JP4513208B2 - Colored photosensitive resin composition with excellent storage stability - Google Patents

Description

（式中、Ｒ¹およびＲ²はそれぞれ独立に水素原子、アルキル基、シクロアルキル基またはアリール基を示す。）
で示される置換基を有する化合物、具体的には一般式（Ｉ−１）

（式中、Ｒ¹およびＲ²はそれぞれ前記と同じ意味を示し、Ｒ³はアルキル基、シクロアルキル基またはアリール基を示す。）
で示される化合物が挙げられる。ここで、Ｒ¹、Ｒ²およびＲ³におけるアルキル基としては、例えばメチル基、エチル基、プロピル基などの炭素数１〜１０程度のアルキル基が、シクロアルキル基としては、例えばシクロヘキシル基などの炭素数３〜１０程度のシクロアルキル基が、アリール基としては、例えばフェニル基などがそれぞれ挙げられる。これらのアルキル基、シクロアルキル基、アリール基は、置換基を有していてもよい。
【０００８】
かかるアミン化合物としては、例えばＮ−メチルアミン、Ｎ−エチルアミン、Ｎ−シクロヘキシルアミン、ｐ−アミノフェノール、
【０００９】
Ｎ−ジメチルアミン、Ｎ−ジエチルアミン、Ｎ−メチルフェニルアミン、Ｎ−メチルシクロヘキシルアミン、Ｎ−トリメチルアミン、Ｎ−トリエチルアミン、Ｎ−メチルジフェニルアミン、Ｎ−ジメチルシクロヘキシルアミン、Ｎ−メチルフェニルシクロヘキシルアミン、Ｎ−トリフェニルアミンなどが挙げられる。
【００１０】
ピリジン化合物としては、例えばピリジンのほか、一般式（II）

（式中、Ｒ⁴はアルキル基を示し、ｉは０〜４の整数を示す。）
で示される置換基を有する化合物が挙げられ、具体的には一般式（II−１）

（式中、Ｒ⁴およびｉはそれぞれ前記と同じ意味を示し、ｎは１〜８の整数を示し、Ｒ⁵はアルキル基を示し、ｊは０〜４の整数を示す。）
で示される化合物が挙げられる。ここで、Ｒ⁴およびＲ⁵におけるアルキル基としては、Ｒ¹、Ｒ²およびＲ³において上記下と同様の炭素数１〜１０程度のアルキル基が挙げられる。かかるアルキル基は置換基を有していてもよい。
【００１１】
かかるピリジン化合物としては、例えばジ（４−ピリジル）メタン、ジ（２−メチル−２−ピリジル）メタン、ジ（２−エチル−２−ピリジル）メタン、ジ（２−プロピル−２−ピリジル）メタン、ジ（４−ピリジル）メタン、ジ（２−メチル−３−ピリジル）メタン、ジ（２−エチル−３−ピリジル）メタン、ジ（２−プロピル−３−ピリジル）メタン、ジ（４−ピリジル）メタン、ジ（２−メチル−４−ピリジル）メタン、ジ（２−エチル−４−ピリジル）メタン、ジ（２−プロピル−４−ピリジル）メタン、
【００１２】
１，２−ジ（４−ピリジル）エタン、１，２−ジ（２−メチル−２−ピリジル）エタン、１，２−ジ（２−エチル−２−ピリジル）エタン、１，２−ジ（２−プロピル−２−ピリジル）エタン、１，２−ジ（４−ピリジル）エタン、１，２−ジ（２−メチル−３−ピリジル）エタン、１，２−ジ（２−エチル−３−ピリジル）エタン、１，２−ジ（２−プロピル−３−ピリジル）エタン、１，２−ジ（４−ピリジル）エタン、１，２−ジ（２−メチル−４−ピリジル）エタン、１，２−ジ（２−エチル−４−ピリジル）エタン、１，２−ジ（２−プロピル−４−ピリジル）エタン、
【００１３】
１，３−ジ（４−ピリジル）プロパン、１，３−ジ（２−メチル−２−ピリジル）プロパン、１，３−ジ（２−エチル−２−ピリジル）プロパン、１，３−ジ（２−プロピル−２−ピリジル）プロパン、１，３−ジ（４−ピリジル）プロパン、１，３−ジ（２−メチル−３−ピリジル）プロパン、１，３−ジ（２−エチル−３−ピリジル）プロパン、１，３−ジ（２−プロピル−３−ピリジル）プロパン、１，３−ジ（４−ピリジル）プロパン、１，３−ジ（２−メチル−４−ピリジル）プロパン、１，３−ジ（２−エチル−４−ピリジル）プロパン、１，３−ジ（２−プロピル−４−ピリジル）プロパン、
【００１４】
１，４−ジ（２−メチル−２−ピリジル）ブタン、１，４−ジ（２−エチル−２−ピリジル）ブタン、１，４−ジ（２−プロピル−２−ピリジル）ブタン、１，４−ジ（２−メチル−３−ピリジル）ブタン、１，４−ジ（２−エチル−３−ピリジル）ブタン、１，４−ジ（２−プロピル−３−ピリジル）ブタン、１，４−ジ（２−メチル−４−ピリジル）ブタン、１，４−ジ（２−エチル−４−ピリジル）ブタン、１，４−ジ（２−プロピル−４−ピリジル）ブタン、
【００１５】
１，５−ジ（２−メチル−２−ピリジル）ペンタン、１，５−ジ（２−エチル−２−ピリジル）ペンタン、１，５−ジ（２−プロピル−２−ピリジル）ペンタン、１，５−ジ（２−メチル−３−ピリジル）ペンタン、１，５−ジ（２−エチル−３−ピリジル）ペンタン、１，５−ジ（２−プロピル−３−ピリジル）ペンタン、１，５−ジ（２−メチル−４−ピリジル）ペンタン、１，５−ジ（２−エチル−４−ピリジル）ペンタン、１，５−ジ（２−プロピル−４−ピリジル）ペンタンなどが挙げられる。
【００１６】
本発明の着色感光性樹脂組成物は、色素として染料（Ｂ）を含有する。染料は感光性樹脂組成物に溶解し得て、カラーフィルターの色フィルタ層を形成し得る染料であれば、特に限定されるものではない。例えば黄色の色フィルタ層を形成するために用いられる着色感光性樹脂組成物には、シー・アイ・ソルベント・イエロー８２（C.I.Solvent Yellow 82）、シー・アイ・ソルベント・イエロー１６２（C.I.Solvent Yellow 162）などの染料を用いることができる。
【００１７】
本発明の着色感光性樹脂組成物は、アルカリ可溶性樹脂（Ｃ）を含む。アルカリ可溶性樹脂とは、アルカリ性の現像液に溶解し得る樹脂であり、通常の感光性樹脂組成物に用いられると同様のアルカリ可溶性樹脂を用いることができる。かかるアルカリ可溶性樹脂としては、例えばノボラック樹脂、ビニルフェノール樹脂などが挙げられ、好ましくはノボラック樹脂である。ノボラック樹脂としては、ｐ−クレゾールとホルムアルデヒドとが縮合されてなるノボラック樹脂、ｐ−クレゾールおよびｍ−クレゾールとホルムアルデヒドとが縮合されてなるノボラック樹脂、式（１）

