JPH06230212A - Alkali-developable photosensitive colored composition - Google Patents
Alkali-developable photosensitive colored compositionInfo
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- JPH06230212A JPH06230212A JP1314893A JP1314893A JPH06230212A JP H06230212 A JPH06230212 A JP H06230212A JP 1314893 A JP1314893 A JP 1314893A JP 1314893 A JP1314893 A JP 1314893A JP H06230212 A JPH06230212 A JP H06230212A
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- compound
- photosensitive
- vinyl
- vinyl group
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルカリ水溶液にて現
像可能な感光性着色組成物に関する。更に詳しくは，固
体撮像素子、液晶表示装置等に用いられるカラーフィル
ターに関わり、紫外線露光の後アルカリ水溶液にて現像
（以下アルカリ現像とする）できる高品質のカラーフィ
ルター用着色組成物に関する。FIELD OF THE INVENTION The present invention relates to a photosensitive coloring composition which can be developed with an aqueous alkaline solution. More specifically, the present invention relates to a color filter used for a solid-state image pickup device, a liquid crystal display device, and the like, and relates to a high-quality coloring composition for a color filter, which can be developed with an aqueous alkali solution after exposure to ultraviolet rays (hereinafter referred to as alkaline development).
【０００２】近年、液晶表示装置等は薄型化、大型化の
傾向にあり、用いられるカラーフィルターも無欠陥薄膜
化が求められ、更には明るさや高いコントラストが要求
されている。また、カラーフィルター製造の低コスト化
が求められ、歩留り向上や工程短縮が必要となってい
る。カラーフィルターは、ガラス等の透明な基板の表面
に３原色をトライアングル配列、モザイク配列、ストラ
イプ配列に画素配置したものからなり、ＣＣＤ用の画素
は数ミクロンから数十ミクロンという微細な形状であ
る。また、ＬＣＤ用の画素は数十ミクロンから 200ミク
ロン程度であり、しかも色相ごとに所定の順序で整然と
配列する必要がある。In recent years, liquid crystal display devices and the like tend to be thinner and larger, and the color filters used are required to have a defect-free thin film, and further, brightness and high contrast are required. Further, it is required to reduce the cost of manufacturing color filters, and it is necessary to improve the yield and shorten the process. The color filter is formed by arranging pixels of three primary colors in a triangle arrangement, a mosaic arrangement, and a stripe arrangement on the surface of a transparent substrate such as glass, and the pixels for CCD have a fine shape of several microns to several tens of microns. In addition, the pixels for LCD are several tens of microns to 200 microns, and it is necessary to arrange them in order in a predetermined order for each hue.
【０００３】従来、カラーフィルターの製造法について
は、アルカリ現像可能な熱可塑性共重合化合物および感
光性組成物に顔料等の色素材を分散した感光性着色組成
物をガラス基板に塗布し紫外線露光した後、アルカリ現
像を行いパターン形成することを繰り返す方法が行われ
ている。しかしながら、アルカリ現像可能な熱可塑性共
重合化合物を用いているため、アルカリ現像前後でのパ
ターン部分の膜厚変化や耐熱性、耐溶剤性に劣るという
欠点があった。また、アルカリ現像可能な熱可塑性共重
合化合物としては、ビニル系共重合化合物が主に用いら
れており、十分な膜硬度を得るためにはメタクリル酸お
よびメタクリル酸誘導体を主成分とし高分子量であるこ
とが望ましい。しかし、分子量が大きくなると着色組成
物の分散性が悪く粘度が上昇し、かつ顔料等の色素材濃
度が上げられないなどにより薄膜化ができなかった。Conventionally, as for the method for producing a color filter, a photosensitive coloring composition prepared by dispersing a color material such as a pigment in an alkali-developable thermoplastic copolymer compound and a photosensitive composition is applied to a glass substrate and exposed to ultraviolet rays. After that, a method of repeating alkali development and pattern formation is performed. However, since the alkali-developable thermoplastic copolymer compound is used, there is a defect that the change in the film thickness of the pattern portion before and after the alkali development, the heat resistance and the solvent resistance are poor. In addition, as the alkali-developable thermoplastic copolymer compound, a vinyl copolymer compound is mainly used, and in order to obtain sufficient film hardness, methacrylic acid and a methacrylic acid derivative are the main components and have a high molecular weight. Is desirable. However, when the molecular weight is large, the dispersibility of the coloring composition is poor, the viscosity is increased, and the concentration of color materials such as pigments cannot be increased.
【０００４】本発明者は、上記従来技術の欠点を解決す
るために鋭意検討を重ねた結果、スチレン、カルボキシ
ル基を有するビニル化合物および水酸基を有するビニル
化合物からなるビニル系共重合化合物にイソシアネート
基を介して感光性のビニル基を導入した感光性共重合化
合物を含むアルカリ現像型感光性着色組成物が、耐熱
性、耐溶剤性さらに分散性に優れ、薄膜化が容易であ
り、かつパターン形状が良好で高品質なカラーフィルタ
ーを製造できることを見出し、本発明に至った。As a result of intensive studies to solve the above-mentioned drawbacks of the prior art, the present inventor has found that a vinyl-based copolymer compound comprising styrene, a vinyl compound having a carboxyl group and a vinyl compound having a hydroxyl group has an isocyanate group. The alkali-developable photosensitive coloring composition containing a photosensitive copolymer compound having a photosensitive vinyl group introduced through it is excellent in heat resistance, solvent resistance, and dispersibility, is easy to form a thin film, and has a pattern shape. The present inventors have found that a good and high-quality color filter can be manufactured, and have completed the present invention.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は (A)
スチレン 5〜55重量％、ビニル基１個と水酸基を有する
化合物10〜40重量％、ビニル基１個とカルボキシル基を
有する化合物10〜30重量％およびビニル基１個を有する
化合物 0〜75重量％からなるビニル系共重合化合物に、
イソシアネート基１個と少なくとも１個以上のビニル基
を有する化合物を 5〜25モル％反応させて得られる酸価
50〜150 の感光性共重合化合物、 (B)感光性モノマーお
よび／またはオリゴマー、 (C)光重合開始剤、 (D)色素
材および(E)溶剤を含むアルカリ現像型感光性着色組成
物を提供する。[Means for Solving the Problems] That is, the present invention provides (A)
Styrene 5 to 55% by weight, compound having 1 vinyl group and hydroxyl group 10 to 40% by weight, compound having 1 vinyl group and carboxyl group 10 to 30% by weight, and compound having 1 vinyl group 0 to 75% by weight A vinyl-based copolymer compound consisting of
Acid value obtained by reacting 5 to 25 mol% of a compound having one isocyanate group and at least one vinyl group
An alkali-developable photosensitive coloring composition containing 50 to 150 of a photosensitive copolymer compound, (B) a photosensitive monomer and / or oligomer, (C) a photopolymerization initiator, (D) a color material and (E) a solvent. provide.
