TW202315897A - Colored photosensitive composition, cured product, and image display apparatus including cured product - Google Patents

Colored photosensitive composition, cured product, and image display apparatus including cured product Download PDF

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TW202315897A
TW202315897A TW111130624A TW111130624A TW202315897A TW 202315897 A TW202315897 A TW 202315897A TW 111130624 A TW111130624 A TW 111130624A TW 111130624 A TW111130624 A TW 111130624A TW 202315897 A TW202315897 A TW 202315897A
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photosensitive composition
meth
colored photosensitive
acrylate
group
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間下𤥨史
加賀大樹
吉澤恵理
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日商日本化藥股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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  • Chemical & Material Sciences (AREA)
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Abstract

It is an object of the present invention to provide a colored photosensitive composition excellent in dispersibility of a coloring agent or the like and excellent in development characteristics even at a high coloring agent concentration, a colored photosensitive composition excellent in heat resistance, and cured products thereof. Provided is a colored photosensitive composition containing an unsaturated group-containing polycarboxylic acid resin (A), a coloring agent (B), and a solvent (C), the unsaturated group-containing polycarboxylic acid resin (A) is obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride with a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group obtained by reacting an alicyclic isocyanurate type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2).

Description

著色感光性組成物、硬化物、具備硬化物之圖像顯示裝置 Colored photosensitive composition, cured product, image display device with cured product

本發明係關於一種著色感光性組成物、硬化物、具備硬化物之圖像顯示裝置。詳而言之，係關於一種遮蔽性及製版特性優異的感光性著色組成物、及其用途。 The present invention relates to a colored photosensitive composition, a cured product, and an image display device with the cured product. More specifically, it relates to a photosensitive coloring composition excellent in masking properties and plate-making properties, and uses thereof.

傳統之顯示器係常使用形成有使用有機顏料之紅色、綠色、藍色的像素之彩色濾光片、著色間隔物及黑色矩陣。 Conventional displays often use color filters, colored spacers, and black matrices formed with red, green, and blue pixels using organic pigments.

近年來，為了降低顯示器之低功耗並擴大色域，已研究使用量子點等發光性奈米結晶粒子而形成像素的彩色濾光片。具體而言，已知具有包含紅色發光性的奈米結晶粒子之紅色像素、包含綠色發光性之奈米結晶粒子的綠色像素、穿透來自光源的藍色光之藍色像素。 In recent years, in order to reduce the low power consumption of displays and expand the color gamut, color filters using luminescent nano crystal particles such as quantum dots to form pixels have been studied. Specifically, there are known red pixels including red luminescent nanocrystal particles, green pixels including green luminescent nanocrystal particles, and blue pixels that transmit blue light from a light source.

作為彩色濾光片之製造方法已知有光蝕刻法及噴墨法，後者係可降低印墨材料之損失(專利文獻1)。 The photolithography method and the inkjet method are known as the manufacturing method of the color filter, and the latter can reduce the loss of the ink material (Patent Document 1).

藉由噴墨法製造包含發光性奈米結晶粒子之彩色濾光片時，在預先製作之隔牆包圍的區域(像素部)吐出印墨而形成像素。為了防止與該隔牆相鄰之像素部間的印墨彼此混合等，尚必須為高精細的圖型(微細的圖型)。又，已知有使用包含著色劑的感光性組成物(著色感光性組成物)藉由光蝕刻法形成具有遮光效果者(專利文獻2)。 When manufacturing a color filter containing luminescent nanocrystalline particles by the inkjet method, ink is ejected from the region (pixel portion) surrounded by prefabricated partition walls to form pixels. A high-definition pattern (fine pattern) is also required in order to prevent mixing of inks between pixel portions adjacent to the partition wall. Moreover, it is known to form what has a light-shielding effect by the photoetching method using the photosensitive composition (colored photosensitive composition) containing a coloring agent (patent document 2).

其他，亦已知一種應用於硬化物的嘗試，該硬化物係使碳黑等分散於以酚芳烷基型環氧樹脂作為基本骨架之酸改性環氧基丙烯酸酯中，並使用於液晶顯示面板等(專利文獻3)。 In addition, there is also known an attempt to apply to a hardened product in which carbon black or the like is dispersed in an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton and used in liquid crystals. Display panels and the like (Patent Document 3).

[先前技術文獻] [Prior Art Literature]

[專利文獻] [Patent Document]

[專利文獻1]日本特開2019-086745號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2019-086745

[專利文獻2]日本特開2007-10795號公報 [Patent Document 2] Japanese Unexamined Patent Publication No. 2007-10795

[專利文獻3]日本特開2005-055814號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2005-055814

然而，若使用專利文獻2之感光性組成物，有下列問題：藉由光蝕刻法所得到的圖型之顯影性差，且有時無法獲得所希望的形狀之圖型。又，在具有遮光效果之隔牆、及黑色矩陣、著色間隔物、彩色光阻中，即使進一步含有著色劑，亦必須為分散性良好的著色感光性組成物。 However, if the photosensitive composition of Patent Document 2 is used, there are following problems: the developability of the pattern obtained by the photolithography method is poor, and the pattern of the desired shape may not be obtained. In addition, even if a colorant is further contained in a partition wall having a light-shielding effect, a black matrix, a colored spacer, and a color resist, it must be a colored photosensitive composition with good dispersibility.

本發明之目的在於提供一種可改善上述習知技術的問題點，著色劑等之分散性優異、且以高的著色劑濃度亦具有良好的顯影特性之著色感光性組成物、再者，耐熱性為良好的著色感光性組成物、及其等之硬化物。 The object of the present invention is to provide a colored photosensitive composition which can improve the above-mentioned problems of the prior art, has excellent dispersibility of colorants, etc., and has good developing properties even at a high concentration of colorant, and furthermore, has excellent heat resistance It is a good colored photosensitive composition and its hardened product.

本發明人等為解決前述之課題，經致力研究之結果，發現可提供一種著色劑等分散性優異、且以高的著色劑濃度亦具有良好的顯影特性之著色感光性組成物，又，視情況之耐熱性良好的著色感光性組成物、及其等之硬化物。該著色感光性組成物係包含：含有不飽和基的聚羧酸樹脂(A)、著色劑(B)、及溶劑(C)，而該含有不飽和基的聚羧酸樹脂(A)係使藉由脂環式三聚異氰酸酯型聚異氰酸酯(a1)與脂環式三羧酸酐(a2)之反應所得到的具有末端酸基或酸酐基的聚醯胺醯亞胺樹脂(a3)、與一分子中具有環氧基之(甲基)丙烯酸酯化合物(b)及脂肪族二羧酸酐(c)反應而得者。 The inventors of the present invention, as a result of diligent research to solve the aforementioned problems, have found that it is possible to provide a coloring and photosensitive composition having excellent dispersibility of coloring agents and the like and having good developing properties even at a high concentration of the coloring agent. Colored photosensitive composition with good heat resistance and cured product thereof. The colored photosensitive composition system includes: polycarboxylic acid resin (A) containing unsaturated group, colorant (B) and solvent (C), and the polycarboxylic acid resin (A) containing unsaturated group is made of The polyamide imide resin (a3) with terminal acid group or acid anhydride group obtained by the reaction of alicyclic isocyanate polyisocyanate (a1) and alicyclic tricarboxylic anhydride (a2), and a It is obtained by reacting (meth)acrylate compound (b) with epoxy group and aliphatic dicarboxylic acid anhydride (c) in the molecule.

亦即，本發明係有關下列之(1)至(7)。 That is, the present invention relates to the following (1) to (7).

(1)一種著色感光性組成物，係包含：含有不飽和基的聚羧酸樹脂(A)、著色劑(B)、及溶劑(C)，該含有不飽和基的聚羧酸樹脂(A)係使藉由脂環式三聚異氰酸酯型聚異氰酸酯(a1)與脂環式三羧酸酐(a2)之反應所得到的具有末端酸基或酸酐基的聚醯胺醯亞胺樹脂(a3)、與一分子中具有環氧基之(甲基)丙烯酸酯化合物(b)及脂肪族二羧酸酐或脂肪族三羧酸酐(c)反應而得者。 (1) A colored photosensitive composition comprising: a polycarboxylic acid resin (A) containing an unsaturated group, a colorant (B), and a solvent (C), the polycarboxylic acid resin (A) containing an unsaturated group ) is a polyamide imide resin (a3) having a terminal acid group or an anhydride group obtained by reacting an alicyclic isocyanate-type polyisocyanate (a1) with an alicyclic tricarboxylic anhydride (a2) . A product obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride or aliphatic tricarboxylic anhydride (c).

(2)如(1)所述之著色感光性組成物，係含有交聯劑(D)。 (2) The colored photosensitive composition as described in (1) containing a crosslinking agent (D).

(3)如(1)或(2)所述之著色感光性組成物，係含有光聚合起始劑(E)。 (3) The colored photosensitive composition as described in (1) or (2) containing a photoinitiator (E).

(4)如(1)至(3)中任一項所述之著色感光性組成物，係含有硬化劑(F)。 (4) The colored photosensitive composition as described in any one of (1)-(3) containing a hardening|curing agent (F).

(5)如(1)至(4)中任一項所述之著色感光性組成物，其中，前述著色劑(B)包含黑色顏料。 (5) The colored photosensitive composition as described in any one of (1)-(4) whose said coloring agent (B) contains a black pigment.

(6)一種硬化物，係(1)至(5)中任一項所述之著色感光性組成物之硬化物。 (6) A cured product of the colored photosensitive composition described in any one of (1) to (5).

(7)一種圖像顯示裝置，係具備(6)所述之硬化物。 (7) An image display device comprising the cured product described in (6).

本發明之包含含有不飽和基的聚羧酸樹脂(A)、著色劑(B)、溶劑(C)之著色感光性組成物，係感光性優異，以高的著色劑濃度亦可分散，且具有良好的顯影特性。 The colored photosensitive composition of the present invention comprising unsaturated group-containing polycarboxylic acid resin (A), colorant (B), and solvent (C) has excellent photosensitivity and can be dispersed at high colorant concentration, and Has good developing properties.

≪著色感光性組成物≫ ≪Colored photosensitive composition≫

本發明之著色感光性組成物係包含：含有不飽和基的聚羧酸樹脂(A)、著色劑(B)、溶劑(C)。 The colored photosensitive composition of the present invention comprises: polycarboxylic acid resin (A) containing unsaturated groups, colorant (B), and solvent (C).

以下，說明有關著色感光性組成物含有的必要、及任意之成分。 Hereinafter, essential and optional components contained in the colored photosensitive composition will be described.

著色感光性組成物係包含含有不飽和基的聚羧酸樹脂(A)。 The colored photosensitive composition system contains an unsaturated group-containing polycarboxylic acid resin (A).

本發明之含有不飽和基的聚羧酸樹脂(A)係使藉由脂環式三聚異氰酸酯型聚異氰酸酯(a1)與脂環式三羧酸酐(a2)之反應所得到的具有末端酸基或酸酐基的聚醯胺醯亞胺樹脂(a3)、與一分子中具有環氧基之(甲基)丙烯酸酯化合物(b)及脂肪族二羧酸酐或脂肪族三羧酸酐(c)反應而得者。 The polycarboxylic acid resin (A) containing an unsaturated group of the present invention is obtained by reacting an alicyclic isocyanate-type polyisocyanate (a1) with an alicyclic tricarboxylic anhydride (a2) having a terminal acid group or acid anhydride-based polyamide imide resin (a3), react with a (meth)acrylate compound (b) having an epoxy group in one molecule, and an aliphatic dicarboxylic anhydride or aliphatic tricarboxylic anhydride (c) And the winner.

亦即，本發明之含有不飽和基的聚羧酸樹脂(A)係以二個反應步驟而製造。首先，係使環式三聚異氰酸酯型聚異氰酸酯(a1)與脂環式三羧酸酐(a2)反應而得到的聚醯胺醯亞胺樹脂(a3)之步驟。在本發明中，係以該步驟作為醯胺醯亞胺化步驟。 That is, the unsaturated group-containing polycarboxylic acid resin (A) of the present invention is produced in two reaction steps. First, it is the process of making polyamide-imide resin (a3) obtained by reacting cyclic isocyanate type polyisocyanate (a1) and alicyclic tricarboxylic acid anhydride (a2). In the present invention, this step is used as an amidoimidization step.

然後，係使所得到的聚醯胺醯亞胺樹脂(a3)、一分子中具有環氧基之(甲基)丙烯酸酯化合物(b)及脂肪族二羧酸酐或脂肪族三羧酸酐(c)反應的步驟。在本發明係以該步驟作為羧酸酯化步驟。 Then, the obtained polyamideimide resin (a3), (meth)acrylate compound (b) having an epoxy group in one molecule, and aliphatic dicarboxylic acid anhydride or aliphatic tricarboxylic anhydride (c ) reaction steps. In the present invention, this step is used as the carboxylic acid esterification step.

首先，詳述有關醯胺醯亞胺化步驟。 First, the amide imidization step will be described in detail.

本發明中使用於聚醯胺醯亞胺樹脂(a3)的製造之脂環式三聚異氰酸酯型聚異氰酸酯(a1)係使含有脂環式二異氰酸酯化合物之二異氰酸酯化合物在三聚觸媒之存在下或不存在下進行三聚異氰酸酯化而得者。 The alicyclic isocyanate-type polyisocyanate (a1) used in the production of the polyamide imide resin (a3) in the present invention is obtained by using a diisocyanate compound containing an alicyclic diisocyanate compound in the presence of a trimerization catalyst. Trimeric isocyanate with or without the presence of those obtained.

在本說明書中所謂脂環式係在與本發明之相關中，意指碳原子排列成環之化合物(如從與所謂「脂肪族」及「環狀」之2個用語一起記載者為相同已經暗示)。因此，所謂脂環式亦為環狀脂肪族之同義語。結果，脂環式化合物係屬於同環化合物群，此時，係包含環烷烴、環烯烴、及環炔烴。芳香族化合物及雜環式化合物、甚至雜環式化合物之飽和化合物例在本發明之意義的範圍內，不被視為脂環式。 The so-called alicyclic type in this specification refers to a compound in which carbon atoms are arranged in a ring in relation to the present invention (if it is described together with the two terms "aliphatic" and "cyclic"), it means the same hint). Therefore, the so-called alicyclic is also a synonym for cycloaliphatic. As a result, alicyclic compounds belong to the group of homocyclic compounds, and in this case, cycloalkanes, cycloalkenes, and cycloalkynes are included. Aromatic compounds and heterocyclic compounds, even saturated examples of heterocyclic compounds, are not regarded as alicyclic within the scope of the meaning of the present invention.

含有脂環式二異氰酸酯化合物的二異氰酸酯可列舉例如：異佛酮二異氰酸酯、氫化甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、降莰烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯等。 As diisocyanates containing an alicyclic diisocyanate compound, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. are mentioned, for example.

作為三聚觸媒並無特別指定，可列舉例如：如2,4,6-三(二甲基胺基甲基)酚、2,4-雙(二甲基胺基甲基)酚、2,4,6-三(二烷基胺基烷基)六 氫-S-三嗪等胺化合物、乙酸鉀、2-乙基己酸鉀、辛酸鉀之碳數2至12的羧酸之鹼金屬鹽、羧酸之4級銨鹽等。作為市售品係可列舉如：DABCO P15(三共AIR PRODUCTS製)、DABCO K15(三共AIR PRODUCTS製)、PELCAT9540(PERLON製)、DABCO TMR(三共AIR PRODUCTS製)、TOYOCAT TR20(TOSOH製)、U-CAT 18X(SAN-APRO製)等。 It is not particularly specified as the trimerization catalyst, and examples thereof include: 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2 ,4,6-tris(dialkylaminoalkyl)hexa Amine compounds such as hydrogen-S-triazine, potassium acetate, potassium 2-ethylhexanoate, alkali metal salts of carboxylic acids with 2 to 12 carbon atoms of potassium octanoate, quaternary ammonium salts of carboxylic acids, etc. Examples of commercially available products include DABCO P15 (manufactured by Sankyo Air Products), DABCO K15 (manufactured by Sankyo Air Products), PELCAT9540 (manufactured by Perlon), DABCO TMR (manufactured by Sankyo Air Products), TOYOCAT TR20 (manufactured by Tosoh), U -CAT 18X (manufactured by SAN-APRO), etc.

前述脂環式三聚異氰酸酯型聚異氰酸酯(a1)可列舉例如：由異佛酮二異氰酸酯所合成的脂環式三聚異氰酸酯型三異氰酸酯(包含5聚體等聚合物)、由氫化甲苯二異氰酸酯所合成的脂環式三聚異氰酸酯型三異氰酸酯(包含5聚體等聚合物)、由氫化二甲苯二異氰酸酯所合成的脂環式三聚異氰酸酯型三異氰酸酯(包含5聚體等聚合物)、由降莰烷二異氰酸酯所合成的三聚異氰酸酯型三異氰酸酯(包含5聚體等聚合物)、由氫化二苯基甲烷二異氰酸酯所合成的脂環式三聚異氰酸酯型三異氰酸酯(包含5聚體等聚合物)等。其中，以由異佛酮二異氰酸酯所合成的脂環式三聚異氰酸酯型異氰酸酯為佳。在使用由異佛酮二異氰酸酯所合成的脂環式三聚異氰酸酯型聚異氰酸酯時，黏性及硬化收縮優異。 The aforementioned alicyclic isocyanate-type polyisocyanate (a1) includes, for example, alicyclic isocyanate-type isocyanate (including polymers such as pentamers) synthesized from isophorone diisocyanate, hydrogenated toluene diisocyanate The synthesized alicyclic isocyanate triisocyanate (including polymers such as 5-mer), the alicyclic isocyanate-type triisocyanate synthesized from hydrogenated xylene diisocyanate (including polymers such as 5-mer), Trimeric isocyanate triisocyanate (including polymers such as 5-mer) synthesized from norbornane diisocyanate, alicyclic trimeric isocyanate-type triisocyanate (including 5-mer) synthesized from hydrogenated diphenylmethane diisocyanate other polymers) etc. Among them, alicyclic isocyanate isocyanate synthesized from isophorone diisocyanate is preferred. When using alicyclic isophorone diisocyanate-type polyisocyanate synthesized from isophorone diisocyanate, it has excellent viscosity and curing shrinkage.

在本發明中使用於聚醯胺醯亞胺樹脂(a3)的製造之脂環式三羧酸酐(a2)係可列舉如：環己烷-1,3,4-三羧酸-3,4-酐、環己烷-1,3,5-三羧酸-3,5-酐、環己烷-1,2,3-三羧酸-2,3-酐等。其中，以黏性或硬化收縮優異的環己烷-1,3,4-三羧酸-3,4-酐為佳。 The alicyclic tricarboxylic acid anhydride (a2) used in the manufacture of the polyamideimide resin (a3) in the present invention can be exemplified by: cyclohexane-1,3,4-tricarboxylic acid-3,4 -anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride excellent in viscosity and curing shrinkage is preferable.

