JP4255299B2 - Pigment dispersion composition, ionizing radiation curing resin composition, color filter and liquid crystal display device - Google Patents

Description

【０１１３】
（５）重量平均分子量（Ｍｗ）、Ｍｗ／Ｍｎ、低分子量成分量
ポリスチレンを標準物質とし、ＴＨＦを溶離液としてショウデックスＧＰＣシステム−２１Ｈ（ショウデックス社製、商品名「Ｓｈｏｄｅｘ ＧＰＣ Ｓｙｓｔｅｍ−２１Ｈ」）によりＭｗ、Ｍｗ／Ｍｎを測定した。
また、ポリスチレンを標準物質とする分子量校正曲線から分子量が１００〜１０００の領域を求め、共重合体全体の面積に対する分子量１００〜１０００の領域の面積の割合として、低分子量成分の含有量を求めた。
【０１１４】
（６）酸価
樹脂溶液３ｇを精秤し、アセトン７０ｇ／水３０ｇ混合溶媒に溶解し、チモールブルーを指示薬として０．１Ｎ ＫＯＨ水溶液で滴定し、固形分の濃度から固形分１ｇ当たりの酸価を求めた。
【０１１５】
（７）固形分
アルミ皿に樹脂溶液１．０ｇを精秤し、１６０℃で５時間真空乾燥を行い揮発分を除去した後の質量から求めた。
【０１１６】
（８）水分量
新カールフィッシャー滴定用溶媒ハヤシ−ソルベントＣＥ（ＨＡＹＡＳＨＩ−Ｓｏｌｖｅｎｔ ＣＥ）脱水溶媒を用い、試料１ｇを滴定溶媒３０ｇに溶解し、カールフィッシャー測定装置（京都電子工業社製、商品名「ＭＫＳ−３Ｐ」）にて水分量を測定した。
【０１１７】
合成例１
（共重合体1溶液の合成）
３Ｌの重合槽に、溶媒としてジエチレングリコールジメチルエーテル（ＤＭＤＧ）４０．０部を仕込み、窒素雰囲気下に９０℃に昇温した後、滴下系１としてシクロヘキシルマレイミド（ＣＨＭＩ）６．１６部、ジエチレングリコールジメチルエーテル（ＤＭＤＧ）６．１６部、メチルメタクリレート（ＭＭＡ）１２．１２部、メタクリル酸（ＭＡＡ）１２．５５部、滴下系２として、パーブチルＯ（ＰＢＯ）（商品名、日本油脂社製）０．６２部、滴下系３としてｎ‐ドデシルメルカプタン（ｎ−ＤＭ）１．２３部を、それぞれ３時間かけて連続的に供給した。その後、３０分９０℃を保持した後、温度を１１０℃に昇温し、３時間重合を継続した。ガスクロクロマトグラフィー（ＧＣ）測定による未反応モノマーは、ＣＨＭＩが０．１％、ＭＭＡが０．１％、ＭＡＡが０．１％であった。分子量１００〜１０００の低分子量成分の含有量は、全マレイミド系共重合体中の２．５質量％であった。
【０１１８】
次いで、この反応液にメタクリル酸グリシジル（ＧＭＡ）１２．７３部、触媒としてトリエチルアミン０．１３部、重合禁止剤として２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）（商品名「アンテージＷ４００」、川口化学工業社製）０．０７部を追加し、５％酸素濃度に調整した空気、窒素混合ガスを２００ｍｌ／分の流量でバブリングしながら８時間反応を継続した。反応液をＧＣで測定したところ未反応のＧＭＡは検出されなかった。ＤＭＤＧ７．５部を加えて希釈した後、冷却し、シクロヘキシルマレイミド樹脂溶液１を得た。ＧＰＣで測定した分子量１００〜１０００の低分子量成分は、全マレイミド系共重合体中の４．５質量％であった。重量平均分子量（Ｍｗ）は１７０００、重量平均分子量と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）は２．５であった。
乾燥法で求めた固形分濃度は４４．７％、滴定法で測定したマレイミド系共重合体の酸価は７５ｍｇＫＯＨ／ｇであった。
【０１１９】
重合液を、ＤＭＤＧで、ポリマー濃度が２０％となるように希釈し、スピンコータを用いて無アルカリガラス板上に、２μｍ厚の塗膜を形成し、ホットプレートを用いて２５０℃で一時間加熱し、光線透過率を測定したところ、３８０〜７８０ｎｍの領域で、光線透過率は９９％以上であった。また、得られた重合液をテトラヒドロフランで希釈し、大量のヘキサン中に注いで共重合体を析出させ、ろ別乾燥する操作を２回繰り返し、共重合体１を分離した。この共重合体は、１％ＫＯＨ水溶液、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）、酢酸３−メトキシブチルに完全に溶解した。
【０１２０】
合成例２
シクロヘキシルマレイミドに代えてベンジルマレイミドを使用した以外は合成例１と同様の操作を行い、マレイミド系アルカリ可溶性共重合体溶液（共重合体溶液２）を得た。共重合体溶液２の分析値を表１に示す。
【０１２１】
合成例３
シクロヘキシルマレイミドに代えてフェニルマレイミドを使用した以外は合成例１と同様の操作を行い、マレイミド系アルカリ可溶性共重合体溶液（共重合体溶液３）を得た。共重合体溶液３の分析値を表１に示す。
【０１２２】
比較合成例１
（比較共重合体1溶液の合成）
３Ｌの重合槽に、溶媒としてジエチレングリコールジメチルエーテル（ＤＭＤＧ）４０．０部、シクロヘキシルマレイミド（ＣＨＭＩ）６．１６部、ジエチレングリコールジメチルエーテル（ＤＭＤＧ）６．１６部、メチルメタクリレート（ＭＭＡ）１２．１２部、メタクリル酸（ＭＡＡ）１２．５５部、パーブチルＯ（ＰＢＯ）（商品名、日本油脂社製）０．６２部、ドデシルメルカプタン（ｎ−ＤＭ）１．２３部を仕込み、窒素雰囲気下に９０℃に昇温した。その後、３時間９０℃を保持した。ガスクロクロマトグラフィー（ＧＣ）測定による未反応モノマーは、ＣＨＭＩが１．５％、ＭＭＡが１．３％、ＭＡＡが２．１％であった。分子量１００〜１０００の低分子量成分の含有量は、全マレイミド系共重合体中の１２質量％であった。
【０１２３】
次いで、この反応液にメタクリル酸グリシジル（ＧＭＡ）１２．７３部、触媒としてトリエチルアミン０．１３部、重合禁止剤として２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）（商品名「アンテージＷ４００」、川口化学工業社製）０．０７部を追加し、５％酸素濃度に調整した空気、窒素混合ガスを２００ｍｌ／分の流量でバブリングしながら３２時間反応を継続した。反応液をＧＣで測定したところ未反応のＧＭＡは０．４％であった。ＤＭＤＧ７．５部を加えて希釈した後、冷却し、シクロヘキシルマレイミド樹脂溶液１を得た。
ＧＰＣで測定した分子量１００〜１０００の低分子量成分は、全マレイミド系共重合体中の１３質量％であった。重量平均分子量（Ｍｗ）は２２０００、重量平均分子量と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）は４．５であった。
乾燥法で求めた固形分濃度は４４％、滴定法で測定したマレイミド系共重合体の酸価は８０ｍｇＫＯＨ／ｇであった。比較重合体１の分析値を表１に示す。
【０１２４】
【表１】

【０１２５】
表１について、以下に説明する。ＤＭＤＧとは、ジエチレングリコールジメチルエーテルであり、ＣＨＭＩとは、シクロヘキシルマレイミドであり、ＢｚＭＩとは、ベンジルマレイミドであり、ＰＭＩとは、フェニルマレイミドであり、ＭＭＡとは、メタクリル酸メチルであり、ＭＡＡとは、メタクリル酸であり、ＰＢＯとは、パーブチルＯ（商品名、日本油脂社製）であり、ｎ−ＤＭとは、ｎ−ドデシルメルカプタンであり、ＧＭＡとは、メタクリル酸グリシジルである。
【０１２６】
実施例１
顔料分散組成物の調製
顔料及び分散剤と共に合成例１で得られた共重合体溶液１を下記分量で混合し、ペイントシェーカーを用い、０．３ｍｍジルコニアビーズによって３時間ビーズ分散し、青色顔料分散組成物１を得た。得られた青色顔料分散組成物１は、顔料、分散剤及び共重合体1の固形分質量比（顔料／分散剤／シクロヘキシルマレイミド樹脂）が、１／０．２／０．４であった。
【０１２７】
＜顔料分散組成物１の組成＞
・ピグメントブルー１５：６（銅フタロシアニン系青色顔料、商品名「リオノールブルーＥＳＣＦＢ６３４０ＥＣ」、、東洋インキ社製大日精化社製）：１３部・分散剤（商品名「ＰＢ−８２１ディスパービック２００１」、ビックケミー味の素社製）：５．６５部（固形分４６．０％）
・シクロヘキシルマレイミド樹脂溶液１（ＣＨＭＩ／ＭＭＡ／ＭＡＡ／ＧＭＡ−ＭＡＡ共重合体、固形分４４．７％）：１１．５６部
・プロピレングリコールモノメチルエーテルアセテート：６９．７９部
【０１２８】
青色レジスト１の調製
顔料分散組成物１に、共重合体溶液1及び他の成分を下記分量で配合し、青色レジスト１を調製した。得られた青色レジスト1は、メインポリマーである共重合体1、モノマーであるジペンタエリスリトールペンタアクリレート（商品名「サートマーＳＲ３９９Ｅ」、日本化薬社製）及び開始剤１及び２の固形分の質量比（共重合体1／ジペンタエリスリトールペンタアクリレート／開始剤１と２の合計）が、３５／４５／３５であった。
【０１２９】
＜青色レジスト１の組成＞
・顔料分散組成物１：３４．３部
・共重合体溶液1：８．０３部
・ジペンタエリスリトールペンタアクリレート（商品名「サートマーＳＲ３９９Ｅ」、日本化薬社製）：６．０３部
・開始剤１（商品名「イルガキュアー１８４９０７」、チバスペシャリティーケミカルズ製）：３．８７部
・開始剤２（商品名「ハイキュアーＡＢＰ」、川口薬品社製）：０．３５部
・プロピレングリコールモノメチルエーテルアセテート：５２．６部
【０１３０】
顔料分散組成物１及び青色レジスト１について、以下の方法により評価を行い、結果を表２に示した。
【０１３１】
（１）顔料分散性
顔料分散組成物１の５０％平均顔料粒子径を、日機装社製のレーザードップラー散乱光解析粒度分析計（商品名「Ｍｉｃｒｏｔｒａｃ９３４ＵＰＡ」）を用いて測定した。
【０１３２】
（２）現像形態、現像時間、分光特性、耐熱性、パターンの断面形状
アルカリ洗浄済みのガラス基板上に、青色レジスト1をスピンコーティングした後、室温で３分間、更に８０℃のホットプレート上で３分間乾燥させ、膜厚１．３μｍの塗膜を形成した。この塗膜を１００ｍＪ／ｃｍ2でマスク露光し、スピン現像し、現像液に６０秒間接液させた後に純水で洗浄し、パターン形成された基板を２３０℃のオーブン中で３０分間ベイクした。この現像過程において、現像形態が溶解型か剥離型かを観察すると共に、現像時間を測定した。
【０１３３】
次に、得られた青色パターン付き基板を、国際照明委員会の規定するＣ光源を用い、オリンパス光学工業社製の顕微分光測光装置（商品名「ＯＳＰ ＳＰ−１００」）により、ＪＩＳ Ｚ８７０１に定める明るさＹ値を測定した。その後、この青色パターン付き基板を２５０℃のオーブン中で１時間加熱し、同様の方法で明るさＹ値を測定し、耐熱試験前のＹ値を基準にして試験前後のＹ値の変化率を算出した。また、２３０℃、３０分間のベイク後の段階で得られた青色パターン付き基板の着色層の断面形状をＳＥＭ（走査型電子顕微鏡）で観察すると共に、ＳＥＭ写真を用いて着色層の立上がり角度と、下底の長さに対する上底の長さの比を算出した。
【０１３４】
（３）現像残渣
裏面にクロムを蒸着したガラス基板上に、青色レジスト1をスピンコーティングした後、室温で３分間、更に８０℃のホットプレート上で３分間乾燥させ、膜厚１．３μｍの塗膜を形成した。この塗膜をスピン現像し、現像液に６０秒間接液させた後に純水で洗浄した。
洗浄後、ガラス基板を投光器により目視観察し、残渣の有無を確認した。また、基板の表面をエタノール付きウエスで拭き取り、ウエス上に拭き取られた残渣の有無を確認した。
【０１３５】
（４）コントラスト比
上記（２）で得られた青色レジスト1塗布基板を２枚の偏光板（日東電工社製、商品名「ＮＰＦ‐Ｇ １２２０ＤＵ」）で挟み込み、バックライト（東芝社製、商品名「メロウ５Ｄ ＦＬ１０ＥＸ‐Ｄ‐Ｈ」、色温度６５００Ｋ）を点灯し、偏光板の直交時と平行時の輝度を輝度計（ミノルタ社製、商品名「ＳＬ‐１００」）により測定した。コントラスト比は輝度の測定値を用い、以下の式により導き出せる。
コントラスト比＝平行輝度（ｃｄ／ｍ2）／直交輝度（ｃｄ／ｍ2）
【０１３６】
（５）表面粗度、密着性、解像度、碁盤目ピール試験
製版性（表面粗度（Ｒａ）、ラインアンドスペースによる密着性と解像度、碁盤目ピール試験）に関する評価を行った。
【０１３７】
透明レジスト１の調整
共重合体溶液１をＤＭＤＧで希釈し、固形分２０％に調整し、下記に示す材料を室温で攪拌・混合し、透明レジスト１を得た。
・共重合体溶液1（固形分２０％）：６９．０部
・ジペンタエリスリトールペンタアクリレート（サートマー社製、商品名「ＳＲ３９９」）：１１．０部
・オルソクレゾールノボラック型エポキシ樹脂（油化シェルエポキシ社製、商品名「エピコート１８０Ｓ７０」）：１５．０部
・２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパノン−１：２．１部
・２，２′−ビス（Ｏ−クロロフェニル）−４，５，４′，５′−テトラフェニル−１，２′−ビイミダゾール：１．５部
・ジエチレングリコールジメチルエーテル：６６．０部
【０１３８】
透明レジスト１について、以下の評価を行い、結果を表３に示した。
【０１３９】
（６）１８０℃での硬さ
１０ｃｍ画のガラス基板上に、透明レジスト１をスピンコータ（ＭＩＫＡＳＡ社製、形式１Ｈ−ＤＸ２）により、塗布、乾燥し、乾燥膜厚５．４μｍの塗布膜を形成した。この塗布膜をホットプレート上で９０℃、３分間加熱した。加熱後、２．０ｋＷの超高圧水銀ランプを装着したＵＶアライナー（大日本スクリーン社製、形式ＭＡ １２００）によって１００ｍＪ／ｃｍ2の強度（４０５ｎｍ照度換算）で紫外線を照射した。紫外線の照射後、塗布膜をクリーンオーブン（忍足研究所社製、商品名「ＳＣＯＶ−２５０ Ｈｙ−Ｓｏ」）により２００℃で３０分間乾燥し、膜厚５．０μｍの硬化膜を得た。得られた硬化膜の硬度を、超微少硬度計（フィッシャーインストルメンツ社製、商品名「ＷＩＮ−ＨＣＵ」）を用い、加熱治具で硬化膜の表面温度が１８０℃になったときに、ビッカース圧子の最大荷重２０ｍＮとなる条件で表面硬度を測定したときのユニバーサル硬さ（試験荷重／試験荷重下でのビッカース圧子の表面積）で評価した。
【０１４０】
（７）弾性変形率
１０ｃｍ画のガラス基板上に、透明レジスト１をスピンコータ（ＭＩＫＡＳＡ社製、形式１Ｈ−ＤＸ２）により、塗布、乾燥し、乾燥膜厚５．４μｍの塗布膜を形成した。この塗布膜をホットプレート上で９０℃、３分間加熱した。加熱後、２．０ｋＷの超高圧水銀ランプを装着したＵＶアライナー（大日本スクリーン社製、形式ＭＡ １２００）によって１００ｍＪ／ｃｍ2の強度（４０５ｎｍ照度換算）で紫外線を照射した。紫外線の照射後、塗布膜をクリーンオーブン（忍足研究所社製、商品名「ＳＣＯＶ−２５０ Ｈｙ−Ｓｏ」）により２００℃で３０分間乾燥し、膜厚５．０μｍの硬化膜を得た。得られた硬化膜の硬度を、超微少硬度計（フィッシャーインストルメンツ社製、商品名「ＷＩＮ−ＨＣＵ」）を用い、加熱治具で硬化膜の表面温度が１８０℃になったときに、ビッカース圧子の最大荷重２０ｍＮとなる条件で表面硬度を測定したときの全仕事量に対する弾性変形の仕事量の割合から評価した。
【０１４１】
（８）現像性の評価
１０ｃｍ画のガラス基板上に、透明レジスト１をスピンコータ（ＭＩＫＡＳＡ社製、形式１Ｈ−ＤＸ２）により、塗布、乾燥し、乾燥膜厚２．２μｍの塗布膜を形成した。この塗布膜をホットプレート上で９０℃、３分間加熱した。加熱後、塗布膜から１００μｍの距離にフォトマスクを配置して２．０ｋＷの超高圧水銀ランプを装着したＵＶアライナー（大日本スクリーン社製、形式ＭＡ １２００）によって１００ｍＪ／ｃｍ2又は５０ｍＪ／ｃｍ2の強度（４０５ｎｍ照度換算で紫外線を照射した。得られた膜の現像性を光学顕微鏡（オリンパス光学工業社製、商品名「ＭＨＬ１００」）と触針式表面粗度測定装置（日本アネルバ社製、商品名「Ｄｅｋｔａｋ １６００」）によりレリーフパターンの形状を観察し、形状の悪いものを×、良いものを○、非常に良いものを◎とした
【０１４２】
紫外線照射後、塗布膜に０．０５％の水酸化カリウム水溶液をスピン現像機（Ａｐｐｌｉｅｄ Ｐｒｏｃｅｓｓ Ｔｅｃｈｎｏｌｏｇｙ，ＩＮＫ社製、ＭＯＤＥＬ：９１５）にて６０秒間散布し、未露光部を溶解、除去し、残った露光部を純水で６０秒間水洗することにより現像した。現像後、露光部の膜をクリーンオーブン（忍足研究所社製、商品名「ＳＣＯＶ−２５０ Ｈｙ−Ｓｏ」）により、２００℃で３０分間加熱した。そして、得られた膜の現像性を光学顕微鏡（オリンパス光学工業社製、商品名「ＭＨＬ１００」）と触針式表面粗度測定装置（日本アネルバ社製、商品名「Ｄｅｋｔａｋ １６００」）によりレリーフパターンの形状を観察し、形状の悪いものを×、良いものを○、非常に良いものを◎とした。
【０１４３】
（９）塗膜表面の荒れ
アルカリ現像処理後、塗膜表面を顕微鏡で観察し、塗膜表面の平滑性を観察した。
◎：極めて平滑、〇：平滑、△：表面に荒れが見られる、×：表面の荒れが激しく、塗膜白化が見られる
【０１４４】
（１０）耐温純水性
硬化後の塗膜を８０℃の純水に３０分浸漬し、基盤目ピール試験法により密着性を確認した。
〇：塗膜剥がれなし、△：５０％未満の塗膜に剥がれ、欠損あり、×：５０％以上の塗膜に剥がれ、欠損あり
【０１４５】
（１１）硬化膜物性の黄変性評価
１０ｃｍ画のガラス基板上に、透明レジスト１をスピンコーター（ＭＩＫＡＳＡ社製、形式１Ｈ−ＤＸ２）により、塗布、乾燥し、乾燥膜厚１．２μｍの塗布膜を形成した。この塗布膜をホットプレート上で９０℃、３分間加熱した。加熱後、２．０ｋＷの超高圧水銀ランプを装着したＵＶアライナー（大日本スクリーン社製、形式ＭＡ １２００）によって１００ｍＪ／ｃｍ2の強度（４０５ｎｍ照度換算）で紫外線を照射した。
【０１４６】
