Colored photosensitive composition, cured product, and image display device including the cured product

Abstract

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

Description

Technical Field

[0001] The present invention relates to a colored photosensitive composition, a cured product, and an image display device including the cured product. Specifically, it relates to a photosensitive coloring composition excellent in shielding properties and plate-making characteristics and its uses.

Background Art

[0002] Conventional displays frequently use color filters, colored spacers, and black matrices that form red, green, and blue pixels using organic pigments. In recent years, for the purpose of reducing power consumption and widening the color gamut of displays, color filters that form pixels using light-emitting nanocrystal particles such as quantum dots have been studied. Specifically, those having a red pixel containing red light-emitting nanocrystal particles, a green pixel containing green light-emitting nanocrystal particles, and a blue pixel that transmits blue light from a light source are known. As methods for manufacturing color filters, there are a photolithography method and an inkjet method, and it is known that the latter can reduce the loss of ink materials (Patent Document 1). When manufacturing a color filter containing light-emitting nanocrystal particles by the inkjet method, ink is ejected into a region (pixel portion) surrounded by previously formed partition walls to form pixels. These partition walls not only prevent mixing of inks between adjacent pixel portions but also require a high-definition pattern (fine pattern). Also, there are those formed by the photolithography method using a photosensitive composition (colored photosensitive composition) containing a colorant as having a light-shielding effect (Patent Document 2). In addition, attempts have also been made to apply it to a cured product used in a liquid crystal display panel or the like by dispersing carbon black or the like in an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

[0004] 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 a desired shape may not be obtained or may not be formed. Further, in a partition wall having a light shielding effect, a black matrix, a colored spacer, and a color resist, a colored photosensitive composition containing an additional colorant and having good dispersibility is required.

[0005] An object of the present invention is to improve the above-mentioned problems of the prior art, and to provide a colored photosensitive composition having excellent dispersibility of a colorant or the like, good developing characteristics even at a high colorant concentration, and further a colored photosensitive composition having good heat resistance, and cured products thereof. [Means for Solving the Problems]

[0006] As a result of intensive efforts to solve the above problems, the present inventors have found that a polyamideimide resin (a3) having a terminal acid group or acid anhydride group obtained by the reaction of an alicyclic isocyanurate type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2) is reacted with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride (c) to obtain an unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), and a solvent (C). The colored photosensitive composition has excellent dispersibility of a colorant or the like, and also has good developing characteristics even at a high colorant concentration. In some cases, it provides a colored photosensitive composition having good heat resistance and cured products thereof.

[0007] That is, the present invention relates to the following (1) to (7). (1) 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 acid anhydride group, which is obtained by reacting an alicyclic isocyanurate type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c), a colorant (B), and a solvent (C). (2) The colored photosensitive composition according to (1), containing a crosslinking agent (D). (3) The colored photosensitive composition according to (1) or (2), containing a photopolymerization initiator (E). (4) The colored photosensitive composition according to any one of (1) to (3), containing 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 including the cured product according to (6).

Advantages of the Invention

[0008] The colored photosensitive composition characterized by containing the unsaturated group-containing polycarboxylic acid resin (A), the colorant (B), and the solvent (C) of the present invention is excellent in photosensitivity, can be dispersed even at a high colorant concentration, and can have good development characteristics.

Embodiments for Carrying Out the Invention

[0009] ≪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).

[0010] Hereinafter, the essential and optional components included in the colored photosensitive composition will be described.

[0011] 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 acid anhydride group, which is obtained by the reaction of a cyclic isocyanurate type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c).

[0012] That is, the unsaturated group-containing polycarboxylic acid resin (A) in the present invention is produced through two reaction steps. First, it is a step of reacting a cyclic isocyanurate type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2) to obtain a polyamideimide resin (a3). In the present invention, this step is referred to as the amide-imidation step. Next, it is a step of reacting the obtained polyamideimide resin (a3), a (meth)acrylate compound (b) having an epoxy group in one molecule, and an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c). In the present invention, this step is referred to as the carboxylation step.

[0013] First, the amide-imidation step will be described in detail. The cyclic isocyanurate type polyisocyanate (a1) used in the production of the polyamideimide resin (a3) in the present invention is obtained by isocyanurating a diisocyanate compound containing an alicyclic diisocyanate compound in the presence or absence of a trimerization catalyst.