【０００６】ビニル基１個と水酸基を有する化合物とし
ては、例えばアクリル酸またはメタクリル酸（以下（メ
タ）アクリル酸とする）の2-ヒドロキシエチルエステ
ル、2-ヒドロキシプロピルエステル、2-ヒドロキシオク
チルエステル等やN-メチロールアクリルアミド、アリル
アルコール等が挙げられる。また、ビニル基１個とカル
ボキシル基を有する化合物としては、アクリル酸、メタ
クリル酸やイタコン酸等が挙げられる。Examples of the compound having one vinyl group and a hydroxyl group include 2-hydroxyethyl ester, 2-hydroxypropyl ester and 2-hydroxyoctyl ester of acrylic acid or methacrylic acid (hereinafter referred to as (meth) acrylic acid). And N-methylol acrylamide, allyl alcohol and the like. Examples of the compound having one vinyl group and a carboxyl group include acrylic acid, methacrylic acid and itaconic acid.
【０００７】ビニル基１個を有する化合物としては、
（メタ）アクリル酸メチル、（メタ）アクリル酸エチ
ル、（メタ）アクリル酸プロピル、（メタ）アクリル酸
ブチル、（メタ）アクリル酸2-エチルヘキシル、（メ
タ）アクリル酸ラウリル、（メタ）アクリル酸ステアリ
ル、（メタ）アクリル酸メトキシエチル、（メタ）アク
リル酸エトキシエチル、（メタ）アクリル酸ブトキシエ
チル、（メタ）アクリル酸シクロヘキシル、（メタ）ア
クリル酸グリシジル、アクリロニトリル、（メタ）アク
リル酸メチルアミノ等が挙げられる。As a compound having one vinyl group,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, acrylonitrile, methylamino (meth) acrylate, etc. Can be mentioned.
【０００８】イソシアネート基１個と少なくとも１個以
上のビニル基を有する化合物としては、少なくとも１分
子内にｎ個（ｎは２以上）のイソシアネート基を有する
ポリイソシアネート化合物 1モルと１分子内に１個のイ
ソシアネート基と反応する基、例えば水酸基を有し、か
つ少なくとも１個以上のビニル基を有するビニル化合物
n-1モルとを40〜100 ℃にて反応させて得られる化合
物、あるいはイソシアネートエチルメタクリレート、メ
タクリロイルイソシアネート等が用いられる。As the compound having one isocyanate group and at least one vinyl group, 1 mol of a polyisocyanate compound having at least n (n is 2 or more) isocyanate groups in one molecule and one molecule in one molecule Vinyl compound having a group that reacts with one isocyanate group, for example, a hydroxyl group, and at least one vinyl group
A compound obtained by reacting with n-1 mol at 40 to 100 ° C., or isocyanate ethyl methacrylate, methacryloyl isocyanate or the like is used.
【０００９】ポリイソシアネート化合物としては、2,4-
トルエンジイソシアネート、2,6-トルエンジイソシアネ
ート、4,4'−ジフェニルメタンジイソシアネート、ヘキ
サメチレンジイソシアネート、イソホロンジイソシアネ
ート、水添 4,4'-ジフェニルメタンジイソシアネート、
水添トルエンジイソシアネート等が挙げられる。水酸基
１個を有するビニル化合物としては、（メタ）アクリル
酸の2-ヒドロキシエチルエステル、2-ヒドロキシプロピ
ルエステル、2-ヒドロキシオクチルエステル等やN-メチ
ロールアクリルアミド、アリルアルコール、グリセロー
ルジ（メタ）アクリレート、グリセロール（メタ）アク
リレートアルキレート、グリセロール（メタ）アクリレ
ートアルケニレート、ブチルグリシジルエーテル（メ
タ）アクリレート、フェニルグリシジルエーテル（メ
タ）アクリレート、ポリエチレングリコールモノ（メ
タ）アクリレート、ポリカプロネート（メタ）アクリレ
ート、テトラメチロールメタントリ（メタ）アクリレー
ト等が挙げられる。As the polyisocyanate compound, 2,4-
Toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate,
Examples include hydrogenated toluene diisocyanate. Examples of vinyl compounds having one hydroxyl group include (meth) acrylic acid 2-hydroxyethyl ester, 2-hydroxypropyl ester, 2-hydroxyoctyl ester, N-methylol acrylamide, allyl alcohol, glycerol di (meth) acrylate, Glycerol (meth) acrylate alkylate, glycerol (meth) acrylate alkenylate, butyl glycidyl ether (meth) acrylate, phenyl glycidyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, polycapronate (meth) acrylate, tetra Methylol methane tri (meth) acrylate etc. are mentioned.
【００１０】スチレン、ビニル基１個と水酸基１個を有
する化合物、ビニル基１個とカルボキシル基を有する化
合物およびビニル基１個を有する化合物からなるビニル
系共重合化合物は、公知の方法によって製造できるが、
着色組成物のガラス基板への薄膜化塗布およびイソシア
ネート基を介してビニル基を導入し感光性共重合化合物
とすることから、シクロヘキサノン、セロソルブアセテ
ート、ジエチレングリコールジメチルエーテル、エチル
ベンゼン、エチレングリコールジエチルエーテル、キシ
レン等の溶剤中での溶液重合によって製造することが好
ましい。A vinyl copolymer compound comprising styrene, a compound having one vinyl group and one hydroxyl group, a compound having one vinyl group and a carboxyl group, and a compound having one vinyl group can be produced by a known method. But,
By coating a thin film on a glass substrate of a coloring composition and introducing a vinyl group through an isocyanate group to form a photosensitive copolymer compound, cyclohexanone, cellosolve acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, etc. It is preferably produced by solution polymerization in a solvent.
【００１１】この際、スチレンの共重合割合は 5〜55重
量％である。この割合が 5重量％未満であると露光時の
感度が低くまた色素材の分散が悪くなり、55重量％を超
えると現像され難くなりパターンの解像性が得られな
い。また、ビニル基１個と水酸基１個を有する化合物の
共重合割合は10〜40重量％である。この割合が10重量％
未満であると、後に反応させて得られる感光性基が減り
露光感度が低下すると共に基板への密着性も悪く、40重
量％を超えると現像され易くなり解像性が悪くなる。ビ
ニル基１個とカルボキシル基を有する化合物の共重合割
合は10〜30重量％である。この割合が10重量％未満であ
ると現像性が悪く、30重量％を超えると現像され易くな
り解像性が悪くなる。さらに、ビニル基１個を有する化
合物を75重量％以下の共重合割合で用いてもよい。この
割合が75重量％を超えると現像され難くなりパターンの
解像性が得られない。At this time, the copolymerization ratio of styrene is 5 to 55% by weight. If this ratio is less than 5% by weight, the sensitivity at the time of exposure is low and the dispersion of the color material is poor, and if it exceeds 55% by weight, it becomes difficult to develop and the resolution of the pattern cannot be obtained. The copolymerization ratio of the compound having one vinyl group and one hydroxyl group is 10 to 40% by weight. This percentage is 10% by weight
If it is less than 40% by weight, the number of photosensitive groups obtained by the subsequent reaction is reduced, the exposure sensitivity is lowered, and the adhesion to the substrate is poor, and if it exceeds 40% by weight, it is likely to be developed and the resolution is deteriorated. The copolymerization ratio of the compound having one vinyl group and the carboxyl group is 10 to 30% by weight. If this ratio is less than 10% by weight, the developability will be poor, and if it exceeds 30% by weight, development will be facilitated and the resolution will be poor. Further, the compound having one vinyl group may be used in a copolymerization ratio of 75% by weight or less. If this proportion exceeds 75% by weight, it becomes difficult to develop and the resolution of the pattern cannot be obtained.
