JP4245259B2 - Manufacturing method of color filter - Google Patents

Description

【０１４１】
ただし、ｎは２以上の整数であり、Ｒ¹，Ｒ²はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アリールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ¹、Ｒ²がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有する。
【０１４２】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコン化合物をバインダに混合してもよい。
【０１４３】
光触媒含有層には上記の光触媒、バインダの他に、界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることかでき、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【０１４４】
また、光触媒含有層には上記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【０１４５】
光触媒含有層中の光触媒の含有量は、５〜６０重量％、好ましくは２０〜４０重量％の範囲で設定することができる。また、光触媒含有層の厚みは、０．０５〜１０μｍの範囲内が好ましい。
【０１４６】
上記各成分を溶解、分散する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。バインダとして紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより光触媒含有層を形成することができる。
【０１４７】
ｂ）濡れ性可変層の下側に光触媒含有層を備え、濡れ性可変層の親水性が増大するもの
このタイプの濡れ性可変層を形成するには、先ず、バインダー及び光触媒を溶解、分散した塗工液を、カラーフィルターの透明基板上に塗布した後、加水分解あるいは重縮合反応進行させて光触媒含有層を形成するか、又は、光触媒単体の光触媒含有層を形成する。次いで、光触媒含有層の上に、疎水性の有機物からなる薄膜の濡れ性可変層を形成する。光触媒、バインダー、或いは溶剤等は、上記ａ）のタイプで用いるのと同じものを用いてよい。
【０１４８】
有機物の薄膜の形成には、溶液の塗布、表面グラフト処理、界面活性剤処理、ＰＶＤ、ＣＶＤ等の気相による成膜法を用いることができる。有機物としては、低分子化合物、高分子化合物、界面活性剤等で、光触媒によって濡れ性が変化するものを用いることができる。具体的には、光触媒の作用により有機基が水酸基に変化する、シラン化合物で、シランカップリング剤、クロロシラン、アルコキシシラン、あるいはこれらの２種以上の加水分解縮合物、共加水分解縮合物を挙げることができる。
【０１４９】
なお、上記例示の濡れ性可変層は、当該濡れ性可変層自体が光触媒を含有する光触媒含有層であるか、又は、当該濡れ性可変層の透明基板側に設けられた光触媒含有層を備えており、当該光触媒含有層に光線を照射することによって光触媒を活性化し、活性化された当該光触媒の作用により、親水性が大きくなる方向に濡れ性を変化させるものである。すなわち、例示の濡れ性可変層は、いずれも、光線を照射されることによって親水性が大きくなる方向に濡れ性を変化させるものである。
【０１５０】
しかしながら、本発明において濡れ性可変層は、その表面の濡れ性を、外からの刺激、例えば物理的刺激、化学的刺激等により変化させることができる層であれば特に限定されるものではない。例えば、酸またはアルカリ等により表面の粗さの状態が変化し、濡れ性が変化する層等であってもよいし、また紫外線や可視光、さらには熱等のエネルギーの照射により濡れ性可変層内の物質が変化して濡れ性が変化する層等であってもよい。
【０１５１】
また、例示の方法で用いられている光触媒含有層は、画素部形成領域に光線を照射して親水性が増大させ、第二発明の熱硬化性インキ組成物を選択的に付着させるが、何らかの刺激によって親水性が減少するような濡れ性可変層をカラーフィルターの透明基板上に設け、画素部形成領域のネガパターン状に濡れ性を変化させる刺激を与えることによっても、第二発明の熱硬化性インキ組成物を所望の領域だけに選択的に付着させることが可能である。
【０１５２】
次に、第二発明のカラーフィルター用熱硬化性インキ組成物であって、１又は２以上の着色剤を配合してなる、各色の画素部形成用インキを用意する。そして、上述した図２（Ｃ）の工程において親水性を増大させた画素部形成領域４Ｒ、４Ｇ、４Ｂに、対応する色の画素部形成用インキを選択的に付着させて、図２（Ｄ）に示すようなインキ層６Ｒ、６Ｇ、６Ｂを形成する。
【０１５３】
画素部形成用インキは、印刷等の任意の方法で画素部形成領域に付着させることができるが、図２（Ｄ）に示すように、インクジェット方式により画素部形成領域に吹き付けるのが好ましい。第二発明の熱硬化性インキ組成物は、画素部形成用インキに限らず、インクジェット方式に対する適性に優れている。従って、第二発明の熱硬化性インキ組成物を、濡れ性を変化させて親水性を増大させた所定のパターン形成領域にインクジェット方式により吹き付けることによって、正確に且つ均一に付着させることができ、正確なパターンで色ムラや色抜けのない画素部を形成することができる。また、各色の画素部形成用インキを、複数のヘッド５を使って同時に基板上に吹き付けることもできるので、各色ごとに画素部を形成する場合と比べて作業効率を向上させることができる。
【０１５４】
次に、図２（Ｅ）に示すように、各色のインキ層６Ｒ、６Ｇ、６Ｂを必要に応じて乾燥させ、その後、加熱して硬化させて画素部を形成する。次に、図２（Ｆ）に示すように、透明基板の画素部８Ｒ、８Ｇ、８Ｂを形成した側に、保護層９を形成する。図２（Ｅ）及び図２（Ｆ）に示すような第二発明における熱硬化工程及び保護層形成工程は、第一発明の場合と同様に行うことができる。
【０１５５】
このようにして、第二発明のカラーフィルター用熱硬化性インキ組成物を用いてカラーフィルター１０１Ｂが製造される。この例においては、第二発明のカラーフィルター用熱硬化性インキ組成物である画素部形成用インキを用いて画素部を形成するが、第二発明のカラーフィルター用熱硬化性インキ組成物を、基板表面の濡れ性の差を利用して親インキ性領域だけに選択的に付着させることによって、画素部以外の硬化層、例えば、遮光層２や撥インキ性凸部３などを、所望のパターン状に形成することもできる。
【０１５６】
遮光層２を形成したい場合には、先ず、第二発明のカラーフィルター用熱硬化性インキ組成物であって黒色顔料などの遮光性着色剤を配合してなる遮光層形成用インキを調製する。次に、透明基板１の上に濡れ性変化層１０を形成し、遮光層を形成すべき領域の濡れ性を変化させて親水性を増大させ、予め用意しておいた遮光層形成用インキを、親水性（親インキ性）が増大した遮光層形成領域にインクジェット等の方法により選択的に付着させてインキ層を所定のパターン状に形成し、当該インキ層を加熱して硬化させることによって遮光層を形成できる。
【０１５７】
また、撥インキ性凸部３を形成したい場合には、先ず、第二発明のカラーフィルター用熱硬化性インキ組成物であって、撥インキ性のバインダーを配合してなる撥インキ性凸部形成用インキを調製する。次に、透明基板１の上に、遮光層１及び濡れ性変化層１０を順次形成する。次に、遮光層２の上面の中央に、当該遮光層２の長手方向に沿って当該遮光層２よりも幅狭のパターン状に、濡れ性を変化させた撥インキ性凸部形成領域を形成する。次に、親水性（親インキ性）が増大した撥インキ性凸部形成領域にインクジェット等の方法により選択的に付着させてインキ層を所定のパターン状に形成し、当該インキ層を加熱して硬化させることによって撥インキ性凸部３を形成できる。
【実施例】
【０１５８】
（実施例１）
（１）光触媒含有層用塗工液の調製
下記の成分を混合し、１００℃で２０分間攪拌して、光触媒含有層用塗工液を調製した。
〈光触媒含有層用塗工液の組成〉
・イソプロピルアルコール：３ｇ
・フルオロアルキルシラン（トーケムプロダクツ製ＭＦ−１６０Ｅ：Ｎ−［３−（トリメトキシシリル）プロピル］−Ｎ−エチル−パーフルオロオクタンスルホンアミドのイソプロピルエーテル５０重量％溶液）：０．０７ｇ
・酸化チタンゾル（石原産業製ＳＴＫ−０１）：３ｇ
・シリカゾル（日本合成ゴム製グラスカＨＰＣ７００２）：０．６ｇ
・アルキルアルコキシシラン（日本合成ゴム製ＨＰＣ４０２Ｃ）：０．２ｇ
（２）光触媒含有層の形成
開口部７６μｍ×２５９μｍで線幅２３μｍのクロム薄膜パターンからなるブラックマトリックスを有するソーダガラス製の透明基板上に、上記の光触媒含有層用塗工液をスピンコーターにより塗布し、１５０℃、１０分間の乾燥処理後、加水分解、重縮合反応を進行させて、光触媒がオルガノポリシロキサン中に強固に固定された厚み０．５μｍの透明な光触媒含有層を形成した。
【０１５９】
この光触媒含有層に、マスクを介して水銀灯（波長３６５ｎｍ）により７０ｍＷ／ｃｍ²の照度で３分間、光線を照射し、非照射部位と照射部位の水に対する接触角を測定した。接触角の測定は、接触角測定器（協和界面科学（株）製ＣＡ−Ｚ型）を用い、非照射部位又は照射部位にマイクロシリンジから水滴を滴下して３０秒後に行った。その結果、非照射部位における水の接触角は７０°であるのに対して、照射部位における水の接触角は１０°以下であり、照射部位が高親水性となって、照射部位と非照射部位との濡れ性の差を利用してパターン形成が可能なことが確認された。
【０１６０】
さらに、ＪＩＳ Ｋ６７６８に規定する濡れ試験において示された標準液を用い、光触媒含有層の表面の非照射部位に液滴を接触させて３０秒後の接触角（θ）を測定し、ジスマンプロット（横軸：標準液の表面張力、縦軸：ｃｏｓθ）を作成し、グラフを外挿したところ、ｃｏｓθ＝０となる点が示す表面張力、すなわち、非照射部位の臨界表面張力は３０ｍＮ／ｍだった。同じ方法で、照射部位における臨界表面張力を測定したところ、７０ｍＮ／ｍだった。
【０１６１】
（３）光触媒含有層の露光
パターンピッチが７６μｍ×２５９μｍで、且つ、上記ブラックマトリックスの線幅（２３μｍ）よりも狭い幅（１０μｍ）の遮光パターンを有するマスクを、上記透明基板の光触媒含有層上に配置し、ブラックマトリックスと重なるように位置合わせした後、このマスクを介して水銀灯（波長３６５ｎｍ）により７０ｍＷ／ｃｍ²の照度で５０秒間、光触媒含有層を露光して、照射部位を高親水性とした。各照射部位は、ブラックマトリックス上に存在する幅１０μｍの非照射部により区画され、ブラックマトリックスに囲まれた７６μｍ×２５９μｍの大きさの画素部形成領域と、その周囲のブラックマトリックスと重なる領域を有していた。
【０１６２】
（４）画素部用着色インキの調製
下記の成分のうち、先ず、顔料、高分子分散剤及び溶剤を混合し、３本ロールとビーズミルを用いて顔料分散液を得た。その顔料分散液をディソルバー等で十分攪拌しながら、その他の材料を少量ずつ添加し、赤色画素部用着色インキを調製した。
〈赤色画素部用着色インキの組成〉
・顔料（Ｃ．Ｉ．ピグメントレッド２５４）：５重量部
・高分子分散剤（ＡＶＥＣＩＡ社製ソルスパース２４０００）：１重量部
・バインダー（グリシジルメタクリレート−スチレン共重合体）：３重量部
・第一エポキシ樹脂（ノボラック型エポキシ樹脂、油化シェル社製エピコート１５４）：２重量部
・第二エポキシ樹脂（ネオペンチルグリコールジグリシジルエーテル）：５重量部
・硬化剤（トリメリット酸）：４重量部
・溶剤：３−エトキシプロピオン酸エチル：８０重量部
上記成分のうち、溶剤である３−エトキシプロピオン酸エチルは、ＪＩＳ Ｋ６７６８に規定する濡れ試験において示された標準液を用い、液滴を接触させて３０秒後の接触角（θ）を測定し、ジスマンプロットのグラフにより求めた臨界表面張力が３０ｍＮ／ｍの試験片の表面に対する接触角が１８°であり、且つ、臨界表面張力が７０ｍＮ／ｍの試験片の表面に対する接触角が０°であった。
【０１６３】
また、第二エポキシ樹脂であるネオペンチルグリコールジグリシジルエーテルは、同様の試験において、臨界表面張力が３０ｍＮ／ｍの試験片表面に対する接触角が３７°であり、且つ、臨界表面張力が７０ｍＮ／ｍの試験片表面に対する接触角が０℃であった。
【０１６４】
さらに、下記組成中のＣ．Ｉ．ピグメントレッド２５４に代えてＣ．Ｉ．ピグメントグリーン３６を同量用いるほかは赤色画素部用着色インキの場合と同様にして緑色赤色画素部用着色インキを調製した。さらに、下記組成中のＣ．Ｉ．ピグメントレッド２５４に代えてＣ．Ｉ．ピグメントブルー１５：６を同量用いるほかは赤色画素部用着色インキの場合と同様にして青色画素部用着色インキを調製した。
【０１６５】
（５）カラーフィルターの製造
上記の赤色画素部用着色インキを、ヘッドから赤色用の各画素部形成領域の中心部に、ドット径３０μｍで滴下した。同様に、緑色画素部用着色インキを、ヘッドから緑色用の各画素部形成領域の中心部に、ドット径３０μｍで滴下した。さらに、青色画素部用着色インキを、ヘッドから青色用の各画素部形成領域の中心部に、ドット径３０μｍで滴下した。滴下した各色の画素部用着色インキは、ブラックマトリックス上の非照射部ではじかれ、各色の画素部形成領域においては均一に拡散して選択的に付着された。
【０１６６】
その後、各色の着色インキ層を８０℃、３分間、真空乾燥させてから、オーブンにより２００℃で６０分間加熱して硬化させ、画素部を形成した。
【０１６７】
次いで、二液混合型熱硬化剤（日本合成ゴム（株）製ＳＳ７２６５）をスピンコーターにて画素部上に塗布し、２００℃、３０分間の硬化処理を施して保護層を形成し、カラーフィルターを得た。
【０１６８】
（実施例２）
（１）画素部用着色インキの調製
下記組成の赤色画素部用着色インキ（赤色インキ２−１及び２−２）を調製した。どちらの着色インキの場合も、先ず、顔料、高分子分散剤及び溶剤を混合し、３本ロールとビーズミルを用いて顔料分散液を調製し、その顔料分散液をディソルバー等で十分攪拌しながら、その他の材料を少量ずつ添加し、赤色画素部用着色インキを調製した。
〈赤色画素部用着色インキ２−１の組成〉
赤色インキ２−１としては、実施例１で調製したのと同じ赤色画素部用着色インキを、そのまま用いた。
〈赤色画素部用着色インキ２−２の組成〉
・顔料（Ｃ．Ｉ．ピグメントレッド２５４）：５重量部