[0014] As used herein, in the context of the present invention, "alicyclic" means a compound in which carbon atoms are arranged in a ring (as already suggested by being the same as the combination of the two terms "aliphatic" and "cyclic"). Thus, "alicyclic" is also synonymous with "cycloaliphatic". As a result, alicyclic compounds belong to the group of homocyclic compounds, and in this case, include cycloalkanes, cycloalkenes, and cycloalkynes. Aromatic compounds, heterocyclic compounds, and saturated compounds of heterocyclic compounds are not considered alicyclic within the scope of the meaning of the present invention.

[0015] Examples of the diisocyanate containing an alicyclic diisocyanate compound include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like.

[0016] Without particular designation, examples of the trimerization catalyst include amine compounds such as 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 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, 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), PELCAT 9540 (manufactured by Perron), DABCO TMR (manufactured by Sankyo Air Products), TOYOCAT TR20 (manufactured by Tosoh), U-CAT 18X (manufactured by San Apro), and the like.

[0017] Examples of the alicyclic isocyanurate type polyisocyanate (a1) include alicyclic isocyanurate type triisocyanates synthesized from isophorone diisocyanate (including polymers such as pentamers), alicyclic isocyanurate type triisocyanates synthesized from hydrogenated tolylene diisocyanate (including polymers such as pentamers), alicyclic isocyanurate type triisocyanates synthesized from hydrogenated xylene diisocyanate (including polymers such as pentamers), isocyanurate type triisocyanates synthesized from norbornane diisocyanate (including polymers such as pentamers), alicyclic isocyanurate type triisocyanates synthesized from hydrogenated diphenylmethane diisocyanate (including polymers such as pentamers), etc. Among them, alicyclic isocyanurate type isocyanates synthesized from isophorone diisocyanate are preferred. By using alicyclic isocyanurate type polyisocyanates synthesized from isophorone diisocyanate, it is excellent in tackiness and curing shrinkage.

[0018] 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, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, etc. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, which is excellent in tackiness and curing shrinkage, is preferred.

[0019] The reaction of the alicyclic isocyanurate type polyisocyanate (a1) and the alicyclic tricarboxylic anhydride (a2) is preferably such that the total of the acid anhydride group and the carboxylic acid is 1.0 mol to 3.0 mol, more preferably 1.2 mol to 2.8 mol, and even more preferably 1.4 mol to 2.6 mol, per 1 mol of the isocyanate group possessed by the alicyclic isocyanurate type polyisocyanate (a1). When the total of the acid anhydride group and the carboxylic acid exceeds 1.0 mol, the residual isocyanate group can be prevented, the increase in molecular weight can be suppressed, and the developability becomes good. When the total of the acid anhydride group and the carboxylic acid is lower than 3.0 mol, the residual alicyclic tricarboxylic anhydride can be prevented, and the development residue can be suppressed.

[0020] The amidimidation step uses a solvent-free or organic solvent without a hydroxyl group. Specifically, it is also included in solvent (C). For example, ethylene glycol dialkyl ethers such as ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, 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 dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether; 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;Polypropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, etc.; or dialkyl ethers of copolymer polyether glycols such as low molecular weight ethylene-propylene copolymers, or monoacetate monoalkyl ethers of copolymer polyether glycols; or alkyl esters of such polyether glycols; monoalkyl ester monoalkyl ethers of polyether glycols, and further, it can be reacted in a single or mixed organic solvent such as a crosslinking agent (D) described later that does not have a hydroxyl group.;

[0021] The amidation reaction is preferably carried out by mixing one or more of the alicyclic isocyanurate type polyisocyanates (a1) and one or more of the alicyclic tricarboxylic anhydrides (a2) in a solvent or without a solvent, and raising the temperature while stirring.

[0022] The reaction temperature of the amidation reaction is preferably in the range of 50°C to 250°C, particularly preferably in the range of 70°C to 180°C. By setting the reaction temperature in such a range, it has the effect of accelerating the reaction rate. The reaction involves the formation of an imide group from an anhydride group and an isocyanate group and the formation of an amide group from a carboxylic acid group and an isocyanate while accompanied by decarboxylation. During the reaction, antioxidants, leveling agents, defoaming agents, surfactants, etc. can be used as necessary.

[0023] The progress of the amidation reaction can be traced by analytical means such as infrared spectra, 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 further at 1860 cm-1 and 850 cm -1 The acid anhydride groups having characteristic absorption at this wavenumber decrease. On the other hand, the absorption of imide groups increases at 1780 cm -1 and 1720 cm -1 The reaction is preferably allowed to proceed until the characteristic absorption of the isocyanate group at 2270 cm -1 disappears, since the reaction is easy to control.