相對於前述脂環式三聚異氰酸酯型聚異氰酸酯(a1)具有的異氰酸酯基1mol，前述脂環式三聚異氰酸酯型聚異氰酸酯(a1)與前述脂環式三羧酸酐(a2)之反應較佳係酸酐基與羧酸之合計為1.0mol至3.0mol，更佳 係1.2mol至2.8mol，又更佳係1.4mol至2.6mol。酸酐基與羧酸之合計超過1.0mol時，防止異氰酸酯基之殘存且抑制高分子量化，並顯影性變佳。酸酐基與羧酸之合計低於3.0mol時，可防止脂環式三羧酸酐殘留並可抑制顯影殘渣。 The reaction between the aforementioned alicyclic isocyanate type polyisocyanate (a1) and the aforementioned alicyclic tricarboxylic acid anhydride (a2) is preferably The total of acid anhydride group and carboxylic acid is 1.0mol to 3.0mol, more preferably It is 1.2 mol to 2.8 mol, more preferably 1.4 mol to 2.6 mol. When the total of the acid anhydride group and the carboxylic acid exceeds 1.0 mol, the isocyanate group is prevented from remaining, the increase in molecular weight is suppressed, and the developability becomes favorable. When the total of the acid anhydride group and the carboxylic acid is less than 3.0 mol, it is possible to prevent residues of an alicyclic tricarboxylic acid anhydride and to suppress image development residue.

前述醯胺醯亞胺化步驟係使用無溶劑或者不具有羥基之有機溶劑。具體上係亦包含溶劑(C)，惟例如，可在乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酮、甲基乙基酮、甲基異丁基酮、環戊酮、環己酮、乙二醇二甲醚、乙二醇二***、乙二醇二丁醚等乙二醇二烷醚類；二乙二醇二甲醚、二乙二醇二***、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇二***、三乙二醇二丁醚等聚乙二醇二烷醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯等乙二醇單烷醚乙酸酯類；二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、三乙二醇單甲醚乙酸酯、三乙二醇單***乙酸酯、三乙二醇單丁醚乙酸酯等聚乙二醇單烷醚乙酸酯類；丙二醇二甲醚、丙二醇二***、丙二醇二丁醚等丙二醇二烷醚類；二丙二醇二甲醚、二丙二醇二***、二丙二醇二丁醚、三丙二醇二甲醚、三丙二醇二***、三丙二醇二丁醚等聚丙二醇二烷醚類；丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丁醚乙酸酯等丙二醇單烷醚乙酸酯類；二丙二醇單甲醚乙酸酯、二丙二醇單***乙酸酯、二丙二醇單丁醚乙酸酯、三丙二醇單甲醚乙酸酯、三丙二醇單***乙酸酯、三丙二醇單丁醚乙酸酯等聚丙二醇單烷醚乙酸酯類；或者，如低分子之乙烯-丙烯共聚物之共聚合聚醚甘醇之二烷醚、或共聚合聚醚甘醇之單乙酸酯單烷醚類；或者如此方式的聚醚甘醇之烷酯類；聚醚甘醇之單烷酯單烷醚類、 再者係後述之交聯劑(D)之中不具有羥基的交聯劑(D)等之單獨或混合有機溶劑中反應。 The aforesaid amide imidization step uses solvent-free or organic solvents without hydroxyl groups. Specifically, the solvent (C) is also included, but for example, it can be used in ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and other ethylene glycol dialkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether and other polyethylene glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetic acid Esters, ethylene glycol monobutyl ether acetate and other ethylene glycol monoalkyl ether acetates; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate and other polyethylene glycol monoalkyl ether acetates; Propylene glycol dimethyl Ether, propylene glycol diethyl ether, propylene glycol dibutyl ether and other propylene glycol dialkyl ethers; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether Polypropylene glycol dialkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and other propylene glycol monoalkyl ether acetates; dipropylene glycol monomethyl ether acetate, dipropylene glycol Monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate and other polypropylene glycol monoalkyl ether acetates; Or, such as the dialkyl ether of copolymerized polyether glycol of low molecular weight ethylene-propylene copolymer, or the monoacetate monoalkyl ether of copolymerized polyether glycol; Esters; monoalkyl esters of polyether glycol monoalkyl ethers, Furthermore, among the crosslinking agents (D) described later, the crosslinking agent (D) not having a hydroxyl group is reacted alone or in a mixed organic solvent.

前述醯胺醯亞胺化反應較佳係在溶劑中或者無溶劑中，混合前述脂環式三聚異氰酸酯型聚異氰酸酯(a1)之1種以上、與脂環式三羧酸酐(a2)之1種以上，一邊進行攪拌一邊進行昇溫。 The aforementioned amidoimidation reaction is preferably carried out in a solvent or without a solvent by mixing one or more of the aforementioned alicyclic isocyanate-type polyisocyanates (a1) and one or more of the alicyclic tricarboxylic anhydrides (a2). More than one kind, heat up while stirring.

前述醯胺醯亞胺化反應之反應溫度較佳係在50℃至250℃之範圍，特佳係70℃至180℃之範圍。藉由設為如此的反應溫度，具有反應速度變炔之效果。反應係一邊伴隨著去羧，同時酸酐基與異氰酸酯基形成醯亞胺基，羧酸基與異氰酸酯形成醯胺基。在反應時依照需要，可使用抗氧化劑、調平劑、消泡劑、界面活性劑等。 The reaction temperature of the aforementioned amidoimidation reaction is preferably in the range of 50°C to 250°C, particularly preferably in the range of 70°C to 180°C. By setting such a reaction temperature, there is an effect that the reaction rate becomes alkyne. The reaction system is accompanied by decarboxylation, and at the same time, the acid anhydride group and the isocyanate group form an imide group, and the carboxylic acid group and isocyanate group form an amido group. An antioxidant, a leveling agent, an antifoaming agent, a surfactant, etc. can be used as needed at the time of reaction.

前述醯胺醯亞胺化反應之進行係可藉由紅外光譜、或酸價、凝膠浸透層析、液體層析、氣相層析、H-NMR、C-NMR、異氰酸酯基之定量等分析手段來進行追蹤。在紅外光譜中，異氰酸酯基之特性吸收在2270cm-1會隨反應而減少，再者，在1860cm-1與850cm-1具有特性吸收之酸酐基會減少。另一方面，在1780cm-1與1720cm-1醯亞胺基之吸收會增加。進行反應直至異氰酸酯基之特性吸收的2270cm-1消失，因容易控制反應而佳。 The progress of the aforementioned amidoimidation reaction can be analyzed by infrared spectroscopy, or acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, quantitative analysis of isocyanate groups, etc. means of tracking. In the infrared spectrum, the characteristic absorption of the isocyanate group will decrease with the reaction at 2270cm -1 , and the acid anhydride group with characteristic absorption at 1860cm -1 and 850cm -1 will decrease. On the other hand, at 1780cm -1 and 1720cm -1 the absorption of the imide group increases. It is preferable to carry out the reaction until the 2270 cm -1 of the characteristic absorption of the isocyanate group disappears, because it is easy to control the reaction.

藉由前述環式三聚異氰酸酯型聚異氰酸酯(a1)與脂環式三羧酸酐(a2)之反應所得到的具有末端酸基或酸酐基之聚醯胺醯亞胺樹脂(a3)的較佳分子量範圍在GPC中之聚苯乙烯換算重量平均分子量為1000至20,000之範圍，更佳係1,500至15,000，特佳係2000至10,000。 The preferred polyamide imide resin (a3) with terminal acid groups or acid anhydride groups obtained by the reaction of the aforementioned cyclic isocyanate polyisocyanate (a1) and alicyclic tricarboxylic anhydride (a2) The molecular weight range is the polystyrene-equivalent weight average molecular weight in GPC of 1,000 to 20,000, more preferably 1,500 to 15,000, and most preferably 2,000 to 10,000.

然後，詳述有關羧酸酯化步驟。 Then, the step of carboxylic acid esterification will be described in detail.

使用於前述含有不飽和基的聚羧酸樹脂(A)的製造之1分子中具有環氧基的(甲基)丙烯酸酯(b)，係只要在分子構造中具有(甲基)丙烯醯基與環氧基者，其他之具體構造並無特別限定，可使用各式各樣的化合物。其一例係可列舉例如：(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸4-羥基丁酯環氧丙醚、(甲基)丙烯酸環氧基環己基甲酯等含環氧丙基的(甲基)丙烯酸酯單體；二羥基苯二環氧丙醚、二羥基萘二環氧丙醚、聯酚二環氧丙醚、雙酚二環氧丙醚等二環氧丙醚化合物的單(甲基)丙烯酸酯化物等。此等之含有環氧基的(甲基)丙烯酸酯化合物係可單獨使用，亦可併用2種以上。此等之中，因容易控制反應，故以具有1個環氧基之(甲基)丙烯酸酯化合物為佳，從反應性、硬化性之觀點而言，以甲基丙烯酸環氧丙酯、甲基丙烯酸環氧基環己基甲酯為佳。 The (meth)acrylate (b) having an epoxy group in one molecule used in the production of the aforementioned unsaturated group-containing polycarboxylic acid resin (A) is as long as it has a (meth)acryl group in its molecular structure As for the epoxy group, other specific structures are not particularly limited, and various compounds can be used. An example of it can include, for example: glycidyl (meth)acrylate, 4-hydroxybutyl glycidyl (meth)acrylate, epoxycyclohexylmethyl (meth)acrylate, etc. (meth)acrylate monomer; Dihydroxyphenyl Diglycidyl Ether, Dihydroxynaphthalene Diglycidyl Ether, Biphenol Diglycidyl Ether, Bisphenol Diglycidyl Ether and other Diglycidyl Ether Compounds mono(meth)acrylates, etc. These epoxy group-containing (meth)acrylate compounds may be used alone or in combination of two or more. Among these, since it is easy to control the reaction, a (meth)acrylate compound having one epoxy group is preferable. From the viewpoint of reactivity and hardening property, glycidyl methacrylate, methyl Epoxycyclohexylmethyl acrylate is preferred.

又，從硬化收縮、感光度之觀點而言，較佳係在前述一分子中具有環氧基的(甲基)丙烯酸酯(b)與前述脂環式三羧酸酐(a2)之莫耳比((b)/(a2))為滿足0.8至2.0之範圍。更佳係0.9至1.80，又更佳係1.0至1.5。 Also, from the viewpoint of curing shrinkage and sensitivity, the molar ratio of the (meth)acrylate (b) having an epoxy group in one molecule to the alicyclic tricarboxylic anhydride (a2) is preferable ((b)/(a2)) satisfies the range of 0.8 to 2.0. More preferably, it is 0.9 to 1.80, and more preferably, it is 1.0 to 1.5.

使用於前述含有不飽和基的聚羧酸樹脂(A)之製造的脂肪族二羧酸酐或脂肪族三羧酸酐(c)之脂肪族二羧酸酐係可列舉如：琥珀酸酐、1,2-環丙烷二羧酸酐、2,2-二甲基琥珀酸酐、卡龍酸酐(Caronic anhydride)、1,2-環己烷二羧酸酐、丁基琥珀酸酐、4-甲基環己烷-1,2-二羧酸酐、正辛基琥珀酸酐、癸基琥珀酸酐、十二烷基琥珀酸酐等。又，脂肪族三羧酸酐係可列舉如：具有線狀脂肪族構造之三羧酸酐、具有脂環式構造之三羧酸酐等。具有線狀脂肪族構造之三羧酸酐可列舉例如：丙烷三羧酸酐等。具有脂環式構造之三羧酸酐可列舉例如：與例示於前述脂環式三羧酸酐(a2)之 化合物為相同者。在此等之中，從電性特性之觀點而言，以脂肪族二羧酸酐為佳。又，從鹼水溶液顯影性、耐熱性、耐水解性等而言，以具有脂環式構造之三羧酸酐等為佳。以環己烷-1,3,4-三羧酸-3,4-酐更佳。 Examples of aliphatic dicarboxylic anhydrides or aliphatic tricarboxylic anhydrides (c) used in the production of the polycarboxylic acid resin (A) containing unsaturated groups include: succinic anhydride, 1,2- Cyclopropane dicarboxylic anhydride, 2,2-dimethylsuccinic anhydride, Caronic anhydride, 1,2-cyclohexanedicarboxylic anhydride, butylsuccinic anhydride, 4-methylcyclohexane-1, 2-Dicarboxylic acid anhydride, n-octyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, etc. Moreover, examples of aliphatic tricarboxylic anhydrides include tricarboxylic anhydrides having a linear aliphatic structure, tricarboxylic anhydrides having an alicyclic structure, and the like. Examples of the tricarboxylic anhydride having a linear aliphatic structure include propanetricarboxylic anhydride and the like. Tricarboxylic anhydrides having an alicyclic structure include, for example: those exemplified in the aforementioned alicyclic tricarboxylic anhydrides (a2). The compounds are the same. Among these, aliphatic dicarboxylic acid anhydrides are preferable from the viewpoint of electrical properties. In addition, tricarboxylic acid anhydrides having an alicyclic structure are preferable in terms of aqueous alkali developability, heat resistance, hydrolysis resistance, and the like. Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is more preferred.

又，在前述一分子中脂肪族二羧酸酐或脂肪族三羧酸酐(c)與具有環氧基之(甲基)丙烯酸酯(b)的莫耳比((c)/(b))為滿足0.05至1.5之範圍，從顯影性、保存安定性之觀點而言，為佳。更佳係0.1至1.2。 Also, the molar ratio ((c)/(b)) of the aliphatic dicarboxylic anhydride or aliphatic tricarboxylic anhydride (c) to the (meth)acrylate (b) having an epoxy group in the aforementioned molecule is Satisfying the range of 0.05 to 1.5 is preferable from the viewpoint of developability and storage stability. More preferably, it is 0.1 to 1.2.

在反應時，為了抑制熱聚合反應，以加入熱聚合抑制劑為佳，相對於在具有末端酸基或酸酐基之聚醯胺醯亞胺樹脂(a3)中加入一分子中具有環氧基之(甲基)丙烯酸酯化合物(b)及脂肪族二羧酸酐或脂肪族三羧酸酐(c)、溶劑而成之反應物的總量100質量份，熱聚合抑制劑之使用量為0.05至10質量份。作為熱聚合抑制劑係可列舉如：氫醌、2-甲基氫醌、氫醌單甲醚、2,6-二第三丁基-對甲酚等。 During the reaction, in order to suppress the thermal polymerization reaction, it is better to add a thermal polymerization inhibitor. Compared with adding a polyamide imide resin (a3) with an acid group or an anhydride group at the end, a molecule with an epoxy group (Meth)acrylate compound (b) and aliphatic dicarboxylic acid anhydride or aliphatic tricarboxylic anhydride (c), the total amount of 100 parts by mass of the reactant, the amount of thermal polymerization inhibitor used is 0.05 to 10 parts by mass. Examples of thermal polymerization inhibitors include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol, and the like.

又，在反應時，為了促進反應，以使用觸媒為佳，相對於在具有末端酸基或酸酐基之聚醯胺醯亞胺樹脂(a3)中加入一分子中具有環氧基之(甲基)丙烯酸酯化合物(b)及脂肪族二羧酸酐或脂肪族三羧酸酐(c)、溶劑之反應物的總量100質量份，該觸媒之使用量係0.05至10質量份。此時之反應溫度為60至150℃，又，反應時間較佳係3至60小時。在該反應使用之觸媒係可列舉例如：二甲基胺基吡啶、三乙基胺、苯甲基二甲基胺、氯化三乙基銨、溴化苯甲基三甲基銨、碘化苯甲基三甲基銨、三苯基膦、三苯基銻、甲基三苯基銻、2-乙基己酸鉻、辛酸鉻、2-乙基己酸鋅、辛酸鋅、辛酸鋯、二甲基硫醚、二苯基硫醚等。 Also, during the reaction, in order to promote the reaction, it is better to use a catalyst, compared to adding (formaldehyde) with epoxy groups in a molecule to the polyamide imide resin (a3) with terminal acid groups or acid anhydride groups. base) acrylate compound (b) and aliphatic dicarboxylic acid anhydride or aliphatic tricarboxylic anhydride (c), the total amount of reactant 100 parts by mass, the amount of the catalyst used is 0.05 to 10 parts by mass. The reaction temperature at this time is 60 to 150° C., and the reaction time is preferably 3 to 60 hours. The catalyst system used in this reaction can include, for example: dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, iodine Benzyltrimethylammonium, Triphenylphosphine, Triphenylantimony, Methyltriphenylantimony, Chromium 2-Ethylhexanoate, Chromium Octanoate, Zinc 2-Ethylhexanoate, Zinc Octanoate, Zirconium Octanoate , Dimethyl sulfide, diphenyl sulfide, etc.

前述羧酸酯化步驟係可以無溶劑或有機溶劑進行稀釋而反應。該有機溶劑係可列舉例如：與前述醯胺醯亞胺化步驟所例示的溶劑為相同者。 The aforementioned carboxylic acid esterification step can be reacted by diluting with no solvent or an organic solvent. Examples of the organic solvent include the same solvents as those exemplified in the aforementioned imidization step.

前述羧酸酯化步驟之反應溫度較佳係60℃至160℃之範圍，特佳係70℃至150℃之範圍，又，反應時間較佳係3至60小時。 The reaction temperature of the aforementioned carboxylic esterification step is preferably in the range of 60°C to 160°C, particularly preferably in the range of 70°C to 150°C, and the reaction time is preferably in the range of 3 to 60 hours.

前述羧酸酯化步驟之反應較佳係進行至環氧當量(固形分環氧當量)成為10,000g/cq以上。固形分環氧當量係依據JIS K 7236，藉由通常之中和滴定法來測定。又，若知道溶液中之該樹脂的濃度，亦可從溶液之環氧當量計算固形分環氧當量而求得。 It is preferable to carry out the reaction in the said carboxylation step until the epoxy equivalent (solid content epoxy equivalent) becomes 10,000 g/cq or more. The solid content epoxy equivalent is measured by the usual neutralization titration method based on JIS K 7236. Also, if the concentration of the resin in the solution is known, it can also be obtained by calculating the epoxy equivalent of the solid content from the epoxy equivalent of the solution.

使在具有末端酸基或酸酐基之聚醯胺醯亞胺樹脂(a3)、與一分子中具有環氧基之(甲基)丙烯酸酯化合物(b)及脂肪族二羧酸酐或脂肪族三羧酸酐(c)反應所得到的含有不飽和基的聚羧酸樹脂(A)之較佳分子量範圍，係在GPC中之聚苯乙烯換算重量平均分子量為1,500至30,000之範圍，更佳係2,000至20,000，特佳係2,500至15,000。 Polyamideimide resin (a3) having terminal acid group or acid anhydride group, (meth)acrylate compound (b) having epoxy group in one molecule and aliphatic dicarboxylic acid anhydride or aliphatic three The preferred molecular weight range of the unsaturated group-containing polycarboxylic acid resin (A) obtained by the reaction of carboxylic anhydride (c) is in the range of 1,500 to 30,000 in terms of polystyrene equivalent weight average molecular weight in GPC, more preferably 2,000 up to 20,000, and 2,500 to 15,000 for the special series.

在本發明之感光性著色組成物中的含有不飽和基的聚羧酸樹脂(A)之含量比並無特別限定，但在全部固形分中，通常為5質量%以上，較佳係10質量%以上，更佳係15質量%以上，又，通常為90質量%以下，較佳係80質量%以下，更佳係70質量%以下。例如為5至90質量%，較佳係10至90質量%，更佳係15至90質量%，又更佳係15至80質量%,特佳係15至70質量%。 The content ratio of the unsaturated group-containing polycarboxylic acid resin (A) in the photosensitive coloring composition of the present invention is not particularly limited, but in the total solid content, it is usually 5% by mass or more, preferably 10% by mass % or more, more preferably at least 15% by mass, and usually at most 90% by mass, preferably at most 80% by mass, more preferably at most 70% by mass. For example, it is 5 to 90% by mass, preferably 10 to 90% by mass, more preferably 15 to 90% by mass, more preferably 15 to 80% by mass, and most preferably 15 to 70% by mass.