・高分子分散剤（ＡＶＥＣＩＡ社製ソルスパース２４０００）：１重量部
・バインダー（グリシジルメタクリレート−スチレン共重合体）：７重量部
・第一エポキシ樹脂（ノボラック型エポキシ樹脂、油化シェル社製エピコート１５４）：３重量部
・硬化剤（トリメリット酸）：４重量部
・溶剤：３−エトキシプロピオン酸エチル：８０重量部
（２）粘度の測定
各赤色インキの粘度を、粘度測定器ＶＩＢＲＯＶＩＳＣＯＭＥＴＥＲ ＣＪＶ５０００（Ａ＆Ｄ社製）を用い、温度２０℃で測定した。
【０１６９】
（２）吐出性の試験
インクジェットヘッドに各赤色インキを充填し当該ヘッドから吐出して、実施例１の場合と同様にして光触媒含有層を設けて所定のパターン状に露光したガラス製透明基板の赤色用画素部形成領域の中心部に、ドロップ径３０μｍで滴下した。さらに、初期吐出を停止してヘッドを１分間静止させた後、同じヘッドから別の赤色用画素部形成領域の中心部に、ドロップ径３０μｍで滴下した。このような間歇吐出において、最初に吐出動作を行った時の吐出性（初期吐出性）と、その後に再吐出を行った時の吐出性（間歇吐出安定性）を観察し、下記基準に従って評価した。
＜初期吐出性の評価基準＞
○：ヘッドの全部の穴からインキを吐出することが可能である。
△：ヘッドにインキの出ない穴が一部ある。
×：ヘッドのほとんどの穴からインキが出ない。
＜間歇吐出安定性の評価基準＞
○：初期に吐出できたヘッドの穴の全部からインキを再吐出することが可能である。
△：ヘッドにインキの出ない穴が一部ある。
×：ヘッドのほとんどの穴からインキが出ない。
【０１７０】
（３）実施例２の結果
第１表に示すように、２乃至３官能のエポキシ基含有モノマーと４官能以上のエポキシ基含有樹脂を組み合わせた赤色インキ２−１は、初期粘度が低く、初期吐出性及び間歇吐出安定性が共に良好だった。これに対して、４官能以上のエポキシ基含有樹脂しか用いない赤色インキ２−２は、初期粘度が比較的高く、初期吐出性及び間歇吐出安定性はいずれも赤色インキ２−１と比べて劣っていた。ただし、赤色インキ２−２は赤色インキ２−１と同じ溶剤を用いており、赤色用画素部形成領域からはみ出すことなく均一に拡散した。
【０１７１】
【表１】

【０１７２】
（実施例３）
（１）画素部用着色インキの調製
下記組成の赤色画素部用着色インキ（赤色インキ３−１及び３−２）を調製した。どちらの着色インキの場合も、先ず、顔料、高分子分散剤及び溶剤を混合し、３本ロールとビーズミルを用いて顔料分散液を調製し、その顔料分散液をディソルバー等で十分攪拌しながら、その他の材料を少量ずつ添加し、赤色画素部用着色インキを調製した。
【０１７３】
また、赤色インキ３−１について実施例１で測定したのと同様に、赤色インキ３−２について臨界表面張力が３０ｍＮ／ｍの試験片の表面、及び、臨界表面張力が７０ｍＮ／ｍの試験片の表面に対する接触角を測定した。
〈赤色画素部用着色インキ３−１の組成〉
赤色インキ３−１としては、実施例１で調製したのと同じ赤色画素部用着色インキを、そのまま用いた。
〈赤色画素部用着色インキ３−２の組成〉
溶剤を、７８重量部の３−エトキシプロピオン酸エチルに代えて、同量のオクタンを用いたほかは赤色インキ３−１と同じ組成である。
【０１７４】
（２）パターン形成試験
実施例１と同様にしてソーダガラス製の透明基板に光触媒含有層を形成した。この光触媒含有層を、未露光部の幅１０μｍ、露光部の幅８９μｍのストライプ状に露光し、照射部位にインクジェットヘッドから各赤色インキを、次の吐出条件で吐出した。
＜吐出条件＞
・ドロップ径：３０μｍ
・ヘッド周波数：２０００Ｈｚ
・基板の送りスピード：５０ｍｍ／ｓｅｃ．
このような吐出を行った時の赤色インキの広がり具合を観察し、下記基準に従って評価した。
＜パターン形成の評価基準＞
○：赤色インキが照射部位に十分広がり、非照射部位へのインキのはみ出しが少ない。
×：非照射部位、又は、隣の照射部位までインクが塗れ広がっていく。
【０１７５】
（３）実施例３の結果
実施例３の結果を第２表に示す。赤色インキ３−１は実施例１において述べたように、臨界表面張力が３０ｍＮ／ｍの試験片の表面に対する接触角と臨界表面張力が７０ｍＮ／ｍの試験片の表面に対する接触角の差を大きくとることができ、良好なパターン形成を示した。これに対して、溶剤としてオクタンを用いた赤色インキ３−２は、上記各試験片に対する接触角の差が全くなく、今回用いた濡れ性可変層の照射部位に選択的に付着させることはできなかった。ただし、赤色インキ３−２は、赤色インキ３−１と同様に２乃至３官能モノマーと４官能以上のエポキシ基含有樹脂を組み合わせて用いており、インクジェットヘッドからの初期吐出性及び間歇吐出安定性は共に良好だった。
【０１７６】
【表２】

【発明の効果】
【０１７７】
以上説明したように、本発明の第一発明においては、カラーフィルター用熱硬化性インキ組成物中に、熱硬化性成分として２官能乃至３官能のエポキシ基含有モノマーを用いるので、インクジェット方式の吹き付け作業中に、ヘッドの先端での粘度上昇が起こり難く、ヘッドの目詰まりが発生せず、作業中におけるインキの吐出性が安定する。そのため、インキの吐出量や吐出方向が一定に保たれ、インキを基板上に所定のパターン通り正確に、且つ、均一に付着させることができる。
【０１７８】
また、本発明の第二発明においては、カラーフィルター用熱硬化性インキ組成物の溶剤として、ＪＩＳ Ｋ６７６８に規定する濡れ試験において示された標準液を用い、液滴を接触させて３０秒後の接触角（θ）を測定し、ジスマンプロットのグラフにより求めた臨界表面張力が３０ｍＮ／ｍの試験片の表面に対する接触角が１０°以上を示し、且つ、同じ測定法により求めた臨界表面張力が７０ｍＮ／ｍの試験片の表面に対する接触角が１０°以下を示すものを用いるので、濡れ性可変層の表面の一部の濡れ性を親水性が大きくなる方向に変化させて形成した所定パターンのインキ層形成領域に対する熱硬化性インキ組成物の濡れ性と、その周囲の領域に対する熱硬化性インキ組成物の濡れ性の差を大きくとることができる。そのため、第二発明のカラーフィルター用熱硬化性インキ組成物を、インキ層形成領域に正確に、且つ、均一に付着させることができる。
【図面の簡単な説明】
【図１】 第一発明のインク組成物を用いてカラーフィルターを製造する方法の説明図である。
【図２】 第二発明のインク組成物を用いてカラーフィルターを製造する方法の説明図である。
【符号の説明】
１…透明基板
２…遮光部
３…撥インキ性凸部
４…画素部形成領域
５…インクジェットヘッド
６…インキ層
７…光線
８…画素部
９…保護膜
１０…光触媒含有層
１１…フォトマスク
１２…露光部[0001]
BACKGROUND OF THE INVENTION
[0002]
  The present invention uses a thermosetting ink composition used to form a cured layer having a predetermined pattern such as a pixel portion (colored layer) on a substrate of a color filter, and the thermosetting ink composition. The present invention relates to a method for manufacturing a color filter.
[Prior art]
[0003]
  In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. However, since this color liquid crystal display is expensive, there is an increasing demand for cost reduction, and in particular, there is a high demand for cost reduction for a color filter having a high specific gravity.
[0004]
  In such a color filter, it is usually provided with coloring patterns of three primary colors of red (R), green (G), and blue (B), and electrodes corresponding to the respective pixels of R, G, and B are turned on, By turning it off, the liquid crystal operates as a shutter, and light passes through each of the R, G, and B pixels, and color display is performed.
[0005]
  As a conventional method for producing a color filter, for example, a staining method can be mentioned. In this dyeing method, first, a water-soluble polymer material, which is a dyeing material, is formed on a glass substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To get a colored pattern. By repeating this three times, R, G, and B color filter layers are formed.
[0006]
  Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers.
[0007]
  Still other methods include an electrodeposition method, a method in which a pigment is dispersed in a thermosetting resin, R, G, and B are printed three times, and then the resin is thermoset.
[0008]
  However, in any method, in order to color three colors of R, G, and B, it is necessary to repeat the same process three times, which causes a problem of high cost, and the yield decreases because the same process is repeated. There is a problem of doing.
[Problems to be solved by the invention]
[0009]
  As a method of manufacturing a color filter that solves these problems, a method of forming a colored layer (pixel portion) by spraying colored ink by an inkjet method has been proposed (Japanese Patent Laid-Open No. 59-75205). Here, when ink having good wettability with respect to the glass substrate is used, a method of printing a convex portion that is a boundary in advance with a substance with poor wettability with respect to the ink, or poor wettability with respect to the glass. In the case of using ink, a method is disclosed in which a pattern is formed in advance with a material having good wettability with ink, and the ink is fixed. However, there is no description on how to specifically paint a material having good wettability and a material having poor wettability.
[0010]
  Another method for producing a color filter by spraying colored ink by an ink jet method to produce a color filter is disclosed in JP-A-9-203803, in which a recess is treated with an ink-philic treatment agent. It is disclosed. In this method, a convex portion is formed on a substrate in advance, and the convex portion is made ink repellent, and then the entire substrate is surface-treated with an ink-philic treatment agent. However, this method has a problem in that it is necessary to perform the ink repellent process and the parent ink process twice because the convex portion needs to be made ink repellent in advance when performing the parent ink process.
