JP2004302245A - Resist material for color filter and color filter - Google Patents
Resist material for color filter and color filter Download PDFInfo
- Publication number
- JP2004302245A JP2004302245A JP2003096466A JP2003096466A JP2004302245A JP 2004302245 A JP2004302245 A JP 2004302245A JP 2003096466 A JP2003096466 A JP 2003096466A JP 2003096466 A JP2003096466 A JP 2003096466A JP 2004302245 A JP2004302245 A JP 2004302245A
- Authority
- JP
- Japan
- Prior art keywords
- color filter
- solvent
- resist material
- meth
- surface tension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、カラーフィルター用レジスト材料及びカラーフィルターに関するものである。詳しくは、カラーフィルターの着色硬化膜を形成する塗膜形成材料とこれを用いて得られるカラーフィルターに関するものである。
【０００２】
【従来の技術】
カラー液晶表示装置に使われるカラーフィルターは、感光性樹脂に光重合開始剤や各種添加剤と赤色（Ｒ）、緑色（Ｇ）、青色（Ｂ）の各着色剤を加えた後、溶剤によってこれら樹脂成分等の濃度等を調整したカラーレジストを塗布、乾燥後、一連の工程によりパターンをフォトリソ法などで形成したものが知られている。その際、塗布工程に於いては一般にスピンコーター、スリット＆スピンコーター、スリットコーター、ロールコーター、バーコーターなどによる塗工が行われ、均一な塗布板を得ており、これを真空乾燥もしくは加熱乾燥により塗布膜を作成している。この時、塗布膜の面内に於いて塗布ムラに伴う色調ムラの発生はカラーフィルターの欠陥となる。
【０００３】
カラーフィルターは、通常スピンコーター、スリット＆スピンコーター、スリットコーター、ロールコーター、バーコーター等の塗布装置を用いて塗布されたのち、溶剤を除くためにオーブンやホットプレートで加熱乾燥するか、減圧乾燥装置で減圧乾燥を行い、均一な塗膜を形成した後パターンを露光、現像する。この乾燥工程の際、オーブンやホットプレートを使用する場合には、均一な加熱が行なわれず熱ムラが発生する。その結果、カラーフィルターの表示領域に雲状のムラが発生し、表示品位を落とす。一方、減圧乾燥による場合は急激な溶剤の揮発により蒸発ムラが発生し、オーブンやホットプレートを用いた場合と同様、カラーフィルターの表示領域に雲状のムラが発生する。そして、この雲状のムラは最終硬化工程後も存続する。
【０００４】
このような塗布ムラの発生傾向は、単一の溶剤を用いた場合に特に顕著である。そこで、従来より、塗布性を向上させるため高沸点の溶剤との併用が行われてきている。これは溶剤の蒸発速度を緩慢にして表面部分のみが先に乾燥する「革張り」と呼ばれる状態を回避し、全体的に均一に乾燥膜が形成されるようにする手段である。しかしながら、高沸点溶剤を併用した場合には、乾燥時間が長くなるほか、乾燥膜表面にタックが残りやすくなり、その結果、異物も付着しやすい。例えば、スピンコートによる保護膜膜厚の不均一性を防止するため、高沸点の溶剤を用いて、塗布時の溶剤蒸発を抑制する方法が、特許文献１に提案されている。しかし、この方法は沸点１９０℃以上の溶剤を全溶剤の３０〜６０重量％含むため、真空乾燥時の乾燥時間が長くなるほか、膜表面にタックが残りやすくなり、その結果、異物も付着しやすいという欠点を有する。
【０００５】
一方、一般に、塗布性の向上のためには界面活性剤の添加が有効であることが知られている。界面活性剤は、乾燥時に生じる「ベナードセル」などの蒸発ムラを防止するために添加される。すなわち、これは表面張力を低い値で安定させることで溶剤蒸発時に発生する膜内の表面張力の変化を防止して「ベナードセル」などを発生し難くするものである。しかしながら、表面張力の低下はスピンコート時のガラス基板周辺部におけるレジスト液の戻りが生じ易く、塗布ムラとレジスト液の戻り幅のバランスをとり難いという問題がある。このような事情から、カラーフィルター用レジスト材料として、膜内の表面張力を極端に低下させず、均一に維持する手法が望まれていた。
【０００６】
なお、エポキシ（メタ）アクリレート化合物等の光重合性化合物、光重合開始剤、着色剤を主成分とする材料を溶剤に溶解してなるカラーフィルター用レジスト材料は、特許文献２等において知られている。
【特許文献１】
特開２０００−８６９０６号公報
【特許文献２】
特開平６−１９３８号公報
【０００７】
【発明が解決しようとする課題】
本発明の目的は、従来のカラーフィルター用レジスト材料の欠点を解消し、塗布ムラが生じにくく、塗布性に優れたカラーフィルター用レジスト材料を提供することを目的とする。また、本発明はこのカラーフィルター用レジスト材料から得られる硬化膜、及びこの硬化膜を有するカラーフィルターを提供することでもある。
【０００８】
【課題を解決するための手段】
本発明者らは、上述の問題点を解決すべく鋭意検討を行った結果、カラーフィルター用レジスト材料に使用する溶剤として、２種以上の溶剤を用い、その表面張力に注目し、これを制御することで塗布ムラ、塗布性が改善され、色調ムラが解消されたカラーフィルター硬化膜を形成し得ることを見出し本発明を完成した。
【０００９】
すなわち、本発明は、エポキシ（メタ）アクリレート化合物（Ａ１）を必須成分とする光重合性化合物（Ａ）、光重合開始剤（Ｂ）、着色剤（Ｃ）を主成分とする樹脂成分等を溶剤（Ｄ）に溶解してなるカラーフィルター用レジスト材料において、溶剤（Ｄ）は沸点の異なる２種以上の有機溶剤を含み、かつ溶剤中に１ｗｔ％以上含まれる有機溶剤の内、表面張力値が最大の有機溶剤と表面張力値が最小の有機溶剤の表面張力値の差が３ｄｙｎ／ｃｍ以内であることを特徴とするカラーフィルター用レジスト材料である。
【００１０】
ここで、有機溶剤の少なくとも１種が１６０℃以下の低沸点溶剤であり、それの溶剤中の含有量が５０ｗｔ％以上であること、又は、エポキシ（メタ）アクリレート化合物（Ａ１）が、下記一般式（１）
【化３】
【化４】
【００１１】
更に、本発明は、前記のカラーフィルター用レジスト材料を塗布、乾燥、硬化して得られるカラーフィルター硬化膜である。また、本発明は、前記のカラーフィルター硬化膜を有するカラーフィルターである。
【００１２】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明のカラーフィルター用レジスト材料は、光重合可能な成分を必須成分として含む樹脂成分等（溶剤以外の成分をいう）を、溶剤に溶解した溶液である。この樹脂成分等は、（Ａ）成分：エポキシ（メタ）アクリレート化合物（Ａ１）成分を必須とする光重合性化合物、（Ｂ）成分：光重合開始剤及び（Ｃ）成分：着色剤を主成分とする。かかる樹脂成分等は特許文献２等により公知であり、これらに記載されたものが広く使用できる。具体的には、次のような各成分が使用できる。
【００１３】
（Ａ１）成分であるエポキシ（メタ）アクリレート化合物としては、各種ジグリシジルエーテルと（メタ）アクリル酸との付加化合物あるいは各種ビスフェノールジグリシジルエーテルと（メタ）アクリル酸との付加化合物であるジヒドロキシプロピルアクリレート樹脂、又はこれに多価カルボン酸又はその酸無水物を反応させて得られる化合物を例示することができる。
【００１４】
グリシジルエーテルは、エチレングリコール、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、水添ビスフェノールＡ、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）スルホン、２，２−ビス（４−ヒドロキシフェニル）プロパン、ビス（４−ヒドロキシフェニル）エーテル、ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパン、９，９−ビス（４−ヒドロキシフェニル）フルオレン、ビス（４−ヒドロキシフェニル）ジメチルシラン、４，４’−ビフェノール等のジオール化合物から誘導されるものが例示され、本発明では、これらジグリシジルエーテルと（メタ）アクリル酸との付加化合物をエポキシ（メタ）アクリレート化合物として用いることができる。
【００１５】
レジスト材料にアルカリ可溶性を付与するためには、エポキシ（メタ）アクリレート化合物中にカルボキシル基を有していることが好ましく、その他、レジスト材料としての特性等を考慮すると、上記一般式（１）で表されるエポキシ（メタ）アクリレート化合物と多塩基酸又はその酸無水物とを反応させて得られる不飽和基含有化合物が好ましい。ここで、Ｘとしては上記した基が好ましく挙げられる。
【００１６】
多塩基酸又はその酸無水物としては、マレイン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、ビフェニルエーテルテトラカルボン酸、ジフェニルスルホンテトラカルボン酸及びこれらの酸の無水物が例示できる。
