JP3611616B2 - Photopolymerizable composition, color filter using the same, and method for producing the same - Google Patents

Description

【００１３】
〔式中、
Ａｒ^１ ：フェニル基（該フェニル基は炭素数１から４のアルキル基、炭素数１から４のアルコキシ基、炭素数６から１０のアリール基、炭素数８から１２のアラルキル基、ハロゲン原子またはそれらの２種以上の組み合わせで置換されてもよい）
ｘ、ｙ：樹脂中での繰り返し単位のモル分率で、ｘ＝０．８５〜０．５５、ｙ＝０．１５〜０．４５
を表す。〕
Ｒ−ＮＨ_２ （ＩＩＩ）
〔式中、
Ｒ：炭素数１から１２のアルキル基、炭素数７から１６のアラルキル基、炭素数６から１８のアリール基を表す。（該アルキル基、アラルキル基、アリール基はそれぞれ分岐を有してもよく、更に炭素数１から４のアルキル基、炭素数１から６のアルコキシ基、炭素数６から１０のアリール基、炭素数７から１２のアラルキル基、ハロゲン原子またはそれらの２種以上の組み合わせで置換されてもよい）
を表す。〕
以下、本発明を詳細に説明する。
【００１４】
本発明に用いられる樹脂の組成は、繰り返し単位の組成比がｘ＝０．８５〜０．５５、ｙ＝０．１５〜０．４５が好ましいが、特に好ましくはｘ＝０．８０〜０．５５、ｙ＝０．２０〜０．４５である。該ｘの組成比が０．５５未満では光重合性組成物の露光部のアルカリ現像液への耐性が不足し、０．８５を越えると未露光部の該現像液による現像性が劣る。
【００１５】
樹脂の数平均分子量としては、５００から３０，０００の分子量を持つものが好ましいがより好ましくは７００から２０，０００である。数平均分子量が５００未満の共重合体は製造が難しく、３０，０００を越えると、感光性層のアルカリ現像性が劣るとともに、耐現像液性も劣る。すなわち、アルカリ現像性が劣るので長時間現像液に浸漬することになり、露光部も膨潤しやすくなるので良質な画像が得られない。
【００１６】
本発明に使用する樹脂は、例えば無水マレイン酸と以下の群の単量体の一種以上を常法に従い適当な溶媒中で重合開始剤の存在下で共重合させることにより得られる。単量体の例としては、スチレン、メチルスチレン、エチルスチレン、プロピルスチレン、イソプロピルスチレン、ブチルスチレン、ｓｅｃ−ブチルスチレン、ｔｅｒｔ−ブチルスチレン、ジメチルスチレン、ジエチルスチレン、メトキシスチレン、エトキシスチレン、プロポキシスチレン、ブトキシスチレン、ビニルビフエニル、ベンジルスチレン、クロロスチレン、フロロスチレン、ブロモスチレン、クロロ−メチルスチレン等が挙げられる。
【００１７】
また本発明の樹脂の性能を損なわない範囲で更にこれらと共重合可能な単量体と共重合させても良い。これらの内、特に好ましい例としてはスチレン／マレイン酸無水物共重合体が挙げられる。
【００１８】
本発明に用いられる同一分子中に１級アミノ基とエチレン性不飽和二重結合を有する化合物としては例えばアミノメチルスチレン、アミノスチレン、２−アミノエチル（メタ）アクリルアミド、３−アミノプロピル（メタ）アクリルアミド等が挙げられる。これらの内ではアミノメチルスチレンが特に好ましい。
【００１９】
また上記のアミノメチルスチレンの他に一般式（ＩＩＩ）で示される１級アミンを併用してもよい。この様な１級アミンの具体例としては、ベンジルアミン、フェネチルアミン、３−フェニル−１−プロピルアミン、４−フェニル−１−ブチルアミン、５−フェニル−１−ペンチルアミン、６−フェニル−１−ヘキシルアミン、α−メチルベンジルアミン、２−メチルベンジルアミン、３−メチルベンジルアミン、４−メチルベンジルアミン、２−（ｐ−トリル）エチルアミン、β−メチルフェネチルアミン、１−メチル−３−フェニルプロピルアミン、２−クロロベンジルアミン、３−クロロベンジルアミン、４−クロロベンジルアミン、２−フロロベンジルアミン、３−フロロベンジルアミン、４−フロロベンジルアミン、４−ブロモフェネチルアミン、２−（２−クロロフェニル）エチルアミン、２−（３−クロロフェニル）エチルアミン、２−（４−クロロフェニル）エチルアミン、２−（２−フロロフェニル）エチルアミン、２−（３−フロロフェニル）エチルアミン、２−（４−フロロフェニル）エチルアミン、４−フロロ−α、α−ジメチルフェネチルアミン、２−メトキシベンジルアミン、３−メトキシベンジルアミン、４−メトキシベンジルアミン、２−エトキシベンジルアミン、２−メトキシフェネチルアミン、３−メトキシフェネチルアミン、４−メトキシフェネチルアミン等を挙げる事ができる。特に好ましい１級アミンの例はベンジルアミン、フェネチルアミンである。
【００２０】
本発明において、アミノメチルスチレンのみを用いることも可能だが、原材料コストの面からは性能上問題の無い範囲内で一般式（ＩＩＩ）で示される１級アミンを併用することが望ましい。アミノメチルスチレン又は同一分子中に１級アミノ基とエチレン性不飽和二重結合を有する化合物と一般式（ＩＩＩ）又は（ＩＶ）で示される１級アミンの比率の好ましい範囲としては、１００：０〜１０：９０モル比であり、特に好ましくは１００：０〜２０：８０モル比である。該１級アミンの比率が９０モル％を越えると透明導電性層の形成性に劣る。
【００２１】
又、本発明において、（ａ）該共重合体と（ｂ）アミノメチルスチレン、及び必要に応じて併用する１級アミンの反応比率、また、同一分子中に１級アミノ基とエチレン性不飽和二重結合を有する化合物及びこれと併用する１級アミンの反応比率は、マレイン酸無水物基の１当量に対し、０．１から１．０当量が好ましいが、特に好ましくは０．２から１．０当量である。０．１当量未満では光重合性組成物の露光後の耐アルカリ現像液性が劣る。またアミンの仕込量をマレイン酸無水物当量より過剰にすることで目的の反応を効率的に進行させることができるが、その場合は過剰のアミンを共重合体の再沈澱などの方法により除去、精製することが望ましい。
【００２２】
光重合性組成物中における樹脂の全量は、組成物中の固形分に対して２０重量％から９０重量％であり、特に好ましくは３０重量％から７０重量％である。２０重量％未満では感光性層のタッキネスが増加してしまい取り扱い性に劣り、９０重量％を超えると組成物の露光部のアルカリ現像液への耐性が劣る。
【００２３】
エチレン性不飽和二重結合を有する付加重合性モノマーは単独でまたは他のモノマーとの組み合わせで使用することができるもので、具体的には、ｔ−ブチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、２−エチル−２−ブチル−プロパンジオールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ポリオキシエチル化トリメチロールプロパントリ（メタ）アクリレート、トリス（２−（メタ）アクリロイルオキシエチル）イソシアヌレート、１，４−ジイソプロペニルベンゼン、１，４−ジヒドロキシベンゼンジ（メタ）アクリレート、デカメチレングリコールジ（メタ）アクリレート、スチレン、ジアリルフマレート、トリメリット酸トリアリル、ラウリル（メタ）アクリレート、（メタ）アクリルアミドまたはキシリレンビス（メタ）アクリルアミドが含まれる。また２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等のようなヒドロキシル基を有する化合物とヘキサメチレンジイソシアネート、トルエンジイソシアネート、キシレンジイソシアネート等のジイソシアネートとの反応物も使用できる。これらの内、特に好ましいのはペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート、トリス（２−アクリロイルオキシエチル）イソシアヌレートである。
【００２４】
光重合性組成物中におけるモノマーの全量は、組成物の全固形分に対して１０重量％から８０重量％であり、特に好ましくは３０重量％から７０重量％である。１０重量％未満では組成物の露光部のアルカリ現像液への耐性が劣り、８０重量％を越えると感光性層のタッキネスが増加してしまい取り扱い性に劣る。
【００２５】