で示される構造単位を有するノボラック樹脂などが挙げられる。ビニルフェノール樹脂としては、例えばポリビニルフェノール、スチレン−ビニルフェノール共重合体などが挙げられる。
【００１８】
本発明の着色感光性樹脂組成物は、感光剤（Ｄ）を含む。感光剤とは、光線を照射されることによってアルカリ可溶性樹脂がアルカリ性溶液へ溶解することを防止する機能を有する化合物であって、通常の感光性樹脂組成物に用いられると同様の感光剤を用いることができる。かかる感光剤としては、例えばフェノール化合物とｏ−ナフトキノンジアジドスルホン酸化合物とのエステル化合物が挙げられる。ここで、フェノール化合物としては、例えば式（２）

で示される化合物が挙げられる。ｏ−ナフトキノンジアジドスルホン酸化合物としては、ｏ−ナフトキノンジアジド−５−スルホン酸、ｏ−ナフトキノンジアジド−４−スルホン酸などが挙げられる。
【００１９】
本発明の着色感光性樹脂組成物は硬化剤（Ｅ）を含む。硬化剤としては、通常、加熱されることによって色フィルタ層を硬化させることができる熱硬化剤が使用される。かかる熱硬化剤としては、例えば式（３）

〔式中、Ｚは−ＮＱ⁵Ｑ⁶で示される置換基またはフェニル基を示し、Ｑ¹〜Ｑ⁶はそれぞれ独立に水素原子、−（ＣＨ₂）_sＯＨで示される置換基または−（ＣＨ₂）_sＯＱ⁰で示される置換基を示す。Ｑ⁰はアルキル基を示し、ｓは１〜４の整数を示す。ただしＱ¹〜Ｑ⁶のうちの少なくとも一つは−（ＣＨ₂）_sＯＨで示される置換基または−（ＣＨ₂）_sＯＱ⁰で示される置換基を示す。〕
で示される化合物、式（３１）〜（３６）

