JP7704718B2 - Colored photosensitive composition, cured product, and image display device including the cured product - Google Patents

Description

The present invention relates to a colored photosensitive composition, a cured product, and an image display device comprising the cured product. In particular, the present invention relates to a photosensitive colored composition that has excellent shielding properties and plate-making characteristics, and uses thereof.

Conventional displays often use color filters that form red, green, and blue pixels using organic pigments, colored spacers, and black matrices.
In recent years, in order to reduce the power consumption and widen the color gamut of displays, color filters in which pixels are formed using luminescent nanocrystalline particles such as quantum dots have been studied. Specifically, color filters having red pixels containing red-luminescent nanocrystalline particles, green pixels containing green-luminescent nanocrystalline particles, and blue pixels that transmit blue light from a light source are known.
There are two methods for manufacturing color filters: photolithography and inkjet printing. The latter method is known to reduce the loss of ink material (Patent Document 1).
When manufacturing a color filter containing luminescent nanocrystalline particles by the inkjet method, ink is ejected into a region (pixel portion) surrounded by a partition wall prepared in advance to form pixels. This partition wall is required to prevent the inks from mixing with each other between adjacent pixel portions, and to have a highly precise pattern (fine pattern). In addition, a photosensitive composition containing a colorant (colored photosensitive composition) that has a light-shielding effect is known to be formed by a photolithography method (Patent Document 2).
In addition, there is also known an attempt to disperse carbon black or the like in an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton and apply it to a cured product used in liquid crystal display panels or the like (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, there is a problem that the developability of the pattern obtained by the photolithography method is poor, and a pattern of the desired shape may not be obtained or formed. In addition, there is a need for a colored photosensitive composition that has good dispersibility even when further colorants are contained in partition walls having a light-shielding effect, black matrices, colored spacers, and color resists.

The present invention aims to improve the problems of the conventional techniques described above, and to provide a colored photosensitive composition that has excellent dispersibility of colorants and the like and has good development characteristics even at high colorant concentrations, and further, a colored photosensitive composition that has good heat resistance, and a cured product thereof.

As a result of earnest efforts to solve the above problems, the present inventors have found that a colored photosensitive composition containing an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2) 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 colored agent (B) and a solvent (C) provides a colored photosensitive composition that has excellent dispersibility of colorants and the like and has good development characteristics even at a high colorant concentration, and in some cases has good heat resistance, and a cured product thereof.

That is, the present invention relates to the following (1) to (7).
(1) A colored photosensitive composition comprising an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group, obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), with 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), a colorant (B), and a solvent (C).
(2) The colored photosensitive composition according to (1), further comprising a crosslinking agent (D).
(3) The colored photosensitive composition according to (1) or (2), further comprising a photopolymerization initiator (E).
(4) The colored photosensitive composition according to any one of (1) to (3), further comprising a curing agent (F).
(5) The colored photosensitive composition according to any one of (1) to (4), wherein the colorant (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 of the present invention, which is characterized by containing the unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), and a solvent (C), has excellent photosensitivity, can be dispersed even at high colorant concentrations, and has good development characteristics.

≪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).

Below, we will explain the essential and optional components contained in the colored photosensitive composition.

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 obtained by reacting a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group, which is obtained by reacting a cyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), with 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).

That is, the unsaturated group-containing polycarboxylic acid resin (A) in the present invention is produced through two reaction steps. The first step is to react a cyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2) to obtain a polyamide-imide resin (a3). In the present invention, this step is called an amide-imidization step.
Next, the resulting polyamide-imide resin (a3) is reacted with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c). In the present invention, this step is referred to as a carboxylation step.

First, the amide-imidization step will be described in detail.
The alicyclic isocyanurate type polyisocyanate (a1) used in the production of the polyamideimide resin (a3) in the present invention can be obtained by isocyanurating a diisocyanate compound containing an alicyclic diisocyanate compound in the presence or absence of a trimerization catalyst.

Alicyclic in the present specification means, in the context of the present invention, compounds in which the carbon atoms are arranged in a ring (as already suggested by the identity of the two terms "aliphatic" and "cyclic" written together). Alicyclic is therefore also a synonym for cycloaliphatic. As a result, alicyclic 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 alicyclic 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, but examples thereof include amine compounds such as 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-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), and U-CAT 18X (manufactured by San-Apro).

Examples of the alicyclic isocyanurate type polyisocyanate (a1) include alicyclic isocyanurate type triisocyanate (including polymers such as pentamer) synthesized from isophorone diisocyanate, alicyclic isocyanurate type triisocyanate (including polymers such as pentamer) synthesized from hydrogenated tolylene diisocyanate, alicyclic isocyanurate type triisocyanate (including polymers such as pentamer) synthesized from hydrogenated xylene diisocyanate, isocyanurate type triisocyanate (including polymers such as pentamer) synthesized from norbornane diisocyanate, alicyclic isocyanurate type triisocyanate (including polymers such as pentamer) synthesized from hydrogenated diphenylmethane diisocyanate, etc. Among them, alicyclic isocyanurate type isocyanate synthesized from isophorone diisocyanate is preferred. By using alicyclic isocyanurate polyisocyanate synthesized from isophorone diisocyanate, it has excellent tackiness and curing shrinkage.

Examples of the alicyclic tricarboxylic anhydride (a2) used in the production of the polyamideimide resin (a3) in the present invention include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, and cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride. Among these, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, which has excellent tackiness and cure shrinkage, is preferred.