紫外線の照射後、塗布膜をクリーンオーブン（忍足研究所社製、商品名「ＳＣＯＶ−２５０ Ｈｙ−Ｓｏ」）により２３０℃で３０分間乾燥し、膜厚１．０μｍの硬化膜を得た。このようにして得られたガラス基板上の硬化膜の色度を、リファレンスにガラス基板を用い、測色機（オリンパス光学工業社製、商品名「ＯＳＰ−ＳＰ２００」）を用いて測定した。
【０１４７】
次いで、測定した硬化膜付きガラス基板をＵＶオゾン洗浄機で６．７Ｊ／ｃｍ2の強度（４０５ｎｍ照度換算）で紫外線の照射、洗浄を行い、更にクリーンオーブン（忍足研究所社製、商品名「ＳＣＯＶ−２５０ Ｈｙ−Ｓｏ」）により２５０℃で１時間加熱し、加熱試験硬化膜を得た。このようにして得られたガラス基板上の硬化膜の色度をガラス基板をリファレンスとし、測色機（オリンパス光学工業社製、商品名「ＯＳＰ−ＳＰ２００」）を用いて測定した。
【０１４８】
上記加熱試験前後の色度の変化から硬化膜の耐熱性を評価した。
ここで、ΔＥａｂとは、ＣＩＥ１９７６（Ｌ＊，ａ＊，ｂ＊）空間表色系による以下の色差公式から求められる値である（日本色彩学会編 新編色彩科学ハンドブック（昭和６０年）ｐ．２６６）。
ΔＥａｂ＝｛（ΔＬ）2＋（Δａ）2＋（Δｂ）2｝1/2
【０１４９】
実施例２及び３
（顔料分散組成物２及び３、青色レジスト2及び3、透明レジスト2及び3の調製）共重合体溶液１の代わりに、共重合体溶液２及び３をそれぞれ用いたこと以外は実施例１と同様に組成物の調製を行い、顔料分散組成物２及び3、青色レジスト２及び３、透明レジスト2及び3を得た。この顔料分散組成物及び硬化性樹脂組成物を用いて、実施例１と同じ方法により塗布膜を形成し、評価を行った。結果を表２及び表３に示す。
【０１５０】
比較例１
（顔料分散組成物４、青色レジスト４の調製）
合成例１で得られた共重合体溶液1の代わりに、比較合成例１で得られた比較共重合体溶液１をそれぞれ用いたこと以外は実施例１と同様に組成物の調製を行い、顔料分散組成物４、青色レジスト４、透明レジスト4を得た。この顔料分散組成物及び硬化性樹脂組成物を用いて、実施例１と同じ方法により塗布膜を形成し、評価を行った。結果を表２及び表３に示す。
【０１５１】
【表２】

【０１５２】
【表３】

【０１５３】
表２より、実施例１〜３で製造した顔料分散組成物は、顔料を分散させた時の粒子径が小さく、また室温で一週間保持後の粒子径の変化が小さいことから、顔料分散性に優れていた。比較例１では、顔料の粒子径が大きく、更に室温で一週間保持後の粒子径変化が大きく、顔料分散性に劣っていた。
【０１５４】
また、実施例1〜３で製造した電離放射線硬化用樹脂組成物（青色レジスト及び透明レジスト）は、耐熱黄変性、残渣、精細なパターンを形成することが可能であり、しかも硬い塗膜を形成することができた。比較例１では、現像後の塗膜表面の荒れが起こった。また、耐熱黄変性、残渣、膜の硬度等の諸物性において実施例１〜３と比較して劣っていた。
【０１５５】
【発明の効果】
本発明の顔料分散組成物は、顔料分散性に優れ、また保存中に顔料が凝集することがない。
また本発明の電離放射線硬化用樹脂組成物は、耐熱黄変性に優れて硬度が高く、電離放射線量による硬化性が優れ、現像後のパターン形状の精度を向上することができ、しかもパターニングの精度及び硬化後の諸物性に優れていることから、カラーフィルター中に含まれている様々な薄膜層やパターンを形成する材料として好適に用いることができ、また、透明性を必要としない部分だけでなく、保護層や着色層のように透明性を必要とする部分も形成することができることから、カラーフィルターにおける着色層や保護層、スペーサーを形成することができるものである。このようなカラーフィルターやそれを用いた液晶表示装置は、画素の透明性やパターン形状の精度等が優れることになる。
【図面の簡単な説明】
【図１】液晶パネルの一例についての模式的断面図である。
【図２】液晶パネルの別の例についての模式的断面図である。
【符号の説明】
１ カラーフィルター
２ 電極基板
３ 間隙部（Ｌ；液晶化合物）
４ シール材
５ 透明基板
６ ブラックマトリックス層
７（７Ｒ、７Ｇ、７Ｂ） 着色層
８ 保護層
９ 透明電極膜
１０ 配向膜
１１ パール
１２ 柱状スペーサー
１０１、１０２ 液晶パネル[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pigment dispersion composition, a resin composition for ionizing radiation curing, a color filter, and a liquid crystal display device. Specifically, a pigment dispersion composition, an ionizing radiation curable resin composition, which is used for forming a thin film layer or a fine pattern such as a color filter, which contains a maleimide-based alkali-soluble copolymer as an essential component, and the resin composition are used. The present invention relates to a color filter in which a thin layer or a fine pattern such as a colored layer, a protective layer, and a spacer is formed, and a liquid crystal display device assembled by using the color filter.
[0002]
[Prior art]
Maleimide copolymers have a high glass transition temperature and can improve thermal characteristics, and thus are attracting attention in the field of electronic resins such as electronic materials and substrate materials. In such a field, a material that is not easily yellowed even when heat is applied in the process of assembling electric / electronic components is required, and it is preferable to use a maleimide copolymer. In recent years, with the rapid spread of color liquid crystal display devices as flat displays for personal computers and the like, ionizing radiation curing used to form thin film layers or fine patterns such as color filters constituting liquid crystal panels. Since the demand for a polymer that is a constituent element of an automotive resin composition is rapidly increasing, a maleimide copolymer that can be applied to such a field has been studied.
[0003]
The liquid crystal panel has a structure in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and a liquid crystal compound is sealed between them to form a thin liquid crystal layer. A liquid crystal display device incorporating such a liquid crystal panel selectively changes the amount of transmitted or reflected light of the display side substrate by electrically controlling the liquid crystal alignment in the liquid crystal layer by the liquid crystal drive side substrate of the liquid crystal panel. By doing so, the display is performed. In such liquid crystal panels, there are various driving methods such as a static driving method, a simple matrix method, and an active matrix method. In recent years, liquid crystals of an active matrix method or a simple matrix method have been used as flat displays for personal computers and personal digital assistants. Color liquid crystal display devices using panels are rapidly spreading.
[0004]
FIG. 1 is a configuration example of an active matrix type liquid crystal panel. The liquid crystal panel 101 is provided with a gap portion 3 of about 1 to 10 μm with the color filter 1 serving as a display side substrate and the TFT array substrate (electrode substrate) 2 serving as a liquid crystal drive side substrate facing each other. The liquid crystal L is filled and the periphery thereof is sealed with a sealing material 4. The color filter 1 includes a black matrix layer 6 formed in a predetermined pattern on the transparent substrate 5 to shield the boundary between pixels, and a plurality of colors (usually red (R (R)) to form each pixel. ), Green (G), blue (B) three primary colors) arranged in a predetermined order, a colored layer (pixel portion) 7, a protective layer (protective film) 8, and a transparent electrode film 9 are close to a transparent substrate. It has a stacked structure in this order from the side. Recently, a pixel may be formed using a color hologram instead of the colored layer 7. On the other hand, the TFT array substrate 2 has a structure in which TFT elements are arranged on a transparent substrate and a transparent electrode film is provided (not shown). An alignment film 10 is provided on the inner surface side of the color filter 1 and the electrode substrate 2 facing the color filter 1. Further, in the gap 3, pearls 11 having a constant particle diameter are dispersed as spacers in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2. Then, a color image is obtained by controlling the light transmittance of each pixel colored in each color or the liquid crystal layer behind the color hologram.
[0005]
As a method of maintaining the cell gap, as shown in FIG. 1, a large number of spherical or rod-like particle spacers 11 of a certain size made of glass, alumina, plastic, or the like are scattered in the gap 3 as a spacer. There is a method in which the TFT array substrate 2 is bonded and liquid crystal is injected. However, when the fine pearls 11 as shown in FIG. 1 are dispersed as spacers, the pearls are behind the black matrix layer 6. Regardless of whether they are behind pixels or not, they are randomly distributed. When the pearl is arranged in the display region, that is, the pixel portion, the light of the backlight is transmitted through the pearl portion, and the orientation of the liquid crystal around the pearl is disturbed, so that the quality of the display image is remarkably lowered. Therefore, as shown in FIG. 2, instead of dispersing the pearl, a columnar spacer 12 having a height corresponding to the cell gap is provided in a region overlapping the position where the black matrix layer 6 is formed on the inner surface side of the color filter. Has come to be done.
[0006]
The colored layer 7 included in the structure of the color filter is formed by using one or more pigments selected so as to be able to develop a predetermined color such as RGB by a so-called pigment dispersion method, a binder resin or light. A photosensitive colored composition (colored resin composition for ionizing radiation curing) is prepared by blending with a photocurable resin composition (resin composition for ionizing radiation curing) composed of an initiator and the like on a transparent substrate. A predetermined region of the obtained coating film is selectively exposed and cured, and developed with an organic solvent or an alkali solution.