で示される化合物などを用いることができる。
【００２０】
本発明の着色感光性樹脂組成物は通常、染料（Ｂ）、アルカリ可溶性樹脂（Ｃ）および感光剤（Ｄ）の合計量１００重量部中に染料（Ｂ）を２５〜５５重量部、アルカリ可溶性樹脂（Ｃ）を３〜５０重量部、感光剤（Ｄ）を１５〜５５重量部それぞれ含む。また、硬化剤（Ｅ）は通常、染料（Ｂ）、アルカリ可溶性樹脂（Ｃ）および感光剤（Ｄ）の合計量１００重量部あたり硬化剤を１０〜３５重量部含む。
【００２１】
染料（Ｂ）、アルカリ可溶性樹脂（Ｃ）、感光剤（Ｄ）および硬化剤（Ｅ）を含む着色感光性樹脂組成物にアミン化合物およびピリジン化合物から選ばれる少なくとも１種の化合物（Ａ）を含有させることにより、着色感光性樹脂組成物が保存安定化され、保存による感度の低下が少なく、安定して保存することができる。
【００２２】
本発明の着色感光性樹脂組成物は、溶剤で希釈されていてもよい。溶剤としては、例えばメチルセルソルブ、エチルセルソルブ、メチルセルソルブアセテート、エチルセルソルブアセテート、ジ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モノイソプロピルエーテル、プロピレングリコールモノメチルエーテル、ｎ−メチルピロリドン、γ−ブチロラクトン、ジメチルスルホキシド、Ｎ，Ｎ’−ジメチルホルムアミド、シクロヘキサン、酢酸エチル、酢酸ｎ−ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸エチル、乳酸エチルなどが挙げられる。かかる溶剤はそれぞれ単独で用いてもよいし、２種以上を混合して用いてもよい。溶剤で希釈する場合、溶剤は、染料、感光剤、アルカリ可溶性樹脂および硬化剤の合計１００重量部あたり、通常１８０〜４００重量部程度用いられる。
【００２３】
本発明の着色感光性樹脂組成物は、例えば染料、感光剤、アルカリ可溶性樹脂および硬化剤を混合することにより製造され、溶剤中でこれらを混合することにより、溶剤で希釈された着色感光性樹脂組成物を製造することができる。
【００２４】
かかる本発明の着色感光性樹脂組成物は、保存中の感度の低下が低減されているので、かかる着色感光性樹脂組成物をパターンニングして色フィルタ層を形成する工程を有する方法によりカラーフィルターを製造することとすれば、保存後の着色感光性樹脂組成物であっても、製造直後の着色感光性樹脂組成物を用いたと同様の光線強度、照射時間で露光して、色フィルタ層を形成することができる。
【００２５】
本発明の着色感光性樹脂組成物を用いてパターンニングするには、通常と同様に、基板（１）の表面上に全面に亙って本発明の着色感光性樹脂組成物からなる層（２）を形成し（図１(a)）、該層（２）にレチクル（３）を介して光線（４）を照射して露光すればよい(図１(b)）。
【００２６】
基板（１）は、ガラス板などであってもよいし、シリコンウェハーなどであってもよい。シリコンウェハーは、その表面に電荷結合素子（ＣＣＤ）などの固体撮像素子などが形成されていてもよい。かかる基板の上に本発明の着色感光性樹脂組成物層（２）を形成するには、通常と同様にスピンコート法などの方法により着色感光性樹脂組成物を塗布すればよい。着色感光性樹脂組成物を溶剤で希釈された状態で塗布した場合には、塗布後、加熱するなどして溶剤を揮発させてもよい。
【００２７】
光線（４）としては、例えばｉ線（波長３６５ｎｍ）を用いることができる。露光は、通常の露光機を用いて行うことができる。レチクル（３）と着色感光性樹脂組成物層（２）との間には、光学レンズ（図示せず。）が配置されていてもよい。光学レンズは、例えばレチクルを透過した光線を集光して、レチクルよりも小さなサイズの色フィルタ層を形成するために用いられる。
【００２８】
レチクル（３）には光線（４）を透過する領域（３１）と遮蔽する領域（３２）とが設けられているので、着色感光性樹脂組成物層（２）には光線が照射される領域（２１）と光線が照射されない領域（２２）とが生ずる（図１(b)）。露光における光線の強度や照射時間は、適宜選択されるが、本発明の着色感光性樹脂組成物は保存中の感度の低下が低減されているので、比較的長期間保存したのちの着色感光性樹脂組成物を用いた場合であっても、製造直後の着色感光性樹脂組成物を用いた場合の光線の強度および照射時間と同様の強度および照射時間で露光すればよい。
【００２９】
露光後、着色感光性樹脂組成物層（２）をアルカリ性水溶液で処理することにより、着色感光性樹脂組成物層（２）のうちの光線が照射された領域（２１）がアルカリ性水溶液に溶解し、光線が照射されなかった領域（２２）が溶解することなく残って、色フィルタ層（５１）を構成する（図１(c)）。アルカリ性水溶液としては、感光性樹脂組成物の現像に通常用いられると同様のものと用いることができ、現像液として市販されているものと用いることもできる。アルカリ水溶液で処理するには、例えば露光後の感光性樹脂組成物層（２）を基板（１）とともにアルカリ性の水溶液に浸漬すればよい。アルカリ性水溶液で処理したのち、水洗し、乾燥することにより、色フィルタ層（５１）を得る。
【００３０】
かかる色フィルタ層は、着色感光性樹脂組成物に含有される染料によって着色されている。また、そのパターンはレチクルの光線を遮蔽する領域（３２）と同様であって、例えば帯状であってもよいし（図２(a)）、モザイク状であってもよい（図２(b)）。
【００３１】
アルカリ性水溶液で処理したのち、通常は加熱する。加熱することのより、得られた色フィルタ層（５１）が硬化して、その機械的強度を向上することができる。
【００３２】
次いで、着色感光性樹脂組成物に含まれる染料の色を換えて上記と同様の操作を繰り返し行うことにより、三原色に対応した各色の色フィルタ層（５２、５３）を順次形成して、カラーフィルター（６）を得ることができる（図３）。
【００３３】
かくして得られるカラーフィルター（６）は、カラー液晶表示装置、カラー固体撮像装置などのカラーフィルターとして有用である。
【００３４】
【発明の効果】
本発明の着色感光性樹脂組成物は、保存中の感度の低下が少ないので、保存後であっても、製造直後の着色感光性樹脂組成物を用いた場合の光線の強度および照射時間と同様の強度および照射時間で露光することができる。
【００３５】
【実施例】
以下、実施例により本発明をより詳細に説明するが、本発明はかかる実施例により限定されるものではない。
【００３６】
実施例１
（着色感光性樹脂組成物の製造）
シー・アイ・ソルベント・イエロー８２（染料）１７．７５重量部、シー・アイ・ソルベント・イエロー１６２（染料）１７．７５重量部、ｏ−ナフトキノンジアジド−５−スルホン酸のエステル化合物（感光剤）２６．５重量部、式（１）で示される構造単位を有するノボラック樹脂（アルカリ可溶性樹脂）１８重量部、式（３０）