[0011]
  Similarly, as a method for producing a color filter by forming a colored layer by the ink jet method, an ink absorbing layer is provided on a substrate in Japanese Patent Application Laid-Open Nos. 8-230314 and 8-227102. A method is described in which a colored layer (pixel portion) is formed by changing the ink absorptivity of the absorbing layer between an exposed portion and a non-exposed portion. However, in this method, an absorbing layer is formed and the ink is absorbed into the absorbing layer to form a colored layer. Therefore, there is a difference in coloring between the center portion and the peripheral portion of the ink dot, and color unevenness There is a problem that color loss occurs. In addition, this absorbing layer also has a problem that a predetermined thickness is necessary for its function of absorbing ink.
[0012]
  Japanese Patent Application Laid-Open No. 9-21910 discloses that a colored layer (pixel portion) is formed by spraying a colored ink containing a thermosetting resin onto a substrate by an inkjet method and heating. However, if a conventional thermosetting colored ink is used as it is in an ink jet system, the ink is dried at the tip of the ink jet head while the colored ink is being sprayed, and the viscosity gradually increases, resulting in poor ejection properties. . As a result, the discharge amount and the discharge direction of the colored ink may become unstable, or the inkjet head may be clogged.
[0013]
  The present invention has been accomplished in view of the above-described actual situation, and achieves at least one of the following objects.
[0014]
  The first purpose is to form an ink-philic ink layer forming region with different wettability from the surroundings on the surface of the color filter substrate, and when ink is selectively attached to the ink layer forming region, To provide a thermosetting ink composition having a high affinity for a layer formation region and a large repulsion property to surrounding ink repellency regions, which can be adhered accurately and uniformly only to a predetermined region on a color filter substrate. It is in.
[0015]
  In addition, a second object of the present invention is to provide a thermosetting ink composition that can omit the steps that have been conventionally cured by light irradiation, and can reduce the number of steps and the process time.
[0016]
  In addition, a third object of the present invention is to provide a cured layer having a predetermined pattern such as a pixel portion (colored layer) by an inkjet method using a thermosetting ink composition that can achieve the first or second object. An object of the present invention is to provide a method for manufacturing a color filter, which can be formed accurately and uniformly.
[Means for Solving the Problems]
[0017]
The method for producing a color filter of the present invention includes (1) a step of forming a wettability variable layer capable of changing wettability in a direction in which hydrophilicity increases on a substrate;
  (2) selectively changing the wettability in a predetermined region on the surface of the wettability variable layer to form an ink layer forming region having a higher hydrophilicity than the surroundings;
  (3) Using the standard solution shown in the wetting test specified in JIS K6768 for the ink layer formation region, the contact angle (θ) after 30 seconds was measured after contacting the droplet, and the graph of the Zisman plot The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined by the above is 10 ° or more, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 10 ° showing diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, dimethyl adipate, diethyl adipate, Thermosetting inkjet ink composition for color filters, in which at least a binder and a thermosetting component are dissolved or dispersed in a solvent consisting only of dimethyl succinate, dimethyl glutarate, dimethyl malonate, diethyl malonate, or a mixture thereof. A step of selectively attaching an object by an ink jet method to form an ink layer;
  (4) a step of curing the ink layer by heating to form a cured layer of a predetermined pattern;
  It is characterized by including.
[0018]
Of the present inventionManufacturing method of color filterUses the standard solution shown in the wetting test specified in JIS K6768 as the solvent, measured the contact angle (θ) after 30 seconds of contact with the droplets, and obtained from the Zisman plot graph. The contact angle with respect to the surface of the test piece having a tension of 30 mN / m is 10 ° or more, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 10 ° or less. Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, dimethyl adipate, diethyl adipate, dimethyl succinate In this case, the wettability of the surface of the wettability variable layer is changed in the direction of increasing the hydrophilicity, because the solvent is made of only ruthenium, dimethyl glutarate, dimethyl malonate, diethyl malonate, or a mixture thereof. The difference between the wettability of the thermosetting ink composition with respect to the formed ink layer forming region of the predetermined pattern and the wettability of the thermosetting ink composition with respect to the surrounding region can be greatly increased. Therefore, the present inventionIn the color filter manufacturing method,Adhere the thermosetting inkjet ink composition for color filters precisely and uniformly to the ink layer forming area.It is possible to provide a method for producing a color filter capable of accurately and uniformly forming a cured layer having a predetermined pattern.
[0019]
  Various patterns and protective films can be formed on the color filter using the above-mentioned thermosetting ink composition for color filters. In particular, a colorant is blended in this ink composition to form a pixel portion. It is used suitably for doing.
[0021]
  When using a thermosetting component for the thermosetting ink composition for color filters of this invention, it is preferable to use the thermosetting component which shows the behavior similar to the solvent mentioned above regarding wettability. That is, in the present invention, using the standard solution shown in the wetting test specified in JIS K6768, the contact angle (θ) after 30 seconds was measured by contacting the droplet, and the criticality obtained from the graph of the Zisman plot was obtained. The contact angle with respect to the surface of the test piece having a surface tension of 30 mN / m is 10 ° or more, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 10 ° or less. It is preferable to use a thermosetting component.
[0022]
  When a thermosetting component that satisfies the same conditions as the solvent described above with respect to wettability is blended in the thermosetting ink composition, the thermosetting ink composition is variable before the wettability of the wettability variable layer is changed. After the surface of the layer is more repulsive and the wettability variable layer is changed in wettability to increase the hydrophilicity, the wettability variable layer surface is further improved. This is preferable because it shows a great affinity.
[0024]
  And the color part can be mix | blended and used for the thermosetting ink composition for color filters of this invention, and the pixel part as said hardened layer can be formed.
[0026]
  The wettability variable layer is obtained by measuring the contact angle (θ) after 30 seconds of contact with a droplet using the standard solution shown in the wetting test specified in JIS K6768, and obtaining it from the graph of the Zisman plot. The critical surface tension is preferably 10 to 50 mN / m before changing the wettability, and preferably 40 to 80 mN / m after changing the wettability.
[0027]
  When the wettability variable layer that can change the critical surface tension in this way is used, the thermosetting ink composition of the present invention changes the wettability and forms a pattern such as a pixel portion forming region in which the hydrophilicity is increased. A very small contact angle is exhibited in the region, while a very large contact angle is exhibited around the pattern formation region, and the difference in wettability can be made very large.
[0028]
  As the wettability variable layer, one that changes wettability in the direction of increasing hydrophilicity when irradiated with light can be used.
[0029]
  As such a wettability variable layer, there exists a thing using the effect | action of a photocatalyst, for example. Specifically, the wettability variable layer itself is a photocatalyst-containing layer containing a photocatalyst, or is provided with a photocatalyst-containing layer provided on the substrate side of the wettability variable layer, and light is applied to the photocatalyst-containing layer. It is possible to use a photocatalyst that is activated by irradiation and that changes wettability in the direction of increasing hydrophilicity by the activated photocatalyst.
DETAILED DESCRIPTION OF THE INVENTION
[0030]
  In the following, the thermosetting ink composition according to the first invention capable of maintaining good dischargeability of the inkjet head, the method for producing a color filter using the ink composition, and the change in wettability on the color filter substrate The thermosetting ink composition according to the second invention that can be adhered accurately and uniformly in a predetermined pattern using the above and a method for producing a color filter using the ink composition will be sequentially described.
[0031]
  (1) Thermosetting ink composition according to the first invention and method for producing a color filter
  The thermosetting ink composition according to the first invention (first thermosetting ink composition) contains at least a binder and a bifunctional to trifunctional epoxy group-containing monomer as essential components. And You may mix | blend a coloring agent, a dispersing agent, a hardening accelerator, or another additive with a 1st thermosetting ink composition as needed. Moreover, in order to provide the thermosetting ink composition with appropriate fluidity and dischargeability for application to the ink jet system, each of the above components may be dissolved or dispersed in a solvent (diluent). The first thermosetting ink composition may be used in combination with a bifunctional or trifunctional epoxy group-containing monomer and a tetrafunctional or higher functional epoxy group-containing resin.
[0032]
  (binder)
  As the binder, any of a resin having no polymerization reactivity per se and a resin having a polymerization reactivity per se may be used, or two or more binders may be used in combination.
[0033]
  When a resin having no polymerization reactivity is used as a binder, a bifunctional to trifunctional epoxy group-containing monomer which is an essential component in the thermosetting ink composition, and other thermosetting components which are desired components are included. It is polymerized by heating and cured.
[0034]
  As such a non-polymerizable binder, for example, a copolymer comprising two or more of the following monomers can be used: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer.
[0035]
  More specifically, acrylic acid / benzyl acrylate copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer, Acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl Acrylate / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate macromono -Copolymer, Acrylic acid / Benzyl methacrylate copolymer, Acrylic acid / Methyl methacrylate / Styrene copolymer, Acrylic acid / Benzyl methacrylate / Styrene copolymer, Acrylic acid / Methyl methacrylate / Polystyrene macromonomer copolymer, Acrylic Acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / Benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethylmeta It can be used acrylic acid copolymers such as Li rate macromonomer copolymer.
[0036]
  Further specific examples include methacrylic acid / benzyl acrylate copolymer, methacrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer. , Methacrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxy Ethyl acrylate / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl Methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer , Methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxy Ethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate It can be exemplified DOO / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers methacrylic acid copolymers such as such.
[0037]
  Among the non-polymerizable binders exemplified above, in particular, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, benzyl methacrylate / styrene copolymer, benzyl methacrylate macromonomer / styrene copolymer, A benzyl methacrylate / styrene macromonomer copolymer is preferred.
[0038]
  On the other hand, as the binder having polymerizability per se, it is possible to use an oligomer obtained by introducing a thermally polymerizable functional group such as an epoxy group into a non-polymerizable binder molecule or a polymer having a higher molecular weight than the oligomer. it can. The molecules of the polymerizable binder are polymerized with the binders, and are also polymerized with the bifunctional to trifunctional polyfunctional monomer and other polymerizable monomers which are desired components and thermally cured.
[0039]
  As the thermopolymerizable binder, for example, a homopolymer or copolymer obtained by polymerizing one or more monomers containing an ethylenically unsaturated bond and an epoxy group as shown below can be used. : Glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4 -Epoxybutyl, methacrylic acid-4,5-epoxypentyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, etc. ) Acrylates; o-vinylphenylglycidyl ether, m-vinylphenylglycidyl ether Ter, p-vinylphenyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc .; 2,3-diglycidyloxystyrene, 3,4-di Glycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether, vinyl phlorog Ricinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl Ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, and 1,3,5-trihydroxymethylstyrene Triglycidyl ether.
[0040]
  Further, a copolymer obtained by polymerizing one or more monomers containing an ethylenically unsaturated bond and an epoxy group as described above and a monomer not containing an epoxy group as described below is also thermally polymerizable. Can be used as a binder: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer.
[0041]
  A binder is normally mix | blended in the ratio of 1 to 50 weight% with respect to the solid content whole quantity of a thermosetting ink composition. Here, the solid content of the thermosetting ink composition for specifying the blending ratio includes all components except the solvent, and a liquid polymerizable monomer is also included in the solid content.
[0042]
  (Coloring agent)
  When a colored pattern such as a pixel portion is formed on the color filter substrate using the thermosetting ink composition of the present invention, a colorant is blended in the thermosetting ink composition. Any one of organic colorants and inorganic colorants can be selected and used in accordance with the desired colors such as R, G, and B of the pixel portion. As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Moreover, as an inorganic coloring agent, an inorganic pigment, an extender pigment, etc. can be used, for example. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. As organic pigments, for example, compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), specifically, the following Color Index (CI) numbers are attached. Can be mentioned.
[0043]
  CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment .... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175;
  CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Buy Olet 32, C.I. pigment violet 36, C.I. pigment violet 38;
  CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58 : 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI pigmentless 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 77, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red . 64, C.I Pigment Red 265;
  CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25 CI pigment black 1, pigment black 7.
[0044]
  Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In this invention, a coloring agent can be used individually or in mixture of 2 or more types.