【００１２】上記ビニル系共重合化合物に対し、イソシ
アネート基１個と少なくとも１個以上のビニル基を有す
る化合物を 5〜25モル％で、好ましくは10〜20モル％の
割合で反応させて (A)感光性共重合化合物が得られる。
この際、反応量が 5モル％未満では露光感度が大きく低
下し、アルカリ現像前後での膜厚変化が大きくなり耐熱
性、耐溶剤性に劣り、25モル％を超えると露光時にハレ
ーション効果が現れ解像性が悪くなると共に溶剤乾燥時
に焼付きが起こる。 (A) 感光性共重合化合物の酸価については、アルカリ現
像液による現像性をより良好とするために50〜150 に調
製する。50より低い酸価では現像時間が長く、現像され
ずに地汚れの原因となる。また、酸価が150 より高くな
ると現像時間が短すぎて作業巾が得られず、現像後のパ
ターン形状の細りや断面形状が逆台形となるなどの問題
が生じる。A compound having one isocyanate group and at least one vinyl group is reacted with the above vinyl-based copolymer compound in an amount of 5 to 25 mol%, preferably 10 to 20 mol%. ) A photosensitive copolymer compound is obtained.
At this time, if the reaction amount is less than 5 mol%, the exposure sensitivity is significantly reduced, the film thickness change before and after alkali development is large, and the heat resistance and solvent resistance are poor, and if it exceeds 25 mol%, the halation effect appears at the time of exposure. The resolution deteriorates and seizure occurs during solvent drying. The acid value of the photosensitive copolymer compound (A) is adjusted to 50 to 150 in order to improve the developability with an alkaline developer. If the acid value is lower than 50, the development time is long and the development is not performed, which causes scumming. On the other hand, when the acid value is higher than 150, the developing time is too short to obtain a working width, resulting in problems such as a narrowed pattern shape after development and an inverted trapezoidal sectional shape.
【００１３】本発明においては、着色組成物の粘度を低
くし露光感度を高める目的から、 (B)感光性モノマーおよび／またはオリゴマーを併用す
る。モノマーとしては、2-ヒドロキシ（メタ）アクリレ
ート、β−（メタ）アクリロイルオキシエチルハイドロ
ゲンサクシネート等の１官能モノマー、エチレングリコ
ールジ（メタ）アクリレート、1,6-ヘキサンジオールジ
（メタ）アクリレート、ネオペンチルグリコールジ（メ
タ）アクリレート、2,2-ビス〔4-（メタクリロキシエト
キシ）フェニル〕プロパン、2,2-ビス〔4-アクリロキシ
・ジエトキシ）フェニル〕プロパン等の２官能モノマ
ー、トリメチロールプロパントリ（メタ）アクリレート
（新中村化学社製 NKエステル ATMPT等）、テトラメチ
ロールメタンテトラ（メタ）アクリレート等の３官能以
上のモノマーが挙げられる。一方、オリゴマーとして
は、ジペンタエリスリトールヘキサアクリレート（日本
化薬社製 カヤラッドDPHA等）、ジペンタエリスリトー
ルのカプロラクトン付加物のヘキサアクリレート、メラ
ミンアクリレート（新中村化学社製 NKオリゴN-6A,N-3
A 等）、エポキシ（メタ）アクリレートプレポリマー
（新中村化学社製 NKオリゴEA-800,EA-6300等）等が挙
げられる。これらは、単独もしくは混合して用いること
ができる。In the present invention, the photosensitive monomer and / or oligomer (B) is used in combination for the purpose of lowering the viscosity of the coloring composition and increasing the exposure sensitivity. Monomers such as 2-hydroxy (meth) acrylate, β- (meth) acryloyloxyethyl hydrogen succinate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Difunctional monomers such as pentyl glycol di (meth) acrylate, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4-acryloxydiethoxy) phenyl] propane, trimethylolpropane tri Examples include tri- or higher functional monomers such as (meth) acrylate (NK ester ATMPT manufactured by Shin-Nakamura Chemical Co., Ltd.) and tetramethylolmethane tetra (meth) acrylate. On the other hand, as the oligomer, dipentaerythritol hexaacrylate (Kayarad DPHA, etc. manufactured by Nippon Kayaku Co., Ltd.), hexaacrylate of a caprolactone adduct of dipentaerythritol, melamine acrylate (NK oligo N-6A, N-3 manufactured by Shin Nakamura Chemical Co., Ltd.
A), epoxy (meth) acrylate prepolymer (NK oligo EA-800, EA-6300, etc., manufactured by Shin Nakamura Chemical Co., Ltd.) and the like. These can be used alone or in combination.
【００１４】感光性着色組成物を紫外線により重合ない
し架橋反応させるために、 (C)光重合開始剤を加える。
光重合開始剤としては、ベンゾフェノン、オルトベンゾ
イル安息香酸メチル、4-ジメチルアミノ安息香酸エチル
（日本化薬社製 カヤキュアーEPA 等）、2,4-ジエチル
チオキサンソン（日本化薬社製 カヤキュアーDETX
等）、2-メチル-1-[4-（メチルチオ）フェニル]-2-モル
ホリノプロパノン-1（チバガイギー社製 イルガキュア
ー907 等）、テトラ（t-ブチルパ−オキシカルボニル）
ベンゾフェノン、ベンジル，2-ヒドロキシ−2-メチル−
1-フェニル−プロパン−1-オン、4,4-ビスジエチルアミ
ノベンゾフェノン、2,2'−ビス（2-クロロフェニル)-4,
5,4',5'-テトラフェニル-1,2'-ビイミダゾール（保土谷
化学社製 B-CIM 等）等が使用でき、必要に応じて光増
感剤を加えることができる。A photopolymerization initiator (C) is added in order to polymerize or crosslink the photosensitive coloring composition with ultraviolet rays.