前述著色感光性組成物係包含遮光劑等著色劑(B)。 The said colored photosensitive composition contains a coloring agent (B), such as a light-shielding agent.

作為著色劑(B)係可列舉如：遮光劑、或遮光劑以外之著色劑。 Examples of the coloring agent (B) include light-shielding agents and coloring agents other than light-shielding agents.

作為前述遮光劑係可列舉例如：內醯胺系顏料、碳黑、染料、苝系顏料、以銀錫(AgSn)合金作為主成分之微粒子、鈦黑、銅、鐵、錳、鈷、鉻、鎳、鋅、鈣、銀等之金屬氧化物、複合氧化物、金屬硫化物、金屬硫酸鹽或金屬碳酸鹽等不論有機物、無機物之各種顏料。作為遮光劑係以黑色顏料為佳。 Examples of the aforementioned light-shielding agent system include lactam-based pigments, carbon black, dyes, perylene-based pigments, fine particles mainly composed of silver-tin (AgSn) alloys, titanium black, copper, iron, manganese, cobalt, chromium, Metal oxides, composite oxides, metal sulfides, metal sulfates or metal carbonates of nickel, zinc, calcium, silver, etc., regardless of organic or inorganic pigments. Black pigments are preferred as opacifiers.

≪碳黑≫ ≪Carbon Black≫

作為碳黑係可使用歷來使用作為遮光劑之各種碳黑。作為碳黑具體上係可使用槽黑、爐黑、熱碳黑、燈黑等公知之碳黑。又，碳黑係可用以樹脂、染料、含酸性基的化合物等有機物經被覆處理者。碳黑係可單獨使用1種，亦可組合2種以上而使用。 Various carbon blacks conventionally used as a light-shielding agent can be used as carbon black. Specifically, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used as the carbon black. In addition, carbon black can be coated with organic substances such as resins, dyes, and acidic group-containing compounds. Carbon blacks may be used alone or in combination of two or more.

≪染料≫ ≪Dye≫

染料係只要從公知材料之中適當選擇即可。 The dye system may be appropriately selected from known materials.

可應用於著色感光性組成物的染料可列舉例如：偶氮染料、金屬錯合物偶氮染料、蒽醌染料、三苯基甲烷染料、二苯并哌喃染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞青素染料等。 Dyes that can be used to color photosensitive compositions include, for example, azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, cyanine dyes, and naphthoquinone dyes. , quinoneimine dyes, methine dyes, phthalocyanine dyes, etc.

又，有關此等染料係可進行色澱化(氯化)而分散於有機溶劑等中，再使用此作為遮光劑。 In addition, these dyes can be laked (chlorinated) and dispersed in an organic solvent or the like, and then used as a light-shielding agent.

在此等染料以外，較佳亦可使用例如：日本特開2013-225132號公報、日本特開2014-178477號公報、日本特開2013-137543號公報、日本特開2011-38085號公報、日本特開2014-197206號公報等記載之染料等。 In addition to these dyes, it is also preferable to use, for example: Japanese Patent Application Publication No. 2013-225132, Japanese Patent Application Publication No. 2014-178477, Japanese Patent Application Publication No. Dyes and the like described in JP-A-2014-197206, etc.

其他著色劑的具體例係可列舉在色指數(C.I.；The Society of Dyers and Colourists公司發行)中被分類成顏料(Pigment)之化合物，具體上係賦予如下述之色指數(C.I.)編號者。 Specific examples of other colorants include compounds classified as pigments in the color index (C.I.; issued by The Society of Dyers and Colourists, Inc.), and specifically assigned a color index (C.I.) number as follows.

C.I.顏料黃1(以下，「C.I.顏料黃」係相同，僅記載編號。)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、168、175、180、185；C.I.顏料橙1(以下，「C.I.顏料橙」係相同，僅記載編號。)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、73；C.I.顏料紫1(以下，「C.I.顏料紫」係相同，僅記載編號。)、19、23、29、30、32、36、37、38、39、40、50；C.I.顏料紅1(以下，「C.I.顏料紅」係相同，僅記載編號。)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：2、58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、243、245、254、255、264、265；C.I.顏料藍1(以下，「C.I.顏料藍」係相同， 僅記載編號。)、2、15、15：3、15：4、15：6、16、22、60、64、66；C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠37；C.I.顏料棕23、C.I.顏料棕25、C.I.顏料棕26、C.I.顏料棕28；C.I.顏料黑1、C.I.顏料黑7。 C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same, only the number is described.), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61 , 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120 , 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185; C.I. Pigment Orange 1 (Hereafter, "C.I. Pigment Orange" is the same, only the number is described.), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; C.I. Pigment Violet 1 (Hereafter, "C.I. Pigment Violet" is the same, only the number is described.), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40 , 50; C.I. Pigment Red 1 (Hereafter, "C.I. Pigment Red" is the same, only the number is recorded.), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same, Only the serial number is recorded. ), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66; C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37; C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28; C.I. Pigment Black 1, C.I. Pigment Black 7.

就良好的遮光性之點而言，相對於著色劑(B)之總質量，碳黑之質量的比率係以70質量%以上為佳，以80質量%以上更佳，以90質量%以上又更佳，以100質量%為特佳。 In terms of good light-shielding properties, the mass ratio of carbon black to the total mass of the colorant (B) is preferably at least 70% by mass, more preferably at least 80% by mass, and more preferably at least 90% by mass. Even better, especially preferably 100% by mass.

使用於著色感光性組成物之調製的著色劑(B)之形態並無特別限定。著色劑(B)係可作為粉體而使用，亦可作為分散液而使用。著色劑(B)較佳係作為分散液而使用於著色感光性組成物之調製。 The form of the coloring agent (B) used for preparation of a colored photosensitive composition is not specifically limited. The colorant (B) can be used as a powder or as a dispersion. The coloring agent (B) is preferably used for preparation of a colored photosensitive composition as a dispersion liquid.

就分散液而言，可使用包含2種以上之著色劑(B)的分散液。又，亦可使用包含分別不同種類之著色劑的2種以上之分散液。 As a dispersion liquid, a dispersion liquid containing two or more kinds of coloring agents (B) can be used. In addition, two or more types of dispersion liquids containing different types of coloring agents can also be used.

作為分散劑係可使用例如：丙二醇單甲醚乙酸酯、溶纖劑乙酸酯、3-甲氧基丁基乙酸酯、甲氧基丙基乙酸酯、2-甲氧基乙基乙酸酯、3-乙氧基乙基丙酸酯、丙二醇單甲醚丙酸酯等有機溶劑、或水等。 As a dispersant system, for example, propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate, Organic solvents such as acetate, 3-ethoxyethyl propionate, and propylene glycol monomethyl ether propionate, or water.

為了使著色劑(B)在分散液中的分散安定化、或在著色感光性組成物中之著色劑(B)的分散性為良好，可在著色劑(B)中加入分散劑。 A dispersant may be added to the colorant (B) in order to stabilize the dispersion of the colorant (B) in the dispersion liquid or to improve the dispersibility of the colorant (B) in the colored photosensitive composition.

作為分散劑較佳係使用聚乙亞胺系分散劑、胺基甲酸乙酯系分散劑、丙烯酸樹脂系分散劑等之高分子分散劑。從顯影後不易產生殘渣之點而言，在此等分散劑之中係以胺基甲酸乙酯系分散劑為佳。 Polymer dispersants such as polyethyleneimine-based dispersants, urethane-based dispersants, and acrylic resin-based dispersants are preferably used as the dispersant. Among these dispersants, urethane-based dispersants are preferred because residues are less likely to be generated after development.

又，可使用銅化合物等分散助劑。銅化合物係可列舉例如：銅酞菁。 Moreover, dispersion aids, such as a copper compound, can be used. As a copper compound system, copper phthalocyanine is mentioned, for example.

又，亦有起因於分散劑之腐蝕性的氣體自硬化膜產生的情形。因此，著色劑(B)為不使用分散劑而以分散處理者亦為較佳態樣之一例。 Also, gas self-curing film may be generated due to the corrosiveness of the dispersant. Therefore, the coloring agent (B) is an example of a preferable aspect which disperse|distributes without using a dispersing agent.

著色劑(B)包含分散劑時，著色劑(B)中的分散劑之比率例如為5質量%以上60質量%以下，以10質量%以上50質量%以下為佳。 When the colorant (B) contains a dispersant, the ratio of the dispersant in the colorant (B) is, for example, 5 mass % to 60 mass %, preferably 10 mass % to 50 mass %.

著色劑(B)之分散液的黏度並無特別限制。分散液之黏度係以錐板(cone plate)型黏度計所得在25℃的測定值係以3mPa‧s以上200mPa‧s以下為佳。 The viscosity of the dispersion of the colorant (B) is not particularly limited. The viscosity of the dispersion is preferably 3mPa‧s or more and 200mPa‧s or less as measured by a cone plate viscometer at 25°C.

分散液中之著色劑(B)的粒徑作為分散平均粒徑係以80nm以上300nm以下為佳。分散平均粒徑係可使用雷射繞射式之粒度分布系而測定。 The particle size of the coloring agent (B) in the dispersion liquid is preferably 80 nm or more and 300 nm or less as the dispersion average particle size. The dispersed average particle size can be measured using a laser diffraction particle size distribution system.

相對於著色感光性組成物之固形分整體的質量，著色劑(B)之含量比並無特別限定，惟著色劑(B)之含量的總量之上限值可為70質量%以下，可為65質量%以下，亦可為60質量%以下。下限在全部固形分中通常為1質量%以上，例如為10質量%以上，以20質量%以上為佳，以30質量%以上更佳。 The content ratio of the colorant (B) is not particularly limited relative to the mass of the total solid content of the colored photosensitive composition, but the upper limit of the total content of the colorant (B) may be 70% by mass or less. It is 65 mass % or less, and may be 60 mass % or less. The lower limit is usually at least 1% by mass, for example, at least 10% by mass, preferably at least 20% by mass, more preferably at least 30% by mass, of the total solid content.

又，本說明書中，對於上述著色劑(B)量，可定義為亦包含與著色劑(B)一起存在的分散劑之量的值。 Moreover, in this specification, the said coloring agent (B) quantity can be defined as the value which also includes the quantity of the dispersing agent which exists with a coloring agent (B).

著色感光性組成物係含有溶劑(C)。作為溶劑(C)係在合成含有不飽和的聚羧酸樹脂(A)時亦列舉出例，惟可列舉例如：乙二醇單甲醚、乙二醇單***、乙二醇正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單***、丙二醇單甲醚、丙二醇單***、丙二醇單正丙醚、丙二 醇單正丁醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單***等(聚)烷二醇單烷醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等(聚)烷二醇單烷醚乙酸酯類；二乙二醇二甲醚、二乙二醇甲基***、二乙二醇二***、四氫呋喃等其他醚類；甲基乙基酮、環己酮、2-庚酮、3-庚酮等酮類；2-羥基丙酸甲酯、2-羥基丙酸乙酯等乳酸烷酯類；2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯基乙酸甲酯、乙醯基乙酸乙酯、2-側氧丁烷酸乙酯等其他酯類；甲苯、二甲苯等芳香族烴類；N-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類等、乙酸苯甲酯、丙酸苯甲酯、丁酸苯甲酯、及戊酸苯甲酯等脂肪族羧酸的苯甲酯。此等之溶劑係可單獨使用，亦可組合2種以上而使用。 The colored photosensitive composition contains a solvent (C). Examples of the solvent (C) are also listed when synthesizing the polycarboxylic acid resin (A) containing unsaturated, but for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethyl alcohol Diethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethyl Glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol Alcohol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly)alkanediol monoalkane Ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate and other (poly) alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2- Ethyl methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxy Ethyl acetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3 -Methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, propyl n-butyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate , ethyl acetylacetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide , Amides such as N,N-dimethylacetamide, etc., benzyl esters of aliphatic carboxylic acids such as benzyl acetate, benzyl propionate, benzyl butyrate, and benzyl valerate. These solvents may be used alone or in combination of two or more.

在上述溶劑之中，丙二醇單甲醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、二乙二醇二甲醚、二乙二醇甲基***、環己酮、3-甲氧基丁基乙酸酯係相對於後面所示的光聚合起始劑(E)，因顯示優異的溶解性而佳，以使用丙二醇單甲醚乙酸酯、3-甲氧基丁基乙酸酯為特佳。又，就塗佈性等之點而言，可在前述較佳的溶劑中組合 前述脂肪族羧酸之苯甲酯而使用，包含前述脂肪族羧酸之苯甲酯時的脂肪族羧酸之苯甲酯的含量係相對於溶劑(C)整體，以1質量%以上10質量%以下為佳。溶劑(C)之含量並無特別限定，惟較佳係感光性組成物之固形分濃度成為1質量%以上80質量%以下的量，以成為5質量%以上70質量%以下的量更佳。 Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl Diethyl ether, cyclohexanone, and 3-methoxybutyl acetate are preferred because they exhibit excellent solubility compared to the photopolymerization initiator (E) shown below, and propylene glycol monomethyl ether acetate is used , 3-methoxybutyl acetate is particularly preferred. Also, in terms of coatability, etc., it can be combined in the above-mentioned preferable solvent When the benzyl ester of the aliphatic carboxylic acid is used and the benzyl ester of the aliphatic carboxylic acid is included, the content of the benzyl ester of the aliphatic carboxylic acid is 1% by mass or more to 10% by mass relative to the whole solvent (C). Below % is better. The content of the solvent (C) is not particularly limited, but the solid content concentration of the photosensitive composition is preferably in an amount of 1% by mass to 80% by mass, more preferably in an amount of 5% by mass to 70% by mass.

上述感光性樹脂組成物係可含有交聯劑(D)。可使用於上述感光性樹脂組成物的交聯劑(D)係可列舉如：自由基反應型之丙烯酸酯類、陽離子反應型之環氧化合物類、對該兩者感應之乙烯基化合物、馬來醯亞胺化合物類等化合物。 The said photosensitive resin composition system may contain a crosslinking agent (D). The cross-linking agent (D) that can be used in the above-mentioned photosensitive resin composition can be exemplified: free radical reaction type acrylates, cationic reaction type epoxy compounds, vinyl compounds responsive to both, horses Compounds such as imide compounds.

自由基反應型之丙烯酸酯類係可列舉如：單官能(甲基)丙烯酸酯類、多官能(甲基)丙烯酸酯等。 Examples of free radical reactive acrylates include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, and the like.

該單官能(甲基)丙烯酸酯類係可列舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸月桂酯、聚乙二醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯單甲醚、(甲基)丙烯酸苯基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯醯胺、羥甲基(甲基)丙烯醯胺、甲氧基甲基(甲基)丙烯醯胺、乙氧基甲基(甲基)丙烯醯胺、丙氧基甲基(甲基)丙烯醯胺、丁氧基甲氧基甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、(甲基)丙烯酸、富馬酸、馬來酸、馬來酸酐、伊康酸、伊康酸酐、檸槺酸、檸槺酸酐、巴豆酸、2-丙烯醯胺-2-甲基丙烷磺酸、第三-丁基丙烯醯胺磺酸、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸 2-苯氧基-2-羥基丙酯、2-(甲基)丙烯醯氧基-2-羥基丙基酞酸酯、甘油單(甲基)丙烯酸酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、酞酸衍生物之半(甲基)丙烯酸酯等。此等單官能單體係可單獨或組合2種以上而使用。 Examples of the monofunctional (meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol Alcohol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, Benzyl (meth)acrylate, tetrahydrofurfurylmethyl (meth)acrylate, (meth)acrylamide, hydroxymethyl(meth)acrylamide, methoxymethyl(meth)acrylamide, Ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, N-hydroxymethyl(methyl)acrylamide ) acrylamide, N-hydroxymethyl(meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citric acid, citric acid Anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, 2-ethylhexyl (meth)acrylate, 2-hydroxyl (meth)acrylate Ethyl ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylic acid 2-Phenoxy-2-hydroxypropyl ester, 2-(meth)acryloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurylmethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, (meth)acrylate 2, 2,3,3-Tetrafluoropropyl ester, hemi(meth)acrylate of phthalic acid derivatives, etc. These monofunctional monosystems can be used individually or in combination of 2 or more types.

該多官能(甲基)丙烯酸酯類可列舉例如：丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、壬二醇二(甲基)丙烯酸酯、癸二醇二(甲基)丙烯酸酯、十二烷二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙基三聚異氰酸酯、聚丙二醇二(甲基)丙烯酸酯、己二酸環氧基二(甲基)丙烯酸酯、雙酚環氧乙烷二(甲基)丙烯酸酯、氫化雙酚環氧乙烷二(甲基)丙烯酸酯、雙酚二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇之ε-己內酯加成物之二(甲基)丙烯酸酯、二新戊四醇與ε-己內酯之反應物的聚(甲基)丙烯酸酯、二新戊四醇聚(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥乙基丙烷三(甲基)丙烯酸酯或其環氧乙烷加成物、新戊四醇三(甲基)丙烯酸酯或其環氧乙烷加成物、新戊四醇四(甲基)丙烯酸酯或其環氧乙烷加成物、二新戊四醇六(甲基)丙烯酸酯或其環氧乙烷加成物、乙氧化己二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、乙氧化新戊二醇二(甲基)丙烯酸酯、聚(乙烯-丙烯)甘醇二(甲基)丙烯酸酯、聚四亞甲二醇二(甲基)丙烯酸酯、乙氧化雙酚A二(甲基)丙烯酸酯、丙氧化雙酚 A二(甲基)丙烯酸酯、丙氧化乙氧化雙酚A二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、2,2-雙(4-(甲基)丙烯醯氧基二乙氧基苯基)丙烷、2,2-雙(4-(甲基)丙烯醯氧基聚乙氧基苯基)丙烷、2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、乙二醇二環氧丙醚二(甲基)丙烯酸酯、二乙二醇二環氧丙醚二(甲基)丙烯酸酯、酞酸二環氧丙酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油聚環氧丙醚聚(甲基)丙烯酸酯、胺基甲酸乙酯(甲基)丙烯酸酯(亦即，甲苯二異氰酸酯、三甲基六亞甲基二異氰酸酯、或六亞甲基二異氰酸酯等與2-羥基乙基(甲基)丙烯酸酯之反應物)、亞甲基雙(甲基)丙烯醯胺、(甲基)丙烯醯胺亞甲醚、多元醇與N-羥甲基(甲基)丙烯醯胺之縮合物、三丙烯酸基甲醛、2,4,6-三側氧六氫-1,3,5-三嗪-1,3,5-三乙醇三丙烯酸酯、及2,4,6-三側氧基六氫-1,3,5-三嗪-1,3,5-三乙醇二丙烯酸酯等。 Examples of the polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, azelaic Alcohol di(meth)acrylate, Decanediol di(meth)acrylate, Dodecanediol di(meth)acrylate, Ethylene glycol di(meth)acrylate, Diethylene glycol di( Meth)acrylate, polyethylene glycol di(meth)acrylate, tri(meth)acryloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipate epoxy di (Meth)acrylate, Bisphenol oxirane di(meth)acrylate, Hydrogenated bisphenol oxirane di(meth)acrylate, Bisphenol di(meth)acrylate, Hydroxytrimethyl Di(meth)acrylate of ε-caprolactone adduct of neopentyl glycol acetate, poly(meth)acrylate of reaction product of dipenteopentyl glycol and ε-caprolactone, dineopentyl tetra Alcohol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate or its ethylene oxide adduct, neopentylthritol tri( Meth)acrylate or its ethylene oxide adduct, neopentylthritol tetra(meth)acrylate or its ethylene oxide adduct, dipenteoerythritol hexa(meth)acrylate or its Ethylene oxide adduct, ethoxylated hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 2-hydroxy-3-(meth)acryloxypropane triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate ) acrylate, poly(ethylene-propylene) glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bis phenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate base) acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri( Meth)acrylate, glycerol di(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth) base) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether bis(methyl) ) Acrylate, Diethylene Glycol Diglycidyl Ether Di(meth)acrylate, Diglycidyl Phthalate Di(Meth)acrylate, Glycerin Triacrylate, Glycerin Polyglycidyl Ether Poly(meth)acrylate base) acrylate, urethane (meth)acrylate (that is, toluene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate, etc. base) acrylate), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, condensation product of polyhydric alcohol and N-methylol(meth)acrylamide , Triacrylate formaldehyde, 2,4,6-trioxyhexahydro-1,3,5-triazine-1,3,5-triethanol triacrylate, and 2,4,6-trioxyl Hexahydro-1,3,5-triazine-1,3,5-triethanol diacrylate, etc.