本発明の光重合性組成物中に含ませる光重合開始剤または光重合開始剤系は、実質的に、既知の全ての開始剤あるいは開始剤系を使用する事ができる。例としては、ｐ−メトキシフェニル−２，４−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−ブトキシスチリル）−５−トリクロロメチル−１，３，４−オキサジアゾール、９−フェニルアクリジン、９，１０−ジメチルベンズフェナジン、ベンゾフェノン／ミヒラーズケトン、ヘキサアリールビイミダゾール／メルカプトベンズイミダゾール、ベンジルジメチルケタール、チオキサントン／アミン、特願平６−２１２７９４号公報に記載のビス（ハロゲン置換メチルオキサジアゾール）、特願平６−２５３７５６号公報に記載のトリハロメチル−ｓ−トリアジン、特願平６−２６８９５３号公報に記載のビス（トリハロメチル−ｓ−トリアジン）などがある。特に好ましいのは２−（ｐ−ブトキシスチリル）−５−トリクロロメチル−１，３，４−オキサジアゾールのようなトリハロメチル基含有化合物である。光重合開始剤の添加量は全固形分の０．１重量％から２０重量％、特に好ましくは０．５重量％から５重量％である。０．１重量％未満では組成物の光硬化の効率が低いので露光に長時間がかかり、２０重量％を越えると、紫外線領域から可視領域での光透過率が劣化するのでカラーフィルターの保護層には不適となる。更に公知の添加剤、例えば可塑剤、充填剤、安定化剤等を含有させる事ができ、カラーフイルターの保護層以外の用途には顔料、染料等を添加することもできる。
【００２６】
本発明の光重合性組成物は、カラーフィルターの保護層形成用材料として好適である。即ち、本発明の光重合性組成物を前記画素を有するカラーフィルターの上に層状に設けた後、露光・現像・加熱等の工程を経て保護層を形成する。層状に設けるには、例えば溶液をロールコーター、バーコーターなどにより塗布する方法、溶液を噴霧吹き付け・液中に浸漬するなどの公知の手段により塗布する方法、もしくは仮支持体上に光重合性組成物層を形成し、これを転写する方法等がある。
保護層の厚さは通常０．１μｍから５０μｍであり、特に好ましくは、０．５μｍから５μｍである。
【００２７】
カラーフィルターの支持体としては、金属性支持体、金属張り合わせ支持体、ガラス、セラミック、合成樹脂フイルム等を使用することができる。特に好ましくは、透明で寸度安定性の良好なガラスや合成樹脂フイルムを挙げることができる。
【００２８】
本発明の光重合性組成物は層転写材料としても使用される。即ち、光重合性組成物は仮支持体、好ましくはポリエチレンテレフタレートフィルム上に直接、または酸素遮断層、剥離層、もしくは剥離層および酸素遮断層を設けたポリエチレンテレフタレートフィルム上に層状に設け、通常その上に取扱上の保護のために除去可能な合成樹脂製カバーシートを積層する。または仮支持体上にアルカリ可溶性熱可塑性樹脂層及び中間層を設け、更に光重合性組成物層を設けた層構成（特開平５−１７３３２０号公報に記載）も適用できる。
【００２９】
使用時に該カバーシートを除去し、光重合性組成物層を永久支持体上、例えばカラーフィルター画素を有する支持体表面に積層する。ついで、酸素遮断層、剥離層等があるときはそれらの層と仮支持体の間で、剥離層および酸素遮断層があるときは剥離層と酸素遮断層の間で、剥離層も酸素遮断層もないときには仮支持体と光重合性組成物層の間で剥離して、仮支持体を除去することにより、該組成物層をカラーフィルター層上に積層する。ついで露光を行うが、ＳＴＮの場合の様に、カラーフィルター層上に保護層を介して透明電極を形成する時には、マスクを通して露光し、現像して保護層をパターンニングする。現像は重合していない領域を適当なアルカリ現像液で洗い去ることによっておこなわれる。
一方、ＴＦＴの場合の様に、全面に透明導電層を有する時には、マスクを必要としない。
【００３０】
本発明の光重合性組成物の現像液としては、アルカリ性物質の希薄水溶液を使用するが、さらに水と混和性の有機溶剤を少量添加したものも含まれる。適当なアルカリ性物質はアルカリ金属水酸化物類（例えば水酸化ナトリウム、水酸化カリウム）、アルカリ金属炭酸塩類（例えば炭酸ナトリウム、炭酸カリウム）、アルカリ金属重炭酸塩類（炭酸水素ナトリウム、炭酸水素カリウム）、アルカリ金属ケイ酸塩類（ケイ酸ナトリウム、ケイ酸カリウム）アルカリ金属メタケイ酸塩類（メタケイ酸ナトリウム、メタケイ酸カリウム）、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、モルホリン、テトラアルキルアンモンニウムヒドロキシド類（例えばテトラメチルアンモニウムヒドロキシド）または燐酸三ナトリウムである。アルカリ性物質の濃度は、０．０１重量％〜３０重量％であり、ｐＨは８〜１４が好ましい。
【００３１】
水と混和性のある適当な有機溶剤は、メタノール、エタノール、２−プロパノール、１−プロパノール、ブタノール、ジアセトンアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノｎ−ブチルエーテル、ベンジルアルコール、アセトン、メチルエチルケトン、シクロヘキサノン、ε−カプロラクトン、γ−ブチロラクトン、ジメチルホルムアミド、ジメチルアセトアミド、ヘキサメチルホスホルアミド、乳酸エチル、乳酸メチル、ε−カプロラクタム、Ｎ−メチルピロリドンである。水と混和性の有機溶剤の濃度は０．１重量％〜３０重量％である。さらに公知の界面活性剤を添加することができる。界面活性剤の濃度は０．０１重量％〜１０重量％が好ましい。
【００３２】
現像液は、浴液としても、あるいは噴霧液としても用いることができる。光重合性組成物層の未硬化部分を除去するには現像液中で回転ブラシで擦るか湿潤スポンジで擦るなどの方法を組み合わせることができる。現像液の液温度は通常室温付近から４０℃が好ましい。現像処理の後に水洗工程を入れることも可能である。
【００３３】
現像工程の後、加熱処理を行う。即ち、露光により光重合した層（以下、光硬化層と称する）を有する支持体を電気炉、乾燥器等の中で加熱する、または光硬化層に赤外線ランプを照射する。加熱の温度及び時間は使用した重合性組成物の組成や形成された層の厚みに依存する。一般に、十分な耐溶剤性、耐アルカリ性を獲得するのに、約１２０℃から約２５０℃で約１０分から約６０分間加熱することが好ましい。
【００３４】
次に、こうして形成された保護層の上にＩＴＯ（酸化インジウムスズ）層をスパッタ法により形成する。ＩＴＯ層を透明電極として加工する場合には、該ＩＴＯ層上にフォトレジスト層を形成し、電極パターンを焼き付け、フォトレジスト層を現像し、該ＩＴＯ層をエッチングし、該フォトレジストを剥離する。さらに配向膜の形成には、一般的にはＮ−メチルピロリドンやγ−ブチロラクトンのような極性有機溶媒を溶剤として含むポリイミドのような配向膜形成用塗液が塗布され、乾燥され、配向処理が施される。
【００３５】
本発明の光重合性組成物は、公知の種々の方法、例えば転写法、着色レジスト法、染色法、印刷法、電着法等のいずれの方法で作成されたカラーフィルターに対しても、保護層形成用材料として有用である。
【００３６】
本発明の光重合性組成物はカラーフィルター層上の保護層形成に好適に使用できるが、この用途に限定されるものではない。染料、顔料を含有させて高度の耐薬品性が必要とされるカラーフィルター画素形成用の着色レジスト（例えば特開昭６３−２９８３０４に開示）、プリント基板用ソルダーレジスト（例えば特開平３−２２３８５６に開示）、無電解メッキ用レジスト（同公報に開示）、電気素子の保護膜、層間絶縁膜、接着剤（以上例えば特開平３−１２６９５０に開示）、スペーサー材料等にも有用である。
以下、本発明を実施例によって説明するが、本発明はこれらに限定されるものではない。特に断らない限り、「部」は重量部を、「％」は重量％を表す。
【００３７】
【実施例】
合成例１
スチレン／マレイン酸無水物＝６８／３２モル比の共重合体（数平均分子量＝２８００）１１０．３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／メチルエチルケトン＝１／１重量比の混合溶媒４４１．２部に溶解した。これにアミノメチルスチレン１４．４部（酸無水物に対して０．５当量）、ベンジルアミン２７．０部（酸無水物に対して０．５当量）、２，５−ジ−ｔ−ヘキシルハイドロキノン０．０２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／メチルエチルケトン＝１／１重量比の混合溶媒１６５．６部に溶解した溶液を室温で約１時間かけて滴下した。更に室温下で６時間攪拌することでスチレン／マレイン酸無水物共重合体の変性体を得た。
【００３８】
実施例１
＜カラーフィルター層の作成＞
厚さ１００μｍのポリエチレンテレフタレートフィルム仮支持体の上に下記の処方Ｈ１からなる塗布液を塗布、乾燥させ、乾燥膜厚が２０μｍの熱可塑性樹脂層を設けた。
【００３９】