In the reaction between the alicyclic isocyanurate type polyisocyanate (a1) and the alicyclic tricarboxylic anhydride (a2), the total of the acid anhydride group and the carboxylic acid is preferably 1.0 mol to 3.0 mol per mol of isocyanate group in the alicyclic isocyanurate type polyisocyanate (a1), more preferably 1.2 mol to 2.8 mol, and even more preferably 1.4 mol to 2.6 mol. When the total of the acid anhydride group and the carboxylic acid exceeds 1.0 mol, the remaining of the isocyanate group is prevented, the increase in molecular weight is suppressed, and the developability is improved. When the total of the acid anhydride group and the carboxylic acid is less than 3.0 mol, the remaining of the alicyclic tricarboxylic anhydride is prevented, and the development residue can be suppressed.

The amide-imidization process uses a solvent-free or hydroxyl-free organic solvent. Specifically, the solvent (C) includes, 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 dibutyl ether, and other ethylene glycol dialkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, and other polyethylene glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and other polyethylene glycol dialkyl ethers; ethylene glycol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate; polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate and triethylene glycol monobutyl ether acetate; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether and other propylene glycol dialkyl ether acetates. alkyl ethers; polypropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and dipropylene glycol monobutyl Polypropylene glycol monoalkyl ether acetates such as ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, and tripropylene glycol 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; or alkyl esters of such polyether glycols; monoalkyl ester monoalkyl ethers of polyether glycols, and further crosslinking agents (D) that do not have a hydroxyl group among the crosslinking agents (D) described below, can be reacted alone or in a mixed organic solvent.

The amide-imidization reaction is preferably carried out by mixing one or more of the alicyclic isocyanurate polyisocyanates (a1) with one or more of the alicyclic tricarboxylic anhydrides (a2) in a solvent or without a solvent, and raising the temperature while stirring.

The reaction temperature of the amide-imidization reaction is preferably in the range of 50°C to 250°C, and particularly preferably in the range of 70°C to 180°C. By using such a reaction temperature, the reaction rate is increased. In the reaction, the anhydride group and the isocyanate group form an imide group accompanied by decarboxylation, and the carboxylic acid group and the isocyanate form an amide group. During the reaction, an antioxidant, a leveling agent, an antifoaming agent, a surfactant, etc. can be used as necessary.

The progress of the amide-imidization reaction can be tracked by analytical means such as infrared spectrum, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and quantification of isocyanate groups. 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 decreases. Meanwhile, the absorption of the imide group increases at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It is preferable to proceed with the reaction until the characteristic absorption of the isocyanate group at 2270 cm ⁻¹ disappears, as this makes it easier to control the reaction.

The preferred molecular weight range of the polyamideimide resin (a3) having terminal acid groups or acid anhydride groups obtained by the reaction of the cyclic isocyanurate polyisocyanate (a1) with the alicyclic tricarboxylic anhydride (a2) is a weight average molecular weight in terms of polystyrene measured by GPC of 1000 to 20,000, more preferably 1,500 to 15,000, and particularly preferably 2000 to 10,000.

Next, the carboxylation step will be described in detail.
The (meth)acrylate (b) having an epoxy group in one molecule used in the production of the unsaturated group-containing polycarboxylic acid resin (A) is not particularly limited in structure as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. Examples of such compounds include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene 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 preferred because the reaction can be easily controlled, and glycidyl methacrylate and epoxycyclohexylmethyl methacrylate are preferred from the viewpoints of reactivity and curability.
From the viewpoint of cure shrinkage and sensitivity, it is preferable that the molar ratio ((b)/(a2)) of the (meth)acrylate having an epoxy group in one molecule (b) to the alicyclic tricarboxylic anhydride (a2) is in the range of 0.8 to 2.0, more preferably 0.9 to 1.80, and even more preferably 1.0 to 1.5.

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

During the reaction, it is preferable to add a thermal polymerization inhibitor to suppress the thermal polymerization reaction, and the amount is 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the reaction mixture of polyamide-imide resin (a3) having a terminal acid group or acid anhydride group, (meth)acrylate compound (b) having an epoxy group in one molecule, and aliphatic dicarboxylic anhydride or aliphatic tricarboxylic anhydride (c), and a solvent. Examples of thermal polymerization inhibitors include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-tert-butyl-p-cresol.

In addition, it is preferable to use a catalyst during the reaction to promote the reaction, and the amount of the catalyst used is 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the reaction mixture of the polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group, the (meth)acrylate compound (b) having an epoxy group in one molecule, the aliphatic dicarboxylic anhydride or aliphatic tricarboxylic anhydride (c), and the solvent. The reaction temperature 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, chromium 2-ethylhexanoate, chromium octanoate, zinc 2-ethylhexanoate, zinc octanoate, zirconium octanoate, dimethylsulfide, and diphenylsulfide.

The carboxylation step can be carried out without a solvent or by diluting with an organic solvent. Examples of the organic solvent include the same solvents as those exemplified in the amide-imidization 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.

It is preferable to allow the reaction in the carboxylation step to proceed until the epoxy equivalent (solid epoxy equivalent) is 10,000 g/eq or more. The solid epoxy equivalent is measured by a normal neutralization titration method in accordance with JIS K 7236. In addition, if the concentration of the resin in the solution is known, the solid epoxy equivalent can also be calculated from the epoxy equivalent of the solution.

The preferred molecular weight range of the unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group with 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) is a weight average molecular weight in terms of polystyrene measured by GPC of 1,500 to 30,000, more preferably 2,000 to 20,000, and 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 is usually 5% by mass or more, preferably 10% by mass or more, more preferably 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, based on the total solid content. For example, it is 5 to 90% by mass, preferably 10 to 90% by mass, more preferably 15 to 90% by mass, even more preferably 15 to 80% by mass, and particularly preferably 15 to 70% by mass.

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

Examples of the light-blocking agent include lactam pigments, carbon black, dyes, perylene pigments, fine particles mainly composed of silver-tin (AgSn) alloys, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, metal sulfates, and metal carbonates, and various other pigments, whether organic or inorganic. Black pigments are preferred as light-blocking agents.

