JP4651800B2 - Negative photosensitive thermosetting transfer material for interlayer insulating film, method for forming interlayer insulating film, high aperture type liquid crystal display device and manufacturing method thereof - Google Patents

Description

【００７１】
一般式（II）中、Ｒ²及びＲ³は、それぞれ独立に、置換基若しくは不飽和結合を有していてもよい炭化水素基、或いはヘテロ環基を表し、互いに同一であっても異なっていてもよい。Ｒ⁴及びＲ⁵は、それぞれ独立に水素原子、置換基若しくは不飽和結合を有していてもよい炭化水素基、ヘテロ環基、ヒドロキシル基、置換オキシ基、メルカプト基、置換チオ基を表し、互いに同一であっても異なっていてもよい。また、Ｒ⁴及びＲ⁵は相互に結合して環を形成してもよく、結合したＲ⁴及びＲ⁵は、環の連結主鎖として−Ｏ−、−ＮＲ⁶−、−Ｏ−ＣＯ−、−ＮＨ−ＣＯ−、−Ｓ−、及び／又は、−ＳＯ₂−を含んでいてもよい炭素数２〜８のアルキレン基を表す。Ｒ⁶及びＲ⁷は、それぞれ独立に水素原子、置換基若しくは不飽和結合を有していてもよい炭化水素基、或いは置換カルボニル基を表す。
【００７２】
前記一般式（II）で表される化合物としては、例えば、ｐ−メトキシフェニル２−Ｎ，Ｎ−ジメチルアミノプロピルケトンオキシム−Ｏ−アリルエーテル、ｐ−メチルチオフェニル２−モルフォリノプロピルケトンオキシム−Ｏ−アリルエーテル、ｐ−メチルチオフェニル２−モルフォリノプロピルケトンオキシム−Ｏ−ベンジルエーテル、ｐ−メチルチオフェニル２−モルフォリノプロピルケトンオキシム−Ｏ−ｎ−ブチルエーテル、ｐ−モルフォリノフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−アリルエーテル、ｐ−メトキシフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−ｎ−ドデシルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−メトキシエトキシエチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−ｐ−メトキシカルボニルベンジルエーテル、
【００７３】
ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−メトキシカルボニルメチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−エトキシカルボニルメチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−４−ブトキシカルボニルブチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−２−エトキシカルボニルエチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−メトキシカルボニル−３−プロペニルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−ベンジルオキシカルボニルメチルエーテル等が挙げられる。但し、本発明においては、これらに限定されるものではない。
【００７４】
前記ヘキサアリールビイミダゾールとしては、例えば、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ，ｐ−ジクロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｍ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ，ｏ’−ジクロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−ニトロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−メチルフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（ｏ−トリフルオロメチルフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール等が挙げられる。
上記ヘキサアリールビイミダゾールは、例えば、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，３３，５６５（１９６０）及びＪ．Ｏｒｇ．Ｃｈｅｍ，３６（１６）２２６２（１９７１）に記載の方法により容易に合成することができる。
【００７５】
前記ケトオキシムエーテルとしては、例えば、３−ベンゾイロキシイミノブタン−２−オン、３−アセトキシイミノブタン−２−オン、３−プロピオニルオキシイミノブタン−２−オン、２−アセトキシイミノペンタン−３−オン、２−アセトキシイミノ−１−フェニルプロパン−１−オン、２−ベンゾイロキシイミノ−１−フェニルプロパン−１−オン、３−ｐ−トルエンスルホニルオキシイミノブタン−２−オン、２−エトキシカルボニルオキシイミノ−１−フェニルプロパン−１−オン等が挙げられる。
【００７６】
前記重合開始剤は、一種単独で用いてもよいし、同一種中の複数、又は異種間の複数を併用してもよい。
前記重合開始剤の含有量としては、ネガ型感光性熱硬化性樹脂組成物の全固形分（質量）の０．１〜５０質量％が好ましく、０．５〜３０質量％がより好ましい。
【００７７】
（Ｃ）カルボキシル基含有アルカリ可溶性樹脂
前記カルボキシル基含有アルカリ可溶性樹脂（以下、単に「アルカリ可溶性樹脂」ということがある。）は、カルボキシル基含有モノマーとカルボキシル基非含有モノマーとの共重合体、セルロース類、ＰＶＡ等、水酸基含有樹脂の高分子反応により得られ、弱アルカリ水溶液に可溶な樹脂である。
【００７８】
前記弱アルカリ水溶液に可溶なアルカリ可溶性樹脂としては、例えば、アルカリ可溶性光重合性樹脂に用いられる、公知の高分子結合剤が挙げられ、具体的には、（メタ）アクリル酸と（メタ）アクリル酸アルキルエステル（アルキル基としては、メチル基、エチル基、ブチル基等）との共重合物、ポリ（メタ）アクリル酸、スチレンと無水マレイン酸等の不飽和二塩基酸無水物との共重合物、及び該共重合物とアルコール類、若しくはセルロースの多塩基酸無水物との反応物等が挙げられる。
【００７９】
上記のうち、本発明においては、スチレン／無水マレイン酸共重合体、特開昭６０−２５８５３９号公報に記載のメタクリル酸メチル／メタクリル酸／メタクリル酸２−エチルヘキシル／メタクリル酸ベンジル四元共重合体、特公昭５５−３８９６１号公報に記載のスチレン／マレイン酸モノ−ｎ−ブチルエステル共重合体、特公昭５４−２５９５７号公報に記載のスチレン／メタクリル酸メチル／アクリル酸エチル／メタクリル酸の四元共重合体、特開昭５２−９９８１０号公報に記載のメタクリル酸ベンジル／メタクリル酸共重合体、特公昭５８−１２５７７号公報に記載のアクリロニトリル／メタクリル酸２−エチルヘキシル／メタクリル酸の三元共重合体、特公昭５５−６２１０号公報に記載のメタクリル酸メチル／アクリル酸エチル／アクリル酸の三元共重合体とイソプロパノールで一部分エステル化したスチレン／無水マレイン酸共重合体の２種、等が好適に挙げられる。
【００８０】
前記アルカリ可溶性樹脂は、通常、５０〜３００ｍｇＫＯＨ／１ｇの酸価と、１０００〜３０００００の重量平均分子量を有するものが選択される。
前記酸価が、５０ｍｇＫＯＨ／１ｇ未満であると、アルカリ現像性が大きく低下することがあり、３００ｍｇＫＯＨ／１ｇを超えると、高濃度の遮光性画像が得られ難くなることがある。
また、前記アルカリ可溶性樹脂の重量平均分子量としては、１００００〜２５００００が特に好ましい。前記重量平均分子量が、１０００未満であると、高濃度の遮光性画像の形成が困難となることがあり、３０００００を超えると、現像性が極端に低下することがある。
【００８１】
前記カルボキシル基含有アルカリ可溶性樹脂は、一種単独で用いてもよいし、二種以上を組合わせて併用してもよい。
前記カルボキシル基含有アルカリ可溶性樹脂の含有量としては、ネガ型感光性熱硬化性樹脂組成物の全固形分（質量）の１０〜８０質量％が好ましく、２０〜６０質量％がより好ましい。
また、コンタクトホール形状をすり鉢型に保つ観点からは、前記成分(Ａ)と成分(Ｃ)の質量比（Ａ／Ｃ）としては、０．５〜０．９が好ましい。
【００８２】
（Ｄ）光及び／又は熱により非揮発性酸を発生する化合物
前記光及び／又は熱により非揮発性酸を発生する化合物（以下、「酸発生化合物」ということがある。）は、露光及び加熱の少なくとも一方を付与することにより、酸を発生する化合物であり、該酸発生化合物としては、(1)下記一般式（III）で表されるヨードニウム塩、(2)下記一般式（IV）で表されるスルホニウム塩、(3)後述の一般式（Ｖ）で表されるジスルホン誘導体、(4)後述の一般式（VI）で表されるイミノスルホネート誘導体、(5)後述の一般式（VII）で表されるｏ−ニトロベンジル型光酸発生剤が好適に挙げられる。
【００８３】
まず、(1)下記一般式（III）で表されるヨードニウム塩、及び(2)一般式（IV）で表されるスルホニウム塩について説明する。
【化２】

【００８４】
一般式（III）中、Ａｒ¹及びＡｒ²は、それぞれ独立に置換若しくは未置換のアリール基を表す。置換された置換アリール基の置換基としては、例えば、アルキル基、ハロアルキル基、シクロアルキル基、アリール基、アルコキシ基、ニトロ基、カルボキシル基、アルコキシカルボニル基、ヒロドキシ基、メルカプト基、ハロゲン原子等が挙げられる。
【００８５】
一般式（IV）中のＲ²⁰³、Ｒ²⁰⁴、Ｒ²⁰⁵は、それぞれ独立に置換若しくは未置換のアルキル基、アリール基を表す。前記アルキル基、アリール基としては、それぞれ炭素数１〜８のアルキル基、炭素数６〜１４のアリール基、及びこれらの置換誘導体が好ましい。
また、置換された置換アルキル基の置換基としては、例えば、炭素数１〜８のアルコキシ基、カルボキシル基、アルコシキカルボニル基が挙げられ、置換された置換アリール基の置換基としては、例えば、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキル基、ニトロ基、カルボキシル基、ヒロドキシ基、ハロゲン原子等が挙げられる。
【００８６】
一般式（III）及び（IV）中のＺ^-は対アニオンを表し、例えば、ＢＦ₄ ^-、ＡｓＦ₆ ^-、ＰＦ₆ ^-、ＳｂＦ₆ ^-、ＳｉＦ₆ ^2-、ＣｌＯ₄ ^-、ＣＦ₃ＳＯ₃ ^-等のパーフルオロアルカンスルホン酸アニオン、ペンタフルオロベンゼンスルホン酸アニオン、ナフタレン−１−スルホン酸アニオン等の縮合多核芳香族スルホン酸アニオン、アントラキノンスルホン酸 アニオン、スルホン酸基含有染料等を挙げることができる。但し、これらに限定されるものではない。
また、Ｒ²⁰³、Ｒ²⁰⁴、Ｒ²⁰⁵のうちの２つ、及びＡｒ¹及びＡｒ²は、それぞれ単結合又は置換基を介して結合されていてもよい。
【００８７】
前記一般式（III）又は（IV）で表される化合物の具体例を以下に示す。但し、本発明においてはこれらに限定されるものではない。
例えば、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアルセネート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムトリフルオロメタンスルホネート、フェニル（ｐ−メトキシフェニル）ヨードニウムヘキサフルオロホスフェート、フェニル（ｐ−メトキシフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ｍ−ニトロフェニル）ヨードニウムヘキサフルオロホスフェート、フェニル（ｐ−ニトロフェニル）ヨードニウムトリフルオロメタンスルフォネート、ビス（ｐ−トリル）ヨードニウムヘキサフルオロアルセネート、ビス（ｍ，ｐ−ジメチルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ｐ−ｎ−ヘプチルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ｐ−クロロフェニル）ヨードニウムヘキサフルオロフォスフェート、ビス（ｐ−トリフルオロメチルフェニル）ヨードニウムトリフルオロメタンスルホネート、
【００８８】
ビス（ｍ−メトキシカルボニルフェニル）ヨードニウムヘキサフルオロフォスフェート、ビス（ｏ，ｐ−ジクロロフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウムヘキサフルオロホスフェート、ジベンズヨードニウムヘキサフルオロホスフェート、１−クロロ−ジベンズヨードニウムトリフルオロメタンスルホネート、ビス（１−ナフチル）ヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウム９，１０−ジメトキシアントラセン−２−スルホネート、ビス（ｐ−ｔｅｒｔ−ペンチルフェニル）ヨードニウム９，１０−ジメトキシアントラセン−２−スルホネート、ジフェニルヨードニウム４−エトキシナフタレン−１−スルホネート、ジフェニルヨードニウム１−アニリノナフタレン−７−スルホネート、ビス（ｐ−ｎ−ペンチルフェニル）ヨードニウムピレン−２−スルホネート、ビス（ｐ−クロロフェニル）ヨードニウムアントラキノン−２−スルホネート、ジフェニルヨードニウム３−メトキシベンゾフェノン−２−スルホネート、
【００８９】
トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアルセネート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムパーフルオロオクタンスルホネート、トリフェニルスルホニウムペンタフルオロベンゼンスルホネート、ビス（ｐ−エトキシフェニル）−ｐ−トリルスルホニウムトリフルオロメタンスルホネート、ビス（ｐ−クロロフェニル）−ｐ−メトキシフェニルスルホニウムトリフルオロメタンスルホネート、ｐ−ヒドロキシフェニル−ジメチルスルホニウムヘキサフルオロホスフェート、３，５−ジメチル−４−ヒドロキシフェニルジメチルスルホニウムヘキサフルオロアンチモネート、ｐ−ヒドロキシフェニルテトラヒドロチオフェニウムテトラフルオロボレート、３，５−ジメトキシ−４−ヒドロキシフェニルテトラヒドロチオフェニウムトリフルオロメタンスルホネート、３，５−ジ（ｎ−ブチル）−４−ヒドロキシフェニルテトラヒドロチオフェニウムヘキサフルオロホスフェート、
【００９０】
４−ヒドロキシ−２−メチルフェニルヘキサヒドロチオピリジウムテトラフルオロボレート、３，５−ジメチル−４−ヒドロキシフェニル−１，４−オキサチアニウムトリフルオロメタンスルホネート、フェニルジベンゾチオフェニウムヘキサフルオロアルセネート、フェニルジベンゾチオフェニウムパーフルオロオクタンスルフォネート、フェナシルジメチルスルホニウムヘキサフルオロアンチモネート、フェナシルテトラヒドロチオフェニウムヘキサフルオロフォスフェート、フェナシルテトラヒドロチオフェニウムヘキサフルオロアルセネート、ｍ−クロロフェナシルテトラヒドロチオフェニウムヘキサフルオロアルセネート、フェナシルヘキサヒドロチオピリジウムヘキサフルオロホスフェート、２−ナフトイルメチルテトラヒドロチオフェニウムヘキサフルオロアルセネート、フェナシルジ（ｎ−ブチル）スルホニウムヘキサフルオロフォスフェート、ジフェニル（４−フェニルチオフェニル）スルホニウムオクタンスルホネート、ジフェニル（４−フェニルチオフェニル）スルホニウムヘキサフルオロアンチモネート、
【００９１】
１，４−チオビスフェニレン−ビス−ジフェニルスルホニウムトリフルオロメタンスルホネート、１，４−チオビスフェニレン−ビス−ジフェニルスルホニウムヘキサフルオロアルセネート、トリフェニルスルフォニウム−９，１０−ジメトキシアントラセン−２−スルホネート、ビス（ｐ−エトキシフェニル）−ｐ−トリルスルフォニウムペンタフルオロベンゼンスルホネート、クロロメチルメチルフェニルスルホニウムアントラセン−１−スルホネート、フェナシルテトラヒドロチオフェニウムペンタフルオロスルホネート、トリフェニルスルホニウム−１−アニリノナフタレン−７−スルホネート等である。
【００９２】
前記一般式（III）及び（IV）で表されるオニウム塩は公知であり、例えば、Ｊ．Ｗ．Ｋｎａｐｃｚｙｋｅｔａｌ，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，９１，１４５（１９６９）、Ａ．Ｌ．Ｍａｙｃｏｋｅｔａｌ，Ｊ．Ｏｒｇ．Ｃｈｅｍ．，３５，２５３２，（１９７０）、Ｅ．Ｇｏｅｔｈａｓｅｔａｌ，Ｂｕｌｌ．Ｓｏｃ．Ｃｈｅｍ．Ｂｅｌｇ．，７３，５４６，（１９６４）、Ｈ．Ｍ．Ｌｅｉｃｅｓｔｅｒ、Ｊ．Ａｍｅ．Ｃｈｅｍ．Ｓｏｃ．，５１，３５８７（１９２９）、Ｊ．Ｖ．Ｃｒｉｖｅｌｌｏｅｔａｌ，Ｊ．Ｐｏｌｙｍ．Ｃｈｅｍ．Ｅｄ．，１８，２６７７（１９８０）、米国特許第２，８０７，６４８号、同４，２４７，４７３号、特開昭５３−１０１，３３１号公報等に記載の方法により合成することができる。
【００９３】
次に、(3)下記一般式（Ｖ）で表されるジスルホン誘導体、及び(4)下記一般式（VI）で表されるイミノスルホネート誘導体について説明する。
【化３】

【００９４】
前記一般式（Ｖ）中、Ａｒ³及びＡｒ⁴は、それぞれ独立に置換若しくは未置換のアリール基を表す。前記一般式（VI）中のＲ²⁰⁶は、置換若しくは未置換のアルキル基、アリール基を表し、Ａは、置換若しくは未置換のアルキレン基、アルケニレン基、アリーレン基を表す。
【００９５】
前記一般式（Ｖ）又は（VI）で表される化合物の具体例を以下に示す。但し、本発明においては、これらに限定されるものではない。
例えば、ビス（ｐ−クロロフェニル）ジスルホン、ビス（ｐ−トリル）ジスルホン、ビス（ｐ−メトキシフェニル）ジスルホン、ｐ−トリル（ｐ−クロロフェニル）ジスルホン、ビス（ｐ−トリクロロメチルフェニル）ジスルホン、１−ナフチル（ｏ−クロロフェニル）ジスルホン、４−エトキシ−１−ナフチル（ｐ−クロロフェニル）ジスルホン、２−ナフチル（ｐ−クロロフェニル）ジスルホン、２−ナフチル（ｐ−トリル）ジスルホン、６−クロロ−２−ナフチル（ｐ−メトキシフェニル）ジスルホン、６−クロロ−フェニル（４−メトキシ−１−ナフチル）ジスルホン、フェニル（ｐ−イソプロピルフェニル）ジスルホン、ビス（ペンタフルオロフェニル）ジスルホン、Ｎ−ベンゼンスルホニルオキシフタルイミド、Ｎ−ｐ−トルエンスルホニルオキシフタルイミド、
【００９６】
Ｎ−ｐ−メトキシベンゼンスルホニルオキシフタルイミド、Ｎ−ｐ−トリフルオロメチルベンゼンスルホニルオキシフタルイミド、Ｎ−ナフタレン−１−スルホニルオキシフタルイミド、Ｎ−４−メトキシナフタレン−１−スルホニルオキシフタルイミド、Ｎ−エタンスルホニルオキシマレイミド、Ｎ−ベンゼンスルホニルオキシマレイミド、Ｎ−ベンゼンスルホニルオキシアルファフェニルマレイミド、Ｎ−エタンスルホニルオキシナフタルイミド、Ｎ−ヘキサデカンスルホニルオキシナフタルイミド、Ｎ−ベンゼンスルホニルオキシナフタルイミド、Ｎ−トリフルオロメタンスルホニルオキシナフタルイミド、Ｎ−ペンタフルオロベンゼンスルホニルオキシナフタルイミド、Ｎ−テトラフルオロベンゼンスルホニルオキシフタルイミド、等である。
【００９７】
次に、(5)下記一般式（VII）で表されるｏ−ニトロベンジル型光酸発生剤について説明する。
【化４】

