JP2023055623A - Coloring photosensitive composition, cure product and image display device having cured product - Google Patents

Abstract

To provide a coloring photosensitive composition having excellent dispersibility of a colorant or the like and having good developing characteristics even at a high colorant concentration, a coloring photosensitive composition having good heat resistance and a cured product thereof.SOLUTION: There is provided a coloring photosensitive composition which comprises an unsaturated group-containing polycarboxylic acid resin (A) 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 (c) with a polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group obtained by the reaction of an alicyclic isocyanurate polyisocyanate (a1) and an alicyclic tricarboxylic acid anhydride (a2), a colorant (B) and a solvent (C).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a colored photosensitive composition, a cured product, and an image display device comprising the cured product. Specifically, the present invention relates to a photosensitive coloring composition excellent in shielding properties and plate-making properties, and uses thereof.

Conventional displays often use color filters, colored spacers, and black matrices that form red, green, and blue pixels using organic pigments.
In recent years, in order to reduce power consumption and widen the color gamut of displays, color filters in which pixels are formed using luminescent nanocrystal particles such as quantum dots have been studied. Specifically, it is known to have a red pixel containing nanocrystalline particles emitting red light, a green pixel containing nanocrystalline particles emitting green light, and a blue pixel transmitting blue light from a light source.
As a method for manufacturing a color filter, there are a photolithography method and an inkjet method, and it is known that the latter method can reduce the loss of ink materials (Patent Document 1).
When a color filter containing luminescent nanocrystalline particles is manufactured by an ink jet method, pixels are formed by ejecting ink onto a region (pixel portion) surrounded by prefabricated partition walls. In addition to preventing mixing of inks between adjacent pixel portions, the partition wall requires a high-definition pattern (fine pattern). Further, as a material having a light-shielding effect, a photosensitive composition containing a coloring agent (colored photosensitive composition) is known to be formed by a photolithographic method (Patent Document 2).
In addition, an attempt to disperse carbon black or the like in an acid-modified epoxy acrylate having a phenol aralkyl epoxy resin as a basic skeleton and apply it to a cured product used in liquid crystal display panels and the like is also known (Patent Document 3).

JP 2019-086745 A JP 2007-10795 A JP 2005-055814 A

However, when the photosensitive composition of Patent Document 2 is used, the pattern obtained by photolithography has poor developability, and there is a problem that a pattern having a desired shape cannot be obtained in some cases. Further, there is a need for a colored photosensitive composition that exhibits good dispersibility even when an additional coloring agent is contained in barrier ribs having a light-shielding effect, black matrix, colored spacer, and color resist.

The present invention solves the above-mentioned problems of the prior art, and provides a colored photosensitive composition that is excellent in dispersibility of a coloring agent and the like and has good developing properties even at a high coloring agent concentration. An object of the present invention is to provide photosensitive compositions and cured products thereof.

As a result of diligent efforts to solve the above problems, the present inventors have found a terminal acid group obtained by the reaction of an alicyclic isocyanurate-type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2) Or unsaturated group-containing obtained by reacting a polyamideimide resin (a3) having an acid anhydride group with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride (c) A colored photosensitive composition containing a polycarboxylic acid resin (A), a colorant (B), and a solvent (C) has excellent dispersibility of the colorant and the like, and has good development characteristics even at a high colorant concentration. The present inventors have found to provide a photosensitive composition, and in some cases, a colored photosensitive composition having good heat resistance, and a cured product thereof.

That is, the present invention relates to the following (1) to (7).
(1) Polyamideimide resin (a3) having terminal acid groups or acid anhydride groups obtained by reaction of alicyclic isocyanurate-type polyisocyanate (a1) and alicyclic tricarboxylic acid anhydride (a2) An unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a (meth)acrylate compound (b) having an epoxy group in the molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c) and a coloring agent (B) and a solvent (C).
(2) The colored photosensitive composition according to (1), which contains a cross-linking agent (D).
(3) The colored photosensitive composition according to (1) or (2), which contains a photopolymerization initiator (E).
(4) The colored photosensitive composition according to any one of (1) to (3), which contains a curing agent (F).
(5) The colored photosensitive composition according to any one of (1) to (4), wherein the coloring agent (B) contains a black pigment.
(6) A cured product of the colored photosensitive composition according to any one of (1) to (5).
(7) An image display device comprising the cured product according to (6).

The colored photosensitive composition characterized by containing the unsaturated group-containing polycarboxylic acid resin (A), the colorant (B), and the solvent (C) of the present invention has excellent photosensitivity and can be dispersed even at a high colorant concentration. possible and have good development properties.

<<Colored photosensitive composition>>
The colored photosensitive composition of the present invention contains an unsaturated group-containing polycarboxylic acid resin (A), a colorant (B) and a solvent (C).

The essential and optional components contained in the colored photosensitive composition are described below.

The colored photosensitive composition contains an unsaturated group-containing polycarboxylic acid resin (A).
The unsaturated group-containing polycarboxylic acid resin (A) in the present invention is a terminal acid group or an acid anhydride obtained by reacting a cyclic isocyanurate-type polyisocyanate (a1) and an alicyclic tricarboxylic acid anhydride (a2) obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c) with a polyamideimide resin (a3) having a group .

That is, the unsaturated group-containing polycarboxylic acid resin (A) in the present invention is produced through two reaction steps. First, a step of reacting a cyclic isocyanurate-type polyisocyanate (a1) and an alicyclic tricarboxylic acid anhydride (a2) to obtain a polyamide-imide resin (a3). In the present invention, this step is referred to as an amidimidation step.
Next, a step of reacting the obtained polyamideimide resin (a3), a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c) is. In the present invention, this step is referred to as the carboxylation step.

First, the amidimidation step will be described in detail.
The alicyclic isocyanurate-type polyisocyanate (a1) used for producing the polyamide-imide resin (a3) in the present invention is a diisocyanate compound containing an alicyclic diisocyanate compound in the presence or absence of a trimerization catalyst. obtained by converting

Alicyclic as used herein, in the context of the present invention, means a compound in which the carbon atoms are arranged in a ring (the two terms "aliphatic" and "cyclic" being described together). (as already suggested by being identical). Cycloaliphatic is therefore also synonymous with cycloaliphatic. Consequently, cycloaliphatic compounds belong to the group of homocyclic compounds, which in this case include cycloalkanes, cycloalkenes and cycloalkynes. Aromatic and heterocyclic compounds, as well as saturated examples of heterocyclic compounds, are not considered to be cycloaliphatic within the meaning of the present invention.

Examples of diisocyanates containing alicyclic diisocyanate compounds include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, norbornane diisocyanate, and hydrogenated diphenylmethane diisocyanate.

The trimerization catalyst is not particularly specified. Examples include amine compounds such as S-triazine, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate, and quaternary ammonium salts of carboxylic acids. 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 ( San-Apro) and the like.

Examples of the alicyclic isocyanurate-type polyisocyanate (a1) include an alicyclic isocyanurate-type triisocyanate synthesized from isophorone diisocyanate (including polymers such as pentamers), and a hydrogenated tolylene diisocyanate synthesized from alicyclic isocyanurate-type triisocyanate (including polymers such as pentamers), alicyclic isocyanurate-type triisocyanates synthesized from hydrogenated xylene diisocyanate (including polymers such as pentamers), norbornane Isocyanurate-type triisocyanates synthesized from diisocyanates (including polymers such as pentamers), alicyclic isocyanurate-type triisocyanates synthesized from hydrogenated diphenylmethane diisocyanate (including polymers such as pentamers), etc. is mentioned. Among them, alicyclic isocyanurate-type isocyanates synthesized from isophorone diisocyanate are preferred. By using an alicyclic isocyanurate-type polyisocyanate synthesized from isophorone diisocyanate, it is excellent in tackiness and cure shrinkage.

Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3 as the alicyclic tricarboxylic acid anhydride (a2) used for producing the polyamideimide resin (a3) in the present invention ,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride and the like. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferred because of its excellent tackiness and cure shrinkage.

The reaction between the alicyclic isocyanurate-type polyisocyanate (a1) and the alicyclic tricarboxylic acid anhydride (a2) is carried out by The total amount of the physical group and the carboxylic acid is preferably from 1.0 mol to 3.0 mol, more preferably from 1.2 mol to 2.8 mol, and still more preferably from 1.4 mol to 2.6 mol. When the total amount of acids exceeds 1.0 mol, residual isocyanate groups are prevented to suppress increase in molecular weight, resulting in good developability. When the total amount of the acid anhydride group and the carboxylic acid is less than 3.0 mol, it is possible to prevent the alicyclic tricarboxylic acid anhydride from remaining and suppress development residuals.

The amidimidation step uses no solvent or an organic solvent having no hydroxyl group. Specifically included in the solvent (C), for example, 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 Ethylene glycol dialkyl ethers such as dibutyl ether; Polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether; Ethylene glycol monomethyl ether acetate , ethylene glycol monoethyl ether acetate, 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 mono polyethylene glycol monoalkyl ether acetates such as ethyl ether acetate and triethylene glycol monobutyl ether acetate; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether; dipropylene glycol dimethyl ether and dipropylene glycol diethyl Polypropylene glycol dialkyl ethers such as ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate Propylene glycol monoalkyl ether acetates such as; 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 polypropylene glycol monoalkyl ether acetates such as monobutyl ether acetate; or dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers, and monoacetate monoalkyl ethers of copolymerized polyether glycols; Alkyl esters of polyether glycol; monoalkyl esters of polyether glycol, monoalkyl ethers, and among the crosslinking agents (D) described later, a crosslinking agent (D) having no hydroxyl group, etc. alone or in a mixed organic solvent can be reacted.

The amidimidation reaction is carried out by mixing one or more alicyclic isocyanurate-type polyisocyanates (a1) and one or more alicyclic tricarboxylic acid anhydrides (a2) in a solvent or in the absence of a solvent. It is preferable to raise the temperature while stirring.

The reaction temperature for the amidimidation reaction is preferably in the range of 50°C to 250°C, particularly preferably in the range of 70°C to 180°C. Setting the reaction temperature to such a temperature has the effect of increasing the reaction rate. The reaction, accompanied by decarboxylation, forms an imide group between an anhydride group and an isocyanate group, and an amide group between a carboxylic acid group and an isocyanate group. Antioxidants, leveling agents, antifoaming agents, surfactants and the like can be used as necessary during the reaction.

The progress of the amidimidation reaction can be monitored by analytical means such as infrared spectrum, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and isocyanate group quantification. can be done. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2270 cm ^-1 decreases with the reaction, and the acid anhydride group having characteristic absorptions at 1860 cm ^-1 and 850 cm ^-1 also decreases. On the other hand, the absorption of the imide group increases at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It is preferable to allow the reaction to proceed until 2270 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappears, because the reaction can be easily controlled.

As a preferred molecular weight range of the polyamideimide resin (a3) having a terminal acid group or an acid anhydride group obtained by the reaction of the cyclic isocyanurate-type polyisocyanate (a1) and the alicyclic tricarboxylic acid anhydride (a2) has a polystyrene equivalent weight average molecular weight in the range of 1,000 to 20,000, more preferably 1,500 to 15,000, and particularly preferably 2,000 to 10,000 in GPC.

Next, the carboxylation step will be described in detail.
The (meth)acrylate (b) having epoxy in one molecule used in the production of the unsaturated group-containing polycarboxylic acid resin (A) has a (meth)acryloyl group and an epoxy group in the molecular structure. Other specific structures are not particularly limited as long as they are compounds, and a wide variety of compounds can be used. Examples thereof include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, glycidyl group-containing (meth)acrylate monomers such as epoxycyclohexylmethyl (meth)acrylate; Examples include mono(meth)acrylates of diglycidyl ether compounds such as naphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more. Among these, a (meth)acrylate compound having one epoxy group is preferable because the reaction can be easily controlled, and glycidyl methacrylate and epoxycyclohexylmethyl methacrylate are preferable from the viewpoint of reactivity and curability.
Further, the molar ratio ((b)/(a2)) between the (meth)acrylate (b) having an epoxy group in one molecule and the alicyclic tricarboxylic acid anhydride (a2) is 0.8 to 2.0. A range satisfying 0 is preferable from the viewpoint of cure shrinkage and sensitivity. It is more preferably 0.9 to 1.80, more preferably 1.0 to 1.5.

As the aliphatic dicarboxylic acid anhydride used in the production of the unsaturated group-containing polycarboxylic acid resin (A) or the aliphatic tricarboxylic acid anhydride (c), succinic anhydride, 1, 2-cyclopropanedicarboxylic anhydride, 2,2-dimethylsuccinic anhydride, caronic anhydride, 1,2-cyclohexanedicarboxylic anhydride, butylsuccinic anhydride, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, n-octylsuccinic anhydride, decylsuccinic anhydride, dodecylsuccinic anhydride and the like. Examples of aliphatic tricarboxylic acid anhydrides include tricarboxylic acid anhydrides having a linear aliphatic structure and tricarboxylic acid anhydrides having an alicyclic structure. Examples of the tricarboxylic anhydride having a linear aliphatic structure include propanetricarboxylic anhydride. Examples of the tricarboxylic anhydride having an alicyclic structure include the same compounds as those exemplified for the alicyclic tricarboxylic anhydride (a2). Among these, aliphatic dicarboxylic acid anhydrides are preferable from the viewpoint of electrical properties. Tricarboxylic acid anhydrides having an alicyclic structure are preferred in terms of alkaline aqueous solution developability, heat resistance, hydrolysis resistance, and the like. Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is more preferred.
Further, the molar ratio of the aliphatic dicarboxylic anhydride or the aliphatic tricarboxylic anhydride (c) and the (meth)acrylate (b) having an epoxy group in one molecule is ((c)/(b)) From the viewpoint of developability and storage stability, it is preferable that the ratio is in the range of 0.05 to 1.5. It is more preferably 0.1 to 1.2.

It is preferable to add a thermal polymerization inhibitor in order to suppress the thermal polymerization reaction during the reaction, and a (meth)acrylate compound (b ), aliphatic dicarboxylic acid anhydride or aliphatic tricarboxylic acid anhydride (c), and 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the reactants to which the solvent is added. Thermal polymerization inhibitors include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol and the like.

In addition, it is preferable to use a catalyst to promote the reaction during the reaction, and the amount of the catalyst used is the polyamideimide resin (a3) having a terminal acid group or an acid anhydride group having an epoxy group in one molecule. (Meth) acrylate compound (b) and aliphatic dicarboxylic acid anhydride or aliphatic tricarboxylic acid anhydride (c), 0.05 to 10 parts by weight per 100 parts by weight of the total amount of the reaction product added solvent . The reaction temperature at that time is 60 to 150° C., and the reaction time is preferably 3 to 60 hours. Examples of catalysts used in this reaction include dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, 2 -chromium ethylhexanoate, chromium octanoate, zinc 2-ethylhexanoate, zinc octanoate, zirconium octanoate, dimethylsulfide, diphenylsulfide and the like.