で示される化合物であるヘキサメトキシメチルメラミン（硬化剤）２０重量部、ｐ−アミノフェノール（アミン化合物）０．１重量部、乳酸エチル（溶剤）２５５．６重量部およびＮ，Ｎ’−ジメチルホルムアミド（溶剤）１０９．５重量部を混合し、メンブランフィルター（孔径０．１μｍ）で濾過して着色感光性樹脂組成物を得た。
【００３７】
（評価）
（１）製造直後の感度
上記で得た直後の着色感光性樹脂組成物をシリコンウェハー（１）の上にスピンコート法にて塗布し、１００℃で１分間加熱して溶剤を揮発させて着色感光性樹脂組成物層（２）を形成した（図１(a)）。次いで、露光機〔ニコン(株)製、「Ｎｉｋｏｎ ＮＳＲ １７５５ｉ７Ａ」〕を用いてレチクル（３）を介してｉ線（波長３６５ｎｍ）を照射して露光したのち（図１(b)）、現像液（住友化学工業(株)製、「ＳＯＰＤ−Ｔ」、２３℃）に１分間浸漬して現像し、水洗、乾燥して、線幅が５０μｍで厚みが０．８μｍの帯状のパターンで形成された黄色フィルタ層（５１）を形成した（図３(a)）。
露光における露光時間を変えながら上記と同様の操作を繰り返し行い、着色感光性樹脂組成物層（２）のうちの露光において光が照射された領域（２１）が現像で完全に除去されるのに要する最小の露光時間を（Ｔ₀）とした。
（２）保存後の着色感光性樹脂組成物の感度
上記で得た着色感光性樹脂組成物を褐色のガラス瓶に入れ、常温で２週間保管したのち、上記と同様に操作して、着色感光性樹脂組成物層（２）のうちの露光において光が照射された領域（２１）が現像で完全に除去されるのに要する最小の露光時間を（Ｔ₁）とした。
（３）感度の変化率の計算
上記で得た露光時間Ｔ₀、Ｔ₁から計算式（４）
Ｒ＝Ｔ₁／Ｔ₀ （４）
により感度の変化率（Ｒ）を算出した。結果を表１に示す。
【００３８】
実施例２
ｐ−アミノフェノールに代えて１，３−ジ−４−ピリジルプロパン（ピリジン化合物）０．１重量部を用いる以外は、実施例１と同様に操作して、着色感光性樹脂組成物を得、評価を行い感度の変化率（Ｒ）を求めた。結果を表１に示す。
【００３９】
比較例１
ｐ−アミノフェノールを用いることなく着色感光性樹脂組成物を得る以外は実施例１と同様に操作して、着色感光性樹脂組成物を得、評価を行い感度の変化率（Ｒ）を求めた。結果を表１に示す。
【００４０】
【表１】