陽離子反應型之環氧化合物類只要為包含環氧化合物(i)且具有環氧基之化合物即可，並無特別限定，可列舉例如：(甲基)丙烯酸環氧丙酯、甲基環氧丙醚、乙基環氧丙醚、丁基環氧丙醚、雙酚-A二環氧丙醚、3,4-環氧環己基甲基-3,4-環氧基環己烷羧酸酯(UNION CARBIDE公司製「CYRACURE UVR-6110」等)、3,4-環氧基環己基乙基-3,4-環氧基環己烷羧酸酯、乙烯基環己烯二氧化物(UNION CARBIDE公司製「ELR-4206」等)、檸檬烯二氧化物(DAICEL股份有限公司製「CELLOXIDE 3000」等)、烯丙基環己烯二氧化物、3,4-環氧基-4-甲基環己基-2-環氧丙烷、2-(3,4-環 氧基環己基-5,5-螺-3,4-環氧基)環己烷-間-二噁烷、雙(3,4-環氧環己基)己二酸酯(UNION CARBIDE公司製「CYRACURE UVR-6128」等)、雙(3,4-環氧基環己基甲基)己二酸酯、雙(3,4-環氧基環己基)醚、雙(3,4-環氧基環己基甲基)醚、雙(3,4-環氧基環己基)二乙基矽氧烷等。 Cationic reactive epoxy compounds are not particularly limited as long as they contain epoxy compound (i) and have an epoxy group. For example, glycidyl (meth)acrylate, methyl epoxy Propyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid Esters ("CYRACURE UVR-6110" manufactured by UNION CARBIDE, etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexene dioxide ( "ELR-4206" manufactured by UNION CARBIDE, etc.), limonene dioxide ("CELLOXIDE 3000" manufactured by DAICEL Co., Ltd., etc.), allylcyclohexene dioxide, 3,4-epoxy-4-methyl Cyclohexyl-2-epoxypropylene, 2-(3,4-cyclo Oxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate (manufactured by UNION CARBIDE Co., Ltd. CYRACURE UVR-6128", etc.), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxy Cyclohexylmethyl) ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, etc.

該乙烯基化合物類係可列舉如：乙烯醚類、苯乙烯類、其他乙烯基化合物等。 Examples of such vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds.

該乙烯醚類可列舉例如：乙基乙烯醚、丙基乙烯醚、羥基乙基乙烯醚、乙二醇二乙烯醚等。 Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and the like.

該苯乙烯類可列舉例如：苯乙烯、甲基苯乙烯、乙基苯乙烯等。 Examples of the styrenes include styrene, methylstyrene, ethylstyrene and the like.

其他乙烯基化合物可列舉例如：三烯丙基三聚異氰酸酯、三甲基烯丙基三聚異氰酸酯等。 As other vinyl compounds, triallyl isocyanurate, trimethallyl isocyanurate, etc. are mentioned, for example.

馬來醯亞胺化合物類係只要為分子中具有一個以上之馬來醯亞胺基的化合物即可，並無特別限定。其具體例係可列舉如：N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-羥基苯基馬來醯亞胺、N-苯胺基苯基馬來醯亞胺、N-羧基苯基馬來醯亞胺、N-(4-羧基-3-羥基苯基)馬來醯亞胺、6-馬來醯亞胺己酸、4-馬來醯亞胺丁酸、雙(4-馬來醯亞胺苯基)甲烷、2,2-雙{4-(4-馬來醯亞胺苯氧基)-苯基}丙烷、4,4-二苯基甲烷雙馬來醯亞胺、雙(3,5-二甲基-4-馬來醯亞胺苯基)甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、雙(3,5-二乙基-4-馬來醯亞胺苯基)甲烷、苯基甲烷馬來醯亞胺、鄰伸苯基雙馬來醯亞胺、間伸苯基雙馬來醯亞胺、對伸苯基雙馬來醯亞胺、鄰伸苯基雙檸槺醯亞胺、間伸苯基雙檸槺醯亞胺、對伸苯基雙檸槺醯亞胺、2,2-雙(4-(4-馬來醯亞胺苯氧基)-苯基)丙烷、3,3-二甲基-5,5-二乙基-4,4-二 苯基甲烷雙馬來醯亞胺、4-甲基-1,3-伸苯基雙馬來醯亞胺、1,2-雙馬來醯亞胺乙烷、1,4-雙馬來醯亞胺丁烷、1,5-雙馬來醯亞胺戊烷、1,5-雙馬來醯亞胺-2-甲基戊烷、1,6-雙馬來醯亞胺己烷、1,6-雙馬來醯亞胺-(2,2,4-三甲基)己烷、1,8-雙馬來醯亞胺-3,6-二氧辛烷、1,11-雙馬來醯亞胺-3,6,9-三氧十一烷、1,3-雙(馬來醯亞胺甲基)環己烷、1,4-雙(馬來醯亞胺甲基)環己烷、4,4-二苯醚雙馬來醯亞胺、4,4-二苯基碸雙馬來醯亞胺、1,3-雙(3-馬來醯亞胺苯氧基)苯、1,3-雙(4-馬來醯亞胺苯氧基)苯、4,4-二苯基甲烷雙檸槺醯亞胺、2,2-雙[4-(4-檸槺醯亞胺苯氧基)苯基]丙烷、雙(3,5-二甲基-4-檸槺醯亞胺苯基)甲烷、雙(3-乙基-5-甲基-4-檸槺醯亞胺苯基)甲烷、雙(3,5-二乙基-4-檸槺醯亞胺苯基)甲烷、聚苯基甲烷馬來醯亞胺、聚苯基甲烷馬來醯亞胺等式(6)所示的馬來醯亞胺化合物、式(7)所示的馬來醯亞胺化合物、螢光素-5-馬來醯亞胺、及此等馬來醯亞胺化合物之預聚物、或馬來醯亞胺化合物與胺化合物之預聚物等。 The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Its specific examples can be listed such as: N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide , N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimide caproic acid, 4-maleimide butyric acid , bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethanebis Maleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl) Methane, bis(3,5-diethyl-4-maleimidephenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide Phenyl imide, p-phenylene bis-maleimide, o-phenylene bis-citrate imide, m-phenylene bis-citrate imide, p-phenylene bis-citrate imide, 2 ,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-di Phenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimide ethane, 1,4-bismaleimide Iminobutane, 1,5-bismaleimide pentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimide hexane, 1 ,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,8-bismaleimide-3,6-dioxoctane, 1,11-bismaleimide Laimide-3,6,9-trioxyundecane, 1,3-bis(maleimidemethyl)cyclohexane, 1,4-bis(maleimidemethyl)cyclohexane Hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylbismaleimide, 1,3-bis(3-maleimidephenoxy)benzene , 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethane biscitralimide, 2,2-bis[4-(4-citraimide Aminophenoxy)phenyl]propane, Bis(3,5-Dimethyl-4-citramidylphenyl)methane, Bis(3-Ethyl-5-methyl-4-citralimide Aminophenyl)methane, bis(3,5-diethyl-4-citralimidephenyl)methane, polyphenylmethanemaleimide, polyphenylmethanemaleimide, etc. ( 6) Maleimide compound shown in, maleimide compound shown in formula (7), luciferin-5-maleimide, and prepolymerization of these maleimide compounds compounds, or prepolymers of maleimide compounds and amine compounds, etc.

下述式(1)所示的馬來醯亞胺化合物亦可利用市售品，可列舉例如：大和化成工業股份有限公司製BMI-2300(商品名)。式(2)所示的馬來醯亞胺化合物亦可利用市售品，可列舉例如：日本化藥股份有限公司製MIR-3000(商品名)。式(3)所示的馬來醯亞胺化合物亦可利用市售品，可列舉例如：日本化藥股份有限公司製MIR-5000(商品名)。 A commercial item can also be used for the maleimide compound represented by following formula (1), For example, BMI-2300 (brand name) by Daiwa Chemical Industry Co., Ltd. is mentioned. The maleimide compound represented by Formula (2) can also use a commercial item, For example, Nippon Kayaku Co., Ltd. MIR-3000 (brand name) is mentioned. The maleimide compound represented by Formula (3) can also use a commercial item, For example, Nippon Kayaku Co., Ltd. MIR-5000 (brand name) is mentioned.

Figure 111130624-A0202-12-0022-1
Figure 111130624-A0202-12-0022-1

式(1)中，R1係分別獨立地顯示氫原子或甲基。n1係表示1以上之整數，較佳係表示1至10之整數，更佳係表示1至5之整數。 In formula (1), R 1 each independently represents a hydrogen atom or a methyl group. n 1 represents an integer of 1 or more, preferably represents an integer of 1 to 10, and more preferably represents an integer of 1 to 5.

Figure 111130624-A0202-12-0022-2
Figure 111130624-A0202-12-0022-2

式(2)中，R2係分別獨立地表示氫原子或甲基。n2係表示1以上之整數，較佳係表示1至5之整數。 In formula (2), R 2 are each independently representing a hydrogen atom or a methyl group. n 2 represents an integer of 1 or more, preferably an integer of 1 to 5.

Figure 111130624-A0202-12-0022-3
Figure 111130624-A0202-12-0022-3

式(3)中，R3係分別獨立地表示氫原子、碳素數1至5之烷基、或苯基，l2係分別獨立地表示1至3之整數，n3係表示1至10之整數。 In the formula (3), R 3 are each independently representing a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, l 2 are independently representing an integer of 1 to 3, and n 3 are independently representing an integer of 1 to 10 Integer of .

碳數1至5之烷基可列舉例如：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、及新戊基。 Examples of alkyl groups with 1 to 5 carbons include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, and new Amyl.

交聯劑(D)可單獨使用，亦可混合2種以上而使用。包含交聯劑(D)時之交聯劑(D)的著色感光性組成物中之含量並無特別限定，惟相對於著色感光性組成物之固形分整體的質量，以1質量%以上50質量%以下為佳，以5質量%以上40質量%以下更佳。藉由設為上述範圍，會有容易取得感光度、顯影性、解析性之均衡的傾向。 A crosslinking agent (D) may be used individually, or may mix and use 2 or more types. When the crosslinking agent (D) is included, the content of the crosslinking agent (D) in the colored photosensitive composition is not particularly limited, but relative to the mass of the entire solid content of the colored photosensitive composition, it is 1% by mass or more to 50% or more. It is preferably not more than 5 mass %, more preferably not more than 5 mass % and not more than 40 mass %. By setting it as the said range, there exists a tendency for the balance of sensitivity, developability, and resolution to be acquired easily.

著色感光性組成物係可包含光聚合起始劑(E)。 The colored photosensitive composition system may contain a photopolymerization initiator (E).

光聚合起始劑(E)並無特別限定，可使用以往公知之光聚合起始劑。 The photopolymerization initiator (E) is not particularly limited, and conventionally known photopolymerization initiators can be used.

作為光聚合起始劑(E)具體上係可列舉如：1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、雙(4-二甲基胺基苯基)酮、2-甲基-1-[4-(甲基硫基)苯基]-2-N-嗎福林基丙烷-1-酮、2-苯甲基-2-二甲基胺基-1-(4-嗎福林基苯基)-丁烷-1-酮、O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基]乙酮肟、(9-乙基-6-硝基-9H-咔唑-3-基)[4-(2-甲氧基-1-甲基乙氧基)-2-甲基苯基]甲酮O-乙醯基肟、2-(苯甲醯氧基亞胺基)-1-[4-(苯基硫基)苯基]-1-辛酮、2,4,6-三甲基苯甲醯基二苯基膦氧化物、4-苯甲醯基-4’-甲基二甲基硫醚、4-二甲基胺基苯甲酸、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸丁酯、4-二甲基胺基-2-乙基己基苯甲酸、4-二甲基胺基-2-異戊基苯甲酸、苯甲基-β-甲氧基乙基乙縮醛、苯甲基二甲基縮酮、1-苯基-1,2-丙烷二酮-2- (O-乙氧基羰基)肟、鄰苯甲醯基苯甲酸甲酯、2-氯硫雜蒽酮、2,4-二甲基硫雜蒽酮、1-氯-4-丙氧基硫雜蒽酮、硫雜蒽、2-氯硫雜蒽、2,4-二乙基硫雜蒽、2-甲基硫雜蒽、2-異丙基硫雜蒽、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌、偶氮雙異丁腈、過氧化苯甲醯、過氧化氫異丙苯、2-氫硫基苯并咪唑、2-氫硫基苯并噁唑、2-氫硫基苯并噻唑、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)-咪唑基二聚體、二苯甲酮、2-氯二苯甲酮、p,p’-雙二甲基胺基二苯甲酮、4,4’-雙二乙基胺基二苯甲酮、4,4’-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、聯苯甲醯、苯偶姻、苯偶姻甲醚、苯偶姻***、苯偶姻異丙醚、苯偶姻-正丁醚、苯偶姻異丁醚、苯偶姻丁醚、乙醯苯、2,2-二乙氧基乙醯苯、對二甲基乙醯苯、對二甲基胺基丙醯苯、二氯乙醯苯、三氯乙醯苯、對第三丁基乙醯苯、對二甲基胺基乙醯苯、對第三丁基三氯乙醯苯、對第三丁基二氯乙醯苯、α,α-二氯-4-苯氧基乙醯苯、硫雜蒽酮、2-甲基硫雜蒽酮、2-異丙基硫雜蒽酮、二苯并環庚酮、戊基-4-二甲基胺基苯甲酸酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三嗪、2,4,6-三(三氯甲基)-s-三嗪、2-甲基-4,6-雙(三氯甲基)-s-三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-s-三嗪、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基-s-三嗪、2,4-雙- 三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基-s-三嗪、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基-s-三嗪、2-乙基蒽醌、2-第三丁基蒽醌、2-氯蒽醌、2-戊基蒽醌、2,4-二乙基硫雜蒽酮、2-異丙基硫雜蒽酮、2-氯硫雜蒽酮、乙醯苯二甲基縮酮、聯苯甲醯二甲基縮酮、二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫醚、4,4’-雙甲基胺基二苯甲酮等二苯甲酮、2,4,6-三甲基苯甲醯基二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物等。此等光聚合始劑係可單獨或組合2種以上而使用。 As the photopolymerization initiator (E), the specific system can include such as: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxyl-2-methyl-1-phenylpropan-1-ketone, 1-[4-( 2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-keto, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane- 1-keto, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-N-morpholinopropane-1- Ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, O-acetyl-1-[6-(2- Toluyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-( 2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyl oxime, 2-(benzoyloxyimino)-1-[4-( Phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide ether, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4- Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl)oxime, methyl phthalylbenzoate, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone Xanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, Octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercapto Benzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazolyl dimer body, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4 '-Dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, diphenamide, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylacetophenone Dimethylaminoacylbenzene, Dichloroacetylbenzene, Trichloroacetylbenzene, p-Tertiary Butyl Acetylbenzene, p-Dimethylaminoacetylbenzene, p-Tertiary Butyltrichloroacetylbenzene , p-tert-butyldichloroacetylbenzene, α,α-dichloro-4-phenoxyacetylbenzene, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone Ketone, dibenzocycloheptanone, amyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5 -Bis-(9-acridyl)pentane, 1,3-bis-(9-acridyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s -Triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6- Bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2 -(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethyl Oxyphenyl) vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)- s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4, 6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4 -Bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis- Trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methyl Oxy)styrylphenyl-s-triazine, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone, 2,4-diethylanthraquinone Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, acetophenyldimethylketal, biphenyldimethylketal, benzophenone, 4-benzene Formyl-4'-methyldiphenyl sulfide, benzophenones such as 4,4'-bismethylaminobenzophenone, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. These photopolymerization initiators can be used individually or in combination of 2 or more types.

此等之中，就感光度之面而言，以使用肟系之光聚合起始劑為特佳。在肟系之光聚合起始劑之中，特佳者係可列舉如：O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基]乙酮肟、乙酮,1-[9-乙基-6-(吡咯-2-基羰基)-9H-咔唑-3-基],1-(O-乙醯基肟)、及2-(苯甲醯氧基亞胺基)-1-[4-(苯基硫基)苯基]-1-辛酮。 Among them, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. Among the oxime-based photopolymerization initiators, the most preferred ones include: O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carba Azol-3-yl]ethanone oxime, ethyl ketone, 1-[9-ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazol-3-yl], 1-(O-acetyl oxime), and 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone.

如上述，著色感光性組成物較佳係包含肟酯化合物作為光聚合起始劑(E)。肟酯化合物係吸收紫外線而產生自由基之能力優異。因此，肟酯化合物係高感光度，且即使為包含高濃度之遮光劑等著色劑(B)時，亦可以少的曝光量而容易使著色感光性組成物充分硬化。包含許多著色劑(B)之著色感光性組成物時，形成著色感光性組成物的膜之光學濃度為3時，深層部之紫外線曝光量比表層部(最表面)之紫外線曝光量更少，但肟酯化合物係以如此的相對少的紫外線曝光量，亦可產生自由基，並可使著色感光性組成物良好地硬化。 As mentioned above, it is preferable that the coloring photosensitive composition contains an oxime ester compound as a photoinitiator (E). Oxime ester compounds are excellent in absorbing ultraviolet rays and generating free radicals. Therefore, the oxime ester compound has high sensitivity, and even when it contains coloring agents (B) such as a high-concentration light-shielding agent, it is easy to fully harden the colored photosensitive composition with a small amount of exposure. In the case of a colored photosensitive composition containing many colorants (B), when the optical density of the film forming the colored photosensitive composition is 3, the amount of ultraviolet light exposure in the deep layer is less than that in the surface layer (most surface), However, the oxime ester compound can also generate free radicals with such a relatively small amount of ultraviolet exposure, and can harden the colored photosensitive composition well.