In the carboxylation step, the reaction can be carried out without a solvent or after being diluted with an organic solvent. Examples of the organic solvent include the same solvents as those exemplified in the amidimidization step.

The reaction temperature in the carboxylation 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 3 to 60 hours.

The reaction in the carboxylation step is preferably allowed to proceed until the epoxy equivalent (solid content epoxy equivalent) reaches 10,000 g/eq or more. The solid content epoxy equivalent is measured by a normal neutralization titration method according to JIS K 7236. Also, if the concentration of the resin in the solution is known, the epoxy equivalent of the solid content can be calculated from the epoxy equivalent of the solution.

A (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c As a preferred molecular weight range of the unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting ), the polystyrene equivalent weight average molecular weight in GPC is in the range of 1,500 to 30,000, more preferably 2, 000 to 20,000, particularly preferably 2,500 to 15,000.

The content of the unsaturated group-containing polycarboxylic acid resin (A) in the photosensitive coloring composition of the present invention is not particularly limited, but the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably is 15% by mass or more, and is usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less. For example, it is 5 to 90% by mass, preferably 10 to 90% by mass, more preferably 15 to 90% by mass, still more preferably 15 to 80% by mass, particularly preferably 15 to 70% by mass.

The colored photosensitive composition contains a coloring agent (B) such as a light shielding agent.
Examples of the coloring agent (B) include light shielding agents and coloring agents other than light shielding agents.

Examples of the light-shielding agent include lactam-based pigments, carbon black, dyes, perylene-based pigments, silver-tin (AgSn) alloy-based fine particles, titanium black, copper, iron, manganese, cobalt, chromium, nickel, and zinc. , calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates and metal carbonates, and various organic and inorganic pigments. A black pigment is preferable as the light shielding agent.

≪Carbon Black≫
As the carbon black, various carbon blacks conventionally used as light shielding agents can be used. As carbon black, specifically, known carbon blacks such as channel black, furnace black, thermal black and lamp black can be used. Moreover, the carbon black may be coated with an organic substance such as a resin, a dye, or an acid group-containing compound. One type of carbon black may be used alone, or two or more types may be used in combination.

≪Dye≫
Dyes may be appropriately selected from known materials.
Examples of dyes applicable to the colored photosensitive composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, and the like. can be mentioned.
Further, these dyes can be dispersed in an organic solvent or the like by forming a lake (chlorination) and used as a light shielding agent.
In addition to these dyes, for example, JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206, etc. The described dyes and the like can also be preferably used.

Specific examples of other colorants include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists), specifically, the following color indexes: (C.I.) numbers are included.

C. I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same and 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; I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same and 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; I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same and only the number is described.), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; . I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same and only the number is described.), 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; I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same and only the number is described.), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64 , 66; I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37; C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26, C.I. I. Pigment Brown 28; C.I. I. Pigment Black 1, C.I. I. Pigment Black 7.

From the viewpoint of good light-shielding properties, the ratio of the mass of carbon black to the total mass of the colorant (B) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and 100% by mass. % by mass is particularly preferred.

The form of the colorant (B) used for preparing the colored photosensitive composition is not particularly limited. Colorant (B) may be used as a powder or as a dispersion. The colorant (B) is preferably used as a dispersion for preparing the colored photosensitive composition.
As the dispersion, a dispersion containing two or more colorants (B) may be used. Also, two or more dispersions, each containing a different kind of colorant, may be used.

Examples of the dispersion medium include organic solvents such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate, 3-ethoxyethyl propionate, and propylene glycol monomethyl ether propionate. or water or the like can be used.

In order to stabilize the dispersion of the colorant (B) in the dispersion and to improve the dispersibility of the colorant (B) in the colored photosensitive composition, a dispersant is added to the colorant (B). good too.
As the dispersant, it is preferable to use a polymer dispersant such as a polyethyleneimine-based dispersant, a urethane-based dispersant, or an acrylic resin-based dispersant. Among these dispersants, urethane-based dispersants are preferable from the viewpoint of less generation of residue after development.
Moreover, you may use dispersing aids, such as a copper compound. Copper compounds include, for example, copper phthalocyanine.
In some cases, corrosive gas originating from the dispersant is generated from the cured film. Therefore, it is also a preferred embodiment that the colorant (B) is dispersed without using a dispersant.
When the colorant (B) contains a dispersant, the proportion of the dispersant in the colorant (B) is, for example, 5% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less.

The viscosity of the dispersion of the colorant (B) is not particularly limited. The viscosity of the dispersion is preferably 3 mPa·s or more and 200 mPa·s or less as measured at 25° C. with a cone-plate viscometer.

The particle size of the colorant (B) in the dispersion is preferably 80 nm or more and 300 nm or less as a dispersion average particle size. The dispersion average particle size can be measured using a laser diffraction particle size distribution system.

The content of the colorant (B) relative to the mass of the total solid content of the colored photosensitive composition is not particularly limited, but the upper limit of the total content of the colorant (B) may be 70% by mass or less, It may be 65% by mass or less, and may be 60% by mass or less. The lower limit is usually 1% by mass or more, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, in the total solid content.
In this specification, the amount of the coloring agent (B) can be defined as a value including the amount of the dispersant present together with the coloring agent (B).

A colored photosensitive composition contains a solvent (C). As the solvent (C), examples were also given when synthesizing the unsaturated-containing polycarboxylic acid resin (A). Examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ale, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono - (poly)alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl (Poly)alkylene glycol monoalkyl ether acetates such as ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, Ketones such as cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate and 3-methoxypropionic acid methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 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, isopentyl acetate, n-propionate Other esters such as butyl, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Aromatic hydrocarbons such as toluene and xylene; Amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc., benzyl acetate, benzyl propionate, benzyl butanoate, and pentane Benzyl esters of aliphatic carboxylic acids such as benzyl acid can be mentioned. These solvents may be used alone or in combination of two or more.

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 ethyl ether, cyclohexanone, 3-methoxybutyl acetate, photopolymerization shown later Propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferred because they exhibit excellent solubility in the initiator (E). In addition, from the viewpoint of coating properties, etc., the above-mentioned preferred solvent may be used in combination with the benzyl ester of the aliphatic carboxylic acid. The amount is preferably 1% by mass or more and 10% by mass or less with respect to the entire solvent (C). The content of the solvent (C) is not particularly limited, but it is preferably an amount such that the solid content concentration of the photosensitive composition is 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less. .

The photosensitive resin composition may contain a cross-linking agent (D). Examples of the cross-linking agent (D) used in the photosensitive resin composition include radical-reactive acrylates, cationic-reactive epoxy compounds, and compounds such as vinyl compounds and maleimide compounds sensitive to both of them.

Examples of radical reactive acrylates include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

Examples of the monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, and polyethylene glycol (meth)acrylate. monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl ( meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric Acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-ethylhexyl (meth) Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy- 2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N,N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) ) acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, half (meth)acrylate of phthalic acid derivative, and the like. These monofunctional monomers can be used singly or in combination of two or more.

Examples of the polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, meth)acrylate, dodecanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate ) acrylate, adipate epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth) acrylate, hydrogenated bisphenol ethylene oxide di(meth) acrylate, bisphenol di(meth) acrylate, ε-caprolactone adduct of neopentyl glycol hydroxybivalate di(meth)acrylate, dipentaerythritol and ε-caprolactone reaction product poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate or ethylene oxide adduct thereof, pentaerythritol tri(meth)acrylate or ethylene oxide adduct thereof, pentaerythritol tetra(meth)acrylate or ethylene oxide adduct thereof, dipentaerythritol hexa(meth)acrylate or ethylene oxide adduct thereof, ethoxylated hexanediol diol (Meth)acrylates, tricyclodecanedimethanol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth) acrylates, tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, poly(ethylene-propylene) glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate (Meth)acrylates, propoxylated bisphenol 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 Acrylates, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, 2,2 -bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth) Acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane ( meth)acrylates (that is, reaction products of tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate or the like with 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, polyvalent Condensates of alcohols with N-methylol(meth)acrylamide, triacrylformal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate, and 2 , 4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol diacrylate and the like.