[0007]
Incidentally, in order for the liquid crystal display device to exhibit excellent display performance, the color space expression capability of the pixel is important. Each RGB pixel is toned so that the color reproduction region determined by the chromaticity coordinates (x, y) in the XYZ color system can be sufficiently widened, and the brightness represented by the stimulus value Y is sufficiently high. It is required to have excellent transparency and color purity. However, in the manufacturing process of the color filter, there is a problem that transparency and color characteristics of the colored layer are impaired due to yellowing of the binder resin contained in the colored layer. Specifically, the color filter is produced through a high temperature during post-baking or ITO film formation, and is also produced through a heating process with a high temperature ranging from 120 ° C. to 250 ° C. in the liquid crystal display device assembly process, such as polyimide alignment film formation. Although it is exposed, there is a problem in that the color characteristics of the colored layer are deteriorated because the material for forming the colored layer turns yellow in such a heating process, causing wavelength absorption around 400 nm. Among each color, when the blue pixel is yellowish, the transparency, the color characteristics are deteriorated, and the luminance is most significantly deteriorated. Therefore, it is particularly important to prevent the blue pixel from yellowing.
[0008]
In addition, the ability to form fine patterns such as developability and plate-making characteristics of the colored resin composition for ionizing radiation curing that forms the colored layer also greatly affects the display performance of the liquid crystal display device. When producing a fine pattern such as a pixel by the pigment dispersion method, there is no residue, no fine line defect, no foreign matter, no surface roughness, resolution, and resolution. Performance such as a high thickness, an accurate shape after development, and a uniform film thickness are required.
[0009]
A residue is a colored product that remains in a portion that should not remain after development, and is likely to occur when developability is poor due to a large amount of pigment or dispersant. Fine line defects are likely to occur when the adhesion is inferior due to a small amount of the curing component in the colored resin composition for ionizing radiation curing and a low affinity with the substrate. The foreign matter is generated due to a part of the pixel being missing when there are few curing components in the colored resin composition for ionizing radiation curing, or a colored piece produced by peeling development with few developing components. Surface roughness also occurs when there are few curing components in the colored resin composition for ionizing radiation curing.
[0010]
In such a liquid crystal display device, in order to improve the resolution, a pattern with many curved portions and corners has appeared in the color filter unlike the conventional stripe pattern due to the advancement of the liquid crystal driving method. Even a simple pattern needs to be formed accurately. As for the shape after development, there is a problem that it becomes an inverted trapezoid (reverse tapered shape) when the ionizing radiation curable colored resin composition has poor photosensitivity. If the post-development shape becomes an inverted trapezoid, the upper part of the pixel tends to be chipped due to water pressure during development, which causes the above-mentioned foreign matter. Furthermore, when the reverse trapezoidal film has low heat resistance, the portion protruding in a comb shape may hang down due to heat and form a hole after post-baking. This hole not only lowers the display quality but also lowers the resolution. In addition, when the liquid crystal panel is heated and bursts, the liquid crystal is contaminated.
[0011]
The uniformity of the film thickness in forming a fine pattern is not a big problem at the individual pixel level. However, for the purpose of cost reduction, the substrate size has been steadily increasing and has been applied to the metric class. In that case, if the film thickness is different between the glass center and the edge, the color varies, resulting in a defective product.
[0012]
In order to accurately form a fine pattern using a colored resin composition for ionizing radiation curing, it is required to satisfy all of these factors. However, in general, increasing the solubility of the photosensitive coloring composition with a developer so as not to leave a residue tends to cause fine line defects, foreign matter, surface roughness, and the like, so it is very difficult to prevent the residue. It is.
[0013]
Further, the mechanical or chemical properties of the completed pixel are not only important for the mechanical or temporal durability of the color filter and the liquid crystal display device, but also greatly affect the display performance. The physical properties that affect the display performance are required to have properties such as hardness, elasticity, impurity N-methylpyrrolidone, γ-butyrolactone and elution resistance to liquid crystals.
[0014]
Spacers such as spherical spacers and columnar spacers are not only directly formed on the substrate of the color filter, but may be provided in an upper layer than the pixels and the black matrix. In this case, if the hardness and elasticity of the pixel are inferior, no matter how high the spacer is formed, the base is deformed and the uniformity of the cell gap is impaired. For this reason, the pixels are also required to have high hardness and elastic modulus.
[0015]
Moreover, impurity elution from the pixel causes liquid crystal contamination. Since the liquid crystal does not perform the switching function only by mixing a small amount of ionic impurities, it is important that the ionic molecules do not dissolve into the liquid crystal layer from the color filter. However, pigments and dispersants used for pixels often contain ionic molecules as impurities, and it is required to suppress impurity elution from the colored layer.
[0016]
In addition, the physical property after hardening of a pixel can be improved by making a coloring resin composition for ionizing radiation hardening fully contain a hardening component. However, adding a large amount of a dispersant to finely disperse the pigment in the colored resin composition for ionizing radiation curing to increase the transparency of the pixel results in a decrease in the concentration of the curing component and improve the physical properties of the pixel. Will not be able to. In addition, when a large amount of dispersant is used, the pigment concentration is also lowered, so that the color reproduction ability is also inferior.
[0017]
1 and 2, the protective layer 8 is required to have characteristics such as transparency, adhesion, strength, hardness, heat resistance, pattern shape accuracy, and coating film flatness. The protective layer is solidly coated on the colored layer, but it is preferable that only the region where the colored layer is formed on the transparent substrate can be selectively covered in consideration of the adhesion and sealing property of the seal portion. . In addition, although it is not formed in a pattern as fine as the colored layer, the protective layer is also required to have an accurate pattern shape like the colored layer. Further, since the columnar spacer 12 is formed on the black matrix layer, transparency is not required, but other required characteristics are common to the colored layer and the protective layer. In addition, the colored layer and the protective layer, particularly the columnar spacer, that form these color filters are required to have sufficient hardness so as to keep the liquid crystal layer constant. Application of an ionizing radiation curable resin composition containing a maleimide copolymer to the formation of a colored layer, a protective layer, a columnar spacer, and the like of such a color liquid crystal display device has been studied. In this case, for example, the ionizing radiation curable resin composition is applied onto the substrate and cured with ionizing radiation so as to form a pattern, and the uncured portion is developed with alkaline water or the like.
[0018]
Regarding such a resin composition for ionizing radiation curing, a photosensitive coloring composition using a copolymer containing an N-substituted maleimide and a monomer having an acid group as a binder resin is disclosed (for example, see Patent Document 1). ). Moreover, the radiation sensitive composition for color filters containing the alkali-soluble resin containing the copolymer of N position- substituted maleimide monomer and the other copolymerizable monomer is disclosed (for example, refer patent document 2). . Furthermore, a monomer mixture containing 1 to 6% by mass of α, β-ethylenically unsaturated carboxylic acid, 10 to 80% by mass of α, β-ethylenically unsaturated carboxylic acid ester and 5 to 30% by mass of N-substituted maleimide is polymerized. An acrylic resin composition for a color filter obtained by blending an acrylic resin obtained by doing so is disclosed (for example, see Patent Document 3).
[0019]
However, in these compositions, when cured and developed with ionizing radiation so as to form a pattern shape on a substrate, the composition is cured with a small amount of ionizing radiation at the time of curing, or the pattern shape accuracy after development is high. There was room to devise to improve. In other words, curing with a small amount of ionizing radiation makes it possible to shorten the curing time and improve efficiency, and further improving the accuracy of the pattern shape can provide a liquid crystal display device with improved performance and quality. Therefore, there was room for such research.
[0020]
In addition, regarding a colored image forming material containing a polymer having a maleimide group in the skeleton, when the polymer has a carboxyl group, a photopolymerizable sensitivity can be obtained by adding and introducing an active double bond to the carboxyl group. (See, for example, Patent Document 4). However, even such materials have problems such as insufficient light transmittance due to insufficient pigment dispersibility and large heat-induced yellowing due to heating during the production of color filters. In addition, there is room for improvement so that a liquid crystal display device with improved performance and quality can be efficiently manufactured by improving the accuracy of the pattern shape after development.
[0021]
[Patent Document 1]
JP 10-31308 A (page 1-2)
[Patent Document 2]
JP-A-10-300922 (page 1-2)
[Patent Document 3]
Japanese Patent Laid-Open No. 10-60214 (page 1-2)
[Patent Document 4]
Japanese Patent Laid-Open No. 11-15147 (page 1-2)
[0022]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation, and has excellent pigment dispersibility, excellent heat yellowing resistance, high hardness, excellent solubility in a solvent, and is easy to form a uniform coating film, which is uncured. Ionizing radiation curing comprising a maleimide-based alkali-soluble copolymer that can be sufficiently dissolved in alkaline water, has excellent curability by ionizing radiation dose, and can improve the accuracy of pattern shape after development. An object of the present invention is to provide a resin composition. Moreover, it aims at providing the color filter and liquid crystal display device which were formed using this resin composition for ionizing radiation curing.
[0023]
[Means for Solving the Problems]
The present inventors have studied a pigment dispersion composition containing various maleimide copolymers as essential components, and a resin composition for ionizing radiation curing. Along with maleimide alkali-soluble copolymers, radical polymerizable compounds and photopolymerization Focusing on the usefulness of the ionizing radiation curable resin composition containing an initiator for forming a thin film layer or a fine pattern such as a color filter, the acid value of the maleimide-based alkali-soluble copolymer is 20 to 200 mgKOH / g. When the content of the low molecular weight component having a molecular weight of 100 to 1000 is 10% by mass or less, the pigment dispersibility and heat-resistant yellowing are excellent, the curability by ionizing radiation dose is excellent, and the pattern shape accuracy after development is improved. I found out that it can be improved, and came up with the idea that the above problems can be solved brilliantly. Moreover, it discovered that the curability by ionizing radiation was further excellent by making a double bond equivalent into the range of 300-100,000. A color filter in which at least one of a colored layer, a protective layer, and a spacer is formed by such an ionizing radiation curable resin composition, and a liquid crystal display device using the color filter have pixel transparency and pattern shape. It has been found that the high-performance and high-quality products are obtained due to the excellent accuracy and the like, and the present invention has been achieved.
[0024]
That is, the present invention relates to a pigment dispersion composition containing a maleimide-based alkali-soluble copolymer, a pigment and a solvent, and a maleimide-based alkali-soluble copolymer, a radical polymerizable compound, and a photopolymerization initiator for ionizing radiation curing. A resin composition, wherein the maleimide-based alkali-soluble copolymer has an acid value of 20 to 200 mgKOH / g, and a low molecular weight component having a molecular weight of 100 to 1000 and a content of a pigment dispersion composition of 10% by mass or less, and It is a resin composition for ionizing radiation curing.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0025]
The ionizing radiation curable resin composition of the present invention comprises a maleimide-based alkali-soluble copolymer, a radical polymerizable compound, and a photopolymerization initiator. The maleimide alkali-soluble copolymer, radical polymerizable compound and photopolymerization initiator may be used alone or in combination of two or more. In such an ionizing radiation curable resin composition, it is formed by coating a color filter substrate and exposing it to the excellent physical properties and alkali developability of the maleimide-based alkali-soluble copolymer and a radically polymerizable compound. With the three-dimensional network structure, it is possible to form a cured film excellent in various physical properties such as adhesion to the surface of the substrate to be coated (substrate surface), film strength, heat resistance, heat-resistant pure water, and chemical resistance. In some cases, an accurate pattern can be formed when developing in a predetermined pattern.
[0026]
The maleimide-based alkali-soluble copolymer has an N-substituted maleimide monomer unit as an essential component, an acid value of 20 to 200 mgKOH / g, and a content of low molecular weight components having a molecular weight of 100 to 1000 is 10% or less. . A preferred form of such a maleimide-based alkali-soluble copolymer is a form having an N-substituted maleimide monomer unit, a (meth) acrylic acid monomer unit, and a (meth) acrylic acid ester monomer unit as essential. Can be mentioned. Among them, the N-substituted maleimide monomer unit is preferably a phenylmaleimide, cyclohexylmaleimide and / or benzylmaleimide monomer unit. Of these, cyclohexylmaleimide and benzylmaleimide are more preferable, and benzylmaleimide is most preferable. These monomer units can be used alone or in combination of two or more.
[0027]
As a mass ratio of the monomer unit which comprises the said maleimide type | system | group alkali-soluble copolymer, N-substituted maleimide monomer unit is 5-50 mass%, for example, (meth) acrylic acid monomer unit is 5-30. It is preferable that a mass% and (meth) acrylic acid ester monomer unit are 30-87 mass%. When the mass ratio of these monomer units is out of the above range, there is a possibility that the function and effect exhibited by each monomer unit in the present invention cannot be obtained. More preferable forms of the above mass range include 5 to 40% by mass of cyclohexylmaleimide and / or benzylmaleimide monomer units, 8 to 30% by mass of (meth) acrylic acid monomer units, and (meth) acrylic acid esters. 30 to 80% by weight of monomer units, most preferably 5 to 30% by weight of cyclohexylmaleimide and / or benzylmaleimide monomer units, 10 to 25% by weight of (meth) acrylic acid monomer units, and (meta ) Acrylic acid ester monomer unit 35 to 70% by mass. In addition, the said mass range is based on 100 mass% of maleimide type | system | group alkali-soluble copolymers. The composition of the copolymer can be determined by, for example, a method of quantifying unreacted monomers by gas chromatography at the end of polymerization.
[0028]
In the present invention, the monomer unit other than the essential monomer unit may or may not have a monomer unit. The total mass ratio of the essential monomer unit is, for example, 50 masses. % Or more is preferable. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.
The arrangement form of the monomer units in the maleimide alkali-soluble copolymer is not particularly limited. For example, any of a random copolymer, an alternating copolymer, a block copolymer and the like may be used.
[0029]
The maleimide-based alkali-soluble copolymer preferably has a double bond equivalent of 300 to 100,000. If the double bond equivalent is less than 300, the amount of double bonds is too large, so that curing occurs too much, the shrinkage of curing increases, and the adhesion to the substrate decreases, and the molecular weight increases over time. Increases the storage stability and decreases the storage stability, which may cause gelation. Further, as described later, it is preferable to introduce a double bond into the copolymer using a compound having an oxirane ring and a copolymerizable double bond. If a large amount remains, the hydrophilicity will increase too much, so that the surface of the coating film after development will become rough and the coating film will be whitened. Furthermore, such maleimide-based alkali-soluble copolymers are difficult to produce. If it exceeds 100,000, the amount of double bonds is too small, so when developing with a small amount of exposure, curing does not occur sufficiently, so developability becomes insufficient, and the coating surface becomes rough. It will be. Furthermore, when manufacturing a color filter, manufacturing efficiency will fall or the precision of a pattern shape will fall.
If the double bond equivalent is within the above range, development is possible with a small exposure amount, for example, an exposure amount of 50 mJ / cm @ 2, and a hard coating film can be obtained. The preferable range of the double bond equivalent in the present invention is 300 to 10,000. More preferably, it is 300-3000, More preferably, it is 300-2000, Especially preferably, it is 400-2000, Most preferably, it is 450-1000. The double bond equivalent is a weight average molecular weight per double bond in the maleimide-based alkali-soluble copolymer.