[0045]
  When the pattern of the light shielding layer is formed on the substrate of the color filter using the thermosetting ink composition of the present invention, a black colorant having a high light shielding property is blended in the thermosetting ink composition. As the black colorant having a high light-shielding property, for example, an inorganic colorant such as carbon black or iron trioxide or an organic colorant such as cyanine black can be used.
[0046]
  In addition, when the first thermosetting ink composition is used to form a colorless transparent layer or a cured layer that does not require color adjustment in a predetermined pattern, it is not necessary to use a colorant. .
[0047]
  When forming a pixel part, normally, a coloring agent is mix | blended in the ratio of 1 to 60 weight% normally with respect to solid content whole quantity of a thermosetting ink composition, Preferably it is 15 to 40 weight%. When there are too few coloring agents, there exists a possibility that the permeation | transmission density | concentration at the time of apply | coating a thermosetting ink composition to predetermined | prescribed film thickness (usually 0.1-2.0 micrometers) may not be enough. Moreover, when there are too many coloring agents, there exists a possibility that the characteristics as coating films, such as adhesion to a board | substrate when a thermosetting ink composition is apply | coated and hardened on a board | substrate, and coating film hardness, may become inadequate. is there.
[0048]
  (Thermosetting component)
  In the first invention, a bifunctional to trifunctional epoxy group-containing monomer is used alone or in combination of two or more as a thermosetting component of the ink. A bifunctional to trifunctional epoxy group-containing monomer has a relatively low viscosity among thermosetting resins and has a small increase in viscosity due to drying. The ink used as the curable component hardly raises the viscosity at the tip of the head during the spraying operation by the ink jet method, does not cause clogging of the head, and stabilizes the ink ejection property during the operation. Therefore, the discharge amount and discharge direction of the ink are kept constant, and the ink can be adhered to the substrate accurately and uniformly according to a predetermined pattern.
[0049]
  Examples of the bifunctional to trifunctional epoxy group-containing monomer include, for example, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2, 3 -Diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4 Dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene Examples thereof include triglycidyl ether and 1,3,5-trihydroxymethylstyrene triglycidyl ether, and one of these can be used alone or two or more can be used in combination.
[0050]
  The blending ratio of the bifunctional to trifunctional epoxy group-containing monomer is usually 20 to 70% by weight based on the total solid content of the thermosetting ink composition.
[0051]
  Here, when the blending ratio of the bifunctional to trifunctional epoxy group-containing monomer is less than 20% by weight of the total solid content (all components other than the solvent), the ink composition is not sufficiently diluted with the monomer, The viscosity of the ink is high from the beginning or becomes high after volatilization of the solvent component, which may cause clogging of the inkjet head. Moreover, when the blending ratio of the bifunctional to trifunctional epoxy group-containing monomer exceeds 70% by weight of the total solid content, the crosslinking density of the coating film is lowered, and the solvent resistance, adhesion, and hardness of the coating film are reduced. Is inferior, and sufficient characteristics may not be obtained.
[0052]
  In addition, the thermosetting ink composition of the first aspect of the invention includes a monofunctional epoxy group-containing monomer and / or a tetrafunctional or higher functional group, as necessary, together with the bifunctional to trifunctional epoxy group-containing monomer. You may mix | blend thermosetting components other than an epoxy group containing resin and / or an epoxy group containing monomer.
[0053]
  Monofunctional epoxy group-containing monomers include methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butyl phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, polypropylene glycol glycidyl ether Examples include ether and butoxypolyethylene glycol monoglycidyl ether.
[0054]
  Examples of the thermosetting component other than the epoxy group-containing monomer include melamine resin, urea resin, alkyd resin, phenol resin, and cyclopentadiene resin.
[0055]
  In the first invention, it is particularly preferable to blend a tetrafunctional or higher functional epoxy group-containing resin together with a bifunctional to trifunctional epoxy group-containing monomer. When all of the epoxy group-containing components blended in the thermosetting ink composition are bifunctional to trifunctional, since the viscosity increase due to drying of the ink hardly occurs, the ejection property of the inkjet head is stabilized. On the other hand, the film strength of the cured layer obtained by curing the ink layer and the adhesion to the substrate may be insufficient. Therefore, by blending an appropriate amount of a tetrafunctional or higher functional epoxy group-containing resin together with the bifunctional to trifunctional epoxy group-containing monomer, sufficient film strength and adhesion can be imparted to the pattern of the cured layer.
[0056]
  Examples of the tetrafunctional or higher functional epoxy group-containing resin include novolak resins such as phenol novolac epoxy and cresol novolac epoxy, glycidyl amine resins such as tetraglycidyldiaminodiphenylmethane and tetraglycidylmetaxylenediamine, tetraphenylglycidyl ether ethane, Glycidyl ether resins such as phenyl glycidyl ether methane can be used.
[0057]
  The tetrafunctional or higher functional epoxy group-containing resin is usually blended at a ratio of 1 to 30% by weight with respect to the total solid content of the thermosetting ink composition. In addition, in order to balance discharge stability by containing a bi- or tri-functional epoxy group and improvement in strength and adhesion by a tetra- or higher-functional epoxy group-containing resin, it is based on 100 parts by weight of a bi- to trifunctional monomer. The blending ratio of the tetrafunctional or higher epoxy group-containing resin is usually 1 to 50 parts by weight, preferably the lower limit of the blending ratio is 2 parts by weight and / or the upper limit of the blending ratio is 35 parts by weight. The following.
[0058]
  Here, when the blending ratio of the tetrafunctional or higher functional epoxy group-containing resin is less than 1 part by weight with respect to 100 parts by weight of the bifunctional or trifunctional monomer, the hardness after curing the ink and the solvent resistance There is a possibility that characteristics such as property cannot be obtained sufficiently. Moreover, when the said mixture ratio of the epoxy functional group resin more than tetrafunctional exceeds 50 weight part, there exists a possibility that the cure speed of ink may become slow and process speed may become slow.
[0059]
  (Curing agent)
  A curing agent is usually blended in the thermosetting ink composition for color filters of the present invention. For example, a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid is used as the curing agent.
[0060]
  Specific examples of polyhydric carboxylic acid anhydrides include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Containing acid anhydrides, particularly preferably aromatic poly It may be mentioned carboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.
[0061]
  Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.
[0062]
  These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids can be used singly or in combination of two or more. The compounding quantity of the hardening | curing agent used for this invention is the range of 1-100 weight part normally per 100 weight part of components (monomer and resin) containing an epoxy group, Preferably it is 5-50 weight part. When the blending amount of the curing agent is less than 1 part by weight, curing becomes insufficient and a tough coating film cannot be formed. Moreover, when the compounding quantity of a hardening | curing agent exceeds 100 weight part, while the adhesiveness with respect to the board | substrate of a coating film is inferior, a uniform and smooth coating film cannot be formed.
[0063]
  (Dispersant)
  The dispersant is blended in the thermosetting ink composition as necessary in order to disperse the colorant satisfactorily. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.
[0064]
  That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Polymeric surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.
[0065]
  (Other ingredients)
  The thermosetting ink composition for color filters of the present invention may contain one or more other additives as required. The following can be illustrated as such an additive.
[0066]
  a) Curing accelerator (chain transfer agent): For example, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, etc.
  b) Dispersing aid: For example, blue pigment derivatives such as copper phthalocyanine derivatives, yellow pigment derivatives and the like.
[0067]
  c) Filler: For example, glass, alumina and the like.
[0068]
  d) Adhesion promoter: for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
[0069]
  e) Antioxidant: For example, 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and the like.
[0070]
  f) Ultraviolet absorber: For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
[0071]
  g) Anti-aggregation agent: for example, sodium polyacrylate or various surfactants.
[0072]
  (solvent)
  In the present invention, the thermosetting ink composition is usually diluted with a solvent in order to give the thermosetting ink composition for a color filter appropriate fluidity for use in an inkjet method.
[0073]
  Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; and diethylene glycol monoalkyl ethers such as diethylene glycol mono-n-butyl ether acetate. Acetates; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether; ketones such as cyclohexanone, 2-heptanone and 3-heptanone; Hydroxypropionic acid ethyl Lactic acid alkyl esters such as: 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-butyl acetate, isobutyl acetate, formic acid Other esters such as n-amyl, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate; high-boiling solvents such as γ-butyrolactone can be used.
[0074]
  An ink composition coating solution is prepared using such a solvent in a proportion of 40 to 95% by weight based on the total amount of the thermosetting ink composition containing the solvent. If the amount of the solvent is too small, the viscosity of the ink is high and it becomes difficult to discharge from the inkjet head. Also, if there is too much solvent, the ink film deposited on the wettability change site will be broken before the ink deposit (ink deposition amount) for the predetermined wettability change site (ink layer formation site) is not sufficient. , It protrudes into the surrounding unexposed areas and further spreads to the adjacent wettability change site (ink layer formation site). In other words, the amount of ink that can be deposited without sticking out from the wettability change site (ink layer forming site) to which the ink is to be deposited becomes insufficient, the film thickness after drying is too thin, The transmission density cannot be obtained.
[0075]
  (Preparation of thermosetting ink composition for color filter of the first invention)
  A binder, a bifunctional or trifunctional epoxy group-containing monomer, and other components as necessary are mixed in an arbitrary order, or these components are added to the above solvent in an arbitrary order, and a dissolver, etc. The thermosetting ink composition for color filters of the first invention can be prepared by sufficiently stirring and uniformly dissolving and dispersing.
[0076]
  (Manufacture of color filter in the first invention)
  The ink for forming a pixel portion obtained by blending a desired colorant such as R, G, or B with the thermosetting ink composition for a color filter of the first invention described above is applied to a predetermined region on the substrate of the color filter by an inkjet method. The pixel portion can be formed by selectively adhering and then heating and curing.
[0077]
  An example of a method for producing a color filter including such steps will be described below. First, a transparent substrate 1 for a color filter is prepared as shown in FIG. The transparent substrate is not particularly limited as long as it has been conventionally used for color filters, for example, a transparent rigid material having no flexibility such as quartz glass, pyrex glass, synthetic quartz plate, Or the transparent flexible material which has flexibility, such as a transparent resin film and an optical resin board, can be used. Among them, Corning 7059 glass is a material having a small coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the active matrix. Suitable for color filters for color liquid crystal display devices. In the present invention, a transparent substrate is usually used, but a reflective substrate or a white colored substrate can also be used. Moreover, you may use the board | substrate which surface-treated for the purpose of alkali elution prevention, gas barrier property provision, and other purposes as needed.
[0078]
  Next, as illustrated in FIG. 1B, the light shielding portion 2 is formed in a region that is a boundary between the pixel portions on the one surface side of the transparent substrate 1. The light shielding part 2 can be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum vapor deposition method or the like, and patterning this thin film. As this patterning method, a normal patterning method such as sputtering can be used.
[0079]
  The light shielding part 2 may be a layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more kinds, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. As a method for patterning such a resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.
[0080]
  Next, as shown in FIG. 1C, an ink-repellent convex portion having a width narrower than that of the light shielding portion is formed in the center in the width direction of the pattern of the light shielding portion as necessary. The composition of such an ink repellency convex part is not particularly limited as long as it is a resin composition having ink repellency. Moreover, it does not need to be transparent in particular and may be colored. For example, a material that is used for the light-shielding portion and does not include a black material can be used. Specifically, a composition in which one or more aqueous resins such as polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose are mixed, or an O / W emulsion type resin composition, for example, reactive silicone emulsion And the like. In the present invention, a photocurable resin is preferably used for reasons such as easy handling and curing. In addition, since the ink-repellent convex portion is more preferable as the ink repellency is stronger, the surface may be treated with an ink-repellent treatment agent such as a silicone compound or a fluorine-containing compound.
[0081]
  The patterning of the ink-repellent convex portions can be performed by printing using an ink-repellent resin composition coating liquid or photolithography using a photo-curable coating liquid. The height of the ink-repellent convex portion is preferably high to some extent because it is provided to prevent ink from being mixed when colored by the inkjet method as described above. In consideration of the overall flatness of the case, the thickness is preferably close to the thickness of the pixel portion. Specifically, although it varies depending on the amount of ink deposited, it is preferably in the range of 0.1 to 2 μm.