【００９８】
前記一般式（VII）中、Ｒ²⁰⁷、Ｒ²⁰⁸、Ｒ²⁰⁹及びＲ²¹⁰は、それぞれ独立に水素原子、炭素数１〜６のアルキル基、炭素数５〜１４のアリール基、炭素数６〜２０のアラルキル基、炭素数３〜６のシクロアルキル基、炭素数１〜６のパーフルオロアルキル基、炭素数５〜１４のパーフルオロアリール基、ニトロ基、シアノ基を表し、互いに同一であっても異なっていてもよい。
Ｒ²¹¹は、水素原子、炭素数１〜６のアルキル基、炭素数５〜１４のアリール基を表し、Ｙは、−ＳＯ₂−Ｒ²¹²を表す。ここで、Ｒ²¹²は、炭素数１〜６のアルキル基；炭素数５〜１４のアリール基；炭素数１〜６のアルコキシ基を有する炭素数５〜１４のアリール基；炭素数６〜２０のアラルキル基；炭素数３〜６のシクロアルキル基；炭素数１〜６のパーフルオロアルキル基；水素原子の代えて炭素数１〜６のパーフルオロアルキル基又はフッ素原子を置換基とする炭素数５〜１４のアリール基；を表す。
【００９９】
前記一般式（VII）で表される化合物の具体例を以下に示す。但し、本発明においては、これらに限定されるものではない。
例えば、２，６−ジニトロベンジルベンゼンスルホネート、２，６−ジニトロベンジルｐ−メトキシベンゼンスルホネート、２，６−ジニトロベンジルパーフルオロベンゼンスルホネート、２，６−ジニトロベンジルｐ−トリフルオロメチルベンゼンスルホネート、２，６−ジニトロベンジルｐ−トルエンスルホネート、２，６−ジニトロベンジルメタンスルホネート、２，６−ジニトロベンジルトリフルオロメタンスルホネート、２，６−ジニトロベンジルナフタレン−２−スルホネート、２，６−ジニトロ−α−メチルベンジルｐ−メトキシベンゼンスルホネート、２，６−ジニトロ−α−メチルベンジルパーフルオロベンゼンスルホネート、２，６−ジニトロ−α−メチルベンジルメタンスルホネート、２−ニトロ−６−トリフルオロメチルベンジルベンゼンスルホネート、２−ニトロ−６−トリフルオロメチルベンジルｐ−メトキシベンゼンスルホネート、
【０１００】
２−ニトロ−６−トリフルオロメチルベンジルパーフルオロベンゼンスルホネート、２−ニトロ−６−トリフルオロメチルベンジルｐ−トリフルオロメチルベンゼンスルホネート、２−ニトロ−６−トリフルオロメチルベンジルｐ−トルエンスルホネート、２−ニトロ−６−トリフルオロメチルベンジルメタンスルホネート、２−ニトロ−６−トリフルオロメチルベンジルトリフルオロメタンスルホネート、２−ニトロ−６−トリフルオロメチルベンジルナフタレン−２−スルホネート、２−ニトロ−６−トリフルオロメチル−α−メチルベンジルｐ−メトキシベンゼンスルホネート、２−ニトロ−６−トリフルオロメチル−α−メチルベンジルパーフルオロベンゼンスルホネート、
【０１０１】
２−ニトロ−６−トリフルオロメチル−α−メチルベンジルメタンスルホネート、２−ニトロ−６−シアノベンジルベンゼンスルホネート、２−ニトロ−６−シアノベンジルｐ−メトキシベンゼンスルホネート、２−ニトロ−６−シアノベンジルパーフルオロベンゼンスルホネート、２−ニトロ−６−シアノベンジルｐ−トリフルオロメチルベンゼンスルホネート、２−ニトロ−６−シアノベンジルｐ−トルエンスルホネート、２−ニトロ−６−シアノベンジルメタンスルホネート、２−ニトロ−６−シアノベンジルトリフルオロメタンスルホネート、２−ニトロ−６−シアノベンジルナフタレン−２−スルホネート、２−ニトロ−６−シアノ−α−メチルベンジルｐ−メトキシベンゼンスルホネート、２−ニトロ−６−シアノ−α−メチルベンジルパーフルオロベンゼンスルホネート、２−ニトロ−６−シアノ−α−メチルベンジルメタンスルホネート、等である。
【０１０２】
本発明においては、上記の光及び／又は熱により非揮発性酸を発生する化合物の中でも、オニウム塩、ジスルホン、ｏ−ニトロベンジル型酸発生剤が好ましい。
【０１０３】
前記光及び／又は熱により非揮発性酸を発生する化合物は、一種単独で用いてもよいし、二種以上を組合わせて併用してもよい。
前記光及び／又は熱により非揮発性酸を発生する化合物の含有量としては、ネガ型感光性熱硬化性樹脂組成物の全固形分（質量）の０．１〜１０質量％が好ましく、０．５〜５質量％がより好ましい。
【０１０４】
（Ｅ）酸で架橋可能な架橋剤
前記酸で架橋可能な架橋剤（以下、単に「架橋剤」ということがある。）、は、適当な酸により架橋可能な架橋剤であり、例えば、部分的又は完全にエーテル化されたポリヒドロキシメチルメラミン（例えば、ヘキサメトキシメチルメラミン等）、下記一般式（VIII）で表される化合物等が挙げられる。
【０１０５】
【化５】

【０１０６】
前記一般式（VIII）中、Ｚは、Ｏ、Ｓ、炭素数１〜８のアルキレン基を表し、例えば、ＣＨ₂、Ｃ(ＣＨ₃)₂、ＳＯ₂等が挙げられる。Ｒは、水素原子、低級アルキル基、アシル基を表す。ｎは１又は２を表す。
【０１０７】
本発明においては、有機カルボキサミドのＮ−メチロール化合物、フェノールのｏ−メチロール化合物、フェノールエーテルのｏ−メチロール化合物、芳香族炭化水素のｏ−メチロール化合物等が好適である。
以下、具体例を示すが、本発明においてはこれらに限定されるものではない。
【０１０８】
前記有機カルボキサミドのＮ−メチロール化合物としては、例えば、Ｎ，Ｎ'−ジメチロール尿素、Ｎ，Ｎ'−ジメチロールオキサミド、Ｎ，Ｎ'−ジメチロールマロンアミド、Ｎ，Ｎ'−ジメチロールスクシンアミド、Ｎ，Ｎ'−ジメチロールセバクアミド、Ｎ，Ｎ'，Ｎ"−トリメチロールシトラミド、１，３−ジメチロールイミダゾリジン−２−オン、１，３−ジメチロール−４，５−ジヒドロキシイミダゾリジン−２−オン、１，３−ジメチロールペルヒドロピリミジン−２−オン、トリメチロールメラミン、テトラメチロールメラミン、ヘキサメチロールメラミン、１，３−ジメチロール−５−メチルペルヒドロ−１，３，５−トリアジン−２−オン、１，３−ジメチロール−５−アリルペルヒドロ−１，３，５−トリアジン−２−オン、１，３−ジメチロール−５−ブチルペルヒドロ−１，３，５−トリアジン−２−オン、１，２−ビス−［１，３−ジメチロールペルヒドロ−１，３，５−トリアジン−２−オン−５−イル］エタン、テトラメチロールヒドラジンジカルボキサミド、Ｎ，Ｎ'‐ジメチロールテレフタルアミド、Ｎ，Ｎ'‐ジメチロールベンゼン−１，３−ジスルホンアミド及びテトラメチロールグリコルリル等が挙げられる。
【０１０９】
前記フェノール、フェノールエーテル又は芳香族炭化水素のｏ−メチロール化合物としては、例えば、２，４，６−トリメチロールフェノール、２，６−ジメチロール−４−メチルアニソール、２，６−ジメチロール−４−メチルフェノール、１，３−ジメチロール−４，６−ジイソプロピルベンゼン、２，２−ビス−（４−ヒドロキシ−３，５−ジメチロールフェニル）プロパン、３，３'−ジメチロール−４，４'ジヒドロキシジフェニルスルホン等が挙げられる。
【０１１０】
前記メチロール化合物に代えて、例えば、相当するメチル、エチル又はブチルエーテル、又は酢酸又はプロピオン酸のエステルを使用することもでき、以下の化合物が挙げられる。
例えば、４，４'−ビス−メトキシメチルジフェニルエーテル、トリス−メトキシメチルジフェニルエーテル、テトラキス−メトキシメチルヒドラジンジカルボキサミド、テトラキス−メトキシメチル−グリコルリル、テトラキス−ヒドロキシエトキシメチル−グリコルリル、ビス−アセトキシメチルジフェニルエーテル、ヘキサメトキシメチルメラミン等である。
【０１１１】
具体的には、メラミンにホルムアルデヒドを作用させた化合物又はそのアルキル変性物の例として、三井サイアナミド（株）製のサイメル（登録商標）３００、３０１、３０３、３５０、７３６、７３８、３７０、７７１、３２５、３２７、７０３、７０１、２６６、２６７、２８５、２３２、２３５、２３８、１１４１、２７２、２５４、２０２、１１５６、１１５８が挙げられ、ベンゾグアナミンにホルムアルデヒドを作用させた化合物又はそのアルキル変性物の例として、サイメル（登録商標）１１２３、１１２５、１１２８が挙げられ、グリコールウリルにホルムアルデヒドを作用させた化合物又はそのアルキル変性物の例として、サイメル（登録商標）１１７０、１１７１、１１７４、１１７２が挙げられ、尿素にホルムアルデヒドを作用させた化合物又はそのアルキル変性物の例として、三井サイアナミド（株）製のＵＦＲ（登録商標）６５、３００が挙げられる。
【０１１２】
前記酸で架橋可能な架橋剤の含有量としては、ネガ型感光性熱硬化性樹脂組成物の全固形分（質量）の１〜３０質量％が好ましく、２〜２０質量％がより好ましい。
前記含有量が、１質量％未満であると、十分な架橋構造を有する薄膜が得られないことがあり、３０質量％を超えると、現像処理において、塗膜の未照射部分の厚みが著しく減少し、得られる塗膜の透明性が低下することがある。
【０１１３】
（Ｆ）他の成分
本発明のネガ型感光性熱硬化性樹脂組成物においては、既述の（Ａ）〜（Ｅ）の必須成分のほか、種々の目的で界面活性剤、密着促進剤、消色性着色剤、熱重合禁止剤、酸素の重合阻害防止剤、可塑剤等の各種添加剤を添加することができる。
【０１１４】
−界面活性剤−
塗布性、得られる塗膜の平滑性を向上させる目的で、界面活性剤を添加することができ、例えば、フッ素系界面活性剤、シリコーン系界面活性剤が挙げられ、市販品としては、ＢＭ−１０００（ＢＭ Ｃｈｅｍｉｅ社製）；メガファックＦ１４２Ｄ、同Ｆ１７２、同Ｆ１７３、同Ｆ１８３（大日本インキ化学工業（株）製）；フロラードＦＣ−１３５、同ＦＣ−１７０Ｃ、フロラードＦＣ−４３０、同ＦＣ−４３１（住友スリーエム（株）製）；サーフロンＳ−１１２、同Ｓ−１１３、同Ｓ−１３１、同Ｓ−１４１、同Ｓ−１４５（旭硝子（株）製）；ＳＨ−２８ＰＡ、ＳＨ−１９０、ＳＨ−１９３、ＳＺ−６０３２、ＳＦ−８４２８、ＤＣ−５７、ＤＣ−１９０（東レシリコーン（株）製）等が挙げられる。
【０１１５】
前記界面活性剤の添加量としては、ネガ型感光性熱硬化性樹脂組成物の全固形分（質量）の５質量％以下が好ましく、２質量％以下がより好ましい。
【０１１６】
−密着促進剤−
本発明のネガ型感光性熱硬化性樹脂組成物を用いてアクティブマトリックス基板上に層間絶縁膜（感光性熱硬化性樹脂層）を形成する場合には、基板との密着性を向上させる目的で、密着促進剤を添加することができる。
前記密着促進剤としては、官能性シランカップリング剤が好適である。ここに、官能性シランカップリング剤とは、カルボキシル基、メタクリロイル基、イソシアネート基、エポキシ基等の反応性置換基を有するシラン化合物を意味し、例えば、トリメトキシシリル安息香酸、γ−メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、γ−イソシアネートプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等が挙げられる。
【０１１７】
前記密着促進剤の添加量としては、感光性熱硬化性樹脂層の全固形分（質量）の１０質量％以下が好ましく、０．０５〜５質量％がより好ましい。
【０１１８】
−消色性着色剤−
本発明のネガ型感光性熱硬化性樹脂組成物を含む感光性熱硬化性樹脂層を有するネガ型感光性熱硬化性転写材料の製造、使用に際して、塗布形成された感光性熱硬化性樹脂層の表面性状や塗布欠陥を容易に検査することが可能なように、感光性熱硬化性樹脂層が着色されていることが好ましく、かつ最終的に実質的に無色透明な硬化画像が得られることが必要である。即ち、加熱や光照射により消色する消色性着色剤を含有することが好適であり、該消色性着色剤は、ネガ型感光性熱硬化性樹脂組成物に添加されていてもよい。
【０１１９】
前記消色性着色剤は、それ自身が通常１５０℃以上の温度下で１０〜１５０分間熱処理されると分解し、消色するもの、系外に飛散するもの、又は他の成分と反応して分解し消色するもの、等が挙げられる。具体的には、紫外領域において、透明性が高く、熱処理による脱色性に優れたトリフェニルメタン染料が好適であり、例えば、クリスタルバイオレット、メチルバイオレット、エチルバイオレット、オイルブルー＃６０３、ビクトリアピュアーブルーＢＯＨ、マラカイトグリーン、ダイアモンドグリーン等、特開平１０−９７０６１号公報、特開平１０−１０４８２７号公報、特公平３−６８３７５号公報に記載の着色剤等が好適に挙げられる。
【０１２０】
前記消色性着色剤の添加量としては、感光性熱硬化性樹脂層の全固形分（質量）の１０質量％以下が好ましく、０．０５〜５質量％がより好ましい。
【０１２１】
−熱重合防止剤−
感光性熱硬化性樹脂層を形成する工程、あるいは該層の保存時において、既述の少なくとも２個のエチレン性不飽和結合を有する付加重合可能な化合物が不要に熱重合するのを回避する観点からは、少量の熱重合防止剤を添加することが望ましい。
前記熱重合防止剤としては、例えば、ハロイドキノン、ｐ−メトキシフェノール、ジ−ｔ−ブチル−ｐ−クレゾール、ピロガロール、ｔ−ブチルカテコール、ベンゾキノン、４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、フェノチアジン、Ｎ−ニトロソフェニルヒドロキシアミン第一セリウム塩等が挙げられる。
前記熱重合防止剤の添加量としては、感光性熱硬化性樹脂層の全固形分（質量）の約０．０１質量％〜約５質量％が好ましい。
【０１２２】
−その他−
上記のほか、必要に応じて、酸素の存在による前記付加重合性化合物の重合阻害を防止する目的で、ベヘン酸やベヘン酸アミド等の高級脂肪酸誘導体等を添加し、感光性熱硬化性樹脂層形成用の塗布液の塗布後の乾燥過程で該層の表面に偏在させてもよい。この場合の前記高級脂肪酸誘導体の添加量としては、形成された感光性熱硬化性樹脂層の全固形分の０．５〜１０質量％が好ましい。
【０１２３】
硬化後の感光性熱硬化性樹脂層、即ち層間絶縁膜の物性を改良する目的で、無機充填剤や可塑剤等の公知の添加剤を加えてもよい。
前記可塑剤としては、例えば、ジオクチルフタレート、ジドデシルフタレート、トリエチレングリコールジカプリレート、ジメチルグリコールフタレート、トリクレジルホスフェート、ジオクチルアジペート、ジブチルセバケート、トリアセチルグリセリン等が挙げられる。該可塑剤の添加量としては、感光性熱硬化性樹脂層の全固形分（質量）の１０質量％以下が好ましい。
【０１２４】
＜ネガ型感光性熱硬化性転写材料＞
ＨＡ型液晶表示装置において、既述の本発明のネガ型感光性熱硬化性樹脂組成物を含んでなる層間絶縁膜を形成する場合、該層間絶縁膜の形成手段としては、既述のように、ラミネート法により転写材料の感光性熱硬化性樹脂層を転写形成する方法が好ましい。
上記１）〜７）を満足するネガ型感光性熱硬化性転写材料の中でも、支持体上に本発明のネガ型感光性熱硬化性樹脂組成物を含む感光性熱硬化性樹脂層を有してなるネガ型感光性熱硬化性転写材料が好ましい。
【０１２５】
本発明のネガ型感光性熱硬化性転写材料は、本発明のネガ型感光性熱硬化性樹脂組成物を含む感光性熱硬化性樹脂層を少なくとも有してなり、必要に応じてアルカリ可溶性熱可塑性樹脂層、中間層、保護フィルム等の他の層を有してなる。
【０１２６】
−感光性熱硬化性樹脂層−
前記感光性熱硬化性樹脂層は、既述の本発明のネガ型感光性熱硬化性樹脂組成物を含んでなり、必要に応じて他の成分を含んでなり、例えば、感光性熱硬化性樹脂層形成用の塗布液（以下、単に「感光性熱硬化性樹脂層用塗布液」という。
）を調製し、該塗布液を支持体上に塗布、乾燥して形成することができる。
【０１２７】
（感光性熱硬化性樹脂層用塗布液の調製）
前記感光性熱硬化性樹脂層は、本発明のネガ型感光性熱硬化性樹脂組成物を構成する、既述の成分(Ａ)、成分(Ｂ)、成分(Ｃ)、成分(Ｄ)、成分(Ｅ)、及び必要に応じて(Ｆ)他の成分を、有機溶剤中に均一に溶解混合して調製した溶液を塗布液として、該塗布液を支持体上に塗布、乾燥することにより形成することができる。
【０１２８】
前記有機溶剤としては、前記成分(Ａ)〜(Ｅ)及び(Ｆ)他の成分を溶解でき、かつこれらの成分と反応しないものであれば適宜選択することができる。
具体的には、メタノール、エタノール等のアルコール類；テトラヒドロフラン等のエーテル類；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ジメチルエーテル、エチレングリコールメチルエチルエーテル、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エーテル類；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等のエチレングリコールアルキルエーテルアセテート類；ジエチレングリコールモノメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチ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ブチルエーテル等のジエチレングリコール類；
【０１２９】
プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート等のプロピレングリコールアルキルエーテルアセテート類；トルエン、キシレン等の芳香族炭化水素類；メチルエチルケトン、シクロヘキサノン、４−ヒドロキシ−４−メチル−２−ペンタノン等のケトン類；２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ−２−メチルプロピオン酸メチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−２−メチルブタン酸メチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、酢酸エチル、酢酸ブチル等のエステル類が挙げられる。
前記有機溶剤は、一種単独で用いてもよいし、二種以上を組合わせて併用してもよい。
【０１３０】
上記の中でも、各成分の溶解性及び塗布時の膜形成性の点で、エチレングリコールジメチルエーテル等のグリコールエーテル類；エチルセロソルブアセテート等のエチレングリコールアルキルエーテルアセテート類；２−ヒドロキシプロピオン酸エチル、３−メトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル等のエステル類；ジエチレングリコールジメチルエーテル等のジエチレングリコール類；等が好ましい。
【０１３１】
前記有機溶剤と共に、更に高沸点溶剤を添加することもできる。該高沸点溶剤としては、例えば、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルホルムアニリド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン、ジメチルスルホキシド、ベンジルエチルエーテル、ジヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、１−オクタノール、１−ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、γ−ブチロラクトン、炭酸エチレン、炭酸プロピレン、フェニルセロソルブアセテート等が挙げられる。
【０１３２】
（ネガ型感光性熱硬化性転写材料の作製）
上記のようにして調製した感光性熱硬化性樹脂層塗布液を支持体の表面に直接塗布し、通常はオーブン中で加熱乾燥を行うことにより溶剤を除去して、ネガ型感光性熱硬化性樹脂組成物を含む塗膜、即ち、感光性熱硬化性樹脂層を形成する。ここで、感光性熱硬化性樹脂層塗布液は、例えば、孔径０．２μｍのミクロ濾過フィルター等を用いて濾過した後、使用に供することもできる。更に、場合により保護フィルムを感光性熱硬化性樹脂層の上に貼り合わせてもよい。
【０１３３】
感光性熱硬化性樹脂層塗布液の塗布方法としては、特に制限はなく、例えば、スプレー法、ロールコート法、回転塗布法、スリットコート法、エクストルージョンコート法、カーテンコート法、ダイコート法、ワイヤーバーコート法、ナイフコート法等の公知の方法が挙げられる。
【０１３４】
プリベークの条件としては、各成分の種類、使用割合等によっても異なるが、通常６０〜１１０℃で３０秒間〜１５分間程度である。
【０１３５】
ネガ型感光性熱硬化性転写材料を構成する支持体としては、感光性熱硬化性樹脂層、又は後述のアルカリ可溶性熱可塑性樹脂層に対して良好な剥離性を有し、化学的及び熱的に安定であって、可撓性を備える材料が好ましい。具体的には、テフロン、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリアリレート、ポリカーボネート、ポリエチレン、ポリプロピレン等の薄いシートもしくはこれらの積層物が好ましい。良好な剥離性を得る観点からは、グロー放電等の表面処理はせず、ゼラチン等の下塗りも設けないのが一般的である。
【０１３６】
前記支持体の厚さとしては、５〜３００μｍが適当であり、１０〜１５０μｍが特に好ましい。前記厚さが５μｍ以下であると、ラミネート時の引張り強度が不足して伸びてしまい不都合なシワが入ることがあり、３００μｍを超えると、ラミネート時の加熱による熱伝導性が低下し、ラミネート時の搬送速度を上げることができないことがある。
【０１３７】
前記感光性熱硬化性樹脂層の層厚としては、目的に応じて適宜選択でき、中でも０．１〜１０μｍが好ましい。前記層厚が、０．１μｍ未満であると、耐性に劣る硬化膜しかできないことがあり、１０μｍを超えると、現像性の低下、画像再現性の低下等の問題を生ずることがある。ＨＡ型液晶表示装置に設けられる層間絶縁膜としては、誘電率に応じて膜厚が決まり、誘電率が３〜３．５では膜厚は３〜５μｍが好ましい。
【０１３８】
−他の層−
既述のように、支持体と感光性熱硬化性樹脂層との間に、更にアルカリ可溶性熱可塑性樹脂層、中間層、保護フィルムが設けられた、多層構成よりなるネガ型感光性熱硬化性転写材料とすることもできる。
【０１３９】
−アルカリ可溶性熱可塑性樹脂層−
前記アルカリ可溶性熱可塑性樹脂層は、アルカリ可溶性熱可塑性樹脂を主成分に含有してなり、他の成分を含んでいてもよい。
前記アルカリ可溶性熱可塑性樹脂としては、アルカリ可溶性であって、実質的な軟化点が８０℃以下の熱可塑性樹脂が挙げられ、例えば、エチレンとアクリル酸エステル共重合体のケン化物、スチレンと（メタ）アクリル酸エステル共重合体のケン化物、ビニルトルエンと（メタ）アクリル酸エステル共重合体のケン化物、ポリ（メタ）アクリル酸エステル、（メタ）アクリル酸ブチルと酢酸ビニル等の（メタ）アクリル酸エステル共重合体などのケン化物等が挙げられる。
【０１４０】
また、「プラスチック性能便覧」（日本プラスチック工業連盟、全日本プラスチック成形工業連合会編著、工業調査会発行、１９６８年１０月２５日発行）に記載の、軟化点が約８０℃以下の有機高分子のうち、アルカリ水溶液に可溶なものも挙げられる。
熱可塑性樹脂は、一種単独で用いてもよいし、二種以上を併用してもよい。
【０１４１】
また、軟化点が８０℃以上の有機高分子物質であっても、その有機高分子物質中に該高分子物質と相溶性の各種可塑剤を添加して実質的な軟化点を８０℃以下に下げて用いることも可能である。前記有機高分子物質中には、支持体との接着力を調節する目的で、更に実質的な軟化点が８０℃を越えない範囲で各種ポリマーや、過冷却物質、密着改良剤、界面活性剤、離型剤等を添加することも可能である。
【０１４２】
前記可塑剤としては、例えば、ポリプロピレングリコール、ポリエチレングリコール、ジオクチルフタレート、ジヘプチルフタレート、ジブチルフタレート、トリクレジルフォスフェート、クレジルジフェニルフォスフェートビフェニルジフェニルフォスフェートを好適に挙げることができる。
【０１４３】
前記アルカリ可溶性熱可塑性樹脂層の層厚としては、６μｍ以上が好ましい。
前記層厚が、６μｍ未満であると、被転写体の表面に存在する１μｍ以上の凹凸を完全に吸収することが困難となることがある。また、上限については、現像性、製造適性の点で、約１００μｍ以下が一般的であり、約５０μｍ以下が好ましい。
【０１４４】
−中間層−
前記中間層は、露光時の酸素遮断の目的と、アルカリ可溶性熱可塑性樹脂層と感光性熱硬化性樹脂層との間の混じり合いを防止する目的で設けられる。
中間層は、水又はアルカリ水溶液に分散若しくは溶解し、酸素透過性の低いものであればよく、公知のものを適用することができる。
【０１４５】
例えば、特開昭４６−２１２１号公報や特公昭５６−４０８２４号公報に記載の、ポリビニルエーテル／無水マレイン酸重合体、カルボキシアルキルセルロースの水溶性塩、水溶性セルロースエーテル類、カルボキシアルキル澱粉の塩、水塩、ポリビニルアルコール、ポリビニルピロリドン、各種のポリアクリルアミド類、各種の水溶性ポリアミド、ポリアクリル酸の水溶性塩、ゼラチン、エチレンオキサイド重合体、各種の澱粉及びその類似物からなる群の水溶性塩、スチレン／マレイン酸の共重合体、マレイネート樹脂等が挙げられる。また、これら二種以上を組合わせたものであってもよい。
【０１４６】
中でも特に、ポリビニルアルコールとポリビニルピロリドンの組合わせが好ましい。前記ポリビニルアルコールとしては、鹸化率が８０モル％以上のものが好ましい。前記ポリビニルピロリドンの含有率としては、中間層（酸素遮断層）の固形分（質量）の１〜７５質量％が一般的であり、中でも１〜６０質量％が好ましく、１０〜５０質量％がより好ましい。前記含有率が、１質量％未満であると、感光性熱硬化性樹脂層との十分な接着性が得られないことがあり、７５質量％を超えると、酸素遮断能が低下することがある。
【０１４７】
中間層（酸素遮断層）の層厚は、非常に薄層に設けられ、中でも約０．１〜５μｍが好ましく、０．５〜２μｍがより好ましい。前記層厚が、約０．１μｍ未満であると、酸素の透過性が高すぎることがあり、約５μｍを越えると、現像時又は中間層除去時に、長時間を要することがある。
【０１４８】
−保護フィルム−
前記保護フィルムは、貯蔵の際の不純物付着や損傷を避ける観点からは設けておく方が望ましい。
前記保護フィルムは、支持体と同一若しくは類似の材料からなるものであってもよく、感光性熱硬化性樹脂層から容易に剥離しうる物である必要がある。また、感光性熱硬化性樹脂層に積層する側の表面の平滑性が重要となり、感光性熱硬化性樹脂層の表面の損傷を回避する観点から、約０．１μｍ程度を超える突起が存在しないことが好ましい。
【０１４９】
保護フィルムに使用可能な材料としては、例えば、シリコーン紙、ポリオレフィン若しくはポリテトラフルオルエチレンシートが好ましく、中でも特に、ポリプロピレンフィルム、ポリエチレンフィルムが好ましい。
保護フィルムの厚みとしては、約５〜１００μｍが好ましく、７〜１５μｍがより好ましい。
【０１５０】
以上のように、ＨＡ型液晶表示装置の製造にネガ型感光性熱硬化性転写材料が用いられ、特に本発明のネガ型感光性熱硬化性樹脂組成物を含む感光性熱硬化性樹脂層を有する転写材料（本発明のネガ型感光性熱硬化性転写材料）は、保存環境に依存しない優れた保存安定性（アルカリ現像性）を有し、かつ１，２−キノンジアジドの分解等に伴う着色（変色）がなく、エッチング用レジストを剥離する剥離液等の有機溶剤に対する耐性（耐溶剤性）を有する層間絶縁膜を形成することができる。
【０１５１】
＜ＨＡ型液晶表示装置＞
本発明のＨＡ型液晶表示装置は、既述の本発明の液晶表示装置の製造方法により得られ、制御信号を伝送するゲート信号線と映像信号を伝送するソース信号線とが交差して形成され、信号線の交差部に、スイッチング装置が前記信号線と接合されて割り当てられ配列形成され、前記スイッチング装置及び信号線を覆う層間絶縁膜と該層間絶縁膜上にマトリックス状に形成された画素電極とが設けられたアクティブマトリクス基板と、該アクティブマトリックス基板に対向配置された対向基板と、前記アクティブマトリクス基板と対向基板との間に介在された液晶層とを備えてなる。前記アクティブマトリクス基板においては、複数のゲート信号線と複数のソース信号線とが交差し、交差する複数の交差部にスイッチング装置がマトリックス状に配列形成されていてもよい。
【０１５２】
即ち、薄膜トランジスタ（ＴＦＴ）等のスイッチング装置及び信号線と、スイッチング装置及び信号線を覆う層間絶縁膜上に設けられた画素電極（導電層）とが配列形成された駆動側基板（アクティブマトリックス基板）と、カラーフィルタ及び対向電極（導電層）を備えるフィルタ側基板（対向基板）とを例えばスペーサを介在させて空隙を有して対向配置し、その間隙部に液晶材料を封入して構成されてなる。
【０１５３】
前記アクティブマトリックス基板は、例えば図１に示すように、スイッチング装置１０及び各信号線を覆う層間絶縁膜を有し、更に該層間絶縁膜にコンタクトホール２０が設けられて、該コンタクトホール２０を通じて層間絶縁膜上にマトリックス状に画素電極を有するＨＡ型のアクティブマトリックス基板である。
【０１５４】
前記導電層としては、例えば、ＩＴＯ膜；Ａｌ、Ｚｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｏ等の金属膜；ＳｉＯ₂等の金属酸化膜などが挙げられ、中でも透明性のものが好ましく、ＩＴＯ膜が特に好ましい。
【０１５５】
本発明の液晶表示装置は、該液晶表示装置を構成する基板の両方に導電層が形成されており、該両導電層間に電圧が印可されその間に狭持される液晶材料がその電圧に応じて配向状態を変化させることにより表示を行うことができる。
【０１５６】
以上のように、ＨＡ型液晶表示装置を構成するＨＡ型アクティブマトリックス基板の層間絶縁膜がラミネート法により転写形成され、かつ転写された層に加工を施しコンタクトホールが形成されているので、塗布ムラ等がなく均一厚の層間絶縁膜を備える結果、スイッチング装置及び信号線は十分に絶縁され、高精度のコンタクトホールを有し、動作不良を生ずることなく安定した画像表示を行うことができる。しかも、層間絶縁膜は、実質的に無色透明で保存安定性、耐溶剤性に優れ、高精細で色純度の高い画像を表示することができる。
【０１５７】
【実施例】
以下、実施例により本発明を説明するが、本発明はこれらの実施例に限定されるものではない。尚、実施例中の「部」及び「％」は、それぞれ「質量部」及び「質量％」を示す。
【０１５８】
（実施例１）
〔ネガ型感光性熱硬化性転写材料の作製〕
ベンジルメタクリレート７３モル％とメタクリル酸２７モル％とからなる共重合体（酸価１０１ｍｇＫＯＨ／１ｇ、重量平均分子量約１０万）２１部を、プロピレングリコールモノメチルエーテルアセテート３０部とメチルエチルケトン１３部との混合溶液に溶解し、該混合溶液に更に下記化合物を溶解して感光性熱硬化性樹脂層塗布液Ｃ１を得た。