[0030]
The double bond is preferably a copolymerizable double bond, and is preferably in the side chain of the maleimide alkali-soluble copolymer. As a result, the double bond of the maleimide-based alkali-soluble copolymer sufficiently contributes to ionizing radiation curability, so that the sensitivity of the ionizing radiation curable resin composition by ionizing radiation can be sufficiently improved. It becomes possible. That is, since the curability of the ionizing radiation curable resin composition by ionizing radiation is excellent, it is possible to shorten the curing time to improve efficiency, and to sufficiently improve the accuracy of the pattern shape after development. .
[0031]
The method for producing the maleimide-based alkali-soluble copolymer is not particularly limited. For example, an N-substituted maleimide monomer, a (meth) acrylic acid monomer, and a (meth) acrylic acid ester monomer After the monomer component containing is copolymerized to produce a copolymer, the copolymer can be produced by introducing a double bond into the copolymer. In this case, the mass ratio of each monomer in the monomer component is appropriately set so that the mass ratio of each monomer unit in the maleimide alkali-soluble copolymer is in the above range. Incidentally, in response to the fact that the maleimide-based alkali-soluble copolymer of the present invention may have a monomer unit other than these monomer units, one type of monomer other than the above-mentioned monomers. Or you may use the monomer component containing 2 or more types.
[0032]
The N-substituted maleimide monomer is not particularly limited. For example, aromatic substituted maleimide such as phenylmaleimide, benzylmaleimide, naphthylmaleimide, o-chlorophenylmaleimide; cyclohexylmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide, isopropylmaleimide And alkyl-substituted maleimides. Among these, it is preferable to use cyclohexylmaleimide, phenylmaleimide, and benzylmaleimide. More preferred are cyclohexylmaleimide and benzylmaleimide, which can fully exhibit the effects of the present invention. Further, as the cyclohexylmaleimide, it is preferable to use a cyclohexylmaleimide in which the content of cyclohexylamino succinic anhydride contained as a by-product in the cyclohexylmaleimide is reduced to 1% by mass or less.
[0033]
In the monomer component, examples of the (meth) acrylic acid monomer include acrylic acid and methacrylic acid. Furthermore, as the (meth) acrylic acid ester monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl etc. are mentioned. “(Meth) acrylic acid” means that either acrylic acid or methacrylic acid may be used. In addition, the unit which added the glycidyl (meth) acrylate etc. to (meth) acrylic acid mentioned later naturally is contained in a (meth) acrylic acid ester monomer.
[0034]
The other monomer contained in the monomer component is not particularly limited. For example, an aromatic vinyl monomer such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene; acrylonitrile, And vinyl cyanide compounds such as methacrylonitrile; unsaturated dicarboxylic acid anhydrides such as maleic anhydride. However, aromatic vinyl monomers such as styrene are preferably 15% by mass or less and more preferably 10% by mass or less because non-polymerizable low molecular weight products are easily generated by addition reaction with N-substituted maleimide.
[0035]
As a preferable form for producing the maleimide-based alkali-soluble copolymer in the present invention, for example, a method of polymerizing a monomer component using a radical polymerization initiator and, if necessary, a molecular weight regulator is suitable. In this case, the polymerization can be performed by bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or a combination of these as appropriate. Among these, it is preferable to perform polymerization by solution polymerization. More preferably, the polymerization is performed by batch solution polymerization.
In particular, when batch solution polymerization is performed, the monomer initially charged in the reaction tank may be less than 50% of the total monomers, and polymerization may be performed while continuously or intermittently supplying the remaining monomers. preferable. Preferably it is less than 30%, more preferably 20%. When the amount of the monomer charged in the initial stage exceeds the above range, the change in the concentration of the monomer becomes large in the initial and second half of the polymerization. As a result, the molecular weight distribution increases, the amount of low molecular weight components generated increases, the unreacted monomer increases, and pigment dispersibility and heat-resistant yellowing may decrease, and the heat generation at the initial stage of polymerization increases, making it difficult to remove heat. It is not preferable in industrial production.
[0036]
Further, the unreacted monomer after completion of the polymerization is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. When the amount of the unreacted monomer exceeds the above range, the low molecular weight component having a molecular weight of 100 to 1000 increases. Especially when a large amount of (meth) acrylic acid remains, (meth) acrylic acid forms a low molecular weight adduct with a compound containing a group capable of binding to an acid group such as glycidyl (meth) acrylate and / or a double bond. In addition to greatly reducing the pigment dispersibility, heat yellowing may also be reduced.
[0037]
As a method of reducing unreacted monomers after the completion of polymerization, a method of continuously or intermittently adding a polymerization initiator after the supply of all monomers is completed, or a supply of all monomers After completion of the polymerization, there is a method of raising the polymerization temperature by 10 ° C. or more to complete the polymerization. Among them, in the method of adding the polymerization initiator after completion of the monomer supply, the resulting polymer may be colored or the polymerization initiator may remain, an addition reaction step such as glycidyl methacrylate, pigment dispersion composition There is a risk of thickening and gelation during storage of the product or ionizing radiation curable resin composition. Therefore, a method in which the polymerization temperature is increased after the supply of all the monomers is completed is preferable.
[0038]
When producing the maleimide-based alkali-soluble copolymer, the radical polymerization initiator, polymerization conditions and the like are not particularly limited, and may be appropriately set according to the polymerization method, the type of monomer to be copolymerized, the use ratio, and the like. That's fine. For example, the solvent used for the polymerization by solution polymerization should be a liquid that does not hinder solution polymerization and can dissolve both the monomer component as a raw material and the maleimide-based alkali-soluble copolymer to be produced. Examples thereof include, but are not limited to, for example, aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol and glycol; cellosolvs such as cellosolve and butylcellosolve; carbitols such as carbitol and butylcarbitol; cellosolve acetate; Esters such as carbitol acetate and propylene glycol monomethyl ether acetate; Ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; Cyclic ethers such as tetrahydrofuran; Cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones; dimethyl sulfoxide, an organic solvent may be used or the like having a polarity such as dimethyl formamide. The solvent used for the polymerization by non-aqueous dispersion polymerization may be a liquid in which the monomer component as a raw material can be dissolved and the maleimide alkali-soluble copolymer to be formed is insoluble. For example, liquid hydrocarbons such as benzene, toluene, hexane, and cyclohexane, other nonpolar organic solvents, and the like can be used. These may be used alone or in combination of two or more. As a quantity of the solvent used for solution polymerization or non-aqueous dispersion polymerization, it is preferable to set it as 20-400 mass% with respect to 100 mass% of all the monomer components, for example. If it is less than 20% by mass, there is a possibility that sufficient stirring cannot be performed due to thickening at the end of the polymerization. If it exceeds 400% by mass, the molecular weight of the maleimide-based alkali-soluble copolymer to be formed becomes too small. There is a fear. More preferably, it is 50-200 mass%.
[0039]
As said radical polymerization initiator, 1 type (s) or 2 or more types, such as a well-known radical polymerization initiator, for example, a peroxide, an azo initiator, can be used. As a usage-amount of a polymerization initiator, it is preferable to use in the ratio of 0.001-5.0 mass% with respect to 100 mass% of all monomer components, for example, More preferably, it is 0.5-3.0. %.
[0040]
Moreover, as a molecular weight regulator, 1 type (s) or 2 or more types, such as (alpha) -methylstyrene dimer and a mercaptan-type chain transfer agent, can be used, for example. Among these, a long chain alkyl mercaptan having 8 or more carbon atoms is preferable in terms of odor and little coloring.
[0041]
What is necessary is just to set suitably as polymerization temperature in the said copolymerization by the radical polymerization initiator etc. to be used, Although it does not specifically limit, For example, it is preferable to set it as 50-200 degreeC. When the temperature is lower than 50 ° C., it is necessary to use an initiator having a low decomposition temperature, which may be disadvantageous for industrial production, for example, a facility for cooling and storing the initiator is required. If it exceeds 200 ° C., the monomer component may start to undergo thermal polymerization before reaching the decomposition temperature of the initiator. Preferably, it is 85-150 degreeC.
[0042]
When a maleimide-based alkali-soluble copolymer is produced by the above production method, it is preferable to use it in a solution state without separating the solid content.
[0043]
As a method of synthesizing an alkali-soluble maleimide copolymer having a double bond equivalent of 300,000 to 100,000, an acid group is bonded to a copolymer having an acid group as a precursor and an N-substituted maleimide monomer unit. It is preferable to react a compound having a group and / or a double bond. In the above case, for example, (meth) acrylic acid is preferably used as the monomer having an acid group.
[0044]
Examples of the compound having a group capable of bonding to an acid group and a copolymerizable double bond include, for example, isopropenyl oxazoline, glycidyl (meth) acrylate, alicyclic epoxy (meth) acrylate, and oxetane (meth) acrylate. (3,4-epoxycyclohexyl) methyl (meth) acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester and other double bonds copolymerizable with oxirane rings A compound having: unsaturated alcohol such as allyl alcohol, 2-blanc-1-ol-free furyl alcohol, oleyl alcohol, cinnamyl alcohol; 2-hydroxyethyl (meth) acrylate; N-methylol acrylamide; 2-acryl Yl oxyethyl isocyanate, 2-methacryloyloxy can be used acryloyloxyethyl isocyanate, and among them, it is preferable to use a compound having a double bond of an oxirane ring and a copolymerizable. Thereby, the double bond which has copolymerizability can be reliably and efficiently introduce | transduced into the copolymer which has an acid group. More preferably, isopropenyl oxazoline and glycidyl (meth) acrylate are used. In particular, glycidyl (meth) acrylate is most preferred from the standpoint of industrial availability, high reactivity with acid groups, and good balance between hydrophilicity and hydrophobicity of the resulting copolymer. Moreover, the usage-amount of such a compound will be suitably set so that the double bond equivalent of a maleimide type | system | group alkali-soluble copolymer may become said range.
[0045]
A preferred method for adding glycidyl (meth) acrylate to the carboxyl group includes a method of reacting in the temperature range of 90 ° C. to 120 ° C. for 2 hours to 24 hours in the presence of a catalyst and a polymerization inhibitor. Catalysts include tertiary amines such as triethylamine and dimethylbenzylamine, quaternary ammonium salts such as tetrabutylammonium bromide, phosphines such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, lithium chloride, and zinc octylate. Metal salts such as are preferably used, and tertiary amines are most preferable from the viewpoint of reactivity. In addition, when the temperature range is less than 90 ° C, the addition reaction rate is very slow and economically disadvantageous. When the temperature range exceeds 120 ° C, crosslinking due to thermal polymerization occurs, and the molecular weight may become too high or gel may occur. This is not preferable.
[0046]
In addition, in order to make the low molecular weight component having a molecular weight of 100 to 1000 present in the reaction system 10% or less after reacting a compound having a bond capable of bonding with an acid group and / or a double bond, the above-mentioned As described above, it is preferable to reduce the remaining monomer by operating the polymerization method of a copolymer having an acid group as a precursor and an N-substituted maleimide monomer unit. In particular, an adduct of (meth) acrylic acid and glycidyl (meth) acrylate may greatly reduce pigment dispersibility, so the amount of (meth) acrylic acid is preferably 1% or less, and preferably 0.5% or less. More preferred is 0.3% or less. Moreover, in that case, it is preferable to perform addition reaction, without passing through the removal operation of the low molecular weight component containing a residual monomer. Adopting the precursor copolymer into a poor solvent and precipitating, removing the low molecular weight component including the residual monomer, filtering and recovering, and re-dissolving the It is not preferable as an industrial production method because it is necessary.
[0047]
The low molecular weight component having a molecular weight (Mw) of 100 to 1000 contained in the maleimide-based alkali-soluble copolymer needs to be 10% or less, preferably 7% or less, more preferably. 5% or less.
The content of the low molecular weight component can be determined using polystyrene as a standard substance by GPC (gel permeation chromatography).
If the low molecular weight component exceeds 10%, the pigment dispersibility may be lowered or the heat-resistant yellowing may be lowered. Further, there is a possibility that development residue increases or the liquid crystal is contaminated by elution into the liquid crystal of the liquid crystal display device.
[0048]
The low molecular weight component mainly includes oligomers, residual monomers, groups capable of binding to acid groups and / or reaction products of double bond-containing compounds and monomers, decomposition products of polymerization initiators, polymerization inhibitors. , A mixture of a catalyst, a reaction product between monomers, a residual chain transfer agent, and the like.
[0049]
As a method for setting the content of the low molecular weight component to 10% or less, it is preferable to perform polymerization under the above-described polymerization conditions.
A method of precipitating the maleimide alkali-soluble copolymer in a poor solvent and removing the low molecular weight component can also be adopted, but in order to sufficiently reduce the low molecular weight component, the precipitation, filtration and re-dissolution operations are repeated many times. Since it needs to be repeated, it is not preferable as an industrial production method because a large amount of poor solvent is required.
[0050]
As a molecular weight of the said maleimide type | system | group alkali-soluble copolymer, it is preferable that a weight average molecular weight is 5000-50,000, for example. If it is less than 5,000, the heat resistance and thermal stability may be lowered, and if it exceeds 50,000, the solubility in alkaline water may be lowered. More preferably, it is 5000-35000, More preferably, it is 7000-32000.
[0051]
Moreover, it is preferable that ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight measured by GPC (gel permeation chromatography) is 4.0 or less. If it exceeds 4.0, heat-resistant yellowing and alkali water solubility may be reduced. More preferably, it is 3.5 or less, More preferably, it is 3.0 or less.
[0052]
The solubility of the maleimide-based alkali-soluble copolymer in alkaline water is preferably soluble in, for example, a 1% aqueous KOH solution. In this case, it is preferable that 20% by mass of the copolymer is added to 1% KOH aqueous solution and completely dissolved when stirred for 3 hours. In the ionizing radiation curable resin composition containing such a maleimide-based alkali-soluble copolymer, an uncured portion can be dissolved in alkaline water to form a clear pattern. Moreover, it is preferable that the aqueous alkali solution insoluble content with respect to 0.5% KOH aqueous solution is 10 weight% or less. More preferably, it is 5 weight% or less, More preferably, it is 3 weight% or less. The solubility of the maleimide-based alkali-soluble copolymer soluble in an aqueous alkali solution is, for example, a solubility test in a 200 ml 0.5% KOH aqueous solution at 50 ° C. using a 50 μm thick film of the maleimide-based alkali-soluble copolymer. It can evaluate by calculating | requiring the quantity of an alkaline water insoluble content.
[0053]
The acid value of the maleimide alkali-soluble copolymer is preferably 20 to 200 mgKOH / g. If it is less than 20 mgKOH / g, the solubility in alkaline water may be lowered, and if it exceeds 200 mgKOH / g, the alkali solubility of the maleimide-based alkali-soluble copolymer becomes too strong, and the pigment dispersibility may be lowered. In addition, the alkali resistance after curing may be reduced. More preferably, it is 40-150 mgKOH / g, Most preferably, it is 50-100 mgKOH / g.