【００４０】
次に上記熱可塑性樹脂層上に下記処方Ｂ１から成る塗布液を塗布、乾燥させ、乾燥膜厚が１．６μｍ厚の分離層を設けた。

【００４１】
上記熱可塑性樹脂層及び分離層を有する４枚の仮支持体の上に、それぞれ表１の処方を有する、黒（Ｂｌ層用）、赤（Ｒ層用）、青（Ｂ層用）及び緑（Ｇ層用）の４色の感光性溶液を塗布、乾燥させ、乾燥膜厚が２μｍの着色感光性樹脂層を形成した。
【００４２】

【００４３】
さらに上記感光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、赤色、青色、緑色および黒色感光性転写材料を作成した。この感光性転写材料を用いて、以下の方法でカラーフィルターを作成した。赤色感光性転写材料の被覆シートを剥離し、感光性樹脂層面を透明ガラス基板（厚さ１．１ｍｍ）にラミネーター（大成ラミネータ（株）製ＶＰ−ＩＩ）を用いて加圧（０．８ｋｇ／ｃｍ^２）、加熱（１３０℃）して貼り合わせ、続い て分離層と熱可塑性樹脂層との界面で剥離し、仮支持体と熱可塑性樹脂層を同時に除去した。次に所定のフォトマスクを介して露光し、下記処方の現像液を用いて３５℃で８０秒間浸漬し、不要部を除去した後、水洗・乾燥を行い、ガラス基板上に赤色画素パターンを形成した。
【００４４】
現像液処方
・炭酸ナトリウム １５ｇ
・ブチルセロソルブ １ｇ
・水 １ｋｇ
【００４５】
次いで、赤色画素パターンが形成されたガラス基板上に、緑色感光性転写材料を上記と同様にして貼り合わせ、剥離、露光、現像を行ない、緑色画素パターンを形成した。同様な工程を青色、黒色感光性転写材料で繰り返し、透明ガラス基板上にカラーフィルターを形成した。
【００４６】
＜保護層形成用塗液の製造＞
次の組成で混合溶解し、０．２μｍの穴径のフィルターでろ過し保護層形成用塗液を調製した。

【００４７】
＜保護層の製造＞
１．１ｍｍ厚のガラス基板（大きさ３５０ｍｍ×４００ｍｍ）上に形成された、Ｒ（赤）、Ｇ（緑）、Ｂ（青）の画素を有するカラーフィルター層上に前記の保護層形成用塗液を、スピンコーターで塗布して乾燥し、３μｍ厚みの保護層形成用感光性層を形成した。超高圧水銀灯光源のアライナーを用い、保護層焼き付け用マスクを通して２００ｍｊ／ｃｍ^２ の光量で紫外線照射した。その後、１％炭酸ナトリウム水溶液である現像液をこの基板上に噴霧する事により現像し、水洗した。その後、加熱処理のため、２００℃の乾燥器中に２０分間放置したあとで冷却した。
【００４８】
こうして得られたカラーフィルター層上の保護層に、ＩＴＯ膜をスパッタする事により０．２μｍ厚で設け、さらにＩＴＯ膜上にポジ型フォトレジスト（フジハントエレクトロニクステクノロジー社製、ＦＨ２１３０）を形成後、電極パターンマスクを介して露光し、現像し、塩酸／塩化鉄水溶液でＩＴＯ層をエッチングし、レジスト剥離液（フジハントエレクトロニクステクノロジー社製、ＭＳ２００１）で剥離したところ、全く欠陥のないＩＴＯ電極が得られた。粘着テープを用いてこの電極を剥離しようとしたが剥がれなかった。またこの上に配向膜塗液（ポリイミド樹脂のＮ−メチルピロリドン／γ−ブチロラクトン溶液）を、スピンコーターで塗布し乾燥したが、膨潤する事なく配向膜層が得られた。
その他の項目の評価結果を表３に示す。
【００４９】
実施例２ （フィルム状保護層形成用材料）
実施例１の保護層形成用塗液を厚さ７５μｍのポリエチレンテレフタレートフィルム仮支持体上に塗布し、乾燥して３μｍ厚の保護層形成用感光性層を形成した。この上に厚さ１５μｍのポリプロピレン製カバーシートをラミネートし、フィルム状保護層形成用材料を得た。実施例１に記載のカラーフィルター層を有するガラス基板を用意した。まず、該フィルム状保護層形成用材料からカバーシートを除去し、該感光性層をカラーフィルター層と接触するように重ね、ラミネータを用い積層した。その後該仮支持体を剥したところ、カラーフィルター層上に感光性層が形成された。以下は実施例１と同様に、感光性層を露光現像し、加熱処理する事で、保護層が形成された。この保護層上に、実施例１と同様にＩＴＯの電極を形成したところ、密着し、欠陥のないＩＴＯ電極が得られた。また同様に保護層が膨潤する事なく、配向膜も形成する事ができた。
又、その他の項目の評価結果を表３に示す。
【００５０】
実施例３
実施例１で作成した熱可塑性層と分離層を有するポリエチレンテレフタレートフィルム仮支持体上に、実施例１の保護像形成用塗液を塗布し、この上に厚さ１５μｍのポリプロピレン製カバーフィルムをラミネートしてフィルム状感光性転写材料を得た。実施例２と同様にしてカラーフィルター層を有するガラス基板上に該フィルム状感光性転写材料を積層し、仮支持体を剥離除去後、実施例１と同様にして露光現像し、加熱処理を施したところ、カラーフィルター層の画素部に気泡やピンホール等の欠陥の無い保護層が得られた。鉛筆硬度は５Ｈであった。この保護層上に、実施例１と同様にＩＴＯの電極を形成したところ、シワやクラック等の欠陥もなくまた密着も申し分のないＩＴＯ電極が得られた。また同様に保護層が膨潤することなく、配向膜も形成できた。
又、その他の項目の評価結果を表３に示す。
【００５１】
合成例２〜１１
表２に示した樹脂、同一分子中に１級アミノ基とエチレン性不飽和二重結合を有する化合物、及び必要に応じて更にその他の１級アミンを用いて、合成例１と同様にしてスチレン／マレイン酸無水物共重合体の変性体（分子中にマレイン酸モノアミドとエチレン性不飽和二重結合とを有する樹脂）、又は比較用にスチレン／マレイン酸無水物共重合体のアミン変性体（分子中にマレイン酸モノアミドを有する樹脂）等を得た。
【００５２】