Examples of the photopolymerization initiator include benzophenone, methyl orthobenzoyl benzoate, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethylthioxanthone (Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.).
Etc.), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (Irgacure 907 manufactured by Ciba-Geigy), tetra (t-butylperoxycarbonyl)
Benzophenone, benzyl, 2-hydroxy-2-methyl-
1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2,2'-bis (2-chlorophenyl) -4,
5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM etc. manufactured by Hodogaya Chemical Co., Ltd.) can be used, and a photosensitizer can be added if necessary.
【００１５】(D)色素材は、光の３原色と呼ばれる赤、
緑、青と、ブラックマトリックス部の黒の４色である。
色素材としては、染料および顔料があるが、耐熱性、耐
光性の点から顔料が優位であり、このような顔料として
下記のものが挙げられる。いずれもカラーインデックス
(C.I.)ナンバーにて示す。C.I.黄色顔料２０、２４、８
６、９３、１０９、１１０、１１７、１２５、１３７、
１３８、１４７、１４８、１５３、１５４、１６６、１
６８、C.I.オレンヂ顔料３６、４３、５１、５５、５
９、６１、C.I.赤色顔料９、９７、１２２、１２３、１
４９、１６８、１７７、１８０、１９２、２１５、２１
６、２１７、２２０、２２３、２２４、２２６、２２
７、２２８、２４０、C.I.バイオレット顔料１９、２
３、２９、３０、３７、４０、５０、C.I.青色顔料１
５、１５：１、１５：４、１５：６、２２、６０、６
４、C.I.緑色顔料７、３６、C.I.ブラウン顔料２３、２
５、２６、C.I.黒色顔料７およびチタンブラック等が例
示できる。The color material (D) is red, which is called the three primary colors of light,
The four colors are green, blue, and black in the black matrix portion.
Color materials include dyes and pigments, and pigments are dominant in terms of heat resistance and light resistance, and examples of such pigments include the following. All are color indexes
Indicated by (CI) number. CI yellow pigment 20, 24, 8
6, 93, 109, 110, 117, 125, 137,
138, 147, 148, 153, 154, 166, 1
68, CI orange pigment 36, 43, 51, 55, 5
9, 61, CI red pigments 9, 97, 122, 123, 1
49, 168, 177, 180, 192, 215, 21
6, 217, 220, 223, 224, 226, 22
7, 228, 240, CI violet pigment 19, 2
3, 29, 30, 37, 40, 50, CI blue pigment 1
5, 15: 1, 15: 4, 15: 6, 22, 60, 6
4, CI green pigment 7, 36, CI brown pigment 23, 2
5, 26, CI black pigment 7, titanium black, and the like.
【００１６】本発明における感光性着色組成物は、顔料
等の色素材を十分に分散させること、およびガラス基板
上に１〜３ミクロンの膜厚となるように塗布されること
から (E)溶剤を用いる。溶剤としては、例えばシクロヘキサ
ノン、セロソルブアセテート、ジエチレングリコールジ
メチルエーテル、エチルベンゼン、エチレングリコール
ジエチルエーテル、キシレン、エチルセロソルブ、メチ
ル−ｎアミルケトン、プロピレングリコールモノメチル
エーテル等が挙げられ、単独もしくは混合して用いる。Since the photosensitive coloring composition of the present invention sufficiently disperses color materials such as pigments and is applied on a glass substrate so as to have a film thickness of 1 to 3 μm, (E) solvent To use. Examples of the solvent include cyclohexanone, cellosolve acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, and propylene glycol monomethyl ether, which may be used alone or in combination.
【００１７】この他、貯蔵安定性を考慮する場合は、重
合禁止剤を少々加えてもよい。一方、顔料の感光性共重
合化合物等への分散には、三本ロールミル、二本ロール
ミル、サンドミル、ニーダー等の各種分散手段を使用で
きる。また、これらの分散を良好とするために、適宜分
散助剤を添加できる。このような分散助剤としては、各
種界面活性剤、顔料の誘導体が使用できる。このような
分散助剤は、顔料の分散に優れ、分散後の顔料の再凝集
を防止する効果が大きいので透明性に優れたカラーフィ
ルターが得られる。In addition to this, when considering storage stability, a small amount of a polymerization inhibitor may be added. On the other hand, various dispersing means such as a three-roll mill, a two-roll mill, a sand mill and a kneader can be used to disperse the pigment in the photosensitive copolymer compound and the like. Further, in order to improve the dispersion of these, a dispersion aid can be added as appropriate. As such a dispersion aid, various surfactants and pigment derivatives can be used. Such a dispersion aid is excellent in the dispersion of the pigment and has a great effect of preventing the reaggregation of the pigment after the dispersion, so that a color filter having excellent transparency can be obtained.
【００１８】本発明の感光性着色組成物は、ガラス基板
上に、スプレーコートやスピナーコート等の塗布方法に
より塗布される。乾燥された膜は１〜３ミクロンであ
り、所定のパターンを有するポジまたはネガのマスクを
接触あるいは非接触を通して紫外線露光を行う。その後
アルカリ現像液に浸漬もしくはスプレーなどにより噴霧
して未硬化部を除去し、以下同様の操作を繰り返す。更
に感光性樹脂の重合を促進するため、加熱を施すことも
必要に応じ行える。The photosensitive coloring composition of the present invention is applied onto a glass substrate by a coating method such as spray coating or spinner coating. The dried film has a thickness of 1 to 3 μm and is exposed to ultraviolet light through a positive or negative mask having a predetermined pattern through contact or non-contact. After that, the uncured portion is removed by immersing in an alkali developing solution or spraying by spraying, and the same operation is repeated. Furthermore, in order to accelerate the polymerization of the photosensitive resin, heating can be performed as necessary.
【００１９】現像に際しては、アルカリ現像液として炭
酸ソーダ、苛性ソーダ等の水溶液が使用され、ジメチル
ベンジルアミン、トリエタノールアミン等のアミンを添
加することもできる。なお、紫外線露光感度を上げるた
めに、着色組成物を塗布乾燥後水溶性あるいはアルカリ
水溶性樹脂、例えば水溶性アクリル樹脂やポリビニルア
ルコール樹脂等を塗布乾燥し紫外線露光を行うこともで
きる。At the time of development, an aqueous solution of sodium carbonate, caustic soda or the like is used as an alkaline developer, and an amine such as dimethylbenzylamine or triethanolamine may be added. In order to increase the sensitivity of exposure to ultraviolet light, it is also possible to apply the coloring composition and then dry it with a water-soluble or alkaline water-soluble resin, for example, a water-soluble acrylic resin or polyvinyl alcohol resin, and dry it.