[0054]
As a compounding quantity of the said maleimide type alkali-soluble copolymer, it is preferable to set it as 5-80 mass% with respect to 100 mass% of resin compositions for ionizing radiation hardening, for example. If it is less than 5% by mass, the viscosity may be too low, and the coating film stability after coating and drying may not be sufficient. If it exceeds 80% by mass, the viscosity becomes too high and the fluidity decreases, There is a risk of inconvenience such as poor applicability. More preferably, it is 10-50 mass%.
[0055]
The maleimide-based alkali-soluble copolymer can also exhibit excellent pigment dispersibility. The maleimide-based alkali-soluble copolymer is blended with a pigment in a solvent, and a dispersant is added as necessary. By replenishing, a pigment dispersion composition having excellent pigment dispersibility can be prepared. Such a pigment dispersion composition is suitable as a material for preparing the ionizing radiation curable resin composition of the present invention.
[0056]
As the pigment, one or more of various organic or inorganic colorants can be used. As the organic colorant, dyes, organic pigments, natural pigments and the like can be used. Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) numbers. What is attached | subjected is suitable.
[0057]
C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Yellow pigments such as C.I. Pigment Yellow 185; I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 254, C.I. I. Red pigments such as C.I. Pigment Red 177; I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. Blue pigments such as CI Pigment Blue 15: 6; I. Violet pigments such as CI Pigment Violet 23:19; and green pigments such as Pigment Green 7 and Pigment Green 36.
[0058]
As the inorganic colorant, inorganic pigments and extender pigments are suitable. Titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red , Ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. Among these pigments, phthalocyanine pigments used as blue or green pigments are preferred because of their excellent affinity with maleimide-based alkali-soluble copolymers. Among them, phthalocyanine-based blue pigments such as copper phthalocyanine are preferred. Is preferred. By combining a maleimide-based alkali-soluble copolymer and these pigments, a composition capable of obtaining excellent transparency, color characteristics, ability to form a fine pattern, and film properties after curing can be obtained. . Further, since the maleimide-based alkali-soluble copolymer is excellent in color characteristics such as transparency and yellowing resistance, it is preferable to combine it with a blue pigment having a remarkable adverse color tone due to yellowing.
[0059]
In the pigment dispersion composition, the pigment, the maleimide-based alkali-soluble copolymer, and the solvent can each be used alone or in combination of two or more. Of the blue pigments, phthalocyanine blue pigments are particularly preferable.
[0060]
The amount of maleimide-based alkali-soluble copolymer used in the pigment dispersion composition is 70-110 for maleimide-based alkali-soluble copolymer with respect to the total amount of pigment, that is, 100 parts by mass of the total amount of pigment in the pigment composition. It is preferable to set it as a mass part. Thereby, excellent pigment dispersibility can be obtained. More preferably, it is 80-100 mass parts.
[0061]
The pigment dispersion composition may be used in combination with a dispersant, but the blending ratio of the dispersant (dispersant / pigment) with respect to the total amount of pigment is preferably 0.5 or less in terms of mass ratio. Thereby, the pigment dispersion composition becomes more suitable as a material for forming a color filter or the like. More preferably, it is 0.3 or less. The smaller the amount of the dispersant, the better. However, in order to make the dispersing action of the dispersant effective, it is generally preferable that the ratio of the pigment and the dispersant is 0.05 or more.
[0062]
As the dispersant, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric ones, silicone surfactants, fluorine surfactants and the like can be used. Among them, a polymer surfactant (polymer dispersant) is used. preferable. Examples of polymer surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and other polyoxyethylene alkyl ethers. Suitable are oxyethylene alkyl phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes.
[0063]
As a solvent (dispersion solvent) for preparing the pigment dispersion composition, an organic solvent is suitable. As the organic solvent, an organic solvent used as a diluting solvent in order to prepare the ionizing radiation curable resin composition described later can be used. As a usage-amount of a solvent, it is preferable to set it as 100-1000 mass parts with respect to 100 mass parts of pigments. More preferably, it is 200-900 mass parts.
[0064]
The pigment dispersion composition can be prepared by replacing a part of the dispersant with the maleimide-based alkali-soluble copolymer in a conventionally known procedure for preparing a pigment dispersion composition. That is, the pigment, the maleimide-based alkali-soluble copolymer, the dispersant, and other components as necessary are mixed with the solvent in any order, and the kneader, roll mill, attritor, super mill, dissolver, homomixer, sand mill, etc. A pigment dispersion composition can be prepared by dispersing using a known disperser. Specifically, a method in which a mixture of an organic pigment and a binder is added and dispersed in a solvent, a method in which a pigment and a binder are added and dispersed in a solvent; a liquid in which only a pigment is dispersed in a solvent; and a binder only in a solvent A method of mixing the dispersed liquid or a method of adding a binder to a liquid in which only the pigment is dispersed in a solvent is suitable.
[0065]
The pigment dispersion composition is suitable as a preliminary preparation for preparing a coating liquid such as an ionizing radiation curable resin composition excellent in pigment dispersibility. If a pigment or a pigment dispersant is directly added and mixed with a binder component in a diluent solvent, sufficient dispersibility may not be obtained. On the other hand, an additional component of the binder and other components are mixed into the pigment dispersion composition, or a solvent for adjusting the solid content concentration of the pigment dispersion composition, additional component of the binder and other components. By adding to (diluting solvent), a coating liquid excellent in pigment dispersibility can be easily prepared.
[0066]
In the present invention, the radically polymerizable compound is not particularly limited as long as it is a compound capable of curing the ionizing radiation curable resin composition by causing cross-linking by the action of ionizing radiation, for example, in one molecule. It is preferable to use a photopolymerizable compound having three or more ethylenically unsaturated double bonds (a trifunctional or higher functional photocopolymerizable compound), and in addition, a bifunctional photocopolymerizable compound or the like may be used. it can. Examples of the tri- or higher functional photo-copolymerizable compound include poly (meth) acrylates of trihydric or higher polyhydric alcohols, or dicarboxylic acid modified products thereof. Examples include methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Among these, it is preferable to use dipentaerythritol pentaacrylate and dipentaerythritol hexa (meth) acrylate. “(Meth) acrylate” means that either acrylate or methacrylate may be used.
[0067]
As a compounding quantity of the said radically polymerizable compound, it is preferable to set it as 5-70 mass% with respect to 100 mass% of resin compositions for ionizing radiation hardening, for example. If it is less than 5% by mass, there is a possibility that the unexposed part will be lost during development. If it exceeds 70% by mass, the viscosity becomes too low and the coating film stability after coating and drying becomes insufficient. And there is a risk of inconvenience such as impairing the suitability of development. More preferably, it is 10-40 mass%.
[0068]
In the ionizing radiation curable resin composition of the present invention, a monofunctional photocopolymerizable monomer or the like as a reaction diluent is blended with one or more of the radical polymerizable compounds as necessary. Can do. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.
[0069]
In the present invention, the photopolymerization initiator is a compound that can generate active species such as radicals, cations, anions, etc. by ionizing radiation having a wavelength of 365 nm or less, and can initiate the polymerization reaction of the above-described radical polymerizable compound. Although it will not specifically limit if there is, it is preferable that it is a thing with high solubility to the solvent contained in the resin composition for ionizing radiation curing. As such a photoinitiator, a compound that generates free radicals by the energy of ultraviolet rays can be used. For example, benzophenone derivatives such as benzoin and benzophenone or derivatives thereof; xanthone and thioxanthone derivatives; chlorosulfonyl Halogen-containing compounds such as chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethyl benzophenones; triazines; imidazolines; fluorenones; haloalkanes; redox couples of photoreducing dyes and reducing agents; Organic sulfur compounds; peroxides and the like. Among these, it is preferable to use triazines and imidazolines.
[0070]
As a compounding quantity of the said photoinitiator, it is preferable to set it as 0.05-20 mass% with respect to 100 mass% of resin compositions for ionizing radiation hardening, for example. If it is less than 0.05% by mass, the curability of the coating film formed from the ionizing radiation curable resin composition may not be sufficient, and if it exceeds 20% by mass, the unexposed part may be lost during development. There is a risk that it will worsen or inconvenience such as yellowing of the coating film after post-baking. More preferably, it is 2 to 15% by mass.
[0071]
The ionizing radiation curable resin composition of the present invention may contain one or more components other than the essential components described above, if necessary, for example, a sensitizer; a pigment; a reaction with an acid by heating and curing. It is preferable to include a thermosetting resin or the like.
When the sensitizer is included, the sensitivity of the ionizing radiation curable resin composition can be improved. As such a sensitizer, a styryl compound or a coumarin compound is preferably used. Specifically, as the styryl compound, 2- (p-dimethylaminostyryl) quinoline, 2- (p-diethylaminostyryl) is used. ) Quinoline, 4- (p-dimethylaminostyryl) quinoline and the like, and as coumarin compounds, 7-diethylamino-4-methylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 4,6-diethylamino- 1 type, or 2 or more types, such as 7-ethylamino coumarin, are mentioned. As a compounding quantity of the said sensitizer, it is preferable to set it as 0.01-50 mass% with respect to 100 mass% of resin compositions for ionizing radiation hardening, for example.
[0072]
When the pigment is included, the colored layer of the color filter can be formed using the ionizing radiation curable resin composition. The ionizing radiation curable resin composition capable of forming such a colored coating film is also referred to as an ionizing radiation curable colored resin composition. Since the maleimide-based alkali-soluble copolymer can exhibit excellent pigment dispersibility, ionizing radiation can be reduced by reducing the amount of dispersant used in such a colored resin composition for ionizing radiation curing. The film physical property of the colored resin composition for curing can be improved, and a colored coating film having excellent post-curing physical properties such as hardness and elasticity can be formed. Such a resin composition for ionizing radiation curing (a colored resin composition for ionizing radiation curing) further containing a pigment is one of the preferred embodiments of the present invention. Moreover, the color filter which provided the colored layer formed by hardening | curing the resin composition for ionizing radiation curing containing the said pigment is also one of this invention.
[0073]
Examples of the pigment include one or more of organic pigments, inorganic pigments, and the like. Among the organic colorants and inorganic colorants described above, according to colors required for R, G, B, etc. of the pixel portion. Therefore, fine particles having heat resistance that can withstand the heating process of the color filter and that can be well dispersed can be selected and used. Among the pigments, phthalocyanine-based pigments are preferable because they have excellent affinity with maleimide-based alkali-soluble copolymers as described above. In addition, it is preferable to combine a maleimide-based alkali-soluble copolymer with a blue pigment because it is very effective.
[0074]
The blending amount of the coloring material is preferably 40 to 75% by mass with respect to 100% by mass of the total solid content in the ionizing radiation curing resin composition, for example. If it is less than 40% by mass, the coloring power of each colored layer will not be sufficient, so there is a risk that it will be difficult to display a clear image. If it exceeds 75% by mass, the light transmittance in each colored layer will not be sufficient. There is a risk of inconvenience. More preferably, it is 45-70 mass%.
[0075]
When the pigment is contained, one or more dispersants may be blended in order to disperse the pigment uniformly and stably. Such a dispersant and its blending amount are the same as those in the pigment dispersion composition described above.
[0076]
When a thermosetting resin that cures by reacting with an acid by heating is included, the cured resin composition for ionizing radiation curing is applied to the surface of the substrate, exposed to a desired pattern, and developed to form a cured pattern. After the formation, when the cured pattern is heated to a predetermined temperature, the thermosetting resin reacts with the carboxyl groups remaining in the cured pattern and consumes carboxyl groups, so that the alkali resistance is improved and the thermosetting property is increased. The physical properties of the cured pattern are improved by the crosslinking reaction of the resin. As a result, the heat resistance, adhesion, hot pure water resistance, and chemical resistance (particularly alkali resistance) of the film or pattern formed by the ionizing radiation curable resin composition of the present invention are improved.
[0077]
As the acid-reactive thermosetting resin, for example, an epoxy resin, particularly an epoxy resin having two or more epoxy groups in one molecule is preferable, and specifically, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. 1 type (s) or 2 or more types, such as a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and an alicyclic epoxy resin.
[0078]
As a compounding quantity of the said thermosetting resin, it is preferable to set it as 1-20 mass% with respect to 100 mass% of resin compositions for ionizing radiation curing, for example. If it is less than 1% by mass, there is a possibility that sufficient alkali resistance may not be imparted to the coating film formed by curing the ionizing radiation curable resin composition, and if it exceeds 20% by mass, it is for ionizing radiation curing. There is a possibility that inconveniences such as a decrease in storage stability and developability of the resin composition may occur. More preferably, it is 3 to 15% by mass.
[0079]
Various additives other than those described above can be blended in the ionizing radiation curable resin composition of the present invention as necessary. Examples of such additives include silane coupling agents such as vinyl silane, acrylic silane, and epoxy silane. By adding such an additive, adhesion to the substrate and other adjacent coating layers is exemplified. Can be improved.
[0080]
The production method of the ionizing radiation curable resin composition of the present invention is not particularly limited. For example, the maleimide-based alkali-soluble copolymer, the radical polymerizable compound, the photopolymerization initiator, and, if necessary, the above-described essential components It can be produced by a method in which things other than the components are mixed or added to a solvent and stirred to dissolve and disperse uniformly. In such a production method, the mixing order and the like are not particularly limited. Moreover, as an apparatus used for stirring, a dissolver and a homomixer are suitable.
[0081]
The usage form of the ionizing radiation curable resin composition of the present invention is not particularly limited, but is usually diluted with a solvent in consideration of coating and suitability for coating. As such a solvent, it is preferable to use a solvent that dissolves a maleimide-based alkali-soluble copolymer, a radical polymerizable compound, a photopolymerization initiator, and the like, has a high boiling point, and good spin coating properties. For example, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate Ester solvents such as butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; cellosolve acetate such as methoxyethyl acetate, ethoxyethyl acetate and ethyl cellosolve acetate Solvents: Carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; diethyl ether, ethylene glycol Ether solvents such as coal dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone Organic solvents such as unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; More than seeds can be used. Among these, it is preferable to use 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, or the like.
The amount of the solvent used may be adjusted as appropriate depending on the dissolved state of the compounding components, coating properties, and the like. For example, the solid content concentration is preferably 5 to 50% by mass.
[0082]
An example of a method for forming a cured film (including those formed in a predetermined pattern) using the ionizing radiation curable resin composition of the present invention will be described below. First, the ionizing radiation curable resin composition of the present invention is applied to the surface of a substrate such as a substrate, and the formed coating film is exposed to ionizing radiation such as ultraviolet rays or electron beams to be exposed and cured. When the coating film is irradiated with ionizing radiation, active species are first generated from the photopolymerization initiator by the action of ionizing radiation in the coating film, and the crosslinking reaction of the radical polymerizable compound is initiated by the action of the active species. The film is cured.