The cation-reactive epoxy compounds are not particularly limited as long as they are compounds having an epoxy group, including the epoxy compound (i). Examples include glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, and butyl glycidyl ether. , bisphenol-A diglyzidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ("Cyracure UVR-6110" manufactured by Union Carbide, etc.), 3,4-epoxycyclohexylethyl-3,4 - Epoxy cyclohexane carboxylate, vinyl cyclohexene dioxide (“ELR-4206” manufactured by Union Carbide, etc.), limonene dioxide (“Celoxide 3000” manufactured by Daicel Corporation, etc.), allylcyclohexene dioxide, 3,4-epoxy- 4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate (union Carbide Co., Ltd. "Cyracure UVR-6128" etc.), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis ( 3,4-epoxycyclohexyl)diethylsiloxane and the like.

Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds.
Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether and the like.
Examples of the styrenes include styrene, methylstyrene, ethylstyrene and the like.
Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

The maleimide compounds are not particularly limited as long as they are compounds having one or more maleimide groups in the molecule. Specific examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6 -maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3, 5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy) -phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimidoethane, 1,4-bis maleimidobutane, 1,5-bismaleimidopentane, 1,5-bismaleimido-2-methylpentane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1 ,8-bismaleimido-3,6-dioxaoctane, 1,11-bismaleimido-3,6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl) ) cyclohexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4- Diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl- 4-citraconimidophenyl)methane, bis(3,5-diethyl-4-citraconimidophenyl)methane, polyphenylmethanemaleimide, maleimide compounds represented by formula (6) such as polyphenylmethanemaleimide, formula (7) and fluorescein-5-maleimide, prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds.

As the maleimide compound represented by the following formula (1), a commercially available product can be used, for example, BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. can be mentioned. As the maleimide compound represented by formula (2), a commercially available product can be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. can be mentioned. As the maleimide compound represented by formula (3), a commercially available product can be used, for example, MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd. can be mentioned.

In formula (1), each R ₁ independently represents a hydrogen atom or a methyl group. n ₁ represents an integer of 1 or more, preferably an integer of 1-10, more preferably an integer of 1-5.

In formula (2), each R ₂ independently represents a hydrogen atom or a methyl group. _n2 represents an integer of 1 or more, preferably an integer of 1-5.

In formula (3), each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group; each l ₂ independently represents an integer of 1 to ₃ ; , represents an integer from 1 to 10.
Examples of alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, and neopentyl groups.

The cross-linking agent (D) can be used alone or in combination of two or more. The content of the cross-linking agent (D) in the colored photosensitive composition when the cross-linking agent (D) is included is not particularly limited. % or less is preferable, and 5 mass % or more and 40 mass % or less is more preferable. By setting the amount within the above range, there is a tendency that sensitivity, developability, and resolution are easily balanced.

The colored photosensitive composition can contain a photoinitiator (E).
The photopolymerization initiator (E) is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator (E) include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1-[6-(2- methylbenzoyl)-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-acetyloxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl -4'-methyldimethylsulfide, 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, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4, 4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, 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-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert -butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9- Phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4 ,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4 ,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4- diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-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-methoxy)styrylphenyl-s-triazine, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2- amyl anthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, acetophenone dimethyl ketal, benzyl dimethyl ketal, benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethyl benzophenones such as aminobenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and the like. These photopolymerization initiators can be used alone or in combination of two or more.

Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. Among the oxime photopolymerization initiators, particularly preferred are O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime and ethanone. , 1-[9-ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazol-3-yl], 1-(O-acetyloxime), and 2-(benzoyloxyimino)-1-[4 -(phenylthio)phenyl]-1-octanone.

As described above, the colored photosensitive composition preferably contains an oxime ester compound as the photoinitiator (E). Oxime ester compounds are excellent in ability to absorb ultraviolet rays and generate radicals. Therefore, the oxime ester compound has high sensitivity, and even when it contains a coloring agent (B) such as a light-shielding agent at a high concentration, it is easy to sufficiently cure the colored photosensitive composition with a small amount of exposure. In the case of a colored photosensitive composition containing a large amount of the coloring agent (B), when the optical density of the film formed with the colored photosensitive composition is 3, the amount of UV exposure in the deep layer is the UV exposure of the surface layer (outermost surface). Although considerably smaller than the amount, the oxime ester compound can generate radicals even at such relatively low UV exposure doses and cure the colored photosensitive composition well.

Further, when the coloring agent (B) described above is blended into the colored photosensitive composition at a high concentration, primary aggregates (aggregates) of the coloring agent (B) are inevitably formed in the coating film made of the colored photosensitive composition. naturally occur. However, when a colored photosensitive composition containing an oxime ester compound is used as the photopolymerization initiator (E), the photopolymerization initiator (E) generates radicals when irradiated with ultraviolet light even in the slightest gaps between aggregates that are intricately overlapped. Let
As a result, the cured product of the colored photosensitive composition not only has excellent adhesion to the substrate and electrical resistivity (insulation) in an environment of normal temperature, normal humidity and atmospheric pressure, but also can be cured at high temperature, high humidity and high pressure. Even when exposed to the environment, adhesion to substrates and electrical resistivity (insulation) are less likely to decrease. Durability in a high-temperature, high-humidity, and high-pressure environment can be confirmed by a so-called PCT test (pressure cooker test).
For this reason, the cured product (colored film) of the colored photosensitive composition containing the oxime ester compound is less likely to deteriorate in performance even when used in a hot or humid environment.

As the photopolymerization initiator (E), an oxime ester compound and a photopolymerization initiator other than the oxime ester compound may be used in combination. In this case, the mass ratio of the oxime ester compound to the total mass of the photopolymerization initiator (E) is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, and 40% by mass. The above are particularly preferred.

As a photopolymerization initiator other than the oxime ester compound, for example, an aminoalkylphenone-based photopolymerization initiator can be preferably used.
Examples of aminoalkylphenone compounds include 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (eg IRGACURE369 manufactured by Ciba Specialty Chemicals), 2 -(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (for example, IRGACURE379 manufactured by Ciba Specialty Chemicals), 2-(4-ethylbenzyl) )-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-isopropylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane -1-one, 2-(4-n-butylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-isobutylbenzyl)-2-( Dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1- one, 2-(3,4-dimethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-methoxybenzyl)-2-(dimethylamino) -1-(4-morpholinophenyl)butan-1-one, 2-(4-ethoxybenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-( 4-hydroxymethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-[4-(2-hydroxyethoxy)benzyl]-2-(dimethylamino)- 1-(4-morpholinophenyl)butan-1-one, 2-[4-(2-methoxyethoxy)benzyl]-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one , 2-(4-isopropylbenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-morpholinophenyl)butan-1-one, 2-(4-n-butylbenzyl)- 2-[(n-butyl)(methyl)amino]-1-(4-morpholinophenyl)butan-1-one, 2-(4-isopropylbenzyl)-2-(dimethylamino)-1-(4- morpholinophenyl)pentan-1-one, 2-(4-isobutylbenzyl)-2-[(n-butyl)(methyl)amino]]-1-(4-morpholinophenyl)pentan-1-one, 2 -(4-n-butyloxybenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-morpholinophenyl)pentan-1-one, 2-(4-methylbenzyl)-2 -[di(n-octyl)amino]-1-(4-morpholinophenyl)hexan-1-one and 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4- morpholinophenyl)octan-1-one and the like.
Among them, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one is preferred.