【００１７】
本発明においては、光重合性化合物である（Ａ）成分には、上記（Ａ１）成分の他、必要に応じて他の光重合性モノマーやオリゴマー等の光重合性化合物（Ａ２）を添加できる。使用される他の光重合性のモノマーやオリゴマーとしては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等の水酸基を有するモノマーや、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、テトラメチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、グリセロール（メタ）アクリレート等の（メタ）アクリル酸エステル類等を挙げることができ、これらはその１種のみを単独で用いてもよく、また、２種以上を併用することもできる。
【００１８】
（Ａ）成分として、（Ａ１）成分と共に（Ａ２）成分を使用する場合は、その使用量は本発明のレジスト材料（インクということがある）の性質を損なわない範囲で選択することができるが、（Ａ１）成分の１００重量部に対して、（Ａ２）成分２５〜１００重量部の範囲が望ましい。
【００１９】
更に、本発明では、カラーレジストの他の性能を阻害しない範囲でアルカリ物質等への耐性を付与するためエポキシ樹脂を添加しても良い。エポキシ樹脂としては、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、脂環式エポキシ樹脂等を代表的なものとして例示することができる。エポキシ樹脂を使用する場合、その添加量は（Ａ）成分１００重量部に対して０〜３０重量部であり、５〜２０重量部が最も良好である。
【００２０】
（Ｂ）成分の光重合開始剤としては、アセトフェノン、ｐ−ｔｅｒｔ−ブチルアセトフェノン等のアセトフェノン類、ベンゾフェノン、２−クロロベンゾフェノン、ｐ，ｐ’−ビス（ジメチルアミノ）ベンゾフェノン等のベンゾフェノン類、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインブチルエーテル等のベンゾインエーテル類、２−メチル−１ ［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１等のα−アミノアルキルフェノン類、ビス（２，４，６−トリメチルベンゾイル）−フェニル−ホスファイン−オキサイド等のビスアシルフォスフィンオキサイド類、Ｎ−フェニルグリシン等のグリシン類、２，４−トリクロロメチル−（ピぺロニル）−６−トリアジン、２，４− トリクロロメチル−（４’−メトキシスチリル）−６−トリアジン等のトリアジン類が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。また、本発明における光重合開始剤は、ｐ−ジメチルアミノ安息香酸イソアミルエステル、ｐ−ジメチルアミノ安息香酸エチルエステル等の公知の光重合促進剤（増感剤）と併用することもできる。
【００２１】
なお、本発明で用いる（Ｂ）成分の光重合開始剤や光重合促進剤（増感剤）は、（Ａ１）成分ばかりでなく、必要に応じて配合される他の光重合性のモノマーやオリゴマー等の（Ａ２）成分の光重合開始剤としても用いられるものである。したがって、（Ｂ）成分の使用量は、（Ａ１）成分１００重量部に対して、５〜２５重量部であることが好ましいが、（Ａ１）成分の他に（Ａ２）成分を使用する場合にはこれらの合計量１００重量部に対して、１〜１５重量部使用することが好ましい。
【００２２】
（Ｃ）成分の着色剤は、顔料を含む着色剤であることが好ましい。具体的には、顔料とこれを微細分散し安定化させるのに必要な分散剤等との顔料組成物である。顔料には、有機顔料と無機顔料がある。有機顔料としては、アゾレーキ系、不溶性アゾ（ＰＹ−１５０）系、フタロシアニン系（ＰＧ−７、ＰＧ−３６＆ＰＢ−１５．６）、キノフタロン系（ＰＹ１３８）、キナクドリン系、ジオキサジン（ＰＶ−２３）系、イソインドリノン（ＰＹ−１３９）系、ベリノン系、アントラキノン（ＰＲ−１７７）系、ピロロピロール系（ＰＲ−２５４）、ペリレン系等が例示され、これらを併用することもできる。また、無機顔料としてはミロリブルー、酸化鉄、コバルト系、マンガン系、群青、紺青、コバルトブルー、セルリアンブルー、ピリジアン、エメラルドグリーン、コバルトグリーン等が例示され、これらを併用することもできる。これらの顔料については、塗膜の透明性を維持しつつ着色するために、可視光の波長の下限である０．４μｍ以下の平均粒子径に分散されることが好ましい。実用的に好ましい平均粒子径範囲は０．２〜０．３μｍである。
【００２３】
本発明のレジスト材料は、前記（Ａ）、（Ｂ）及び（Ｃ）成分を主成分とする樹脂成分等を溶剤に溶解してなるが、この樹脂成分等は大別すると樹脂又は硬化後に樹脂を形成するモノマー等の樹脂固形分と、非樹脂系の成分があり、これらは乾燥、硬化後においても、殆どが残存する。そして、樹脂固形分には上記（Ａ）成分、他のバインダ樹脂、分散剤等の樹脂成分が含まれ得る。非樹脂系の成分には光重合開始剤や光安定剤等の添加剤、着色剤等が含まれ得る。そして、（Ｃ）成分の着色剤は樹脂固形分１００重量部に対して、５０〜２００重量部配合することが好ましい。
【００２４】
本発明においては、（Ｄ）成分の溶剤として、沸点の異なる２種以上の有機溶剤を用いる。ここで、溶剤中に１ｗｔ％以上含まれる有機溶剤の内、表面張力値が最大の有機溶剤と最小の有機溶剤の表面張力値の差（以下、Δγという）を３ｄｙｎ／ｃｍ以内の範囲とすることを必須とする。
【００２５】
有機溶剤としては、例えば、メチルエチルケトン、シクロヘキサノン、メチルシクロヘキサノン等のケトン類、メチルセロソルブ、エチルセロソルブ、セロソルブアセテート等のセロソルブ類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールｎ−プロピルエーテル、プロピレングリコールｎ−ブチルエーテル等のプロピレングリコールモノアルキルエーテル類、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールｎ−プロピルエーテルアセテート、プロピレングリコールｎ−ブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル等のジエチレングリコールジアルキルエーテル類、乳酸メチル、乳酸エチル等の乳酸エステル類、酢酸ｎ−ブチル等の酢酸エステル類の他、γ−ブチロラクトン、Ｎ−メチルピロリドン、ジメチルスルホキシド等が有用なものとして例示され、これらを前記した条件に合致するもの、すなわち、その表面張力の値が近いものを２種以上選択して併用する。
【００２６】
２溶剤系の例としては、プロピレングリコールモノメチルエーテルアセテート（ｂｐ．１４６℃、γ ２８．８）とジエチレングリコールジメチルエーテル（ｂｐ．１６２℃、γ ２９．５）のように沸点が異なり表面張力が近しい溶剤を選択する。なお、＜ｂｐ．＞は沸点を＜γ＞は物質の化学構造から計算されるパラコート値を用いて計算した表面張力の値を示す。
【００２７】
また、３溶剤系の例としては、プロピレングリコールモノメチルエーテルアセテート（ｂｐ．１４６℃、γ ２８．８）とジエチレングリコールジメチルエーテル（ｂｐ．１６２℃、γ ２９．５）ジエチレングリコールジエチルエーテル（ｂｐ．１８８℃、γ
２７．７）の様な組み合わせがある。
【００２８】
本発明において用いられる溶剤は、上記要件を満たせば、これらの混合比は任意であるが、低沸点成分が主体になる方が乾燥後にタックなどの問題を回避出来ることから好ましい。すなわち、本発明においては、全溶剤の５０重量％以上を沸点が１６０℃以下の溶剤で構成し、残りの溶剤をこれと表面張力が近いものを用いることが好ましい。溶剤が２種の溶剤からなる場合には、該低沸点溶剤との表面張力の差が３ｄｙｎ／ｃｍ以内のものを用い、３種以上溶剤を用いる場合は該低沸点溶剤を含む全溶剤がいずれも他の溶剤に対し表面張力の最大値と最小値の差が３ｄｙｎ／ｃｍ以内とする。なお、溶剤には通常不純物が微量〜少量含まれるが１ｗｔ％に満たない成分は単なる不純物として扱う。
【００２９】
この点を考慮し、上記に例示した２溶剤系及び３溶剤系での好ましい態様を示せば、例えば２溶剤系ではプロピレングリコールモノメチルエーテルアセテート１００重量部に対して、ジエチレングリコールジメチルエーテルが１〜５０重量部の範囲が望ましく、特に３５重量部以下が良好であり、また、３溶剤系では、プロピレングリコールモノメチルエーテルアセテート１００重量部に対して、ジエチレングリコールジメチルエーテル１〜５０部、ジエチレングリコールジエチルエーテル１〜２０部の範囲が望ましい。特にプロピレングリコールモノメチルエーテルアセテート１００重量部に対してジエチレングリコールジメチルエーテル１〜３５重量部、ジエチレングリコールジエチルエーテル１〜５重量部が良好である。
【００３０】
溶剤（Ｄ）の使用量は、全樹脂成分等１００重量部に対して、２５０〜６００重量部が適当である。
【００３１】
本発明のカラーフィルター用レジスト材料には、本発明の効果を損なわない範囲であれば、他の成分を含有してもよい。例えば、濡れ性の向上のためには界面活性剤が、密着性向上のためにはカップリング剤が好ましく使用される。この場合、界面活性剤は０．０１〜０．２重量％の範囲で含有させることが好ましい。