[0083]
At this time, when it is desired to form the coating film in a predetermined pattern such as a pixel or a columnar spacer, the film is exposed to a predetermined pattern and developed by performing exposure through a photomask. Since the maleimide-based alkali-soluble copolymer has a carboxyl group, the coating film can remove unexposed portions where the radically polymerizable compound is not cross-linked by alkali development. A cured coating can be formed.
[0084]
The coated film is exposed and cured, developed as necessary, and then further cured by heating to obtain a cured film. When the ethylenic double bond derived from the radical polymerizable compound remains in the exposure-cured coating film, the crosslinking reaction can be further advanced by a heating step. If the coating film contains a thermosetting resin such as a polyfunctional epoxy resin, it reacts with the carboxyl group of the maleimide-based alkali-soluble copolymer remaining in the coating film, As groups are consumed, cross-linking occurs. As a result, the heat resistance, adhesion, hot pure water resistance, and chemical resistance (particularly alkali resistance) of the cured film are improved.
[0085]
The cured film formed using the ionizing radiation curable resin composition of the present invention is excellent in various physical properties such as adhesion to the surface of the coated body, film strength, heat resistance, hot pure water resistance, chemical resistance, and the like. A pattern can be accurately formed by alkali development. Furthermore, it is excellent in heat resistance stability with respect to transparency and color tone, in particular, without causing yellowing even when exposed to a high temperature environment such as a heating process when forming an alignment film in the color filter manufacturing process. A high protective layer and a colored layer having a desired color tone can be formed. That is, one of the preferred embodiments of the ionizing radiation curable resin composition of the present invention is that the ionizing radiation curable resin composition is applied onto a glass substrate by spin coating, and after exposure at a dose of 100 mJ / cm 2, 200 ° C. In the case of forming a coating film having a film thickness of 5 μm by heating for 30 minutes, after the coating film is further heated at 250 ° C. for 1 hour, the coating film maintains a light transmittance of 380 nm at 90% or more. Such a form can be achieved by the present invention.
[0086]
In a preferred embodiment of the present invention, the ionizing radiation curable resin composition is a series of treatments that are further heated at 250 ° C. for 1 hour after ultraviolet irradiation with an ultrahigh pressure mercury lamp when the film thickness after curing is 1.0 μm. The color difference (ΔEab) before and after the process is 2.0 or less. That is, when a film having a thickness of 1.0 μm after curing formed from an ionizing radiation curing resin composition is irradiated with ultraviolet light with an ultrahigh pressure mercury lamp and then heated at 250 ° C. for 1 hour, the coated film before and after ultraviolet irradiation The color difference (ΔEab) is 2.0 or less. Such an ionizing radiation curable resin composition is suitable as a material for forming a transparent protective layer because it is excellent in heat resistance stability regarding transparency and color tone. More preferably, the color difference (ΔEab) is 1.0 or less.
[0087]
Here, the color difference (ΔEab) is a value obtained from the following color difference formula according to the CIE 1976 (L *, a *, b *) space color system (New Color Science Handbook edited by the Japan Color Society (Showa 60)). ) P.266).
ΔEab = {(ΔL) 2+ (Δa) 2+ (Δb) 2} 1/2
[0088]
The coating film produced from the ionizing radiation curable resin composition of the present invention has sufficient hardness as well as heat resistance stability related to transparency and color tone. For example, the ionizing radiation curable resin composition is such that a 5 μm thick cured film formed on a transparent substrate has a universal hardness at 180 ° C. of 200 N / mm 2 or more and an elastic deformation rate of 30% or more. is there. Specifically, the ionizing radiation curing resin composition is applied onto a glass substrate by spin coating, exposed at a dose of 100 mJ / cm 2, and then heated at 200 ° C. for 30 minutes to form a coating film having a thickness of 5 μm. When the surface hardness of the coating film is measured at a surface temperature of 180 ° C. and the maximum load of the Vickers indenter is 20 mN, the universal hardness (test load / surface area of the Vickers indenter under the test load) is 200 N / mm2 or more can be achieved. Regarding universal hardness, material testing technology vol. 43 No. 2 (April 1998) p. 72 and can be evaluated according to the German standard DIN 50359-1. Such a resin composition for ionizing radiation curing is suitable as a material for forming a columnar spacer included in a color filter.
[0089]
The ionizing radiation-curing resin composition (ionizing radiation-curing colored resin composition) containing at least one pigment selected from the group consisting of at least a blue pigment and a phthalocyanine-based pigment is a blue colored cured film or A colored coating film containing a phthalocyanine pigment can be formed. Such an ionizing radiation curable resin composition is particularly useful for forming a pattern of a blue pixel that constitutes a color filter or a pixel that contains a phthalocyanine pigment, preferably a pattern of a blue pixel that contains a phthalocyanine blue pigment. It is very suitable, and a high-performance and high-quality color filter can be obtained. It is a preferred embodiment of the present invention to form a colored layer (pixel pattern) of a color filter, particularly a blue pixel, with such an ionizing radiation curable resin composition.
[0090]
With respect to color characteristics, the ionizing radiation curable resin composition can form bright pixels with high transparency, particularly when a blue cured film is formed. As such a preferable form, when the ionizing radiation curing resin composition has a film thickness after curing of 1.35 μm or less, the x-coordinate is 0.05 in the C light source side color XYZ color system 2 degree field of view. ≦ x ≦ 0.30, a cured film capable of displaying a color space in which the y coordinate is 0.05 ≦ y ≦ 0.30 and the stimulus value Y is 20 or more is formed. Specifically, the ionizing radiation curing resin composition is applied onto a glass substrate by spin coating, dried at 80 ° C. for 3 minutes, exposed at a dose of 100 mJ / cm 2, and then heated at 230 ° C. for 30 minutes. When forming a blue cured film, the x-coordinate in the C light source color measurement XYZ color system 2 degree visual field when the formed blue cured film is color-measured with a single pixel with a film thickness of 1.35 μm or less. Is a color space in which 0.05 ≦ x ≦ 0.30, the y coordinate is 0.05 ≦ y ≦ 0.30, and the stimulus value Y is 20 or more. More preferably, a cured film capable of displaying a color space in the range of 21.0 or more is formed.
[0091]
The ionizing radiation curable resin composition also uses a maleimide-based alkali-soluble copolymer with high heat resistance, and since there are few low molecular weight components that may cause yellowing, it is difficult to cause yellowing, A blue cured film having high heat resistance with respect to color tone can be formed. As a preferred embodiment, the ionizing radiation curable resin composition has a cured film thickness of 1.3 μm and the C light source side color XYZ color system 2 field of view before and after heating at 250 ° C. for 1 hour, y = When measuring the stimulation value Y at 0.1400, a cured film is formed in which the change rate {(Y2 / Y1) × 100} of the measured value Y2 after heating with respect to the measured value Y1 before heating is 97% or more It is. Specifically, the ionizing radiation curing resin composition is applied onto a glass substrate by spin coating, dried at 80 ° C. for 3 minutes, exposed at a dose of 100 mJ / cm 2, and then heated at 230 ° C. for 30 minutes. After forming a blue cured film with a film thickness of about 1.3 μm, heating is performed for 1 hour at 250 ° C. assuming a heating process for forming an electrode by ITO sputtering and an alignment film such as polyimide on the color filter on the blue cured film. After the test for the measured value Y1 before the test, when the stimulus value Y value is measured before and after the heat resistance test, the C light source colorimetric XYZ color system 2 field of view, y = 0.1400 The change rate (Y2 / Y1) of the measured value Y2 can be maintained at 97% or more.
[0092]
The ionizing radiation curable resin composition is excellent in various aspects such as development form, development time, residue, surface roughness, adhesion, resolution, cross-sectional shape, and contrast with respect to fine pattern forming ability such as plate making characteristics and developability. It is. As a preferred embodiment, the ionizing radiation curable resin composition forms a cured film having a contrast ratio of 2000 or more. In addition, it is also preferable that the ionizing radiation curing resin composition forms a cured film having a surface roughness (Ra) of 50 mm or less in the measurement method based on JIS B0601-1994. More preferably, it is a form in which a cured film of 30 mm or less is formed.
[0093]
Furthermore, as a preferable form in the present invention, a cured film having a line width of 25 μm or less that generates defects when a coating film formed from an ionizing radiation curable resin composition is exposed and cured through a line-and-space mask. Can be mentioned. More preferably, it is 20 μm or less. Further, it is preferable to form a cured film having a resolution of 24 μm or less when the coating film formed from the ionizing radiation curing resin composition is exposed and cured through a line and space mask, more preferably. Forms a cured film of 20 μm or less.
[0094]
In the negative resist development process, the uncured unexposed portion of the resist layer is dissolved by the alkali developer and leaves the substrate. However, as the development form, the portion to be removed is mainly large. There are a peelable type that peels off as a lump and a dissolved type that gradually dissolves and diffuses so that the dye dissolves in water. The former peeling type is a development form that is not preferred because a solid lump remains as a foreign substance and remains in the system and easily contaminates pixels of other colors. In contrast, the ionizing radiation curable resin composition of the present invention is the latter dissolution type and takes a preferred development form. In addition, the ionizing radiation curable resin composition of the present invention has a shorter development time compared to the case of using an acrylic resin binder, so that the throughput is shortened accordingly, and the amount of developer used and the development line are shortened. It is possible.
[0095]
In the developing process of the negative resist, the uncured unexposed portion of the resist layer is dissolved by the alkali developer and separated from the substrate, but the resist remains on the substrate without being sufficiently detached. There is a case. If a pixel is formed by applying and developing a resist of another color in a place where such a development residue remains, adverse effects such as a change in color characteristics and a decrease in smoothness are caused. On the other hand, the ionizing radiation curable resin composition of the present invention does not leave a residue in the dissolved portion during development, so that the quality of pixels other than blue can be improved. Generally, if the residue is reduced, the solubility of the resist becomes too strong, which causes problems such as surface roughness, poor adhesion and reduced resolution, and the accuracy of the pattern is impaired. A cured film produced using the resin composition is accurately formed in a predetermined pattern without leaving a residue in a portion to be removed by development.
[0096]
In the ionizing radiation curing resin composition, the cross-sectional shape of the cured film can be formed into a tapered shape. When a colored resist is applied on the substrate and the coating film is developed, the cross-sectional shape of the resulting colored layer is such that the length of the lower base (contact surface with the substrate) is the upper base (surface facing the contact surface with the substrate). When the taper shape (trapezoidal shape) is larger than the length (ie (upper surface / lower surface) <1), when the cross-sectional shape is rectangular (ie (upper surface / lower surface) = 1), and the lower bottom of the cross-sectional shape May have a reverse tapered shape (reverse trapezoidal shape) that is smaller than the length of the upper base (that is, (upper surface / lower surface)> 1). When the cross section of the colored layer becomes an inversely tapered shape, when the ITO electrode layer is deposited on the colored layer, the ITO does not sufficiently wrap around the side surface of the colored layer, and the portion where the ITO layer cannot be formed is near the lower bottom In other words, there is a problem in the electrode layer due to the lack of electrical continuity and partial resistance. Such a problem occurs when a color filter pixel pattern is formed using a colored resist. In addition, the reverse-tapered colored layer has corners that fall off during various processes and drops off and adheres to other portions of the color filter, which causes a protrusion defect. Therefore, it is desirable that the colored layer pattern formed by applying, developing, and post-baking a resist on a substrate has a tapered shape (trapezoidal shape) in cross section. In response to this demand, if the ionizing radiation curing resin composition of the present invention is used, a tapered blue layer pattern (substantially trapezoidal shape, (upper surface / lower surface) <1) is formed. It is possible to cover or prevent protrusion defects. That is, one of preferred embodiments in the present invention is a form in which the rising angle of the cross section of the cured film produced using the ionizing radiation curable resin composition is 90 ° or less with respect to the coated surface, Alternatively, the cross-sectional shape of the cured film is such that the ratio of the length of the upper base to the length of the lower base is less than 1. More preferably, a cured film is formed in which the rising angle of the cross section is 50 ° or less with respect to the coated surface.
[0097]
The ionizing radiation curable resin composition (ionizing radiation curable colored resin composition) in the above preferred form is suitable as a material for forming a colored layer constituting a color filter. A color filter provided with a colored layer obtained by curing the ionizing radiation curing resin composition is one of the preferred embodiments of the present invention.
[0098]
The ionizing radiation curable resin composition of the present invention is excellent in heat resistance stability concerning transparency and color tone in addition to various physical properties required for an ionizing radiation curable resin such as alkali developability. A color filter in which at least one of a colored layer, a protective layer, and a spacer is formed by such an ionizing radiation curing resin composition, and a liquid crystal display device using the color filter have pixel transparency, pattern shape accuracy, and the like. Due to its superiority, it has high performance and high quality.
[0099]
The present invention also includes a transparent substrate and a colored layer formed on the transparent substrate as an essential component, or in order to maintain a distance between a protective layer covering the colored layer and / or an electrode substrate facing the transparent layer. A color filter comprising a spacer provided at a position overlapping with a non-display portion on the transparent substrate, wherein at least one of the colored layer, the protective layer and the spacer is the ionizing radiation curable resin composition It is also a color filter formed by curing.
[0100]
As a form of the color filter, (1) a form provided with a colored layer on a transparent substrate, (2) a form provided with a colored layer and a protective layer, (3) a form provided with a colored layer and a spacer, (4) Examples include a colored layer, a protective layer, and a spacer. For example, a part of the colored layer is formed in a predetermined pattern on a black matrix layer formed in a predetermined pattern on a transparent substrate. Is preferred. Further, a transparent electrode for driving liquid crystal may be formed on the protective layer as necessary. The method for forming the black matrix is not particularly limited, and for example, the black matrix can be formed by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. Further, it may be formed by a chromium sputtering method or the like.
[0101]
The colored layer is usually arranged in a desired form such as a red pattern, a green pattern and a blue pattern in a mosaic type, a stripe type, a triangle type, a four-pixel arrangement type, an island type arranged in a "<" shape. Thus, the black matrix is provided between the colored patterns and in a predetermined area outside the colored layer forming area. A method for forming such a colored layer is not particularly limited, but it is preferably formed by a pigment dispersion method using a resin composition for ionizing radiation curing.
[0102]
In the case of forming a colored layer by the pigment dispersion method, for example, a coating material is prepared by dispersing the colored pigment in a resin composition for ionizing radiation curing, applied to one side of a transparent substrate, and a photomask is applied. It is possible to form a colored layer by irradiating with ionizing radiation such as ultraviolet rays, and after alkali development, followed by heat curing in a clean oven or the like. The thickness of the colored layer is usually preferably about 1.5 μm.
[0103]
As a method for preparing the protective layer, for example, an ionizing radiation curable resin coating solution can be applied by a spin coater, a die coater, a printing method, or the like. When using a spin coater, the number of revolutions is preferably set at 500 to 1500 revolutions / minute. The coating film of the ionizing radiation curable resin composition is exposed by irradiating ionizing radiation through a photomask, and after alkali development, it is heated and cured in a clean oven or the like to form a protective layer. The thickness of the protective layer is usually preferably about 2 μm.