又，使上述之著色劑(B)以高濃度調配於著色感光性組成物時，在由著色感光性組成物所構成的塗佈膜中，不可避免地產生著色劑(B) 之一次凝集體(aggregate)。但，使用包含肟酯化合物之著色感光性組成物作為光聚合起始劑(E)時，一次凝集體複雜地互相重疊之些微間隙，光聚合起始劑(E)在紫外線照射時亦產生自由基。 Moreover, when the above-mentioned colorant (B) is blended in a colored photosensitive composition at a high concentration, the colorant (B) is inevitably generated in the coating film composed of the colored photosensitive composition. One of the aggregates (aggregate). However, when a colored photosensitive composition containing an oxime ester compound is used as the photopolymerization initiator (E), the photopolymerization initiator (E) also generates free space when the primary aggregates are complexly overlapped with each other when irradiated with ultraviolet rays. base.

該結果，著色感光性組成物之硬化物在常溫常濕且大氣壓之環境下，對基板之密著性或電阻率(絕緣性)不僅優異，硬化物被曝露於高溫高濕高壓環境時，對基板之密著性、或電阻率(絕緣性)亦不易降低。在高溫高濕高壓環境下之耐久性係可藉由所謂的PCT試驗(Pressure Cooker Test：壓力鍋試驗)進行確認。 As a result, the cured product of the colored photosensitive composition not only has excellent adhesion to the substrate or resistivity (insulation) in an environment of normal temperature, humidity and atmospheric pressure, but also has excellent resistance to the cured product when exposed to a high temperature, high humidity and high pressure environment. Adhesion or resistivity (insulation) of the substrate is not easily reduced. The durability under high temperature, high humidity and high pressure environment can be confirmed by the so-called PCT test (Pressure Cooker Test: pressure cooker test).

因此，包含肟酯化合物之著色感光性組成物的硬化物(著色膜)係使用環境即使為高溫或多濕時，亦不易產生性能之降低。 Therefore, even when the cured product (colored film) of the colored photosensitive composition containing the oxime ester compound is used in a high temperature or high humidity environment, performance degradation is unlikely to occur.

作為光聚合起始劑(E)係可組合肟酯化合物、與肟酯化合物以外之光聚合起始劑而使用。此時，相對於光聚合起始劑(E)整體之質量，肟酯化合物之質量的比率係以20質量%以上為佳，以30質量%以上更佳，以35質量%以上又更佳，以40質量%以上為特佳。 As the photopolymerization initiator (E), it can be used in combination with an oxime ester compound and photopolymerization initiators other than the oxime ester compound. At this time, the ratio of the mass of the oxime ester compound to the mass of the entire photopolymerization initiator (E) is preferably at least 20% by mass, more preferably at least 30% by mass, and more preferably at least 35% by mass. More than 40% by mass is particularly preferred.

肟酯化合物以外之光聚合起始劑係例如，可適合使用胺基烷基酚系光聚合起始劑。 As the photopolymerization initiator system other than the oxime ester compound, for example, an aminoalkylphenol-based photopolymerization initiator can be used suitably.

作為胺基烷基酚系化合物之例係可列舉如：2-苯甲基-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮(例如，CIBA SEPCIALTY CHEMICALS公司製之IRGACURE 369)、2-(4-甲基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮(例如，CIBA SEPCIALTY CHEMICALS公司製之IRGACURE 379)、2-(4-乙基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-異丙基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷- 1-酮、2-(4-正丁基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-異丁基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-正十二烷基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-(3,4-二甲基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-甲氧基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-乙氧基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-羥基甲基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-[4-(2-羥基乙氧基)苯甲基]-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-[4-(2-甲氧基乙氧基)苯甲基]-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-異丙基苯甲基)-2-[(正丁基)(甲基)胺基]-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-正丁基苯甲基)-2-[(正丁基)(甲基)胺基]-1-(4-嗎福林基苯基)丁烷-1-酮、2-(4-異丙基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)戊烷-1-酮、2-(4-異丁基苯甲基)-2-[(正丁基)(甲基)胺基]]-1-(4-嗎福林基苯基)戊烷-1-酮、2-(4-正丁氧基苯甲基)-2-[(正丁基)(甲基)胺基]-1-(4-嗎福林基苯基)戊烷-1-酮、2-(4-甲基苯甲基)-2-[二(正辛基)胺基]-1-(4-嗎福林基苯基)己烷-1-酮、及2-(4-正十二烷基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)辛烷-1-酮等。 As an example of the aminoalkylphenol series compound, can enumerate such as: 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl) butane-1-one ( For example, IRGACURE 369 manufactured by CIBA SEPCIALTY CHEMICALS), 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butane-1 - Ketone (for example, IRGACURE 379 manufactured by CIBA SEPCIALTY CHEMICALS), 2-(4-ethylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butyl Alkan-1-one, 2-(4-isopropylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butane- 1-ketone, 2-(4-n-butylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butane-1-one, 2-(4 -Isobutylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butane-1-one, 2-(4-n-dodecylbenzyl Base)-2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 2-(3,4-dimethylbenzyl)-2-( Dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 2-(4-methoxybenzyl)-2-(dimethylamino)-1 -(4-morpholinylphenyl)butan-1-one, 2-(4-ethoxybenzyl)-2-(dimethylamino)-1-(4-morpholinyl Phenyl)butane-1-one, 2-(4-hydroxymethylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butane-1- Ketone, 2-[4-(2-hydroxyethoxy)benzyl]-2-(dimethylamino)-1-(4-morpholinylphenyl)butane-1-one, 2 -[4-(2-Methoxyethoxy)benzyl]-2-(dimethylamino)-1-(4-morpholinylphenyl)butane-1-one, 2- (4-isopropylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-morpholinylphenyl)butan-1-one, 2-(4 -n-butylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-morpholinylphenyl)butan-1-one, 2-(4-iso Propylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)pentan-1-one, 2-(4-isobutylbenzyl)-2 -[(n-butyl)(methyl)amino]]-1-(4-morpholinylphenyl)pentane-1-one, 2-(4-n-butoxybenzyl)-2 -[(n-butyl)(methyl)amino]-1-(4-morpholinylphenyl)pentan-1-one, 2-(4-methylbenzyl)-2-[di (n-octyl)amino]-1-(4-morpholinylphenyl)hexan-1-one, and 2-(4-n-dodecylbenzyl)-2-(dimethyl Amino)-1-(4-morpholinylphenyl)octan-1-one, etc.

其中，以2-(4-甲基苯甲基)-2-(二甲基胺基)-1-(4-嗎福林基苯基)丁烷-1-酮為佳。 Among them, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)butan-1-one is preferred.

若使胺基烷基酚系光聚合起始劑與肟酯化合物一起組合，則容易控制使用著色感光性組成物所形成的圖型化之著色膜的剖面形狀。 When an aminoalkylphenol-based photopolymerization initiator is combined with an oxime ester compound, it becomes easy to control the cross-sectional shape of a patterned colored film formed using a colored photosensitive composition.

認為此係有胺基烷基酚系光聚合起始劑相對性地對於著色感光性組成物之表層部分(與進行曝光之光對峙的面及其附近)而產生光聚合自由基之傾向，肟酯化合物係有相對性地對於著色感光性組成物之深層部分亦產生光聚合自由基的傾向之故。該傾向係著色感光性組成物之膜厚愈厚，愈顯著地顯現，但即使為1μm以下之薄的膜厚亦可觀察到。 It is considered that the aminoalkylphenol-based photopolymerization initiator tends to generate photopolymerization radicals relative to the surface layer part of the colored photosensitive composition (the surface facing the exposed light and its vicinity), and oxime The ester compound tends to relatively generate photopolymerization radicals also in the deep layer of the colored photosensitive composition. This tendency appears remarkably as the film thickness of the colored photosensitive composition becomes thicker, but it is observed even at a thin film thickness of 1 μm or less.

又，使用肟酯化合物以及胺基烷基酚系光聚合起始劑之副生成的效果，整體的感光度會提升，可以少的曝光量獲得著色感光性組成物之硬化物。再者，使用肟酯化合物以及胺基烷基酚系光聚合起始劑時，線邊緣之直線度與對基板的密著性更為良好，容易形成圖型之缺陷少的圖型化之著色膜。 In addition, the use of the oxime ester compound and the by-product effect of the aminoalkylphenol-based photopolymerization initiator increases the overall sensitivity, and a cured colored photosensitive composition can be obtained with a small amount of exposure. Furthermore, when using an oxime ester compound and an aminoalkylphenol-based photopolymerization initiator, the straightness of the line edge and the adhesion to the substrate are better, and it is easy to form a patterned color with fewer defects in the pattern. membrane.

在著色感光性組成物中，光聚合起始劑(E)為包含肟酯化合物、及胺基烷基酚系光聚合起始劑時，相對於肟酯化合物之質量及胺基烷基酚系光聚合起始劑之質量的合計，胺基烷基酚系光聚合起始劑之質量的比率係以20質量%以上75質量%以下為佳，以25質量%以上70質量%以下更佳，以30質量%以上60質量%以下為特佳。 In the colored photosensitive composition, when the photopolymerization initiator (E) contains an oxime ester compound and an aminoalkylphenol-based photopolymerization initiator, the mass of the oxime ester compound and the aminoalkylphenol-based photopolymerization initiator The total mass of the photopolymerization initiator, the ratio of the mass of the aminoalkylphenol-based photopolymerization initiator is preferably 20 mass % to 75 mass %, more preferably 25 mass % to 70 mass %, More than 30% by mass and not more than 60% by mass are particularly preferred.

在著色感光性組成物中之光聚合起始劑(E)的含量在不阻礙本發明之目的的範圍，並無特別限定。相對於著色感光性組成物之固形分的質量，光聚合起始劑(E)之含量係以0.1質量%以上30質量%以下為佳，以0.3質量%以上20質量%以下更佳，以0.5質量%以上10質量%以下為特佳。 Content of the photopolymerization initiator (E) in a colored photosensitive composition is not specifically limited in the range which does not hinder the object of this invention. The content of the photopolymerization initiator (E) is preferably from 0.1 mass % to 30 mass %, more preferably from 0.3 mass % to 20 mass %, more preferably from 0.5 mass % to the mass of the solid content of the colored photosensitive composition. More than 10% by mass is particularly preferable.

可使用本發明之著色感光性組成物中所使用的硬化劑(F)。作為硬化劑(F)可列舉例如：環氧化合物、噁嗪化合物等。硬化劑(F)係可在硬 化處理中添加用以提高後續的耐熱性，且藉由加熱並與著色感光性組成物中所含的羧基或羥基反應，特別可用在提高耐熱分解性。 The hardening|curing agent (F) used for the colored photosensitive composition of this invention can be used. Examples of the curing agent (F) include epoxy compounds, oxazine compounds, and the like. Hardener (F) is available in hard It is added during chemical treatment to improve subsequent heat resistance, and it can be used to improve thermal decomposition resistance by heating and reacting with carboxyl or hydroxyl groups contained in the colored photosensitive composition.

作為硬化劑(F)之環氧化合物的具體例係可列舉如：酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、三羥基苯基甲烷型環氧樹脂、二環戊二烯酚型環氧樹脂、雙酚-A型環氧樹脂、雙酚-F型環氧樹脂、聯酚型環氧樹脂、雙酚-A酚醛清漆型環氧樹脂、乙二醛型環氧樹脂、含有萘骨架的環氧樹脂、含有卡多(cardo)骨架的環氧樹脂、雙酚茀型環氧樹脂、雜環式環氧樹脂等。 Specific examples of the epoxy compound as the hardener (F) include: phenol novolak type epoxy resin, cresol novolac type epoxy resin, trihydroxyphenylmethane type epoxy resin, dicyclopentadiene Phenol epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin, biphenol epoxy resin, bisphenol-A novolac epoxy resin, glyoxal epoxy resin, Naphthalene-skeleton-containing epoxy resins, cardo-skeleton-containing epoxy resins, bisphenol-stilbene-type epoxy resins, heterocyclic-type epoxy resins, and the like.

該酚酚醛清漆型環氧樹脂可列舉例如：EPICLON N-770(DIC股份有限公司製)、D.E.N438(DOW CHEMICAL公司製)、jER154(日本環氧樹脂股份有限公司製)、EPPN-201、RE-306(任一者皆為日本化藥股份有限公司製)等。 Examples of the phenol novolac epoxy resin include EPICLON N-770 (manufactured by DIC Co., Ltd.), D.E.N438 (manufactured by DOW CHEMICAL Co., Ltd.), jER154 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201, RE -306 (all are manufactured by Nippon Kayaku Co., Ltd.), etc.

該甲酚酚醛清漆型環氧樹脂可列舉例如：EPICLON N-695(DIC股份有限公司製)、EOCN-102S、EOCN-103S、EOCN-104S(任一者皆為日本化藥股份有限公司製)、UVR-6650(UNION CARBIDE公司製)、ESCN-195(住友化學工業股份有限公司製)等。 Examples of the cresol novolak-type epoxy resin include: EPICLON N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, and EOCN-104S (all of which are manufactured by Nippon Kayaku Co., Ltd.) , UVR-6650 (manufactured by UNION CARBIDE), ESCN-195 (manufactured by Sumitomo Chemical Industries, Ltd.), and the like.

該三羥基苯基甲烷型環氧樹脂可列舉例如：EPPN-503、EPPN-502H、EPPN-501H(任一者皆為日本化藥股份有限公司製)、TACTIX-742(DOW CHEMICAL公司製)、jER E1032H60(日本環氧樹脂股份有限公司製)等。 Examples of this trishydroxyphenylmethane epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all of which are manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by DOW CHEMICAL), jER E1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.), etc.

該二環戊二烯酚型環氧樹脂可列舉例如：EPICLON EXA-7200(DIC股份有限公司製)、TACTIX-556(DOW CHEMICAL公司製)等。 As this dicyclopentadienol type epoxy resin, Epiclon EXA-7200 (made by DIC Corporation), TACTIX-556 (made by DOW CHEMICAL), etc. are mentioned, for example.

該雙酚型環氧樹脂可列舉例如：jER828、jER1001(任一者皆為日本環氧樹脂股份有限公司製)、UVR-6410(UNION CARBIDE公司製)、D.E.R-331(DOW CHEMICAL公司製)、YD-8125(東都化成股份有限公司製)、NER-1202、NER-1302(任一者皆為日本化藥股份有限公司製)等雙酚-A型環氧樹脂、UVR-6490(UNION CARBIDE公司製)、YDF-8170(東都化成股份有限公司製)、NER-7403、NER-7604(任一者皆為日本化藥股份有限公司製)等雙酚-F型環氧樹脂等。 Examples of this bisphenol-type epoxy resin include jER828, jER1001 (all of which are manufactured by Japan Epoxy Resin Co., Ltd.), UVR-6410 (manufactured by UNION CARBIDE), D.E.R-331 (manufactured by DOW CHEMICAL), Bisphenol-A epoxy resins such as YD-8125 (manufactured by Tohto Kasei Co., Ltd.), NER-1202, NER-1302 (all of which are manufactured by Nippon Kayaku Co., Ltd.), UVR-6490 (manufactured by UNION CARBIDE Co., Ltd. Bisphenol-F type epoxy resins such as YDF-8170 (manufactured by Tohto Kasei Co., Ltd.), NER-7403, NER-7604 (all of which are manufactured by Nippon Kayaku Co., Ltd.).

該聯酚型環氧樹脂可列舉例如：NC-3000、NC-3000-H、NC-3000-L(任一者皆為日本化藥股份有限公司製)等聯酚型環氧樹脂、YX-4000(日本環氧樹脂股份有限公司製)聯二甲酚型環氧樹脂、YL-6121(日本環氧樹脂股份有限公司製)等。 Examples of the biphenol-type epoxy resin include biphenol-type epoxy resins such as NC-3000, NC-3000-H, and NC-3000-L (all of which are manufactured by Nippon Kayaku Co., Ltd.), YX- 4000 (manufactured by Japan Epoxy Resin Co., Ltd.), bixylenol-type epoxy resin, YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd.), and the like.

該雙酚A酚醛清漆型環氧樹脂可列舉例如：EPICLON N-880(DIC股份有限公司製)、jER E157S75(日本環氧樹脂股份有限公司製)等。 As this bisphenol A novolak type epoxy resin, Epiclon N-880 (made by DIC Corporation), jER E157S75 (made by Japan Epoxy Resin Co., Ltd.), etc. are mentioned, for example.

該含有萘骨架的環氧樹脂可列舉例如：NC-7000(日本化藥股份有限公司製)、EXA-4750(DIC股份有限公司製)等。 As this naphthalene skeleton-containing epoxy resin, NC-7000 (made by Nippon Kayaku Co., Ltd.), EXA-4750 (made by DIC Corporation), etc. are mentioned, for example.

該含有卡多骨架的環氧樹脂可列舉例如：PG-100、CG-500、EG-200、EG-280(大阪GAS CHEMICALS股份有限公司製)等。 Examples of the cardo skeleton-containing epoxy resin include PG-100, CG-500, EG-200, and EG-280 (manufactured by Osaka Gas Chemicals Co., Ltd.).

該乙二醛型環氧樹脂可列舉例如：GTR-1800(日本化藥股份有限公司製)等。 As this glyoxal type epoxy resin, GTR-1800 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned, for example.

該脂環式環氧樹脂可列舉例如：EHPE-3150(DAICEL股份有限公司製)等。該雜環式環氧樹脂可列舉例如：TEPIC(日產化學股份有限公司製)等。 As this alicyclic epoxy resin, EHPE-3150 (made by DAICEL Co., Ltd.), etc. are mentioned, for example. As this heterocyclic epoxy resin, TEPIC (manufactured by Nissan Chemical Co., Ltd.) etc. are mentioned, for example.

作為硬化劑(F)之噁嗪化合物的具體例可列舉例如：B-m型苯并噁嗪、P-a型苯并噁嗪、B-a型苯并噁嗪(任一者皆為四國化成工業股份有限公司製)。 Specific examples of the oxazine compound as the hardener (F) include, for example: B-m type benzoxazine, P-a type benzoxazine, B-a type benzoxazine (all are Shikoku Chemical Industry Co., Ltd. system).

硬化劑(F)係可單獨使用，亦可混合2種以上而使用。 The curing agent (F) may be used alone or in combination of two or more.

硬化劑(F)之含量並無特別限定，惟相對於著色感光性組成物之固形分的質量，以0至40質量%為佳，以3至30質量%更佳。藉由使多官能交聯性化合物(D)之含量設為上述範圍，容易獲得可形成耐熱性高的硬化膜之感光性樹脂組成物。 The content of the hardener (F) is not particularly limited, but is preferably 0 to 40% by mass, more preferably 3 to 30% by mass relative to the mass of the solid content of the colored photosensitive composition. By making content of a polyfunctional crosslinkable compound (D) into the said range, it becomes easy to obtain the photosensitive resin composition which can form the cured film with high heat resistance.

上述著色感光性組成物除了含有不飽和基的聚羧酸樹脂(A)、著色劑(B)、溶劑(C)以外，尚含有交聯劑(D)、光聚合起始劑(E)，藉此作成之著色感光性組成物具有高的感光性，即使高的著色劑濃度亦可分散，且具有良好的顯影特性，以及在必要時亦含有硬化劑(F)，可提高耐熱性。 The above colored photosensitive composition contains a crosslinking agent (D) and a photopolymerization initiator (E) in addition to the unsaturated group-containing polycarboxylic acid resin (A), colorant (B), and solvent (C), The colored photosensitive composition thus produced has high photosensitivity, can be dispersed even at a high concentration of colorant, has good developing properties, and contains a hardener (F) when necessary to improve heat resistance.