【０１５９】
５７０ｍｍ幅、５μｍ厚のロール状のポリエチレンテレフタレートフィルムウエッブ上に、前記感光性熱硬化性樹脂層塗布液Ｃ１をスリットコート型の塗布機を用いて連続塗布し、１００℃の乾燥オーブン中で２分間乾燥して、層厚５μｍのネガ型の感光性熱硬化性樹脂層を形成した。塗布層厚の分布は±０．０５μｍ以内であった。また、感光性熱硬化性樹脂層上に３０μｍ厚のポリエチレンフィルムを連続積層して、本発明のネガ型感光性熱硬化性転写材料ロールを得た。
【０１６０】
〔ＨＡ型アクティブマトリックス基板の作製〕
−層間絶縁膜の形成−
上記より得たネガ型感光性熱硬化性転写材料ロールからポリエチレンフィルムを剥離した。そして、０．７ｍｍ厚のガラス基板上にアルミニウム配線からなる複数のゲート信号線及びソース信号線が交差して形成され、交差する複数の交差部に複数のＴＦＴが前記信号線と接合されて割り当てられマトリックス状に配列形成されたアクティブマトリックス基板（５５０×６５０ｍｍ）の、ＴＦＴ等が設けられた側の表面に感光性熱硬化性樹脂層の表面を重ね合わせて、日立テクノ（株）製の連続ラミネータを用い、フィルム搬送速度１ｍ／分、ヒートロール温度１３０℃で加熱しながら密着、積層した。
【０１６１】
この積層体のポリエチレンテレフタレートフィルム側の表面に、コンタクトホール径が１０μｍとなる、コンタクトホールパターンを有するフォトマスクを重ねて、プロキシミティギャップ７０μｍで２ＫＷ超高圧水銀灯から、３００ｍｊ／ｃｍ²の露光量で露光を行った。続いて、ポリエチレンテレフタレートフィルムを剥離し、アクティブマトリックス基板上に感光性熱硬化性樹脂層を転写し、該感光性熱硬化性樹脂層を１％モノエタノールアミン水溶液を用いてスプレー現像機で現像して未照射部を溶解除去し、コンタクトホールが設けられた層間絶縁膜を形成した。その後、２００℃のオーブン中で３０分間加熱（ベーク）し硬化させた。
【０１６２】
得られた層間絶縁膜は、その膜厚の均一性は±０．０５μｍと良好であり、塗布形成した場合のような塗布ムラ状の厚みムラ（段差）もなく、均一厚で表面平滑性に優れていた。しかも、コンタクトホール部の穴径は１４μｍで、アクティブマトリックス基板の全面において現像残膜もなく、いずれのコンタクトホール形状においてもスロープが３３度と良好であり、形状精度にも優れていた。更に、層自身の変色（着色）も認められず、実質上無色透明性の層間絶縁膜が形成された。また、ベーク後の膜厚変化はベーク前の−１０％であり、耐熱性に優れ、層間絶縁膜の透過率は、３５０ｎｍの波長光で９７％で良好であった。
一方、得られたネガ型感光性熱硬化性転写材料を容器に密閉し、５０℃環境下で４日間放置後、上記同様に現像したときの現像時間の変化を測定したところ、全く変化がないことが認められ、保存安定性にも優れることが判った。
【０１６３】
−画素電極（導電層）の形成−
続いて、前記層間絶縁膜上に、スパッタ法により２００℃で０．２μｍ厚のＩＴＯ膜を形成した。該膜上に、更に市販のポジ型のＩＴＯエッチング用レジストをスピンコート法でコーティングし、乾燥し、フォトマスクを介して露光した後、露光部を現像除去した。続いて、塩化鉄／塩酸エッチャントを用いて、ＩＴＯエッチング用レジストで被覆されていない部分のＩＴＯ膜を除去した後、ＩＴＯエッチング用レジストを８０℃のモノエタノールアミンとジメチルスルホキシド（質量比７：３）からなるレジスト剥離液に１０分間浸漬して剥離した。ここで、層間絶縁層の膨潤もなく、層間絶縁膜上に最終的に形成すべきＩＴＯ膜の密着も良好で剥がれ落ちてしまうこともなかった。形成されたＩＴＯ膜のパターンは、すべてのコンタクトホールの底部において露出するドレイン配線との密着に優れ、現像残膜のないことが認められた。
以上のようにして、ＨＡ型アクティブマトリックス基板を作製した。
【０１６４】
〔ハイアパーチャー型液晶表示装置の作製〕
更に、得られたＨＡ型アクティブマトリックス基板を用いて以下のようにして本発明の液晶表示装置を製造することができる。
即ち、所定サイズのガラス基板上に、膜厚０．１μｍのクロム（Ｃｒ）金属膜をスパッタリングにより形成し、続いて、フォトレジストを用いてエッチングし、所定サイズ、形状からなる格子状のブラックマトリックスを形成した後、特開平１１−６４６２１号公報に記載のカラーフィルタの製造方法により、所定の位置にＲ(赤色)、Ｇ(緑色)、Ｂ(青色)からなる着色膜を形成する。
次に、着色膜及びブラックマトリックス上に、スピンコーターによりアクリル樹脂系の液を塗布して保護層を形成し平坦化した後、該保護層上に更に導電層としてスパッタリング法によりＩＴＯ膜を成膜し、対向基板を得ることができる。
【０１６５】
ＨＡ型アクティブマトリックス基板の層間絶縁膜及びＩＴＯ膜の表面に対向させて、前記対向基板のＩＴＯ膜の表面とが対向するように配置し、スペーサを介在させて間隙を有して固定する。そして、この間隙に液晶材料を封入し、画像表示を担う液晶層を設けることにより、本発明のハイアパーチャー型液晶表示装置を作製することができる。
【０１６６】
以上より得られた液晶表示装置は、層間絶縁膜の膜厚差に伴う絶縁不均一により生ずる動作不良がなく、開口率が高く、層間絶縁膜の着色による色相ズレもなく光透過性に優れ、鮮やかで高精細な画像表示を行うことができる。
【０１６７】
（比較例１）
実施例１と同様のアクティブマトリックス基板（５５０×６５０ｍｍ）と感光性熱硬化性樹脂層塗布液とを準備し、該アクティブマトリックス基板上に、スピン塗布機を用いて感光性熱硬化性樹脂層塗布液を直接塗布し、乾燥させることにより感光性熱硬化性樹脂層を設けたこと以外、実施例１と同様にして層間絶縁膜を形成した。
【０１６８】
前記感光性熱硬化性樹脂層塗布液は、本発明のネガ型感光性熱硬化性樹脂組成物を含んで構成されているので、ＩＴＯ膜形成、エッチング用レジスト像の形成、エッチング後のレジスト剥離液による剥離の点では十分な耐性を有していた。
しかし、得られた層間絶縁膜の表面性状は、塗布ムラ状の厚みムラ（段差）が認められ、アクティブマトリックス基板上のＴＦＴ及び信号線を均一に絶縁する絶縁機能に劣っていた。しかも、コンタクトホール径のサイズのバラツキが大きく、基板中央部におけるＩＴＯ膜の密着不良も認められた。これは、基板中央部の層間絶縁膜の膜厚が基板周囲部における膜厚より厚いため現像残膜が発生したものと考えられる。
【０１６９】
（実施例２）
〔多層型のネガ型感光性熱硬化性転写材料の作製〕
５７０ｍｍ幅、厚さ１００μｍのロール状のポリエチレンテレフタレートフィルムよりなる支持体上に、下記組成からなる熱可塑性樹脂層用塗布液Ｈ１を塗布、乾燥させ、乾燥層厚が２０μｍの熱可塑性樹脂層を形成した。
【０１７０】
［熱可塑性樹脂層用塗布液Ｈ１の組成］
・メチルメタクリレート／２−エチルヘキシルアクリレート／ベンジルメタク
リレート／メタクリル酸共重合体 …１５．０部
（共重合比（モル比）＝５５／１１．７／４．５／２８．８、
重量平均分子量＝８００００）
・ＢＰＥ−５００（多官能アクリレート） … ７．０部
（新中村化学（株）製）
・フッ素系界面活性剤 … ０．３部
（Ｆ１７７Ｐ、大日本インキ（株）製）
・メタノール …３０．０部
・メチルエチルケトン …１９．０部
・１−メトキシ−２−プロパノール …１０．０部
【０１７１】
次に、前記熱可塑性樹脂層上に、下記組成からなる中間層用塗布液Ｂ１を塗布し、乾燥させて乾燥層厚が１．６μｍの中間層を形成した。
［中間層用塗布液Ｂ１の組成］
・ポリビニルアルコール … １３０部
（ＰＶＡ−２０５，鹸化度８０モル％、（株）クラレ製）
・ポリビニルピロリドン … ６０部
（Ｋ−３０、ＧＡＦコーポレーション社製）
・蒸留水 …２１１０部
・メタノール …１７５０部
【０１７２】
前記熱可塑性樹脂層及び中間層が設けられた支持体上に、実施例１と同様に調製した感光性熱硬化性樹脂層用塗布液Ｃ１を塗布、乾燥させ、乾燥層厚が５μｍの感光性熱硬化性樹脂層を形成し、更にこの感光性熱硬化性樹脂層の上に、ポリプロピレン（厚さ１２μｍ）の被覆シートを圧着して、多層のネガ型感光性熱硬化性転写材料を作製した。
【０１７３】
〔ＨＡ型アクティブマトリックス基板の作製〕
−層間絶縁膜の形成−
上記より得たネガ型感光性熱硬化性転写材料ロールから被覆シートを剥離した。そして、０．７ｍｍ厚のガラス基板上にアルミニウム配線からなる複数のゲート信号線及びソース信号線が交差して形成され、交差する複数の交差部に複数のＴＦＴが前記信号線と接合されて割り当てられマトリックス状に配列形成されたアクティブマトリックス基板（５５０×６５０ｍｍ）の、ＴＦＴ等が設けられた側の表面に感光性熱硬化性樹脂層の表面を重ね合わせて、日立テクノ（株）製の連続ラミネータでフィルム搬送速度３ｍ／分、ヒートロール温度１３０℃で加熱しながら密着、積層した。
【０１７４】
この積層体から支持体を除去した後の熱可塑性樹脂層上に、コンタクトホールパターンを有するフォトマスクを重ねて、プロキシミティギャップ７０μｍで２ＫＷ超高圧水銀灯から、１００ｍｊ／ｃｍ²の露光量でＵＶ露光を行った。続いて、１％トリエタノールアミン水溶液を用いて熱可塑性樹脂層及び中間層を溶解除去した。この際、感光性熱硬化性樹脂層は実質的に現像されていなかった。
【０１７５】
次いで、１％モノエタノールアミン水溶液を使用して未露光部を現像除去した後、１８０℃のオーブン中で１時間加熱（ベーク）し硬化させた。
露光され、熱硬化された感光性熱硬化性樹脂層よりなる層間絶縁膜の膜厚は、４μｍであり、鉛筆硬度は５Ｈ、誘電率は２．８（１ｋＨｚ）であった。
【０１７６】
得られた層間絶縁膜は、膜厚の均一性が±０．０５μｍと良好であり、塗布形成した場合のような塗布ムラ状の厚みムラ（段差）もなく、均一厚で表面平滑性に優れていた。しかも、コンタクトホール部の形状は、底部のサイズが１０μｍφで傾斜角が２５度で良好な、すり鉢状であり、形状精度にも優れていた。また、形成された層間絶縁膜は変色（着色）も認められず、実質上無色透明性であり、光透過率は３５０ｎｍの波長光で９７％で良好であった。
【０１７７】
−画素電極（導電層）の形成−
続いて、前記層間絶縁膜上に、スパッタ法により２００℃で０．２μｍ厚のＩＴＯ膜を形成した。該膜上に、更に市販のポジ型のＩＴＯエッチング用レジストをスピンコート法でコーティングし、乾燥し、フォトマスクを介して露光した後、露光部を現像除去した。続いて、塩化鉄／塩酸エッチャントを用いて、ＩＴＯエッチング用レジストで被覆されていない部分のＩＴＯ膜を除去した後、ＩＴＯエッチング用レジストを８０℃のモノエタノールアミンとジメチルスルホキシド（質量比７：３）からなるレジスト剥離液に１０分間浸漬して剥離した。ここで、層間絶縁層の膨潤もなく、層間絶縁膜上に最終的に形成すべきＩＴＯ膜の密着も良好で剥がれ落ちてしまうこともなかった。したがって、膨潤によるシワ等の損傷も認められなかった。形成されたＩＴＯ膜のパターンは、すべてのコンタクトホールの底部において露出するドレイン配線との密着に優れ、現像残膜のないことが認められた。
以上のようにして、ＨＡ型アクティブマトリックス基板を作製した。
【０１７８】
また、得られたＨＡ型アクティブマトリックス基板を用いて、実施例１と同様に、本発明の液晶表示装置を製造することができ、得られた液晶表示装置は、層間絶縁膜の膜厚差に伴う絶縁不均一により生ずる動作不良がなく、開口率が高く、層間絶縁膜の着色による色相ズレもなく光透過性に優れ、鮮やかで高精細な画像表示を行うことができる。
【０１７９】
（比較例２）
実施例２で用いた感光性熱硬化性樹脂層用塗布液Ｃ１に代えて、下記組成よりなる感光性絶縁層用塗布液Ｃ２（特開平１０−９７０６１号公報の実施例１）を用い、乾燥層厚を２μｍとしたこと以外、実施例２と同様にして、ＨＡ型アクティブマトリックス基板の作製した。
【０１８０】
［感光性絶縁層用塗布液Ｃ２の組成］
・スチレン／無水マレイン酸共重合体のベンジルアミン変性物 …１４部
（スチレン／無水マレイン酸＝６０／４０（モル比）、
無水マレイン酸に等量のベンジルアミンを反応させたもの、
酸価＝１５０ｍｇＫＯＨ／１ｇ、重量平均分子量＝１．３万）
・フッ素系界面活性剤 … ０．１部
（Ｆ−１７６、大日本インキ化学工業（株）製）
・ハイドロキノンモノメチルエーテル … ０．０１部
・ジペンタエリスリトールヘキサアクリレート …１１部
・２−（ｐ−ブトキシスチリル）−５−トリクロロ … ０．５部
メチル）−１，３，４−オキサジアゾール
・アイゼンマラカイトグリーン（保土ケ谷化学（株）製） … ０．５部
・メタノール …２５部
・プロピレングリコールモノメチルエーテル …２５部
・メチルエチルケトン …２５部
【０１８１】
上記より形成された層間絶縁膜は、モノエタノールアミンとジメチルスルホキシドの混合溶液中に浸漬してレジストを剥離する際に膨潤し、層間絶縁膜上に最終的に形成すべきＩＴＯ膜の密着不良によりＩＴＯ膜が剥がれ落ちてしまい、有機溶剤系剥離液に対する耐性（耐溶剤性）の点で劣っていた。また、感光性絶縁層用塗布液Ｃ２を用いて得られたネガ型感光性熱硬化性転写材料ロールでは、２０μｍ径より小さなのコンタクトホールを形成することはできなかった。
【０１８２】
【発明の効果】
本発明によれば、ＨＡ型液晶表示装置を構成するＨＡ型アクティブマトリックス基板の形成に好適であって、実質的に無色透明で保存安定性、耐溶剤性に優れたネガ型感光性熱硬化性樹脂組成物を含んでなり、塗布ムラ等のない均一な膜厚を有し、絶縁性及びコンタクトホールの形状精度に優れ、実質的に無色透明で保存安定性、耐溶剤性に優れた層間絶縁膜の形成が可能な層間絶縁膜用ネガ型感光性熱硬化性転写材料、並びに該ネガ型感光性熱硬化性転写材料を用い、絶縁性及びコンタクトホールの形状精度に優れ、実質的に無色透明で保存安定性、耐溶剤性に優れた層間絶縁膜の形成に好適な層間絶縁膜の形成方法を提供することができる。
また、均一厚であって、絶縁性及びコンタクトホールの形状精度に優れ、実質的に無色透明で保存安定性、耐溶剤性に優れた層間絶縁膜を安定的に形成し得るハイアパーチャー（ＨＡ）型液晶表示装置の製造方法、及び該ＨＡ型液晶表示装置の製造方法により得られ、開口率が高く、色相ズレがなく光透過性に優れ、高精細かつ鮮明な画像表示が可能なＨＡ型液晶表示装置を提供することができる。
【図面の簡単な説明】
【図１】 本発明の液晶表示装置におけるハイアパーチャー型（ＨＡ型）アクティブマトリクス基板の１画素部分の構成を説明するための概略断面図である。
【図２】 層間絶縁膜を形成する工程を説明するための概略工程図である。
【符号の説明】
１０…スイッチング装置（ＴＦＴ）
１１…透明基板
１２…ゲート信号線
１６ａ…ソース電極
１６ｂ…ドレイン電極
１７…ソース信号線（金属層）
１７’…接続信号線（金属層）
１８…層間絶縁膜
１９…画素電極（ＩＴＯ膜）
２０…コンタクトホール
３０…ＨＡ型アクティブマトリックス基板[0001]
BACKGROUND OF THE INVENTION
  The present invention is suitable for manufacturing a high aperture type active matrix substrate having an interlayer insulating film covering a switching device such as a thin film transistor.For interlayer insulation filmNegative photosensitive thermosetting transfer material,layerOf forming inter-layer insulation film, HaEar aperture type liquid crystal display deviceAnd itsManufacturing methodTo the lawRelated.
[0002]
[Prior art]
In recent years, high definition of the liquid crystal display of the active matrix liquid crystal display device has been an issue, and many studies have been made to improve the aperture ratio of the liquid crystal display device. In other words, when trying to achieve high definition, the pixel size is reduced, and as a result, the aperture ratio decreases and the light transmittance decreases. Therefore, it is effective to increase the aperture ratio in order to prevent a decrease in light transmittance.
[0003]
Recently, as a means for realizing a high aperture ratio, for example, techniques called a so-called high aperture (HA) method and color filter on array (COA) method have appeared. Among these, the HA method is a technique with high possibility of practical use.
This HA method is configured by providing a pixel electrode so as to overlap a signal wiring with respect to an active matrix substrate including a signal wiring and a switching element such as a thin film transistor (hereinafter referred to as “TFT”). Therefore, a transparent interlayer insulating film is formed in advance on a switching device such as a TFT or a signal wiring, and a pixel electrode is formed on the film. Hereinafter, the active matrix substrate obtained by the method is referred to as a high aperture (HA) type active matrix substrate.
[0004]
The transparent interlayer insulating film formed by the HA method has been conventionally formed using a photosensitive insulating resin, and can manufacture a TFT substrate having a high aperture ratio with suppressed capacitance crosstalk with high productivity. Are known (Japanese Patent Laid-Open No. 6-242433, US Pat. No. 5,780,871).
Japanese Patent Laid-Open No. 9-96837 discloses only the transmittance of the color filter by defining the step (level difference) on the surface of the TFT substrate in the HA method, the thickness of the transparent interlayer insulating film, the dielectric constant, and the light transmittance. In addition, a technique for improving the viewing angle is disclosed.
[0005]
Here, a configuration example of a high aperture (HA) type active matrix substrate in the transmissive liquid crystal display device employing the HA method will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view for explaining the configuration of one pixel portion of a high aperture type (HA type) active matrix substrate in a liquid crystal display device of the present invention.
A gate electrode 12 is provided on the transparent insulating substrate 11, and a gate insulating film 13 is provided to cover the gate electrode 12. A semiconductor layer 14 is provided so as to overlap the gate electrode 12 via the gate insulating film 13, and a channel protective layer 15 is further placed on the upper center of the semiconductor layer 14. Further, a source electrode 16 a and a drain electrode 16 b made of an n + Si layer are stacked so as to cover the channel protective layer 15 and the semiconductor layer 14 and are separated on the channel protective layer 15. Thus, the thin film transistor (TFT) 10 is formed on the transparent insulating substrate 11.
[0006]
A source signal line made of a metal layer 17 is formed at one end of the source electrode 16a constituting the TFT on the side not in contact with the channel protective layer 15 so as to be joined at the upper part thereof. Further, a metal layer 17 ′ is formed at one end of the drain electrode 16 b on the side not in contact with the channel protective layer 15 so as to be joined at the upper part thereof. Further, the TFT, the gate signal line 12, the source signal line 17, and the connection signal line (metal layer) 17 'are covered with a contact hole 20 on the extension of the metal layer 17' and photosensitive insulating. A transparent interlayer insulating film 18 made of a conductive resin is laminated, and a pixel electrode 19 made of a transparent conductive film is provided so as to be joined to the connection signal line 17 ′ in the contact hole 20. That is, the pixel electrode 19 is electrically connected to the drain electrode 16b of the TFT through the connection signal line 17 '.
The channel protective film 15 can be simplified depending on the manufacturing process. The transparent interlayer insulating film may be a single layer or a multilayer made of the same or different materials.
[0007]
Here, as a photosensitive insulating resin used for forming an interlayer insulating film in the HA method, a liquid photosensitive resin is generally applied and can be formed into a layer by coating or the like (coating method), and is mass-productive. This is useful in terms of improvement and cost reduction. Also, in the case of the coating method, as compared with the sputtering method, if there are irregularities in the lower part of the formed transparent interlayer insulating film, the surface of the transparent interlayer insulating film formed on the upper part of the irregularities has undulations or steps (height difference). However, when the transparent interlayer insulating film is formed using a coating liquid having an initial viscosity of 100 cps or less, the difference in level of undulations and steps can be reduced to 500 mm or less. In addition, when a photosensitive material is used, steps such as resist coating and stripping can be simplified, and cost can be further reduced. Furthermore, when the thickness is 1.5 μm or more, leakage defects and the like can be reduced, reliability can be improved, yield can be improved, and cost reduction accompanying improvement in yield can be expected.
Therefore, a manufacturing method using a coating method has been generally used.
[0008]
However, in recent years, as the size of liquid crystal display devices has increased, various problems have become apparent in the formation of an interlayer insulating film by a coating method. In other words, the occurrence of coating unevenness due to the coating method cannot be ignored.
That is, in the case where a large number of TFTs are provided on a large substrate, non-uniformity in insulation is caused by uneven coating, resulting in malfunction. Due to the variation in the thickness of the applied interlayer insulating film, the potential of the pixel capacitance due to the capacitance between the edge of the pixel electrode 19 and the gate signal line 12 is not uniform, and the display quality and reliability are impaired. It was. Furthermore, there are problems such as poor accuracy of the shape of the contact hole due to coating unevenness and large variation in the amount of remaining film after development at the bottom of the contact hole.
[0009]
On the other hand, the photosensitive resin material itself used for forming the transparent interlayer insulating film has a problem.
For example, as a positive photosensitive resin, JP-A-11-174673 discloses an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, an epoxy group-containing unsaturated compound, and other olefinic unsaturated compounds. Disclosed is a radiation-sensitive resin composition for forming a display panel spacer containing a copolymer and a 1,2-quinonediazide compound. The radiation-sensitive resin composition is applied by a spin coating method or the like, dried, and alkali-developed. Thereafter, the entire surface is irradiated with radiation such as ultraviolet rays and further heated at 150 to 250 ° C. for 5 to 90 minutes to form a hard film. In this method, a good chemical resistance and a contact hole having a good shape can be obtained, but coloring in the insulating film based on the decomposition of 1,2-quinonediazide is inevitable, and an epoxy group and a carboxylic acid are present in the molecule. Sufficient storage stability cannot be ensured because a polymer material having mutually reactive groups called groups is used.
[0010]
In addition, US Pat. No. 5,641,974 discloses a technique for forming an insulating transparent resin structure on a TFT array substrate in order to realize an HA type liquid crystal display, and the connection between the transparent electrode and the drain electrode is disclosed. In order to form a contact hole for this purpose, benzocyclobutene (BCB) having a dielectric constant of about 5 or less or a transparent photopolymerizable photosensitive resin is used as a negative photosensitive resin. Furthermore, in JP-A-11-323057, as an example of a negative photosensitive resin, an acrylic copolymer, an acidic group-containing monomer / allyl methacrylate copolymer, a radiation-sensitive compound and a solvent are used. A radiation curable composition for spacer formation or protective layer formation is disclosed.
Although these negative photosensitive resins are excellent in transparency and insulation, they are not satisfactory in terms of resistance (chemical resistance) and resolution to organic solvent-based stripping solutions used in the stripping process for stripping the resist for ITO etching. It was enough. On the other hand, benzocyclobutene is excellent to some extent in terms of resolution, but since development with an aqueous alkali solution is impossible, development with a solvent is unavoidable, and the working environment deteriorates.
[0011]
On the other hand, in JP-A-10-97061 and JP-A-10-206888, a photosensitive resin material having a photosensitive resin layer is formed by previously applying a photosensitive composition on a film support and drying, A so-called transfer method in which the photosensitive resin layer is transferred onto a substrate is disclosed, and it is stated that productivity and high-quality thin film formation can be improved. That is, in the transfer method, a method of forming an interlayer insulating film by attaching an overcoat film by a laminating method and patterning is disclosed.
However, an interlayer insulating film made of a photosensitive resin material has a problem that it has poor solvent resistance against an organic solvent-based stripping solution for stripping an etching resist.
[0012]
[Problems to be solved by the invention]
  An object of the present invention is to solve the conventional problems and achieve the following objects. That is,
  INDUSTRIAL APPLICABILITY The present invention is suitable for forming an HA type active matrix substrate constituting a high aperture (HA; hereinafter, simply referred to as “HA”) type liquid crystal display device, and is substantially colorless and transparent, and has storage stability. , Negative photosensitive thermosetting resin composition with excellent solvent resistanceThingsInterlayer insulation film that has a uniform film thickness with no coating unevenness, excellent insulation and contact hole shape accuracy, is substantially colorless and transparent, and has excellent storage stability and solvent resistance.forUsing negative photosensitive thermosetting transfer material, and negative photosensitive thermosetting transfer material, it has excellent insulation and contact hole shape accuracy, is virtually colorless and transparent, and has excellent storage stability and solvent resistance. Another object of the present invention is to provide a method for forming an interlayer insulating film suitable for forming an interlayer insulating film.
[0013]
In addition, the present invention provides a high thickness capable of stably forming an interlayer insulating film having a uniform thickness, excellent insulating properties and contact hole shape accuracy, substantially colorless and transparent, excellent in storage stability and solvent resistance. Obtained by a manufacturing method of an aperture (HA) type liquid crystal display device and a manufacturing method of the HA type liquid crystal display device, a high aperture ratio, no hue shift, excellent light transmittance, and high-definition and clear image display are possible. An object of the present invention is to provide an HA type liquid crystal display device.
[0014]
[Means for Solving the Problems]
  Means for solving the above-mentioned problems are as follows. That is,
  <1>On the support,(A) Addition-polymerizable compound having at least two ethylenically unsaturated bonds, (B) a photopolymerization initiator, (C) a carboxyl group-containing alkali-soluble resin, and (D) light and / or heat. Contains a compound that generates a non-volatile acid and (E) a crosslinking agent that can be cross-linked with an acid.A negative-type photosensitive thermosetting transfer material for an interlayer insulating film, comprising a photosensitive thermosetting resin layer, wherein at least the photosensitive thermosetting resin layer is transferred and used as an interlayer insulating filmIt is.
[0016]
  <2> A gate signal line for transmitting a control signal, a source signal line for transmitting a video signal, and an intersection of the signal lines are allocated on the transparent substrate so as to be joined to the signal line. A method of forming the interlayer insulating film of a high-aperture active matrix substrate comprising a switching device formed in an array and an interlayer insulating film covering the switching device and a signal line,
  On the surface of the transparent substrate on the side provided with the switching device and the signal line, the <1> A negative photosensitive thermosetting transfer material, and a step of transferring at least the photosensitive thermosetting resin layer, exposing the transferred photosensitive thermosetting resin layer in a pattern, Developing and removing unexposed areas to form a substantially colorless and transparent pattern;The colorless and transparent patternA method of forming an interlayer insulating film, comprising: a step of heat-treating and curing.
[0017]
  <3> A gate signal line for transmitting a control signal and a source signal line for transmitting a video signal are formed on a transparent substrate so as to intersect with each other, and a switching device is joined to the signal line at the intersection of the signal lines. An active matrix substrate formed in an array, a counter substrate disposed opposite to the active matrix substrate, and a liquid crystal layer interposed between the active matrix substrate and the counter substrate, and on the active matrix substrate In the method of manufacturing a high aperture type liquid crystal display device provided with an interlayer insulating film that covers the switching device and the signal line and a pixel electrode that is arranged on the interlayer insulating film, the interlayer insulating film comprises:Contains a decolorizable colorant that becomes substantially colorless upon heat treatmentProduction of a high-aperture liquid crystal display device, wherein a negative-type photosensitive thermosetting transfer material having a photosensitive thermosetting resin layer is formed by transferring the photosensitive thermosetting resin layer by a laminating method Is the method.
[0018]
  <4>A gate signal line for transmitting a control signal and a source signal line for transmitting a video signal are formed on a transparent substrate so as to intersect with each other, and a switching device is joined and allocated to the intersection of the signal lines to form an array. An active matrix substrate, a counter substrate disposed opposite to the active matrix substrate, and a liquid crystal layer interposed between the active matrix substrate and the counter substrate, and a switching device on the active matrix substrate In the method of manufacturing a high aperture type liquid crystal display device provided with an interlayer insulating film that covers the signal line and a pixel electrode that is arranged on the interlayer insulating film, the interlayer insulating film is formed according to <1>. DescribedNegative photosensitive thermosettingsexPhotosensitive thermosetting resin layer of transfer materialIt is formed by transferring by a laminating methodThis is a method of manufacturing a high aperture type liquid crystal display device.
  <5>The photosensitive thermosetting resin layer contains a decolorizable colorant that becomes substantially colorless by heat treatment.<4> A method for manufacturing a high aperture type liquid crystal display device according to <4>.The
[0019]
DETAILED DESCRIPTION OF THE INVENTION
  Of the present inventionFor interlayer insulation filmNegative photosensitive thermosettingTransfer materialIs used for forming HA type active matrix substrateThe abovePhotosensitive thermosetting resinlayerComprising. In the method for forming an interlayer insulating film of the present invention, the negative photosensitive thermosetting transfer material of the present invention is used. In the method for manufacturing a high aperture (HA) type liquid crystal display device of the present invention, an interlayer insulating film is formed by transferring a negative photosensitive thermosetting transfer material onto an active matrix substrate by a laminating method. The HA type liquid crystal display device of the present invention is obtained by the method for manufacturing the HA type liquid crystal display device of the present invention.
  Hereinafter, the manufacturing method of the high aperture (HA) type liquid crystal display device of the present invention will be described in detail, and the HA type liquid crystal display device of the present invention will be described.,NeThe ga-type photosensitive thermosetting transfer material and the method for forming the interlayer insulating film will also be described in detail.
[0020]
<Method for Forming Interlayer Insulating Film and Method for Manufacturing HA Type Liquid Crystal Display>
[Method for forming interlayer insulating film]
First, a method for forming an interlayer insulating film according to the present invention will be described.
The method for forming an interlayer insulating film according to the present invention comprises a transparent substrate having a switching device and a signal line, that is, a negative photosensitive film according to the present invention, which will be described later, on the surface of the active matrix substrate on which the switching device and the signal line are provided. And a step of transferring at least the photosensitive thermosetting resin layer (hereinafter, also referred to as “transfer step”) and patterning the transferred photosensitive thermosetting resin layer. A step of forming a substantially colorless and transparent pattern by removing the unexposed portion by alkaline development and alkali development (hereinafter sometimes referred to as (patterning step)), and a step of curing the exposed portion by heat treatment (Hereinafter, also referred to as (heat treatment step)), and an interlayer insulating film patterned into a desired shape is formed on the transparent substrate.
In the present invention, “substantially colorless and transparent” means that there is no coloring that lowers the color purity of the three primary colors and the light transmittance is excellent. The same applies to the following.
[0021]
Hereinafter, an example of manufacturing an HA type active matrix substrate by forming an interlayer insulating film on an active matrix substrate by the method of forming an interlayer insulating film of the present invention will be described with reference to FIG. (The switching device is not shown). FIG. 2 is a schematic process diagram for explaining a process of forming an interlayer insulating film.
[0022]
First, a transparent substrate and an active matrix substrate provided with a switching device such as a thin film transistor on the transparent substrate are prepared. For example, in the latter case, as shown in FIG. 2- (A), a thin film of metal or nonmetal is loaded on the transparent substrate 21 by sputtering of a semiconductor, a resistor or a conductor by a conventional method, or by a CVD method, By combining photolithography, a TFT array and a drain signal line 22 connected to the TFT array are formed (by Suzuki Yasuji, Introduction to Liquid Crystal Display Engineering, p. 28-36, published by Nikkan Kogyo Shimbun, 1998) An active matrix substrate is obtained. Hereinafter, it is referred to as an active matrix substrate 21 '.
[0023]
The transparent substrate can be appropriately selected from light transmissive and insulating substrates, such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, etc. And known glass plates or plastic films.
[0024]
(Transfer process)
Subsequently, using the negative photosensitive thermosetting transfer material of the present invention having a photosensitive thermosetting resin layer, as shown in FIG. 2- (B), photosensitivity of the negative photosensitive thermosetting transfer material. The photosensitive thermosetting resin layer is superposed so as to be in contact with the surface of the active matrix substrate 21 ′ obtained above from which the TFT array 10 is provided, and the photosensitive thermosetting resin layer is formed on the active matrix substrate 21 ′. 23 is transferred by a laminating method to form an interlayer insulating film 23.
[0025]
Here, if necessary, a known silane coupling treatment step may be provided for the purpose of improving the adhesion to the active matrix substrate 21 ′.
As a method for the silane coupling treatment, the substrate is dipped in an aqueous solution of silane coupling agent having a concentration of 0.1 to 10% by mass at room temperature to 50 ° C. for several seconds to several minutes, and then washed with water and dried. As the conditions for the treatment, it is preferable that the concentration of the silane coupling agent aqueous solution is 1 to 5% by mass and dip for several minutes at room temperature to 30 ° C.
Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
[0026]
(Patterning process)
Subsequently, as shown in FIG. 2C, UV exposure is performed through a photomask 24 for forming a recess (contact hole) for interlayer connection at an arbitrary position on the drain signal line 22.
The exposure amount is preferably 3 to 10 times the minimum exposure amount required for the interlayer insulating film 23 to be cured, and the exposure method is not particularly limited, and for example, a proximity exposure method is preferable. . In the case of the proximity exposure method, the proximity gap amount is preferably 40 to 150 μm.
Subsequently, as shown in FIG. 2D, by developing with an alkaline developer, when the unexposed portion is dissolved and removed, a recess 25 is formed and patterned.
[0027]
(Heat treatment process)
Thereafter, as shown in FIG. 2E, the contact hole 25 is baked at a temperature of 150 ° C. or more for 10 to 150 minutes to cause a melt flow after the exposure, thereby forming the concave portion 25 with a smooth inclination angle. Form. In this heat treatment step, the curing reaction further proceeds at the exposed portion of the photosensitive photocurable resin layer, and is cured in the shape shown in FIG.
[0028]
Subsequently, as shown in FIG. 2- (F), an ITO film 26 is formed by a sputtering method usually at a temperature of 180 to 250 ° C. The thickness of the ITO film 26 is usually preferably 1500 to 2500 mm (0.15 to 0.25 μm).
[0029]
Subsequently, as shown in FIG. 2G, for patterning of the ITO film 26, an ITO film etching photoresist 28 is coated on the entire surface of the ITO film, dried, and then patterned with an ITO film pattern mask 27. UV light is radiated through. Here, the thickness after coating and drying of the photoresist 28 is preferably about 1 μm to about 3 μm.
After UV irradiation, as shown in FIG. 2- (H), development is performed and the irradiated portion of the photoresist is dissolved and removed.
[0030]
Subsequently, as shown in FIG. 2- (I), the ITO film 26 in a region not covered with the photoresist is dissolved and removed by an acidic etching solution such as a normal iron chloride / hydrochloric acid mixture or hydrobromic acid aqueous solution. Then, the photoresist is removed by a resist stripping solution, and the HA type active matrix substrate 30 can be manufactured.
[0031]
Examples of the resist stripping solution include those described in JP-A-51-72503, JP-A-57-84456, US Pat. No. 4,165,294, European Patent 0119337, JP-A-6-222573, and the like. A typical resist stripping solution is a 7: 3 (mass ratio) mixture of monoethanolamine and dimethyl sulfoxide.
[0032]
Stripping of the photoresist is usually performed by immersing in a resist stripping solution at a temperature of 50 to 80 ° C. for 2 to 10 minutes. Here, the exposed portion of the photosensitive thermosetting resin layer needs to have sufficient solvent resistance with respect to the resist stripping solution. If the solvent resistance is insufficient, the ITO film patterned on the interlayer insulating film may be detached. In addition, the interlayer insulating film needs to have a desired insulating property, and the dielectric constant of the interlayer insulating film is preferably 4 or less from the viewpoint of realizing a thin and sufficient insulating property. 5 or less is more preferable.
[0033]
As described above, the negative type photosensitive thermosetting transfer material of the present invention, which will be described later, is used and transferred by a laminating method to form an interlayer insulating film. Therefore, even when covering the switching device and the signal line on the substrate, it is sufficient. It is possible to obtain an interlayer insulating film that can ensure insulation, is substantially colorless and transparent, and has excellent storage stability and solvent resistance. In addition, the contact hole can be formed with high accuracy.
[0034]
[Method for Manufacturing HA Type Liquid Crystal Display Device]
In the method of manufacturing a high aperture (HA) type liquid crystal display device of the present invention, a gate signal line for transmitting a control signal and a source signal line for transmitting a video signal are formed to intersect, and switching is performed at the intersection of the signal lines. A negative photosensitive thermosetting having a photosensitive thermosetting resin layer to cover the switching device and the signal line, particularly for the active matrix substrate in which the apparatus is joined and arranged with the signal line. A mold transfer material is bonded by a laminating method, and the photosensitive thermosetting resin layer is transferred and pasted onto the active matrix substrate (transfer process), exposed in a pattern, and alkali-developed (patterning process) After that, the interlayer insulating film is formed by heat treatment and curing (heat treatment step). In the active matrix substrate, a plurality of gate signal lines and a plurality of source signal lines may intersect, and switching devices may be arranged in a matrix at a plurality of intersecting portions.
[0035]
In the method of manufacturing the HA type liquid crystal display device of the present invention, the fabrication of the HA type active matrix substrate is performed in the same steps as the interlayer insulating film forming method of the present invention described above (that is, transfer step, patterning step, heat treatment). For example, the HA type active matrix substrate constituting the HA type liquid crystal display device can be manufactured by the steps shown in FIGS. 2- (A) to (I). However, in the method for producing the HA type liquid crystal display device of the present invention, the negative photosensitive thermosetting transfer material is not particularly limited and can be appropriately selected.
Then, for example, after the HA type active matrix substrate 30 shown in FIG. 2 (I) is manufactured, the counter substrate is disposed so as to be opposed to the interlayer insulating film 23 and the ITO film 26 of the substrate while maintaining a certain space. The liquid crystal display device of the present invention can be manufactured by enclosing a liquid crystal material in the space and interposing a liquid crystal layer.
[0036]
In the method for producing the HA type liquid crystal display device of the present invention, before curing, 1) lamination on an active matrix substrate, 2) image formability (photographic property), 3) heat flow property after image formation, 4) It has curability (heat resistance) after heat flow, and after curing, the interlayer insulating film on the substrate has 5) solvent resistance to resist stripping solution, 6) insulation, 7) colorless transparency, etc. It is necessary.
From the viewpoint of satisfying the above 1) to 7), the interlayer insulating film constituting the HA type active matrix substrate preferably contains the negative type photosensitive thermosetting resin composition of the present invention. Therefore, the negative photosensitive thermosetting transfer material of the present invention described later is particularly preferable among the negative photosensitive thermosetting transfer materials used.
[0037]
Below, an example of the concrete manufacturing method of a HA type liquid crystal display device is shown.
(Preparation)
First, as a substrate, a plurality of gate signal lines that transmit control signals and a plurality of source signal lines that transmit video signals are formed to intersect, and a switching device such as a thin film transistor (TFT) is formed at a plurality of intersecting intersections. An active matrix substrate is prepared, which is bonded and allocated to the signal lines and arranged in a matrix.
As described above, each signal line, TFT, etc. is formed by stacking thin films of metals and nonmetals by sputtering of semiconductors, resistors and conductors by conventional methods, and CVD methods, and combining TFTs by combining photolithography. A drain signal line connected to this is formed (Suzuki Hachiji, Introduction to Liquid Crystal Display Engineering, p. 28-36, published by Nikkan Kogyo Shimbun, 1998).
[0038]
(Transfer process)
Using a negative photosensitive thermosetting transfer material having a photosensitive thermosetting resin layer on a support, the surface of the negative photosensitive thermosetting resin layer is provided on the side where the TFT of the active matrix substrate is provided. The layers are superposed so as to come into contact with the surface, and in a superposed state, they are brought into close contact under heat and pressure with a laminator. Further, the support is peeled off, and a photosensitive thermosetting resin layer is laminated and transferred onto the active matrix substrate.
[0039]
The temperature of the thermocompression-bonding roll during transfer is preferably 50 to 150 ° C., and the linear pressure of the thermocompression-bonding roll is preferably 5 to 25 Kg / cm. Moreover, as a conveyance speed of a thermocompression-bonding roll, 0.2-4 m / min is preferable.
Especially, the conditions of the temperature of a thermocompression-bonding roll are 130-140 degreeC, a linear pressure is 10-15 kg / cm, and a conveyance speed is 1-3 m / min.
[0040]
(Patterning process)
After the photosensitive thermosetting resin layer is laminated and transferred onto the active matrix substrate, the photosensitive thermosetting resin layer is irradiated with light through a mask having a predetermined pattern and developed with a developer. A pattern is formed by removing an unirradiated portion.
As the light to be irradiated, for example, g-line (wavelength 436 nm), i-line (wavelength 365 nm), continuous and / or bright line from a known light source such as an ultra-high pressure mercury lamp, xenon lamp, carbon arc lamp, argon laser, etc. And ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Among these, g-line, i-line, and ultraviolet rays in the region of 300 to 440 nm including these are preferable.
Moreover, you may use together the optical filter etc. of the light transmittance of 2% or less in the wavelength range of 400 nm or more as described in Unexamined-Japanese-Patent No. 6-59119.
[0041]
Examples of the developer include a dilute aqueous solution of an alkaline substance, and a developer to which a small amount of an organic solvent miscible with water may be added. Examples of the alkaline substance include alkali metal hydroxides (for example, sodium hydroxide and potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate and the like), alkali metal bicarbonates (for example, Sodium bicarbonate, potassium bicarbonate, etc.), alkali metal silicates (eg, sodium silicate, potassium silicate, etc.), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate, etc.), ammonia, ethylamine, n-propylamine, diethylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylamine) Monium hydroxide, tetraethylammonium hydroxide, etc.), pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, phosphorus Examples include trisodium acid.
[0042]
The concentration of the alkaline substance in the developer is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.
[0043]
Examples of the water-miscible organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, Examples include benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone.
[0044]
As a density | concentration of the organic solvent miscible with water in the said developing solution, 0.1-30 mass% is common.
A known surfactant can also be added to the developer. The concentration of the surfactant is preferably 0.01 to 10% by mass.
[0045]
The developer may be used as a bath solution or a spray solution, and examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, and a spray method.
The temperature of the developer is usually preferably in the range of about room temperature to 40 ° C.
[0046]
In order to remove the development scum in the exposed area, a method such as rubbing with a rotating brush in the developer or rubbing with a wet sponge, or a method utilizing the spray pressure when the developer is sprayed is preferable.
It is also possible to put a water washing step after the development processing.
After the development process, the patterned interlayer insulating film is rinsed by, for example, running water cleaning, and further cured by baking the film with a heating device such as a hot plate or oven.
[0047]
As a calcination temperature in the curing treatment, for example, 150 to 250 ° C. is suitable, and as a calcination time, for example, 5 to 90 minutes (in the case of calcination on a hot plate, calcination in an oven for 5 to 30 minutes) 30 to 90 minutes) is preferable.
As described above, an interlayer insulating film excellent in solvent resistance and transparency can be formed on the surface of the active matrix substrate.
[0048]
Further, the negative photosensitive thermosetting transfer material used in the method for manufacturing the HA type liquid crystal display device of the present invention has irregularities on the surface of the material to be transferred as described in JP-B-2794242 and JP-A-10-97061. Due to the presence of the transfer material, it may be a transfer material having a multilayer structure capable of avoiding the problem that bubbles are generated during high-speed lamination between the substrate and the photosensitive thermosetting resin layer during transfer. That is, the multi-layered transfer material is obtained by, for example, a method similar to that described in JP-A-10-97061, on a support, an alkali-soluble thermoplastic resin layer, an intermediate layer, and the negative photosensitive heat-sensitive material of the present invention. A multilayer negative photosensitive thermosetting, in which a photosensitive thermosetting resin layer containing a curable composition is applied and formed in this order, and a protective film is laminated on the photosensitive thermosetting resin layer as necessary. Transferable materials can also be suitably used.
[0049]
The layer thickness of the photosensitive curable resin layer provided on the alkali-soluble thermoplastic resin layer and the intermediate layer can be appropriately selected according to the purpose, and is specifically as described above.
[0050]
As described above, the interlayer insulating film of the HA type active matrix substrate constituting the HA type liquid crystal display device is transferred and formed by a laminating method, and the transferred layer is processed to form a contact hole. Thus, an interlayer insulating film having a uniform thickness can be formed. As a result, even when the switching device and the signal line on the substrate are covered, sufficient insulation can be ensured and a contact hole with high shape accuracy can be formed. In addition, it is possible to obtain an interlayer insulating film that is substantially colorless and transparent and has excellent storage stability and solvent resistance.
[0051]
<Negative photosensitive thermosetting resin composition>
The negative photosensitive thermosetting resin composition of the present invention comprises (A) an addition-polymerizable compound having at least two ethylenically unsaturated bonds, (B) a photopolymerization initiator, and (C) a carboxyl group. Containing an alkali-soluble resin, (D) a compound that generates a non-volatile acid by light and / or heat, and (E) a cross-linking agent that can be cross-linked with an acid. May be included.
[0052]
(A) Addition-polymerizable compound having at least two ethylenically unsaturated bonds
The addition-polymerizable compound having at least two ethylenically unsaturated bonds (hereinafter sometimes referred to simply as “addition-polymerizable compound”) is a carboxyl which is component (C) described below before the polymerization reaction. If the polymerization is carried out by receiving radiation without impairing the solubility of the group-containing alkali-soluble resin in the aqueous alkali solution, the solubility in the aqueous alkali solution together with the component (C) is reduced.
[0053]
Hereinafter, the addition polymerizable compound used in the present invention will be described in detail.
The addition polymerizable compound can be appropriately selected from compounds having two or more terminal ethylenically unsaturated bonds in one molecule. For example, a monomer, a prepolymer (that is, a dimer, a trimer, and an oligomer). Etc.) or mixtures thereof, and those having a chemical structure such as copolymers thereof.
[0054]
Examples of the monomer and copolymer thereof include esters of unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds, Examples include amides of saturated carboxylic acids and aliphatic polyvalent amine compounds.
[0055]
Specific examples of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene. Glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, etc. And
[0056]
Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate. Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy -2-hydroxy Propoxy) phenyl] dimethyl methane, bis [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like,
Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaco And sorbitol tetritaconate.
[0057]
Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
Furthermore, the mixture of these ester can also be mentioned.
[0058]
Specific examples of the amide of the unsaturated carboxylic acid and the aliphatic polyvalent amine compound include, for example, methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis- Examples include methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
[0059]
In addition, for example, a vinyl monomer containing a hydroxyl group represented by the following general formula (I) was added to a polyisocyanate compound having two or more isocyanate groups per molecule described in JP-B-48-41708. Examples thereof include vinyl urethane compounds having two or more polymerizable vinyl groups in one molecule.
CH₂= C (R) COOCH₂CH (R¹) OH ... General formula (I)
[However, R and R¹Are each independently a hydrogen atom or CH_ThreeRepresents. ]
[0060]
Further, urethane acrylates described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and epoxy resins And polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting (meth) acrylic acid. Furthermore, what was introduced as a photocurable monomer and oligomer in the Japan Adhesion Association magazine vol.20, No.7, p.300-308 (1984) can also be used.
[0061]
The above addition polymerizable compounds may be used singly or in combination of two or more.
The content of the addition-polymerizable compound having at least two ethylenically unsaturated bonds is preferably 20 to 80% by mass of the total solid content (mass) of the negative photosensitive thermosetting resin composition, 30 -60 mass% is more preferable.
[0062]
(B) Photopolymerization initiator
The photopolymerization initiator is capable of substantially starting the photopolymerization reaction of the addition polymerizable compound as the component (A).
As the photopolymerization initiator, any compound having the ability to initiate the polymerization reaction of the aforementioned (A) addition polymerizable compound can be used, and among these, photosensitivity to ultraviolet light ( Those having photosensitivity are preferred. Moreover, in this invention, the activator which acts with a photoexcited sensitizer and produces | generates an active radical may be sufficient.
[0063]
Particularly suitable photopolymerization initiators include, for example, halogenated hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, ketoxime ethers, and the like.
Of these, halogenated hydrocarbons having a triazine skeleton, ketoxime compounds, and hexaarylbiimidazoles are particularly preferable from the viewpoints of high sensitivity, excellent storage stability, and good adhesion of the coating film to the substrate.
[0064]
Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, Bull. Chem. Soc. Japan, Wakabayashi et al., 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) ) -4,6-bis (trichloromethyl) -s-triazine and the like;
[0065]
Compounds described in GB 1388492, for example 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-s-triazine and the like;
Compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho) -1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -s -Triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloro) Methyl) -s-triazine and the like;
[0066]
Compounds described in DE 33 37 024, for example 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-methoxystyrylphenyl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloro Methyl) -s-triazine, 2- (4-thiophene-2-vinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-furan-2-vinylenephenyl) -4,6-bis (trichloromethyl) -s-to Azine, 2- (4-benzofuran-2-vinylene) -4,6-bis (trichloromethyl) -s-triazine and the like;
Can be mentioned.
[0067]
Also, according to F. C. Schaefer et al. Org. Chem. 29, 1527 (1964), such as 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2-amino-4-methyl-6-tribromomethyl-s-triazine, 2-methoxy-4-methyl-6-trichloromethyl-s-triazine etc;
[0068]
Compounds described in JP-A-62-58241, for example, 2- (4-phenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-naphthyl-1-acetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-tolylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-methoxyphenyl) Acetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-isopropylphenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- p-ethylphenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine and the like;
[0069]
Compounds described in JP-A-5-281728, such as 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-difluorophenyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-dibromophenyl) -4 , 6-bis (trichloromethyl) -s-triazine and the like;
2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine described in JP-A-5-34920;
Etc. can also be mentioned.
[0070]
Examples of the ketoxime compound include compounds represented by the following general formula (II).
[Chemical 1]