【００２０】[0020]
【実施例】以下、実施例に基づいて本発明を説明する。
例中、部とは重量部を、％とは重量％をそれぞれ表す。
実施例に先立ち、樹脂合成例を示す。 ＩＰＤＩアダクトの合成 イソホロンジイソシアネート（IPDI） 222部を窒素気流
中１L の４つ口フラスコ内で80℃に加熱後、2-ヒドロキ
シエチルアクリレート 116部およびハイドロキノン0.13
部を２時間かけて滴下し、次いで80℃で３時間反応させ
て、液状のイソシアネート基１個とビニル基１個を有す
る化合物（IPDIアダクト）を得た。EXAMPLES The present invention will be described below based on examples.
In the examples, “part” means “part by weight” and “%” means “% by weight”.
Prior to the examples, resin synthesis examples will be shown. Synthesis of IPDI Adduct After heating 222 parts of isophorone diisocyanate (IPDI) to 80 ° C in a 1 L 4-neck flask in a nitrogen stream, 116 parts of 2-hydroxyethyl acrylate and 0.13 of hydroquinone.
Parts were added dropwise over 2 hours and then reacted at 80 ° C. for 3 hours to obtain a liquid compound having one isocyanate group and one vinyl group (IPDI adduct).
【００２１】樹脂合成例（ａ） １L の４つ口フラスコに、ジエチレングリコールジメチ
ルエーテル 175.0部、スチレン 8.8部、2-ヒドロキシメ
タクリレート43.8部、メタクリル酸26.3部、メタクリル
酸エチル96.3部を仕込み90℃に加熱し、事前にジエチレ
ングリコールジメチルエーテル 145.0部、スチレン 8.8
部、2-ヒドロキシメタクリレート43.8部、メタクリル酸
26.3部、メタクリル酸エチル96.3部とナイパーBMT （日
本油脂社製、過酸化ベンゾイル）2.92部を混合溶解した
ものを３時間で滴下し、90℃にて３時間反応させた。さ
らに、ナイパーBMT 1.75部をジエチレングリコールジメ
チルエーテル10部で溶解させたものを添加し、１時間反
応を続けた。次いで、フラスコ内温を80℃としIPDIアダ
クト34.3部、オクチル酸錫0.02部をジエチレングリコー
ルジメチルエーテル20部で溶解したものを約10分で滴下
し、滴下後２時間反応させた。反応生成物の酸価は約90
であった。Resin Synthesis Example (a) A 1 L 4-necked flask was charged with 175.0 parts of diethylene glycol dimethyl ether, 8.8 parts of styrene, 43.8 parts of 2-hydroxymethacrylate, 26.3 parts of methacrylic acid and 96.3 parts of ethyl methacrylate and heated to 90 ° C. , Diethylene glycol dimethyl ether 145.0 parts, styrene 8.8 in advance
Parts, 2-hydroxymethacrylate 43.8 parts, methacrylic acid
A mixture of 26.3 parts, 96.3 parts of ethyl methacrylate and 2.92 parts of Nyper BMT (manufactured by NOF CORPORATION, benzoyl peroxide) was added dropwise over 3 hours and reacted at 90 ° C for 3 hours. Further, 1.75 parts of Nyper BMT dissolved in 10 parts of diethylene glycol dimethyl ether was added, and the reaction was continued for 1 hour. Then, the temperature inside the flask was adjusted to 80 ° C., 34.3 parts of IPDI adduct and 0.02 part of tin octylate dissolved in 20 parts of diethylene glycol dimethyl ether were added dropwise over about 10 minutes, and the reaction was carried out for 2 hours after the addition. The acid value of the reaction product is about 90.
Met.
【００２２】樹脂合成例（ｂ） １L の４つ口フラスコに、ジエチレングリコールジメチ
ルエーテル 175.0部、スチレン17.5部、2-ヒドロキシメ
タクリレート43.8部、アクリル酸26.3部、メタクリル酸
ブチル87.7部を仕込み90℃に加熱し、事前にジエチレン
グリコールジメチルエーテル 140.0部、スチレン17.5
部、2-ヒドロキシメタクリレート43.8部、アクリル酸2
6.3部、メタクリル酸ブチル87.7部とナイパーBMT 2.92
部を混合溶解したものを３時間で滴下し、90℃にて３時
間反応させた。さらに、ナイパーBMT1.75部をジエチレ
ングリコールジメチルエーテル10部で溶解させたものを
添加し、１時間反応を続けた。次いで、フラスコ内温を
80℃としIPDIアダクト45.5部、オクチル酸錫0.13部をジ
エチレングリコールジメチルエーテル25部で溶解したも
のを約10分で滴下し、滴下後２時間反応させた。反応生
成物の酸価は約 105であった。Resin Synthesis Example (b) A 1 L four-necked flask was charged with 175.0 parts of diethylene glycol dimethyl ether, 17.5 parts of styrene, 43.8 parts of 2-hydroxymethacrylate, 26.3 parts of acrylic acid and 87.7 parts of butyl methacrylate and heated to 90 ° C. , Diethylene glycol dimethyl ether 140.0 parts, styrene 17.5 in advance
Part, 2-hydroxymethacrylate 43.8 parts, acrylic acid 2
6.3 parts, butyl methacrylate 87.7 parts and Niper BMT 2.92
What mixed and melt | dissolved 1 part was dripped in 3 hours, and it was made to react at 90 degreeC for 3 hours. Further, 1.75 parts of Nyper BMT dissolved in 10 parts of diethylene glycol dimethyl ether was added, and the reaction was continued for 1 hour. Then, the temperature in the flask
At 80 ° C., 45.5 parts of IPDI adduct and 0.13 part of tin octylate dissolved in 25 parts of diethylene glycol dimethyl ether were added dropwise over about 10 minutes, and the reaction was carried out for 2 hours after the addition. The acid value of the reaction product was about 105.
【００２３】樹脂合成例（ｃ） １L の４つ口フラスコに、シクロヘキサノン175.0 部、
スチレン43.8部、2-ヒドロキシアクリレート43.8部、ア
クリル酸35.0部、メタクリル酸ブチル52.5部を仕込み90
℃に加熱し、事前にシクロヘキサノン145.0 部、スチレ
ン43.8部、2-ヒドロキシアクリレート43.8部、アクリル
酸35.0部、メタクリル酸ブチル52.5部とアゾビスイソブ
チロニトリル1.75部を混合溶解したものを３時間で滴下
し、90℃にて３時間反応させた。さらに、アゾビスイソ
ブチロニトリル0.70部をシクロヘキサノン10部で溶解さ
せたものを添加し、１時間反応を続けた。次いで、フラ
スコ内温を80℃としIPDIアダクト38.2部、オクチル酸錫
0.13部をシクロヘキサノン20部で溶解したものを約10分
で滴下し、滴下後２時間反応させた。反応生成物の酸価
は約 140であった。Resin Synthesis Example (c) In a 1 L four-necked flask, 175.0 parts of cyclohexanone,
Charge styrene 43.8 parts, 2-hydroxy acrylate 43.8 parts, acrylic acid 35.0 parts, butyl methacrylate 52.5 parts 90
After heating to ℃, mix and dissolve cyclohexanone 145.0 parts, styrene 43.8 parts, 2-hydroxy acrylate 43.8 parts, acrylic acid 35.0 parts, butyl methacrylate 52.5 parts and azobisisobutyronitrile 1.75 parts in advance in 3 hours. It was dropped and reacted at 90 ° C. for 3 hours. Further, a solution prepared by dissolving 0.70 part of azobisisobutyronitrile in 10 parts of cyclohexanone was added, and the reaction was continued for 1 hour. Next, the temperature inside the flask was set to 80 ° C, and 38.2 parts of IPDI adduct and tin octylate were used.