[0104]
When forming a transparent electrode on the protective layer, the transparent electrode is usually made of a sputtering method using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof. A general method such as a vacuum deposition method or a CVD method is used, and a predetermined pattern is formed by etching using a photoresist or using a jig as necessary. The thickness of the transparent electrode is preferably about 20 to 500 nm, for example. More preferably, it is about 100 to 300 nm.
[0105]
The spacer is preferably a columnar spacer having a height corresponding to the cell gap. For example, the spacer is preferably provided on the transparent electrode plate, the colored layer, or the protective layer according to the region where the black matrix layer is formed. As a method of forming the columnar spacer on the transparent electrode or the like, for example, the ionizing radiation curable resin coating liquid of the present invention is applied by a method such as a spin coater, a die coater, printing, etc., and by ionizing radiation irradiation through a photomask. It can be formed by exposure and alkali development, followed by heat curing in a clean oven or the like. The rotational speed of the spin coater may be set at 500 to 1500 revolutions / minute, as in the case of forming the protective layer. The thickness (height) of the columnar spacer is preferably about 5 μm, for example.
[0106]
In the color filter of the present invention, at least one of the colored layer, the protective layer, and the columnar spacer is formed by curing the ionizing radiation curable resin composition. Therefore, it is possible to form a high-performance and high-quality liquid crystal display device.
[0107]
The present invention is also a liquid crystal display device in which the color filter and the electrode substrate are opposed to each other, and a liquid crystal compound is sealed therebetween. The liquid crystal display device of the present invention can be manufactured, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling the gap portion with a liquid crystal compound and sealing. The liquid crystal compound used in the liquid crystal display device of the present invention is not particularly limited. Moreover, it does not specifically limit as an electrode substrate, What was manufactured by the normal method can be used. Such a liquid crystal display device will sufficiently exhibit the effects of the ionizing radiation curable resin composition, and has excellent basic performance and excellent display image quality. It can be suitably applied as a display device such as a display.
[0108]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
[0109]
The analysis methods in Examples and Comparative Examples are shown below.
(1) Unreacted monomer and polymer composition
It was determined by quantifying the unreacted monomer at the end of the polymerization by gas chromatography.
[0110]
(2) 380 nm transmittance
The copolymer solution is diluted with diethylene glycol dimethyl ether (DMDG) to a polymer concentration of 20%, and a coating film is formed on a glass substrate using a spin coater. The resulting solution is 30 minutes at room temperature, 30 minutes at 90 ° C., and 30 minutes at 200 ° C. The mixture was heated and dried for 2 minutes to form a 2 μm thick coating film. Then, it heated at 250 degreeC for 1 hour, and measured the light transmittance in the range of 380-780 nm.
[0111]
(3) Viscosity
The resin solution is put into a 300 ml tall beaker, held in a constant temperature water bath of 25 ± 0.2 ° C., adjusted to 25 ± 0.5 ° C., and a B type digital viscometer (DVM-B manufactured by Toki Sangyo Co., Ltd. Type) and rotor no. The viscosity was measured at 3, 6 rpm.
[0112]
(4) Double bond equivalent
The weight of the consumed monomer was calculated from the amount of the monomer used and the residual amount of the monomer determined by gas chromatography, and was obtained by dividing by the number of moles of GMA consumed.

[0113]
(5) Weight average molecular weight (Mw), Mw / Mn, low molecular weight component amount
Mw and Mw / Mn were measured by Showdex GPC System-21H (trade name “Shodex GPC System-21H”, manufactured by Showdex Co., Ltd.) using polystyrene as a standard substance and THF as an eluent.
Moreover, the area | region of molecular weight 100-1000 was calculated | required from the molecular weight calibration curve which uses polystyrene as a reference material, and content of the low molecular weight component was calculated | required as a ratio of the area of the area | region of molecular weight 100-1000 with respect to the area of the whole copolymer. .
[0114]
(6) Acid value
3 g of the resin solution was precisely weighed, dissolved in a mixed solvent of 70 g of acetone / 30 g of water, titrated with 0.1N KOH aqueous solution using thymol blue as an indicator, and the acid value per 1 g of the solid content was determined from the solid content concentration.
[0115]
(7) Solid content
The resin solution 1.0g was precisely weighed on the aluminum dish, and it calculated | required from the mass after carrying out vacuum drying at 160 degreeC for 5 hours, and removing a volatile matter.
[0116]
(8) Moisture content
A new Karl Fischer titration solvent, Hayashi-Solvent CE (dehydrated solvent), 1 g of a sample is dissolved in 30 g of a titration solvent, and a Karl Fischer measuring device (trade name “MKS-3P”, manufactured by Kyoto Electronics Industry Co., Ltd.) The water content was measured at
[0117]
Synthesis example 1
(Synthesis of copolymer 1 solution)
A 3 L polymerization tank was charged with 40.0 parts of diethylene glycol dimethyl ether (DMDG) as a solvent, heated to 90 ° C. in a nitrogen atmosphere, and then dropped as a dropping system 1 with 6.16 parts of cyclohexyl maleimide (CHMI) and diethylene glycol dimethyl ether (DMDG). ) 6.16 parts, methyl methacrylate (MMA) 12.12 parts, methacrylic acid (MAA) 12.55 parts, dropping system 2, perbutyl O (PBO) (trade name, manufactured by NOF Corporation) 0.62 parts, As dropping system 3, 1.23 parts of n-dodecyl mercaptan (n-DM) was continuously fed over 3 hours. Then, after maintaining 90 degreeC for 30 minutes, temperature was heated up to 110 degreeC and superposition | polymerization was continued for 3 hours. The unreacted monomer as measured by gas chromatography (GC) was 0.1% CHMI, 0.1% MMA, and 0.1% MAA. Content of the low molecular weight component of molecular weight 100-1000 was 2.5 mass% in all the maleimide-type copolymers.
[0118]
Next, 12.73 parts of glycidyl methacrylate (GMA), 0.13 part of triethylamine as a catalyst, and 2,2′-methylenebis (4-methyl-6-t-butylphenol) as a polymerization inhibitor (trade name “ Antage W400 "(manufactured by Kawaguchi Chemical Industry Co., Ltd.) was added 0.07 part, and the reaction was continued for 8 hours while bubbling a mixed gas of air and nitrogen adjusted to 5% oxygen concentration at a flow rate of 200 ml / min. When the reaction solution was measured by GC, unreacted GMA was not detected. After adding and diluting 7.5 parts of DMDG, it cooled and the cyclohexyl maleimide resin solution 1 was obtained. The low molecular weight component having a molecular weight of 100 to 1000 as measured by GPC was 4.5% by mass in the total maleimide copolymer. The weight average molecular weight (Mw) was 17000, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight (Mn) was 2.5.
The solid content concentration determined by the drying method was 44.7%, and the acid value of the maleimide copolymer measured by the titration method was 75 mgKOH / g.
[0119]
The polymerization solution is diluted with DMDG so that the polymer concentration becomes 20%, a 2 μm-thick coating film is formed on an alkali-free glass plate using a spin coater, and heated at 250 ° C. for 1 hour using a hot plate. When the light transmittance was measured, the light transmittance was 99% or more in the region of 380 to 780 nm. In addition, the obtained polymerization solution was diluted with tetrahydrofuran, poured into a large amount of hexane to precipitate the copolymer, and the operation of filtration and drying was repeated twice to separate the copolymer 1. This copolymer was completely dissolved in 1% KOH aqueous solution, propylene glycol monomethyl ether acetate (PGMEA), and 3-methoxybutyl acetate.
[0120]
Synthesis example 2
A maleimide-based alkali-soluble copolymer solution (copolymer solution 2) was obtained in the same manner as in Synthesis Example 1 except that benzylmaleimide was used instead of cyclohexylmaleimide. Analytical values of the copolymer solution 2 are shown in Table 1.
[0121]
Synthesis example 3
A maleimide-based alkali-soluble copolymer solution (copolymer solution 3) was obtained in the same manner as in Synthesis Example 1 except that phenylmaleimide was used instead of cyclohexylmaleimide. The analytical values of the copolymer solution 3 are shown in Table 1.
[0122]
Comparative Synthesis Example 1
(Synthesis of comparative copolymer 1 solution)
In a 3 L polymerization tank, 40.0 parts of diethylene glycol dimethyl ether (DMDG), 6.16 parts of cyclohexylmaleimide (CHMI), 6.16 parts of diethylene glycol dimethyl ether (DMDG), 12.12 parts of methyl methacrylate (MMA), methacrylic acid (MAA) 12.55 parts, perbutyl O (PBO) (trade name, manufactured by NOF Corporation) 0.62 parts, dodecyl mercaptan (n-DM) 1.23 parts are charged, and the temperature is raised to 90 ° C. in a nitrogen atmosphere. did. Then, 90 degreeC was hold | maintained for 3 hours. The unreacted monomer as measured by gas chromatography (GC) was 1.5% for CHMI, 1.3% for MMA, and 2.1% for MAA. The content of the low molecular weight component having a molecular weight of 100 to 1000 was 12% by mass in the total maleimide copolymer.
[0123]
Next, 12.73 parts of glycidyl methacrylate (GMA), 0.13 part of triethylamine as a catalyst, and 2,2′-methylenebis (4-methyl-6-t-butylphenol) as a polymerization inhibitor (trade name “ The reaction was continued for 32 hours while bubbling a mixed gas of air and nitrogen adjusted to 5% oxygen at a flow rate of 200 ml / min. When the reaction solution was measured by GC, the unreacted GMA was 0.4%. After adding and diluting 7.5 parts of DMDG, it cooled and the cyclohexyl maleimide resin solution 1 was obtained.
The low molecular weight component having a molecular weight of 100 to 1000 as measured by GPC was 13% by mass in the total maleimide copolymer. The weight average molecular weight (Mw) was 22,000, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight (Mn) was 4.5.
The solid content concentration determined by the drying method was 44%, and the acid value of the maleimide copolymer measured by the titration method was 80 mgKOH / g. The analytical values of Comparative Polymer 1 are shown in Table 1.
[0124]
[Table 1]

[0125]
Table 1 will be described below. DMDG is diethylene glycol dimethyl ether, CHMI is cyclohexylmaleimide, BzMI is benzylmaleimide, PMI is phenylmaleimide, MMA is methyl methacrylate, and MAA is Methacrylic acid, PBO is perbutyl O (trade name, manufactured by NOF Corporation), n-DM is n-dodecyl mercaptan, and GMA is glycidyl methacrylate.
[0126]
Example 1
Preparation of pigment dispersion composition
The copolymer solution 1 obtained in Synthesis Example 1 together with the pigment and the dispersing agent was mixed in the following amount, and dispersed with 0.3 mm zirconia beads for 3 hours using a paint shaker to obtain a blue pigment dispersion composition 1. . The resulting blue pigment dispersion composition 1 had a mass ratio of pigment, dispersant and copolymer 1 (pigment / dispersant / cyclohexyl maleimide resin) of 1 / 0.2 / 0.4.
[0127]
<Composition of Pigment Dispersion Composition 1>
Pigment Blue 15: 6 (copper phthalocyanine-based blue pigment, trade name “Lionol Blue ESCFB6340EC”, manufactured by Toyo Ink Co., Ltd., Dainichi Seika Co., Ltd.): 13 parts Dispersant (trade name “PB-821 Dispervic 2001”) , Manufactured by Big Chemie Ajinomoto Co.): 5.65 parts (solid content: 46.0%)
Cyclohexylmaleimide resin solution 1 (CHMI / MMA / MAA / GMA-MAA copolymer, solid content 44.7%): 11.56 parts
Propylene glycol monomethyl ether acetate: 69.79 parts
[0128]
Preparation of blue resist 1
The pigment dispersion composition 1 was blended with the copolymer solution 1 and other components in the following amounts to prepare a blue resist 1. The obtained blue resist 1 is composed of copolymer 1 as a main polymer, dipentaerythritol pentaacrylate as a monomer (trade name “Sartomer SR399E”, manufactured by Nippon Kayaku Co., Ltd.) and masses of solids of initiators 1 and 2. The ratio (copolymer 1 / dipentaerythritol pentaacrylate / total of initiators 1 and 2) was 35/45/35.
[0129]
<Composition of blue resist 1>
Pigment dispersion composition 1: 34.3 parts
-Copolymer solution 1: 8.03 parts
Dipentaerythritol pentaacrylate (trade name “Sartomer SR399E”, manufactured by Nippon Kayaku Co., Ltd.): 6.03 parts
Initiator 1 (trade name “Irgacure 184907”, manufactured by Ciba Specialty Chemicals): 3.87 parts
Initiator 2 (trade name “Hycure ABP”, manufactured by Kawaguchi Pharmaceutical): 0.35 parts
Propylene glycol monomethyl ether acetate: 52.6 parts
[0130]
The pigment dispersion composition 1 and the blue resist 1 were evaluated by the following methods, and the results are shown in Table 2.
[0131]
(1) Pigment dispersibility
The 50% average pigment particle size of the pigment dispersion composition 1 was measured using a laser Doppler scattered light analysis particle size analyzer (trade name “Microtrac 934UPA”) manufactured by Nikkiso Co., Ltd.
[0132]
(2) Development form, development time, spectral characteristics, heat resistance, pattern cross-sectional shape
A blue resist 1 was spin-coated on a glass substrate that had been cleaned with alkali, and then dried at room temperature for 3 minutes and further on a hot plate at 80 ° C. for 3 minutes to form a coating film having a thickness of 1.3 μm. This coating film was exposed to a mask at 100 mJ / cm @ 2, spin-developed, indirect liquid was applied for 60 seconds, washed with pure water, and the patterned substrate was baked in an oven at 230 DEG C. for 30 minutes. During this development process, whether the development form was a dissolution type or a peeling type was observed, and the development time was measured.
[0133]
Next, the obtained blue-patterned substrate is defined in JIS Z8701 by a microspectrophotometer (trade name “OSP SP-100”) manufactured by Olympus Optical Co., Ltd. using a C light source defined by the International Commission on Illumination. The brightness Y value was measured. Then, this blue patterned substrate is heated in an oven at 250 ° C. for 1 hour, the brightness Y value is measured by the same method, and the rate of change of the Y value before and after the test is determined based on the Y value before the heat resistance test. Calculated. Moreover, while observing the cross-sectional shape of the colored layer of the board | substrate with a blue pattern obtained in the stage after baking at 230 degreeC for 30 minutes with SEM (scanning electron microscope), the rise angle of a colored layer using a SEM photograph, The ratio of the length of the upper base to the length of the lower base was calculated.
[0134]
(3) Development residue
A blue resist 1 was spin-coated on a glass substrate on which chromium was vapor-deposited on the back surface, and then dried on a hot plate at 80 ° C. for 3 minutes at room temperature to form a coating film having a film thickness of 1.3 μm. This coating film was spin-developed, and the developer was indirectly liquid for 60 seconds, followed by washing with pure water.