著色感光性組成物在不阻礙本發明之目的的範圍，作為其他成分(G)，係可包含：含有不飽和基的聚羧酸(A)、交聯劑(D)、及硬化劑(F)以外之樹脂、或表面調整劑、密著性提升劑、其他的各種添加劑。對於其他成分(G)的添加量，並無特別限制。可使用在不阻礙本發明之目的的範圍之量的其他成分(G)。 The colored photosensitive composition may contain, as other component (G), an unsaturated group-containing polycarboxylic acid (A), a crosslinking agent (D), and a curing agent (F ) other than resins, or surface modifiers, adhesion enhancers, and other various additives. The addition amount of other components (G) is not specifically limited. Other ingredients (G) may be used in an amount within a range that does not hinder the object of the present invention.

≪表面調整劑≫ ≪Surface conditioner≫

表面調整劑係藉由降低著色感光性組成物之表面張力，以抑制表面缺陷、或起因於顏料等著色劑之不均勻分布的外觀不良(顏料等之著色劑的不均勻分布)之發生。具體而言，係可適合使用聚二甲基矽氧烷、聚醚改性聚矽氧烷、聚甲基烷基矽氧烷、經芳烷基或聚酯鏈改性之聚矽氧烷等。 Surface modifiers suppress the occurrence of surface defects or appearance defects (uneven distribution of colorants such as pigments) caused by uneven distribution of colorants such as pigments by reducing the surface tension of colored photosensitive compositions. Specifically, polydimethylsiloxane, polyether-modified polysiloxane, polymethylalkylsiloxane, polysiloxane modified by aralkyl or polyester chain, etc. can be suitably used .

≪密著性提升劑≫ ≪Adhesion Improver≫

可使用矽烷偶合劑、酞酸酯偶合劑、鋁酸酯偶合劑等公知之偶合劑。其中，從提高與玻璃基板之密著性的觀點而言，可適合使用矽烷偶合劑。 Well-known coupling agents, such as a silane coupling agent, a phthalate coupling agent, and an aluminate coupling agent, can be used. Among these, a silane coupling agent can be used suitably from a viewpoint of improving the adhesiveness with a glass substrate.

著色感光性組成物係可依需要而含有上述以外之各種添加劑。具體而言，可例示敏化劑、硬化促進劑、光交聯劑、光敏劑、分散助劑、填充劑、抗氧化劑、紫外線吸收劑、抗凝集劑、熱聚合抑制劑、消泡劑、界面活性劑、撥液劑、鏈轉移劑、光起始助劑、溶劑等。任一者之添加劑亦可使用以往公知者。 The colored photosensitive composition may contain various additives other than the above as needed. Specifically, sensitizers, hardening accelerators, photocrosslinking agents, photosensitizers, dispersion aids, fillers, antioxidants, ultraviolet absorbers, anticoagulants, thermal polymerization inhibitors, defoamers, Surfactants, liquid repellents, chain transfer agents, photoinitiation aids, solvents, etc. Any of the additives can also use conventionally known ones.

作為界面活性劑可列舉例如：陰離子系化合物、陽離子系化合物、非離子系化合物等。 As a surfactant, an anionic compound, a cationic compound, a nonionic compound, etc. are mentioned, for example.

作為熱聚合抑制劑可列舉例如：氫醌、氫醌單***等。 As a thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example.

作為消泡劑可列舉例如：聚矽氧系化合物、氟系化合物等。 Examples of the antifoaming agent include silicone-based compounds, fluorine-based compounds, and the like.

鏈轉移劑可列舉例如：硫醇系化合物、鹵素系化合物、醌系化合物、α-甲基苯乙烯二聚體等。藉由含有鏈轉移劑，可良好地控制圖型形狀(尤其，孔洞圖型之CD變化、曝光邊緣)。其中，除了上述效果，尚就可降低昇華物或著色、臭氣之點而言，2,4-二苯基-4-甲基-1-戊烯(α-甲基苯乙烯二聚體)為佳。 As a chain transfer agent, a mercaptan type compound, a halogen type compound, a quinone type compound, (alpha)-methylstyrene dimer etc. are mentioned, for example. By containing the chain transfer agent, the shape of the pattern (especially, the CD change of the hole pattern, the exposure edge) can be well controlled. Among them, in addition to the above-mentioned effects, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) better.

光起始助劑可列舉例如：三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、4-二甲基胺基苯甲酸2-乙基己酯、苯甲酸2-二甲基胺基乙酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲基胺基)二苯甲酮(通稱米希勒酮)、4,4’-雙(二乙基胺基)二苯甲酮、9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二 乙氧基蒽、及2-乙基-9,10-二乙氧基蒽等。此等光起始助劑係可使用1種或組合2種以上而使用。 Photoinitiation aids can be listed for example: triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-di Isoamyl methylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4 ,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxy Anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethoxy Ethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene, etc. These photoinitiation aids can be used 1 type or in combination of 2 or more types.

作為撥液劑係可列舉如：具有交聯基之含氟原子的樹脂等。因可對隔牆之表面賦予撥印墨性，故認為當使用著色感光性組成物形成隔牆時，可防止各像素之混色。 Examples of the liquid repellent include fluorine atom-containing resins having crosslinking groups. Since repelling ink can be imparted to the surface of the partition wall, it is considered that when the partition wall is formed using a colored photosensitive composition, color mixing of each pixel can be prevented.

作為交聯基係可列舉如：環氧基或乙烯性不飽和基，從抑制撥液劑之對顯影液的流出的觀點而言，以乙烯性不飽和基為佳。又，具有交聯基之含氟原子的樹脂較佳係具有全氟烷基及全氟伸烷醚鏈之任一者或兩者。作為全氟烷基係可列舉如：全氟丁基、全氟己基、全氟辛基等。作為全氟伸烷醚鏈係可列舉如：-CF2-O-、-(CF2)2-O-、-(CF2)3-O-、-CF2-C(CF3)O-、-C(CF3)-CF2-O-及具有此等重複單元的2價基。 Examples of the crosslinking group include epoxy groups and ethylenically unsaturated groups, and ethylenically unsaturated groups are preferred from the viewpoint of suppressing the outflow of the liquid-repellent agent to the developer. Also, the fluorine atom-containing resin having a crosslinking group preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Examples of the perfluoroalkyl group include perfluorobutyl, perfluorohexyl, and perfluorooctyl. Examples of perfluoroalkylene ether chains include: -CF 2 -O-, -(CF 2 ) 2 -O-, -(CF 2 ) 3 -O-, -CF 2 -C(CF 3 )O- , -C(CF 3 )-CF 2 -O- and divalent groups having these repeating units.

具有交聯基之含氟原子的樹脂之具體例係可列舉例如：具有環氧基及全氟烷基之丙烯酸共聚合樹脂、具有環氧基及全氟伸烷醚鏈之丙烯酸共聚合樹脂、具有乙烯性不飽和基及全氟烷基之丙烯酸共聚合樹脂、具有乙烯性不飽和基及全氟伸烷醚鏈之丙烯酸共聚合樹脂、具有環氧基及全氟烷基之環氧基(甲基)丙烯酸酯樹脂、具有環氧基及全氟伸烷醚鏈之環氧基(甲基)丙烯酸酯樹脂、具有乙烯性不飽和基及全氟烷基之環氧基(甲基)丙烯酸酯樹脂、具有乙烯性不飽和基及全氟伸烷醚鏈之環氧基(甲基)丙烯酸酯樹脂等。其中，從撥印墨性之觀點而言，以具有乙烯性不飽和基及全氟烷基之丙烯酸共聚合樹脂、具有乙烯性不飽和基及全氟伸烷醚鏈之丙烯酸共聚合樹脂為佳，以具有乙烯性不飽和基及全氟伸烷醚鏈之丙烯酸共聚合樹脂又更佳。具有此等交聯基的含氟原子的樹脂之市售品係可使用以下 述商品名販售之含氟有機化合物：DIC公司製「MEGAFACE(註冊商標，以下相同。)F116」、「MEGAFACE F120」、「MEGAFACE F142D」、「MEGAFACE F144D」、「MEGAFACE F150」、「MEGAFACE F160」、「MEGAFACE F171」、「MEGAFACE F172」、「MEGAFACE F173」、「MEGAFACE F177」、「MEGAFACE F178A」、「MEGAFACE F178K」、「MEGAFACE F179」、「MEGAFACE F183」、「MEGAFACE F184」、「MEGAFACE F191」、「MEGAFACE F812」、「MEGAFACE F815」、「MEGAFACE F824」、「MEGAFACE F833」、「MEGAFACE RS101」、「MEGAFACE RS102」「MEGAFACE RS105」、「MEGAFACE RS201」、「MEGAFACE RS202」、「MEGAFACE RS301」、「MEGAFACE RS303」「MEGAFACE RS304」、「MEGAFACE RS401」、「MEGAFACE RS402」、「MEGAFACE RS501」、「MEGAFACE RS502」、「MEGAFACE RS-72-K」、「MEGAFACE RS-78」、「MEGAFACE RS-90」、「DEFENSA(註冊商標，以下相同。)MCF300」、「DEFENSAMCF310」、「DEFENSAMCF312」、「DEFENSAMCF323」、3M JAPAN公司製「FLUORAD FC430」、「FLUORAD FC431」、「FC-4430」、「FC4432」、AGC公司製「ASAHIGUARD(註冊商標。)AG710」、「SURFLON(註冊商標，以下相同。)S-382」、「SURFLON SC-101」、「SURFLON SC-102」、「SURFLON SC-103」、「SURFLON SC-104」、「SURFLON SC-105」、「SURFLON SC-106」等。 Specific examples of resins containing fluorine atoms with crosslinking groups include, for example: acrylic copolymer resins with epoxy groups and perfluoroalkyl groups, acrylic copolymer resins with epoxy groups and perfluoroalkylene ether chains, Acrylic copolymer resins with ethylenically unsaturated groups and perfluoroalkyl groups, acrylic copolymer resins with ethylenically unsaturated groups and perfluoroalkylene ether chains, epoxy groups with epoxy groups and perfluoroalkyl groups ( Meth)acrylate resin, epoxy (meth)acrylate resin with epoxy group and perfluoroalkylene ether chain, epoxy (meth)acrylic acid resin with ethylenically unsaturated group and perfluoroalkyl group Ester resins, epoxy (meth)acrylate resins with ethylenically unsaturated groups and perfluoroalkylene ether chains, etc. Among them, from the point of view of printing ink, acrylic copolymer resins with ethylenically unsaturated groups and perfluoroalkyl groups, and acrylic copolymer resins with ethylenically unsaturated groups and perfluoroalkylene ether chains are preferred. , it is more preferable to use an acrylic copolymer resin with ethylenically unsaturated groups and perfluoroalkylene ether chains. Commercially available strains of resins containing fluorine atoms having such crosslinking groups can use the following Fluorine-containing organic compounds sold under the above trade names: "MEGAFACE (registered trademark, the same below.) F116", "MEGAFACE F120", "MEGAFACE F142D", "MEGAFACE F144D", "MEGAFACE F150", "MEGAFACE F160" manufactured by DIC Corporation ", "MEGAFACE F171", "MEGAFACE F172", "MEGAFACE F173", "MEGAFACE F177", "MEGAFACE F178A", "MEGAFACE F178K", "MEGAFACE F179", "MEGAFACE F183", "MEGAFACE F184", "MEGAFACE F191 ", "MEGAFACE F812", "MEGAFACE F815", "MEGAFACE F824", "MEGAFACE F833", "MEGAFACE RS101", "MEGAFACE RS102", "MEGAFACE RS105", "MEGAFACE RS201", "MEGAFACE RS202", "MEGAFACE RS301" , "MEGAFACE RS303", "MEGAFACE RS304", "MEGAFACE RS401", "MEGAFACE RS402", "MEGAFACE RS501", "MEGAFACE RS502", "MEGAFACE RS-72-K", "MEGAFACE RS-78", "MEGAFACE RS- 90", "DEFENSA (registered trademark, the same below.) MCF300", "DEFENSAMCF310", "DEFENSAMCF312", "DEFENSAMCF323", "FLUORAD FC430", "FLUORAD FC431", "FC-4430", "FC4432" manufactured by 3M JAPAN ", "ASAHIGUARD (registered trademark.) AG710", "SURFLON (registered trademark, the same below.) S-382", "SURFLON SC-101", "SURFLON SC-102", "SURFLON SC-103" manufactured by AGC Corporation , "SURFLON SC-104", "SURFLON SC-105", "SURFLON SC-106", etc.

≪著色感光性組成物之調製方法≫ ≪Preparation method of colored photosensitive composition≫

著色感光性組成物係例如將上述各成分均勻地攪拌、混合使均勻地溶解、分散而調製。混合時，係可用輥磨機、球磨機、砂磨機等攪拌機進行混合。依需要可用2μm過濾膜等過濾器進行過濾而調製。 The colored photosensitive composition is prepared, for example, by uniformly stirring and mixing the above-mentioned components, and uniformly dissolving and dispersing them. When mixing, it can be mixed with a mixer such as a roller mill, a ball mill, or a sand mill. If necessary, it can be prepared by filtering with a filter such as a 2 μm filter membrane.

≪著色膜及圖型化之著色膜≫ ≪Colored film and patterned colored film≫

藉由使上述著色感光性組成物進行硬化，可獲得著色膜。 A colored film can be obtained by hardening the said colored photosensitive composition.

著色膜之製造方法係包含：塗佈著色感光性組成物而形成塗佈膜之步驟、及使塗佈膜進行曝光之步驟。 The method for producing a colored film includes a step of applying a colored photosensitive composition to form a coated film, and a step of exposing the coated film.

又，圖型化之著色膜的製造方法係包含：塗佈著色感光性組成物而形成塗佈膜之步驟；使塗佈膜位置選擇性地進行曝光之步驟；使曝光後之塗佈膜進行顯影之步驟。 In addition, the method for producing a patterned colored film includes: a step of applying a colored photosensitive composition to form a coating film; a step of selectively exposing the coating film; and exposing the exposed coating film. The step of development.

藉由使用上述著色感光性組成物作為負型感光性組成物，即使含有高濃度之著色劑，亦可形成直線度佳且高精細的圖型。 By using the above-mentioned colored photosensitive composition as a negative photosensitive composition, even if it contains a high concentration of colorant, it is possible to form a high-definition pattern with good straightness.

以下，說明有關各步驟。使用著色感光性組成物而形成塗佈膜記載為「塗佈膜形成步驟」。將塗佈膜進行曝光記載為「曝光步驟」。使經曝光之塗佈膜進行顯影記載為「顯影步驟」。 Hereinafter, each step will be described. Formation of a coating film using a colored photosensitive composition is described as "coating film formation process." Exposure of the coating film is described as "exposure step". Developing the exposed coating film is described as "development step".

≪塗佈膜形成步驟≫ ≪Coating film forming process≫

在塗佈膜形成步驟中，將上述著色感光性組成物塗佈於基板上而形成塗佈膜。 In the coating film formation process, the said colored photosensitive composition is coated on a board|substrate, and a coating film is formed.

基板之種類並無特別限定，可適當地使用在液晶顯示元件、有機EL顯示元件、有機TFT陣列等光學元件等所使用的各種基板。作為基板，可列舉例如：石英、玻璃、光學膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等金屬基板、SOG(Spin On Glass：旋塗式玻璃)、聚酯膜、聚 碳酸酯膜、聚醯亞胺膜等聚合物基板、TFT陣列基板、PDP之電極板、玻璃或透明塑膠基板、ITO或金屬等導電性基材、絕緣性基材、矽、氮化矽、多晶矽、氧化矽、非晶矽等半導體製作基板等。再者，例如，在基板上形成積層構造時，成為已在基板上形成之下部構造的任一層，亦包含於作為應用著色感光性組成物的基材之概念。又，基材之形狀亦無特別限定，可為板狀，亦可為卷狀。基材係例如，可藉由各種圖型而於表面具有凹凸。又，作為上述基材係可選擇透光性、或非透光性之基材。 The type of substrate is not particularly limited, and various substrates used in optical elements such as liquid crystal display elements, organic EL display elements, and organic TFT arrays, etc., can be suitably used. Examples of substrates include quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, SOG (Spin On Glass: spin-on glass), poly Ester film, Poly Polymer substrates such as carbonate films and polyimide films, TFT array substrates, PDP electrode plates, glass or transparent plastic substrates, conductive substrates such as ITO or metal, insulating substrates, silicon, silicon nitride, polysilicon , silicon oxide, amorphous silicon and other semiconductor manufacturing substrates. Furthermore, for example, when forming a layered structure on a substrate, any layer that has a lower structure formed on the substrate is also included in the concept of a base material to which a colored photosensitive composition is applied. Moreover, the shape of a base material is not specifically limited, It may be a plate shape, and may be a roll shape. For example, the base material can have unevenness on the surface by various patterns. In addition, as the above-mentioned base material, a light-transmitting or non-light-transmitting base material can be selected.

塗佈膜形成步驟係例如：使用輥塗佈機、逆式塗佈機、桿塗佈機等接觸轉印型塗佈裝置或旋轉塗佈機(旋轉式塗佈裝置)、狹縫式塗佈機、簾流式塗佈機等非接觸型塗佈裝置，將著色感光性組成物塗佈於基板上，依需要，藉由乾燥(預烘烤)去除溶劑而形成塗佈膜。 The coating film forming step is, for example, using a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a spin coater (rotary coater), a slit coater, etc. A non-contact coating device such as a machine and a curtain coater applies a colored photosensitive composition on a substrate, and if necessary, removes the solvent by drying (pre-baking) to form a coating film.

塗佈膜之膜厚並無特別限定。塗佈膜之厚度係以0.05μm以上為佳，以1μm以上更佳。塗佈膜之厚度例如可為7μm以上，亦可為10μm以上。塗佈膜之厚度的上限並無特別限制，例如可為50μm以下，亦可為20μm以下。 The film thickness of the coating film is not particularly limited. The thickness of the coating film is preferably at least 0.05 μm, more preferably at least 1 μm. The thickness of the coating film may be, for example, 7 μm or more, or may be 10 μm or more. The upper limit of the thickness of the coating film is not particularly limited, and may be, for example, 50 μm or less, or 20 μm or less.

塗佈膜可依需要而乾燥。乾燥方法並無特別限定。乾燥方法係可列舉例如：(1)在加熱板以80℃以上120℃以下，較佳係90℃以上100℃以下之溫度乾燥60秒以上120秒以下的方法；(2)在室溫下放置數小時至數日之方法；(3)置入溫風加熱器或紅外線加熱器中數十分鐘至數小時以去除溶劑的方法等。 The coating film can be dried as needed. The drying method is not particularly limited. Examples of drying methods include: (1) Drying on a heating plate at a temperature of 80°C to 120°C, preferably 90°C to 100°C, for 60 seconds to 120 seconds; (2) Standing at room temperature The method of several hours to several days; (3) the method of putting it in a warm air heater or an infrared heater for tens of minutes to several hours to remove the solvent, etc.

≪曝光步驟≫ ≪Exposure steps≫

曝光步驟係將以塗佈膜形成步驟所形成的塗佈膜進行曝光。藉此，可獲得著色感光性組成物之硬化膜(著色膜)。依照圖型形狀而選擇性地進行曝光並顯影，可獲得圖型化之硬化膜(著色膜)。 In the exposure step, the coating film formed in the coating film forming step is exposed. Thereby, the cured film (colored film) of a colored photosensitive composition can be obtained. By selectively exposing and developing according to the shape of the pattern, a patterned cured film (colored film) can be obtained.