[0071]
In general formula (II), R²And R^ThreeEach independently represents a hydrocarbon group which may have a substituent or an unsaturated bond, or a heterocyclic group, which may be the same or different. R^FourAnd R^FiveEach independently represents a hydrogen atom, a substituent or a hydrocarbon group optionally having an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, or a substituted thio group, May be different. R^FourAnd R^FiveMay be bonded to each other to form a ring, and the bonded R^FourAnd R^FiveAre -O-, -NR as the linking main chain of the ring⁶-, -O-CO-, -NH-CO-, -S-, and / or -SO.₂-Represents an alkylene group having 2 to 8 carbon atoms which may contain-. R⁶And R⁷Each independently represents a hydrogen atom, a substituent or a hydrocarbon group optionally having an unsaturated bond, or a substituted carbonyl group.
[0072]
Examples of the compound represented by the general formula (II) include p-methoxyphenyl 2-N, N-dimethylaminopropyl ketone oxime-O-allyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O. Allyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-O-benzyl ether, p-methylthiophenyl 2-morpholinopropyl ketone oxime-On-butyl ether, p-morpholinophenyl-2-morpholinopropyl Ketone oxime-O-allyl ether, p-methoxyphenyl-2-morpholinopropyl ketone oxime-O-n-dodecyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxyethoxyethyl ether, - methylthiophenyl-2-morpholinopropyl ketone oxime -O-p-methoxycarbonyl benzyl ether,
[0073]
p-methylthiophenyl-2-morpholinopropylketone oxime-O-methoxycarbonylmethyl ether, p-methylthiophenyl-2-morpholinopropylketone oxime-O-ethoxycarbonylmethyl ether, p-methylthiophenyl-2-morpholinopropyl Ketone oxime-O-4-butoxycarbonylbutyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-2-ethoxycarbonylethyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxycarbonyl -3-propenyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-benzyloxycarbonylmethyl ether, and the like. However, the present invention is not limited to these.
[0074]
Examples of the hexaarylbiimidazole include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'- Tiger biimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4 ', 5,5'-tetraphenyl biimidazole.
The hexaarylbiimidazoles are described in, for example, Bull. Chem. Soc. Japan, 33, 565 (1960) and Org. Chem., 36 (16) 2262 (1971) can be easily synthesized.
[0075]
Examples of the ketoxime ether include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3- ON, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminotan-2-one, 2-ethoxycarbonyl And oxyimino-1-phenylpropan-1-one.
[0076]
The said polymerization initiator may be used individually by 1 type, and may use multiple in the same type, or multiple in different types.
As content of the said polymerization initiator, 0.1-50 mass% of the total solid (mass) of a negative photosensitive thermosetting resin composition is preferable, and 0.5-30 mass% is more preferable.
[0077]
(C) Carboxyl group-containing alkali-soluble resin
The carboxyl group-containing alkali-soluble resin (hereinafter, sometimes simply referred to as “alkali-soluble resin”) is a copolymer of a carboxyl group-containing monomer and a carboxyl group-free monomer, celluloses, PVA, etc. This resin is obtained by a polymer reaction and is soluble in a weak alkaline aqueous solution.
[0078]
Examples of the alkali-soluble resin soluble in the weak alkaline aqueous solution include known polymer binders used for alkali-soluble photopolymerizable resins. Specifically, (meth) acrylic acid and (meth) Copolymers with acrylic acid alkyl esters (alkyl groups such as methyl, ethyl and butyl groups), poly (meth) acrylic acid, styrene and unsaturated dibasic acid anhydrides such as maleic anhydride Examples thereof include a polymer and a reaction product of the copolymer and an alcohol or a polybasic acid anhydride of cellulose.
[0079]
Among the above, in the present invention, styrene / maleic anhydride copolymer, methyl methacrylate / methacrylic acid / 2-ethylhexyl methacrylate / benzyl methacrylate quaternary copolymer described in JP-A-60-258539 Styrene / maleic acid mono-n-butyl ester copolymer described in JP-B-55-38961, and quaternary styrene / methyl methacrylate / ethyl acrylate / methacrylic acid described in JP-B-54-25957 Copolymer, benzyl methacrylate / methacrylic acid copolymer described in JP-A-52-99810, ternary copolymer of acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid described in JP-B-58-12777 Coalescence, methyl methacrylate / ethyl acrylate described in JP-B-55-6210 / Terpolymer and two isopropanol portion esterified styrene / maleic anhydride copolymer of acrylic acid, and the like preferably.
[0080]
As the alkali-soluble resin, one having an acid value of 50 to 300 mgKOH / 1 g and a weight average molecular weight of 1000 to 300,000 is usually selected.
When the acid value is less than 50 mgKOH / 1 g, the alkali developability may be greatly lowered, and when it exceeds 300 mgKOH / 1 g, it may be difficult to obtain a light-shielding image having a high density.
Moreover, as a weight average molecular weight of the said alkali-soluble resin, 10,000-250,000 are especially preferable. When the weight average molecular weight is less than 1000, it may be difficult to form a high-density light-shielding image, and when it exceeds 300,000, developability may be extremely lowered.
[0081]
The carboxyl group-containing alkali-soluble resin may be used alone or in combination of two or more.
As content of the said carboxyl group-containing alkali-soluble resin, 10-80 mass% of the total solid (mass) of a negative photosensitive thermosetting resin composition is preferable, and 20-60 mass% is more preferable.
Further, from the viewpoint of keeping the contact hole shape in a mortar shape, the mass ratio (A / C) of the component (A) to the component (C) is preferably 0.5 to 0.9.
[0082]
(D) Compound that generates non-volatile acid by light and / or heat
The compound that generates a non-volatile acid by light and / or heat (hereinafter sometimes referred to as “acid generating compound”) is a compound that generates an acid by applying at least one of exposure and heating. The acid generator compound includes (1) an iodonium salt represented by the following general formula (III), (2) a sulfonium salt represented by the following general formula (IV), and (3) a general formula (V) described later. (4) an iminosulfonate derivative represented by the general formula (VI) described later, and (5) an o-nitrobenzyl photoacid generator represented by the general formula (VII) described below. It is mentioned in.
[0083]
First, (1) an iodonium salt represented by the following general formula (III) and (2) a sulfonium salt represented by the general formula (IV) will be described.
[Chemical formula 2]