【図面の簡単な説明】
【図１】着色感光性樹脂組成物を用いて色フィルタ層を得る工程を説明するための断面模式図である。
【図２】得られたカラーフィルターの一例を示す断面模式図である。
【図３】色フィルタ層のパターンの一例を示す模式図である。
【符号の説明】
１ ：基板
２ ：着色感光性樹脂組成物層
３ ：レチクル ３１：光線を透過する領域
３２：光線を遮蔽する領域
４ ：光線
５１：色フィルタ層 ５２：色フィルタ層 ５３：色フィルタ層
６ ：カラーフィルター[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a colored photosensitive resin composition excellent in storage stability, and more particularly to a colored photosensitive resin composition with little decrease in sensitivity due to storage.
[0002]
[Prior art]
The colored photosensitive resin composition (color resist) is a photosensitive resin composition (resist) containing a pigment, and includes a color filter layer constituting a color filter of a color liquid crystal display device, a color solid-state imaging device, or the like. Widely used as a raw material for forming. As such a colored photosensitive resin composition, for example, one containing a dye, an alkali-soluble resin, a photosensitive agent and a curing agent is also known.
[0003]
In order to form the color filter layer (51) using such a colored photosensitive resin composition, for example, the layer (2) made of the colored photosensitive resin composition is formed over the entire surface of the substrate (1). However, there is known a method of exposing the layer (2) by irradiating the layer (2) with a light beam (4) through a reticle (3) (FIG. 1 (b)). By treating the colored photosensitive resin composition layer (2) after exposure with an alkaline aqueous solution, the region (21) irradiated with the light beam (4) in the exposure of the colored photosensitive resin composition layer (2) is alkaline. The area | region (22) which melt | dissolved in aqueous solution and was not irradiated remains without melt | dissolving, and comprises a color filter layer (51). The color filter layers (52, 53) corresponding to the three primary colors are sequentially formed by repeating the same operation while changing the color of the pigment contained in the colored photosensitive resin composition, and the color filter (6) Can be obtained (FIG. 3). As the coloring matter of such a colored photosensitive resin composition, a dye and a pigment can be used, and a dye is preferably used in that a color filter layer can be formed with a finer pattern.
[0004]
However, some colored photosensitive resin compositions that use dyes as pigments have their sensitivity reduced by storage. When the sensitivity of the colored photosensitive resin composition is lowered, a colored photosensitive resin composition that does not dissolve in the alkaline aqueous solution even when irradiated with light in the exposure may be formed, and a color filter layer may be formed with a desired pattern. It becomes difficult.
[0005]
[Problems to be solved by the invention]
Therefore, as a result of intensive studies to develop a colored photosensitive resin composition with little decrease in sensitivity due to storage, the present inventors have found that amine compounds and pyridine compounds (A) have decreased sensitivity of the colored photosensitive resin composition during storage. Has been found to be able to be reduced, leading to the present invention.
[0006]
[Means for Solving the Problems]
That is, the present invention includes at least one compound (A) selected from an amine compound and a pyridine compound, a dye (B), an alkali-soluble resin (C), a photosensitizer (D), and a curing agent (E). A colored photosensitive resin composition is provided.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The colored photosensitive resin composition of the present invention contains at least one compound (A) selected from amine compounds and pyridine compounds. As the amine compound, for example, the general formula (I)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.)
A compound having a substituent represented by formula (I-1), specifically

(Wherein R ¹ and R ² each have the same meaning as described above, and R ³ represents an alkyl group, a cycloalkyl group or an aryl group.)
The compound shown by these is mentioned. Here, as the alkyl group in R ¹ , R ² and R ³ , for example, an alkyl group having about 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group, and as the cycloalkyl group, for example, a cyclohexyl group and the like Examples of the cycloalkyl group having about 3 to 10 carbon atoms and the aryl group include a phenyl group. These alkyl group, cycloalkyl group, and aryl group may have a substituent.
[0008]
Examples of such amine compounds include N-methylamine, N-ethylamine, N-cyclohexylamine, p-aminophenol,
[0009]
N-dimethylamine, N-diethylamine, N-methylphenylamine, N-methylcyclohexylamine, N-trimethylamine, N-triethylamine, N-methyldiphenylamine, N-dimethylcyclohexylamine, N-methylphenylcyclohexylamine, N-tri And phenylamine.
[0010]
Examples of pyridine compounds include general formula (II) in addition to pyridine.

(In the formula, R ⁴ represents an alkyl group, and i represents an integer of 0 to ^4. )
The compound which has a substituent shown by these is mentioned, Specifically, general formula (II-1)