[0082]
  Next, it is the thermosetting ink composition for color filters of 1st invention, Comprising: The ink for pixel part formation of each color formed by mix | blending 1 or 2 or more colorants is prepared. Then, as shown in FIG. 1 (D), on the surface of the transparent substrate 1, the pixel portion forming regions 4R, 4G, and 4B for the respective colors defined by the pattern of the light shielding layer 2 are formed. Ink is sprayed by an ink jet system to form an ink layer. In this ink spraying step, the pixel portion forming ink belonging to the first invention is unlikely to increase in viscosity at the tip portion of the head 5 and can continue to maintain good ejection properties. Therefore, the ink of the corresponding color can be accurately and uniformly deposited in the predetermined pixel portion formation region, and a pixel portion having no color unevenness or color loss can be formed with an accurate pattern. Further, since the pixel portion forming ink of each color can be simultaneously sprayed onto the substrate using a plurality of heads, the working efficiency can be improved as compared with the case where the pixel portion is formed for each color.
[0083]
  Next, as shown in FIG. 1E, the ink layers 6R, 6G, and 6B of the respective colors are dried as necessary, and then heated and cured to form pixel portions. The ink layer is typically dried in a temperature range of 50-200 ° C. using a vacuum dryer, oven, hot plate, or other heat-applied device, and is usually vacuum dryer, oven, hot plate, or other It is heat-cured in a temperature range of 120 to 250 ° C. using an apparatus that can be given heat. The thickness of the pixel portion is usually about 0.1 to 2.0 μm in consideration of optical characteristics and the like.
[0084]
  Next, as shown in FIG. 1F, a protective layer 9 is formed on the side of the transparent substrate where the pixel portions 8R, 8G, and 8B are formed. The protective layer is provided to flatten the color filter and to prevent components contained in the pixel portion and the like from eluting into the liquid crystal layer of the liquid crystal display device. The thickness of the protective layer can be set in consideration of the light transmittance of the material used, the surface state of the color filter, and the like, and can be set, for example, in the range of 0.1 to 2.0 μm. The protective layer can be formed using, for example, a known transparent photosensitive resin, two-component curable transparent resin, or the like having a light transmittance required as a transparent protective layer.
[0085]
  Thus, color filter 101A is manufactured using the thermosetting ink composition for color filters of the first invention. In this example, the pixel portion is formed using the pixel portion forming ink which is the thermosetting ink composition for the color filter of the first invention, but the thermosetting ink composition for the color filter of the first invention is used. According to the inkjet method, a hardened layer other than the pixel portion, for example, the light shielding layer 2 and the ink repellent convex portion 3 can be formed in a desired pattern.
[0086]
  When the light-shielding layer 2 is to be formed, a thermosetting ink composition for color filters according to the first invention, which is prepared by blending a light-shielding colorant such as a black pigment, is prepared. The ink for layer formation is selectively attached to a predetermined area on the surface of the transparent substrate 1 by an ink jet method to form an ink layer in a predetermined pattern, and the ink layer is heated and cured to form a light shielding layer. it can.
[0087]
  In addition, when it is desired to form the ink-repellent convex portion 3, it is the photocurable ink composition for color filters of the first invention, and is an ink-repellent convex portion forming ink comprising an ink-repellent binder. The ink-repellent convex portion forming ink is prepared in a pattern having a width narrower than that of the light shielding layer 2 along the longitudinal direction of the light shielding layer 2 in the center of the upper surface of the light shielding layer 2 by an ink jet method. The ink-repellent convex part 3 can be formed by making it adhere and forming an ink layer and heating the said ink layer and hardening.
[0088]
  (Summary of the first invention)
  The first invention described above is summarized as follows.
[0089]
  In the first embodiment of the present invention, the thermosetting ink composition for a color filter contains at least a binder and a bifunctional to trifunctional epoxy group-containing monomer.
[0090]
  The thermosetting ink composition for color filters according to the first embodiment uses an epoxy group-containing monomer having a relatively small number of bifunctional to trifunctional functional groups as a thermosetting component. It is difficult for the viscosity to increase at the tip, clogging of the head does not occur, and ink discharge performance during operation is stabilized. Therefore, the discharge amount and discharge direction of the ink are kept constant, and the ink can be adhered to the substrate accurately and uniformly according to a predetermined pattern.
[0091]
  Various patterns and protective films can be formed on the color filter using the above-mentioned thermosetting ink composition for color filters. In particular, a colorant is blended in this ink composition to form a pixel portion. It is used suitably for doing.
[0092]
  Specific examples of the bifunctional to trifunctional epoxy group-containing monomer include polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2, 3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether 4-vinyl pyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4 Dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene At least one selected from triglycidyl ether and 1,3,5-trihydroxymethylstyrene triglycidyl ether can be used.
[0093]
  The thermosetting ink composition for a color filter according to the first aspect includes a bifunctional and trifunctional epoxy group-containing monomer, a tetrafunctional or higher functional epoxy group-containing resin, and a bifunctional and trifunctional epoxy group-containing monomer. It is preferable to contain in the ratio of 1-50 weight part with respect to 100 weight part.
[0094]
  When all the thermosetting components blended in the thermosetting ink composition are bi- or tri-functional monomers, the viscosity increase due to drying of the ink is unlikely to occur, and thus the ejection performance of the inkjet head is stable. On the other hand, the film strength of the cured layer obtained by curing the ink layer and the adhesion to the substrate may be insufficient. Therefore, by blending an appropriate amount of a tetrafunctional or higher functional epoxy group-containing resin together with the bifunctional to trifunctional epoxy group-containing monomer, sufficient film strength and adhesion can be imparted to the pattern of the cured layer.
[0095]
  In the first embodiment of the present invention, (1) the thermosetting ink composition for a color filter according to any one of claims 1 to 4 is selectively attached to a predetermined region on the substrate by an inkjet method. Providing a method for producing a color filter, comprising: a step of forming an ink layer; and (2) a step of curing the ink layer by heating to form a cured layer having a predetermined pattern. To do.
[0096]
  And the pixel part as a said hardened layer can be formed by mix | blending and using a coloring agent with the photocurable ink composition for color filters of a 1st form.
[0097]
  (2) Thermosetting ink composition according to the second invention and method for producing a color filter
  The thermosetting ink composition according to the second invention (second thermosetting ink composition) is a standard solution shown in the wetting test specified in JIS K6768, and 30 seconds after contacting the droplets. The contact angle (θ) was measured and the contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined from the Zisman plot graph was 10 ° or more, and the critical surface determined by the same measurement method It is characterized in that at least a binder and a thermosetting component are dissolved or dispersed in a solvent having a contact angle with respect to the surface of a test piece having a tension of 70 mN / m of 10 ° or less. You may mix | blend a coloring agent, a dispersing agent, a hardening accelerator, or another additive with a 2nd thermosetting ink composition as needed.
[0098]
  Since the second invention is characterized in that a thermosetting ink composition is prepared using a solvent having specific properties with respect to wettability, first, the solvent will be described below, and thereafter, the first invention will be described. Each component will be described in the same order.
[0099]
  (Solvent of the second invention)
  In the second invention, the standard solution shown in the wetting test specified in JIS K6768 is used as a solvent for diluting the thermosetting ink composition, and the contact angle (θ ), The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined from the Zisman plot graph is 10 ° or more, and the critical surface tension determined by the same measurement method is 70 mN / m. A solvent having a contact angle of 10 ° or less with respect to the surface of the test piece is used as an essential component.
[0100]
  When a thermosetting ink composition is prepared using a solvent that exhibits the above-mentioned behavior with respect to wettability, the thermosetting ink composition has a surface of the wettability variable layer before changing the wettability of the wettability variable layer described later. After the wettability of the wettability variable layer is changed to increase the hydrophilicity, the wettability variable layer has a great affinity for the surface of the wettability variable layer. Therefore, the wettability of the thermosetting ink composition with respect to the ink layer forming region formed in a predetermined pattern by changing the wettability of a part of the wettability variable layer in the direction of increasing hydrophilicity, and its surroundings The difference in the wettability of the thermosetting ink composition with respect to the above region can be made large.
[0101]
  Here, the test piece having the above characteristics with respect to the critical surface tension may be formed of any material. Examples of test pieces having a critical surface tension of 30 mN / m include, for example, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate having a smooth surface, and the polymer or surface modifier applied on a smooth glass surface. The above test can be actually performed from among those, and the corresponding one can be selected. Moreover, as a test piece which shows critical surface tension 70mN / m, the said test is actually performed from what apply | coated nylon, the glass surface which hydrophilized, etc., and the applicable thing can be selected.
[0102]
  The following can be illustrated as a solvent which shows the said behavior regarding wettability.
[0103]
  a) Glycol ethers: for example, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc .;
  b) Glycol ether esters: for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc .;
  c) Glycol oligomer ethers: for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol monomethyl ether, triethylene glycol Ethylene glycol dimethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monobutyl ether, etc .;
  d) Glycol oligomer ether esters: for example, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol Monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, etc .;
  e) Aliphatic carboxylic acids or acid anhydrides thereof: for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, acetic anhydride and the like;
  f) Aliphatic or aromatic esters: for example, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopropyl propionate, methyl butyrate, butyric acid Ethyl, butyl butyrate, isopentyl butyrate, isobutyl isobutyrate, ethyl 2-hydroxy-2-methyl-propionate, ethyl isovalerate, isopentyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, etc. ;
  g) Dicarboxylic acid diesters: for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dimethyl oxalate, diethyl oxalate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dibutyl malonate, dimethyl succinate, diethyl succinate, Dibutyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc .;
  h) Alkoxycarboxylic acid esters: for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Propyl etc .;
  i) Ketocarboxylic acid esters: for example, methyl acetoacetate, ethyl acetoacetate and the like;
  j) Halogenated carboxylic acids: for example, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and the like;
  k) Alcohols or phenols: For example, methanol, ethanol, propanol, isopropanol, butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, hexanol, heptanol, phenol and the like;
  l) Aliphatic or aromatic ethers: for example, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, butyl vinyl ether, anisole and the like;
  m) Alkoxy alcohols: For example, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxymethylethanol, 2-isopropoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and the like;
  n) Glycol oligomers: for example, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;
  o) Amino alcohols: for example, 2-aminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, triethanolamine, isopropanolamine, triisopropanolamine and the like;
  p) alkoxy alcohol esters: for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate and the like;
  q) Ketones: For example, acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonyl acetone, and the like;
  r) Morpholines: for example, morpholine, N-ethylmorpholine, phenylmorpholine and the like;
  s) Aliphatic or aromatic amines: for example, pentylamine, dipentylamine, tripentylamine, aniline, N-methylaniline and the like;
  Among these, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, dimethyl adipate, diethyl adipate, or those The mixture of is preferably used.
[0104]
  The thermosetting ink composition of the second invention is also usually diluted with a solvent so as to have the same solid content concentration as in the first invention to prepare a coating liquid.
[0105]
  (Thermosetting component)
  In the second invention, a bifunctional to trifunctional epoxy group-containing monomer, a monofunctional epoxy group-containing monomer, and a tetrafunctional or higher functional group described or specifically exemplified as used in the first invention In addition to the epoxy group-containing resin, other thermosetting monomers may be used as the thermosetting component.
[0106]
  In the second invention, as in the first invention, by using a bifunctional to trifunctional epoxy group-containing monomer, the viscosity increase and clogging of the thermosetting ink composition at the tip of the inkjet head are prevented, and the inkjet system This is preferable because the ink dischargeability during the spraying operation can be stabilized.
[0107]
  Moreover, by using a bifunctional or trifunctional epoxy group-containing monomer in combination with a tetrafunctional or higher functional epoxy group-containing resin, the film strength sufficient for the pattern of the cured layer formed using the thermosetting ink composition is obtained. The ability to impart substrate adhesion is the same as in the first invention. Further, the preferable blending ratio of the bifunctional to trifunctional epoxy group-containing monomer and the tetrafunctional or higher functional epoxy group-containing resin is the same as that of the first invention.
[0108]
  In the second invention, it is preferable to use a thermosetting component that exhibits the same behavior as the solvent described above with respect to wettability. That is, in the second invention, the standard solution shown in the wetting test specified in JIS K6768 is used as the thermosetting component before thermosetting, and the contact angle (θ) 30 seconds after the droplet is brought into contact is determined. A test in which the contact angle with respect to the surface of a test piece having a critical surface tension of 30 mN / m measured by a Zisman plot is 10 ° or more, and the critical surface tension obtained by the same measurement method is 70 mN / m It is preferable to use one having a contact angle with respect to the surface of the piece of 10 ° or less.