[0084]
In general formula (III), Ar¹And Ar²Each independently represents a substituted or unsubstituted aryl group. Examples of the substituent of the substituted aryl group include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom. Can be mentioned.
[0085]
R in general formula (IV)²⁰³, R²⁰⁴, R²⁰⁵Each independently represents a substituted or unsubstituted alkyl group or aryl group. As said alkyl group and aryl group, a C1-C8 alkyl group, a C6-C14 aryl group, and these substituted derivatives are respectively preferable.
Examples of the substituent of the substituted alkyl group include an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group. Examples of the substituent of the substituted aryl group substituted include Examples thereof include an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group, and a halogen atom.
[0086]
Z in the general formulas (III) and (IV)^-Represents a counter anion, for example, BF_Four ^-, AsF₆ ^-, PF₆ ^-, SbF₆ ^-, SiF₆ ^2-, ClO_Four ^-, CF_ThreeSO_Three ^-Examples thereof include perfluoroalkanesulfonic acid anions, such as perfluoroalkanesulfonic acid anions, condensed polynuclear aromatic sulfonic acid anions such as naphthalene-1-sulfonic acid anion, anthraquinonesulfonic acid anions, and sulfonic acid group-containing dyes. However, it is not limited to these.
R²⁰³, R²⁰⁴, R²⁰⁵Two of these and Ar¹And Ar²May each be bonded via a single bond or a substituent.
[0087]
Specific examples of the compound represented by the general formula (III) or (IV) are shown below. However, the present invention is not limited to these.
For example, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroantimonate, diphenyliodonium trifluoromethanesulfonate, phenyl (p-methoxyphenyl) iodonium hexafluorophosphate, phenyl (p- Methoxyphenyl) iodonium hexafluoroantimonate, bis (m-nitrophenyl) iodonium hexafluorophosphate, phenyl (p-nitrophenyl) iodonium trifluoromethanesulfonate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (m , P-dimethylphenyl) iodonium hexafluoroa Chimoneto, bis (p-n-heptyl phenyl) iodonium hexafluorophosphate, bis (p- chlorophenyl) iodonium hexafluorophosphate, bis (p- trifluoromethyl phenyl) iodonium trifluoromethanesulfonate,
[0088]
Bis (m-methoxycarbonylphenyl) iodonium hexafluorophosphate, bis (o, p-dichlorophenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) ) Iodonium hexafluorophosphate, dibenziodonium hexafluorophosphate, 1-chloro-dibenziodonium trifluoromethanesulfonate, bis (1-naphthyl) iodonium trifluoromethanesulfonate, diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate, bis ( p-tert-pentylphenyl) iodonium 9,10-dimethoxyanthracene-2-sulfonate, dipheny Iodonium 4-ethoxynaphthalene-1-sulfonate, diphenyliodonium 1-anilinonanaphthalene-7-sulfonate, bis (pn-pentylphenyl) iodonium pyrene-2-sulfonate, bis (p-chlorophenyl) iodonium anthraquinone-2-sulfonate Diphenyliodonium 3-methoxybenzophenone-2-sulfonate,
[0089]
Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium pentafluoro Benzenesulfonate, bis (p-ethoxyphenyl) -p-tolylsulfonium trifluoromethanesulfonate, bis (p-chlorophenyl) -p-methoxyphenylsulfonium trifluoromethanesulfonate, p-hydroxyphenyl-dimethylsulfonium hexafluorophosphate, 3,5- Dimethyl-4-hydroxypheny Dimethylsulfonium hexafluoroantimonate, p-hydroxyphenyltetrahydrothiophenium tetrafluoroborate, 3,5-dimethoxy-4-hydroxyphenyltetrahydrothiophenium trifluoromethanesulfonate, 3,5-di (n-butyl) -4- Hydroxyphenyltetrahydrothiophenium hexafluorophosphate,
[0090]
4-hydroxy-2-methylphenylhexahydrothiopyridinium tetrafluoroborate, 3,5-dimethyl-4-hydroxyphenyl-1,4-oxathianium trifluoromethanesulfonate, phenyldibenzothiophenium hexafluoroarsenate, phenyl Dibenzothiophenium perfluorooctane sulfonate, phenacyldimethylsulfonium hexafluoroantimonate, phenacyltetrahydrothiophenium hexafluorophosphate, phenacyltetrahydrothiophenium hexafluoroarsenate, m-chlorophenacyltetrahydrothiophene Nium hexafluoroarsenate, phenacylhexahydrothiopyridium hexafluorophosphate, 2-naphthoylmethyltetrahydro Off E hexafluoroarsenate, Fenashiruji (n- butyl) sulfonium hexafluorophosphate, diphenyl (4-phenylthiophenyl) sulfonium octane sulfonate, diphenyl (4-phenylthiophenyl) sulfonium hexafluoroantimonate,
[0091]
1,4-thiobisphenylene-bis-diphenylsulfonium trifluoromethanesulfonate, 1,4-thiobisphenylene-bis-diphenylsulfonium hexafluoroarsenate, triphenylsulfonium-9,10-dimethoxyanthracene-2-sulfonate, bis (P-Ethoxyphenyl) -p-tolylsulfonium pentafluorobenzenesulfonate, chloromethylmethylphenylsulfonium anthracene-1-sulfonate, phenacyltetrahydrothiophenium pentafluorosulfonate, triphenylsulfonium-1-anilinonaphthalene-7 -Sulfonates and the like.
[0092]
The onium salts represented by the general formulas (III) and (IV) are known, for example, J. Org. W. Knapczyketal, J. et al. Am. Chem. Soc. 91, 145 (1969), A.A. L. Maycoketal, J.M. Org. Chem. , 35, 2532, (1970), E.I. Goethasetal, Bull. Soc. Chem. Belg. 73, 546 (1964), H .; M.M. Leicester, J.M. Ame. Chem. Soc. 51, 3587 (1929); V. Crivello et al. Polym. Chem. Ed. 18, 2677 (1980), U.S. Pat. Nos. 2,807,648, 4,247,473, and JP-A-53-101,331.
[0093]
Next, (3) a disulfone derivative represented by the following general formula (V) and (4) an iminosulfonate derivative represented by the following general formula (VI) will be described.
[Chemical 3]