【００５３】
合成例１２
スチレン／マレイン酸無水物＝６８／３２モル比の共重合体（数平均分子量＝２８００）１２２．５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／メチルエチルケトン＝５０／５０重量比の混合溶媒４９０．０部に溶解した。これに２−ヒドロキシエチルアクリレート４６．４部（酸無水物に対して１．０当量）、プロピレングリコールモノメチルエーテルアセテート／メチルエチルケトン＝５０／５０重量比の混合溶媒１８５．６部、４−ジメチルアミノピリジン２．４部、２，５−ジ−ｔ−ヘキシルハイドロキノン０．０５部を加え６０℃で１２時間反応させる事によりスチレン／マレイン酸無水物共重合体の変性体（分子中にカルボキシル基とエチレン性不飽和二重結合とを有する樹脂）を得た。
【００５４】
合成例１３
特開平５−２５７００９号明細書に記載の実施例３のメタクリル酸メチル／スチレン／マレイン酸とグリシジルメタクリレートの付加反応物（分子中にカルボキシル基とエチレン性不飽和二重結合とを有する樹脂）に関して実施した。
【００５５】
合成例１４
特開平２−９７５０２号明細書に記載の実施例１のスチレン／メチルメタクリレート／マレイン酸無水物共重合体（数平均分子量３００００、マレイン酸無水物単位は１６モル％、プロピルアミン１．１当量使用）に関して実施した。
【００５６】
実施例４〜１０及び比較例１〜６
実施例３と同様にして合成例２〜８（実施例）及び９〜１４（比較例）の樹脂を用いて保護層形成用塗布液を調製し、同様に評価を行った。
評価結果を表３に示す。
【００５７】
比較例７
実施例３のジペンタエリスリトールヘキサアクリレート１．４部を６．８部に変更する以外は実施例３と同様にして合成例９の樹脂を用いて保護層形成用塗布液を調製し、同様に評価を行った。
評価結果を表３に示す。
各サンプルの性能の評価方法を以下に記す。
【００５８】
１．現像性
ガラス基板上にスピンコーターで、３μｍの膜厚になるように塗布した感光性層を１％炭酸ナトリウム水溶液中に３０℃で１分間浸漬して、溶解するかどうかで評価した。
【００５９】
２．耐現像液性
ガラス基板上に３μｍの膜厚になるように、スピンコーターで塗布した感光性層を、８０μｍ×３００μｍの矩形の画像が得られるマスクを通して２００ｍｊ／ｃｍ^２ 露光し、１％炭酸ナトリウム水溶液中に３０℃で１分間浸漬して、露光部が基板に密着しているかどうかで評価した。
【００６０】
３．平坦性
ガラス基板上の２μｍ厚のカラーフィルター層上（２μｍの凹凸有り）に３μｍになるように感光性層を形成し、露光（２００ｍｊ／ｃｍ^２ ）、現像、後加熱（２００℃、６０分）して得られる保護層の表面の凹凸を、膜厚計を用いて測定して評価した。
【００６１】
４．硬度
ガラス基板上に３μｍ厚の感光性層を形成し、露光（２００ｍｊ／ｃｍ^２）、 現像、後加熱（２００℃、６０分）したあとで、ＪＩＳ Ｋ５４００の鉛筆硬度試験に従って評価した。
【００６２】
５．耐アルカリ性
ガラス基板上に３μｍ厚の感光性層を形成し、露光（２００ｍｊ／ｃｍ^２）、 現像、後加熱（２００℃、６０分）したあとで、５％ＫＯＨ水溶液に５０℃で３０分間浸漬した後で、表面にシワや濁りが生成しないかどうかで評価した。
【００６３】
６．光透過性
ガラス基板上に３μｍ厚の保護層形成用感光性層を形成し、全面露光（２００ｍｊ／ｃｍ^２）、現像、後加熱（２００℃、６０分）したあとで、表面のクリヤ ーなものを透明性良好、曇りの発生するものを透明性不良と判定した。
【００６４】
７．基板密着性
ガラス基板上に３μｍ厚の保護層形成用感光性層を形成し、全面露光（２００ｍｊ／ｃｍ^２）し、現像後、及び後加熱（２００℃、６０分）したあとで、クロ スカットし、マイラーテープで剥離して密着性を評価した。１００ケのクロスカット部に何も剥がれの無いものを密着性良好、１ケ所でも剥がれを生じたものを密着性不良と判定した。
【００６５】
８．透明導電性層の形成性
ガラス基板上に３μｍ厚の保護層形成用感光性樹脂層を形成し、全面露光（２００ｍｊ／ｃｍ^２）、現像、後加熱（２００℃、６０分）したあとで日電アネル バ社製高周波スパッタリング装置を用い、インジウムスズ酸化物（スズ酸化物含有率６重量％）を電圧８００Ｖ、電流１．８Ａ、出力２７０Ｗ、アルゴン圧力５×１０^−４Ｔｏｒｒの条件で１０分間蒸着した。得られた透明導電性層の面状を顕微鏡で観察し、更にテープ剥離による密着テストを行ない、透明導電性層の形成性を評価した。透明導電性層の表面が平坦かつ均一で、密着テストで剥がれ等の故障のないものを透明導電性層の形成性良好、透明導電性層の表面にシワやクラックが発生しているもの、或いは密着テストにより透明導電性層が剥がれてしまうものは形成性不良と判定した。
【００６６】
９．タック
ガラス基板上にスピンコーターで３μｍの膜厚になるように塗布し、８０℃で２分間乾燥して保護層形成様感光性層を得た。指触テストにより表面の粘着性を評価し、同様にして得られたカラーモザイクＫ（富士ハントエレクトロニクステクノロジー製）の塗膜の表面の粘着性と比較し、カラーモザイクＫの塗膜と同等以上を良好とした。
以上の項目の評価結果を表３に示す。
【００６７】
【表１】

【００６８】
これから、評価したすべての項目に於いて、本発明になる光重合性組成物が優れた性能を発揮していることが判る。
【００６９】
【発明の効果】
本発明の光重合性組成物は、優れたアルカリ溶解性を有し、かつ光重合した部分は優れた耐現像液性、硬度、耐アルカリ性、光透過性、基板密着性、透明導電性層形成性、低いタックを有する。カラーフィルターの保護層の形成に特に有用で、耐性の優れた、平坦性の高い保護層を形成することができる。[0001]
[Industrial application fields]
The present invention relates to a photopolymerizable composition that is excellent in chemical resistance of a cured product after photopolymerization and heat treatment and can be developed with an aqueous alkali solution. The photopolymerizable composition according to the present invention is particularly useful for forming a protective layer for a color filter.
[0002]
[Prior art]
A color filter is an important part of a liquid crystal display panel and has various required performance items. Especially when used as an STN or FLC liquid crystal display panel, the formation of a transparent conductive layer provided on the color filter and subsequent transparency In processing into electrodes, heat resistance and chemical resistance are particularly important. That is, the liquid crystal display panel is usually provided with a multicolor pixel layer on a glass transparent substrate. This multi-color pixel layer is usually one in which red, green and blue pixels are alternately arranged in a matrix. Although the size of this pixel varies depending on the purpose of use, one side has a size of about 10 to 100 μm × 50 to 400 μm, and the shape is not necessarily a rectangle of the above size. In some cases, the shape is processed into a desired shape. Further, in some cases, those having a black matrix or a light blocking black matrix between the red, green, and blue pixels or in the outer peripheral portion are also used. Furthermore, a color filter is obtained by forming a protective layer on the layer of such multicolor pixels. A transparent conductive layer is usually formed thereon by sputtering ITO. Thereafter, in the case of an STN type or a ferroelectric liquid crystal type panel, it is further processed into a transparent electrode by photolithography to obtain a color filter with an electrode. Then, an alignment film is formed on the color filter with electrodes. Further, after sealing a transparent electrode and an alignment film on another transparent substrate with a spacer while maintaining a certain gap, a liquid crystal is injected between the two substrates to produce a panel.
[0003]
In the process of forming a color filter for this series of liquid crystal display panels, the protective layer on the multi-color pixel layer 1) provides flatness, and 2) does not sink the spacers in order to secure the liquid crystal cell gap. 3) Resisting to various chemicals (photoresist solvent, acidic etching solution, alkaline resist stripping solution, alignment film coating solution, etc.) used in the photolithography process of the transparent conductive layer, showing sufficient hardness Furthermore, 4) transparency in the visible light region, no cloudiness or turbidity, and 5) direct contact with the multicolor pixel layer, as well as directly on the substrate on which no multicolor pixels are formed. In some cases, it is necessary to have excellent adhesion to the substrate. For this purpose, epoxy compounds described in JP-A-60-216307 and polyvalent carboxylic acids or anhydrides thereof, nylon resins described in JP-A-60-244932, melamine described in JP-A-63-131103 Thermosetting resins such as compounds and epoxy resins have been proposed. Certainly, these thermosetting resins can achieve almost the target in the required performances 1) to 4).
[0004]
However, in order to ensure the seal in the non-pixel portion of the protective layer, there is a request that it must be removed on the transparent substrate, Japanese Patent Laid-Open Nos. 57-42009, 1-130103, and 1 There has been a request that the protective film on the scribe line must be removed as described in JP-A-134306. However, it is difficult to accurately carry out these with the thermosetting resin as described above. Furthermore, since such thermosetting resins are generally a combination of a curing agent and an epoxy resin, mixing these two reactive components causes the reaction to progress over time and increase the viscosity of the coating solution, resulting in a uniform film thickness. However, there are disadvantages that the usable time is short and it is difficult to obtain the accuracy of the film thickness.
[0005]
As an effective means for solving these problems, a so-called photosensitive resin type that is photosensitive and can develop an unexposed portion has been demanded. Examples of known photosensitive, photo-sensitive, provided on a color filter layer by a method such as coating, and photocured to be used as a protective layer include Japanese Patent Application Laid-Open Nos. 57-42009 and UV-curable resin described in JP-A-60-244932, vinylcarbonyl group-containing polymer described in JP-A-59-7317, photosensitive resin comprising PVA and photosensitizer in JP-A-59-184325, JP-A-60 Known are a rubber-based resin described in Japanese Patent No. 42704, a photosensitive resin obtained by removing a pigment from a pigment-dispersed photosensitive resin composition used as a colored layer described in JP-A-2-191901, and the like.
[0006]
Further, a protective layer that is cured by light and can be developed with an alkaline aqueous solution in which the unexposed portion is advantageous in terms of hygiene and pollution control, and then gives a further greater alkali resistance to the cured film by heating, is most preferred. It is known that this method is possible by using the composition described in JP-A-3-126950, the composition described in JP-A-52-132091, and the composition described in JP-B-4-20923. ing.
[0007]
However, these photosensitive protective layer forming compositions still have developability when formed into a photosensitive coating, stickiness of the surface (tack), alkali resistance of coatings and images after curing after development, It was insufficient in terms of solvent resistance, transparency, and adhesion to the substrate. Further, there is a method of forming a photopolymerizable composition layer composed of such a composition on a temporary support and transferring it, but the transferability in such a case is insufficient. Furthermore, when forming a transparent conductive layer on a protective layer, it has resistance to the above-mentioned various chemicals (photoresist solvent, acidic etching solution, alkaline resist stripping solution, alignment film coating solution, etc.). However, there is a problem that defects such as cracks occur in the formed transparent conductive layer.
[0008]
Therefore, as a method for solving such a problem, we have already found a method described in Japanese Patent Application No. 5-202272, Japanese Patent Application Laid-Open No. 5-265208, and the like. However, even in these methods, a large amount of a photopolymerizable monomer component is required in order to ensure developability and formability of the transparent conductive layer, and there is a problem that tack is slightly increased in some cases. .
[0009]
In order to reduce the use amount of the photopolymerizable monomer component, for example, it is conceivable to introduce a polymerizable group into the polymer binder. Such compounds are known per se. For example, Japanese Patent Publication No. 51-37316 describes examples of polymer compounds containing a carboxyl group and an ethylenically unsaturated double bond. Japanese Patent Application Laid-Open No. 5-257209 describes an example in which a polymer compound containing a carboxyl group and an ethylenically unsaturated double bond is used for a protective film of a color filter. However, even in these methods, since carboxyl groups remain in the cured resin, there is a problem in alkali resistance after curing, particularly chemical resistance when forming a transparent conductive layer.
[0010]
[Problems to be solved by the invention]
Therefore, the object of the present invention is to provide each required performance in 1) flatness, 2) hardness, 3) chemical resistance, 4) transparency, 5) adhesion to the substrate, and 6) formability of the transparent conductive layer. An object of the present invention is to provide a photopolymerizable composition excellent in alkali developability and free of tack, which gives a protective layer (OC layer) to be provided, in particular, a binder for constituting it.
The second object of the present invention is to provide a photopolymerizable composition that can be subjected to alkali resistance treatment of a photocured product after development at a relatively low temperature and in a short processing time, and has few components volatilized during the heat treatment. Is to provide.
A third object of the present invention is to provide a method for producing a color filter particularly useful for a liquid crystal display panel, wherein the photopolymerizable composition is used and a protective layer is formed on the color filter by a coating method or a transfer method. There is a thing.
[0011]
[Means for Solving the Problems]
As a result of diligent efforts, the inventors of the present invention
1. (1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) A resin having a repeating unit and having a number average molecular weight of 500 to 30,000, (b) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule, and the following general formula (IV) With primary amine In the following general formula (II) A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of an anhydride group,
Ar ² -R'-NH ₂ (IV)
[Where,
R ′: alkylene having 1 to 6 carbon atoms which may have a branch;
Ar ² : An aryl group (the aryl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a halogen atom, or a 2 thereof) Which may be substituted with a combination of more than one species). ]
2. (1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) A resin having a repeating unit and having a number average molecular weight of 500 to 30,000, (b) aminomethylstyrene, and, if necessary, a primary amine represented by the following general formula (III) In the following general formula (II) A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of an anhydride group, and
3. It has been found that this can be achieved by a color filter having a protective layer prepared using the photopolymerizable composition or the following photopolymerizable compositions a and b, and the present invention has been achieved.
Photopolymerizable composition a
(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) A resin having a repeating unit and having a number average molecular weight of 500 to 30,000 and (b) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule In the following general formula (II) A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of an anhydride group.
Photopolymerizable composition b
(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) (B) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule, and the following general formula (III) The total amount of primary amine In the following general formula (II) A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of an anhydride group.
[0012]
[Chemical Formula 10]