[0109]
  When a thermosetting ink composition is prepared using a thermosetting component that satisfies the same conditions as the solvent described above with respect to wettability, the thermosetting ink composition is before the wettability of the wettability variable layer described later is changed. The surface of the wettability variable layer is further repelled, and after changing the wettability of the wettability variable layer to increase the hydrophilicity, the surface of the wettability variable layer is increased. This is preferable because it shows a greater affinity.
[0110]
  Examples of the bifunctional to trifunctional epoxy group-containing monomer that exhibit the above-described behavior with respect to wettability include, for example, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6 -Diglycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydro Cymethylstyrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether 2,3,4-trihydroxymethylstyrene triglycidyl ether, 1,3,5-trihydroxymethylstyrene triglycidyl ether, and the like.
[0111]
  (Binder, colorant, dispersant)
  Also in the second invention, the same binder, colorant and dispersant used in the first invention can be used in the same blending ratio.
[0112]
  That is, for the second thermosetting ink composition, either a resin that is not polymerized by itself or a resin that itself has a thermopolymerizable property may be used. In addition, when a colored pattern such as a pixel portion or a light shielding layer is formed using the second thermosetting ink composition, a predetermined color should be imparted to the second thermosetting ink composition. One or more colorants are blended. In addition, when the second thermosetting ink composition is used to form a colorless transparent layer or a cured layer that does not require color adjustment in a predetermined pattern, it is not necessary to use a colorant. .
[0113]
  (Other ingredients)
  Also in the second invention, a curing agent and other components can be added to the thermosetting ink composition as necessary. Each additive described or specifically exemplified as used in the first invention described above can also be used in the second invention.
[0114]
  (Preparation of photocurable ink composition for color filter of second invention)
  The second invention is made by adding the above thermosetting resin and other components as necessary to the above solvent in an arbitrary order, stirring sufficiently with a dissolver, etc., and uniformly dissolving and dispersing. The thermosetting ink composition for color filters can be prepared.
[0115]
  (Manufacture of color filters in the second invention)
  A wettability variable layer that can change wettability in the direction of increasing hydrophilicity is formed on the substrate of the color filter, and the wettability in a predetermined region on the surface of the wettability variable layer is selectively changed. In addition, an ink layer forming region having higher hydrophilicity than the surroundings is formed, and in the ink layer forming region, the thermosetting ink composition for a color filter according to the second invention described above has a desired R, G, B or the like. A pixel portion can be formed by selectively adhering a pixel portion forming ink formed by blending a colorant to form an ink layer and heating and curing the ink layer.
[0116]
  An example of a method for producing a color filter including such steps will be described below. First, as shown in FIG. 2A, a light shielding layer 2 is formed in a region serving as a boundary between pixel portions on one surface side of a transparent substrate 1 of a color filter. The pixel portion forming regions 4R, 4G, and 4B for each color are defined by the pattern of the light shielding layer. As the transparent substrate 1, the same one as used in the first invention described above can be used, and the same light shielding part 2 as that in the first invention can be provided.
[0117]
  Next, as shown in FIG. 2B, the photocatalyst containing layer 10 as a wettability variable layer is formed on at least a partial region of the surface of the transparent substrate 1, particularly in this example, the region including the pixel portion forming region. A solid pattern (solid pattern) is formed.
[0118]
  Next, as shown in FIG. 2C, the photocatalyst-containing layer 10 is exposed by irradiating the light beam 7 through the photomask 11, thereby increasing the hydrophilicity of the pixel portion formation regions 4R, 4G, and 4B.
[0119]
  When the wettability of the pixel part forming region of the wettability variable layer such as the photocatalyst containing layer 10 is selectively changed to increase the hydrophilicity, the thermosetting ink composition of the second invention is added to the pixel part forming region. Easily adheres and spreads uniformly, while the surrounding area of the pixel part formation area is strongly repelled and eliminated, so that it adheres selectively and uniformly to the pixel part formation area, and as a result, the color in an accurate pattern A pixel portion free from unevenness and color loss can be formed.
[0120]
  The wettability variable layer used in the second invention uses the standard solution shown in the wetting test specified in JIS K6768 before changing the wettability, and the contact angle (θ) 30 seconds after the droplets are brought into contact with each other. After the critical surface tension obtained from the Zisman plot graph is in the range of 10 to 50 mN / m, preferably in the range of 20 to 45, and the hydrophilicity is increased by changing the wettability. The critical surface tension obtained by the same method is preferably in the range of 40 to 80 mN / m, preferably in the range of 50 to 80.
[0121]
  When the wettability variable layer capable of changing the critical surface tension in this way is used, the thermosetting ink composition of the second invention has a pattern such as a pixel portion forming region in which the wettability is changed and the hydrophilicity is increased. In the formation region, a very small contact angle is shown. On the other hand, in the periphery of the pattern formation region, a very large contact angle is shown, and the difference in wettability can be very large.
[0122]
  When exposure is performed using the photomask 11, the width of the exposed portion 12 is made wider than the width of the pixel portion forming region 4 while ensuring an unexposed portion at the boundary between adjacent pixel portion forming regions. It is preferable to make it. By doing so, every corner of the pixel portion formation region 4 is sufficiently exposed and hydrophilicity is increased, so that inconvenience such as color loss of the pixel portion does not occur. The photocatalyst-containing layer 10 may be exposed in a predetermined pattern by other methods such as photolithography by scanning with a laser beam without using a photomask. Further, when exposure is performed from the back side of the transparent substrate (the side opposite to the side where the photocatalyst-containing layer 10 is provided), the light shielding layer 2 functions as a photomask, so that no photomask is required.
[0123]
  The light applied to the photocatalyst-containing layer 10 may be visible light or invisible light as long as it can activate the photocatalyst, but usually light including ultraviolet light is used. Examples of such a light source including ultraviolet light include a mercury lamp, a metal halide lamp, and a xenon lamp. The wavelength of light used for this exposure can be set within a range of 400 nm or less, preferably 380 nm or less, and the amount of light irradiation during exposure increases the hydrophilicity of the exposed part by the action of a photocatalyst. It can be set as the irradiation amount required to make it.
[0124]
  Examples of the wettability variable layer capable of changing the wettability in the direction of increasing hydrophilicity include, for example, a) a photocatalyst like the illustrated wettability variable layer 10 and the wettability variable layer itself by the action of the photocatalyst. B) The photocatalyst-containing layer is provided on the lower side (transparent substrate side) of the wettability variable layer, and the hydrophilicity of the wettability variable layer is increased by the action of the photocatalyst present in the photocatalyst-containing layer. C) a degradable wettability variable layer comprising a photocatalyst and a binder that is decomposed by the action of the photocatalyst, wherein an exposed portion of the degradable wettability variable layer is decomposed and removed, and has a hydrophilic surface, for example, A photocatalyst-containing layer that is exposed in the photocatalyst-containing layer is provided with a photocatalyst-containing layer below the decomposable wettability variable layer that is exposed from the transparent substrate or the like, or Exposed portion of the degradable wettability-variable layer is decomposed by use, underlying which is removed with a hydrophilic, it can be exemplified, for example, those photocatalyst-containing layer or the like is exposed.
[0125]
  In the present invention, “a wettability variable layer capable of changing the wettability in the direction of increasing hydrophilicity” refers to the wettability of the wettability variable layer forming surface in the laminate in which the wettability variable layer is provided on the substrate. What is necessary is just to change the direction in which hydrophilicity increases, not only those in which the hydrophilicity of the wettability variable layer itself increases as in the above examples a) and b), but also in the above examples c) and d). As described above, the wettability variable layer is decomposed to expose the hydrophilic base.
[0126]
  In the following, the types a) and b) will be described in detail.
[0127]
  a) Photocatalyst-containing layer that increases its own hydrophilicity
  Like the illustrated photocatalyst-containing layer 10, the photocatalyst-containing layer that itself functions as a wettability variable layer is prepared by dispersing a photocatalyst and a binder in a solvent together with other additives as necessary. After the coating solution is applied, hydrolysis and polycondensation reactions are performed to firmly fix the photocatalyst in the binder.
[0128]
  As the photocatalyst, for example, titanium oxide (TiO 2) known as an optical semiconductor.₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)_Three), Tungsten oxide (WO_Three), Bismuth oxide (Bi₂O_Three), And iron oxide (Fe₂O_Three1) or a mixture of two or more selected from these.
[0129]
  The mechanism of action of the photocatalyst in the photocatalyst-containing layer is not necessarily clear, but carriers generated by light irradiation may react directly with nearby compounds, or by active oxygen species generated in the presence of oxygen and water. It is considered that the chemical structure of the organic substance is changed, and the hydrophilicity is increased by, for example, oxidation or decomposition of an organic group or additive which is a part of the binder.
[0130]
  In the present invention, titanium oxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium oxide includes anatase type and rutile type, and both can be used in the present invention, but anatase type titanium oxide is preferable. Anatase type titanium oxide has an excitation wavelength of 380 nm or less.
[0131]
  Examples of such anatase-type titanium oxide include hydrochloric acid peptizer-type anatase-type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.
[0132]
  The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less. Further, the smaller the particle size of the photocatalyst, the smaller the surface roughness of the formed photocatalyst-containing layer, which is preferable. When the particle size of the photocatalyst exceeds 100 nm, the centerline average surface roughness of the photocatalyst-containing layer becomes coarse, and the photocatalyst This is not preferable because the ink repellency of the non-exposed portion of the containing layer is lowered and the ink affinity of the exposed portion becomes insufficient.
[0133]
  The binder used in this type of photocatalyst-containing layer preferably has a high binding energy such that the main skeleton is not decomposed by photoexcitation of the photocatalyst. For example, (1) chloro or alkoxysilane is hydrolyzed by sol-gel reaction or the like. Examples include organopolysiloxanes that exhibit high strength by decomposition and polycondensation, and (2) organopolysiloxanes crosslinked with reactive silicones that are excellent in water repellency and oil repellency.
[0134]
  In the case of (1) above, the general formula:
  YnSiX_(4-n)
  (Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. )
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0135]
  Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrit-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxy Silane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyl Lutriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n -Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane Phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane; tetrachlorosilane Tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, Diphenyldimethoxysilane, diphenyldiethoxysilane;
Phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane, tri-t-butoxyhydrosilane; vinyl Trichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, Trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropro Lutri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycyl Sidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane , Γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane;
γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-butoxy Silane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltrit -Butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; and partial hydrolysates thereof; And mixtures thereof can be used.
[0136]
  As the binder, polysiloxane containing a fluoroalkyl group can be particularly preferably used. Specifically, one or more of the following hydrocondensation condensates and cohydrolysis condensates of fluoroalkylsilanes can be used. And those generally known as fluorine-based silane coupling agents can be used.
[0137]
  CF_Three(CF₂)_ThreeCH₂CH₂Si (OCH_Three)_Three;
  CF_Three(CF₂)_FiveCH₂CH₂Si (OCH_Three)_Three;
  CF_Three(CF₂)₇CH₂CH₂Si (OCH_Three)_Three;
  CF_Three(CF₂)₉CH₂CH₂Si (OCH_Three)_Three;
  (CF_Three)₂CF (CF₂)_FourCH₂CH₂Si (OCH_Three)_Three;
  (CF_Three)₂CF (CF₂)₆CH₂CH₂Si (OCH_Three)_Three;
  (CF_Three)₂CF (CF₂)₈CH₂CH₂Si (OCH_Three)_Three;
  CF_Three(C₆H_Four) C₂H_FourSi (OCH_Three)_Three;
  CF_Three(CF₂)_Three(C₆H_Four) C₂H_FourSi (OCH_Three)_Three;
  CF_Three(CF₂)_Five(C₆H_Four) C₂H_FourSi (OCH_Three)_Three;
  CF_Three(CF₂)₇(C₆H_Four) C₂H_FourSi (OCH_Three)_Three;
  CF_Three(CF₂)_ThreeCH₂CH₂SiCH_Three(OCH_Three)₂;
  CF_Three(CF₂)_FiveCH₂CH₂SiCH_Three(OCH_Three)₂;
  CF_Three(CF₂)₇CH₂CH₂SiCH_Three(OCH_Three)₂;
  CF_Three(CF₂)₉CH₂CH₂SiCH_Three(OCH_Three)₂;
  (CF_Three)₂CF (CF₂)_FourCH₂CH₂SiCH_Three(OCH_Three)₂;
  (CF_Three)₂CF (CF₂)₆CH₂CH₂SiCH_Three(OCH_Three)₂;
  (CF_Three)₂CF (CF₂)₈CH₂CH₂SiCH_Three(OCH_Three)₂;
  CF_Three(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂;
  CF_Three(CF₂)_Three(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂;
  CF_Three(CF₂)_Five(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂;
  CF_Three(CF₂)₇(C₆H_Four) C₂H_FourSiCH_Three(OCH_Three)₂;
  CF_Three(CF₂)_ThreeCH₂CH₂Si (OCH₂CH_Three)_Three;
  CF_Three(CF₂)_FiveCH₂CH₂Si (OCH₂CH_Three)_Three;
  CF_Three(CF₂)₇CH₂CH₂Si (OCH₂CH_Three)_Three;
  CF_Three(CF₂)₉CH₂CH₂Si (OCH₂CH_Three)_Three;and
  CF_Three(CF₂)₇SO₂N (C₂H_Five) C₂H_FourCH₂Si (OCH_Three)_Three.