After washing, the glass substrate was visually observed with a projector to confirm the presence or absence of residues. Further, the surface of the substrate was wiped off with a waste cloth with ethanol, and the presence or absence of a residue wiped on the waste cloth was confirmed.
[0135]
(4) Contrast ratio
The blue resist 1 coated substrate obtained in the above (2) is sandwiched between two polarizing plates (product name “NPF-G 1220DU” manufactured by Nitto Denko Corporation), and back light (product name “Mellow 5D FL10EX” manufactured by Toshiba Corporation). -DH "and a color temperature of 6500 K) were turned on, and the luminance when the polarizing plate was orthogonal and parallel was measured with a luminance meter (trade name" SL-100 "manufactured by Minolta). The contrast ratio can be derived from the following equation using the measured luminance value.
Contrast ratio = parallel luminance (cd / m 2) / orthogonal luminance (cd / m 2)
[0136]
(5) Surface roughness, adhesion, resolution, cross-cut peel test
Evaluation on plate making properties (surface roughness (Ra), adhesion and resolution by line and space, cross peel test) was performed.
[0137]
Adjustment of transparent resist 1
The copolymer solution 1 was diluted with DMDG, adjusted to a solid content of 20%, and the materials shown below were stirred and mixed at room temperature to obtain a transparent resist 1.
-Copolymer solution 1 (solid content 20%): 69.0 parts
Dipentaerythritol pentaacrylate (Sartomer, trade name “SR399”): 11.0 parts
Orthocresol novolac type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name “Epicoat 180S70”): 15.0 parts
-2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1: 2.1 parts
-2,2'-bis (O-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole: 1.5 parts
Diethylene glycol dimethyl ether: 66.0 parts
[0138]
The transparent resist 1 was evaluated as follows, and the results are shown in Table 3.
[0139]
(6) Hardness at 180 ° C
The transparent resist 1 was applied and dried on a 10 cm-drawn glass substrate by a spin coater (Model 1H-DX2 manufactured by MIKASA) to form a coating film having a dry film thickness of 5.4 μm. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, UV rays were irradiated at an intensity of 100 mJ / cm 2 (converted to 405 nm illuminance) by a UV aligner (Dainippon Screen, model MA 1200) equipped with a 2.0 kW ultrahigh pressure mercury lamp. After the irradiation with ultraviolet rays, the coating film was dried at 200 ° C. for 30 minutes by a clean oven (trade name “SCOV-250 Hy-So” manufactured by Nishoku Institute Co., Ltd.) to obtain a cured film having a thickness of 5.0 μm. When the hardness of the cured film obtained was measured using a super micro hardness meter (manufactured by Fischer Instruments, trade name “WIN-HCU”) and the surface temperature of the cured film reached 180 ° C. with a heating jig, Evaluation was made by universal hardness (test load / surface area of the Vickers indenter under the test load) when the surface hardness was measured under the condition that the maximum load of the Vickers indenter was 20 mN.
[0140]
(7) Elastic deformation rate
The transparent resist 1 was applied and dried on a 10 cm-drawn glass substrate by a spin coater (Model 1H-DX2 manufactured by MIKASA) to form a coating film having a dry film thickness of 5.4 μm. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, UV rays were irradiated at an intensity of 100 mJ / cm 2 (converted to 405 nm illuminance) by a UV aligner (Dainippon Screen, model MA 1200) equipped with a 2.0 kW ultrahigh pressure mercury lamp. After the irradiation with ultraviolet rays, the coating film was dried at 200 ° C. for 30 minutes by a clean oven (trade name “SCOV-250 Hy-So” manufactured by Nishoku Institute Co., Ltd.) to obtain a cured film having a thickness of 5.0 μm. When the hardness of the cured film obtained was measured using a super micro hardness meter (manufactured by Fischer Instruments, trade name “WIN-HCU”) and the surface temperature of the cured film reached 180 ° C. with a heating jig, Evaluation was made from the ratio of the work of elastic deformation to the total work when the surface hardness was measured under the condition that the maximum load of the Vickers indenter was 20 mN.
[0141]
(8) Evaluation of developability
A transparent resist 1 was applied and dried on a 10 cm glass substrate with a spin coater (Mikasa, model 1H-DX2) to form a coating film having a dry film thickness of 2.2 μm. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, an intensity of 100 mJ / cm 2 or 50 mJ / cm 2 by a UV aligner (Dainippon Screen, model MA 1200) equipped with a 2.0 kW super high pressure mercury lamp with a photomask placed at a distance of 100 μm from the coating film (Ultraviolet rays were irradiated in terms of 405 nm illuminance. The developability of the obtained film was measured with an optical microscope (manufactured by Olympus Optical Co., Ltd., trade name “MHL100”) and a stylus type surface roughness measuring device (trade name, manufactured by Nippon Anelva Co., Ltd.). “Dektak 1600”) was used to observe the shape of the relief pattern. The bad shape was indicated as “x”, the good shape as “good”, and the very good one as “◎”.
[0142]
After UV irradiation, a 0.05% aqueous potassium hydroxide solution was sprayed on the coating film for 60 seconds with a spin developing machine (Applied Process Technology, INK, MODEL: 915) to dissolve and remove the unexposed portions and leave The exposed portion was developed by washing with pure water for 60 seconds. After development, the film in the exposed area was heated at 200 ° C. for 30 minutes in a clean oven (trade name “SCOV-250 Hy-So” manufactured by Shinobi Institute). Then, the developability of the obtained film was measured with a relief pattern using an optical microscope (manufactured by Olympus Optical Co., Ltd., trade name “MHL100”) and a stylus type surface roughness measuring device (manufactured by Nippon Anelva Co., Ltd., trade name “Dektak 1600”). The poor shape was evaluated as x, the good one as ◯, and the very good as ◎.
[0143]
(9) Roughness of coating film surface
After the alkali development treatment, the surface of the coating film was observed with a microscope, and the smoothness of the coating film surface was observed.
◎: Extremely smooth, ◯: Smooth, Δ: Roughness is observed on the surface, ×: Roughness of the surface is severe, and whitening of the coating film is observed
[0144]
(10) Warm and pure water resistance
The cured coating film was immersed in pure water at 80 ° C. for 30 minutes, and adhesion was confirmed by a base eye peel test method.
○: No peeling of coating film, Δ: Peeling and coating on less than 50% coating film, ×: Peeling and coating on 50% or more coating film
[0145]
(11) Evaluation of yellowing of cured film properties
The transparent resist 1 was applied and dried on a 10 cm glass substrate with a spin coater (Mikasa, model 1H-DX2) to form a coating film having a dry film thickness of 1.2 μm. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After heating, UV rays were irradiated at an intensity of 100 mJ / cm 2 (converted to 405 nm illuminance) by a UV aligner (Dainippon Screen, model MA 1200) equipped with a 2.0 kW ultrahigh pressure mercury lamp.
[0146]
After irradiation with ultraviolet rays, the coating film was dried at 230 ° C. for 30 minutes in a clean oven (trade name “SCOV-250 Hy-So” manufactured by Nishoku Institute Co., Ltd.) to obtain a cured film having a thickness of 1.0 μm. The chromaticity of the cured film on the glass substrate thus obtained was measured using a colorimeter (manufactured by Olympus Optical Co., Ltd., trade name “OSP-SP200”) using the glass substrate as a reference.
[0147]
Next, the glass substrate with the cured film thus measured was irradiated with UV light and washed with a UV ozone cleaner at an intensity of 6.7 J / cm @ 2 (converted to 405 nm illuminance), and further cleaned oven (made by Shinobi Institute, trade name "SCOV"). -250 Hy-So ") for 1 hour at 250 ° C to obtain a heat test cured film. The chromaticity of the cured film on the glass substrate thus obtained was measured using a colorimeter (trade name “OSP-SP200” manufactured by Olympus Optical Co., Ltd.) with the glass substrate as a reference.
[0148]
The heat resistance of the cured film was evaluated from the change in chromaticity before and after the heating test.
Here, ΔEab is a value obtained from the following color difference formula based on the CIE 1976 (L *, a *, b *) space color system (Japanese Color Society edited by New Color Science Handbook (1985) p.266). ).
ΔEab = {(ΔL) 2+ (Δa) 2+ (Δb) 2} 1/2
[0149]
Examples 2 and 3
(Preparation of pigment dispersion compositions 2 and 3, blue resists 2 and 3, and transparent resists 2 and 3) Example 1 except that copolymer solutions 2 and 3 were used instead of copolymer solution 1, respectively. The composition was similarly prepared, and pigment dispersion compositions 2 and 3, blue resists 2 and 3, and transparent resists 2 and 3 were obtained. Using the pigment dispersion composition and the curable resin composition, a coating film was formed by the same method as in Example 1 and evaluated. The results are shown in Tables 2 and 3.
[0150]
Comparative Example 1
(Preparation of pigment dispersion composition 4 and blue resist 4)
A composition was prepared in the same manner as in Example 1 except that the comparative copolymer solution 1 obtained in Comparative Synthesis Example 1 was used instead of the copolymer solution 1 obtained in Synthesis Example 1. A pigment dispersion composition 4, a blue resist 4 and a transparent resist 4 were obtained. Using the pigment dispersion composition and the curable resin composition, a coating film was formed by the same method as in Example 1 and evaluated. The results are shown in Tables 2 and 3.
[0151]
[Table 2]

[0152]
[Table 3]

[0153]
From Table 2, the pigment dispersion compositions produced in Examples 1 to 3 have a small particle size when the pigment is dispersed, and a small change in the particle size after holding for one week at room temperature. It was excellent. In Comparative Example 1, the pigment particle size was large, the change in particle size after holding for one week at room temperature was large, and the pigment dispersibility was poor.
[0154]
In addition, the ionizing radiation curable resin compositions (blue resist and transparent resist) produced in Examples 1 to 3 can form heat-resistant yellowing, residue, fine patterns, and form a hard coating film. We were able to. In Comparative Example 1, roughness of the coating film surface after development occurred. Moreover, it was inferior compared with Examples 1-3 in various physical properties, such as heat-resistant yellowing, a residue, and the hardness of a film | membrane.
[0155]
【The invention's effect】
The pigment dispersion composition of the present invention is excellent in pigment dispersibility, and the pigment does not aggregate during storage.
In addition, the ionizing radiation curable resin composition of the present invention has excellent heat-resistant yellowing and high hardness, excellent curability by the amount of ionizing radiation, can improve pattern shape accuracy after development, and patterning accuracy. In addition, since it has excellent physical properties after curing, it can be suitably used as a material for forming various thin film layers and patterns contained in the color filter, and only in parts that do not require transparency. In addition, since a part requiring transparency such as a protective layer and a colored layer can be formed, a colored layer, a protective layer, and a spacer in the color filter can be formed. Such a color filter and a liquid crystal display device using the color filter are excellent in pixel transparency and pattern shape accuracy.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal panel.
FIG. 2 is a schematic cross-sectional view of another example of a liquid crystal panel.
[Explanation of symbols]
1 Color filter
2 Electrode substrate
3 Gap (L: Liquid crystal compound)
4 Sealing material
5 Transparent substrate
6 Black matrix layer
7 (7R, 7G, 7B) Colored layer
8 Protective layer
9 Transparent electrode film
10 Alignment film
11 Pearl
12 Columnar spacer
101, 102 LCD panel

Claims (7)

A pigment, a maleimide-based alkali-soluble copolymer, and a solvent, the maleimide-based alkali-soluble copolymer having an acid value of 20 to 200 mgKOH / g and a content of a low molecular weight component having a molecular weight of 100 to 1000 is 10 mass. % Of a pigment dispersion composition,
The method for producing the pigment dispersion composition is such that after the supply of the monomer containing the acid group-containing monomer and the maleimide monomer is completed, the polymerization temperature is increased by 10 ° C. or more, and then polymerization is performed. A maleimide-based alkali-soluble copolymer is produced by adding a group capable of binding to an acid group and a compound having a double bond without removing a reactive monomer and / or a low molecular weight component having a molecular weight of 100 to 1,000. And a step of mixing the pigment, the maleimide-based alkali-soluble copolymer, and a solvent,
The maleimide-based alkali-soluble copolymer, are two double bond equivalent is 300 to 100,000 der,
The N-substituted maleimide monomer unit is 5 to 50% by mass, the (meth) acrylic acid monomer unit is 5 to 30% by mass, and the (meth) acrylic acid ester monomer unit is 30 to 87% by mass. A method for producing a pigment dispersion composition.   The method for producing a pigment dispersion composition according to claim 1, wherein the compound capable of binding to the acid group and the compound having a double bond is glycidyl (meth) acrylate. A low molecular weight component having a maleimide alkali-soluble copolymer, a radical polymerizable compound, and a photopolymerization initiator, wherein the maleimide alkali-soluble copolymer has an acid value of 20 to 200 mgKOH / g and a molecular weight of 100 to 1,000. Is a method for producing a resin composition for ionizing radiation curing of 10% by mass or less,
The method for producing the ionizing radiation curable resin composition is such that after the supply of the monomer containing the acid group-containing monomer and the maleimide monomer is completed, the polymerization temperature is increased by 10 ° C. or more to polymerize,
Thereafter, a maleimide-based alkali-soluble copolymer is added by adding a compound capable of binding to an acid group and a compound having a double bond without removing unreacted monomers and / or low molecular weight components having a molecular weight of 100 to 1000. A step of producing a coalescence, and a step of mixing the maleimide-based alkali-soluble copolymer, a radical polymerizable compound and a photopolymerization initiator,
The maleimide-based alkali-soluble copolymer, are two double bond equivalent is 300 to 100,000 der,
The N-substituted maleimide monomer unit is 5 to 50% by mass, the (meth) acrylic acid monomer unit is 5 to 30% by mass, and the (meth) acrylic acid ester monomer unit is 30 to 87% by mass. A process for producing a resin composition for ionizing radiation curing.   The method for producing a resin composition for ionizing radiation curing according to claim 3, wherein the ionizing radiation curable resin composition further contains a pigment.   5. The method for producing a resin composition for ionizing radiation curing according to claim 3, wherein the compound having a group capable of bonding to an acid group and a double bond is glycidyl (meth) acrylate. In order to maintain a distance between the transparent substrate and the colored layer formed on the transparent substrate as an essential component, or to maintain the distance between the protective layer covering the colored layer and / or the electrode substrate facing the transparent layer. A method of manufacturing a color filter having a spacer provided at a position overlapping with a non-display portion,
The method for producing the color filter includes a method for producing a resin composition for ionizing radiation curing according to any one of claims 3 to 5, wherein at least one of the colored layer, the protective layer, and the spacer is A method for producing a color filter, comprising: curing an ionizing radiation curable resin composition obtained by the production method. A method of manufacturing a liquid crystal display device in which a color filter and an electrode substrate are opposed to each other and a liquid crystal compound is sealed between the two,
A method of manufacturing a liquid crystal display device, comprising the method of manufacturing a color filter according to claim 6.

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