[0013]
[Where,
Ar ¹ : Phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or a combination thereof) May be substituted with a combination of more than one species)
x, y: molar fraction of repeating units in the resin, x = 0.85 to 0.55, y = 0.15 to 0.45
Represents. ]
R-NH ₂ (III)
[Where,
R: represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or an aryl group having 6 to 18 carbon atoms. (The alkyl group, aralkyl group and aryl group may each have a branch, and further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number. And may be substituted with 7 to 12 aralkyl groups, halogen atoms, or combinations of two or more thereof)
Represents. ]
Hereinafter, the present invention will be described in detail.
[0014]
The composition of the resin used in the present invention is preferably such that the composition ratio of repeating units is x = 0.85 to 0.55 and y = 0.15 to 0.45, particularly preferably x = 0.80 to 0.00. 55, y = 0.20 to 0.45. When the composition ratio of x is less than 0.55, the resistance of the exposed portion of the photopolymerizable composition to the alkaline developer is insufficient, and when it exceeds 0.85, the developability of the unexposed portion by the developer is poor.
[0015]
The number average molecular weight of the resin is preferably 500 to 30,000, but more preferably 700 to 20,000. A copolymer having a number average molecular weight of less than 500 is difficult to produce, and if it exceeds 30,000, the alkali developability of the photosensitive layer is inferior and the developer resistance is also inferior. That is, since alkali developability is inferior, it will be immersed in a developing solution for a long time, and since an exposed part will also swell easily, a quality image cannot be obtained.
[0016]
The resin used in the present invention can be obtained, for example, by copolymerizing maleic anhydride and one or more monomers of the following groups in an appropriate solvent in the presence of a polymerization initiator according to a conventional method. Examples of monomers include styrene, methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, butyl styrene, sec-butyl styrene, tert-butyl styrene, dimethyl styrene, diethyl styrene, methoxy styrene, ethoxy styrene, propoxy styrene, Examples include butoxystyrene, vinylbiphenyl, benzylstyrene, chlorostyrene, fluorostyrene, bromostyrene, and chloro-methylstyrene.
[0017]
Moreover, you may make it copolymerize with the monomer copolymerizable with these in the range which does not impair the performance of the resin of this invention. Of these, a particularly preferred example is a styrene / maleic anhydride copolymer.
[0018]
Examples of the compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule used in the present invention include aminomethylstyrene, aminostyrene, 2-aminoethyl (meth) acrylamide, and 3-aminopropyl (meth). Examples include acrylamide. Of these, aminomethylstyrene is particularly preferred.
[0019]
Also above Aminomethylstyrene In addition, a primary amine represented by the general formula (III) may be used in combination. Specific examples of such primary amines include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, and 6-phenyl-1-hexyl. Amine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2 -Chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2 -(3-Chlorophenyl) ethylamino , 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine and the like can be mentioned. Examples of particularly preferred primary amines are benzylamine and phenethylamine.
[0020]
In the present invention, Aminomethylstyrene However, from the viewpoint of raw material costs, it is desirable to use a primary amine represented by the general formula (III) in a range where there is no problem in performance. Aminomethylstyrene or Compounds having a primary amino group and an ethylenically unsaturated double bond in the same molecule and the general formula (III) Or (IV) A preferable range of the ratio of primary amines represented by is 100: 0 to 10:90 molar ratio, particularly preferably 100: 0 to 20:80 molar ratio. If the ratio of the primary amine exceeds 90 mol%, the formation of the transparent conductive layer is inferior.
[0021]
In the present invention, (a) the copolymer and (b) Aminomethylstyrene, and optionally used in combination Reaction ratio of primary amine ,Also, Compound having primary amino group and ethylenically unsaturated double bond in the same molecule, and Primary amine used together The reaction ratio is preferably from 0.1 to 1.0 equivalent, particularly preferably from 0.2 to 1.0 equivalent, per 1 equivalent of the maleic anhydride group. If it is less than 0.1 equivalent, the alkali developer resistance after exposure of the photopolymerizable composition is inferior. In addition, the target reaction can be allowed to proceed efficiently by making the amount of amine charged in excess of the maleic anhydride equivalent. In that case, excess amine is removed by a method such as reprecipitation of the copolymer, It is desirable to purify.
[0022]
The total amount of the resin in the photopolymerizable composition is 20% to 90% by weight, particularly preferably 30% to 70% by weight, based on the solid content in the composition. If it is less than 20% by weight, the tackiness of the photosensitive layer is increased, resulting in poor handleability.
[0023]
The addition polymerizable monomer having an ethylenically unsaturated double bond can be used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meta) ) Acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxyethylated trimethylolpropane tri (meth) acrylate Tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxybenzene di (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, Triaryl trimellitic acid, lauryl (meth) acrylate, (meth) acrylamide or xylylene bis (meth) acrylamide are included. Further, a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and the like and a diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate and xylene diisocyanate. Reactants can also be used. Of these, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.
[0024]
The total amount of monomers in the photopolymerizable composition is 10% to 80% by weight, particularly preferably 30% to 70% by weight, based on the total solid content of the composition. If it is less than 10% by weight, the resistance of the exposed portion of the composition to an alkaline developer is poor, and if it exceeds 80% by weight, the tackiness of the photosensitive layer increases and the handleability is poor.
[0025]
As the photopolymerization initiator or photopolymerization initiator system contained in the photopolymerizable composition of the present invention, substantially all known initiators or initiator systems can be used. Examples include p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenyl Acridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, bis (halogen-substituted methyloxadiazole described in Japanese Patent Application No. Hei 6-212794 ), Trihalomethyl-s-triazine described in Japanese Patent Application No. 6-253756, bis (trihalomethyl-s-triazine) described in Japanese Patent Application No. 6-268893, and the like. Particularly preferred are compounds containing a trihalomethyl group such as 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole. The addition amount of the photopolymerization initiator is 0.1% to 20% by weight, particularly preferably 0.5% to 5% by weight, based on the total solid content. If it is less than 0.1% by weight, it takes a long time for exposure because the photocuring efficiency of the composition is low, and if it exceeds 20% by weight, the light transmittance from the ultraviolet region to the visible region deteriorates, so that the protective layer of the color filter It becomes unsuitable for. Furthermore, known additives such as plasticizers, fillers, stabilizers and the like can be added, and pigments, dyes and the like can be added for uses other than the protective layer of the color filter.
[0026]
The photopolymerizable composition of the present invention is suitable as a material for forming a protective layer of a color filter. That is, after providing the photopolymerizable composition of the present invention in a layer on the color filter having the pixels, a protective layer is formed through steps such as exposure, development, and heating. In order to provide the layers, for example, a method of applying the solution with a roll coater or a bar coater, a method of applying the solution by a known means such as spray spraying or dipping in the solution, or a photopolymerizable composition on a temporary support. There is a method of forming a physical layer and transferring it.
The thickness of the protective layer is usually 0.1 μm to 50 μm, and particularly preferably 0.5 μm to 5 μm.
[0027]
As the support for the color filter, a metallic support, a metal bonded support, glass, ceramic, synthetic resin film, or the like can be used. Particularly preferable examples include glass and synthetic resin film which are transparent and have good dimensional stability.
[0028]
The photopolymerizable composition of the present invention is also used as a layer transfer material. That is, the photopolymerizable composition is provided in a layer on a temporary support, preferably a polyethylene terephthalate film directly or on a polyethylene terephthalate film provided with an oxygen barrier layer, a release layer, or a release layer and an oxygen barrier layer. A removable synthetic resin cover sheet is laminated on top for protection in handling. Alternatively, a layer configuration (described in JP-A-5-173320) in which an alkali-soluble thermoplastic resin layer and an intermediate layer are provided on a temporary support and a photopolymerizable composition layer is further provided can be applied.
[0029]
At the time of use, the cover sheet is removed, and the photopolymerizable composition layer is laminated on a permanent support, for example, on the support surface having color filter pixels. Next, when there is an oxygen barrier layer, a release layer, etc., between those layers and the temporary support, when there is a release layer and an oxygen barrier layer, between the release layer and the oxygen barrier layer, the release layer is also an oxygen barrier layer. If not, the composition layer is laminated on the color filter layer by peeling between the temporary support and the photopolymerizable composition layer and removing the temporary support. Then, exposure is performed. When a transparent electrode is formed on the color filter layer via a protective layer as in the case of STN, exposure is performed through a mask, development is performed, and the protective layer is patterned. Development is performed by washing away the unpolymerized areas with a suitable alkaline developer.
On the other hand, when a transparent conductive layer is provided on the entire surface as in the case of TFT, no mask is required.
[0030]
As the developer of the photopolymerizable composition of the present invention, a dilute aqueous solution of an alkaline substance is used, but a developer containing a small amount of an organic solvent miscible with water is also included. Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium bicarbonate, potassium bicarbonate), Alkali metal silicates (sodium silicate, potassium silicate) Alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg Tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01 to 30% by weight, and the pH is preferably 8 to 14.
[0031]
Suitable organic solvents miscible with water are methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone. The concentration of the organic solvent miscible with water is 0.1 to 30% by weight. Furthermore, a known surfactant can be added. The concentration of the surfactant is preferably 0.01% by weight to 10% by weight.
[0032]
The developer can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photopolymerizable composition layer, methods such as rubbing with a rotating brush or rubbing with a wet sponge in a developing solution can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. It is also possible to put a water washing step after the development processing.
[0033]
After the development process, heat treatment is performed. That is, a support having a layer photopolymerized by exposure (hereinafter referred to as a photocured layer) is heated in an electric furnace, a dryer or the like, or the photocured layer is irradiated with an infrared lamp. The heating temperature and time depend on the composition of the polymerizable composition used and the thickness of the formed layer. Generally, it is preferable to heat at about 120 ° C. to about 250 ° C. for about 10 minutes to about 60 minutes in order to obtain sufficient solvent resistance and alkali resistance.
[0034]
Next, an ITO (indium tin oxide) layer is formed on the protective layer thus formed by sputtering. When processing the ITO layer as a transparent electrode, a photoresist layer is formed on the ITO layer, an electrode pattern is baked, the photoresist layer is developed, the ITO layer is etched, and the photoresist is peeled off. Further, the alignment film is generally formed by applying a coating liquid for forming an alignment film such as polyimide containing a polar organic solvent such as N-methylpyrrolidone or γ-butyrolactone as a solvent, and drying the alignment film. Applied.
[0035]
The photopolymerizable composition of the present invention protects against color filters prepared by any of various known methods such as transfer method, colored resist method, dyeing method, printing method, and electrodeposition method. It is useful as a layer forming material.
[0036]
The photopolymerizable composition of the present invention can be suitably used for forming a protective layer on the color filter layer, but is not limited to this application. Color resists for forming color filter pixels that require high chemical resistance by containing dyes and pigments (for example, disclosed in JP-A-63-298304), solder resists for printed circuit boards (for example, in JP-A-3-223856) Disclosure), electroless plating resist (disclosed in the same publication), protective film for electrical elements, interlayer insulating film, adhesive (for example, disclosed in JP-A-3-126950), spacer material, and the like.
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. Unless otherwise specified, “parts” represents parts by weight and “%” represents percent by weight.
[0037]
【Example】
Synthesis example 1
110.3 parts of a styrene / maleic anhydride = 68/32 molar ratio copolymer (number average molecular weight = 2800) was dissolved in 441.2 parts of a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 1/1 weight ratio. did. Aminomethylstyrene 14.4 parts (0.5 equivalent to the acid anhydride), benzylamine 27.0 parts (0.5 equivalent to the acid anhydride), 2,5-di-t-hexyl A solution prepared by dissolving 0.02 part of hydroquinone in 165.6 parts of a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 1/1 weight ratio was added dropwise at room temperature over about 1 hour. Furthermore, the modified body of the styrene / maleic anhydride copolymer was obtained by stirring at room temperature for 6 hours.
[0038]
Example 1
<Creation of color filter layer>
On a polyethylene terephthalate film temporary support having a thickness of 100 μm, a coating liquid comprising the following formulation H1 was applied and dried to provide a thermoplastic resin layer having a dry film thickness of 20 μm.
[0039]