【００３２】
【実施例】
以下、実施例により本発明を、更に詳しく説明するが、本発明はこれに限定されるものではない。なお、実施例中、別段の断りがない限り、部は重量部を表し、％は重量％を表す。また、カラーフィルターレジスト膜の作成及び塗布ムラの評価は別段の断りがない限り、以下の方法による。
【００３３】
［カラーレジスト膜の作成］
ポストベーク後の膜厚が１．５±０．０５μｍとなるスピンコート条件でカラーフィルター用レジスト膜用材料を、ＳｉＯ２をコーティングしたガラス基板に塗布し、プレベーク８０℃，３分で溶剤を蒸発し、カラーフィルター用レジスト膜を作成した（表１中、塗布ムラ評価▲２▼８０℃乾燥の結果参照）。一方、減圧乾燥を模式して実施する場合は、同様にガラス基板にスピンコート塗布したのち、２３℃のクリーンルーム内でガラス基板の四隅を支持して約１ｃｍ浮かせて固定し３０分放置により溶剤をゆっくり蒸発させカラーフィルター用レジスト膜を作成した（表１中、塗布ムラ評価▲１▼２３℃乾燥の結果参照）。更にこれを２３０℃で２０分硬化処理を行い、硬化レジスト膜を作成した（表１中、塗布ムラ評価▲３▼硬化後の結果参照）。
【００３４】
［塗布ムラの評価］
上記カラーレジスト膜の作成方法に従って形成したガラス基板上のカラーフィルター用レジスト膜（１．５±０．０５μｍ）を、ナトリウムランプ光源下で目視により観察し、塗布ムラを評価した。塗膜にムラの無い状態を◎、ムラの有る状態を×、ムラは目視で確認できるが実用性に問題のない軽微な状態を○、として３段階で評価した。
【００３５】
［その他の性能評価］
塗布、露光から硬化処理までの一連の処理を実施したカラーフィルターに対して２５０℃のオーブンに１時間投入して色の変化を測定する試験を耐熱試験とする。更に同一処理したカラーフィルターに対して５％のＮａＯＨ水溶液に２５℃で１０分間浸漬後の色相変化を測定する試験を耐アルカリ試験とした。
双方ともΔＥが３以下を良好とし、評価は○とし、これ以上を×とする。（表１中、その他の性能の結果参照）。
【００３６】
実施例１
サンプル瓶（３００ｍｌ）にテフロン（登録商標）被覆した回転子を入れ、マグネチックスターラーに設置した。プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）４２．０ｇとジエチレングリコールジメチルエーテル（ＤＭＤＧ）４０ｇをサンプル瓶に入れた。攪拌しながら、光重合開始剤の２−メチル−１［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン（チバガイギー社製商品名イルガキュア９０７）０．８ｇと４，４−ジエチルアミノベンゾフェノン（保土ヶ谷化学工業社製 商品名 ＥＡＢ−Ｆ）０．２ｇ、２，４−トリクロロメチル（ピペロニル）−６−トリアジン（日本シーベルへグナー社製トリアジン−ＰＰ）０．６ｇを加える。これらの開始剤が溶解したのを確認後、エポキシ樹脂のＹＸ−４０００Ｈ（ジャパンエポキシレジン社製）を２ｇ加えて更に攪拌する。エポキシ樹脂が溶解したのを確認後、ジペンタエリスリトールヘキサアクリレートＤＰＨＡ（日本化薬社製）９．８ｇとフルオレン型エポキシ型アクリレート／酸無水物重合付加体のＰＧＭＥＡ溶液（新日鐵化学（株）製 Ｖ２５９ＭＥ、樹脂成分等５６．５％）を１７．６ｇ加えて更に攪拌する。
全てが均一に溶解したことを確認後、着色剤として、ＰＲ−２５４（チバスペシャルケミカル社製顔料）を予めＰＧＭＥＡ溶剤と分散剤とで混合分散した顔料分散体（樹脂成分等 １９．２％）８７ｇを入れ十分に攪拌溶解した後に、シランカップリング剤０．６ｇ、界面活性剤０．０６ｇを加えて更に３０分攪拌する。これをろ過して、カラーフィルター用レジスト膜用材料を得た。
【００３７】
得られたカラーフィルター用レジスト膜用材料を用いて、上述の評価方法に従い、ガラス基板上にレジスト膜及び硬化膜を形成し、ナトリウムランプ光源下で塗布ムラを観察し、◎、○、×の３段階で評価した。表１に結果を示す。実施例１によるカラーフィルター用レジスト膜用材料が塗布性に優れることが確認された。
【００３８】
実施例２
溶剤として、ＰＧＭＥＡ、ＤＭＤＧ、ジエチレングリコールジエチルエーテル（ＤＥＤＧ）を用い、その使用量を表１に示す割合に変化させたこと以外は実施例１と同様に行った。結果を表１に示す。カラーフィルター用レジスト膜用材料が塗布性に優れることが確認された。
【００３９】
実施例３
サンプル瓶（３００ｍｌ）にテフロン（登録商標）被覆した回転子を入れ、マグネチックスターラーに設置した。ＰＧＭＥＡ ２５ｇ、ＤＭＤＧ ３８ｇ及びＤＥＤＧ ４ｇをサンプル瓶に入れた。攪拌しながら、光重合開始剤のイルガキュア９０７を０．７６ｇとＥＡＢ−Ｆ ０．１９ｇ、トリアジン−ＰＰ ０．１９ｇを加える。これらの開始剤が溶解したのを確認後、エポキシ樹脂のＹＸ−４０００Ｈを１．５ｇ加えて更に攪拌する。エポキシ樹脂が溶解したのを確認後、ＤＰＨＡ １０．２ｇとＶ２５９ＭＥを２６．７ｇ加えて更に攪拌する。
全てが均一に溶解したことを確認後、ＰＲ−２５４を予めＰＧＭＥＡ溶剤と分散剤とで混合分散した顔料分散体（樹脂成分等１９．２％）を９２ｇ入れ十分に攪拌溶解した後に、シランカップリング剤０．６ｇ、界面活性剤０．０６ｇを加えて更に３０分攪拌する。これをろ過して、カラーフィルター用レジスト膜用材料を得た。
得られたカラーフィルター用レジスト膜用材料について、塗布性を評価した。結果を表１に示す。カラーフィルター用レジスト膜用材料が塗布性に優れることが確認された。
【００４０】
比較例１
実施例１で使用した溶剤のＤＭＤＧをシクロヘキサノン（ＡＮＯＮ ｂｐ．１５５．７℃、γ
３４．２）に変化させたこと以外は実施例１と同様に行った。結果を表１に示す。
実施例記載のカラーフィルター用レジスト用組成物に比較して塗布性に劣ることが確認された。
【００４１】
比較例２
実施例３で使用した溶剤のＤＭＤＧをＡＮＯＮに変化させたこと以外は実施例３と同様に行った。結果を表１に示す。実施例記載のカラーフィルター用レジスト用組成物に比較して塗布性に劣ることが確認される。
【００４２】
【表１】
【発明の効果】
本発明のカラーフィルター用レジスト材料は、塗膜物性や塗布性に優れ、特に、塗布後の色調ムラの原因となる塗布ムラの発生しにくいカラーフィルター用レジスト材料であり、これを用いて形成したカラーフィルターは発色の均一性に優れている。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a color filter resist material and a color filter. More specifically, the present invention relates to a coating film forming material for forming a colored cured film of a color filter and a color filter obtained using the same.
[0002]
[Prior art]
A color filter used in a color liquid crystal display device is prepared by adding a photopolymerization initiator and various additives and each colorant of red (R), green (G), and blue (B) to a photosensitive resin, and then adding a solvent to the resin. It is known that a color resist in which the concentration of a resin component or the like is adjusted is applied and dried, and then a pattern is formed by a series of steps by a photolithography method or the like. At that time, in the coating process, coating is generally performed by a spin coater, slit & spin coater, slit coater, roll coater, bar coater, etc., and a uniform coated plate is obtained, which is vacuum dried or heat dried To form a coating film. At this time, the occurrence of uneven color tone due to the uneven coating in the surface of the coating film causes a defect of the color filter.
[0003]