[0138]
  By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the ink repellency before changing the wettability of the photocatalyst containing layer is increased, so the difference in wettability before and after changing the wettability is reduced. It can be taken big.
[0139]
  In addition, examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.
[0140]
[Chemical 1]

[0141]
  However, n is an integer greater than or equal to 2, R¹, R²Each represents a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less of the total is vinyl, phenyl or phenyl halide in a molar ratio. R¹, R²Is preferably a methyl group because the surface energy becomes the smallest, and the methyl group is preferably 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.
[0142]
  In addition to the above organopolysiloxane, a stable organosilicon compound that does not undergo a crosslinking reaction, such as dimethylpolysiloxane, may be mixed in the binder.
[0143]
  In addition to the above-mentioned photocatalyst and binder, the photocatalyst-containing layer can contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176 can be used, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0144]
  In addition to the above surfactants, the photocatalyst-containing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. It can be included.
[0145]
  The content of the photocatalyst in the photocatalyst containing layer can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.
[0146]
  As the solvent for dissolving and dispersing the above components, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.
[0147]
  b) A photocatalyst-containing layer is provided under the wettability variable layer to increase the hydrophilicity of the wettability variable layer.
  In order to form this type of wettability variable layer, first, a coating solution in which a binder and a photocatalyst are dissolved and dispersed is applied on a transparent substrate of a color filter, and then subjected to hydrolysis or polycondensation reaction to contain a photocatalyst. A layer is formed, or a photocatalyst containing layer of a single photocatalyst is formed. Next, a thin film wettability variable layer made of a hydrophobic organic material is formed on the photocatalyst-containing layer. As the photocatalyst, the binder, the solvent, or the like, the same one as used in the above type a) may be used.
[0148]
  For the formation of the organic thin film, a film forming method using a gas phase such as application of a solution, surface graft treatment, surfactant treatment, PVD, or CVD can be used. As the organic substance, a low molecular compound, a high molecular compound, a surfactant, or the like whose wettability is changed by a photocatalyst can be used. Specifically, it is a silane compound in which an organic group changes to a hydroxyl group by the action of a photocatalyst, and includes a silane coupling agent, chlorosilane, alkoxysilane, or two or more of these hydrolytic condensates and cohydrolytic condensates. be able to.
[0149]
  In addition, the wettability variable layer illustrated above is a photocatalyst containing layer in which the wettability variable layer itself contains a photocatalyst, or includes a photocatalyst containing layer provided on the transparent substrate side of the wettability variable layer. The photocatalyst containing layer is irradiated with light to activate the photocatalyst, and the wettability is changed in the direction of increasing hydrophilicity by the action of the activated photocatalyst. That is, all of the exemplified wettability variable layers change wettability in the direction in which hydrophilicity increases when irradiated with light.
[0150]
  However, in the present invention, the wettability variable layer is not particularly limited as long as the wettability of the surface can be changed by an external stimulus such as a physical stimulus or a chemical stimulus. For example, the surface roughness may be changed by acid or alkali, and the wettability may be changed. The wettability variable layer may be formed by irradiation with energy such as ultraviolet rays, visible light, or heat. It may be a layer or the like in which the wettability is changed by changing the substance inside.
[0151]
  In addition, the photocatalyst-containing layer used in the exemplified method increases the hydrophilicity by irradiating the pixel portion formation region with light, and selectively adheres the thermosetting ink composition of the second invention. The thermosetting of the second invention is also achieved by providing a wettability variable layer on the transparent substrate of the color filter so that the hydrophilicity is reduced by the stimulus, and giving a stimulus that changes the wettability to the negative pattern shape of the pixel portion formation region. It is possible to selectively adhere the ink composition to only a desired region.
[0152]
  Next, it is the thermosetting ink composition for color filters of 2nd invention, Comprising: The ink for pixel part formation of each color formed by mix | blending 1 or 2 or more colorants is prepared. Then, the pixel portion forming ink of the corresponding color is selectively attached to the pixel portion forming regions 4R, 4G, and 4B whose hydrophilicity has been increased in the step of FIG. Ink layers 6R, 6G, and 6B as shown in FIG.
[0153]
  The pixel portion forming ink can be attached to the pixel portion forming region by any method such as printing, but as shown in FIG. 2D, it is preferably sprayed onto the pixel portion forming region by an ink jet method. The thermosetting ink composition of the second invention is excellent not only in the pixel portion forming ink but also in suitability for the ink jet system. Therefore, the thermosetting ink composition of the second invention can be adhered accurately and uniformly by spraying a predetermined pattern formation region with increased wettability by changing wettability by an ink jet method. It is possible to form a pixel portion having no color unevenness or color loss with an accurate pattern. In addition, since the pixel portion forming ink of each color can be simultaneously sprayed onto the substrate using the plurality of heads 5, the working efficiency can be improved as compared with the case where the pixel portion is formed for each color.
[0154]
  Next, as shown in FIG. 2E, the ink layers 6R, 6G, and 6B of the respective colors are dried as necessary, and then heated and cured to form pixel portions. Next, as shown in FIG. 2F, the protective layer 9 is formed on the side of the transparent substrate on which the pixel portions 8R, 8G, and 8B are formed. The thermosetting process and the protective layer forming process in the second invention as shown in FIGS. 2E and 2F can be performed in the same manner as in the first invention.
[0155]
  Thus, the color filter 101B is manufactured using the thermosetting ink composition for color filters of the second invention. In this example, the pixel portion is formed by using the pixel portion forming ink which is the thermosetting ink composition for the color filter of the second invention, but the thermosetting ink composition for the color filter of the second invention, By selectively adhering only to the ink-philic region using the difference in wettability of the substrate surface, a hardened layer other than the pixel portion, for example, the light-shielding layer 2 or the ink-repellent convex portion 3 is formed in a desired pattern. It can also be formed into a shape.
[0156]
  When it is desired to form the light-shielding layer 2, first, a thermosetting ink composition for color filters according to the second invention, which is prepared by blending a light-shielding colorant such as a black pigment, is prepared. Next, the wettability changing layer 10 is formed on the transparent substrate 1, the wettability of the region where the light shielding layer is to be formed is changed to increase the hydrophilicity, and the light shielding layer forming ink prepared in advance is used. In addition, the ink layer is formed in a predetermined pattern by selectively adhering to the light-shielding layer forming region having increased hydrophilicity (ink affinity) by a method such as inkjet, and the ink layer is heated and cured to shield the light. Layers can be formed.
[0157]
  In addition, when it is desired to form the ink-repellent convex portion 3, first, the thermosetting ink composition for a color filter according to the second invention, which is formed by blending an ink-repellent binder. Prepare the ink. Next, the light shielding layer 1 and the wettability changing layer 10 are sequentially formed on the transparent substrate 1. Next, an ink-repellent convexity formation region in which wettability is changed is formed in the center of the upper surface of the light shielding layer 2 in a pattern shape narrower than the light shielding layer 2 along the longitudinal direction of the light shielding layer 2. To do. Next, the ink layer is selectively attached to the ink-repellent convexity forming region having increased hydrophilicity (ink affinity) by a method such as inkjet to form an ink layer, and the ink layer is heated. The ink repellent convex part 3 can be formed by hardening.
【Example】
[0158]
  Example 1
  (1) Preparation of coating solution for photocatalyst containing layer
  The following components were mixed and stirred at 100 ° C. for 20 minutes to prepare a photocatalyst-containing layer coating solution.
<Composition of coating solution for photocatalyst containing layer>
・ Isopropyl alcohol: 3g
Fluoroalkylsilane (MF-160E manufactured by Tochem Products: N- [3- (trimethoxysilyl) propyl] -N-ethyl-perfluorooctanesulfonamide 50% by weight isopropyl ether solution): 0.07 g
・ Titanium oxide sol (Ishihara Sangyo STK-01): 3g
・ Silica sol (Glaska HPC7002 made by Japanese synthetic rubber): 0.6g
・ Alkoxyalkoxysilane (HPC402C made by Nippon Synthetic Rubber): 0.2g
  (2) Formation of photocatalyst containing layer
  The above photocatalyst-containing layer coating solution is applied on a transparent substrate made of soda glass having a black matrix made of a chromium thin film pattern having an opening of 76 μm × 259 μm and a line width of 23 μm, using a spin coater, at 150 ° C. for 10 minutes. After the drying treatment, hydrolysis and polycondensation reactions were advanced to form a transparent photocatalyst-containing layer having a thickness of 0.5 μm in which the photocatalyst was firmly fixed in the organopolysiloxane.
[0159]
  This photocatalyst-containing layer is 70 mW / cm by a mercury lamp (wavelength 365 nm) through a mask.²A light beam was irradiated for 3 minutes at an illuminance of 1, and the contact angle of the non-irradiated part and the irradiated part with water was measured. The contact angle was measured using a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science Co., Ltd.), 30 seconds after dropping water droplets from the microsyringe to the non-irradiated site or irradiated site. As a result, the contact angle of water at the non-irradiated part is 70 °, whereas the contact angle of water at the irradiated part is 10 ° or less, and the irradiated part becomes highly hydrophilic, so that the non-irradiated part and the irradiated part are not irradiated. It was confirmed that pattern formation was possible using the difference in wettability with the part.
[0160]
  Furthermore, using the standard solution shown in the wetting test specified in JIS K6768, the droplet was brought into contact with the non-irradiated portion of the surface of the photocatalyst containing layer, the contact angle (θ) after 30 seconds was measured, (Horizontal axis: surface tension of standard solution, vertical axis: cos θ) Extrapolated from the graph, the surface tension indicated by the point where cos θ = 0, that is, the critical surface tension of the non-irradiated site is 30 mN / m was. The critical surface tension at the irradiated site was measured by the same method and found to be 70 mN / m.
[0161]
  (3) Exposure of photocatalyst containing layer
  A mask having a light shielding pattern having a pattern pitch of 76 μm × 259 μm and a width (10 μm) narrower than the line width (23 μm) of the black matrix is disposed on the photocatalyst containing layer of the transparent substrate and overlaps the black matrix After alignment, the mercury lamp (wavelength 365 nm) was passed through this mask to 70 mW / cm.²The photocatalyst-containing layer was exposed at an illuminance of 50 seconds to make the irradiated portion highly hydrophilic. Each irradiation site is partitioned by a non-irradiated portion having a width of 10 μm existing on the black matrix, and has a pixel portion forming region of a size of 76 μm × 259 μm surrounded by the black matrix and a region overlapping with the surrounding black matrix. Was.
[0162]
  (4) Preparation of colored ink for pixel portion
  Among the following components, first, a pigment, a polymer dispersant, and a solvent were mixed, and a pigment dispersion was obtained using a three roll and bead mill. While sufficiently stirring the pigment dispersion with a dissolver or the like, other materials were added little by little to prepare a color pixel colored ink.