曝光步驟係對塗佈膜照射例如：i射線、g射線、h射線等放射線或電磁波，使塗佈膜進行曝光。形成圖型化之硬化膜(著色膜)時，對塗佈膜進行之曝光係隔著負型之掩膜而選擇性地進行。曝光量亦依著色感光性組成物之組成而異，但例如，以5mJ/cm2以上500mJ/cm2以下左右為佳。以10mJ/cm2以上150mJ/cm2以下左右更佳。 In the exposure step, the coating film is irradiated with radiation such as i-rays, g-rays, and h-rays or electromagnetic waves to expose the coating film. When forming a patterned cured film (colored film), exposure to the coating film is selectively performed through a negative mask. The amount of exposure varies depending on the composition of the colored photosensitive composition, but is preferably about 5 mJ/cm 2 to 500 mJ/cm 2 , for example. It is more preferably about 10 mJ/cm 2 to 150 mJ/cm 2 .

可對藉由曝光而硬化之硬化膜進行加熱。進行加熱時之溫度並無特別限定，而以180℃以上280℃以下為佳，以200℃以上260℃以下更佳，以220℃以上250℃以下為特佳。加熱時間傳統上係以1分鐘以上60分鐘以下為佳，以10分鐘以上50分鐘以下更佳，以20分鐘以上40分鐘以下為特佳。 The cured film cured by exposure can be heated. The heating temperature is not particularly limited, but it is preferably from 180°C to 280°C, more preferably from 200°C to 260°C, and particularly preferably from 220°C to 250°C. Traditionally, the heating time is preferably from 1 minute to 60 minutes, more preferably from 10 minutes to 50 minutes, and particularly preferably from 20 minutes to 40 minutes.

≪顯影步驟≫ ≪Development step≫

顯影步驟中，在曝光步驟曝光之塗佈膜為藉由鹼顯影液顯影。 In the developing step, the coating film exposed in the exposing step is developed with an alkali developing solution.

顯影步驟係藉由使經曝光之塗佈膜以顯影液進行顯影，形成圖型化成所希望之形狀的硬化膜(著色膜)。顯影方法並無特別限定，可使用浸漬法、噴霧法等。顯影液之具體例係可列舉如：氫氧化鈉、氫氧化鉀、碳酸鈉、氨、4級銨鹽等之水溶液。 In the developing step, the exposed coating film is developed with a developer to form a cured film (colored film) patterned into a desired shape. The image development method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developer include, for example, aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

顯影後，可依需要進行後烘烤，顯影後後烘烤之溫度係以80℃以上250℃以下為佳，以100℃以上230℃以下更佳。顯影後後烘烤之時間係以5分鐘以上60分鐘以下為佳，以10分鐘以上30分鐘以下更佳。 After development, post-baking can be carried out as required. The post-baking temperature after development is preferably 80°C to 250°C, more preferably 100°C to 230°C. The post-baking time after development is preferably 5 minutes to 60 minutes, more preferably 10 minutes to 30 minutes.

藉由使用上述著色感光性組成物，如後述實施例所示，高濃度之著色劑可分散、且可形成高精細的圖型，以及欲使耐熱性良好時係可含有硬化劑。 By using the above-mentioned colored photosensitive composition, as shown in the examples below, a high-concentration colorant can be dispersed and a high-definition pattern can be formed, and a hardener can be included to improve heat resistance.

[實施例] [Example]

以下，藉由實施例更詳細說明本發明，但本發明係不受此等實施例所限定者。又，在實施例中，只要不特別言明，份係表示重量份。 Hereinafter, the present invention will be described in more detail by means of examples, but the present invention is not limited by these examples. Moreover, in an Example, unless otherwise stated, a part means a weight part.

環氧當量、酸價係依下列之條件測定。 Epoxy equivalent weight and acid value are determined according to the following conditions.

1)環氧當量(WPE)：依據JIS K 7236：2001之方法進行測定。 1) Epoxy equivalent (WPE): Measured according to the method of JIS K 7236:2001.

2)酸價：依據JIS K 0070：1992之方法進行測定。 2) Acid value: Measured according to the method of JIS K 0070:1992.

3)凝膠滲透層析法(GPC)之測定條件係如以下。 3) The measurement conditions of gel permeation chromatography (GPC) are as follows.

機種：TOSOH HLC-8220GPC Model: TOSOH HLC-8220GPC

管柱：TSKGEL Super HZM-N Column: TSKGEL Super HZM-N

分離液：THF(四氫呋喃)；0.35ml/分鐘、溫度40℃ Separation liquid: THF (tetrahydrofuran); 0.35ml/min, temperature 40°C

檢測器：示差折射計 Detector: Differential refractometer

分子量標準：聚苯乙烯 Molecular weight standard: polystyrene

製造例1 Manufacturing example 1

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標 準之凝膠浸透壓層析法所得到的數平均分子量係1,250，且重量平均分子量4,040之固形分酸價係164mgKOH/g之醯胺醯亞胺樹脂(1)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯494.5g、甲基丙烯酸環氧丙酯170.4g、六氫酞酸酐154.0g、及二丁基羥基甲苯2.27g並攪拌之後，加入三苯基膦2.27g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價94.1mgKOH/g、(甲基)丙烯酸當量629、以GPC所得到的數平均分子量係1,870、且重量平均分子量5,320之含有不飽和基的聚羧酸樹脂(I)。又，測定環氧當量，結果為13,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (1) with a number average molecular weight of 1,250 and a weight average molecular weight of 4,040 with a solid acid value of 164 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. Cool to 60°C, add 494.5 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 154.0 g of hexahydrophthalic anhydride, and 2.27 g of dibutyl hydroxytoluene and stir, then add triphenylphosphine 2.27g, and the temperature was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 94.1 mgKOH/g, a (meth)acrylic acid equivalent of 629, a number average molecular weight of 1,870 obtained by GPC, and a weight average molecular weight of 5,320. Acid Resin (I). In addition, when the epoxy equivalent was measured, it was 13,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例2 Manufacturing example 2

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯661.2g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐198.0g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,290，且重量平均分子量3,590之固形分酸價係155mgKOH/g之醯胺醯亞胺樹脂(2)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯537.5g、甲基丙烯酸環氧丙酯198.8g、六氫酞酸酐154.0g、及二丁基羥基甲苯2.38g並攪拌之後，加入三苯基膦2.38g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價92.2mgKOH/g、(甲基)丙烯酸當量629、以GPC所得到的數平均分子量 係1,710、且重量平均分子量4,930之含有不飽和基的聚羧酸樹脂(II)。又，測定環氧當量，結果為11,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-necked flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 661.2 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 198.0g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (2) with a number average molecular weight of 1,290 and a weight average molecular weight of 3,590 with a solid acid value of 155 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. Cool to 60°C, add 537.5 g of propylene glycol monomethyl ether acetate, 198.8 g of glycidyl methacrylate, 154.0 g of hexahydrophthalic anhydride, and 2.38 g of dibutylhydroxytoluene and stir, then add triphenylphosphine 2.38g, and the temperature was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 92.2 mgKOH/g, a (meth)acrylic acid equivalent of 629, a number average molecular weight obtained by GPC of 1,710, and a weight average molecular weight of 4,930. Acid resin (II). In addition, when the epoxy equivalent was measured, it was 11,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例3 Manufacturing example 3

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,260，且重量平均分子量4,120之固形分酸價係159mgKOH/g之醯胺醯亞胺樹脂(3)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯448.0g、甲基丙烯酸環氧丙酯170.4g、六氫酞酸酐123.2g、及二丁基羥基甲苯2.17g並攪拌之後，加入三苯基膦2.17g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價85.9mgKOH/g、(甲基)丙烯酸當量604、以GPC所得到的數平均分子量係1,750、且重量平均分子量5,500之含有不飽和基的聚羧酸樹脂(III)。又，測定環氧當量，結果為14,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (3) with a number average molecular weight of 1,260 and a weight average molecular weight of 4,120 with a solid acid value of 159 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. Cool to 60°C, add 448.0 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 123.2 g of hexahydrophthalic anhydride, and 2.17 g of dibutyl hydroxytoluene and stir, then add triphenylphosphine 2.17g, and the temperature was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 85.9 mgKOH/g, a (meth)acrylic acid equivalent of 604, a number average molecular weight of 1,750 obtained by GPC, and a weight average molecular weight of 5,500. Acid resin (III). In addition, when the epoxy equivalent was measured, it was 14,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例4 Manufacturing example 4

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質 量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,190，且重量平均分子量3,850之固形分酸價係151mgKOH/g之醯胺醯亞胺樹脂(4)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯494.8g、甲基丙烯酸環氧丙酯170.4g、六氫-4-甲基酞酸酐154.0g、及二丁基羥基甲苯2.44g並攪拌之後，加入三苯基膦2.44g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價95.8mgKOH/g、(甲基)丙烯酸當量641、以GPC所得到的數平均分子量係1,640、且重量平均分子量4,790之含有不飽和基的聚羧酸樹脂(IV)。又，測定環氧當量，結果為12,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (4) with a number average molecular weight of 1,190 and a weight average molecular weight of 3,850 with a solid acid value of 151 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. After cooling to 60°C, 494.8 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 154.0 g of hexahydro-4-methylphthalic anhydride, and 2.44 g of dibutylhydroxytoluene were added and stirred, 2.44 g of triphenylphosphine was added, and the temperature was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 95.8 mgKOH/g, a (meth)acrylic acid equivalent of 641, a number average molecular weight of 1,640 obtained by GPC, and a weight average molecular weight of 4,790. Acid resin (IV). In addition, when the epoxy equivalent was measured, it was 12,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例5 Manufacturing Example 5

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,300，且重量平均分子量3,690之固形分酸價係152mgKOH/g之醯胺醯亞胺樹脂(5)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯491.7g、甲基丙烯酸環氧丙酯170.4g、 1,2,3,6-四氫酞酸酐152.2g、及二丁基羥基甲苯2.31g並攪拌之後，加入三苯基膦2.31g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價97.9mgKOH/g、(甲基)丙烯酸當量628、以GPC所得到的數平均分子量係1,690、且重量平均分子量4,980之含有不飽和基的聚羧酸樹脂(V)。又，測定環氧當量，結果為14,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (5) with a number average molecular weight of 1,300 and a weight average molecular weight of 3,690 with a solid acid value of 152 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. After cooling to 60°C, 491.7 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 152.2 g of 1,2,3,6-tetrahydrophthalic anhydride, and 2.31 g of dibutylhydroxytoluene were added and After stirring, 2.31 g of triphenylphosphine was added, and the temperature was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 97.9 mgKOH/g, a (meth)acrylic acid equivalent of 628, a number average molecular weight of 1,690 obtained by GPC, and a weight average molecular weight of 4,980. Acid resin (V). In addition, when the epoxy equivalent was measured, it was 14,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例6 Manufacturing example 6

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,250，且重量平均分子量3,680之固形分酸價係161mgKOH/g之醯胺醯亞胺樹脂(6)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯261.9g、甲基丙烯酸環氧丙酯170.4g、及二丁基羥基甲苯1.90g並攪拌之後，加入三苯基膦1.90g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價19.2mgKOH/g、以GPC所得到的數平均分子量係1,740、且重量平均分子量6,950之含有不飽和基的聚羧酸樹脂(I’)。又，測定環氧當量，結果為13,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (6) with a number average molecular weight of 1,250 and a weight average molecular weight of 3,680 with a solid acid value of 161 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. Cool to 60°C, add 261.9g of propylene glycol monomethyl ether acetate, 170.4g of glycidyl methacrylate, and 1.90g of dibutylhydroxytoluene and stir, then add 1.90g of triphenylphosphine and raise the temperature to 116 ℃. React at the same temperature for 20 hours to obtain a polycarboxylic acid resin (I') containing unsaturated groups with a solid content of 19.2 mgKOH/g, a number average molecular weight of 1,740 by GPC, and a weight average molecular weight of 6,950. In addition, when the epoxy equivalent was measured, it was 13,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例7 Manufacturing example 7

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,180，且重量平均分子量3,860之固形分酸價係154mgKOH/g之醯胺醯亞胺樹脂(7)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯494.5g、甲基丙烯酸環氧丙酯170.4g、酞酸酐148.1g、及二丁基羥基甲苯1.90g並攪拌之後，加入三苯基膦1.90g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價99.5mgKOH/g、(甲基)丙烯酸當量624、以GPC所得到的數平均分子量係1,630、且重量平均分子量4,830之含有不飽和基的聚羧酸樹脂(II’)。又，測定環氧當量，結果為14,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (7) with a number average molecular weight of 1,180 and a weight average molecular weight of 3,860 with a solid acid value of 154 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. Cool to 60°C, add 494.5 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 148.1 g of phthalic anhydride, and 1.90 g of dibutylhydroxytoluene and stir, then add 1.90 g of triphenylphosphine , and the temperature was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 99.5 mgKOH/g, a (meth)acrylic acid equivalent of 624, a number average molecular weight of 1,630 obtained by GPC, and a weight average molecular weight of 4,830. Acid Resin (II'). In addition, when the epoxy equivalent was measured, it was 14,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例8 Manufacturing example 8

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。冷卻至60℃，加入新戊四醇(三/四)丙烯酸酯混合物(DAICEL‧ALLNEX公司製「PETRA」、羥 基價115mgKOH/g)97.58g，昇溫至116℃，在同溫度下反應10小時，獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,070、重量平均分子量3,080之固形分酸價係135mgKOH/g之醯胺醯亞胺樹脂(8)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯494.8g、甲基丙烯酸環氧丙酯170.4g、六氫-4-甲基酞酸酐154.0g、二丁基羥基甲苯2.44g並攪拌之後，加入三苯基膦2.44g，昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價82.1mgKOH/g、(甲基)丙烯酸當量395、以GPC所得到的數平均分子量係1,370、且重量平均分子量3,700之含有不飽和基的聚羧酸樹脂(III’)。又，測定環氧當量，結果為15,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. Cool to 60°C, add 97.58g of neopentylthritol (tri/tetra) acrylate mixture ("PETRA" manufactured by DAICEL‧ALLNEX company, hydroxyl value 115mgKOH/g), raise the temperature to 116°C, and react at the same temperature for 10 hours. A solution of amidoimide resin (8) with a number average molecular weight of 1,070, a weight average molecular weight of 3,080 and a solid acid value of 135 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. Cool to 60°C, add propylene glycol monomethyl ether acetate 494.8g, glycidyl methacrylate 170.4g, hexahydro-4-methylphthalic anhydride 154.0g, dibutylhydroxytoluene 2.44g and stir, then add 2.44 g of triphenylphosphine was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 82.1 mgKOH/g, a (meth)acrylic acid equivalent of 395, a number average molecular weight of 1,370 obtained by GPC, and a weight average molecular weight of 3,700. Acid Resin (III'). In addition, when the epoxy equivalent was measured, it was 15,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例9 Manufacturing example 9

在具備攪拌裝置、溫度計及冷凝器之四口燒瓶中，加入丙二醇單甲醚乙酸酯250.3g、甲酚酚醛清漆型環氧樹脂(日本化藥股份有限公司製「EOCN-104S」、環氧當量218g/eq)435.7g及二丁基羥基甲苯1.75g並在80℃下攪拌，使環氧樹脂溶解。在此之後，加入丙烯酸酸148.4g、三苯基膦1.75g並昇溫至116℃，在同溫度下反應12小時，獲得固形分酸價2.2mg‧KOH/g、又環氧當量13kg/eq之反應性環氧基羧酸酯樹脂(9)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯48.6g及1,2,3,6-四氫酞酸酐113.5g，昇溫至100℃。在同溫度下反應5小時，獲得固形分酸價61.2mgKOH/g、(甲基)丙烯酸當量349、以GPC所得到的數平均分子量係2058、且重量平均分子量6420之含有不飽和基的聚羧酸樹脂(IV’)。又，測定環氧當量，結果為13,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-necked flask equipped with a stirring device, a thermometer, and a condenser, 250.3 g of propylene glycol monomethyl ether acetate, cresol novolak type epoxy resin ("EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., epoxy Equivalent 218g/eq) 435.7g and dibutyl hydroxytoluene 1.75g were stirred at 80°C to dissolve the epoxy resin. After that, add 148.4g of acrylic acid and 1.75g of triphenylphosphine and raise the temperature to 116°C, and react at the same temperature for 12 hours to obtain a solid with an acid value of 2.2mg‧KOH/g and an epoxy equivalent of 13kg/eq. Reactive epoxy carboxylate resin (9) solution. After cooling to 60°C, 48.6 g of propylene glycol monomethyl ether acetate and 113.5 g of 1,2,3,6-tetrahydrophthalic anhydride were added, and the temperature was raised to 100°C. React at the same temperature for 5 hours to obtain a polycarboxylate containing unsaturated groups with a solid content of 61.2 mgKOH/g, a (meth)acrylic acid equivalent of 349, a number average molecular weight of 2058 obtained by GPC, and a weight average molecular weight of 6420. Acid Resin (IV'). In addition, when the epoxy equivalent was measured, it was 13,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例10 Manufacturing Example 10

如日本特許-6576161之實施例2-1記載的樹脂，進行製造，獲得固形分酸價61.5mgKOH/g、(甲基)丙烯酸當量335、以GPC所得到的數平均分子量係1830、重量平均分子量3520之反應性聚羧酸化合物(V’)。 Manufacture the resin as described in Example 2-1 of Japanese Patent-6576161 to obtain a solid content of 61.5 mgKOH/g, a (meth)acrylic acid equivalent of 335, a number average molecular weight of 1830 obtained by GPC, and a weight average molecular weight 3520 reactive polycarboxylate compound (V').