The color filter is usually applied using a coating device such as a spin coater, slit & spin coater, slit coater, roll coater, bar coater, etc., and then heat dried in an oven or hot plate to remove the solvent, or dried under reduced pressure. After drying under reduced pressure with an apparatus to form a uniform coating film, the pattern is exposed and developed. In the case of using an oven or a hot plate during this drying step, uniform heating is not performed and heat unevenness occurs. As a result, cloud-like unevenness occurs in the display area of the color filter, deteriorating the display quality. On the other hand, in the case of drying under reduced pressure, evaporation unevenness occurs due to rapid evaporation of the solvent, and cloud-like unevenness occurs in the display area of the color filter as in the case of using an oven or a hot plate. The cloud-like unevenness persists after the final curing step.
[0004]
Such a tendency of application unevenness is particularly remarkable when a single solvent is used. Therefore, conventionally, a combination with a solvent having a high boiling point has been used in order to improve coatability. This is a means for slowing down the evaporation rate of the solvent to avoid a state called "leathering" in which only the surface portion is dried first, and to form a uniformly dried film as a whole. However, when a high boiling point solvent is used in combination, the drying time is prolonged, and tack tends to remain on the surface of the dried film, and as a result, foreign matter is also likely to adhere. For example, Patent Document 1 proposes a method of using a solvent having a high boiling point to suppress solvent evaporation during coating in order to prevent nonuniformity of the protective film thickness due to spin coating. However, this method contains a solvent having a boiling point of 190 ° C. or more in an amount of 30 to 60% by weight of the total solvent, so that the drying time in vacuum drying is prolonged, and the tack tends to remain on the film surface. It has the disadvantage of being easy.
[0005]
On the other hand, it is generally known that the addition of a surfactant is effective for improving coatability. The surfactant is added in order to prevent uneven evaporation such as “Benard Cell” generated during drying. That is, by stabilizing the surface tension at a low value, it is possible to prevent a change in the surface tension in the film which occurs at the time of evaporation of the solvent, thereby making it difficult to generate a "Benard cell" or the like. However, a decrease in the surface tension tends to cause the return of the resist liquid in the peripheral portion of the glass substrate during spin coating, and there is a problem that it is difficult to balance application unevenness and the return width of the resist liquid. Under such circumstances, as a resist material for a color filter, there has been a demand for a method of keeping the surface tension in a film uniform without extremely lowering it.
[0006]
In addition, a resist material for a color filter obtained by dissolving a photopolymerizable compound such as an epoxy (meth) acrylate compound, a photopolymerization initiator, and a material mainly containing a colorant in a solvent is known in Patent Document 2 and the like. I have.
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2000-86906 [Patent Document 2]
JP-A-6-1938
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide a resist material for a color filter which solves the drawbacks of the conventional resist material for a color filter, hardly causes uneven coating, and has excellent coatability. Another object of the present invention is to provide a cured film obtained from the resist material for a color filter and a color filter having the cured film.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, used two or more solvents as a solvent to be used for a resist material for a color filter, focused on the surface tension, and controlled the surface tension. By doing so, it was found that coating unevenness and coatability were improved and a color filter cured film in which color tone unevenness was eliminated could be formed, and the present invention was completed.