(Wherein R ⁴ and i each have the same meaning as described above, n represents an integer of 1 to 8, R ⁵ represents an alkyl group, and j represents an integer of 0 to 4)
The compound shown by these is mentioned. Here, examples of the alkyl group in R ⁴ and R ⁵ include the same alkyl group having about 1 to 10 carbon atoms as described above in R ¹ , R ^2, and R ³ . Such an alkyl group may have a substituent.
[0011]
Examples of the pyridine compound include di (4-pyridyl) methane, di (2-methyl-2-pyridyl) methane, di (2-ethyl-2-pyridyl) methane, and di (2-propyl-2-pyridyl) methane. , Di (4-pyridyl) methane, di (2-methyl-3-pyridyl) methane, di (2-ethyl-3-pyridyl) methane, di (2-propyl-3-pyridyl) methane, di (4-pyridyl) ) Methane, di (2-methyl-4-pyridyl) methane, di (2-ethyl-4-pyridyl) methane, di (2-propyl-4-pyridyl) methane,
[0012]
1,2-di (4-pyridyl) ethane, 1,2-di (2-methyl-2-pyridyl) ethane, 1,2-di (2-ethyl-2-pyridyl) ethane, 1,2-di ( 2-propyl-2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-methyl-3-pyridyl) ethane, 1,2-di (2-ethyl-3-) Pyridyl) ethane, 1,2-di (2-propyl-3-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-methyl-4-pyridyl) ethane, 2-di (2-ethyl-4-pyridyl) ethane, 1,2-di (2-propyl-4-pyridyl) ethane,
[0013]
1,3-di (4-pyridyl) propane, 1,3-di (2-methyl-2-pyridyl) propane, 1,3-di (2-ethyl-2-pyridyl) propane, 1,3-di ( 2-propyl-2-pyridyl) propane, 1,3-di (4-pyridyl) propane, 1,3-di (2-methyl-3-pyridyl) propane, 1,3-di (2-ethyl-3-) Pyridyl) propane, 1,3-di (2-propyl-3-pyridyl) propane, 1,3-di (4-pyridyl) propane, 1,3-di (2-methyl-4-pyridyl) propane, 1, 3-di (2-ethyl-4-pyridyl) propane, 1,3-di (2-propyl-4-pyridyl) propane,
[0014]
1,4-di (2-methyl-2-pyridyl) butane, 1,4-di (2-ethyl-2-pyridyl) butane, 1,4-di (2-propyl-2-pyridyl) butane, 1, 4-di (2-methyl-3-pyridyl) butane, 1,4-di (2-ethyl-3-pyridyl) butane, 1,4-di (2-propyl-3-pyridyl) butane, 1,4- Di (2-methyl-4-pyridyl) butane, 1,4-di (2-ethyl-4-pyridyl) butane, 1,4-di (2-propyl-4-pyridyl) butane,
[0015]
1,5-di (2-methyl-2-pyridyl) pentane, 1,5-di (2-ethyl-2-pyridyl) pentane, 1,5-di (2-propyl-2-pyridyl) pentane, 1, 5-di (2-methyl-3-pyridyl) pentane, 1,5-di (2-ethyl-3-pyridyl) pentane, 1,5-di (2-propyl-3-pyridyl) pentane, 1,5- Examples include di (2-methyl-4-pyridyl) pentane, 1,5-di (2-ethyl-4-pyridyl) pentane, and 1,5-di (2-propyl-4-pyridyl) pentane.
[0016]
The colored photosensitive resin composition of the present invention contains a dye (B) as a pigment. The dye is not particularly limited as long as it can be dissolved in the photosensitive resin composition and can form the color filter layer of the color filter. For example, the colored photosensitive resin composition used for forming the yellow color filter layer includes CISolvent Yellow 82, CISolvent Yellow 162, and the like. Can be used.
[0017]
The colored photosensitive resin composition of the present invention contains an alkali-soluble resin (C). The alkali-soluble resin is a resin that can be dissolved in an alkaline developer, and the same alkali-soluble resin as that used in a normal photosensitive resin composition can be used. Examples of such alkali-soluble resins include novolak resins and vinyl phenol resins, and novolak resins are preferred. As the novolak resin, a novolak resin obtained by condensing p-cresol and formaldehyde, a novolak resin obtained by condensing p-cresol and m-cresol and formaldehyde, formula (1)

And novolak resin having a structural unit represented by Examples of the vinyl phenol resin include polyvinyl phenol and styrene-vinyl phenol copolymer.
[0018]
The colored photosensitive resin composition of the present invention contains a photosensitive agent (D). The photosensitive agent is a compound having a function of preventing the alkali-soluble resin from being dissolved in an alkaline solution when irradiated with light, and the same photosensitive agent as that used in a normal photosensitive resin composition is used. be able to. Examples of such a photosensitizer include an ester compound of a phenol compound and an o-naphthoquinone diazide sulfonic acid compound. Here, as the phenol compound, for example, the formula (2)

The compound shown by these is mentioned. Examples of the o-naphthoquinone diazide sulfonic acid compound include o-naphthoquinone diazide-5-sulfonic acid, o-naphthoquinone diazide-4-sulfonic acid, and the like.
[0019]
The colored photosensitive resin composition of the present invention contains a curing agent (E). As the curing agent, a thermosetting agent capable of curing the color filter layer by heating is usually used. As such a thermosetting agent, for example, the formula (3)

[In the formula, Z represents a substituent represented by —NQ ⁵ Q ⁶ or a phenyl group, and Q ^{1 to} Q ⁶ each independently represent a hydrogen atom, a substituent represented by — (CH ₂ ) _s OH, or — (CH a substituent represented by _{2) s} OQ ^0. Q ⁰ represents an alkyl group, and s represents an integer of 1 to 4. However, at least one of Q ^{1 to} Q ^{6 represents} a substituent represented by — (CH ₂ ) _s OH or a substituent represented by — (CH ₂ ) _s OQ ⁰ . ]
Compounds represented by formulas (31) to (36)