What dissolved 0.13 part in 20 parts of cyclohexanone was dripped in about 10 minutes, and it was made to react for 2 hours after dropping. The acid value of the reaction product was about 140.
【００２４】樹脂合成例（ｄ） １L の４つ口フラスコに、シクロヘキサノン 175.0部、
スチレン26.3部、2-ヒドロキシアクリレート43.8部、ア
クリル酸35.0部、メタクリル酸ブチル70.0部を仕込み90
℃に加熱し、事前にシクロヘキサノン 145.0部、スチレ
ン26.3部、2-ヒドロキシアクリレート43.8部、アクリル
酸35.0部、メタクリル酸ブチル70.0部とアゾビスイソブ
チロニトリル1.75部を混合溶解したものを３時間で滴下
し、90℃にて３時間反応させた。さらに、アゾビスイソ
ブチロニトリル0.70部をシクロヘキサノン10部で溶解さ
せたものを添加し、１時間反応を続けた。次いで、フラ
スコ内温を80℃とし、イソシアネートエチルメタクリレ
ート23.5部、オクチル酸錫0.11部をシクロヘキサノン20
部で溶解したものを約10分で滴下し、滴下後２時間反応
させた。反応生成物の酸価は約 145であった。Resin Synthesis Example (d) In a 1 L 4-neck flask, 175.0 parts of cyclohexanone,
Charge styrene 26.3 parts, 2-hydroxy acrylate 43.8 parts, acrylic acid 35.0 parts, butyl methacrylate 70.0 parts 90
It was heated to ℃ and mixed with cyclohexanone 145.0 parts, styrene 26.3 parts, 2-hydroxy acrylate 43.8 parts, acrylic acid 35.0 parts, butyl methacrylate 70.0 parts and azobisisobutyronitrile 1.75 parts in advance in 3 hours. It was dropped and reacted at 90 ° C. for 3 hours. Further, a solution prepared by dissolving 0.70 part of azobisisobutyronitrile in 10 parts of cyclohexanone was added, and the reaction was continued for 1 hour. Then, the flask internal temperature was set to 80 ° C., and 23.5 parts of isocyanate ethyl methacrylate and 0.11 part of tin octylate were added to cyclohexanone 20.
What was dissolved in 1 part was dropped in about 10 minutes, and after the dropping, reaction was carried out for 2 hours. The acid value of the reaction product was about 145.
【００２５】樹脂合成例（ｅ） 樹脂合成例(a) において、IPDIアダクト反応前の反応生
成物で、酸価は約 100であった。Resin Synthesis Example (e) In the resin synthesis example (a), the reaction product before the IPDI adduct reaction had an acid value of about 100.
【００２６】樹脂合成例（ｆ） １L の４つ口フラスコに、ジエチレングリコールジメチ
ルエーテル 175.0部、スチレン26.3部、2-ヒドロキシメ
タクリレート43.8部、メタクリル酸 8.8部、メタクリル
酸エチル96.3部を仕込み90℃に加熱し、事前にジエチレ
ングリコールジメチルエーテル 145.0部、スチレン26.3
部、2-ヒドロキシメタクリレート43.8部、メタクリル酸
8.8部、メタクリル酸エチル96.3部とナイパーBMT 2.92
部を混合溶解したものを３時間で滴下し、90℃にて３時
間反応させた。さらに、ナイパーBMT 1.75部をジエチレ
ングリコールジメチルエーテル10部で溶解させたものを
添加し、１時間反応を続けた。次いで、フラスコ内温を
80℃としIPDIアダクト34.3部、オクチル酸錫0.02部をジ
エチレングリコールジメチルエーテル20部で溶解したも
のを約10分で滴下し、滴下後２時間反応させた。反応生
成物の酸価は約30であった。Resin Synthesis Example (f) A 1 L four-necked flask was charged with 175.0 parts of diethylene glycol dimethyl ether, 26.3 parts of styrene, 43.8 parts of 2-hydroxymethacrylate, 8.8 parts of methacrylic acid and 96.3 parts of ethyl methacrylate and heated to 90 ° C. , Diethylene glycol dimethyl ether 145.0 parts, styrene 26.3 in advance
Parts, 2-hydroxymethacrylate 43.8 parts, methacrylic acid
8.8 parts, ethyl methacrylate 96.3 parts and Niper BMT 2.92
What was mixed and melt | dissolved was dripped in 3 hours, and it was made to react at 90 degreeC for 3 hours. Further, 1.75 parts of Nyper BMT dissolved in 10 parts of diethylene glycol dimethyl ether was added, and the reaction was continued for 1 hour. Then, the temperature in the flask
A solution obtained by dissolving 34.3 parts of IPDI adduct and 0.02 part of tin octylate in 20 parts of diethylene glycol dimethyl ether was added dropwise over about 10 minutes and reacted for 2 hours after the addition. The acid value of the reaction product was about 30.
【００２７】〔実施例１〕 (1) 赤色レジストの作製 樹脂合成例（ａ） １２．５６部 リオノーゲンレッドＧＤ（東洋インキ製造社製） ７．２０部 リオノーゲンエロー３Ｇ（東洋インキ製造社製） ２．４０部 分散剤 ０．５１部 ジエチレングリコールジメチルエーテル ４２．８９部 を混合し、サンドミルにて十分に分散して、赤色のペー
ストを作製した。次いで 赤色ペースト ６５．５６部 ＮＫエステルＡＴＭＰＴ（新中村化学社製） ３．５６部 イルガキュア９０７（チバガイギー社製） ０．１２部 カヤキュアーＤＥＴＸ（日本化薬社製） ０．１２部 カヤキュアーＥＰＡ（日本化薬社製） ０．０６部 ジエチレングリコールジメチルエーテル ３１．８３部 を攪拌可能な容器中で十分に混合し、不揮発分20％の赤
色レジストを作製した。[Example 1] (1) Preparation of red resist Resin synthesis example (a) 12.56 parts Rionogen Red GD (manufactured by Toyo Ink Mfg. Co.) 7.20 parts Rionogen Yellow 3G (manufactured by Toyo Ink Mfg. Co., Ltd.) ) 2.40 parts Dispersant 0.51 part Diethylene glycol dimethyl ether 42.89 parts were mixed and sufficiently dispersed by a sand mill to prepare a red paste. Next, red paste 65.56 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.56 parts Irgacure 907 (manufactured by Ciba Geigy) 0.12 parts Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.12 parts Kayacure EPA (manufactured by Nippon Kayaku) Yakusha) 0.06 parts Diethylene glycol dimethyl ether 31.83 parts were sufficiently mixed in a stirrable container to prepare a red resist having a nonvolatile content of 20%.