[0009]
That is, the present invention relates to a photopolymerizable compound (A) containing an epoxy (meth) acrylate compound (A1) as an essential component, a photopolymerization initiator (B), and a resin component containing a coloring agent (C) as a main component. In the resist material for a color filter dissolved in the solvent (D), the solvent (D) contains two or more kinds of organic solvents having different boiling points, and a surface tension value of an organic solvent contained in the solvent in an amount of 1 wt% or more. Is a resist material for a color filter, characterized in that the difference between the surface tension value of the organic solvent having the largest value and the surface tension value of the organic solvent having the smallest value is within 3 dyn / cm.
[0010]
Here, at least one of the organic solvents is a low-boiling solvent having a temperature of 160 ° C. or lower, and the content in the solvent is 50 wt% or more, or the epoxy (meth) acrylate compound (A1) has the following general formula: Equation (1)
Embedded image
Embedded image
[0011]
Further, the present invention is a color filter cured film obtained by applying, drying and curing the above-mentioned resist material for a color filter. Further, the present invention is a color filter having the color filter cured film.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The resist material for a color filter of the present invention is a solution in which a resin component or the like (referred to as a component other than a solvent) containing a photopolymerizable component as an essential component is dissolved in a solvent. The resin component and the like are mainly composed of a component (A): a photopolymerizable compound essentially including an epoxy (meth) acrylate compound (A1), a component (B): a photopolymerization initiator, and a component (C): a colorant. And Such resin components and the like are known from Patent Document 2 and the like, and those described therein can be widely used. Specifically, the following components can be used.
[0013]
The epoxy (meth) acrylate compound as the component (A1) includes an addition compound of various diglycidyl ethers and (meth) acrylic acid or a dihydroxypropyl acrylate that is an addition compound of various bisphenol diglycidyl ethers and (meth) acrylic acid. Examples thereof include a resin or a compound obtained by reacting a polycarboxylic acid or an acid anhydride thereof with the resin.
[0014]
Glycidyl ether is ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, hydrogenated bisphenol A, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, 2,2-bis (4-hydroxyphenyl) propane , Bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, bis (4-hydroxyphenyl) dimethylsilane, 4,4'-biphenol And the like. In the present invention, an addition compound of diglycidyl ether and (meth) acrylic acid can be used as an epoxy (meth) acrylate compound.
[0015]
In order to impart alkali solubility to the resist material, it is preferable that the epoxy (meth) acrylate compound has a carboxyl group. An unsaturated group-containing compound obtained by reacting the represented epoxy (meth) acrylate compound with a polybasic acid or an acid anhydride thereof is preferred. Here, X is preferably the group described above.
[0016]
As polybasic acids or acid anhydrides thereof, maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid Acids and anhydrides of these acids can be exemplified.
[0017]
In the present invention, in addition to the component (A1), a photopolymerizable compound (A2) such as another photopolymerizable monomer or oligomer can be added to the component (A) which is a photopolymerizable compound, if necessary. . Other photopolymerizable monomers and oligomers used include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acyl And (meth) acrylates such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and glycerol (meth) acrylate, and these may be used alone. They may be used, or two or more kinds may be used in combination.
[0018]
When the component (A2) is used together with the component (A1) as the component (A), the amount of the component (A2) can be selected within a range that does not impair the properties of the resist material (sometimes referred to as ink) of the present invention. The range of 25 to 100 parts by weight of the component (A2) is desirable for 100 parts by weight of the component (A1).
[0019]
Further, in the present invention, an epoxy resin may be added in order to impart resistance to an alkaline substance or the like within a range that does not hinder other performances of the color resist. Examples of the epoxy resin include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin and the like. it can. When an epoxy resin is used, its addition amount is 0 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the component (A).
[0020]
As the photopolymerization initiator of the component (B), acetophenones such as acetophenone and p-tert-butylacetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bis (dimethylamino) benzophenone, and benzoinmethyl Benzoin ethers such as ether, benzoin isopropyl ether and benzoin butyl ether, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( Α-aminoalkylphenones such as 4-morpholinophenyl) -butanone-1, bisacylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine-oxide, N-phenylglycine Glycine etc. And triazines such as 2,4-trichloromethyl- (piperonyl) -6-triazine and 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine. These may be used alone or in combination of two or more. In addition, the photopolymerization initiator in the present invention can be used in combination with a known photopolymerization accelerator (sensitizer) such as isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate.
[0021]
The photopolymerization initiator and photopolymerization accelerator (sensitizer) of the component (B) used in the present invention include not only the component (A1) but also other photopolymerizable monomers that are added as necessary. It is also used as a photopolymerization initiator of the component (A2) such as an oligomer. Therefore, the use amount of the component (B) is preferably 5 to 25 parts by weight based on 100 parts by weight of the component (A1), but when the component (A2) is used in addition to the component (A1). Is preferably used in an amount of 1 to 15 parts by weight based on 100 parts by weight of these components.
[0022]
The colorant of the component (C) is preferably a colorant containing a pigment. Specifically, it is a pigment composition comprising a pigment and a dispersant necessary for finely dispersing and stabilizing the pigment. Pigments include organic pigments and inorganic pigments. As organic pigments, azo lake-based, insoluble azo (PY-150) -based, phthalocyanine-based (PG-7, PG-36 & PB-15.6), quinophthalone-based (PY138), quinacdrine-based, dioxazine (PV-23) -based, Examples include isoindolinone (PY-139), verinone, anthraquinone (PR-177), pyrrolopyrrole (PR-254), and perylene, and these may be used in combination. Examples of the inorganic pigments include, but are not limited to, Miloli blue, iron oxide, cobalt-based, manganese-based, ultramarine, navy blue, cobalt blue, cerulean blue, pyridian, emerald green, and cobalt green. These pigments are preferably dispersed in an average particle diameter of 0.4 μm or less, which is the lower limit of the wavelength of visible light, in order to color while maintaining the transparency of the coating film. A practically preferable average particle size range is 0.2 to 0.3 μm.
[0023]
The resist material of the present invention is obtained by dissolving a resin component or the like having the above-mentioned components (A), (B) and (C) as a main component in a solvent. There is a resin solid content such as a monomer that forms a non-resin, and a non-resin component. Most of these components remain even after drying and curing. The resin solid content may include the above-mentioned component (A), other binder resins, and resin components such as dispersants. The non-resin-based component may include additives such as a photopolymerization initiator and a light stabilizer, and a coloring agent. The colorant (C) is preferably added in an amount of 50 to 200 parts by weight based on 100 parts by weight of the resin solids.
[0024]
In the present invention, as the solvent of the component (D), two or more organic solvents having different boiling points are used. Here, the difference (hereinafter, referred to as Δγ) between the surface tension value of the organic solvent having the largest surface tension value and the surface tension value of the smallest organic solvent among the organic solvents contained at 1 wt% or more in the solvent is within a range of 3 dyn / cm. It is mandatory.
[0025]
Examples of the organic solvent include ketones such as methyl ethyl ketone, cyclohexanone, and methyl cyclohexanone, cellosolves such as methyl cellosolve, ethyl cellosolve, and cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, and propylene. Propylene glycol monoalkyl ethers such as propylene glycol monoalkyl ethers such as glycol n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol n-propyl ether acetate, and propylene glycol n-butyl ether acetate; Diethylene glycol dimethi Ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether, lactate esters such as methyl lactate and ethyl lactate, acetate esters such as n-butyl acetate, γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide And the like are exemplified as useful ones, and two or more of those meeting the above-mentioned conditions, that is, those having similar surface tension values are selected and used in combination.