製造例11 Manufacturing Example 11

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,310，且重量平均分子量3,810之固形分酸價係152mgKOH/g之醯胺醯亞胺樹脂(5)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯338.6g、甲基丙烯酸環氧丙酯142.0g、環己烷-1,3,4-三羧酸-3,4-酐79.2g、及二丁基羥基甲苯2.31g並攪拌之後，加入三苯基膦2.31g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價87.1mgKOH/g、(甲基)丙烯酸當量652、以GPC所得到的數平均分子量係1,870、且重量平均分子量6,010之含有不飽和基的聚羧酸樹脂(VI)。又，測定環氧當量，結果為16,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (5) with a number average molecular weight of 1,310 and a weight average molecular weight of 3,810 with a solid acid value of 152 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. Cool to 60°C, add 338.6g of propylene glycol monomethyl ether acetate, 142.0g of glycidyl methacrylate, 79.2g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and di After stirring 2.31 g of butylhydroxytoluene, 2.31 g of triphenylphosphine was added, and the temperature was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 87.1 mgKOH/g, a (meth)acrylic acid equivalent of 652, a number average molecular weight of 1,870 obtained by GPC, and a weight average molecular weight of 6,010. Acid resin (VI). In addition, when the epoxy equivalent was measured, it was 16,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

製造例12 Manufacturing Example 12

在具備攪拌裝置、溫度計及冷凝器、氮氣管之四口燒瓶中，加入丙二醇單甲醚乙酸酯646.3g、異佛酮二異氰酸酯之三聚異氰酸酯改性體(EVONIK公司製「VESTANATT-1890/100」、異氰酸酯基含量17.3質量%)242.8g及環己烷-1,3,4-三羧酸-3,4-酐188.1g。在系統中吹入氮氣之同時昇溫至116℃，在同溫度下反應30小時。以紅外線光譜確認出屬於異氰酸酯基之特性吸收的2250cm1之吸收完全消失。獲得以聚苯乙烯作為標準之凝膠浸透壓層析法所得到的數平均分子量係1,260，且重量平均分子量3,600之固形分酸價係156mgKOH/g之醯胺醯亞胺樹脂(5)溶液。冷卻至60℃，加入丙二醇單甲醚乙酸酯441.4g、甲基丙烯酸環氧丙酯170.4g、環己烷-1,3,4-三羧酸-3,4-酐118.8g、及二丁基羥基甲苯2.31g並攪拌之後，加入三苯基膦2.31g，並昇溫至116℃。在同溫度下反應20小時，獲得固形分酸價80.6mgKOH/g、(甲基)丙烯酸當量600、以GPC所得到的數平均分子量係1,870、且重量平均分子量6,010之含有不飽和基的聚羧酸樹脂(VII)。又，測定環氧當量，結果為14,000g/eq，亦一併確認出環氧基充分進行反應。 In a four-neck flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen tube, 646.3 g of propylene glycol monomethyl ether acetate and a modified isophorone diisocyanate (manufactured by EVONIK "VESTANATT-1890/ 100", isocyanate group content 17.3% by mass) 242.8g, and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride 188.1g. While blowing nitrogen into the system, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 30 hours. The absorption at 2250 cm 1 , which is the characteristic absorption of the isocyanate group, was confirmed to disappear completely by the infrared spectrum. A solution of amidoimide resin (5) with a number average molecular weight of 1,260 and a weight average molecular weight of 3,600 with a solid acid value of 156 mgKOH/g obtained by gel permeation pressure chromatography using polystyrene as a standard was obtained. Cool to 60°C, add 441.4g of propylene glycol monomethyl ether acetate, 170.4g of glycidyl methacrylate, 118.8g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and di After stirring 2.31 g of butylhydroxytoluene, 2.31 g of triphenylphosphine was added, and the temperature was raised to 116°C. React at the same temperature for 20 hours to obtain a polycarboxylate containing unsaturated groups with a solid acid value of 80.6 mgKOH/g, a (meth)acrylic acid equivalent of 600, a number average molecular weight of 1,870 obtained by GPC, and a weight average molecular weight of 6,010. Acid resin (VII). In addition, when the epoxy equivalent was measured, it was 14,000 g/eq, and it was also confirmed that the epoxy group had sufficiently reacted.

[實施例1、比較例1]有關著色感光性組成物之調製與混練分散性的評定 [Example 1, Comparative Example 1] Evaluation of preparation and kneading dispersibility of colored photosensitive composition

使用製造例1至10所得到之含有不飽和基的聚羧酸樹脂20g、實施例及比較例中作為著色劑(B)之三菱碳黑MA-100(B1)。使用丙二醇單甲醚乙酸酯(C1)作為溶劑(C)，以珠磨機進行混練，確認混練後之狀態。所得到的著色感光性組成物為均勻者係設為○，產生不均勻、且因樹脂所造成的凝 膠化者係設為×。將著色感光性組成物之比率與混練後之狀態的評定結果呈示於表1中。 20 g of unsaturated group-containing polycarboxylic acid resins obtained in Production Examples 1 to 10, and Mitsubishi Carbon Black MA-100 (B1) as a colorant (B) in Examples and Comparative Examples were used. Using propylene glycol monomethyl ether acetate (C1) as a solvent (C), kneading was performed with a bead mill, and the state after kneading was confirmed. The coloring photosensitive composition obtained is uniform and is marked as ○, and unevenness occurs, and condensation caused by the resin Those who gelled were set as ×. Table 1 shows the evaluation results of the ratio of the colored photosensitive composition and the state after kneading.

[表1]

Figure 111130624-A0202-12-0047-4
[Table 1]
Figure 111130624-A0202-12-0047-4

[實施例2、比較例2]有關著色感光性組成物之調製與著色劑分散性的評定 [Example 2, Comparative Example 2] Preparation of colored photosensitive composition and evaluation of colorant dispersibility

在實施例1、比較例1所得到的著色感光性組成物中，置入作為交聯劑(D)之DPHA(商品名：日本化藥股份有限公司製)(D1)、再置入20g之玻璃珠，以油漆搖動器進行分散1小時。使分散結束後之分散液以線棒塗佈機#2塗佈在聚對苯二甲酸乙二酯膜上，以80℃之溫風乾燥機進行乾燥10分鐘。使用60°反射光澤計(堀場製作所IG-331光澤計)測定乾燥結束後之塗膜表面的光澤，評定碳黑之分散性。將結果呈示於表2。光澤之值愈高，顏料分散性愈良好。 In the colored photosensitive composition obtained in Example 1 and Comparative Example 1, DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.) (D1) was placed as a crosslinking agent (D), and 20 g of Glass beads, dispersed with a paint shaker for 1 hour. The dispersion liquid after the dispersion was finished was coated on a polyethylene terephthalate film with a wire bar coater #2, and dried with a warm air dryer at 80° C. for 10 minutes. The gloss of the coating film surface after drying was measured using a 60° reflective gloss meter (Horiba IG-331 gloss meter), and the dispersibility of carbon black was evaluated. The results are shown in Table 2. The higher the gloss value, the better the pigment dispersion.

[表2]

Figure 111130624-A0202-12-0048-5
[Table 2]
Figure 111130624-A0202-12-0048-5

[實施例3、比較例3]著色感光性組成物之調製與顯影性評定 [Example 3, Comparative Example 3] Preparation of colored photosensitive composition and evaluation of developability

對於製造例1至10所得到的含有不飽和基的聚羧酸樹脂(A)、著色劑(B1)、溶劑(C1)、交聯劑(D)、及光聚合起始劑(E)，以表3所示的調配均勻地分散，獲得阻劑樹脂組成物。 For the unsaturated group-containing polycarboxylic acid resin (A), colorant (B1), solvent (C1), crosslinking agent (D) and photopolymerization initiator (E) obtained in Production Examples 1 to 10, Uniformly dispersed in the formulation shown in Table 3 to obtain a resist resin composition.

在實施例及比較例中，使用作為交聯劑(D)之DPCA-20(日本化藥股份有限公司製：ε-己內酯改性二新戊四醇六丙烯酸酯)(D2)、作為光聚合起始劑(E)之IRGACURE-907(CIBA SPECITALTY CHEMICALS製)(E1)與KAYACURE DETX-S(日本化藥股份有限公司製)(E2)、作為硬化劑(F)之YD-134(日鐵CHEMICAL & MATERIAL股份有限公司製：雙酚-A型環氧樹脂)(F1)、及作為熱硬化觸媒(G)之TPP(北興化學工業股份有限公司製：三苯基膦)(G1)。 In Examples and Comparative Examples, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.: ε-caprolactone-modified diperythritol hexaacrylate) (D2) as a crosslinking agent (D), as IRGACURE-907 (manufactured by CIBA SPECITALTY CHEMICALS) (E1) and KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2) as the photopolymerization initiator (E), YD-134 ( Nippon Steel Chemical & Material Co., Ltd.: bisphenol-A epoxy resin) (F1), and TPP as a thermosetting catalyst (G) (Hokuko Chemical Industry Co., Ltd.: triphenylphosphine) (G1 ).

詳述有關評定項目之各別的項目。 Details about the individual items of the assessed items.

顯影性評定(表中簡稱：顯影性) Developability evaluation (abbreviation in the table: developability)

以施用機在壓延銅箔BHY-82F-HA-V2(JX金屬股份有限公司製)上塗佈著色感光性組成物成為20μm之厚度，將塗膜以80℃之熱風乾燥機乾燥30分鐘。對於乾燥後之塗膜塗佈膜，隔著50μm開口之掩膜，使用紫外線 照射器(USHIO製(超高壓水銀燈))以150mJ/cm2之照射量進行硬化。在此之後，使用作為顯影液之1%碳酸鈉水溶液進行噴霧顯影。直至未曝光部之塗膜完全溶解之時間，即所謂斷裂時間(Break Time)作為顯影性之評定(單位：秒)。 The colored photosensitive composition was coated on the rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metal Co., Ltd.) with an applicator to a thickness of 20 μm, and the coating film was dried with a hot air dryer at 80° C. for 30 minutes. The dried coated film was hardened with an irradiation dose of 150 mJ/cm 2 using an ultraviolet irradiator (manufactured by USHIO (ultra-high pressure mercury lamp)) through a mask with an opening of 50 μm. Thereafter, spray development was performed using a 1% sodium carbonate aqueous solution as a developing solution. The time until the coating film of the unexposed part is completely dissolved, that is, the so-called break time (Break Time) is used as the evaluation of developability (unit: second).

△‧‧膜減少 △‧‧film reduction

×‧‧圖型直線度 ×‧‧Graph straightness

××‧‧膨潤剝離； ××‧‧Swelling peeling;

對於「膜減少」係從顯影前之塗佈膜的膜厚與顯影後之圖型的剖面高度所求得，當膜減少時，並非斷裂時間，評定為△。對於(使用電子顯微鏡)「圖型直線度」係彎曲時評定為×。無圖型之直線度，未完美地形成時，並非斷裂時間，評定為×。對於(使用電子顯微鏡)「膨潤剝離」係在顯影時並非溶解顯影，塗膜會膨潤而剝離時，並非斷裂時間，評定為××。 "Film reduction" is obtained from the film thickness of the coating film before development and the cross-sectional height of the pattern after development. When the film decreases, it is not the breaking time, and it is evaluated as △. For "pattern straightness" (using an electron microscope), it was rated as x when it was bent. When the straightness without pattern is not perfectly formed, it is not the breaking time, and it is evaluated as ×. For "swelling and peeling" (using an electron microscope), it is not a dissolution development during development, and when the coating film swells and peels off, it is not the breaking time, and is rated as ××.

耐熱分解性評定(表中簡稱：耐熱分解性) Evaluation of thermal decomposition resistance (abbreviation in the table: thermal decomposition resistance)

以施用機在壓延銅箔BHY-82F-HA-V2(JX金屬股份有限公司製)上塗佈著色感光性組成物成為20μm之厚度，使塗膜以80℃之熱風乾燥機乾燥30分鐘後，使用紫外線照射器(GS YUASA製：CS 30L-1)，以500mJ/cm2之能量照射紫外線。其次，在烘箱內以150℃硬化30分鐘，獲得硬化物。以氯化鐵(III)45°Baumé degree(波美度)(純正化學股份有限公司製)去除銅箔。使所製作之硬化物製作成的試樣3mg在每分鐘100ml之空氣流中使用METTLER製TGA/DSC1而測定重量減少5%時之溫度。 Apply the coloring photosensitive composition to a thickness of 20 μm on the rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metal Co., Ltd.) with an applicator, and dry the coating film with a hot air dryer at 80°C for 30 minutes. Ultraviolet rays were irradiated with an energy of 500 mJ/cm 2 using an ultraviolet irradiator (manufactured by GS YUASA: CS 30L-1). Next, it was cured at 150° C. for 30 minutes in an oven to obtain a cured product. Copper foil was removed with iron(III) chloride 45° Baumé degree (manufactured by Junzheng Chemical Co., Ltd.). The temperature at which the weight decreased by 5% was measured using TGA/DSC1 manufactured by METTLER in an air flow of 100 ml per minute for 3 mg of the prepared cured product.

[表3]

Figure 111130624-A0202-12-0050-6
[table 3]
Figure 111130624-A0202-12-0050-6

從上述之結果，可確認從本發明之著色感光性組成物所得到的塗膜具優異的著色劑分散性，且顯影性高，其硬化物之耐熱分解性亦為優異。 From the above results, it can be confirmed that the coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility, high developability, and excellent thermal decomposition resistance of the cured product.

[實施例4]有關著色感光性組成物之調製與混練分散性的評定 [Example 4] Evaluation of preparation and kneading dispersibility of colored photosensitive composition

使用製造例11、12所得到之含有不飽和基的聚羧酸樹脂20g、及作為著色劑(B)之三菱碳黑MA-100(B1)。以珠磨機進行混練，確認出混練後之 狀態。所得到的著色感光性組成物為均勻者係設為○，產生不均勻、且因樹脂所造成的凝膠化者係設為×。 20 g of unsaturated group-containing polycarboxylic acid resins obtained in Production Examples 11 and 12, and Mitsubishi Carbon Black MA-100 (B1) as a colorant (B) were used. Kneading with a bead mill and confirming that the kneading state. The coloring photosensitive composition obtained was uniform and was made into (circle), and the thing which became uneven and gelatinized by resin was made into x.

[表4]

Figure 111130624-A0202-12-0051-7
[Table 4]
Figure 111130624-A0202-12-0051-7

[實施例5]有關著色感光性組成物之調製與著色劑分散性的評定 [Example 5] Preparation of colored photosensitive composition and evaluation of colorant dispersibility

在實施例4-1、4-2、4-3所得到的著色感光性組成物中，置入作為交聯劑(D)之DPHA(商品名：日本化藥股份有限公司製)(D1)、再置入20g之玻璃珠，以油漆搖動器進行分散1小時。將分散結束後之分散液以線棒塗佈機#2塗佈在聚對苯二甲酸乙二酯膜上，在80℃之溫風乾燥機進行乾燥10分鐘。使用60°反射光澤計(堀場製作所IG-331光澤計)測定乾燥結束後之塗膜表面的光澤，評定碳黑之分散性。將結果呈示於表5。光澤之值愈高，顏料分散性愈良好。 In the colored photosensitive compositions obtained in Examples 4-1, 4-2, and 4-3, DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.) (D1) was placed as a crosslinking agent (D). , Add 20g of glass beads and disperse for 1 hour with a paint shaker. The dispersion liquid after dispersion was coated on the polyethylene terephthalate film with a wire bar coater #2, and dried in a warm air dryer at 80° C. for 10 minutes. The gloss of the coating film surface after drying was measured using a 60° reflective gloss meter (Horiba IG-331 gloss meter), and the dispersibility of carbon black was evaluated. The results are shown in Table 5. The higher the gloss value, the better the pigment dispersion.

[表5]

Figure 111130624-A0202-12-0051-8
[table 5]
Figure 111130624-A0202-12-0051-8

[實施例6]著色感光性組成物之調製與顯影性評定 [Example 6] Preparation of colored photosensitive composition and evaluation of developability

對於製造例11、12所得到的含有不飽和基的聚羧酸樹脂(A)、著色劑(B1)、溶劑(C1)、交聯劑(D)、及光聚合起始劑(E)，以表3所示的調配均勻地分散，獲得阻劑樹脂組成物。 For the unsaturated group-containing polycarboxylic acid resin (A), coloring agent (B1), solvent (C1), crosslinking agent (D) and photopolymerization initiator (E) obtained in Production Examples 11 and 12, Uniformly dispersed in the formulation shown in Table 3 to obtain a resist resin composition.

在實施例中，使用作為交聯劑(D)之DPCA-20(日本化藥股份有限公司製：ε-己內酯改性二新戊四醇六丙烯酸酯)(D2)、作為光聚合起始劑(E)之IRGACURE-907(CIBA SPECITALTY CHEMICALS製)(E1)、KAYACURE DETX-S(日本化藥股份有限公司製)(E2)、作為硬化劑(F)之YD-134(日鐵CHEMICAL & MATERIAL股份有限公司製：雙酚-A型環氧樹脂)(F1)、及作為熱硬化觸媒(G)之TPP(北興化學工業股份有限公司製：三苯基膦)(G1)。 In the examples, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.: ε-caprolactone-modified diperythritol hexaacrylate) (D2) as a crosslinking agent (D), as a photopolymerizer IRGACURE-907 (manufactured by CIBA SPECITALTY CHEMICALS) (E1) as starter (E), KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2), YD-134 (manufactured by Nippon Steel Chemicals Co., Ltd.) as hardener (F) & MATERIAL CO., LTD.: bisphenol-A type epoxy resin) (F1), and TPP as a thermosetting catalyst (G) (BOKING CHEMICAL INDUSTRY CO., LTD.: triphenylphosphine) (G1).

對於評定項目之各別項目係與實施例3相同。各評定項目之評定結果呈示於表6中。 The individual items for the evaluation items are the same as those in Example 3. The evaluation results of each evaluation item are shown in Table 6.

[表6]

Figure 111130624-A0202-12-0052-9
[Table 6]
Figure 111130624-A0202-12-0052-9

從上述之結果，可確認從本發明之著色感光性組成物所得到的塗膜具優異的著色劑分散性，且顯影性高，其硬化物之耐熱分解性亦為優異。 From the above results, it can be confirmed that the coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility, high developability, and excellent thermal decomposition resistance of the cured product.

依據以上，因從本發明之著色感光性組成物所得到的塗膜具優異的著色劑分散性，且顯影性高，其硬化物之耐熱分解性亦為優異，故適用於具有圖像顯示裝置用之遮光效果的隔牆、黑色矩陣、著色間隔物、及彩色光阻劑。 Based on the above, the coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility, high developability, and excellent thermal decomposition resistance of the cured product, so it is suitable for use in image display devices. Partition wall, black matrix, colored spacer, and color photoresist for shading effect.

Claims (7)

一種著色感光性組成物，係包含：含有不飽和基的聚羧酸樹脂(A)、著色劑(B)、及溶劑(C)，該含有不飽和基的聚羧酸樹脂(A)係使藉由脂環式三聚異氰酸酯型聚異氰酸酯(a1)與脂環式三羧酸酐(a2)之反應所得到的具有末端酸基或酸酐基的聚醯胺醯亞胺樹脂(a3)、與一分子中具有環氧基之(甲基)丙烯酸酯化合物(b)及脂肪族二羧酸酐或脂肪族三羧酸酐(c)反應而得者。 A colored photosensitive composition comprising: a polycarboxylic acid resin (A) containing an unsaturated group, a colorant (B), and a solvent (C), the polycarboxylic acid resin (A) containing an unsaturated group is made of The polyamide imide resin (a3) with terminal acid group or acid anhydride group obtained by the reaction of alicyclic isocyanate polyisocyanate (a1) and alicyclic tricarboxylic anhydride (a2), and a It is obtained by reacting (meth)acrylate compound (b) with epoxy group in the molecule and aliphatic dicarboxylic anhydride or aliphatic tricarboxylic anhydride (c). 如請求項1所述之著色感光性組成物，係含有交聯劑(D)。 The colored photosensitive composition as described in Claim 1 contains a crosslinking agent (D). 如請求項1所述之著色感光性組成物，係更含有光聚合起始劑(E)。 The colored photosensitive composition described in Claim 1 further contains a photopolymerization initiator (E). 如請求項1所述之著色感光性組成物，係更含有硬化劑(F)。 The colored photosensitive composition described in Claim 1 further contains a curing agent (F). 如請求項1所述之著色感光性組成物，其中，前述著色劑(B)包含黑色顏料。 The colored photosensitive composition according to claim 1, wherein the colorant (B) contains a black pigment. 一種硬化物，係請求項1至5中任一項所述之著色感光性組成物之硬化物。 A cured product is a cured product of the colored photosensitive composition described in any one of Claims 1 to 5. 一種圖像顯示裝置，係具備請求項6所述之硬化物。 An image display device comprising the cured product described in Claim 6.
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