Carbon black
As the carbon black, various carbon blacks that have been used as light-shielding agents can be used. Specifically, as the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. In addition, the carbon black may be coated with an organic substance such as a resin, a dye, or an acidic group-containing compound. The carbon black may be used alone or in combination of two or more kinds.

≪Dye≫
The dye may be appropriately selected from among known materials.
Examples of dyes that can be used in the colored photosensitive composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
Furthermore, these dyes can be made into lakes (chlorination) and dispersed in organic solvents, etc., and used as light-shielding agents.
In addition to these dyes, for example, dyes described in JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206, 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 Colourists), specifically, those assigned the following Color Index (C.I.) numbers:

C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same, and only the numbers are listed.), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185; C.I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same, and only the numbers are described.), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; C.I. C.I. Pigment Violet 1 (hereinafter, the same applies to "C.I. Pigment Violet", and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; C.I. Pigment Red 1 (hereinafter, the same applies to "C.I. Pigment Red", and only the numbers will be 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, 1 01, 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, 21 7, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; C. I. Pigment Blue 1 (hereinafter, the same applies to "C.I. Pigment Blue", and only the numbers are listed.), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66; C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37; C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28; C.I. Pigment Black 1, C.I. Pigment Black 7.

In terms of good light-blocking properties, the ratio of the mass of carbon black to the total mass of colorant (B) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and especially preferably 100% by mass.

The form of the colorant (B) used in the preparation of the colored photosensitive composition is not particularly limited. The colorant (B) may be used as a powder or a dispersion. The colorant (B) is preferably used in the preparation of the colored photosensitive composition as a dispersion.
As the dispersion liquid, a dispersion liquid containing two or more kinds of colorants (B) may be used. Also, two or more kinds of dispersion liquids each containing a different kind of colorant may be used.

As the dispersion medium, for example, organic solvents such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate 3-ethoxyethyl propionate, propylene glycol monomethyl ether propionate, etc., or water, etc. can be used.

A dispersant may be added to the colorant (B) in order to stabilize the dispersion of the colorant (B) in the dispersion liquid and to improve the dispersibility of the colorant (B) in the colored photosensitive composition.
As the dispersant, it is preferable to use a polymer dispersant such as a polyethyleneimine-based dispersant, a urethane-based dispersant, an acrylic resin-based dispersant, etc. Among these dispersants, a urethane-based dispersant is preferable from the viewpoint of less generation of residues after development.
A dispersing agent such as a copper compound may also be used. An example of the copper compound is copper phthalocyanine.
In addition, since corrosive gas caused by the dispersant may be generated from the cured film, one example of a preferred embodiment is 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, and preferably 10% by mass or more and 50% by mass or less.

The viscosity of the dispersion of 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 using 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 the dispersion average particle size. The dispersion average particle size can be measured using a laser diffraction type particle size distribution system.

The content ratio of the colorant (B) relative to the total mass of the 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 mass% or less, 65 mass% or less, or 60 mass% or less. The lower limit is usually 1 mass% or more, for example, 10 mass% or more, preferably 20 mass% or more, and more preferably 30 mass% or more, based on the total solid content.
In this specification, the amount of the colorant (B) can be defined as a value including the amount of the dispersant present together with the colorant (B).

The colored photosensitive composition contains a solvent (C). Examples of the solvent (C) are the same as those given when synthesizing the unsaturated polycarboxylic acid resin (A), but examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and propylene glycol mono-n-butyl ether. (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; alkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, and 3-methyl-3-methoxypropionate. Examples of the solvent include butyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; and benzyl esters of aliphatic carboxylic acids such as benzyl acetate, benzyl propionate, benzyl butanoate, and benzyl pentanoate. 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, and 3-methoxybutyl acetate are preferred because they exhibit excellent solubility in the photopolymerization initiator (E) described later, and it is particularly preferred to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. In addition, in terms of coatability, the above-mentioned preferred solvents may be used in combination with the above-mentioned benzyl ester of an aliphatic carboxylic acid, and when the above-mentioned benzyl ester of an aliphatic carboxylic acid is included, the content of the benzyl ester of an aliphatic carboxylic acid 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 is preferably an amount that results in a solid content concentration of the photosensitive composition of 1% by mass or more and 80% by mass or less, and more preferably an amount that results in a solid content concentration of 5% by mass or more and 70% by mass or less.

The photosensitive resin composition may contain a crosslinking agent (D). Examples of the crosslinking agent (D) used in the photosensitive resin composition include radical reaction type acrylates, cationic reaction type epoxy compounds, vinyl compounds that react with both, maleimide compounds, and other compounds.

Radical reaction type 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, 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, Examples of the acrylate acrylate include leic acid, 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, and half (meth)acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone 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, 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, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of hydroxypivalic acid neopentyl glycol adduct with ε-caprolactone, dipentaerythritol and ε-caprolactone Poly(meth)acrylates of reaction products of methacrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate or its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate or its ethylene oxide adduct, ethoxylated hexanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, poly(ethylene ethylene-propylene) glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 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, 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, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate, etc., and 2-hydroxyethyl (meth)acrylate reaction products), methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, condensation products of polyhydric alcohols and 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, etc.

The cationic reaction type epoxy compounds are not particularly limited as long as they are compounds having an epoxy group, including the epoxy compound (i), and examples thereof include glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (e.g., "Cyracure UVR-6110" manufactured by Union Carbide), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (e.g., "ELR-4206" manufactured by Union Carbide), limonene dioxide, and the like. oxide (such as "Celloxide 3000" manufactured by Daicel Corporation), 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 (such as "Cyracure UVR-6128" manufactured by Union Carbide), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, etc.