[0026]
Examples of the two-solvent system include solvents having different boiling points and similar surface tensions, such as propylene glycol monomethyl ether acetate (bp. 146 ° C., γ 28.8) and diethylene glycol dimethyl ether (bp. 162 ° C., γ 29.5). select. In addition, <bp. > Indicates the boiling point and <γ> indicates the value of the surface tension calculated using the paraquat value calculated from the chemical structure of the substance.
[0027]
Examples of the three solvent system include propylene glycol monomethyl ether acetate (bp. 146 ° C., γ 28.8) and diethylene glycol dimethyl ether (bp. 162 ° C., γ 29.5) diethylene glycol diethyl ether (bp. 188 ° C., γ
27.7).
[0028]
The solvent used in the present invention may have any mixing ratio as long as it satisfies the above requirements. However, it is preferable to use a low-boiling component as a main component because it can avoid tack and the like after drying. That is, in the present invention, it is preferable that 50% by weight or more of the total solvent is composed of a solvent having a boiling point of 160 ° C. or less, and that the remaining solvent has a surface tension close to this. When the solvent is composed of two kinds of solvents, the one having a surface tension difference of 3 dyn / cm or less from the low boiling point solvent is used. When three or more kinds of solvents are used, all the solvents including the low boiling point solvent are used. Also, the difference between the maximum value and the minimum value of the surface tension with respect to other solvents is set to within 3 dyn / cm. Note that the solvent usually contains a trace amount to a small amount of impurities, but components less than 1 wt% are treated as simple impurities.
[0029]
Taking this point into consideration, preferred embodiments of the two-solvent system and the three-solvent system exemplified above are described. For example, in the two-solvent system, 1 to 50 parts by weight of diethylene glycol dimethyl ether is added to 100 parts by weight of propylene glycol monomethyl ether acetate. In particular, in the case of a three-solvent system, the range of 1 to 50 parts of diethylene glycol dimethyl ether and 1 to 20 parts of diethylene glycol diethyl ether per 100 parts by weight of propylene glycol monomethyl ether acetate is good. Is desirable. In particular, 1 to 35 parts by weight of diethylene glycol dimethyl ether and 1 to 5 parts by weight of diethylene glycol diethyl ether are preferable based on 100 parts by weight of propylene glycol monomethyl ether acetate.
[0030]
The amount of the solvent (D) used is suitably from 250 to 600 parts by weight based on 100 parts by weight of all resin components and the like.
[0031]
The resist material for a color filter of the present invention may contain other components as long as the effects of the present invention are not impaired. For example, a surfactant is preferably used for improving wettability, and a coupling agent is preferably used for improving adhesion. In this case, the surfactant is preferably contained in the range of 0.01 to 0.2% by weight.
[0032]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In Examples, unless otherwise specified, parts represent parts by weight and% represents weight%. Further, the preparation of the color filter resist film and the evaluation of coating unevenness are performed by the following methods unless otherwise specified.
[0033]
[Creation of color resist film]
A material for a resist film for a color filter is applied to a glass substrate coated with SiO 2 under spin coating conditions so that the film thickness after post-baking is 1.5 ± 0.05 μm, and the solvent is evaporated at 80 ° C. for 3 minutes in pre-baking. Then, a resist film for a color filter was prepared (see Table 2). On the other hand, when the drying under reduced pressure is carried out schematically, the glass substrate is spin-coated in the same manner, and the four corners of the glass substrate are supported and fixed in a clean room at 23 ° C. by floating about 1 cm, and the solvent is left for 30 minutes. The resist film was slowly evaporated to form a resist film for a color filter (see Table 1 for evaluation of coating unevenness {1} drying at 23 ° C.). Further, this was subjected to a curing treatment at 230 ° C. for 20 minutes to form a cured resist film (see Table 3, Evaluation of coating unevenness (3) Result after curing).
[0034]
[Evaluation of coating unevenness]
The color filter resist film (1.5 ± 0.05 μm) formed on the glass substrate according to the above-described method for forming a color resist film was visually observed under a sodium lamp light source to evaluate uneven coating. The state where there was no unevenness in the coating film was evaluated as ◎, the state where there was unevenness was evaluated as x, and the unevenness which could be visually confirmed, but was a slight state which had no problem in practicality was evaluated as ○, and evaluated in three levels.
[0035]
[Other performance evaluations]
A heat resistance test is a test in which a color filter that has undergone a series of processes from coating and exposure to curing is put into a 250 ° C. oven for 1 hour to measure a change in color. Further, a test for measuring a change in hue after immersing the same color filter in a 5% NaOH aqueous solution at 25 ° C. for 10 minutes was defined as an alkali resistance test.
In both cases, ΔE was 3 or less, and the evaluation was good. (See other performance results in Table 1).
[0036]
Example 1
The rotor coated with Teflon (registered trademark) was placed in a sample bottle (300 ml), and was placed on a magnetic stirrer. 42.0 g of propylene glycol monomethyl ether acetate (PGMEA) and 40 g of diethylene glycol dimethyl ether (DMDG) were placed in a sample bottle. While stirring, 0.8 g of a photopolymerization initiator, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Geigy) and 4,4-diethylamino 0.2 g of benzophenone (trade name: EAB-F, manufactured by Hodogaya Chemical Industry Co., Ltd.) and 0.6 g of 2,4-trichloromethyl (piperonyl) -6-triazine (triazine-PP, manufactured by Sebel-Hegner Japan) are added. After confirming dissolution of these initiators, 2 g of an epoxy resin YX-4000H (manufactured by Japan Epoxy Resin Co.) is added and further stirred. After confirming that the epoxy resin was dissolved, 9.8 g of dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku) and a PGMEA solution of a fluorene-type epoxy-type acrylate / acid anhydride polymer adduct (Nippon Steel Chemical Co., Ltd.) (V6.5ME, resin component, etc., 56.5%) is added and stirred further.
After confirming that all were dissolved uniformly, as a colorant, PR-254 (a pigment manufactured by Ciba Special Chemical Co., Ltd.) was previously mixed and dispersed with a PGMEA solvent and a dispersant (19.2% of a resin component and the like). After adding 87 g and sufficiently stirring and dissolving, 0.6 g of a silane coupling agent and 0.06 g of a surfactant are added, and the mixture is further stirred for 30 minutes. This was filtered to obtain a material for a resist film for a color filter.
[0037]
Using the obtained color filter resist film material, according to the above evaluation method, to form a resist film and a cured film on a glass substrate, observe the coating unevenness under a sodium lamp light source, ◎, ○, × The evaluation was made in three stages. Table 1 shows the results. It was confirmed that the resist film material for a color filter according to Example 1 had excellent coatability.
[0038]
Example 2
PGMEA, DMDG, and diethylene glycol diethyl ether (DEDG) were used as solvents, and the same procedure as in Example 1 was carried out except that the amounts used were changed to the ratios shown in Table 1. Table 1 shows the results. It was confirmed that the material for a resist film for a color filter was excellent in coatability.
[0039]
Example 3
The rotor coated with Teflon (registered trademark) was placed in a sample bottle (300 ml), and was placed on a magnetic stirrer. 25 g of PGMEA, 38 g of DMDG and 4 g of DEDG were placed in a sample bottle. While stirring, 0.76 g of Irgacure 907 as a photopolymerization initiator, 0.19 g of EAB-F, and 0.19 g of triazine-PP are added. After confirming that these initiators are dissolved, 1.5 g of YX-4000H as an epoxy resin is added and further stirred. After confirming that the epoxy resin has dissolved, 10.2 g of DPHA and 26.7 g of V259ME are added, and the mixture is further stirred.