[0040]
Next, a coating liquid comprising the following formulation B1 was applied onto the thermoplastic resin layer and dried to provide a separation layer having a dry film thickness of 1.6 μm.

[0041]
Black (for the B1 layer), red (for the R layer), red (for the B layer), and green having the formulations shown in Table 1 on the four temporary supports having the thermoplastic resin layer and the separation layer. The four-color photosensitive solution (for G layer) was applied and dried to form a colored photosensitive resin layer having a dry film thickness of 2 μm.
[0042]

[0043]
Further, a polypropylene (thickness: 12 μm) covering sheet was pressure-bonded onto the photosensitive resin layer to prepare red, blue, green and black photosensitive transfer materials. Using this photosensitive transfer material, a color filter was prepared by the following method. The coated sheet of the red photosensitive transfer material is peeled off, and the photosensitive resin layer surface is pressurized to a transparent glass substrate (thickness 1.1 mm) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.) (0.8 kg / cm ² ), Heating (130 ° C.) and bonding, followed by peeling at the interface between the separation layer and the thermoplastic resin layer, and simultaneously removing the temporary support and the thermoplastic resin layer. Next, it is exposed through a predetermined photomask and immersed for 80 seconds at 35 ° C. using a developer having the following formulation to remove unnecessary portions, followed by washing with water and drying to form a red pixel pattern on the glass substrate. did.
[0044]
Developer formulation
・ Sodium carbonate 15g
・ Butyl cellosolve 1g
・ Water 1kg
[0045]
Next, a green photosensitive transfer material was bonded to the glass substrate on which the red pixel pattern was formed in the same manner as described above, and peeling, exposure, and development were performed to form a green pixel pattern. The same process was repeated with blue and black photosensitive transfer materials to form a color filter on a transparent glass substrate.
[0046]
<Manufacture of protective layer forming coating liquid>
The resulting mixture was mixed and dissolved, and filtered through a 0.2 μm pore size filter to prepare a coating solution for forming a protective layer.