[0094]
In the general formula (V), Ar^ThreeAnd Ar^FourEach independently represents a substituted or unsubstituted aryl group. R in the general formula (VI)²⁰⁶Represents a substituted or unsubstituted alkyl group or aryl group, and A represents a substituted or unsubstituted alkylene group, alkenylene group or arylene group.
[0095]
Specific examples of the compound represented by the general formula (V) or (VI) are shown below. However, the present invention is not limited to these.
For example, bis (p-chlorophenyl) disulfone, bis (p-tolyl) disulfone, bis (p-methoxyphenyl) disulfone, p-tolyl (p-chlorophenyl) disulfone, bis (p-trichloromethylphenyl) disulfone, 1-naphthyl (O-chlorophenyl) disulfone, 4-ethoxy-1-naphthyl (p-chlorophenyl) disulfone, 2-naphthyl (p-chlorophenyl) disulfone, 2-naphthyl (p-tolyl) disulfone, 6-chloro-2-naphthyl (p -Methoxyphenyl) disulfone, 6-chloro-phenyl (4-methoxy-1-naphthyl) disulfone, phenyl (p-isopropylphenyl) disulfone, bis (pentafluorophenyl) disulfone, N-benzenesulfonyloxyphthalimide, Np- Torue Sulfonyloxy phthalimide,
[0096]
Np-methoxybenzenesulfonyloxyphthalimide, Np-trifluoromethylbenzenesulfonyloxyphthalimide, N-naphthalene-1-sulfonyloxyphthalimide, N-4-methoxynaphthalene-1-sulfonyloxyphthalimide, N-ethanesulfonyloxy Maleimide, N-benzenesulfonyloxymaleimide, N-benzenesulfonyloxyalphaphenylmaleimide, N-ethanesulfonyloxynaphthalimide, N-hexadecanesulfonyloxynaphthalimide, N-benzenesulfonyloxynaphthalimide, N-trifluoromethanesulfonyloxynaphthalimide N-pentafluorobenzenesulfonyloxynaphthalimide, N-tetrafluorobenzenesulfonyloxyphthalimide, It is.
[0097]
Next, (5) an o-nitrobenzyl type photoacid generator represented by the following general formula (VII) will be described.
[Formula 4]

[0098]
In the general formula (VII), R²⁰⁷, R²⁰⁸, R²⁰⁹And R²¹⁰Are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 5 to 14 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or 1 to 6 carbon atoms. A perfluoroalkyl group, a C 5-14 perfluoroaryl group, a nitro group, and a cyano group, which may be the same or different.
R²¹¹Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 14 carbon atoms, and Y represents -SO₂-R²¹²Represents. Where R²¹²Is an alkyl group having 1 to 6 carbon atoms; an aryl group having 5 to 14 carbon atoms; an aryl group having 5 to 14 carbon atoms having an alkoxy group having 1 to 6 carbon atoms; an aralkyl group having 6 to 20 carbon atoms; A cycloalkyl group having 3 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms instead of a hydrogen atom, or an aryl group having 5 to 14 carbon atoms having a fluorine atom as a substituent Represents.
[0099]
Specific examples of the compound represented by the general formula (VII) are shown below. However, the present invention is not limited to these.
For example, 2,6-dinitrobenzylbenzenesulfonate, 2,6-dinitrobenzyl p-methoxybenzenesulfonate, 2,6-dinitrobenzylperfluorobenzenesulfonate, 2,6-dinitrobenzyl p-trifluoromethylbenzenesulfonate, 2, 6-dinitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzylmethanesulfonate, 2,6-dinitrobenzyltrifluoromethanesulfonate, 2,6-dinitrobenzylnaphthalene-2-sulfonate, 2,6-dinitro-α-methylbenzyl p-methoxybenzenesulfonate, 2,6-dinitro-α-methylbenzylperfluorobenzenesulfonate, 2,6-dinitro-α-methylbenzylmethanesulfonate, 2-nitro-6-trifluoromethyl Le benzyl benzenesulfonate, 2-nitro-6-trifluoromethylbenzyl p- methoxy benzenesulfonate,
[0100]
2-nitro-6-trifluoromethylbenzyl perfluorobenzenesulfonate, 2-nitro-6-trifluoromethylbenzyl p-trifluoromethylbenzenesulfonate, 2-nitro-6-trifluoromethylbenzyl p-toluenesulfonate, 2- Nitro-6-trifluoromethylbenzylmethanesulfonate, 2-nitro-6-trifluoromethylbenzyltrifluoromethanesulfonate, 2-nitro-6-trifluoromethylbenzylnaphthalene-2-sulfonate, 2-nitro-6-trifluoromethyl -Α-methylbenzyl p-methoxybenzenesulfonate, 2-nitro-6-trifluoromethyl-α-methylbenzylperfluorobenzenesulfonate,
[0101]
2-nitro-6-trifluoromethyl-α-methylbenzyl methanesulfonate, 2-nitro-6-cyanobenzylbenzenesulfonate, 2-nitro-6-cyanobenzyl p-methoxybenzenesulfonate, 2-nitro-6-cyanobenzyl Perfluorobenzenesulfonate, 2-nitro-6-cyanobenzyl p-trifluoromethylbenzenesulfonate, 2-nitro-6-cyanobenzyl p-toluenesulfonate, 2-nitro-6-cyanobenzylmethanesulfonate, 2-nitro-6 -Cyanobenzyl trifluoromethanesulfonate, 2-nitro-6-cyanobenzylnaphthalene-2-sulfonate, 2-nitro-6-cyano-α-methylbenzyl p-methoxybenzenesulfonate, 2-nitro-6-cyano-α-methylbenzene Jill perfluoro sulfonate, 2-nitro-6-cyano--α- methylbenzyl methanesulfonate, and the like.
[0102]
In the present invention, among the above compounds that generate a non-volatile acid by light and / or heat, onium salts, disulfones, and o-nitrobenzyl type acid generators are preferred.
[0103]
The compound which generates a non-volatile acid by the light and / or heat may be used alone or in combination of two or more.
As content of the compound which generate | occur | produces a non-volatile acid by the said light and / or heat, 0.1-10 mass% of the total solid (mass) of a negative photosensitive thermosetting resin composition is preferable, 0 More preferably, the content is 5 to 5% by mass.
[0104]
(E) Crosslinker capable of crosslinking with acid
The acid-crosslinkable crosslinker (hereinafter sometimes simply referred to as “crosslinker”) is a crosslinkable agent that is crosslinkable with a suitable acid, such as partially or fully etherified polyhydroxyl Methyl melamine (for example, hexamethoxymethyl melamine etc.), the compound etc. which are represented with the following general formula (VIII) are mentioned.
[0105]
[Chemical formula 5]