After confirming that all were uniformly dissolved, 92 g of a pigment dispersion (19.2% of a resin component and the like) in which PR-254 was previously mixed and dispersed with a PGMEA solvent and a dispersant was added, and sufficiently stirred and dissolved. 0.6 g of a ring agent and 0.06 g of a surfactant are added, and the mixture is further stirred for 30 minutes. This was filtered to obtain a material for a resist film for a color filter.
The coatability of the obtained resist film material for a color filter was evaluated. Table 1 shows the results. It was confirmed that the material for a resist film for a color filter was excellent in coatability.
[0040]
Comparative Example 1
DMDG as a solvent used in Example 1 was converted to cyclohexanone (ANON bp.
Except having changed into 34.2), it carried out similarly to Example 1. Table 1 shows the results.
It was confirmed that the coating properties were inferior to those of the resist composition for color filters described in the examples.
[0041]
Comparative Example 2
Example 3 was carried out in the same manner as in Example 3 except that DMDG as the solvent used in Example 3 was changed to ANON. Table 1 shows the results. It is confirmed that the coating property is inferior to that of the resist composition for a color filter described in the examples.
[0042]
[Table 1]
【The invention's effect】
The resist material for a color filter of the present invention is a resist material for a color filter which is excellent in coating film physical properties and coating properties, and in particular, is less likely to cause coating unevenness which causes color tone unevenness after coating, and was formed using this. Color filters have excellent color uniformity.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003096466A JP4443848B2 (en) | 2003-03-31 | 2003-03-31 | Color filter resist material and color filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003096466A JP4443848B2 (en) | 2003-03-31 | 2003-03-31 | Color filter resist material and color filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004302245A true JP2004302245A (en) | 2004-10-28 |
| JP4443848B2 JP4443848B2 (en) | 2010-03-31 |
Family
ID=33408533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003096466A Expired - Fee Related JP4443848B2 (en) | 2003-03-31 | 2003-03-31 | Color filter resist material and color filter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4443848B2 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006219632A (en) * | 2005-02-14 | 2006-08-24 | Fuji Photo Film Co Ltd | Applying composition, optically functioning layer, reflection-preventing film and method for producing the film |
| JP2007072357A (en) * | 2005-09-09 | 2007-03-22 | Tokyo Ohka Kogyo Co Ltd | Negative photosensitive resin composition and method for producing color filter using same |
| JP2007293050A (en) * | 2006-04-25 | 2007-11-08 | Toyo Ink Mfg Co Ltd | Colored composition for color filter, color filter and method for manufacturing color filter |
| WO2008138732A1 (en) | 2007-05-11 | 2008-11-20 | Basf Se | Oxime ester photoinitiators |
| JP2010152336A (en) * | 2008-11-18 | 2010-07-08 | Sumitomo Chemical Co Ltd | Photosensitive resin composition and display |
| WO2010108835A1 (en) | 2009-03-23 | 2010-09-30 | Basf Se | Photoresist composition |
| EP2402315A1 (en) | 2007-05-11 | 2012-01-04 | Basf Se | Oxime ester photoinitiators |
| WO2012045736A1 (en) | 2010-10-05 | 2012-04-12 | Basf Se | Oxime ester derivatives of benzocarbazole compounds and their use as photoinitiators in photopolymerizable compositions |
| WO2012101245A1 (en) | 2011-01-28 | 2012-08-02 | Basf Se | Polymerizable composition comprising an oxime sulfonate as thermal curing agent |
| WO2013083505A1 (en) | 2011-12-07 | 2013-06-13 | Basf Se | Oxime ester photoinitiators |
| KR101327820B1 (en) * | 2008-06-10 | 2013-11-12 | 주식회사 엘지화학 | Thermally-curable resin composition for color filter overcoat, color filter comprising overcoat, and liquid crystal device |
| WO2013167515A1 (en) | 2012-05-09 | 2013-11-14 | Basf Se | Oxime ester photoinitiators |
| WO2015004565A1 (en) | 2013-07-08 | 2015-01-15 | Basf Se | Oxime ester photoinitiators |
| WO2015036910A1 (en) | 2013-09-10 | 2015-03-19 | Basf Se | Oxime ester photoinitiators |
| US9051397B2 (en) | 2010-10-05 | 2015-06-09 | Basf Se | Oxime ester |
| JP2019174751A (en) * | 2018-03-29 | 2019-10-10 | 株式会社タムラ製作所 | Photosensitive resin composition |
| US10487050B2 (en) | 2014-08-29 | 2019-11-26 | Basf Se | Oxime sulfonate derivatives |
| WO2020152120A1 (en) | 2019-01-23 | 2020-07-30 | Basf Se | Oxime ester photoinitiators having a special aroyl chromophore |
| WO2021175855A1 (en) | 2020-03-04 | 2021-09-10 | Basf Se | Oxime ester photoinitiators |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04181202A (en) * | 1990-11-16 | 1992-06-29 | Canon Inc | Photosensitive colored resin composition for color filter |
| JPH061938A (en) * | 1992-06-19 | 1994-01-11 | Nippon Steel Corp | Alkali-developable photo-sensitive ink for color filter and color filter produced by using the ink |
| JPH10142794A (en) * | 1996-11-14 | 1998-05-29 | Hitachi Chem Co Ltd | Photosensitive solution for forming colored image and manufacture of color filter by using the same and color filter |
| JP2001266644A (en) * | 2000-03-21 | 2001-09-28 | Hitachi Chem Co Ltd | Conductive paste |
| JP2002022925A (en) * | 2000-07-11 | 2002-01-23 | Nippon Steel Chem Co Ltd | Method for producing color filter and colored photosensitive resin composition |
| JP2002372779A (en) * | 2001-06-15 | 2002-12-26 | Toray Ind Inc | Resist for color filter and method for producing color filter |
-
2003
- 2003-03-31 JP JP2003096466A patent/JP4443848B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04181202A (en) * | 1990-11-16 | 1992-06-29 | Canon Inc | Photosensitive colored resin composition for color filter |
| JPH061938A (en) * | 1992-06-19 | 1994-01-11 | Nippon Steel Corp | Alkali-developable photo-sensitive ink for color filter and color filter produced by using the ink |
| JPH10142794A (en) * | 1996-11-14 | 1998-05-29 | Hitachi Chem Co Ltd | Photosensitive solution for forming colored image and manufacture of color filter by using the same and color filter |
| JP2001266644A (en) * | 2000-03-21 | 2001-09-28 | Hitachi Chem Co Ltd | Conductive paste |
| JP2002022925A (en) * | 2000-07-11 | 2002-01-23 | Nippon Steel Chem Co Ltd | Method for producing color filter and colored photosensitive resin composition |
| JP2002372779A (en) * | 2001-06-15 | 2002-12-26 | Toray Ind Inc | Resist for color filter and method for producing color filter |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006219632A (en) * | 2005-02-14 | 2006-08-24 | Fuji Photo Film Co Ltd | Applying composition, optically functioning layer, reflection-preventing film and method for producing the film |
| JP4668016B2 (en) * | 2005-09-09 | 2011-04-13 | 東京応化工業株式会社 | Negative photosensitive resin composition and method for producing color filter using the same |
| JP2007072357A (en) * | 2005-09-09 | 2007-03-22 | Tokyo Ohka Kogyo Co Ltd | Negative photosensitive resin composition and method for producing color filter using same |
| JP2007293050A (en) * | 2006-04-25 | 2007-11-08 | Toyo Ink Mfg Co Ltd | Colored composition for color filter, color filter and method for manufacturing color filter |
| WO2008138732A1 (en) | 2007-05-11 | 2008-11-20 | Basf Se | Oxime ester photoinitiators |