Combining an aminoalkylphenone-based photopolymerization initiator with an oxime ester compound facilitates control of the cross-sectional shape of a patterned colored film formed using a colored photosensitive composition.
This is because the aminoalkylphenone-based photopolymerization initiator tends to generate photopolymerization radicals relatively on the surface layer portion of the colored photosensitive composition (the surface facing the light to be exposed and its vicinity), and the oxime This is probably because the ester compound tends to generate photopolymerization radicals relatively deep in the colored photosensitive composition. This tendency appears more remarkably as the film thickness of the colored photosensitive composition increases, but it is observed even when the film thickness is as thin as 1 μm or less.
In addition, as a secondary effect of using an aminoalkylphenone-based photopolymerization initiator together with an oxime ester compound, overall sensitivity is improved, and a cured product of a colored photosensitive composition can be obtained with a small amount of exposure. Furthermore, when an aminoalkylphenone-based photopolymerization initiator is used together with the oxime ester compound, the linearity of the line edge and the adhesion to the substrate are better, and a patterned colored film with less pattern defects is formed. Cheap.

In the colored photosensitive composition, when the photopolymerization initiator (E) contains an oxime ester compound and an aminoalkylphenone-based photopolymerization initiator, the mass of the oxime ester compound and the aminoalkylphenone-based photopolymerization initiator are The ratio of the mass of the aminoalkylphenone-based photopolymerization initiator to the total mass is preferably 20% by mass or more and 75% by mass or less, more preferably 25% by mass or more and 70% by mass or less, and 30% by mass or more and 60% by mass. The following are particularly preferred.

The content of the photopolymerization initiator (E) in the colored photosensitive composition is not particularly limited as long as the object of the present invention is not impaired. The content of the photopolymerization initiator (E) is preferably 0.1% by mass or more and 30% by mass or less, and 0.3% by mass or more and 20% by mass or less with respect to the mass of the solid content of the colored photosensitive composition. More preferably, 0.5 mass % or more and 10 mass % or less is particularly preferable.

The curing agent (F) used in the colored photosensitive composition of the invention can be used. Examples of the curing agent (F) include epoxy compounds and oxazine compounds. The curing agent (F) can be added during the curing process to improve the subsequent heat resistance, and by reacting with the carboxyl groups and hydroxyl groups contained in the colored photosensitive composition by heating, the heat decomposition resistance is improved. It is particularly preferably used when trying to

Specific examples of the epoxy compound as the curing agent (F) include phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, Bisphenol-F type epoxy resin, biphenol type epoxy resin, bisphenol-A novolac type epoxy resin, glyoxal type epoxy resin, naphthalene skeleton-containing epoxy resin, cardo skeleton-containing epoxy resin, bisphenol fluorene type epoxy resin, heterocyclic epoxy resin, etc. mentioned.

Examples of the phenol novolak type epoxy resin include Epiclon N-770 (manufactured by DIC Corporation), D.I. E. N438 (manufactured by Dow Chemical Co.), jER154 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201, RE-306 (both manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of the cresol novolac epoxy resin include Epiclon N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, and EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 ( Union Carbide), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co.), jER E1032H60 ( manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
Examples of the dicyclopentadiene phenol type epoxy resin include Epiclon EXA-7200 (manufactured by DIC Corporation) and TACTIX-556 (manufactured by Dow Chemical Co.).

Examples of the bisphenol type epoxy resin include jER828, jER1001 (both manufactured by Japan Epoxy Resin Co., Ltd.), UVR-6410 (manufactured by Union Carbide Co., Ltd.), D.I. E. Bisphenol-A epoxy resins such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.), NER-1202, NER-1302 (both manufactured by Nippon Kayaku Co., Ltd.), UVR-6490 (manufactured by Union Carbide Co., Ltd.), YDF-8170 (manufactured by Tohto Kasei Co., Ltd.), NER-7403, NER-7604 (both manufactured by Nippon Kayaku Co., Ltd.) and other bisphenol-F type epoxy resins. mentioned.

Examples of the biphenol-type epoxy resin include biphenol-type epoxy resins such as NC-3000, NC-3000-H, and NC-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), YX-4000 (Japan Epoxy Resin and YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd.).
Examples of the bisphenol A novolac type epoxy resin include Epiclon N-880 (manufactured by DIC Corporation) and jER E157S75 (manufactured by Japan Epoxy Resin Co., Ltd.).

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Corporation).
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.).
Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.).
Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Corporation). Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

Specific examples of the oxazine compound as the curing agent (F) include Bm-type benzoxazine, Pa-type benzoxazine, and Ba-type benzoxazine (all manufactured by Shikoku Kasei Kogyo Co., Ltd.). .

The curing agent (F) can be used alone, or two or more of them can be mixed and used.
Although the content of the curing agent (F) is not particularly limited, it is preferably 0 to 40% by mass, more preferably 3 to 30% by mass, based on the mass of the solid content of the colored photosensitive composition. By setting the content of the polyfunctional crosslinkable compound (D) within the above range, it is easy to obtain a photosensitive resin composition capable of forming a cured film having high heat resistance.

The colored photosensitive composition contains an unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), a solvent (C), a cross-linking agent (D), and a photopolymerization initiator (E). By making it a colored photosensitive composition, it has high photosensitivity, can be dispersed even at a high colorant concentration, and has good developing properties, and if necessary, it also contains a curing agent (F), thereby improving heat resistance can be improved.

The colored photosensitive composition contains, as other components (G), an unsaturated group-containing polycarboxylic acid (A), a cross-linking agent (D), and a curing agent other than (F), as long as the object of the present invention is not impaired. Resins, surface conditioners, adhesion improvers, and other various additives may also be included. There are no particular restrictions on the amount of the other component (G) added. Other components (G) can be used in amounts that do not interfere with the object of the present invention.

≪Surface conditioner≫
The surface modifier reduces the surface tension of the colored photosensitive composition, thereby preventing surface defects and poor appearance due to uneven distribution of colorants such as pigments (uneven distribution of colorants such as pigments). deter Specifically, polydimethylsiloxane, polyether-modified polysiloxane, polymethylalkylsiloxane, polysiloxane modified with an aralkyl group or a polyester chain, and the like can be preferably used.

≪Adhesion improver≫
Known coupling agents such as silane coupling agents, titanate coupling agents and aluminate coupling agents can be used. Among these, the silane coupling agent can be preferably used from the viewpoint of enhancing the adhesion to the glass substrate.

The colored photosensitive composition may contain various additives other than those described above, if necessary. Specifically, sensitizers, curing accelerators, photocrosslinkers, photosensitizers, dispersing aids, fillers, antioxidants, UV absorbers, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, Surfactants, liquid-repellent agents, chain transfer agents, photoinitiator aids, solvents and the like are exemplified. Conventionally known additives can be used for any additive.

Examples of surfactants include anionic compounds, cationic compounds, and nonionic compounds.
Thermal polymerization inhibitors include, for example, hydroquinone and hydroquinone monoethyl ether.
Antifoaming agents include, for example, silicone compounds and fluorine compounds.
Examples of chain transfer agents include mercaptan-based compounds, halogen-based compounds, quinone-based compounds, α-methylstyrene dimers, and the like. Containing a chain transfer agent enables good control of the pattern shape (in particular, the CD change of the hole pattern and the exposure margin). Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferable because it can reduce sublimate, coloring and odor in addition to the above effects.
Examples of photoinitiation aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N,N-dimethylp-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10 -dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photoinitiators may be used singly or in combination of two or more.