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

There is no particular limitation on the maleimide compounds, so long as they have 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-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5 -diethyl-4-maleimidophenyl)methane, phenylmethane maleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimide ethane, 1,4-bismaleimide butane, 1,5-bismaleimide pentane, 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-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethanebiscyclo Examples of the maleimide compounds represented by formula (6) include citraconimide, 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, polyphenylmethane maleimide, and polyphenylmethane maleimide; maleimide compounds represented by formula (7); fluorescein-5-maleimide; and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

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

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

In formula (2), _R2 each independently represents a hydrogen atom or a methyl group, and _n2 represents an integer of 1 or more, preferably an integer of 1 to 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; and n ₃ independently represents an integer of 1 to 10.
Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and a neopentyl group.

The crosslinking agent (D) may be used alone or in a mixture of two or more. The content of the crosslinking agent (D) in the colored photosensitive composition when the crosslinking agent (D) is contained is not particularly limited, but is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, based on the total mass of the solid content of the colored photosensitive composition. By setting the content within the above range, it tends to be easier to balance the sensitivity, developability, and resolution.

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

Specific examples of the photopolymerization initiator (E) include 1-hydroxycyclohexyl phenyl 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-diphenylethane-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-acetyl oxime, 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, 4-dimethylaminobenzoic acid, butyl o-aminobenzoate, 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, benzil, 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 Examples of the photopolymerization initiator include 6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2-ethylanthraquinone, 2-tertiary 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'-bismethylaminobenzophenone and other benzophenones, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. These photopolymerization initiators can be used alone or in combination of two or more.

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

As described above, the colored photosensitive composition preferably contains an oxime ester compound as the photopolymerization initiator (E). The oxime ester compound has an excellent ability to absorb ultraviolet light and generate radicals. Therefore, the oxime ester compound is highly sensitive, and even when it contains a high concentration of a colorant (B) such as a light-shielding agent, 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 colorant (B), when the optical density of the film formed with the colored photosensitive composition is 3, the amount of ultraviolet exposure in the deep layer is significantly smaller than the amount of ultraviolet exposure in the surface layer (outermost surface), but the oxime ester compound generates radicals even with such a relatively small amount of ultraviolet exposure, and can satisfactorily cure the colored photosensitive composition.

In addition, when the colorant (B) is mixed in a high concentration in the colored photosensitive composition, primary aggregates (aggregates) of the colorant (B) are inevitably generated in the coating film made of the colored photosensitive composition. 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 a small gap where aggregates are overlapped in a complex manner.
As a result, the cured product of the colored photosensitive composition not only has excellent adhesion to a substrate and electrical resistivity (insulation) under an environment of normal temperature and humidity and atmospheric pressure, but also is less likely to decrease in adhesion to a substrate and electrical resistivity (insulation) even when the cured product is exposed to a high-temperature, high-humidity, high-pressure environment. The durability under a high-temperature, high-humidity, high-pressure environment can be confirmed by a so-called PCT test (pressure cooker test).
For this reason, the performance of a cured product (colored film) of a colored photosensitive composition containing an oxime ester compound is unlikely to deteriorate even when used in a high-temperature or high-humidity environment.

As the photopolymerization initiator (E), an oxime ester compound may be used in combination with a photopolymerization initiator other than an oxime ester compound. In this case, the ratio of the mass 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 particularly preferably 40% by mass or more.

As a photopolymerization initiator other than the oxime ester compound, for example, an aminoalkylphenone-based photopolymerization initiator can be suitably used.
Examples of the aminoalkylphenone compound include 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., IRGACURE 369 manufactured by Ciba Specialty Chemicals), 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., IRGACURE 379 manufactured by Ciba Specialty Chemicals), 2-(4-ethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-isopropylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-n-butyl benzyl)-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)butan-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, Examples of the morpholinophenyl compound include 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.
Of these, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one is preferred.

By combining an aminoalkylphenone-based photopolymerization initiator with an oxime ester compound, it becomes easier to control the cross-sectional shape of a patterned colored film formed using the colored photosensitive composition.
This is believed to be because the aminoalkylphenone photopolymerization initiator tends to generate photopolymerization radicals relatively in the surface layer portion of the colored photosensitive composition (the surface facing the light to be exposed and its vicinity), while the oxime ester compound tends to generate photopolymerization radicals relatively in the deeper layer portion of the colored photosensitive composition. This tendency is more pronounced as the film thickness of the colored photosensitive composition increases, but is also observed even in a film thickness of 1 μm or less.
In addition, as a secondary effect of using an aminoalkylphenone-based photopolymerization initiator together with an oxime ester compound, the sensitivity is improved overall, and a cured product of the colored photosensitive composition can be obtained with a small amount of exposure. Furthermore, when an aminoalkylphenone-based photopolymerization initiator is used together with an oxime ester compound, the straightness of the line edge and the adhesion to the substrate are better, and it is easy to form a patterned colored film with fewer pattern defects.

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

The content of the photopolymerization initiator (E) in the colored photosensitive composition is not particularly limited as long as it does not impair the object of the present invention. The content of the photopolymerization initiator (E) is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.3% by mass or more and 20% by mass or less, and particularly preferably 0.5% by mass or more and 10% by mass or less, based on the mass of the solid content of the colored photosensitive composition.

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

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

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

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 The Dow Chemical Company), jER E1032H60 (manufactured by Japan Epoxy Resins Co., Ltd.), and the like.
Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by DIC Corporation) and TACTIX-556 (manufactured by The Dow Chemical Company).

Examples of the bisphenol type epoxy resin include bisphenol-A type epoxy resins such as jER828, jER1001 (both manufactured by Japan Epoxy Resins Co., Ltd.), UVR-6410 (manufactured by Union Carbide Corporation), D.E.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.), and bisphenol-F type epoxy resins such as UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (manufactured by Tohto Kasei Co., Ltd.), NER-7403, NER-7604 (both manufactured by Nippon Kayaku Co., Ltd.).