| EP2402315A1 (en) | 2007-05-11 | 2012-01-04 | Basf Se | Oxime ester photoinitiators |
| KR101327820B1 (en) * | 2008-06-10 | 2013-11-12 | 주식회사 엘지화학 | Thermally-curable resin composition for color filter overcoat, color filter comprising overcoat, and liquid crystal device |
| JP2010152336A (en) * | 2008-11-18 | 2010-07-08 | Sumitomo Chemical Co Ltd | Photosensitive resin composition and display |
| JP2015099393A (en) * | 2008-11-18 | 2015-05-28 | 住友化学株式会社 | Photosensitive resin composition and display device |
| JP2015132833A (en) * | 2008-11-18 | 2015-07-23 | 住友化学株式会社 | Photosensitive resin composition and display unit |
| WO2010108835A1 (en) | 2009-03-23 | 2010-09-30 | Basf Se | Photoresist composition |
| US8916621B2 (en) | 2009-03-23 | 2014-12-23 | Basf Se | Photoresist compositions |
| WO2012045736A1 (en) | 2010-10-05 | 2012-04-12 | Basf Se | Oxime ester derivatives of benzocarbazole compounds and their use as photoinitiators in photopolymerizable compositions |
| US9051397B2 (en) | 2010-10-05 | 2015-06-09 | Basf Se | Oxime ester |
| WO2012101245A1 (en) | 2011-01-28 | 2012-08-02 | Basf Se | Polymerizable composition comprising an oxime sulfonate as thermal curing agent |
| WO2013083505A1 (en) | 2011-12-07 | 2013-06-13 | Basf Se | Oxime ester photoinitiators |
| US9365515B2 (en) | 2011-12-07 | 2016-06-14 | Basf Se | Oxime ester photoinitiators |
| EP3354641A1 (en) | 2012-05-09 | 2018-08-01 | Basf Se | Oxime ester photoinitiators |
| US11209734B2 (en) | 2012-05-09 | 2021-12-28 | Basf Se | Oxime ester photoinitiators |
| EP2963015A1 (en) | 2012-05-09 | 2016-01-06 | Basf Se | Oxime ester photoinitiators |
| EP2963016A1 (en) | 2012-05-09 | 2016-01-06 | Basf Se | Oxime ester photoinitiators |
| EP2963014A1 (en) | 2012-05-09 | 2016-01-06 | Basf Se | Oxime ester photoinitiators |
| US11209733B2 (en) | 2012-05-09 | 2021-12-28 | Basf Se | Oxime ester photoinitiators |
| US9864273B2 (en) | 2012-05-09 | 2018-01-09 | Basf Se | Oxime ester photoinitiators |
| US10488756B2 (en) | 2012-05-09 | 2019-11-26 | Basf Se | Oxime ester photoinitiators |
| US11204554B2 (en) | 2012-05-09 | 2021-12-21 | Basf Se | Oxime ester photoinitiators |
| WO2013167515A1 (en) | 2012-05-09 | 2013-11-14 | Basf Se | Oxime ester photoinitiators |
| WO2015004565A1 (en) | 2013-07-08 | 2015-01-15 | Basf Se | Oxime ester photoinitiators |
| WO2015036910A1 (en) | 2013-09-10 | 2015-03-19 | Basf Se | Oxime ester photoinitiators |
| US9957258B2 (en) | 2013-09-10 | 2018-05-01 | Basf Se | Oxime ester photoinitiators |
| US10793555B2 (en) | 2013-09-10 | 2020-10-06 | Basf Se | Oxime ester photoinitiators |
| US10487050B2 (en) | 2014-08-29 | 2019-11-26 | Basf Se | Oxime sulfonate derivatives |
| JP2019174751A (en) * | 2018-03-29 | 2019-10-10 | 株式会社タムラ製作所 | Photosensitive resin composition |
| CN110320753A (en) * | 2018-03-29 | 2019-10-11 | 株式会社田村制作所 | Photosensitive polymer combination |
| WO2020152120A1 (en) | 2019-01-23 | 2020-07-30 | Basf Se | Oxime ester photoinitiators having a special aroyl chromophore |
| WO2021175855A1 (en) | 2020-03-04 | 2021-09-10 | Basf Se | Oxime ester photoinitiators |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4443848B2 (en) | 2010-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4443848B2 (en) | Color filter resist material and color filter | |
| JP5164409B2 (en) | PHOTOCURABLE COMPOSITION, COLOR FILTER, ITS MANUFACTURING METHOD, AND SOLID-STATE IMAGING DEVICE | |
| KR102001628B1 (en) | Photosensitive resin composition for black matrix, and method for producing same | |
| TWI806434B (en) | Photosensitive resin composition, and method for producing same, color filter, and method for producing same, and image display element | |
| CN106019837B (en) | Colored photosensitive resin composition, color filter, and image display device provided with same | |
| TWI445769B (en) | Pigment dispersion composition, colored photocurable composition, and color filter and method for manufacturing the same | |
| KR20070098575A (en) | Light shielding resin composition for color filter and color filter | |
| JP2010085972A (en) | Colored radiation-sensitive composition, color filter, and color liquid crystal display device | |
| JP2009062457A (en) | Processed pigment, pigment dispersion composition using it, coloration photosensitive composition, and color filter | |
| KR20170042245A (en) | Photosensitive resin composition for light-shielding film with the role of spacer, light-shielding film thereof, lcd with that film, and manufacturing process for them | |
| JP4286582B2 (en) | Pigment dispersion for curable coloring composition, curable coloring composition, and color filter | |
| KR101486559B1 (en) | Yellow color resin composition for color filter and yellow color filter using same | |
| JP2010084119A (en) | Processed pigment, pigment dispersion composition, photocurable composition, color filter and method of production of color filter | |
| TWI791563B (en) | Copolymer, polymer composition, photosensitive resin composition for color filter, color filter, image display element, and method for producing a color filter | |
| TWI655504B (en) | Photosensitive resin composition, black pixel defining layer using the same, and display device | |
| TWI829905B (en) | Photosensitve resin composition for black resist,light-shielding layer cured thereof,and color filter with them | |
| JP4210549B2 (en) | Pigment dispersion composition, photosensitive coloring composition, color filter, and liquid crystal display device | |
| WO2016203905A1 (en) | Coloring composition for color filter, color filter, and image display element | |
| KR102012954B1 (en) | A color photosensitive resin composition, color filter and display device comprising the same | |
| KR20160063836A (en) | Photosensitive resin layer, black column spacer using the same and color filter | |
| JP2008250013A (en) | Ink material for red color filter, and color filter using the same | |
| JP2010026471A (en) | Ink composition for color filter, and color filter cured film and color filter obtained by using the ink composition | |
| TW201626107A (en) | Colored photosensitive resin composition, color filter and image display device | |
| TW202124499A (en) | Photosensitive resin composition for black resist, light-shielding film cured the same, color filter and touch panel having the light-shielding film, display device having the color filter and the touch panel | |
| KR20220122884A (en) | A black photosensitive resin composition, a color filter and a display device using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060316 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090625 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090707 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090907 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091006 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091207 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100112 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100113 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4443848 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130122 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160122 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160122 Year of fee payment: 6 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160122 Year of fee payment: 6 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |