JP2002088136A5 - - Google Patents

Description

ここで、Ｘは一般式（Ｉａ）で示される単位であり、
【化２】

Ｒは水素原子またはＣ１〜５の直鎖または分岐アルキル基、Ｙは酸無水物の残基、Ｚは酸二無水物の残基であり、そしてｎは０から２０までの整数を示す。
【請求項２】 請求項１の一般式（Ｉ）で表される光重合性不飽和樹脂の製造方法であって、
次の一般式（II）で示されるビスフェニルフェノールフルオレン型エポキシ化合物にアクリル酸を反応させて、
【化３】

Ｒは水素原子またはＣ１〜５の直鎖または分岐アルキル基である）、一般式（III）で示されるビスフェニルフェノールフルオレン型エポキシアクリレート化合物を得る工程：
【化４】

Ｒは水素原子またはＣ１〜５の直鎖または分岐アルキル基である）；
該ビスフェニルフェノールフルオレン型エポキシアクリレート化合物に、一般式（IV）で示されるテトラカルボン酸二無水物を反応させる工程：
【化５】

（ここで、Ｚはテトラカルボン酸二無水物の残基である）；および
一般式（Ｖ）で示されるジカルボン酸無水物を反応させる工程：
【化６】

（ここで、Ｙはジカルボン酸無水物の残基である）
を包含する方法。
【請求項３】 請求項１の一般式（Ｉ）で表される光重合性不飽和樹脂を含有する感光性樹脂組成物。
【請求項４】 （Ａ）請求項１の一般式（Ｉ）で表される光重合性不飽和樹脂、
（Ｂ）エポキシ基を有する化合物、
（Ｃ）光重合開始剤、および
（Ｄ）顔料、
を含有するアルカリ可溶型感光性着色樹脂組成物。
【請求項５】 前記光重合性不飽和樹脂（Ｉ）１００重量部に対して、前記エポキシ基を有する化合物、光重合開始剤、および顔料がそれぞれ５〜５０重量部、０.１〜３０重量部、および１０〜２００重量部の割合で含有される、請求項４に記載のアルカリ可溶型感光性着色樹脂組成物。
【請求項６】 さらに光重合性のモノマーおよびオリゴマーでなる群から選択される少なくとも１種を、光重合性不飽和樹脂（Ｉ）１００重量部に対して、５０重量部以下の範囲で含有する、請求項５に記載のアルカリ可溶型感光性着色樹脂組成物。
【請求項７】 基板上に着色層がパターン形成されているカラーフィルターであって、該着色層が、請求項４から６のいずれかに記載のアルカリ可溶型感光性着色樹脂組成物を光硬化させて得られる着色層である、カラーフィルター。
【請求項８】 請求項４から６のいずれかに記載のアルカリ可溶型感光性着色樹脂組成物を基板上に塗布し感光性の着色層を形成する工程、
該着色層をパターン露光し、露光部分の感光性着色樹脂組成物を光硬化させる工程、および
該パターン露光した着色層を現像して未露光部分の着色層を除去し、該光硬化した着色層を基板上にパターンとして残す工程、を包含する、
カラーフィルターの製造方法。
【請求項９】 希アルカリ水溶液により現像を行なう、請求項８に記載の製造方法。 [Claims]
1. A photopolymerizable unsaturated resin represented by the general formula (I):
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Here, X is a unit represented by the general formula (Ia),
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R is a hydrogen atom or a C1-5 linear or branched alkyl group, Y is a residue of an acid anhydride, Z is a residue of an acid dianhydride, and n is an integer from 0 to 20.
2. A method for producing a photopolymerizable unsaturated resin represented by the general formula (I) according to claim 1, wherein
By reacting acrylic acid with a bisphenylphenol fluorene type epoxy compound represented by the following general formula (II),
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R is a hydrogen atom or a C1-5 linear or branched alkyl group), and a step of obtaining a bisphenylphenol fluorene type epoxy acrylate compound represented by the general formula (III):
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R is a hydrogen atom or a C1-5 linear or branched alkyl group);
A step of reacting the bisphenylphenol fluorene type epoxy acrylate compound with a tetracarboxylic dianhydride represented by the general formula (IV):
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(Where Z is a residue of a tetracarboxylic dianhydride); and a step of reacting a dicarboxylic anhydride represented by the general formula (V):
Embedded image

(Where Y is the residue of a dicarboxylic anhydride)
A method comprising:
3. A photosensitive resin composition containing the photopolymerizable unsaturated resin represented by the general formula (I) according to claim 1.
(A) a photopolymerizable unsaturated resin represented by the general formula (I) of claim 1,
(B) a compound having an epoxy group,
(C) a photopolymerization initiator, and (D) a pigment,
An alkali-soluble photosensitive colored resin composition containing:
5. The compound having an epoxy group, the photopolymerization initiator and the pigment are each 5 to 50 parts by weight, 0.1 to 30 parts by weight, based on 100 parts by weight of the photopolymerizable unsaturated resin (I). parts and 10 to 200 are contained in a proportion of parts, the alkali-soluble photosensitive colored resin composition of claim 4.
6. The photopolymerizable unsaturated resin (I) further contains at least one selected from the group consisting of photopolymerizable monomers and oligomers in a range of 50 parts by weight or less based on 100 parts by weight of the photopolymerizable unsaturated resin (I). The alkali-soluble photosensitive colored resin composition according to claim 5.
7. A color filter in which a colored layer is formed in a pattern on a substrate, wherein the colored layer is formed by applying the alkali-soluble photosensitive colored resin composition according to claim 4 to light. A color filter, which is a colored layer obtained by curing.
8. A step of applying the alkali-soluble photosensitive colored resin composition according to any one of claims 4 to 6 on a substrate to form a photosensitive colored layer;
Pattern exposure of the colored layer, photo-curing of the photosensitive colored resin composition in the exposed portion, and developing the pattern-exposed colored layer to remove the unexposed portion of the colored layer, the photo-cured colored layer Leaving a pattern on the substrate,
Manufacturing method of color filter.
9. The production method according to claim 8, wherein development is performed using a dilute aqueous alkaline solution.

Furthermore, by using a composition containing an epoxy compound, a photopolymerization initiator, and a pigment based on the photopolymerizable unsaturated resin , high resolution, heat resistance after light irradiation, and transparency are obtained. It has been found that a color filter having excellent adhesion, hardness, solvent resistance and alkali resistance can be obtained, and the present invention has been completed.

In a preferred embodiment, in the alkali-soluble photosensitive colored resin composition, the compound having an epoxy group, a photopolymerization initiator, and 100 parts by weight of the photopolymerizable unsaturated resin (I). The pigments are contained in proportions of 5 to 50 parts by weight, 0.1 to 30 parts by weight, and 10 to 200 parts by weight, respectively.

In a further preferred embodiment, in the alkali-soluble photosensitive colored resin composition, at least one selected from the group consisting of a photopolymerizable monomer and an oligomer in addition to the above-mentioned components includes a photopolymerizable monomer and an oligomer. It is contained in an amount of 50 parts by weight or less based on 100 parts by weight of the unsaturated resin (I).

The composition of the present invention is preferably an alkali-soluble photosensitive colored resin composition, wherein (A) a photopolymerizable unsaturated resin (I), (B) a compound having an epoxy group, and (C) photopolymerization. It contains an initiator and a pigment (D) (hereinafter, these may be referred to as AD components).

Although this mixture was cloudy, the temperature was gradually raised as it was and heated to 120 ° C. to obtain a solution in which the contents were completely dissolved. This gradually became a transparent and viscous solution, but stirring was continued as it was, and the acid value was measured over time. Heating and stirring were continued until the acid value was less than 2.0 mgKOH / g. It took 12 hours for the acid value to reach the target. Thereafter, the mixture was cooled to room temperature to obtain a colorless and transparent PGMEA solution of a bisphenolfluorene-type epoxy acrylate resin whose main component is represented by the formula (VI).

The thus obtained bisphenol fluorene type epoxy acrylate resins 3 03G, was dissolved by adding propylene glycol monomethyl ether acetate 600 g. To this, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added and mixed, and the mixture was gradually heated and reacted at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was added, mixed and reacted at 90 ° C. for 6 hours to obtain a resin represented by the general formula (IX) ( ^{Y 2 / Z 2 = 50/} 50 ( molar ratio)). The disappearance of the acid anhydride was confirmed from the IR spectrum.

The performance of the obtained color filter ink and color filter was evaluated by the following method. Table 2 shows the evaluation results. Table 2 also shows the results of Comparative Example 2 described below.