Examples of liquid repellent agents include fluorine atom-containing resins having cross-linking groups. Since ink repellency can be imparted to the surfaces of the partition walls, it is thought that when the colored photosensitive composition is used to form the partition walls, color mixture in each pixel can be prevented.
Examples of the cross-linking group include an epoxy group and an ethylenically unsaturated group, and an ethylenically unsaturated group is preferable from the viewpoint of suppressing the outflow of the liquid repellent agent to the developer. Also, the fluorine atom-containing resin having a cross-linking group preferably has either one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Perfluoroalkyl groups include perfluorobutyl, perfluorohexyl, and perfluorooctyl groups. 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.

Specific examples of the fluorine atom-containing resin having a cross-linking group include, for example, an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, an ethylenically unsaturated group and Acrylic copolymer resin having a perfluoroalkyl group, acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, epoxya (meth)acrylate resin having an epoxy group and a perfluoroalkyl group, epoxy group and perfluoro Epoxya(meth)acrylate resin having alkylene ether chain, epoxya(meth)acrylate resin having ethylenically unsaturated group and perfluoroalkyl group, epoxya(meth)acrylate resin having ethylenically unsaturated group and perfluoroalkylene ether chain , and so on. Among them, from the viewpoint of ink repellency, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, and an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable. More preferred are acrylic copolymer resins having groups and perfluoroalkylene ether chains. Commercially available fluorine atom-containing resins having these crosslinking groups include DIC's "Megafac (registered trademark, hereinafter the same.) F116", "Megafac F120", "Megafac F142D", and "Megafac F144D". , "Megafuck F150", "Megafuck F160", "Megafuck F171", "Megafuck F172", "Megafuck F173", "Megafuck F177", "Megafuck F178A", "Megafuck F178K", " Megafuck F179", "Megafuck F183", "Megafuck F184", "Megafuck F191", "Megafuck F812", "Megafuck F815", "Megafuck F824", "Megafuck F833", "Megafuck RS101", "Megafuck RS102", "Megafuck RS105", "Megafuck RS201", "Megafuck RS202", "Megafuck RS301", "Megafuck RS303", "Megafuck RS304", "Megafuck RS401", " Megafuck RS402", "Megafuck RS501", "Megafuck RS502", "Megafuck RS-72-K", "Megafuck RS-78", "Megafuck RS-90", "DEFENSA (registered trademark, hereinafter Same.) MCF300", "DEFENSAMCF310", "DEFENSAMCF312", "DEFENSAMCF323", 3M Japan's "Florado FC430", "Florado FC431", "FC-4430", "FC4432", AGC's "Asahi Guard (registered Trademark.) AG710", "Surflon (registered trademark, hereinafter the same) S-382", "Surflon SC-101", "Surfron SC-102", "Surfron SC-103", "Surfron SC-104", " Fluorine-containing organic compounds commercially available under trade names such as "Surflon SC-105" and "Surflon SC-106" can be used.

<<Method for Preparing Colored Photosensitive Composition>>
The colored photosensitive composition is prepared, for example, by uniformly stirring and mixing the components described above, and by uniformly dissolving and dispersing the components. Mixing may be performed using a stirrer such as a roll mill, ball mill, or sand mill. It can be prepared by filtering with a filter such as a 2 μm membrane filter, if necessary.

<<Colored film and patterned colored film>>
A colored film can be obtained by curing the colored photosensitive composition.
A method for producing a colored film includes a step of applying a colored photosensitive composition to form a coating film, and a step of exposing the coating film.
Further, the method for producing a patterned colored film includes the steps of applying a colored photosensitive composition to form a coating film, position-selectively exposing the coating film, and developing the coating film after exposure. and
By using the above-mentioned colored photosensitive composition as a negative photosensitive composition, it is possible to form a highly precise pattern with good linearity even when a high-concentration coloring agent is contained.

Each step will be described below. Forming a coating film using a colored photosensitive composition is referred to as a “coating film forming step”. Exposing the coating film is referred to as an “exposure step”. Developing the exposed coating film is referred to as a “development step”.

≪Coating film formation process≫
In the coating film forming step, the colored photosensitive composition is applied onto a substrate to form a coating film. 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 can be used as appropriate. Examples of substrates include quartz, glass, optical films, ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, SOG (Spin On Glass), polyester films, polycarbonate films, and polyimides. Polymer substrates such as films, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc. and the like. Furthermore, in the case of forming a layered structure on a substrate, for example, any layer that is already formed on the substrate and serves as a substructure is also included in the concept of the substrate to which the colored photosensitive composition is applied. Also, the shape of the substrate is not particularly limited, and may be plate-like or roll-like. The base material may have unevenness on the surface, for example, according to various patterns. Moreover, as the base material, a light-transmitting or non-light-transmitting base material can be selected.

In the coating film forming step, for example, using a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a non-contact type coating device such as a spinner (rotary coating device), a slit coater, a curtain flow coater, etc. A colored photosensitive composition is applied onto a substrate, and if necessary, the solvent is removed by drying (pre-baking) to form a coating film.

The film thickness of the coating film is not particularly limited. The thickness of the coating film is preferably 0.05 μm or more, more preferably 1 μm or more. The thickness of the coating film may be, for example, 7 μm or more, or may be 10 μm or more. Although there is no particular upper limit for the thickness of the coating film, it may be, for example, 50 μm or less, or 20 μm or less.

You may dry a coating film as needed. A drying method is not particularly limited. As a drying method, for example, (1) a method of drying on a hot plate at a temperature of 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds to 120 seconds, (2) at room temperature and (3) placing in a warm air heater or an infrared heater for several tens of minutes to several hours to remove the solvent.

≪Exposure process≫
In the exposure step, the coating film formed in the coating film forming step is exposed. Thereby, a cured film (colored film) of the colored photosensitive composition is obtained. A patterned cured film (colored film) is obtained by position-selectively exposing and developing according to the pattern shape.

In the exposure step, the coating film is exposed to radiation such as i-line, g-line, h-line, or electromagnetic waves. In the case of forming a patterned cured film (colored film), the exposure of the coating film is position-selectively performed through a negative mask. Although the exposure amount varies depending on the composition of the colored photosensitive composition, it is preferably about 5 mJ/cm ² or more and 500 mJ/cm ² or less. About 10 mJ/cm ² or more and 150 mJ/cm ² or less is preferable.

A cured film cured by exposure may be heated. The temperature for heating is not particularly limited, and is preferably 180° C. or higher and 280° C. or lower, more preferably 200° C. or higher and 260° C. or lower, and particularly preferably 220° C. or higher and 250° C. or lower. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.

≪Development process≫
In the developing step, the coating film exposed in the exposing step is developed with an alkaline developer.
In the development step, a cured film (colored film) patterned into a desired shape is formed by developing the exposed coating film with a developer. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salts, and the like.

After development, post-baking may be performed as necessary. The post-development post-baking temperature is preferably 80° C. or higher and 250° C. or lower, more preferably 100° C. or higher and 230° C. or lower. The post-development post-baking time is preferably 5 minutes or more and 60 minutes or less, more preferably 10 minutes or more and 30 minutes or less.

By using the above-mentioned colored photosensitive composition, as shown in Examples described later, it is possible to disperse a high-concentration coloring agent and form a highly precise pattern, and at the same time, when it is desired to improve heat resistance, A curing agent may be included.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, parts are by weight unless otherwise specified.