<Composition of colored ink for red pixel part>
Pigment (CI Pigment Red 254): 5 parts by weight
・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA): 1 part by weight
・ Binder (glycidyl methacrylate-styrene copolymer): 3 parts by weight
First epoxy resin (Novolac type epoxy resin, Epicoat 154 manufactured by Yuka Shell): 2 parts by weight
Second epoxy resin (neopentyl glycol diglycidyl ether): 5 parts by weight
・ Curing agent (trimellitic acid): 4 parts by weight
Solvent: ethyl 3-ethoxypropionate: 80 parts by weight
  Among the above components, ethyl 3-ethoxypropionate, which is a solvent, uses a standard solution shown in a wetting test specified in JIS K6768, and measures a contact angle (θ) after 30 seconds from contact with a droplet. The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined by the Zisman plot graph is 18 °, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m is 0 °. Met.
[0163]
  Further, neopentyl glycol diglycidyl ether as the second epoxy resin has a contact angle of 37 ° with respect to the surface of the test piece having a critical surface tension of 30 mN / m and a critical surface tension of 70 mN / m in the same test. The contact angle with respect to the surface of the test piece was 0 ° C.
[0164]
  Further, C.I. I. Pigment Red 254 instead of C.I. I. A green-red pixel portion colored ink was prepared in the same manner as the red pixel portion colored ink except that the same amount of pigment green 36 was used. Further, C.I. I. Pigment Red 254 instead of C.I. I. A colored ink for a blue pixel portion was prepared in the same manner as in the case of the colored ink for a red pixel portion except that the same amount of pigment blue 15: 6 was used.
[0165]
  (5) Manufacture of color filters
  The colored ink for the red pixel portion was dropped from the head onto the center of each pixel portion forming region for red with a dot diameter of 30 μm. Similarly, the coloring ink for green pixel portions was dropped from the head to the center of each pixel portion forming region for green with a dot diameter of 30 μm. Further, the blue pixel portion colored ink was dropped from the head onto the center of each blue pixel portion forming region with a dot diameter of 30 μm. The dropped colored ink for the pixel portion of each color was repelled by the non-irradiated portion on the black matrix, and was uniformly diffused and selectively adhered in the pixel portion forming region of each color.
[0166]
  Thereafter, the colored ink layer of each color was vacuum-dried at 80 ° C. for 3 minutes and then cured by heating in an oven at 200 ° C. for 60 minutes to form a pixel portion.
[0167]
  Next, a two-component mixed thermosetting agent (SS7265 manufactured by Nippon Synthetic Rubber Co., Ltd.) is applied onto the pixel portion with a spin coater, cured at 200 ° C. for 30 minutes to form a protective layer, and a color filter Got.
[0168]
  (Example 2)
  (1) Preparation of colored ink for pixel portion
  Colored ink for red pixel part (red inks 2-1 and 2-2) having the following composition was prepared. For both colored inks, first, a pigment, a polymer dispersant and a solvent are mixed, a pigment dispersion is prepared using a three roll and a bead mill, and the pigment dispersion is sufficiently stirred with a dissolver or the like. Other materials were added little by little to prepare a color pixel colored ink.
<Composition of colored ink 2-1 for red pixel portion>
  As the red ink 2-1, the same colored ink for red pixel portion as that prepared in Example 1 was used as it was.
<Composition of colored ink 2-2 for red pixel portion>
Pigment (CI Pigment Red 254): 5 parts by weight
・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA): 1 part by weight
Binder (glycidyl methacrylate-styrene copolymer): 7 parts by weight
First epoxy resin (Novolac type epoxy resin, Epicoat 154 manufactured by Yuka Shell): 3 parts by weight
・ Curing agent (trimellitic acid): 4 parts by weight
Solvent: ethyl 3-ethoxypropionate: 80 parts by weight
  (2) Measurement of viscosity
  The viscosity of each red ink was measured at a temperature of 20 ° C. using a viscosity measuring device VIBROVISCOMETER CJV5000 (manufactured by A & D).
[0169]
  (2) Discharge property test
  Each red ink is filled into an ink jet head, ejected from the head, a photocatalyst containing layer is provided in the same manner as in Example 1, and the red pixel portion forming region of the glass transparent substrate exposed in a predetermined pattern is used. It was dripped at the central part with a drop diameter of 30 μm. Further, after the initial ejection was stopped and the head was allowed to stand still for 1 minute, it was dropped from the same head onto the center of another red pixel portion formation region with a drop diameter of 30 μm. In such intermittent discharge, the discharge performance (initial discharge performance) at the time of the first discharge operation and the discharge performance (intermittent discharge stability) at the time of re-discharge are observed and evaluated according to the following criteria. did.
<Evaluation criteria for initial ejection properties>
○: Ink can be ejected from all holes of the head.
Δ: There are some holes in the head where ink does not come out.
X: Ink does not come out from most holes in the head.
<Evaluation criteria for intermittent discharge stability>
○: Ink can be re-discharged from all holes of the head that were able to be discharged in the initial stage.
Δ: There are some holes in the head where ink does not come out.
X: Ink does not come out from most holes in the head.
[0170]
  (3) Results of Example 2
  As shown in Table 1, the red ink 2-1, which is a combination of a bi- or trifunctional epoxy group-containing monomer and a tetrafunctional or higher functional epoxy group-containing resin, has a low initial viscosity and an initial ejection property and intermittent ejection stability. Both were good. On the other hand, the red ink 2-2 that uses only a tetrafunctional or higher epoxy group-containing resin has a relatively high initial viscosity, and both the initial discharge property and the intermittent discharge stability are inferior to the red ink 2-1. It was. However, the red ink 2-2 uses the same solvent as the red ink 2-1, and diffused uniformly without protruding from the red pixel portion formation region.
[0171]
[Table 1]

[0172]
  (Example 3)
  (1) Preparation of colored ink for pixel portion
  Colored ink for red pixel part (red inks 3-1 and 3-2) having the following composition was prepared. For both colored inks, first, a pigment, a polymer dispersant and a solvent are mixed, a pigment dispersion is prepared using a three roll and a bead mill, and the pigment dispersion is sufficiently stirred with a dissolver or the like. Other materials were added little by little to prepare a color pixel colored ink.
[0173]
  In addition, as measured in Example 1 for the red ink 3-1, the surface of the test piece having a critical surface tension of 30 mN / m and the test piece having a critical surface tension of 70 mN / m for the red ink 3-2. The contact angle with respect to the surface of was measured.
<Composition of colored ink 3-1 for red pixel portion>
  As the red ink 3-1, the same colored ink for red pixel portion as that prepared in Example 1 was used as it was.
<Composition of colored ink 3-2 for red pixel portion>
  The composition is the same as that of the red ink 3-1, except that the same amount of octane was used instead of 78 parts by weight of ethyl 3-ethoxypropionate.
[0174]
  (2) Pattern formation test
  A photocatalyst-containing layer was formed on a soda glass transparent substrate in the same manner as in Example 1. This photocatalyst-containing layer was exposed in a stripe shape having a width of 10 μm in the unexposed area and a width of 89 μm in the exposed area, and each red ink was discharged from the inkjet head to the irradiated area under the following discharge conditions.
<Discharge conditions>
・ Drop diameter: 30μm
・ Head frequency: 2000Hz
-Substrate feed speed: 50 mm / sec.
  The extent of spreading of the red ink when such discharge was performed was observed and evaluated according to the following criteria.
<Evaluation criteria for pattern formation>
○: The red ink spreads sufficiently to the irradiated area, and the ink does not protrude to the non-irradiated area.
X: Ink is applied and spreads to a non-irradiated site or an adjacent irradiated site.
[0175]
  (3) Results of Example 3
  The results of Example 3 are shown in Table 2. As described in Example 1, the red ink 3-1 has a large difference between the contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m. And good pattern formation was shown. On the other hand, the red ink 3-2 using octane as a solvent has no difference in the contact angle with respect to each of the above test pieces, and can be selectively attached to the irradiated portion of the wettability variable layer used this time. There wasn't. However, the red ink 3-2 uses a combination of a bi- or trifunctional monomer and a tetrafunctional or higher epoxy group-containing resin in the same manner as the red ink 3-1, and has an initial ejection property and intermittent ejection stability from an inkjet head. Both were good.
[0176]
[Table 2]

【The invention's effect】
[0177]
  As described above, in the first invention of the present invention, since a bifunctional to trifunctional epoxy group-containing monomer is used as a thermosetting component in the thermosetting ink composition for a color filter, ink jet spraying is performed. During the work, the viscosity at the tip of the head hardly increases, the head is not clogged, and the ink discharge performance during the work is stabilized. Therefore, the discharge amount and discharge direction of the ink are kept constant, and the ink can be adhered to the substrate accurately and uniformly according to a predetermined pattern.
[0178]
  In the second invention of the present invention, the standard solution shown in the wetting test specified in JIS K6768 is used as the solvent of the thermosetting ink composition for color filters, and after 30 seconds from contact with the droplets. The contact angle (θ) was measured and the critical surface tension obtained from the Zisman plot graph was 10 ° or more with respect to the surface of the test piece having a critical surface tension of 30 mN / m, and the critical surface tension obtained by the same measurement method. Is a predetermined pattern formed by changing the wettability of a part of the surface of the wettability variable layer in the direction in which the hydrophilicity increases, because the contact angle with respect to the surface of the test piece of 70 mN / m is 10 ° or less. The difference between the wettability of the thermosetting ink composition with respect to the ink layer forming region and the wettability of the thermosetting ink composition with respect to the surrounding region can be greatly increased. Therefore, the thermosetting ink composition for color filters of the second invention can be adhered accurately and uniformly to the ink layer forming region.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of a method for producing a color filter using the ink composition of the first invention.
FIG. 2 is an explanatory diagram of a method for producing a color filter using the ink composition of the second invention.
[Explanation of symbols]
  1 ... Transparent substrate
  2. Shading part
  3. Ink-repellent convex part
  4 ... Pixel part formation region
  5 ... Inkjet head
  6 ... Ink layer
  7 ... Light
  8 ... Pixel part
  9 ... Protective film
  10 ... Photocatalyst containing layer
  11 ... Photomask
  12: Exposure part

Claims (7)

(1) forming a wettability variable layer capable of changing wettability in a direction in which hydrophilicity increases on a substrate;
(2) selectively changing the wettability in a predetermined region on the surface of the wettability variable layer to form an ink layer forming region having a higher hydrophilicity than the surroundings;
(3) Using the standard solution shown in the wetting test specified in JIS K6768 for the ink layer formation region, the contact angle (θ) after 30 seconds was measured after contacting the droplet, and the graph of the Zisman plot The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined by the above is 10 ° or more, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method is ° Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, dimethyl adipate, diethyl adipate Dimethyl succinate, dimethyl glutarate, dimethyl malonate, diethyl malonate, or, in a solvent comprising only mixtures thereof, at least a binder and dissolving the thermosetting component or dispersed allowed for color filters thermosetting inkjet ink composition comprising A step of selectively attaching an object by an ink jet method to form an ink layer;
(4) a step of curing the ink layer by heating to form a cured layer of a predetermined pattern;
A method for producing a color filter, comprising: The method for producing a color filter according to claim 1, wherein the thermosetting inkjet ink composition for a color filter further contains a colorant. The thermosetting component was obtained from a Zisman plot graph by measuring the contact angle (θ) 30 seconds after the droplet was brought into contact with the standard solution shown in the wetting test specified in JIS K6768. The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m is 10 ° or more, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 10 ° or less. The manufacturing method of the color filter of Claim 1 or 2 characterized by the above-mentioned. The manufacturing method according to claim 2 , wherein the pixel portion as the cured layer is formed using the thermosetting ink composition for a color filter according to claim 2 . The wettability variable layer is obtained by measuring the contact angle (θ) after 30 seconds of contact with a droplet using the standard solution shown in the wetting test specified in JIS K6768, and obtaining it from the graph of the Zisman plot. critical surface tension was found before changing the wettability indicates 10~50mN / m, and, after the changing the wettability, characterized in that it presents a 40~80mN / m, to claim 1 4. The production method according to any one of 4 above. The manufacturing method according to claim 1 , wherein the wettability variable layer changes wettability in a direction in which hydrophilicity increases when irradiated with light. The wettability variable layer is a photocatalyst-containing layer in which the wettability variable layer itself contains a photocatalyst, or includes the photocatalyst-containing layer provided on the substrate side of the wettability variable layer. the photocatalyst activated by irradiating light to the containing layer, characterized in that the action of the activated the photocatalyst, thereby changing the wettability in the direction of hydrophilicity increases, according to claim 6 Manufacturing method.

Images