[0047]
<Manufacture of protective layer>
The protective layer-forming coating is formed on a color filter layer having R (red), G (green), and B (blue) pixels formed on a 1.1 mm thick glass substrate (size: 350 mm × 400 mm). The solution was applied by a spin coater and dried to form a protective layer-forming photosensitive layer having a thickness of 3 μm. Using an aligner of an ultra high pressure mercury lamp light source, it is 200 mj / cm through a protective layer baking mask. ² UV irradiation was performed with a light amount of. Thereafter, the developer, which was a 1% sodium carbonate aqueous solution, was developed by spraying on the substrate and washed with water. Then, it cooled after standing in a 200 degreeC dryer for 20 minutes for heat processing.
[0048]
The protective layer on the color filter layer thus obtained was provided with a thickness of 0.2 μm by sputtering an ITO film, and further a positive photoresist (FH2130, manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was formed on the ITO film. Exposure through an electrode pattern mask, development, etching of the ITO layer with hydrochloric acid / iron chloride aqueous solution, and stripping with a resist stripping solution (MS2001, manufactured by Fuji Hunt Electronics Technology), an ITO electrode having no defects is obtained. It was. An attempt was made to peel off this electrode using an adhesive tape, but it did not peel off. Further, an alignment film coating solution (N-methylpyrrolidone / γ-butyrolactone solution of polyimide resin) was applied on this with a spin coater and dried, but an alignment film layer was obtained without swelling.
Table 3 shows the evaluation results of other items.
[0049]
Example 2 (Material for forming a film-like protective layer)
The protective layer-forming coating solution of Example 1 was applied on a 75 μm-thick polyethylene terephthalate film temporary support and dried to form a protective layer-forming photosensitive layer having a thickness of 3 μm. A polypropylene cover sheet having a thickness of 15 μm was laminated thereon to obtain a film-form protective layer forming material. A glass substrate having the color filter layer described in Example 1 was prepared. First, the cover sheet was removed from the material for forming a film-like protective layer, the photosensitive layer was stacked so as to be in contact with the color filter layer, and laminated using a laminator. Thereafter, the temporary support was peeled off, and a photosensitive layer was formed on the color filter layer. In the same manner as in Example 1, the protective layer was formed by exposing and developing the photosensitive layer and subjecting it to a heat treatment. An ITO electrode was formed on the protective layer in the same manner as in Example 1. As a result, an ITO electrode having close contact and no defects was obtained. Similarly, the alignment layer could be formed without swelling of the protective layer.
Table 3 shows the evaluation results of other items.
[0050]
Example 3
On the polyethylene terephthalate film temporary support having the thermoplastic layer and the separation layer prepared in Example 1, the protective image-forming coating liquid of Example 1 was applied, and a polypropylene cover film having a thickness of 15 μm was laminated thereon. Thus, a film-like photosensitive transfer material was obtained. In the same manner as in Example 2, the film-like photosensitive transfer material was laminated on a glass substrate having a color filter layer, and the temporary support was peeled and removed, followed by exposure and development in the same manner as in Example 1, followed by heat treatment. As a result, a protective layer free from defects such as bubbles and pinholes was obtained in the pixel portion of the color filter layer. The pencil hardness was 5H. When an ITO electrode was formed on the protective layer in the same manner as in Example 1, an ITO electrode with no defects such as wrinkles and cracks and excellent adhesion was obtained. Similarly, the alignment layer could be formed without swelling of the protective layer.
Table 3 shows the evaluation results of other items.
[0051]
Synthesis Examples 2 to 11
Styrene in the same manner as in Synthesis Example 1 using the resins shown in Table 2, a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule, and other primary amines if necessary. / Modified product of maleic anhydride copolymer (resin having maleic acid monoamide and ethylenically unsaturated double bond in the molecule), or amine modified product of styrene / maleic anhydride copolymer (for comparison) Resin having maleic acid monoamide in the molecule) and the like.
[0052]

[0053]
Synthesis Example 12
122.5 parts of a styrene / maleic anhydride = 68/32 molar ratio copolymer (number average molecular weight = 2800) was dissolved in 490.0 parts of a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50/50 weight ratio. did. To this, 46.4 parts of 2-hydroxyethyl acrylate (1.0 equivalent based on the acid anhydride), 185.6 parts of a mixed solvent of propylene glycol monomethyl ether acetate / methyl ethyl ketone = 50/50 weight ratio, 4-dimethylaminopyridine 2.4 parts, 0.05 parts of 2,5-di-t-hexylhydroquinone was added and reacted at 60 ° C. for 12 hours to modify the styrene / maleic anhydride copolymer (carboxyl group and ethylene in the molecule). Resin having a polyunsaturated double bond).
[0054]
Synthesis Example 13
Regarding the addition reaction product of methyl methacrylate / styrene / maleic acid and glycidyl methacrylate (resin having a carboxyl group and an ethylenically unsaturated double bond in the molecule) of Example 3 described in JP-A-5-257005 Carried out.
[0055]
Synthesis Example 14
Styrene / methyl methacrylate / maleic anhydride copolymer of Example 1 described in JP-A-2-97502 (number average molecular weight 30000, maleic anhydride unit is 16 mol%, propylamine 1.1 equivalent is used) ).
[0056]
Examples 4 to 10 and Comparative Examples 1 to 6
In the same manner as in Example 3, coating solutions for forming a protective layer were prepared using the resins of Synthesis Examples 2 to 8 (Examples) and 9 to 14 (Comparative Examples), and evaluated in the same manner.
The evaluation results are shown in Table 3.
[0057]
Comparative Example 7
A coating solution for forming a protective layer was prepared using the resin of Synthesis Example 9 in the same manner as in Example 3 except that 1.4 parts of dipentaerythritol hexaacrylate in Example 3 was changed to 6.8 parts. Evaluation was performed.
The evaluation results are shown in Table 3.
The evaluation method of the performance of each sample is described below.
[0058]
1. Developability
The photosensitive layer coated on a glass substrate with a spin coater so as to have a film thickness of 3 μm was immersed in a 1% aqueous sodium carbonate solution at 30 ° C. for 1 minute to evaluate whether it was dissolved.
[0059]
2. Developer resistance
A photosensitive layer coated with a spin coater so as to have a film thickness of 3 μm on a glass substrate is passed through a mask capable of obtaining a rectangular image of 80 μm × 300 μm to 200 mj / cm. ² It exposed, immersed in 1% sodium carbonate aqueous solution for 1 minute at 30 degreeC, and evaluated whether the exposure part was closely_contact | adhered to the board | substrate.
[0060]
3. Flatness
A photosensitive layer is formed on a color filter layer having a thickness of 2 μm on a glass substrate (with 2 μm unevenness) to a thickness of 3 μm, and exposure (200 mj / cm ² ), Unevenness on the surface of the protective layer obtained by development and post-heating (200 ° C., 60 minutes) was measured and evaluated using a film thickness meter.
[0061]
4). hardness
A photosensitive layer having a thickness of 3 μm is formed on a glass substrate and exposed (200 mj / cm ² ), After development and post-heating (200 ° C., 60 minutes), evaluation was made according to the pencil hardness test of JIS K5400.
[0062]
5). Alkali resistance
A photosensitive layer having a thickness of 3 μm is formed on a glass substrate and exposed (200 mj / cm ² ), After development and post-heating (200 ° C., 60 minutes), after immersion in a 5% KOH aqueous solution at 50 ° C. for 30 minutes, the surface was evaluated for wrinkles and turbidity.
[0063]
6). Optical transparency
A protective layer-forming photosensitive layer having a thickness of 3 μm is formed on a glass substrate and exposed to the entire surface (200 mj / cm ² ), After development and post-heating (200 ° C., 60 minutes), a clear surface was judged to have good transparency and a cloudy one was judged to be poor.
[0064]
7). Substrate adhesion
A protective layer-forming photosensitive layer having a thickness of 3 μm is formed on a glass substrate and exposed to the entire surface (200 mj / cm ² After development and after heating (200 ° C., 60 minutes), the film was cut and peeled off with Mylar tape to evaluate adhesion. One having no peeling at 100 crosscut portions was judged as having good adhesion, and one having peeling at one location was judged as poor adhesion.
[0065]
8). Formability of transparent conductive layer
A protective resin-forming photosensitive resin layer having a thickness of 3 μm is formed on a glass substrate and exposed to the entire surface (200 mj / cm ² ), After development and post-heating (200 ° C., 60 minutes), using a high-frequency sputtering apparatus manufactured by Nidec Anelva, indium tin oxide (tin oxide content: 6% by weight) with a voltage of 800 V, a current of 1.8 A, Output 270W, argon pressure 5 × 10 ^-4 Deposition was performed for 10 minutes under the condition of Torr. The surface state of the obtained transparent conductive layer was observed with a microscope, and an adhesion test by tape peeling was performed to evaluate the formability of the transparent conductive layer. The surface of the transparent conductive layer is flat and uniform, and there is no failure such as peeling in the adhesion test, the formation of the transparent conductive layer is good, the surface of the transparent conductive layer is wrinkled or cracked, or Those in which the transparent conductive layer was peeled off by the adhesion test were determined to be poor formability.
[0066]
9. tack
It was applied on a glass substrate with a spin coater so as to have a film thickness of 3 μm, and dried at 80 ° C. for 2 minutes to obtain a protective layer-forming photosensitive layer. The adhesiveness of the surface is evaluated by a finger touch test, and compared with the adhesiveness of the surface of the color mosaic K (manufactured by Fuji Hunt Electronics Technology) obtained in the same manner. It was good.
Table 3 shows the evaluation results of the above items.
[0067]
[Table 1]