Epoxy equivalent and acid value were measured under the following conditions.
1) Epoxy equivalent (WPE): Measured according to JIS K 7236:2001.
2) Acid value: Measured according to JIS K 0070:1992.
3) Measurement conditions for gel permeation chromatography (GPC) are as follows.
Model: TOSOH HLC-8220GPC
Column: TSKGEL Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml/min, temperature 40°C
Detector: Differential refractometer Molecular weight standard: Polystyrene

Production example 1
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (1) having a number average molecular weight of 1,250, a weight average molecular weight of 4,040 and a solid content acid value of 164 mgKOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. After cooling to 60° C., 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 dibutylhydroxytoluene were added and stirred, and 2.27 g of triphenylphosphine was added. °C. Reacting at the same temperature for 20 hours, solid content acid value 94.1 mg KOH / g, (meth) acrylic equivalent 629, number average molecular weight by GPC is 1,870, weight average molecular weight is 5,320 unsaturated group-containing polycarboxylic acid A resin (I) was obtained. Further, when the epoxy equivalent was measured, it was 13,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 2
661.2 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate (“VESTANATT-1890/100” manufactured by EVONIK, containing isocyanate groups) were placed in a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen line. of 17.3% by weight) and 198.0 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (2) having a number average molecular weight of 1,290, a weight average molecular weight of 3,590 and a solid content acid value of 155 mgKOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. After cooling to 60° C., adding 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 stirring, 2.38 g of triphenylphosphine was added. °C. Reacting at the same temperature for 20 hours, solid content acid value 92.2 mg KOH / g, (meth) acrylic equivalent 629, number average molecular weight by GPC is 1,710, weight average molecular weight is 4,930 unsaturated group-containing polycarboxylic acid Resin (II) was obtained. Further, when the epoxy equivalent was measured, it was 11,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 3
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (3) having a number average molecular weight of 1,260, a weight average molecular weight of 4,120 and a solid content acid value of 159 mgKOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. After cooling to 60° C., 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 dibutylhydroxytoluene were added and stirred, and then 2.17 g of triphenylphosphine was added. °C. Reacting at the same temperature for 20 hours, solid content acid value 85.9 mg KOH / g, (meth) acrylic equivalent 604, number average molecular weight by GPC is 1,750, weight average molecular weight is 5,500 unsaturated group-containing polycarboxylic acid Resin (III) was obtained. Moreover, when the epoxy equivalent was measured, it was 14,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 4
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (4) having a number average molecular weight of 1,190, a weight average molecular weight of 3,850 and a solid content acid value of 151 mgKOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. 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. 44 g was added and the temperature was raised to 116°C. Reacting at the same temperature for 20 hours, solid content acid value 95.8 mg KOH / g, (meth) acrylic equivalent 641, number average molecular weight by GPC is 1,640, weight average molecular weight is 4,790 unsaturated group-containing polycarboxylic acid Resin (IV) was obtained. Further, when the epoxy equivalent was measured, it was 12,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 5
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (5) having a number average molecular weight of 1,300, a weight average molecular weight of 3,690 and a solid content acid value of 152 mgKOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. After cooling to 60° C., adding 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 and stirring, 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. Reacting at the same temperature for 20 hours, solid content acid value 97.9 mg KOH / g, (meth) acrylic equivalent 628, number average molecular weight by GPC is 1,690, weight average molecular weight 4,980 unsaturated group-containing polycarboxylic acid A resin (V) was obtained. Moreover, when the epoxy equivalent was measured, it was 14,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 6
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (6) having a number average molecular weight of 1,250, a weight average molecular weight of 3,680 and a solid content acid value of 161 mgKOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. After cooling to 60°C, 261.9 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate and 1.90 g of dibutylhydroxytoluene were added and stirred, then 1.90 g of triphenylphosphine was added and the temperature was raised to 116°C. Reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (I') having a solid content acid value of 19.2 mgKOH/g, a number average molecular weight determined by GPC of 1,740, and a weight average molecular weight of 6,950. rice field. Further, when the epoxy equivalent was measured, it was 13,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 7
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (7) having a number average molecular weight of 1,180, a weight average molecular weight of 3,860 and a solid content acid value of 154 mgKOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. After cooling to 60°C, 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 were added and stirred. The temperature was raised to Reacting at the same temperature for 20 hours, solid content acid value 99.5 mg KOH / g, (meth) acrylic equivalent 624, number average molecular weight by GPC is 1,630, weight average molecular weight is 4,830 unsaturated group-containing polycarboxylic acid Resin (II') was obtained. Moreover, when the epoxy equivalent was measured, it was 14,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 8
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. Cool to 60° C., add 97.58 g of pentaerythritol (tri/tetra) acrylate mixture (“PETRA” manufactured by Daicel-Ornex, hydroxyl value 115 mg KOH/g), raise the temperature to 116° C., and keep at the same temperature for 10 hours. A solution of amide imide resin (8) having a number average molecular weight of 1,070, a weight average molecular weight of 3,080 and a solid content acid value of 135 mgKOH/g was obtained by gel osmotic pressure chromatography using polystyrene as a standard. 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. 44 g was added and the temperature was raised to 116°C. Reacting at the same temperature for 20 hours, solid content acid value 82.1 mg KOH / g, (meth) acrylic equivalent 395, number average molecular weight by GPC is 1,370, weight average molecular weight 3,700 unsaturated group-containing polycarboxylic acid Resin (III') was obtained. Further, when the epoxy equivalent was measured, it was 15,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 9
250.3 g of propylene glycol monomethyl ether acetate and cresol novolac type epoxy resin ("EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 218 g/eq) were placed in a four-necked flask equipped with a stirrer, thermometer and condenser. 435.7 g and 1.75 g of dibutylhydroxytoluene were added and stirred at 80° C. to dissolve the epoxy resin. After that, 148.4 g of acrylic acid and 1.75 g of triphenylphosphine were added, the temperature was raised to 116° C., and the mixture was allowed to react at the same temperature for 12 hours. of the reactive excicarboxylate resin (9) solution was obtained. 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 for 5 hours at the same temperature, solid content acid value 61.2 mg KOH / g, (meth) acrylic equivalent 349, number average molecular weight by GPC is 2058, weight average molecular weight 6420 unsaturated group-containing polycarboxylic acid resin (IV ' ). Further, when the epoxy equivalent was measured, it was 13,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 10
The resin described in Example 2-1 of Patent-6576161 was produced as described, solid content acid value 61.5 mg KOH / g, (meth) acrylic equivalent 335, number average molecular weight by GPC 1830, weight average molecular weight 3520 of reactive polycarboxylic acid compounds (V') were obtained.

Production example 11
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (5) having a number average molecular weight of 1,310, a weight average molecular weight of 3,810 and a solid content acid value of 152 mgKOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. After cooling to 60° C., 338.6 g of propylene glycol monomethyl ether acetate, 142.0 g of glycidyl methacrylate, 79.2 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and 2.31 g of dibutylhydroxytoluene were added. After stirring, 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. Reacting at the same temperature for 20 hours, solid content acid value 87.1 mg KOH / g, (meth) acrylic equivalent 652, number average molecular weight by GPC is 1,870, weight average molecular weight 6,010 unsaturated group-containing polycarboxylic acid Resin (VI) was obtained. Further, when the epoxy equivalent was measured, it was 16,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

Production example 12
646.3 g of propylene glycol monomethyl ether acetate and an isocyanurate modified form of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, containing an isocyanate group) were placed in a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line. of 17.3% by weight) and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. It was confirmed in the infrared spectrum that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, disappeared completely. A solution of amide imide resin (5) having a number average molecular weight of 1,260, a weight average molecular weight of 3,600 and a solid acid content of 156 mg KOH/g was obtained by gel osmotic chromatography using polystyrene as a standard. After cooling to 60° C., 441.4 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 118.8 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and 2.31 g of dibutylhydroxytoluene were added. After stirring, 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. Reacting at the same temperature for 20 hours, solid content acid value 80.6 mg KOH / g, (meth) acrylic equivalent 600, number average molecular weight by GPC is 1,870, weight average molecular weight 6,010 unsaturated group-containing polycarboxylic acid Resin (VII) was obtained. Moreover, when the epoxy equivalent was measured, it was 14,000 g/eq, and it was also confirmed that the epoxy groups were sufficiently reacted.