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.), bixylenol type epoxy resins such as YX-4000 (manufactured by Japan Epoxy Resins Co., Ltd.), and YL-6121 (manufactured by Japan Epoxy Resins Co., Ltd.).
Examples of the bisphenol A novolac type epoxy resin include Epicron N-880 (manufactured by DIC Corporation) and jER E157S75 (manufactured by Japan Epoxy Resins 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.).
An example of the glyoxal type epoxy resin is GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.).
Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Corporation), etc. Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.), etc.

Specific examples of oxazine compounds as the curing agent (F) include B-m type benzoxazine, P-a type benzoxazine, and B-a type benzoxazine (all manufactured by Shikoku Chemical Industry Co., Ltd.).

The curing agent (F) may be used alone or in combination of two or more kinds.
The content of the curing agent (F) is not particularly limited, but is preferably 0 to 40 mass %, more preferably 3 to 30 mass %, based on the mass of the solid content of the colored photosensitive composition. By setting the content of the polyfunctional crosslinking compound (D) within the above range, it is easy to obtain a photosensitive resin composition that can form a cured film with high heat resistance.

The colored photosensitive composition contains an unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), a solvent (C), a crosslinking agent (D), and a photopolymerization initiator (E), and is therefore highly photosensitive, dispersible even at high colorant concentrations, and has good development characteristics. In addition, by containing a curing agent (F) if necessary, the composition can have good heat resistance.

The colored photosensitive composition may contain other components (G) such as resins other than the unsaturated group-containing polycarboxylic acid (A), the crosslinking agent (D), and the curing agent (F), surface conditioners, adhesion improvers, and various other additives, as long as the purpose of the present invention is not impaired. There are no particular limitations on the amount of other components (G) added. Other components (G) can be used in an amount that does not impair the purpose of the present invention.

<Surface conditioner>
The surface conditioner 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). Specifically, polydimethylsiloxane, polyether-modified polysiloxane, polymethylalkylsiloxane, polysiloxane modified with an aralkyl group or polyester chain, etc. can be suitably used.

<Adhesion improver>
Known coupling agents such as silane coupling agents, titanate coupling agents, aluminate coupling agents, etc. can be used. Among these, silane coupling agents are preferably used from the viewpoint of improving adhesion to the glass substrate.

The colored photosensitive composition may contain various additives other than those mentioned above, if necessary. Specific examples include sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersion aids, fillers, antioxidants, UV absorbers, aggregation inhibitors, thermal polymerization inhibitors, defoamers, surfactants, liquid repellents, chain transfer agents, photoinitiator aids, solvents, etc. Any of the additives may be any conventionally known additive.

Examples of the surfactant include anionic compounds, cationic compounds, and nonionic compounds.
Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether.
Examples of the antifoaming agent include silicone-based compounds and fluorine-based compounds.
Examples of the chain transfer agent include mercaptan compounds, halogen compounds, quinone compounds, and α-methylstyrene dimer. By containing a chain transfer agent, the pattern shape (particularly, the CD change and exposure margin of the hole pattern) can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferred in that it can reduce sublimates, coloration, and odor in addition to the above effects.
Examples of the photoinitiator assistant include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photoinitiator assistants may be used alone or in combination of two or more.

Examples of the liquid repellent include a fluorine atom-containing resin having a crosslinking group. Since the liquid repellent can impart ink repellency to the surface of the partition wall, it is considered that the liquid repellent can prevent color mixing between pixels when the colored photosensitive composition is used to form the partition wall.
Examples of the crosslinking group include an epoxy group or an ethylenically unsaturated group, and from the viewpoint of suppressing the outflow of the liquid repellent into the developer, an ethylenically unsaturated group is preferred. The fluorine atom-containing resin having a crosslinking group preferably has either one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Examples of the perfluoroalkyl group include a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Examples of the perfluoroalkylene ether chain 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 fluorine-containing resins having crosslinking groups include, for example, acrylic copolymer resins having epoxy groups and perfluoroalkyl groups, acrylic copolymer resins having epoxy groups and perfluoroalkylene ether chains, acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkyl groups, acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene ether chains, epoxy (meth)acrylate resins having epoxy groups and perfluoroalkyl groups, epoxy (meth)acrylate resins having epoxy groups and perfluoroalkylene ether chains, epoxy (meth)acrylate resins having ethylenically unsaturated groups and perfluoroalkyl groups, epoxy (meth)acrylate resins having ethylenically unsaturated groups and perfluoroalkylene ether chains, etc. Among these, from the viewpoint of ink repellency, acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkyl groups, and acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene ether chains are preferred, and acrylic copolymer resins having ethylenically unsaturated groups and perfluoroalkylene ether chains are even more preferred. Commercially available products of fluorine atom-containing resins having these crosslinking groups include "Megafac (registered trademark, the same applies below) F116", "Megafac F120", "Megafac F142D", "Megafac F144D", "Megafac F150", "Megafac F160", "Megafac F171", "Megafac F172", "Megafac F173", "Megafac F177", "Megafac F178A", "Megafac F178K", "Megafac F179", "Megafac F183", "Megafac F184", "Megafac F191", "Megafac F812", "Megafac F815", "Megafac F824", "Megafac F833", "Megafac RS101", "Megafac RS102", "Megafac RS105", "Megafac RS201", "Megafac RS202", "Megafac RS301", "Megafac RS303", and "Megafac F160". FAC RS304, Megafac RS401, Megafac RS402, Megafac RS501, Megafac RS502, Megafac RS-72-K, Megafac RS-78, Megafac RS-90, DEFENSA (registered trademark, the same applies below) MCF300, DEFENSA MCF310, DEFENSA MCF312, DEFENSA MCF323, 3M Japan's "Florald FC" Fluorine-containing organic compounds commercially available under the trade names of "430", "Fluorard FC431", "FC-4430", "FC4432", "Asahiguard (registered trademark) AG710" manufactured by AGC, "Surflon (registered trademark, the same applies below) S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Surflon SC-106" and the like can be used.