【００２８】 (2) 緑色レジストの作製 樹脂合成例（ａ） １３．６２部 リオノールグリーン２ＹＳ（東洋インキ製造社製） ８．９１部 リオノーゲンエロー３Ｇ（東洋インキ製造社製） １．６５部 分散剤 ０．５５部 ジエチレングリコールジメチルエーテル ４６．９５部 を混合し、サンドミルにて十分に分散して、緑色のペー
ストを作製した。次いで 緑色ペースト ７１．６８部 ＮＫエステルＡＴＭＰＴ（新中村化学社製） ３．９０部 イルガキュア９０７（チバガイギー社製） ０．１８部 カヤキュアーＤＥＴＸ（日本化薬社製） ０．１８部 カヤキュアーＥＰＡ（日本化薬社製） ０．０９部 ジエチレングリコールジメチルエーテル ４７．６９部 を攪拌可能な容器中で十分に混合し、不揮発分18％の緑
色レジストを作製した。(2) Preparation of green resist Resin synthesis example (a) 13.62 parts Rionol green 2YS (manufactured by Toyo Ink Mfg. Co.) 8.91 parts Rionogen Yellow 3G (manufactured by Toyo Ink Mfg. Co.) 1.65 parts Dispersant 0.55 parts Diethylene glycol dimethyl ether 46.95 parts were mixed and sufficiently dispersed with a sand mill to prepare a green paste. Then green paste 71.68 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.90 parts Irgacure 907 (manufactured by Ciba Geigy) 0.18 parts Kayacure DETX (manufactured by Nippon Kayaku Co.) 0.18 parts Kayacure EPA (manufactured by Nippon Kayaku) (Yakusha Co., Ltd.) 0.09 parts Diethylene glycol dimethyl ether 47.69 parts were sufficiently mixed in a stirrable container to prepare a green resist having a nonvolatile content of 18%.
【００２９】 (3) 青色レジストの作製 樹脂合成例（ａ） １３．５４部 リオノールブルーＥＳ（東洋インキ製造社製） ５．６６部 リオノーゲンバイオレットＲＬ（東洋インキ製造社製）１．４２部 分散剤 ０．４０部 ジエチレングリコールジメチルエーテル ３７．４０部 を混合し、サンドミルにて十分に分散して、青色のペー
ストを作製した。次いで 青色ペースト ５９．８４部 ＮＫエステルＡＴＭＰＴ（新中村化学社製） ４．３０部 イルガキュア９０７（チバガイギー社製） ０．２２部 カヤキュアーＤＥＴＸ（日本化薬社製） ０．２２部 カヤキュアーＥＰＡ（日本化薬社製） ０．１１部 ジエチレングリコールジメチルエーテル ３４．３２部 を攪拌可能な容器中で十分に混合し、不揮発分20％の青
色レジストを作製した。(3) Preparation of blue resist Resin synthesis example (a) 13.54 parts Rionol Blue ES (manufactured by Toyo Ink Manufacturing Co., Ltd.) 5.66 parts Rionogen Violet RL (manufactured by Toyo Ink Manufacturing Co., Ltd.) 1.42 parts Dispersant 0.40 parts Diethylene glycol dimethyl ether 37.40 parts were mixed and sufficiently dispersed by a sand mill to prepare a blue paste. Blue paste 59.84 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.30 parts Irgacure 907 (manufactured by Ciba Geigy) 0.22 parts Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.22 parts Kayacure EPA (manufactured by Nippon Kayaku) 0.11 part Diethylene glycol dimethyl ether 34.32 parts was thoroughly mixed in a stirrable container to produce a blue resist having a nonvolatile content of 20%.
【００３０】得られた赤色レジストを１μm の精密濾過
し、既にブラックマトリックスをパターン形成されたガ
ラス基板上に、スピンコーターにて溶剤乾燥後の膜厚が
1.3μm となるようにスピンコートした。次に、60℃20
分のプリベーク後ポリビニルアルコール水溶液をスピン
コートし水を乾燥後、パターン形成用フォトマスクを用
いて露光した。１％の炭酸ソーダ水溶液で現像し、純水
で洗浄したのち 230℃１時間のポストベークを行った。
以下、同様の方法にて、緑、青のパターンを形成し、カ
ラーフィルターを作製した。The resulting red resist was microfiltered to 1 μm, and the film thickness after solvent drying with a spin coater was performed on a glass substrate on which a black matrix had already been patterned.
It was spin-coated so as to have a thickness of 1.3 μm. Next, 60 ℃ 20
After pre-baking for a minute, a polyvinyl alcohol aqueous solution was spin-coated, water was dried, and then exposure was performed using a photomask for pattern formation. It was developed with a 1% aqueous solution of sodium carbonate, washed with pure water, and post-baked at 230 ° C. for 1 hour.
Hereinafter, green and blue patterns were formed by the same method to prepare a color filter.
【００３１】〔実施例２〜４および比較例１〜２〕樹
脂、モノマーおよび開始剤を表１に示したものに代えた
以外は、実施例１と同様にしてカラーフィルターを作成
した。ただし、表中()内の数値は重量比を、DPHAはカヤ
ラッドDPHA（日本化薬社製）を、 B-CIMは B-CIM（保土
谷化学社製）を示す。[Examples 2 to 4 and Comparative Examples 1 to 2] Color filters were prepared in the same manner as in Example 1 except that the resins, monomers and initiators shown in Table 1 were replaced. However, the values in parentheses in the table are weight ratios, DPHA is Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.), and B-CIM is B-CIM (Hodogaya Chemical Co., Ltd.).
【００３２】実施例および比較例で得られたアルカリ現
像型感光性着色組成物の性能を、以下の方法により評価
した。 １．コート性 スピンコーターにて膜厚 1.3μｍに塗布するときの塗膜
の状態（ピンホール、はじきの有無）を、目視で評価。 ２．現像性、感度および解像度 スピンコーターにて塗布・乾燥して得られた塗膜の上
に、テストチャート（凸版印刷社製 線幅 0.5〜50.0μ
ｍ）を介して10〜40mJ/cm2で紫外線照射し、１％の炭酸
ソーダ水溶液で現像するときの露光量および現像時間の
最適値と、そのときの解像度を評価。 ３．透過率 ２と同様にして得られた塗膜を 230℃の熱風循環式乾燥
炉中で60分加熱して、得られた硬化塗膜の透過率（赤色
レジスト510nm 、緑色レジスト540nm 、青色レジスト46
0nm ）を、分光光度計（日立製作所社製）により測定し
た。The performance of the alkali developing type photosensitive coloring compositions obtained in Examples and Comparative Examples was evaluated by the following methods. 1. Coatability The state of the coating film (presence or absence of pinholes and repelling) when coated to a film thickness of 1.3 μm with a spin coater is visually evaluated. 2. Developability, sensitivity and resolution A test chart (Toppan Printing Co., Ltd. line width 0.5 to 50.0 μm was applied on the coating film obtained by coating and drying with a spin coater.