[Example 1, Comparative Example 1] Preparation of colored photosensitive composition and evaluation of kneading dispersibility 20 g of the unsaturated group-containing polycarboxylic acid resin obtained in Production Examples 1 to 10, Mitsubishi Carbon Black MA-100 (B1) was used as the colorant (B). Propylene glycol monomethyl ether acetate (C1) was used as the solvent (C), kneaded in a bead mill, and the state after kneading was confirmed. When the obtained colored photosensitive composition was uniform, it was evaluated as ◯. Table 1 shows the evaluation results of the ratio of the colored photosensitive composition and the state after kneading.

[Example 2, Comparative Example 2] Preparation of colored photosensitive composition and evaluation of colorant dispersibility To the colored photosensitive composition obtained in Example 1 and Comparative Example 1, DPHA ( Trade name: Nippon Kayaku Co., Ltd. (D1), and 20 g of glass beads were added and dispersed for 1 hour with a paint shaker. After completion of dispersion, the dispersion was applied onto a polyethylene terephthalate film using wire bar coater #2 and dried for 10 minutes using a hot air dryer at 80°C. After drying, the glossiness of the coating film surface was measured using a 60° reflection gloss meter (Horiba IG-331 gloss meter) to evaluate the dispersibility of carbon black. Table 2 shows the results. The higher the gloss value, the better the pigment dispersibility.

[Example 3, Comparative Example 3] Preparation of colored photosensitive composition and evaluation of developability ), the cross-linking agent (D), and the photopolymerization initiator (E) were uniformly dispersed according to the formulation shown in Table 3 to obtain a resist resin composition.
In Examples and Comparative Examples, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.: ε-caprolactone-modified dipentaerythritol hexaacrylate) (D2) as a cross-linking agent (D) and Irgacure 907 as a photopolymerization initiator (E) (manufactured by Ciba Specialty Chemicals) (E1) and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2) and YD-134 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.: Bisphenol-A type epoxy resin) (F1), and TPP (manufactured by Hokko Chemical Industry Co., Ltd.: triphenylphosphine) (G1) was used as a thermosetting catalyst (G).

Each item of evaluation items is explained in detail.

Developability evaluation (abbreviation in the table: developability)
A colored photosensitive composition is applied to a rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) so as to have a thickness of 20 μm with an applicator, and the coating film is dried with a hot air dryer at 80 ° C. for 30 minutes. dried for a minute. The coated film after drying was cured through a mask with an opening of 50 μm using an ultraviolet irradiator (manufactured by USHIO (ultra-high pressure mercury lamp)) at an irradiation dose of 150 mJ/cm ² . After that, spray development was carried out using a 1% sodium carbonate aqueous solution as a developer. The developability was evaluated by the time until the coating film in the unexposed area was completely dissolved, that is, the so-called break time (unit: seconds).
△ Film reduction × Pattern straightness XX Swelling and peeling;

"Film reduction" was obtained from the film thickness of the coating film before development and the height of the cross section of the pattern after development. (Using an electron microscope) Regarding "pattern linearity", the case of bending was evaluated as x. If the pattern was not straight and could not be formed neatly, it was evaluated as x instead of the break time. (Using an electron microscope) With regard to "swelling and peeling", when the coating film swelled and peeled off during development instead of dissolution development, it was evaluated as XX instead of break time.

Thermal decomposition resistance evaluation (abbreviation in the table: thermal decomposition resistance)
A colored photosensitive composition is applied to a rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) so as to have a thickness of 20 μm with an applicator, and the coating film is dried with a hot air dryer at 80 ° C. for 30 minutes. After drying for a minute, an ultraviolet irradiator (CS 30L-1, manufactured by GS YUASA) was used to irradiate ultraviolet rays at an energy of 500 mJ/cm ² . Next, it was cured in an oven at 150° C. for 30 minutes to obtain a cured product. The copper foil was removed with iron (III) chloride 45° Pome (manufactured by Junsei Chemical Co., Ltd.). The temperature at which the weight of 3 mg of the cured product was reduced by 5% was measured in an air flow of 100 ml per minute using TGA/DSC1 manufactured by METTLER.

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 and high developability, and the cured product thereof has excellent thermal decomposition resistance.

[Example 4] Preparation of colored photosensitive composition and evaluation of kneading dispersibility 20 g of the unsaturated group-containing polycarboxylic acid resin obtained in Production Examples 11 and 12 and Mitsubishi carbon black MA as a coloring agent (B) -100 (B1) was used. The mixture was kneaded in a bead mill, and the state after kneading was confirmed. When the obtained colored photosensitive composition was uniform, it was evaluated as ◯.

[Example 5] Preparation of colored photosensitive composition and evaluation of colorant dispersibility 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) and 20 g of glass beads were added and dispersed with a paint shaker for 1 hour. After completion of dispersion, the dispersion was applied onto a polyethylene terephthalate film using wire bar coater #2 and dried for 10 minutes using a hot air dryer at 80°C. After drying, the glossiness of the coating film surface was measured using a 60° reflection gloss meter (Horiba IG-331 gloss meter) to evaluate the dispersibility of carbon black. Table 5 shows the results. The higher the gloss value, the better the pigment dispersibility.

[Example 6] Preparation of colored photosensitive composition and evaluation of developability The agent (D) and the photopolymerization initiator (E) were uniformly dispersed according to the formulation shown in Table 3 to obtain a resist resin composition.
In the examples, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.: ε-caprolactone-modified dipentaerythritol hexaacrylate) (D2) as a cross-linking agent (D), Irgacure 907 (Ciba Specialty Co., Ltd.) as a photopolymerization initiator (E) Chi Chemicals) (E1) and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) (E2), and YD-134 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.: Bisphenol-A type epoxy resin) (F1), and TPP (manufactured by Hokko Chemical Industry Co., Ltd.: triphenylphosphine) (G1) was used as the thermosetting catalyst (G).

Each item of the evaluation items is the same as in the third embodiment. Table 6 shows the evaluation results of each evaluation item.

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 and high developability, and the cured product thereof has excellent thermal decomposition resistance.

As described above, the coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility and high developability, and the cured product thereof has excellent heat resistance. and black matrix, colored spacer, and color resist.

Claims (7)

Polyamideimide resin (a3) having terminal acid groups or acid anhydride groups obtained by reaction of alicyclic isocyanurate-type polyisocyanate (a1) and alicyclic tricarboxylic acid anhydride (a2) in one molecule An unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a (meth)acrylate compound (b) having an epoxy group and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c), and a coloring agent (B), a colored photosensitive composition containing a solvent (C). 2. The colored photosensitive composition according to claim 1, comprising a cross-linking agent (D). 2. The colored photosensitive composition according to claim 1, further comprising a photopolymerization initiator (E). 2. The colored photosensitive composition according to claim 1, further comprising a curing agent (F). 2. The colored photosensitive composition according to claim 1, wherein said colorant (B) comprises a black pigment. A cured product of the colored photosensitive composition according to any one of claims 1 to 5. An image display device comprising the cured product according to claim 6 .