<<Method for preparing colored photosensitive composition>>
The colored photosensitive composition is prepared, for example, by uniformly stirring and mixing the above-mentioned components, and uniformly dissolving and dispersing them. The components may be mixed using a stirrer such as a roll mill, a ball mill, or a sand mill. If necessary, the composition may be filtered through a filter such as a 2 μm membrane filter.

<Colored film and patterned colored film>
A colored film can be obtained by curing the colored photosensitive composition.
The 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 to light.
In addition, a method for producing a patterned colored film includes a step of forming a coating film by applying a colored photosensitive composition, a step of position-selectively exposing the coating film, and a step of developing the coating film after exposure.
By using the above colored photosensitive composition as a negative-type photosensitive composition, a highly precise pattern having good linearity can be formed even if a high concentration of colorant is contained.

Each step is explained below. Forming a coating film using a colored photosensitive composition is referred to as a "coating film forming step." Exposing the coating film to light 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, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, SOG (Spin On Glass), polyester films, polycarbonate films, and polymer substrates such as polyimide films, TFT array substrates, electrode plates for PDPs, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, and semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. Furthermore, for example, when a laminated structure is formed on a substrate, any layer that becomes a lower structure already formed on the substrate is also included in the concept of a substrate to which the colored photosensitive composition is applied. In addition, the shape of the substrate is not particularly limited, and may be a plate or a roll. The substrate may have a surface unevenness formed by various patterns, for example. As the substrate, a light-transmitting or light-non-transmitting substrate may be selected.

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

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

The coating film may be dried as necessary. There are no particular limitations on the drying method. Examples of drying methods include (1) drying on a hot plate at a temperature of 80°C to 120°C, preferably 90°C to 100°C, for 60 to 120 seconds, (2) leaving the film at room temperature for several hours to several days, and (3) placing the film in a hot air heater or 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 to light. This results in a cured film (colored film) of the colored photosensitive composition. By selectively exposing and developing the film according to the pattern shape, a patterned cured film (colored film) is obtained.

In the exposure step, the coating film is exposed to radiation or electromagnetic waves such as i-rays, g-rays, and h-rays. When forming a patterned cured film (colored film), the coating film is exposed selectively through a negative mask. The exposure amount varies depending on the composition of the colored photosensitive composition, but is preferably, for example, about 5 mJ/ ^cm2 or more and 500 mJ/ ^cm2 or less. It is preferably about 10 mJ/cm2 or ^more and 150 mJ/ ^cm2 or less.

The cured film cured by exposure may be heated. The temperature at which the film is heated is not particularly limited, and is preferably from 180°C to 280°C, more preferably from 200°C to 260°C, and particularly preferably from 220°C to 250°C. The heating time is typically preferably from 1 minute to 60 minutes, more preferably from 10 minutes to 50 minutes, and particularly preferably from 20 minutes to 40 minutes.

≪Development process≫
In the developing step, the coating film exposed in the exposing step is developed with an alkaline developer.
In the development step, the exposed coating film is developed with a developer to form a cured film (colored film) patterned into a desired shape. The development method is not particularly limited, and a dipping 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, and quaternary ammonium salts.

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

By using the above colored photosensitive composition, it is possible to disperse a high concentration of colorant and form a highly precise pattern, as shown in the examples described below, and a curing agent can be added if good heat resistance is desired.

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.

The epoxy equivalent and acid value were measured under the following conditions.
1) Epoxy equivalent (WPE): Measured according to a method in accordance with JIS K 7236:2001.
2) Acid value: Measured according to a method in accordance with JIS K 0070:1992.
3) The 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
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (1) solution was obtained, which had a number average molecular weight of 1,250 and a weight average molecular weight of 4,040 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 164 mgKOH/g. The mixture was cooled to 60°C, and 494.5g of propylene glycol monomethyl ether acetate, 170.4g of glycidyl methacrylate, 154.0g of hexahydrophthalic anhydride, and 2.27g of dibutylhydroxytoluene were added and stirred, and then 2.27g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (I) having a solid acid value of 94.1mgKOH/g, a (meth)acrylic equivalent of 629, a number average molecular weight by GPC of 1,870, and a weight average molecular weight of 5,320. The epoxy equivalent was measured to be 13,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 2
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 661.2 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 198.0 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (2) solution was obtained, which had a number average molecular weight of 1,290 and a weight average molecular weight of 3,590 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 155 mgKOH/g. The mixture was cooled to 60°C, and 537.5g of propylene glycol monomethyl ether acetate, 198.8g of glycidyl methacrylate, 154.0g of hexahydrophthalic anhydride, and 2.38g of dibutylhydroxytoluene were added and stirred, and then 2.38g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (II) having a solid acid value of 92.2mgKOH/g, a (meth)acrylic equivalent of 629, a number average molecular weight by GPC of 1,710, and a weight average molecular weight of 4,930. The epoxy equivalent was also measured to be 11,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 3
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (3) solution was obtained, which had a number average molecular weight of 1,260 and a weight average molecular weight of 4,120 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 159 mgKOH/g. The mixture was cooled to 60°C, and 448.0g of propylene glycol monomethyl ether acetate, 170.4g of glycidyl methacrylate, 123.2g of hexahydrophthalic anhydride, and 2.17g of dibutylhydroxytoluene were added and stirred, and then 2.17g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (III) having a solid acid value of 85.9mgKOH/g, a (meth)acrylic equivalent of 604, a number average molecular weight by GPC of 1,750, and a weight average molecular weight of 5,500. The epoxy equivalent was also measured to be 14,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 4
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (4) solution was obtained, which had a number average molecular weight of 1,190 and a weight average molecular weight of 3,850 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 151 mgKOH/g. The mixture was cooled to 60°C, and 494.8g of propylene glycol monomethyl ether acetate, 170.4g of glycidyl methacrylate, 154.0g of hexahydro-4-methylphthalic anhydride, and 2.44g of dibutylhydroxytoluene were added and stirred, and then 2.44g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (IV) having a solid acid value of 95.8mgKOH/g, a (meth)acrylic equivalent of 641, a number average molecular weight by GPC of 1,640, and a weight average molecular weight of 4,790. The epoxy equivalent was also measured to be 12,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 5
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (5) solution was obtained, which had a number average molecular weight of 1,300 and a weight average molecular weight of 3,690 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 152 mgKOH/g. The mixture was cooled to 60°C, and 491.7g of propylene glycol monomethyl ether acetate, 170.4g of glycidyl methacrylate, 152.2g of 1,2,3,6-tetrahydrophthalic anhydride, and 2.31g of dibutylhydroxytoluene were added and stirred, and then 2.31g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (V) having a solid acid value of 97.9mgKOH/g, a (meth)acrylic equivalent of 628, a number average molecular weight by GPC of 1,690, and a weight average molecular weight of 4,980. The epoxy equivalent was measured to be 14,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 6
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (6) solution was obtained, which had a number average molecular weight of 1,250 and a weight average molecular weight of 3,680 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 161 mgKOH/g. The mixture was cooled to 60°C, and 261.9g of propylene glycol monomethyl ether acetate, 170.4g of glycidyl methacrylate, and 1.90g of dibutylhydroxytoluene were added and stirred, and then 1.90g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (I') having a solid acid value of 19.2mgKOH/g, a number average molecular weight by GPC of 1,740, and a weight average molecular weight of 6,950. The epoxy equivalent was measured to be 13,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 7
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (7) solution was obtained, which had a number average molecular weight of 1,180 and a weight average molecular weight of 3,860 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 154 mgKOH/g. Cooled 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, and then 1.90 g of triphenylphosphine was added and heated to 116 ° C. Reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (II') with a solid acid value of 99.5 mg KOH / g, a (meth)acrylic equivalent of 624, a number average molecular weight by GPC of 1,630, and a weight average molecular weight of 4,830. In addition, the epoxy equivalent was measured to be 14,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 8
Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line were added 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. Cooled to 60 ° C., 97.58 g of pentaerythritol (tri / tetra) acrylate mixture (Daicel Allnex "PETRA", hydroxyl value 115 mg KOH / g) was added, heated to 116 ° C., and reacted at the same temperature for 10 hours to obtain an amide imide resin (8) solution with a number average molecular weight of 1,070, a weight average molecular weight of 3,080, and a solid acid value of 135 mg KOH / g by gel permeation chromatography using polystyrene as a standard. Cooled 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 dibutyl hydroxytoluene were added and stirred, and then 2.44 g of triphenylphosphine was added and heated to 116 ° C. The reaction was continued at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (III') having an acid value of 82.1 mgKOH/g solid content, a (meth)acrylic equivalent of 395, a number average molecular weight by GPC of 1,370, and a weight average molecular weight of 3,700. The epoxy equivalent was measured to be 15,000 g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 9
In a four-neck flask equipped with a stirrer, a thermometer, and a condenser, 250.3 g of propylene glycol monomethyl ether acetate, 435.7 g of cresol novolac type epoxy resin ("EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 218 g/eq), and 1.75 g of dibutylhydroxytoluene were added and stirred at 80°C to dissolve the epoxy resin. Then, 148.4 g of acrylic acid and 1.75 g of triphenylphosphine were added, and the mixture was heated to 116°C and reacted at the same temperature for 12 hours to obtain a reactive epoxide carboxylate resin (9) solution with a solid acid value of 2.2 mg KOH/g and an epoxy equivalent of 13 kg/eq. The mixture was cooled 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 mixture was heated to 100°C. The reaction was continued at the same temperature for 5 hours to obtain an unsaturated group-containing polycarboxylic acid resin (IV') having an acid value of 61.2 mgKOH/g of solid content, a (meth)acrylic equivalent of 349, a number average molecular weight by GPC of 2058, and a weight average molecular weight of 6420. The epoxy equivalent was measured to be 13,000 g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Production Example 10
The resin described in Example 2-1 of Japanese Patent No. 6,576,161 was produced as described, and a reactive polycarboxylic acid compound (V') having a solid acid value of 61.5 mg KOH/g, a (meth)acrylic equivalent of 335, a number average molecular weight by GPC of 1,830, and a weight average molecular weight of 3,520 was obtained.

Manufacturing Example 1
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (5) solution was obtained, which had a number average molecular weight of 1,310 and a weight average molecular weight of 3,810 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 152 mgKOH/g. The mixture was cooled to 60°C, and 338.6g of propylene glycol monomethyl ether acetate, 142.0g of glycidyl methacrylate, 79.2g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and 2.31g of dibutylhydroxytoluene were added and stirred, and then 2.31g of triphenylphosphine was added and heated to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (VI) having a solid acid value of 87.1mgKOH/g, a (meth)acrylic equivalent of 652, a number average molecular weight by GPC of 1,870, and a weight average molecular weight of 6,010. The epoxy equivalent was also measured to be 16,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

Manufacturing Example 12
A four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line was charged with 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANATT-1890/100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride. The temperature was raised to 116° C. while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectroscopy that the absorption at 2250 cm ⁻¹ , which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (5) solution was obtained, which had a number average molecular weight of 1,260 and a weight average molecular weight of 3,600 by gel permeation chromatography using polystyrene as a standard, and a solid acid content of 156 mg KOH/g. The mixture was cooled to 60°C, and 441.4g of propylene glycol monomethyl ether acetate, 170.4g of glycidyl methacrylate, 118.8g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and 2.31g of dibutylhydroxytoluene were added and stirred, and then 2.31g of triphenylphosphine was added and the temperature was raised to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (VII) having a solid acid value of 80.6mgKOH/g, a (meth)acrylic equivalent of 600, a number average molecular weight by GPC of 1,870, and a weight average molecular weight of 6,010. The epoxy equivalent was also measured to be 14,000g/eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[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 was used in the examples and comparative examples, and Mitsubishi carbon black MA-100 (B1) was used as the colorant (B). Propylene glycol monomethyl ether acetate (C1) was used as the solvent (C), and the mixture was kneaded in a bead mill, and the state after kneading was confirmed. The colored photosensitive composition obtained was homogeneous, with an ◯; the colored photosensitive composition obtained was non-uniform, and gelation due to the resin occurred, with an ×. The proportions of the colored photosensitive composition and the evaluation results of the state after kneading are shown in Table 1.

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

[Example 3, Comparative Example 3] Preparation of colored photosensitive composition and evaluation of developability [0223] The unsaturated group-containing polycarboxylic acid resins (A) obtained in Production Examples 1 to 10, the colorant (B1), the solvent (C1), the crosslinking agent (D), and the photopolymerization initiator (E) were uniformly dispersed in the formulations shown in Table 3 to obtain resist resin compositions.
In the examples and comparative examples, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.: ε-caprolactone-modified dipentaerythritol hexaacrylate) (D2) was used as the crosslinking agent (D), Irgacure 907 (manufactured by Ciba Specialty Chemicals) (E1) and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2) were used as the photopolymerization initiator (E), YD-134 (manufactured by Nippon Steel Chemical & Material Co., Ltd.: bisphenol-A type epoxy resin) (F1) was used as the curing agent (F), and TPP (manufactured by Hokko Chemical Industry Co., Ltd.: triphenylphosphine) (G1) was used as the thermosetting catalyst (G).

Each evaluation item is explained in detail below.

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

"Film loss" was determined from the thickness of the coating film before development and the cross-sectional height of the pattern after development, and if there was any film loss, it was rated as △ rather than as break time. (Electron microscope used) For "pattern straightness," if it was curved it was rated as ×. If the pattern was not straight and was not formed neatly, it was rated as × rather than as break time. (Electron microscope used) For "swelling peeling," if the coating film swelled and peeled off during development rather than being dissolved and developed, it was rated as XX rather than as break time.

Thermal decomposition resistance evaluation (abbreviation in table: thermal decomposition resistance)
The colored photosensitive composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) with an applicator to a thickness of 20 μm, and the coating was dried in a hot air dryer at 80 ° C for 30 minutes, and then irradiated with ultraviolet light at an energy of 500 mJ / cm ² using an ultraviolet irradiator (GS YUASA: CS 30L-1). Next, the material 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 the sample produced by preparing the cured product was reduced by 5% was measured using a METTLER TGA / DSC1 in an air flow of 100 ml per minute.

The above results confirm 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 also has excellent resistance to thermal decomposition.

[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-100 (B1) were used as colorant (B). The mixture was kneaded in a bead mill, and the state after kneading was confirmed. The colored photosensitive composition obtained was marked with ◯ when it was homogeneous, and marked with × when it was non-uniform or gelation occurred due to the resin.

[Example 5] Preparation of colored photosensitive composition and evaluation of colorant dispersibility DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.) (D1) as a crosslinking agent (D) and 20 g of glass beads were added to the colored photosensitive compositions obtained in Examples 4-1, 4-2, and 4-3, and the mixture was dispersed for 1 hour using a paint shaker. The dispersion after dispersion was applied onto a polyethylene terephthalate film using a wire bar coater #2, and dried for 10 minutes using a hot air dryer at 80°C. The gloss of the coating surface after drying was measured using a 60° reflection gloss meter (HORIBA IG-331 gloss meter) to evaluate the dispersibility of carbon black. The results are shown in Table 5. The higher the gloss value, the better the pigment dispersibility.

[Example 6] Preparation of colored photosensitive composition and evaluation of developability [0223] The unsaturated group-containing polycarboxylic acid resin (A) obtained in Production Examples 11 and 12, the colorant (B1), the solvent (C1), the crosslinking agent (D), and the photopolymerization initiator (E) were uniformly dispersed in 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) was used as the crosslinking agent (D), Irgacure 907 (manufactured by Ciba Specialty Chemicals) (E1) and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2) were used as the photopolymerization initiator (E), YD-134 (manufactured by Nippon Steel Chemical & Material Co., Ltd.: bisphenol-A type epoxy resin) (F1) was used as the curing agent (F), and TPP (manufactured by Hokko Chemical Industry Co., Ltd.: triphenylphosphine) (G1) was used as the heat curing catalyst (G).

Each evaluation item is the same as in Example 3. The evaluation results for each evaluation item are shown in Table 6.

From the above results, it can be confirmed that the coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility, high developability, and the cured product also has excellent resistance to thermal decomposition.

As described above, a coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility and high developability, and the cured product thereof also has excellent heat resistance, and is therefore suitable for partition walls having a light-shielding effect for image display devices, as well as black matrices, colored spacers, and color resists.

Claims (7)

A colored photosensitive composition comprising an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group , obtained by reacting an alicyclic isocyanurate polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2), with only 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), a colorant (B), and a solvent (C). The colored photosensitive composition according to claim 1, which contains a crosslinking agent (D). The colored photosensitive composition according to claim 1, further comprising a photopolymerization initiator (E). The colored photosensitive composition according to claim 1, further comprising a curing agent (F). The colored photosensitive composition according to claim 1, wherein the colorant (B) includes 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.