Or the like can be used.
[0020]
The colored photosensitive resin composition of the present invention is usually 25 to 55 parts by weight of the dye (B) and alkali-soluble in 100 parts by weight of the total amount of the dye (B), the alkali-soluble resin (C) and the photosensitive agent (D). 3 to 50 parts by weight of the resin (C) and 15 to 55 parts by weight of the photosensitive agent (D) are included. Moreover, a hardening | curing agent (E) normally contains 10-35 weight part of hardening | curing agents per 100 weight part of total amounts of dye (B), alkali-soluble resin (C), and a photosensitive agent (D).
[0021]
A colored photosensitive resin composition containing a dye (B), an alkali-soluble resin (C), a photosensitive agent (D) and a curing agent (E) contains at least one compound (A) selected from an amine compound and a pyridine compound. By doing so, the colored photosensitive resin composition can be stored and stabilized, there is little decrease in sensitivity due to storage, and it can be stored stably.
[0022]
The colored photosensitive resin composition of the present invention may be diluted with a solvent. Examples of the solvent include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, n-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, N , N′-dimethylformamide, cyclohexane, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, ethyl lactate and the like. Such solvents may be used alone or in combination of two or more. When diluting with a solvent, the solvent is usually used in an amount of about 180 to 400 parts by weight per 100 parts by weight in total of the dye, photosensitizer, alkali-soluble resin and curing agent.
[0023]
The colored photosensitive resin composition of the present invention is produced by, for example, mixing a dye, a photosensitive agent, an alkali-soluble resin, and a curing agent, and by mixing them in a solvent, the colored photosensitive resin diluted with the solvent. A composition can be produced.
[0024]
Such a colored photosensitive resin composition of the present invention has reduced reduction in sensitivity during storage, so that the color filter is formed by a method having a step of patterning the colored photosensitive resin composition to form a color filter layer. Even if it is a colored photosensitive resin composition after storage, it is exposed with the same light intensity and irradiation time as the colored photosensitive resin composition immediately after production, and the color filter layer is formed. Can be formed.
[0025]
In order to pattern using the colored photosensitive resin composition of the present invention, the layer (2) comprising the colored photosensitive resin composition of the present invention over the entire surface of the substrate (1) as usual. ) (FIG. 1 (a)), and the layer (2) is exposed to light (4) through the reticle (3) and exposed (FIG. 1 (b)).
[0026]
The substrate (1) may be a glass plate or the like, or a silicon wafer or the like. The silicon wafer may have a solid-state imaging device such as a charge coupled device (CCD) formed on the surface thereof. In order to form the colored photosensitive resin composition layer (2) of the present invention on such a substrate, the colored photosensitive resin composition may be applied by a method such as spin coating as usual. When the colored photosensitive resin composition is applied in a state diluted with a solvent, the solvent may be volatilized by heating after application.
[0027]
As the light beam (4), for example, i-line (wavelength 365 nm) can be used. The exposure can be performed using a normal exposure machine. An optical lens (not shown) may be arranged between the reticle (3) and the colored photosensitive resin composition layer (2). The optical lens is used, for example, to collect a light beam transmitted through the reticle and form a color filter layer having a size smaller than that of the reticle.
[0028]
Since the reticle (3) is provided with a region (31) that transmits the light beam (4) and a region (32) that shields it, the colored photosensitive resin composition layer (2) is irradiated with the light beam. (21) and a region (22) where no light is irradiated are generated (FIG. 1 (b)). The intensity of the light beam and the irradiation time in the exposure are appropriately selected, but the colored photosensitive resin composition of the present invention has reduced sensitivity during storage, so that the colored photosensitive resin after storage for a relatively long period of time is reduced. Even when the resin composition is used, exposure may be performed with the same intensity and irradiation time as the light intensity and irradiation time when the colored photosensitive resin composition immediately after production is used.
[0029]
After exposure, the colored photosensitive resin composition layer (2) is treated with an alkaline aqueous solution, so that the region (21) irradiated with light in the colored photosensitive resin composition layer (2) is dissolved in the alkaline aqueous solution. The region (22) that has not been irradiated with the light beam remains without being dissolved to form the color filter layer (51) (FIG. 1 (c)). As alkaline aqueous solution, it can use with the thing similar to what is normally used for image development of the photosensitive resin composition, and can also use what is marketed as a developing solution. In order to perform the treatment with the alkaline aqueous solution, for example, the exposed photosensitive resin composition layer (2) may be immersed in an alkaline aqueous solution together with the substrate (1). The color filter layer (51) is obtained by treating with an alkaline aqueous solution, washing with water and drying.
[0030]
Such a color filter layer is colored with a dye contained in the colored photosensitive resin composition. Further, the pattern is the same as the region (32) for shielding the light beam of the reticle, and may be, for example, a belt shape (FIG. 2 (a)) or a mosaic shape (FIG. 2 (b)). ).
[0031]
After the treatment with an alkaline aqueous solution, it is usually heated. By heating, the obtained color filter layer (51) hardens | cures and the mechanical strength can be improved.
[0032]
Next, the color filter layers (52, 53) corresponding to the three primary colors are sequentially formed by changing the color of the dye contained in the colored photosensitive resin composition and repeating the same operation as described above, and the color filter. (6) can be obtained (FIG. 3).
[0033]
The color filter (6) thus obtained is useful as a color filter for color liquid crystal display devices, color solid-state imaging devices and the like.
[0034]
【The invention's effect】
Since the colored photosensitive resin composition of the present invention has little decrease in sensitivity during storage, even after storage, the same as the intensity of light and the irradiation time when the colored photosensitive resin composition immediately after production is used. Can be exposed with the intensity and irradiation time.
[0035]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
[0036]
Example 1
(Production of colored photosensitive resin composition)
C.I. Solvent Yellow 82 (dye) 17.75 parts by weight, C.I. Solvent Yellow 162 (dye) 17.75 parts by weight, o-naphthoquinonediazide-5-sulfonic acid ester compound (photosensitive agent) 26.5 parts by weight, 18 parts by weight of novolak resin (alkali-soluble resin) having the structural unit represented by formula (1), formula (30)

