4]

[0218]
(6) Curability evaluation 3
Each of the photosensitive resin compositions 1 to 13 and the comparative compositions 1 to 4 was spin-coated on a chromium-sputtered glass substrate to obtain a coating film.
[0219]
810 cm with an infrared spectrometer while UV exposure is applied to the coating film.^-1The amount of peak decrease was recorded over time, and it was confirmed how much the disappearance of the double bond had progressed. The atmosphere around the sample at the time of measurement was replaced with nitrogen. The UV exposure apparatus used was Ushio Electric's UV spot cure SP-III type (standard reflector type), and the UV lamp used was USH-255BY made by Ushio Electric. Moreover, BIO RAD FT S6000 was used for the infrared spectrometer.
[0220]
Table 5 shows the results of observations regarding the compatibility with the trifunctional acrylate M305, the odor during exposure, the amount of reduction of the double bond (reaction rate) with respect to the exposure amount, and the coloring of the coating film.
[0221]
Since the comparative composition 2 uses the comparative compound 2 having no photoradical generation site, the double bond hardly reacts. The compositions 1-13 use the compound which has a naphthalimide site | part, The thing with which this compound is compatible with M305 which is an acrylic monomer has high reactivity. It is considered that diffusion of radicals generated by the naphthalimide group-containing compound being compatible with M305 proceeds and reacts.
[0222]
Moreover, the comparative composition 1 uses the comparative compound 1 having a maleimide group, and although the comparative compound 1 is compatible with M305, the reaction is not so advanced. The same applies to benzophenone, which is also a hydrogen abstraction type radical generator. Irg907, which is a commercially available photoradical generator, has a high reaction rate and the reaction proceeds well, but since it is a self-cleaving type radical generator, impurities remain in the coating film.
[0223]
In addition, although compound 3 having a large absorption at the exposure wavelength has better compatibility with the trifunctional monomer M305 than other similar compounds having different substituents, the reaction rate is improved compared to the absorption at the exposure wavelength. There wasn't.
[0224]
This is presumed to be due to the fact that Compound 3 emits strong fluorescence. 1.0 × 10^-5Excitation was performed at a maximum absorption wavelength with a mol / L acetonitrile solution, and the fluorescence emission intensity was measured. Compound 3 was absorbed more than 10 times as much as Compound 1 and Compound 2, and absorbed. It was confirmed that most of the energy was emitted to the outside as fluorescence. This seems to indicate that the absorbed light energy is not fully utilized for radical generation. Therefore, in terms of the reaction rate per time, a naphthalimide compound having a low fluorescence emission intensity is preferred.
[0225]
[Table 5]

[0226]
(7) Curability evaluation 4
5.9 g of poly-4-methylstyrene synthesized in Production Example 1 and 1.4 g of Compound 1 were dissolved in chloroform, and a coating film was formed on a glass substrate by spin coating. (Sample A)
The above-mentioned coating film is exposed to UV while being irradiated with an infrared spectrometer (BTS RAD FTS6000) at 1725 cm.^-1The amount of increase in the peak was recorded over time, and it was confirmed how much the crosslinking reaction had progressed.
[0227]
The UV exposure apparatus used was Ushio Electric's UV spot cure SP-III type (standard reflector type), and the UV lamp used was USH-255BY (Ushio Electric).
[0228]
In addition, in order to confirm whether the naphthalimide moiety is a hydrogen abstraction type radical generator, a coating film in which n-dodecanol was further added to the composition of Sample A so as to be equimolar with the naphthalimide moiety was also prepared. Was done. (Sample B)
The measurement results are shown in FIG. From this result, the system in which dodecanol was added to the coating film was about twice as large, and the amount of increase in the peak was large, so that the crosslinking reaction proceeded more quickly when the hydrogen-donating group was contained in the coating film. I understand that. In terms of mechanism, hydrogen attached to carbon is also extracted, but in the case of a thiol, a hydroxyl group, or an amino group, hydrogen is more easily extracted, so that the radical generation efficiency is increased and the sensitivity is considered to be improved.
[0229]
In other words, it is considered that the sensitivity of the naphthalimide group can be enhanced by exposure in the state where a hydrogen donating group coexists.
[0230]
(8) Curability evaluation 5
In order to confirm that the naphthalimide moiety is a hydrogen abstraction type radical generator, each of the photosensitive resin compositions 14 to 26 and the comparative compositions 5 to 7 was used, and the same procedure as in the above-described curability evaluation 3 was performed. The compatibility with acrylate M305, the odor during exposure, the amount of double bond reduction (reaction rate) with respect to the exposure amount, and the coloration of the coating film were observed. The results are shown in Table 6.
[0231]
With the exception of some samples, the reaction rate was improved by the addition of triethanolamine. In particular, an increase in the reaction rate at a low exposure amount is observed. In other words, it is considered that the sensitivity of the naphthalimide group can be enhanced by exposure in the state where a hydrogen donating group coexists.
[0232]
[Table 6]

[0233]
(9) Solubility in monomer components
When photo-curing a (meth) acryloyl polyfunctional monomer with naphthalimide, the structure of the naphthalimide moiety is the same and the spacer moiety is different to confirm the relationship between the solubility in the matrix and the reaction rate. For compounds 1 and 7, the saturation concentration at 20 ° C. was determined for trifunctional monomer M305 (manufactured by Toagosei Co., Ltd .: trade name) which is a matrix when the above-described sclerosis evaluation was performed. Furthermore, in order to generalize the evaluation of solubility, the saturation concentration at 20 ° C. with respect to methyl acrylate was also determined. The results are shown in Table 7.
[0234]
[Table 7]

[0235]
From this result, it can be seen that a sample having better solubility has a better reaction rate. In other words, when the naphthalimide moiety has the same structure, the solubility in the matrix changes depending on the structure of the side chain extending from the nitrogen atom of the imide bond, and by improving this solubility, a high reaction rate can be achieved even at low exposure. It seems to be obtained.
[0236]
(10) Outgas evaluation
The above photosensitive compositions 1, 2, 3, 7 and comparative composition 3 were spin-coated on a glass substrate and heated on a hot plate at 50 ° C. for 1 minute, and then a manual exposure apparatus (manufactured by Dainippon Screen Co., Ltd., MA-1200), 2000mJ / cm in h-line conversion with a high-pressure mercury lamp²Then, a coating film having a thickness of 25 μm was obtained.
[0237]
The glass substrate on which the coating film was formed was cut into a size of 1 cm × 1.5 cm, and the gas generated during heating at 250 ° C. for 1 hour was analyzed using GC-MS (QP-5000 manufactured by Shimadzu Corporation). analyzed.
[0238]
Other measurement conditions are as follows.
[0239]

As a result, degradation products derived from the polyfunctional monomer M305 were detected in all samples. Furthermore, several types of aromatic compounds that were considered to be decomposed products derived from other photoradical generators were detected only in the coating film using Comparative Composition 3.
[0240]
From the above, it has been clarified that the naphthalimide compound of the present invention does not generate a decomposition product derived from an initiator as a gas by heating.
[0241]
【The invention's effect】
In the radical generator according to the present invention, the naphthalimide structure-containing group functions as a hydrogen abstraction type radical generation site, and can cause a radical reaction by being excited by irradiation with light. The naphthalimide structure-containing group is a hydrogen abstraction type that is more stable than the self-cleavage type and has a naphthalene skeleton with good heat resistance, so that a photoradical generator having high heat resistance, stability, and storage stability is obtained. be able to.
[0242]
In addition, the radical generator according to the present invention can react not only with ethylenically unsaturated bonds but also with various compounds such as aromatic rings, and even a resin composition having no ethylenically unsaturated bonds may be a polymer. Can be crosslinked or radically reacted. Therefore, the photoradical generator according to the present invention is used as a general photoradical polymerization initiator, and for example, as a crosslinking agent for a resin composition containing an aromatic polymer, to improve the solvent resistance after curing. It is possible.
[0243]
In addition, since the radical generator according to the present invention has two or more naphthalimide structure-containing groups that function as radical generating sites in one molecule, the radical generated in one of them binds to a reactant such as a polymer. By doing so, it becomes part of the chemical structure of the reactant such as a polymer. Since the radical generator becomes part of the chemical structure of the reactant such as a polymer, even if the radical generator remains unreacted, it does not remain in a free form in the reactant such as a polymer. Moreover, even if the radical generation site remains unreacted, it is a hydrogen abstraction type and has a highly heat-resistant naphthalimide structure, so that a volatile decomposition product is generated in the cured coating film. There is nothing. Therefore, the radical generator does not volatilize during post-baking and does not remain independently in the coating film as in the past. As a result, problems such as work safety problems, deterioration of light resistance, coloring and fading, peeling of coatings and cracks, deterioration of reliability of the final product, problems of shortening chemical life, and odor Can solve all the problems that occur.
[0244]
Furthermore, the reaction that forms the maleimide structure is not formed unless the dehydration condensation reaction is promoted by heating, a catalyst, or the like. Therefore, there are various problems in the synthesis, but the reaction that forms the naphthalimide structure is similar to that of maleimide. Compared with imides having a five-membered ring structure, the dehydration condensation reaction proceeds more rapidly, the synthesis is very simple, and the solvent solubility is good, which is advantageous for synthesis. Therefore, productivity is improved including yield, reaction rate, management and cost.
[0245]
In the photosensitive resin composition according to the present invention, the naphthalimide structure-containing group of the photoradical polymerization initiator composed of the compound (a) functions as a hydrogen abstraction type radical generation site, and is excited by irradiation with light. Radicalization causes a radical reaction in the resin composition. The radical generated by the naphthalimide structure-containing group can react not only with ethylenically unsaturated bonds but also with various compounds such as aromatic rings, so even a resin composition having no ethylenically unsaturated bonds Can be cross-linked or undergo a radical reaction, causing a change in curing and / or solubility. Further, a radical generated at any one of two or more naphthalimide structure-containing groups is bonded to the resin composition to become a part of the chemical structure of the resin composition. Therefore, the radical generator and its decomposition product do not remain in the resin composition in a free form. As a result, the problem of reducing the reliability of the final product is solved.
[0246]
The photosensitive resin composition according to the present invention is obtained by using a pattern forming material (resist), paint or printing ink, or a color filter, an electronic component, an interlayer insulating film, a wiring coating film, an optical member, an optical circuit, an optical circuit component, When used as a material for forming an antireflection film, hologram, or building material, there is an effect that the product or film has high heat resistance and high stability. In addition, since no odor is generated during exposure, the working environment is improved.
[0247]
The printed matter, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film, hologram, or building material according to the present invention has high heat resistance and high stability. Since at least a part of the cured resin composition is formed, the product or film has high heat resistance and high stability, and therefore has a merit of high production yield.
[Brief description of the drawings]
FIG. 1 is a graph showing measurement results of thermal decomposition temperature.
FIG. 2 is a graph showing measurement results of UV absorption spectra (Compounds 1, 4, and 7).
FIG. 3 is a graph showing measurement results of UV absorption spectra (Compounds 1, 2, 3, 4).
FIG. 4 1725 cm during UV irradiation^-1It is a graph which shows the increase amount of a peak.

Claims (34)

The following formula (2) per molecule

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a substituent, and may be a ring structure bonded to each other. Chemical structure X is n-valent linear and / or branched and / or cyclic organic group selected from saturated, unsaturated polyvalent alkyl group, aryl group and allyl group, and a single bond or ester bond in the inside thereof An ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, a thiocarbamate bond, a carbodiimide bond, and a carbonate bond, and n is an integer of 2 or more.) The radical generator which consists of a compound (a) which has two or more naphthalimide structure containing groups represented by these. In the formula (2) , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an amino group, a cyano group, a silyl group, or a silanol. The radical according to claim 1, which is a group, an alkoxy group, a nitro group, a carboxyl group, an acetyl group, an acetoxy group, a sulfone group, an organic group which may have a substituent, or a ring structure in which they are bonded to each other. Generating agent.   The radical generator according to claim 1 or 2, wherein the molar extinction coefficient of the compound (a) at an emission wavelength of any of the exposure light sources is 0.1 or more. The radical generator according to any one of claims 1 to 3, wherein the compound (a) has a maximum molar extinction coefficient ε _MAX of 2000 or more.   The radical generator according to any one of claims 1 to 4, wherein the compound (a) has absorption at a wavelength of at least 157 nm, 193 nm, 248 nm, 365 nm, 405 nm, and 436 nm.   The radical generator according to any one of claims 1 to 5, wherein a 90% thermal decomposition temperature of the compound (a) is 50 ° C or higher.   The radical generator according to any one of claims 1 to 6, wherein a saturation concentration of the compound (a) with respect to methyl acrylate at 20 ° C is 0.01 mol / L or more. The following formula (2) per molecule

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a substituent, and may be a ring structure bonded to each other. Chemical structure X is n-valent linear and / or branched and / or cyclic organic group selected from saturated, unsaturated polyvalent alkyl group, aryl group and allyl group, and a single bond or ester bond in the inside thereof An ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, a thiocarbamate bond, a carbodiimide bond, and a carbonate bond, and n is an integer of 2 or more.) A compound (a) having two or more naphthalimide structure-containing groups represented by: at least one curing reactive compound selected from a compound having an ethylenically unsaturated bond and an aromatic compound; A photosensitive resin composition, which is contained as an essential component . The photosensitive resin composition of Claim 8 which further contains a hydrogen donor. The photosensitive resin composition of Claim 8 or 9 which contains the said compound (a) in the ratio of 0.1 weight% or more of the whole solid content of the photosensitive resin composition. Components other than the compound (a) contained in the photosensitive resin composition have a transmittance of 20% or more in a wavelength region where the emission wavelength of the irradiation light source and the absorption wavelength of the compound (a) overlap. The photosensitive resin composition according to any one of claims 8 to 10 . The photosensitive resin composition according to claim 8 , which is used as a pattern forming material. The photosensitive resin composition in any one of Claims 8 thru | or 12 used as a coating material.   The photosensitive resin composition in any one of Claims 8 thru | or 12 used as printing ink.   The photosensitive resin composition according to claim 8, which is used as a color filter forming material.   The photosensitive resin composition in any one of Claims 8 thru | or 12 used as a formation material of an electronic component.   The photosensitive resin composition according to claim 8, which is used as a material for forming an interlayer insulating film.   The photosensitive resin composition according to claim 8, which is used as a material for forming a wiring coating film.   The photosensitive resin composition according to claim 8, which is used as a material for forming an optical member.   The photosensitive resin composition according to any one of claims 8 to 12, which is used as a material for forming an optical circuit or an optical circuit component.   The photosensitive resin composition according to claim 8, which is used as a material for forming an antireflection film.   The photosensitive resin composition according to claim 8, which is used as a hologram forming material.   The photosensitive resin composition in any one of Claims 8 thru | or 12 used as a forming material of a building material.   A printed material, at least part of which is formed of a cured product of the photosensitive resin composition according to any one of claims 8 to 12.   A color filter, at least part of which is formed of a cured product of the photosensitive resin composition according to claim 8.   An electronic component, at least part of which is formed of a cured product of the photosensitive resin composition according to any one of claims 8 to 12.   An interlayer insulating film, at least part of which is formed of a cured product of the photosensitive resin composition according to any one of claims 8 to 12.   A wiring coating film, at least part of which is formed of a cured product of the photosensitive resin composition according to any one of claims 8 to 12.   An optical member, at least part of which is formed of a cured product of the photosensitive resin composition according to claim 8.   An optical circuit, at least part of which is formed of a cured product of the photosensitive resin composition according to claim 8.   An optical circuit component, at least part of which is formed of a cured product of the photosensitive resin composition according to any one of claims 8 to 12.   An antireflection film, at least part of which is formed of a cured product of the photosensitive resin composition according to any one of claims 8 to 12.   A hologram, at least part of which is formed of a cured product of the photosensitive resin composition according to claim 8.   A building material, at least part of which is formed of a cured product of the photosensitive resin composition according to any one of claims 8 to 12.

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