[0068]
From this, it can be seen that the photopolymerizable composition according to the present invention exhibits excellent performance in all the evaluated items.
[0069]
【The invention's effect】
The photopolymerizable composition of the present invention has excellent alkali solubility, and the photopolymerized portion has excellent developer resistance, hardness, alkali resistance, light transmission, substrate adhesion, and transparent conductive layer formation. Has low tack. Particularly useful for forming a color filter protective layer, it is possible to form a protective layer having excellent durability and high flatness.

Claims (12)

(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) 1.0 to 0.1 equivalents of the resin having the repeating unit shown and having a number average molecular weight of 500 to 30,000 and (b) aminomethylstyrene based on 1 equivalent of the anhydride group in the following general formula (II) The photopolymerizable composition characterized by including the resin obtained by reacting by the ratio.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or Or a combination of two or more thereof.
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ] (1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) The total amount of (b) aminomethylstyrene and a primary amine represented by the following general formula (III) in the general formula (II) is the total amount of the resin having the repeating units shown and having a number average molecular weight of 500 to 30,000 and (b) aminomethylstyrene . A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of an anhydride group.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or the like) Or a combination of two or more of
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ]
R-NH ₂ (III)
[Where,
R: represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or an aryl group having 6 to 18 carbon atoms. (The alkyl group, aralkyl group and aryl group may each have a branch, and further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number. 7 to 12 aralkyl groups, a halogen atom, or a combination of two or more thereof. ] (1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) A resin having a repeating unit and having a number average molecular weight of 500 to 30,000, (b) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule, and the following general formula (IV) And a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent with respect to 1 equivalent of the anhydride group in the following general formula (II). Photopolymerizable composition.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or the like) Or a combination of two or more of
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ]
Ar ² —R′—NH ₂ (IV)
[Where,
R ′: alkylene having 1 to 6 carbon atoms which may have a branch;
Ar ² : aryl group (the aryl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a halogen atom, or the like) Or a combination of two or more thereof. ] The cured product of the photopolymerizable composition according to any one of claims 1 to 3, on a multicolor layer in which at least red, green and blue pixels are arranged in a matrix on a transparent substrate. A color filter comprising a protective layer. A color filter comprising a protective layer made of a cured product of the following photopolymerizable composition on a multicolor layer in which at least red, green and blue pixels are arranged in a matrix on a transparent substrate.
(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) A resin having a repeating unit and having a number average molecular weight of 500 to 30,000 and (b) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule are dehydrated in the following general formula (II) A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of a physical group.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or Or a combination of two or more thereof.
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ] A color filter comprising a protective layer made of a cured product of the following photopolymerizable composition on a multicolor layer in which at least red, green and blue pixels are arranged in a matrix on a transparent substrate.
(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) A resin having a repeating unit and having a number average molecular weight of 500 to 30,000, (b) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule, and the following general formula (III) The total amount of the primary amine is a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of the anhydride group in the following general formula (II). Photopolymerizable composition.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or Or a combination of two or more thereof.
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ]
R-NH ₂ (III)
[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or an aryl group having 6 to 18 carbon atoms. (The alkyl group, aralkyl group and aryl group may each have a branch, and further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number. 7 to 12 aralkyl groups, a halogen atom, or a combination of two or more thereof. ] The layer of the photopolymerizable composition according to any one of claims 1 to 3 is formed on a multicolor layer in which at least red, green, and blue pixels are arranged in a matrix on a transparent substrate. And then exposing, removing an unexposed portion using an alkaline aqueous solution, and then curing the exposed portion by heating. A layer of the following photopolymerizable composition is formed on a multicolor layer in which at least red, green, and blue pixels are arranged in a matrix on a transparent substrate, exposed, and an unexposed portion using an alkaline aqueous solution. A method for producing a color filter, wherein the exposed portion is cured by heating.
(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) A resin having a repeating unit and having a number average molecular weight of 500 to 30,000 and (b) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule are dehydrated in the following general formula (II) A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of a physical group.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or the like) Or may be substituted with a combination of two or more of
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ] A layer of the following photopolymerizable composition is formed on a multicolor layer in which at least red, green, and blue pixels are arranged in a matrix on a transparent substrate, exposed, and an unexposed portion using an alkaline aqueous solution. A method for producing a color filter, wherein the exposed portion is cured by heating.
(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) (B) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule, and the following general formula (III) And a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent with respect to 1 equivalent of the anhydride group in the following general formula (II). Photopolymerizable composition.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or the like) Or may be substituted with a combination of two or more of
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ]
R-NH ₂ (III)
[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or an aryl group having 6 to 18 carbon atoms. (The alkyl group, aralkyl group and aryl group may each have a branch, and further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number. 7 to 12 aralkyl groups, a halogen atom, or a combination of two or more thereof. ] The photopolymerizable composition according to any one of claims 1 to 3, wherein the photopolymerizable composition is provided on a temporary support on a multicolor layer in which at least red, green, and blue pixels are arranged in a matrix on a transparent substrate. A photosensitive material having an object layer is adhered, the layer of the photopolymerizable composition is transferred onto the multicolor layer, exposed, an unexposed area is removed using an alkaline aqueous solution, and then the exposed area is heated. A method for producing a color filter, characterized by curing. A light-sensitive material having a layer of the following photopolymerizable composition on a temporary support is adhered on a multicolor layer in which at least red, green, and blue pixels are arranged in a matrix on a transparent substrate, and the light A method for producing a color filter, wherein a layer of a polymerizable composition is transferred onto the multicolor layer, exposed, an unexposed portion is removed using an alkaline aqueous solution, and then the exposed portion is cured by heating.
(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) A resin having a repeating unit and having a number average molecular weight of 500 to 30,000 and (b) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule are dehydrated in the following general formula (II) A photopolymerizable composition comprising a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent to 1 equivalent of a physical group.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or the like) Or may be substituted with a combination of two or more of
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ] A light-sensitive material having a layer of the following photopolymerizable composition on a temporary support is adhered on a multicolor layer in which at least red, green, and blue pixels are arranged in a matrix on a transparent substrate, and the light A method for producing a color filter, wherein a layer of a polymerizable composition is transferred onto the multicolor layer, exposed, an unexposed portion is removed using an alkaline aqueous solution, and then the exposed portion is cured by heating.
(1) a photopolymerization initiator or photopolymerization initiator system, (2) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (3) (a) at least in the following general formulas (I) and (II) (B) a compound having a primary amino group and an ethylenically unsaturated double bond in the same molecule, and the following general formula (III) And a resin obtained by reacting at a ratio of 1.0 to 0.1 equivalent with respect to 1 equivalent of the anhydride group in the following general formula (II). Photopolymerizable composition.

[Where,
Ar ¹ : phenyl group (the phenyl group is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 8 to 12 carbon atoms, a halogen atom, or the like) Or may be substituted with a combination of two or more of
x, y: molar fraction of the repeating unit in the resin, which represents x = 0.85 to 0.55 and y = 0.15 to 0.45. ]
R-NH ₂ (III)
[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or an aryl group having 6 to 18 carbon atoms. (The alkyl group, aralkyl group and aryl group may each have a branch, and further have an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number. 7 to 12 aralkyl groups, a halogen atom, or a combination of two or more thereof. ]