Hexamethoxymethylmelamine (curing agent) 20 parts by weight, p-aminophenol (amine compound) 0.1 part by weight, ethyl lactate (solvent) 255.6 parts by weight and N, N′-dimethylformamide (Solvent) 109.5 parts by weight were mixed and filtered through a membrane filter (pore diameter 0.1 μm) to obtain a colored photosensitive resin composition.
[0037]
(Evaluation)
(1) Sensitivity immediately after production The colored photosensitive resin composition obtained immediately above is applied onto a silicon wafer (1) by spin coating, and heated at 100 ° C. for 1 minute to volatilize the solvent and colored. A photosensitive resin composition layer (2) was formed (FIG. 1 (a)). Next, exposure was performed by irradiating with an i-line (wavelength 365 nm) through a reticle (3) using an exposure machine (Nikon NSR 1755i7A, manufactured by Nikon Corporation) (FIG. 1 (b)), and then a developer. (Developed by Sumitomo Chemical Co., Ltd., “SOPD-T”, 23 ° C.) for 1 minute, developed, washed with water and dried to form a strip-like pattern with a line width of 50 μm and a thickness of 0.8 μm. A yellow filter layer (51) was formed (FIG. 3 (a)).
The same operation as described above is repeated while changing the exposure time in exposure, and the region (21) irradiated with light in the exposure of the colored photosensitive resin composition layer (2) is completely removed by development. The minimum exposure time required was defined as (T ₀ ).
(2) Sensitivity of colored photosensitive resin composition after storage The colored photosensitive resin composition obtained above is placed in a brown glass bottle and stored at room temperature for 2 weeks, and then operated in the same manner as described above. The minimum exposure time required to completely remove the region (21) irradiated with light in the exposure of the resin composition layer (2) was defined as (T ₁ ).
(3) Calculation of sensitivity change rate Calculation formula (4) from exposure times T ₀ and T ₁ obtained above
R = T ₁ / T ₀ (4)
Was used to calculate the rate of change in sensitivity (R). The results are shown in Table 1.
[0038]
Example 2
A colored photosensitive resin composition was obtained in the same manner as in Example 1 except that 0.1 part by weight of 1,3-di-4-pyridylpropane (pyridine compound) was used instead of p-aminophenol. Evaluation was made to determine the rate of change in sensitivity (R). The results are shown in Table 1.
[0039]
Comparative Example 1
A colored photosensitive resin composition was obtained in the same manner as in Example 1 except that a colored photosensitive resin composition was obtained without using p-aminophenol, and the rate of change in sensitivity (R) was determined by evaluation. . The results are shown in Table 1.
[0040]
[Table 1]

[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view for explaining a step of obtaining a color filter layer using a colored photosensitive resin composition.
FIG. 2 is a schematic cross-sectional view showing an example of the obtained color filter.
FIG. 3 is a schematic diagram illustrating an example of a pattern of a color filter layer.
[Explanation of symbols]
1: substrate 2: colored photosensitive resin composition layer 3: reticle 31: light transmitting region 32: light blocking region 4: light 51: color filter layer 52: color filter layer 53: color filter layer 6: color filter

Claims (7)

Amine compounds and at least one compound selected from pyridine compounds (A), the dye (B), the alkali-soluble resin (C), seen containing a photosensitive agent (D) and curing agent (E), the amine compound is the general formula ( A colored photosensitive resin composition, which is a compound represented by I-1) .

(In Formula (I-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ³ represents an alkyl group having 1 to 10 carbon atoms and 3 to 10 carbon atoms. A cycloalkyl group or an aryl group of   0.01 weight percent of at least one compound (A) selected from an amine compound and a pyridine compound per 100 weight parts in total of the dye (B), alkali-soluble resin (C), photosensitizer (D), and curing agent (E) The colored photosensitive resin composition according to claim 1, comprising at least part. Pyridine compounds are represented by the general formula (II)

(In the formula, R ⁴ represents an alkyl group, and i represents an integer of 0 to ^4. )
The colored photosensitive resin composition according to claim 1, which is a compound having a substituent represented by the formula: The pyridine compound is represented by the general formula (II-1)

(Wherein R ⁴ and i each have the same meaning as described above, n represents an integer of 1 to 8, R ⁵ represents an alkyl group, and j represents an integer of 0 to 4)
The colored photosensitive resin composition according to claim 3 , which is a compound represented by the formula:   The photosensitive resin composition of Claim 1 diluted with the solvent.   A method for producing a color filter, comprising a step of patterning the colored photosensitive resin composition according to claim 1 to form a color filter layer. A colored photosensitive resin composition containing a dye (B), an alkali-soluble resin (C), a photosensitizer (D), and a curing agent (E) is at least selected from the compound represented by formula (I-1) and a pyridine compound. A method for storage stabilization of a colored photosensitive resin composition, comprising one type of compound ( A ).

(In Formula (I-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and R ³ represents an alkyl group having 1 to 10 carbon atoms and 3 to 10 carbon atoms. A cycloalkyl group or an aryl group of

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