The optimum value of the exposure amount and the developing time and the resolution at that time when ultraviolet rays are irradiated at 10 to 40 mJ / cm 2 through m) to develop with a 1% sodium carbonate aqueous solution are evaluated. 3. The coating film obtained in the same manner as the transmittance 2 was heated in a hot air circulation drying oven at 230 ° C for 60 minutes, and the transmittance of the cured coating film obtained (red resist 510 nm, green resist 540 nm, blue resist 46
0 nm) was measured by a spectrophotometer (manufactured by Hitachi Ltd.).
【００３３】４．表面硬度 ３と同様にして得られた硬化塗膜に対し、JIS K 5400に
規定される試験方法で表面硬度を測定。 ５．耐熱性（分光変化） ３と同様にして得られた硬化塗膜の、熱風対流式乾燥炉
250℃60分加熱前後の、所定（３と同様）の波長におけ
る透過率の変化。 ６．膜減り率 ３と同様にして得られた硬化塗膜の加熱前後の膜厚を、
表面形状測定器（日本真空技術社製 Dektak3030）によ
り測定し、下式で求めた膜減り率。 ７．耐薬品性 ＩＰＡ耐性については、３と同様にして得られた硬化塗
膜をＩＰＡ蒸気中に５分間設置した後に、その他の耐性
については、各種有機溶剤または５％水酸化ナトリウム
水溶液に30分浸漬した後に、目視により浸漬部の界面の
有無を観察。4. The surface hardness of the cured coating film obtained in the same manner as the surface hardness 3 was measured by the test method specified in JIS K 5400. 5. Heat-resistant (spectral change) 3. Hot air convection drying oven for cured coatings obtained in the same way
Change in transmittance at a predetermined wavelength (same as 3) before and after heating at 250 ° C for 60 minutes. 6. The film thickness before and after heating of the cured coating film obtained in the same manner as in the film reduction ratio 3
The film reduction rate measured by a surface profiler (Dektak3030 manufactured by Nippon Vacuum Technology Co., Ltd.) and calculated by the following formula. 7. Chemical resistance For IPA resistance, after setting the cured coating film obtained in the same manner as 3 in IPA vapor for 5 minutes, for other resistance, soak in various organic solvents or 5% sodium hydroxide aqueous solution for 30 minutes. After that, visually observe the presence or absence of the interface of the immersion part.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【発明の効果】本発明によれば、耐熱性、耐溶剤性さら
に分散性に優れ、薄膜化が容易であり、かつパターン形
状が良好で高品質なカラーフィルターを得ることができ
る。すなわち、従来のアルカリ現像型の組成物を用いた
カラーフィルターの製造工程を変更することなく、現像
もしくは熱によるパターン部分の膜厚減少や溶剤耐性が
良好であり、さらに、色素材濃度を高めても十分な膜硬
度が得られるなど、薄膜化、大型化に対応できるカラー
フィルターを製造することを可能にした。According to the present invention, it is possible to obtain a high-quality color filter which is excellent in heat resistance, solvent resistance and dispersibility, can be easily formed into a thin film, and has a good pattern shape. That is, the film thickness reduction and solvent resistance of the pattern portion due to development or heat are good without changing the manufacturing process of the color filter using the conventional alkali development type composition, and further, the color material concentration is increased. It has become possible to manufacture color filters that can be made thinner and larger, such as sufficient film hardness.
フロントページの続き (72)発明者 中島 薫 東京都中央区京橋二丁目３番13号東洋イン キ製造株式会社内 (72)発明者 坂川 誠 東京都台東区台東一丁目５番１号凸版印刷 株式会社内 (72)発明者 谷 瑞仁 東京都台東区台東一丁目５番１号凸版印刷 株式会社内 (72)発明者 伊藤 慎次 東京都台東区台東一丁目５番１号凸版印刷 株式会社内Front page continuation (72) Inventor Kaoru Nakajima 2-33 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd. (72) Inventor Makoto Sakakawa 1-1-5 Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. In-house (72) Inventor Mizuhito Tani 1-5-1, Taito, Taito-ku, Tokyo Within Toppan Printing Co., Ltd. (72) Inventor Shinji Ito 1-5-1, Taito, Taito-ku, Tokyo Within Toppan Printing Co., Ltd.
Claims (1)
と水酸基を有する化合物10〜40重量％、ビニル基１個と
カルボキシル基を有する化合物10〜30重量％およびビニ
ル基１個を有する化合物 0〜75重量％からなるビニル系
共重合化合物に、イソシアネート基１個と少なくとも１
個以上のビニル基を有する化合物を 5〜25モル％反応さ
せて得られる酸価50〜150 の感光性共重合化合物、 (B)
感光性モノマーおよび／またはオリゴマー、 (C)光重合
開始剤、 (D)色素材および (E)溶剤を含むアルカリ現像
型感光性着色組成物。1. (A) 5 to 55% by weight of styrene, 10 to 40% by weight of a compound having one vinyl group and a hydroxyl group, 10 to 30% by weight of a compound having one vinyl group and a carboxyl group, and one vinyl group. A vinyl-based copolymer compound consisting of 0 to 75% by weight of a compound having at least one isocyanate group and at least 1
A photosensitive copolymer compound having an acid value of 50 to 150 obtained by reacting 5 to 25 mol% of a compound having at least one vinyl group, (B)
An alkali developing type photosensitive coloring composition containing a photosensitive monomer and / or oligomer, (C) photopolymerization initiator, (D) color material and (E) solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1314893A JP3218256B2 (en) | 1993-01-29 | 1993-01-29 | Alkali-developing photosensitive coloring composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1314893A JP3218256B2 (en) | 1993-01-29 | 1993-01-29 | Alkali-developing photosensitive coloring composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06230212A true JPH06230212A (en) | 1994-08-19 |
| JP3218256B2 JP3218256B2 (en) | 2001-10-15 |
Family
ID=11825083
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1314893A Expired - Lifetime JP3218256B2 (en) | 1993-01-29 | 1993-01-29 | Alkali-developing photosensitive coloring composition |
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| Country | Link |
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- 1993-01-29 JP JP1314893A patent/JP3218256B2/en not_active Expired - Lifetime
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