[0106]
In the general formula (VIII), Z represents O, S, an alkylene group having 1 to 8 carbon atoms, for example, CH₂, C (CH_Three)₂, SO₂Etc. R represents a hydrogen atom, a lower alkyl group, or an acyl group. n represents 1 or 2.
[0107]
In the present invention, an organic carboxamide N-methylol compound, a phenol o-methylol compound, a phenol ether o-methylol compound, an aromatic hydrocarbon o-methylol compound, and the like are suitable.
Specific examples will be shown below, but the present invention is not limited thereto.
[0108]
Examples of the N-methylol compound of the organic carboxamide include N, N′-dimethylol urea, N, N′-dimethylol oxamide, N, N′-dimethylol malonamide, N, N′-dimethylol succin. Amide, N, N′-dimethylol sebacamide, N, N ′, N ″ -trimethylol citramide, 1,3-dimethylolimidazolidin-2-one, 1,3-dimethylol-4,5-dihydroxy Imidazolidin-2-one, 1,3-dimethylol perhydropyrimidin-2-one, trimethylol melamine, tetramethylol melamine, hexamethylol melamine, 1,3-dimethylol-5-methylperhydro-1,3,5 -Triazin-2-one, 1,3-dimethylol-5-allylperhydro-1,3,5-triazin-2-one, 1 , 3-Dimethylol-5-butylperhydro-1,3,5-triazin-2-one, 1,2-bis- [1,3-dimethylolperhydro-1,3,5-triazin-2-one -5-yl] ethane, tetramethylolhydrazine dicarboxamide, N, N'-dimethylol terephthalamide, N, N'-dimethylolbenzene-1,3-disulfonamide and tetramethylolglycoluril.
[0109]
Examples of the phenol, phenol ether, or aromatic hydrocarbon o-methylol compound include 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methylanisole, and 2,6-dimethylol-4-methyl. Phenol, 1,3-dimethylol-4,6-diisopropylbenzene, 2,2-bis- (4-hydroxy-3,5-dimethylolphenyl) propane, 3,3′-dimethylol-4,4′dihydroxydiphenylsulfone Etc.
[0110]
Instead of the methylol compound, for example, the corresponding methyl, ethyl or butyl ether, or an ester of acetic acid or propionic acid can be used, and the following compounds can be mentioned.
For example, 4,4′-bis-methoxymethyl diphenyl ether, tris-methoxymethyl diphenyl ether, tetrakis-methoxymethyl hydrazine dicarboxamide, tetrakis-methoxymethyl-glycoluril, tetrakis-hydroxyethoxymethyl-glycoluril, bis-acetoxymethyl diphenyl ether, hexamethoxy Methyl melamine and the like.
[0111]
Specifically, as an example of a compound in which formaldehyde is allowed to act on melamine or an alkyl-modified product thereof, Cymel (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, manufactured by Mitsui Cyanamid Co., Ltd. 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, examples of compounds in which formaldehyde is allowed to act on benzoguanamine or alkyl modified products thereof Cymel (registered trademark) 1123, 1125, 1128, and examples of a compound obtained by allowing formaldehyde to act on glycoluril or an alkyl modified product thereof include Cymel (registered trademark) 1170, 1171, 1174, 1172, Formaldehyde in urea Examples of compounds or their alkyl-modified products were allowed to act, Mitsui Cyanamid Co., Ltd. UFR (registered trademark) 65,300 can be mentioned.
[0112]
As content of the crosslinking agent which can be bridge | crosslinked with the said acid, 1-30 mass% of the total solid (mass) of a negative photosensitive thermosetting resin composition is preferable, and 2-20 mass% is more preferable.
When the content is less than 1% by mass, a thin film having a sufficient cross-linked structure may not be obtained. When the content exceeds 30% by mass, the thickness of the unirradiated part of the coating film is remarkably reduced in the development process. In addition, the transparency of the resulting coating film may be reduced.
[0113]
(F) Other ingredients
In the negative photosensitive thermosetting resin composition of the present invention, in addition to the essential components (A) to (E), a surfactant, an adhesion promoter, a decolorizable colorant for various purposes, Various additives such as a thermal polymerization inhibitor, an oxygen polymerization inhibitor, and a plasticizer can be added.
[0114]
-Surfactant-
For the purpose of improving coating properties and smoothness of the resulting coating film, a surfactant can be added, and examples thereof include fluorine-based surfactants and silicone-based surfactants. 1000 (manufactured by BM Chemie); Mega-Fac F142D, F172, F173, F173 (manufactured by Dainippon Ink and Chemicals); Fluorard FC-135, FC-170C, Fluorard FC-430, FC- 431 (manufactured by Sumitomo 3M Limited); Surflon S-112, S-113, S-131, S-141, S-145 (Asahi Glass Co., Ltd.); SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (made by Toray Silicone Co., Ltd.), etc. are mentioned.
[0115]
As addition amount of the said surfactant, 5 mass% or less of the total solid (mass) of a negative photosensitive thermosetting resin composition is preferable, and 2 mass% or less is more preferable.
[0116]
-Adhesion promoter-
In the case of forming an interlayer insulating film (photosensitive thermosetting resin layer) on an active matrix substrate using the negative photosensitive thermosetting resin composition of the present invention, for the purpose of improving the adhesion to the substrate. Adhesion promoters can be added.
A functional silane coupling agent is suitable as the adhesion promoter. Here, the functional silane coupling agent means a silane compound having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. For example, trimethoxysilylbenzoic acid, γ-methacryloxypropyl Examples include trimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. .
[0117]
As addition amount of the said adhesion promoter, 10 mass% or less of the total solid (mass) of the photosensitive thermosetting resin layer is preferable, and 0.05-5 mass% is more preferable.
[0118]
-Decolorizable colorant-
Photosensitive thermosetting resin layer formed by coating in production and use of a negative photosensitive thermosetting transfer material having a photosensitive thermosetting resin layer containing the negative photosensitive thermosetting resin composition of the present invention The photosensitive thermosetting resin layer is preferably colored so that the surface properties and coating defects of the resin can be easily inspected, and finally a substantially colorless and transparent cured image can be obtained. is required. That is, it is preferable to contain a decolorizable colorant that is decolored by heating or light irradiation, and the decolorizable colorant may be added to the negative photosensitive thermosetting resin composition.
[0119]
The decolorizable colorant itself decomposes when subjected to heat treatment for 10 to 150 minutes at a temperature of usually 150 ° C. or higher, reacts with decoloring, splashes outside the system, or reacts with other components. And the like that decompose and discolor. Specifically, in the ultraviolet region, a triphenylmethane dye having high transparency and excellent decolorization property by heat treatment is suitable. For example, crystal violet, methyl violet, ethyl violet, oil blue # 603, Victoria pure blue BOH Preferred examples include colorants described in JP-A-10-97061, JP-A-10-104827, and JP-B-3-68375, such as Malachite Green and Diamond Green.
[0120]
The addition amount of the decolorizable colorant is preferably 10% by mass or less, more preferably 0.05 to 5% by mass based on the total solid content (mass) of the photosensitive thermosetting resin layer.
[0121]
-Thermal polymerization inhibitor-
Viewpoint of avoiding unnecessary thermal polymerization of the aforementioned addition-polymerizable compound having at least two ethylenically unsaturated bonds in the step of forming the photosensitive thermosetting resin layer or during storage of the layer Therefore, it is desirable to add a small amount of a thermal polymerization inhibitor.
Examples of the thermal polymerization inhibitor include haloid quinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t). -Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), phenothiazine, N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass of the total solid content (mass) of the photosensitive thermosetting resin layer.
[0122]
-Others-
In addition to the above, for the purpose of preventing polymerization inhibition of the addition polymerizable compound due to the presence of oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added as necessary, and a photosensitive thermosetting resin layer It may be unevenly distributed on the surface of the layer in the drying process after the coating liquid for forming is applied. In this case, the higher fatty acid derivative is preferably added in an amount of 0.5 to 10% by mass based on the total solid content of the formed photosensitive thermosetting resin layer.
[0123]
For the purpose of improving the physical properties of the photosensitive thermosetting resin layer after curing, that is, the interlayer insulating film, known additives such as inorganic fillers and plasticizers may be added.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The addition amount of the plasticizer is preferably 10% by mass or less based on the total solid content (mass) of the photosensitive thermosetting resin layer.
[0124]
<Negative photosensitive thermosetting transfer material>
In the HA type liquid crystal display device, when an interlayer insulating film comprising the above-described negative photosensitive thermosetting resin composition of the present invention is formed, the means for forming the interlayer insulating film is as described above. A method of transferring and forming a photosensitive thermosetting resin layer of a transfer material by a laminating method is preferable.
Among the negative photosensitive thermosetting transfer materials satisfying the above 1) to 7), the support has a photosensitive thermosetting resin layer containing the negative photosensitive thermosetting resin composition of the present invention on the support. A negative photosensitive thermosetting transfer material is preferred.
[0125]
The negative photosensitive thermosetting transfer material of the present invention has at least a photosensitive thermosetting resin layer containing the negative photosensitive thermosetting resin composition of the present invention, and an alkali-soluble heat as necessary. It has other layers, such as a plastic resin layer, an intermediate | middle layer, and a protective film.
[0126]
-Photosensitive thermosetting resin layer-
The photosensitive thermosetting resin layer includes the above-described negative photosensitive thermosetting resin composition of the present invention, and includes other components as necessary, for example, photosensitive thermosetting. Coating liquid for forming a resin layer (hereinafter, simply referred to as “photosensitive thermosetting resin layer coating liquid”).
), And the coating solution is coated on a support and dried.
[0127]
(Preparation of coating solution for photosensitive thermosetting resin layer)
The photosensitive thermosetting resin layer comprises the above-described component (A), component (B), component (C), component (D), constituting the negative photosensitive thermosetting resin composition of the present invention. By coating and drying the coating solution on a support using a solution prepared by uniformly dissolving and mixing component (E) and, if necessary, other components (F) in an organic solvent. Can be formed.
[0128]
The organic solvent can be appropriately selected as long as it can dissolve the components (A) to (E) and (F) and other components and does not react with these components.
Specifically, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve acetate, ethyl Ethylene glycol alkyl ether acetates such as cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether;
[0129]
Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3- Examples include esters such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, and butyl acetate.
The said organic solvent may be used individually by 1 type, and may be used together in combination of 2 or more type.
[0130]
Among the above, glycol ethers such as ethylene glycol dimethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; ethyl 2-hydroxypropionate, 3- Preferred are esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate; diethylene glycols such as diethylene glycol dimethyl ether; and the like.
[0131]
A high boiling point solvent may be added together with the organic solvent. Examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, carbonic acid Examples include propylene and phenyl cellosolve acetate.
[0132]
(Preparation of negative photosensitive thermosetting transfer material)
The photosensitive thermosetting resin layer coating solution prepared as described above is applied directly to the surface of the support, and the solvent is usually removed by heating and drying in an oven, so that the negative photosensitive thermosetting A coating film containing the resin composition, that is, a photosensitive thermosetting resin layer is formed. Here, the photosensitive thermosetting resin layer coating solution may be used after being filtered using, for example, a microfiltration filter having a pore diameter of 0.2 μm. Further, in some cases, a protective film may be bonded onto the photosensitive thermosetting resin layer.
[0133]
The coating method of the photosensitive thermosetting resin layer coating solution is not particularly limited. For example, spray method, roll coating method, spin coating method, slit coating method, extrusion coating method, curtain coating method, die coating method, wire Well-known methods, such as a bar coat method and a knife coat method, are mentioned.
[0134]
The pre-baking conditions vary depending on the type of each component, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.
[0135]
As a support constituting a negative photosensitive thermosetting transfer material, it has good releasability from a photosensitive thermosetting resin layer or an alkali-soluble thermoplastic resin layer described later, and is chemically and thermally supported. A material that is stable and flexible is preferable. Specifically, a thin sheet such as Teflon, polyethylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. From the viewpoint of obtaining good releasability, surface treatment such as glow discharge is generally not performed, and an undercoat such as gelatin is generally not provided.
[0136]
As thickness of the said support body, 5-300 micrometers is suitable, and 10-150 micrometers is especially preferable. If the thickness is 5 μm or less, the tensile strength at the time of laminating may be insufficient and may cause inconvenience of wrinkles. If the thickness exceeds 300 μm, the thermal conductivity due to heating at the time of laminating decreases, It may not be possible to increase the transport speed.
[0137]
The layer thickness of the photosensitive thermosetting resin layer can be appropriately selected according to the purpose, and is preferably 0.1 to 10 μm. When the layer thickness is less than 0.1 μm, only a cured film having poor durability may be formed. When the layer thickness exceeds 10 μm, problems such as poor developability and poor image reproducibility may occur. The interlayer insulating film provided in the HA type liquid crystal display device has a film thickness determined according to the dielectric constant, and is preferably 3 to 5 μm when the dielectric constant is 3 to 3.5.
[0138]
-Other layers-
As described above, negative photosensitive thermosetting having a multilayer structure in which an alkali-soluble thermoplastic resin layer, an intermediate layer, and a protective film are further provided between the support and the photosensitive thermosetting resin layer. It can also be used as a transfer material.
[0139]
-Alkali-soluble thermoplastic resin layer-
The alkali-soluble thermoplastic resin layer contains an alkali-soluble thermoplastic resin as a main component, and may contain other components.
Examples of the alkali-soluble thermoplastic resin include alkali-soluble thermoplastic resins having a substantial softening point of 80 ° C. or less. For example, saponified products of ethylene and acrylate copolymer, styrene and (meta ) Saponified products of acrylic acid ester copolymers, saponified products of vinyl toluene and (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, (meth) acrylic such as butyl (meth) acrylate and vinyl acetate Examples thereof include saponified products such as acid ester copolymers.
[0140]
In addition, as described in “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968), Among them, those soluble in an alkaline aqueous solution are also included.
A thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.
[0141]
Even if the organic polymer substance has a softening point of 80 ° C. or higher, various plasticizers compatible with the polymer substance are added to the organic polymer substance so that the substantial softening point is 80 ° C. or lower. It is also possible to use it lowered. In the organic polymer substance, various polymers, supercooling substances, adhesion improving agents, surfactants are used in order to adjust the adhesive force with the support so that the substantial softening point does not exceed 80 ° C. It is also possible to add a release agent or the like.
[0142]
Preferred examples of the plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate.
[0143]
The layer thickness of the alkali-soluble thermoplastic resin layer is preferably 6 μm or more.
When the layer thickness is less than 6 μm, it may be difficult to completely absorb the unevenness of 1 μm or more present on the surface of the transfer target. The upper limit is generally about 100 μm or less, preferably about 50 μm or less, in terms of developability and production suitability.
[0144]
-Intermediate layer-
The intermediate layer is provided for the purpose of blocking oxygen during exposure and for preventing mixing between the alkali-soluble thermoplastic resin layer and the photosensitive thermosetting resin layer.
The intermediate layer may be any one that is dispersed or dissolved in water or an aqueous alkali solution and has low oxygen permeability, and a known one can be applied.
[0145]
For example, polyvinyl ether / maleic anhydride polymer, water-soluble salt of carboxyalkyl cellulose, water-soluble cellulose ether, salt of carboxyalkyl starch described in JP-A-46-2121 and JP-B-56-40824 , Water salt, polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches, and the like Examples thereof include salts, styrene / maleic acid copolymers, and maleate resins. Moreover, what combined these 2 or more types may be used.
[0146]
Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80 mol% or more. As content rate of the said polyvinylpyrrolidone, 1-75 mass% of solid content (mass) of an intermediate | middle layer (oxygen interruption | blocking layer) is common, 1-60 mass% is especially preferable, and 10-50 mass% is more preferable. When the content is less than 1% by mass, sufficient adhesion to the photosensitive thermosetting resin layer may not be obtained, and when it exceeds 75% by mass, the oxygen blocking ability may be lowered. .
[0147]
The thickness of the intermediate layer (oxygen barrier layer) is a very thin layer, preferably about 0.1 to 5 μm, more preferably 0.5 to 2 μm. If the layer thickness is less than about 0.1 μm, oxygen permeability may be too high, and if it exceeds about 5 μm, it may take a long time for development or removal of the intermediate layer.
[0148]
-Protective film-
The protective film is preferably provided from the viewpoint of avoiding adhesion and damage of impurities during storage.
The protective film may be made of the same or similar material as that of the support, and needs to be easily peelable from the photosensitive thermosetting resin layer. Further, the smoothness of the surface on the side laminated with the photosensitive thermosetting resin layer is important, and there is no protrusion exceeding about 0.1 μm from the viewpoint of avoiding damage to the surface of the photosensitive thermosetting resin layer. It is preferable.
[0149]
As a material that can be used for the protective film, for example, silicone paper, polyolefin, or polytetrafluoroethylene sheet is preferable, and among them, polypropylene film and polyethylene film are particularly preferable.
As thickness of a protective film, about 5-100 micrometers is preferable and 7-15 micrometers is more preferable.
[0150]
As described above, the negative photosensitive thermosetting transfer material is used for the production of the HA type liquid crystal display device. In particular, the photosensitive thermosetting resin layer containing the negative photosensitive thermosetting resin composition of the present invention is used. The transfer material (negative photosensitive thermosetting transfer material of the present invention) has excellent storage stability (alkali developability) that does not depend on the storage environment, and coloring due to decomposition of 1,2-quinonediazide, etc. An interlayer insulating film having no (discoloration) and having resistance (solvent resistance) to an organic solvent such as a stripping solution for stripping the etching resist can be formed.
[0151]
<HA type liquid crystal display device>
The HA type liquid crystal display device of the present invention is obtained by the above-described manufacturing method of the liquid crystal display device of the present invention, and is formed by intersecting a gate signal line for transmitting a control signal and a source signal line for transmitting a video signal. The switching device is joined to the signal line at the intersection of the signal lines, and is arranged and formed, and an interlayer insulating film covering the switching device and the signal line, and a pixel electrode formed in a matrix on the interlayer insulating film And an active matrix substrate, a counter substrate disposed opposite to the active matrix substrate, and a liquid crystal layer interposed between the active matrix substrate and the counter substrate. In the active matrix substrate, a plurality of gate signal lines and a plurality of source signal lines may intersect, and switching devices may be arranged in a matrix at a plurality of intersecting portions.
[0152]
That is, a driving side substrate (active matrix substrate) in which switching devices and signal lines such as thin film transistors (TFTs) and pixel electrodes (conductive layers) provided on an interlayer insulating film covering the switching devices and signal lines are arranged. And a filter side substrate (counter substrate) having a color filter and a counter electrode (conductive layer), for example, with a spacer interposed therebetween and having a gap, and a liquid crystal material is sealed in the gap. Become.
[0153]
For example, as shown in FIG. 1, the active matrix substrate includes an interlayer insulating film that covers the switching device 10 and each signal line. Further, a contact hole 20 is provided in the interlayer insulating film, and an interlayer is formed through the contact hole 20. This is an HA type active matrix substrate having pixel electrodes in a matrix on an insulating film.
[0154]
Examples of the conductive layer include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; SiO₂In particular, a transparent film is preferable, and an ITO film is particularly preferable.
[0155]
In the liquid crystal display device of the present invention, a conductive layer is formed on both of the substrates constituting the liquid crystal display device, and a voltage is applied between the two conductive layers, and a liquid crystal material sandwiched between the conductive layers depends on the voltage. Display can be performed by changing the orientation state.
[0156]
As described above, the interlayer insulating film of the HA type active matrix substrate constituting the HA type liquid crystal display device is transferred and formed by the laminating method, and the transferred layer is processed to form contact holes. As a result, the switching device and the signal line are sufficiently insulated and have a highly accurate contact hole, so that stable image display can be performed without causing malfunction. Moreover, the interlayer insulating film is substantially colorless and transparent, has excellent storage stability and solvent resistance, and can display an image with high definition and high color purity.
[0157]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.
[0158]
Example 1
[Preparation of negative photosensitive thermosetting transfer material]
21 parts of a copolymer consisting of 73 mol% of benzyl methacrylate and 27 mol% of methacrylic acid (acid value 101 mg KOH / 1 g, weight average molecular weight about 100,000) is mixed with 30 parts of propylene glycol monomethyl ether acetate and 13 parts of methyl ethyl ketone. The following compound was further dissolved in the mixed solution to obtain a photosensitive thermosetting resin layer coating solution C1.

[0159]
The photosensitive thermosetting resin layer coating solution C1 is continuously applied on a roll-like polyethylene terephthalate film web having a width of 570 mm and a thickness of 5 μm using a slit coat type coating machine, and is then dried in a drying oven at 100 ° C. for 2 minutes. By drying, a negative photosensitive thermosetting resin layer having a layer thickness of 5 μm was formed. The distribution of the coating layer thickness was within ± 0.05 μm. Further, a 30 μm thick polyethylene film was continuously laminated on the photosensitive thermosetting resin layer to obtain a negative photosensitive thermosetting transfer material roll of the present invention.
[0160]
[Production of HA type active matrix substrate]
-Formation of interlayer insulation film-
The polyethylene film was peeled from the negative photosensitive thermosetting transfer material roll obtained above. Then, a plurality of gate signal lines and source signal lines made of aluminum wiring are formed on a glass substrate having a thickness of 0.7 mm so as to intersect with each other, and a plurality of TFTs are joined to the signal lines and allocated to the intersecting intersections. The surface of the photosensitive thermosetting resin layer is superimposed on the surface of the active matrix substrate (550 × 650 mm) arranged in a matrix and provided with the TFT and the like, and is continuously manufactured by Hitachi Techno Co., Ltd. A laminator was used to adhere and laminate while heating at a film conveyance speed of 1 m / min and a heat roll temperature of 130 ° C.
[0161]
A photomask having a contact hole pattern with a contact hole diameter of 10 μm is overlaid on the surface of the laminate on the polyethylene terephthalate film side, and a 300 mj / cm from a 2 KW ultrahigh pressure mercury lamp with a proximity gap of 70 μm.²The exposure was performed at the exposure amount of. Subsequently, the polyethylene terephthalate film is peeled off, the photosensitive thermosetting resin layer is transferred onto the active matrix substrate, and the photosensitive thermosetting resin layer is developed with a spray developing machine using a 1% monoethanolamine aqueous solution. The unirradiated portion was dissolved and removed, and an interlayer insulating film provided with contact holes was formed. Then, it was heated (baked) for 30 minutes in an oven at 200 ° C. to be cured.
[0162]
The obtained interlayer insulation film has a good uniformity of film thickness of ± 0.05 μm, and there is no uneven coating thickness unevenness (step) as in the case of coating formation, and the surface is smooth with a uniform thickness. It was excellent. Moreover, the hole diameter of the contact hole portion was 14 μm, there was no developed film on the entire surface of the active matrix substrate, the slope was good at 33 degrees in any contact hole shape, and the shape accuracy was also excellent. Further, no discoloration (coloring) of the layer itself was observed, and a substantially colorless and transparent interlayer insulating film was formed. Moreover, the film thickness change after baking was -10% before baking, and it was excellent in heat resistance, and the transmittance | permeability of the interlayer insulation film was favorable at 97% with the wavelength light of 350 nm.
On the other hand, when the obtained negative photosensitive thermosetting transfer material was sealed in a container and allowed to stand in a 50 ° C. environment for 4 days and then developed in the same manner as described above, no change was found. It was confirmed that the storage stability was excellent.
[0163]
-Formation of pixel electrode (conductive layer)-
Subsequently, an ITO film having a thickness of 0.2 μm was formed on the interlayer insulating film by sputtering at 200 ° C. Further, a commercially available positive-type ITO etching resist was coated on the film by a spin coating method, dried, exposed through a photomask, and the exposed portion was developed and removed. Subsequently, using an iron chloride / hydrochloric acid etchant, the portion of the ITO film not covered with the ITO etching resist was removed, and then the ITO etching resist was mixed with 80 ° C. monoethanolamine and dimethyl sulfoxide (mass ratio 7: 3). For 10 minutes. Here, there was no swelling of the interlayer insulating layer, the adhesion of the ITO film to be finally formed on the interlayer insulating film was good, and it did not peel off. The formed ITO film pattern was found to be excellent in close contact with the drain wiring exposed at the bottom of all contact holes, and no development residual film.
As described above, an HA type active matrix substrate was produced.
[0164]
[Fabrication of high aperture type liquid crystal display device]
Furthermore, the liquid crystal display device of the present invention can be manufactured as follows using the obtained HA type active matrix substrate.
That is, a chromium (Cr) metal film having a film thickness of 0.1 μm is formed on a glass substrate of a predetermined size by sputtering, and subsequently etched using a photoresist to form a grid-like black matrix having a predetermined size and shape. Then, a colored film composed of R (red), G (green), and B (blue) is formed at a predetermined position by the method for manufacturing a color filter described in JP-A-11-64621.
Next, on the colored film and the black matrix, an acrylic resin-based liquid is applied by a spin coater to form a protective layer and flattened. Then, an ITO film is further formed on the protective layer by a sputtering method as a conductive layer. Thus, a counter substrate can be obtained.
[0165]
It arrange | positions so that the surface of the interlayer insulation film and ITO film | membrane of an HA type | mold active matrix substrate may oppose, and the surface of the ITO film | membrane of the said opposing substrate may be opposed, and it fixes with a gap | interval through a spacer. A high aperture type liquid crystal display device of the present invention can be manufactured by enclosing a liquid crystal material in the gap and providing a liquid crystal layer for image display.
[0166]
The liquid crystal display device obtained from the above has no malfunction caused by insulation non-uniformity due to the difference in film thickness of the interlayer insulating film, has a high aperture ratio, is excellent in light transmittance without hue shift due to coloring of the interlayer insulating film, Vivid and high-definition image display can be performed.
[0167]
(Comparative Example 1)
An active matrix substrate (550 × 650 mm) similar to that in Example 1 and a photosensitive thermosetting resin layer coating solution were prepared, and a photosensitive thermosetting resin layer was coated on the active matrix substrate using a spin coater. An interlayer insulating film was formed in the same manner as in Example 1 except that the photosensitive thermosetting resin layer was provided by directly applying and drying the liquid.
[0168]
Since the photosensitive thermosetting resin layer coating liquid is configured to include the negative photosensitive thermosetting resin composition of the present invention, ITO film formation, resist image formation for etching, and resist removal after etching It had sufficient resistance in terms of peeling with the liquid.
However, the surface properties of the obtained interlayer insulating film were found to have uneven coating thickness variations (steps) and were inferior in insulating function to uniformly insulate TFTs and signal lines on the active matrix substrate. In addition, the variation in the contact hole diameter was large, and an adhesion failure of the ITO film at the center of the substrate was also observed. This is presumably because the development residual film was generated because the film thickness of the interlayer insulating film in the central part of the substrate was larger than the film thickness in the peripheral part of the substrate.
[0169]
(Example 2)
[Preparation of multilayer negative photosensitive thermosetting transfer material]
A thermoplastic resin layer coating liquid H1 having the following composition is applied on a support made of a roll-shaped polyethylene terephthalate film having a width of 570 mm and a thickness of 100 μm, and dried to form a thermoplastic resin layer having a dry layer thickness of 20 μm. did.
[0170]
[Composition of Coating Solution H1 for Thermoplastic Resin Layer]
・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate
Relate / methacrylic acid copolymer: 15.0 parts
(Copolymerization ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8,
(Weight average molecular weight = 80000)
・ BPE-500 (polyfunctional acrylate): 7.0 parts
(Manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ Fluorosurfactant: 0.3 parts
(F177P, manufactured by Dainippon Ink Co., Ltd.)
・ Methanol: 30.0 parts
・ Methyl ethyl ketone: 19.0 parts
1-methoxy-2-propanol: 10.0 parts
[0171]
Next, an intermediate layer coating solution B1 having the following composition was applied onto the thermoplastic resin layer and dried to form an intermediate layer having a dry layer thickness of 1.6 μm.
[Composition of Coating Solution B1 for Intermediate Layer]
・ Polyvinyl alcohol: 130 parts
(PVA-205, saponification degree 80 mol%, manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone: 60 parts
(K-30, manufactured by GAF Corporation)
・ Distilled water: 2110 parts
・ Methanol: 1750 parts
[0172]
A photosensitive thermosetting resin layer coating solution C1 prepared in the same manner as in Example 1 was applied on a support provided with the thermoplastic resin layer and the intermediate layer, dried, and a photosensitive layer having a dry layer thickness of 5 μm. A thermosetting resin layer was formed, and a polypropylene (thickness: 12 μm) covering sheet was pressure-bonded onto the photosensitive thermosetting resin layer to produce a multilayer negative photosensitive thermosetting transfer material. .
[0173]
[Production of HA type active matrix substrate]
-Formation of interlayer insulation film-
The coating sheet was peeled from the negative photosensitive thermosetting transfer material roll obtained above. Then, a plurality of gate signal lines and source signal lines made of aluminum wiring are formed on a glass substrate having a thickness of 0.7 mm so as to intersect with each other, and a plurality of TFTs are joined to the signal lines and allocated to the intersecting intersections. The surface of the photosensitive thermosetting resin layer is superimposed on the surface of the active matrix substrate (550 × 650 mm) arranged in a matrix and provided with the TFT and the like, and is continuously manufactured by Hitachi Techno Co., Ltd. The film was adhered and laminated while being heated with a laminator at a film conveyance speed of 3 m / min and a heat roll temperature of 130 ° C.
[0174]
A photomask having a contact hole pattern is overlaid on the thermoplastic resin layer from which the support has been removed from the laminate, and a 100 mj / cm from a 2 KW ultra-high pressure mercury lamp with a proximity gap of 70 μm.²UV exposure was performed at the exposure amount of. Subsequently, the thermoplastic resin layer and the intermediate layer were dissolved and removed using a 1% triethanolamine aqueous solution. At this time, the photosensitive thermosetting resin layer was not substantially developed.
[0175]
Next, the unexposed portion was developed and removed using a 1% monoethanolamine aqueous solution, and then heated (baked) in an oven at 180 ° C. for 1 hour to be cured.
The film thickness of the interlayer insulating film composed of the exposed and heat-cured photosensitive thermosetting resin layer was 4 μm, the pencil hardness was 5H, and the dielectric constant was 2.8 (1 kHz).
[0176]
The obtained interlayer insulating film has a good uniformity of film thickness of ± 0.05 μm, and there is no uneven coating thickness unevenness (step) as in the case of coating formation, and it has a uniform thickness and excellent surface smoothness. It was. In addition, the shape of the contact hole portion was a mortar shape having a bottom portion size of 10 μmφ and an inclination angle of 25 degrees, and was excellent in shape accuracy. Further, the formed interlayer insulating film was not discolored (colored), was substantially colorless and transparent, and the light transmittance was good at 97% with a wavelength of 350 nm.
[0177]
-Formation of pixel electrode (conductive layer)-
Subsequently, an ITO film having a thickness of 0.2 μm was formed on the interlayer insulating film by sputtering at 200 ° C. Further, a commercially available positive-type ITO etching resist was coated on the film by a spin coating method, dried, exposed through a photomask, and the exposed portion was developed and removed. Subsequently, the portion of the ITO film not covered with the ITO etching resist was removed using an iron chloride / hydrochloric acid etchant, and then the ITO etching resist was mixed with 80 ° C. monoethanolamine and dimethyl sulfoxide (mass ratio 7: 3). For 10 minutes. Here, there was no swelling of the interlayer insulating layer, the adhesion of the ITO film to be finally formed on the interlayer insulating film was good, and it did not peel off. Therefore, no damage such as wrinkles due to swelling was observed. It was confirmed that the ITO film pattern formed was excellent in close contact with the drain wiring exposed at the bottom of all contact holes and there was no developed film.
As described above, an HA type active matrix substrate was produced.
[0178]
Further, using the obtained HA type active matrix substrate, the liquid crystal display device of the present invention can be manufactured in the same manner as in Example 1, and the obtained liquid crystal display device has a difference in film thickness of the interlayer insulating film. Accordingly, there is no malfunction caused by the insulation non-uniformity, the aperture ratio is high, there is no hue shift due to coloring of the interlayer insulating film, the light transmittance is excellent, and a vivid and high-definition image display can be performed.
[0179]
(Comparative Example 2)
In place of the photosensitive thermosetting resin layer coating liquid C1 used in Example 2, a photosensitive insulating layer coating liquid C2 having the following composition (Example 1 of JP-A-10-97061) was used and dried. An HA type active matrix substrate was produced in the same manner as in Example 2 except that the layer thickness was 2 μm.
[0180]
[Composition of Coating Solution C2 for Photosensitive Insulating Layer]
・ Benzylamine modified product of styrene / maleic anhydride copolymer: 14 parts
(Styrene / maleic anhydride = 60/40 (molar ratio),
A reaction of an equal amount of benzylamine with maleic anhydride,
Acid value = 150 mgKOH / 1 g, weight average molecular weight = 13,000
・ Fluorosurfactant: 0.1 part
(F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Hydroquinone monomethyl ether: 0.01 parts
・ Dipentaerythritol hexaacrylate: 11 parts
・ 2- (p-butoxystyryl) -5-trichloro 0.5 parts
Methyl) -1,3,4-oxadiazole
・ Eisen Malachite Green (Hodogaya Chemical Co., Ltd.)… 0.5 part
・ Methanol: 25 parts
・ Propylene glycol monomethyl ether: 25 parts
・ Methyl ethyl ketone: 25 parts
[0181]
The interlayer insulating film formed as described above swells when the resist is removed by dipping in a mixed solution of monoethanolamine and dimethyl sulfoxide, and due to poor adhesion of the ITO film to be finally formed on the interlayer insulating film The ITO film peeled off and was inferior in terms of resistance (solvent resistance) to the organic solvent-based stripping solution. Further, in the negative photosensitive thermosetting transfer material roll obtained using the photosensitive insulating layer coating liquid C2, it was impossible to form a contact hole having a diameter smaller than 20 μm.
[0182]
【The invention's effect】
  According to the present invention, it is suitable for forming an HA-type active matrix substrate constituting an HA-type liquid crystal display device, and is a negative-type photosensitive thermosetting that is substantially colorless and transparent, and has excellent storage stability and solvent resistance. Resin compositionThingsIt has a uniform film thickness with no coating unevenness, etc., has excellent insulation and contact hole shape accuracy, is substantially colorless and transparent, and has excellent storage stability and solvent resistance. PossibleFor interlayer insulation filmUsing negative photosensitive thermosetting transfer material, and negative photosensitive thermosetting transfer material, it has excellent insulation and contact hole shape accuracy, is virtually colorless and transparent, and has excellent storage stability and solvent resistance. In addition, a method for forming an interlayer insulating film suitable for forming an interlayer insulating film can be provided.
  High aperture (HA) with uniform thickness, excellent insulation and contact hole shape accuracy, and can stably form an interlayer insulation film that is virtually colorless and transparent, with excellent storage stability and solvent resistance. -Type liquid crystal display device, and HA-type liquid crystal obtained by the method for manufacturing the HA-type liquid crystal display device, having a high aperture ratio, no hue shift, excellent light transmittance, and capable of displaying high-definition and clear images A display device can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view for explaining a configuration of one pixel portion of a high aperture type (HA type) active matrix substrate in a liquid crystal display device of the present invention.
FIG. 2 is a schematic process diagram for explaining a process of forming an interlayer insulating film.
[Explanation of symbols]
10. Switching device (TFT)
11 ... Transparent substrate
12 ... Gate signal line
16a ... Source electrode
16b ... Drain electrode
17 ... Source signal line (metal layer)
17 '... Connection signal line (metal layer)
18 ... Interlayer insulating film
19 ... Pixel electrode (ITO film)
20 ... Contact hole
30 ... HA type active matrix substrate

Claims (5)

    On the support, (A) an addition-polymerizable compound having at least two ethylenically unsaturated bonds, (B) a photopolymerization initiator, (C) a carboxyl group-containing alkali-soluble resin, and (D) light And / or a photosensitive thermosetting resin layer containing a compound that generates a non-volatile acid by heat and (E) a crosslinking agent crosslinkable with an acid, and at least the photosensitive thermosetting resin layer is A negative photosensitive thermosetting transfer material for an interlayer insulating film, which is transferred to an interlayer insulating film. On the transparent substrate, a gate signal line that transmits a control signal, a source signal line that intersects the gate signal line and transmits a video signal, and an array allocated and joined to the signal line at the intersection of the signal lines A method of forming the interlayer insulating film of a high-aperture active matrix substrate comprising a formed switching device and an interlayer insulating film covering the switching device and a signal line,
A step of superimposing the negative photosensitive thermosetting transfer material according to claim 1 on the surface of the transparent substrate on which the switching device and the signal line are provided, and transferring at least the photosensitive thermosetting resin layer; Exposing the transferred photosensitive thermosetting resin layer to a pattern, developing it with an alkali to remove the unexposed areas to form a substantially colorless and transparent pattern, and heating the colorless and transparent pattern And a step of curing the interlayer insulating film. A gate signal line for transmitting a control signal and a source signal line for transmitting a video signal are formed on a transparent substrate so as to intersect with each other, and a switching device is joined and allocated to the intersection of the signal lines to form an array. An active matrix substrate, a counter substrate disposed opposite to the active matrix substrate, and a liquid crystal layer interposed between the active matrix substrate and the counter substrate,
In the method of manufacturing a high aperture type liquid crystal display device, provided on the active matrix substrate is an interlayer insulating film that covers the switching device and the signal line, and a pixel electrode that is arranged on the interlayer insulating film.
The photosensitive thermosetting resin layer of the negative photosensitive thermosetting transfer material, wherein the interlayer insulating film has a photosensitive thermosetting resin layer containing a decolorizable colorant that becomes substantially colorless by heat treatment. A method of manufacturing a high aperture type liquid crystal display device, wherein the high aperture type liquid crystal display device is formed by transferring by a laminating method. A gate signal line for transmitting a control signal and a source signal line for transmitting a video signal are formed on a transparent substrate so as to intersect with each other, and a switching device is joined and allocated to the intersection of the signal lines to form an array. An active matrix substrate, a counter substrate disposed opposite to the active matrix substrate, and a liquid crystal layer interposed between the active matrix substrate and the counter substrate,
In the method of manufacturing a high aperture type liquid crystal display device, on the active matrix substrate, an interlayer insulating film that covers the switching device and the signal line and a pixel electrode that is arranged on the interlayer insulating film are provided.
The interlayer insulating film, a high aperture liquid crystal display device characterized by being formed by transferring a negative photosensitive lamination photosensitive thermosetting resin layer of the thermosetting transfer material according to claim 1 Manufacturing method. The manufacturing method of the high aperture type liquid crystal display device of Claim 4 in which the photosensitive thermosetting resin layer contains the decoloring colorant which becomes substantially colorless by heat processing .

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