[0024] The preferable molecular weight range of the polyamideimide resin (a3) having terminal acid groups or acid anhydride groups obtained by the reaction of the cyclic isocyanurate-type polyisocyanate (a1) and the alicyclic tricarboxylic anhydride (a2) is such that the polystyrene-equivalent weight-average molecular weight in GPC is in the range of 1,000 to 20,000, more preferably 1,500 to 15,000, and particularly preferably 2,000 to 10,000.

[0025] Next, the carboxylation step will be described in detail. As the (meth)acrylate (b) having an epoxy group in one molecule used for the production of the unsaturated group-containing polycarboxylic acid resin (A), other specific structures are not particularly limited as long as they have a (meth)acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. As an example, for example, glycidyl (meth)acrylate, glycidyl ether of 4-hydroxybutyl (meth)acrylate, glycidyl group-containing (meth)acrylate monomers such as epoxycyclohexylmethyl (meth)acrylate; mono(meth)acrylated products of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, bisphenol diglycidyl ether, etc. can be mentioned. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more. Among these, (meth)acrylate compounds having one epoxy group are preferable because the reaction is easy to control, and glycidyl methacrylate and epoxycyclohexylmethyl methacrylate are preferable from the viewpoints of reactivity and curability. Also, from the viewpoints of curing shrinkage and sensitivity, it is preferable that the molar ratio of the (meth)acrylate (b) having an epoxy group in one molecule to the alicyclic tricarboxylic anhydride (a2) satisfies 0.8 to 2.0, i.e., ((b) / (a2)). More preferably, it is 0.9 to 1.80, and even more preferably, it is 1.0 to 1.5.

[0026] Examples of the aliphatic dicarboxylic anhydride or the aliphatic tricarboxylic anhydride (c) used in the production of the unsaturated group-containing polycarboxylic acid resin (A) include succinic anhydride, 1,2-cyclopropanedicarboxylic anhydride, 2,2-dimethylsuccinic anhydride, caronic anhydride, 1,2-cyclohexanedicarboxylic anhydride, butyl succinic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, n-octyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, and the like. Examples of the aliphatic tricarboxylic anhydride include a tricarboxylic anhydride having a linear aliphatic structure and a tricarboxylic anhydride having an alicyclic structure. Examples of the tricarboxylic anhydride having a linear aliphatic structure include, for example, propane tricarboxylic anhydride. Examples of the tricarboxylic anhydride having an alicyclic structure include the same compounds as those exemplified for the alicyclic tricarboxylic anhydride (a2). Among these, aliphatic dicarboxylic anhydrides are preferable from the viewpoint of electrical properties. Also, tricarboxylic anhydrides having an alicyclic structure are preferable from the viewpoints of alkali aqueous solution developability, heat resistance, hydrolysis resistance, and the like. Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is even more preferable. Also, from the viewpoints of developability and storage stability, it is preferable that the molar ratio of the aliphatic dicarboxylic anhydride or the aliphatic tricarboxylic anhydride (c) to the (meth)acrylate (b) having an epoxy group in one molecule satisfies 0.05 to 1.5, i.e., ((c) / (b)). More preferably, it is 0.1 to 1.2.

[0027] It is preferable to add a thermal polymerization inhibitor to suppress the thermal polymerization reaction during the reaction. The amount of the thermal polymerization inhibitor is 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of the reactants obtained by adding a (meth)acrylate compound (b) having an epoxy group in one molecule, an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c), and a solvent to a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group. Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol, and the like.

[0028] Also, it is preferable to use a catalyst to accelerate the reaction during the reaction. The amount of the catalyst used is 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of the reactants obtained by adding a (meth)acrylate compound (b) having an epoxy group in one molecule, an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c), and a solvent to a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group. The reaction temperature at that time is 60 to 150 °C, and the reaction time is preferably 3 to 60 hours. Examples of the catalyst 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, dimethyl sulfide, diphenyl sulfide, and the like.

[0029] The carboxylation step can be carried out by diluting with a solvent-free or organic solvent and reacting. Examples of the organic solvent include the same solvents as those exemplified in the amidoimidation step.

[0030] The reaction temperature of 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.

[0031] The reaction in the carboxylation step is preferably allowed to proceed until the epoxy equivalent (solid content epoxy equivalent) reaches 10,000 g / eq or more. The solid content epoxy equivalent is measured by a normal neutralization titration method in accordance with JIS K 7236. Also, if the concentration of the resin in the solution is known, the solid content epoxy equivalent can be calculated and determined from the epoxy equivalent of the solution.

[0032] The preferable 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 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 such that the polystyrene-reduced weight average molecular weight in GPC is in the range of 1,500 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 2,500 to 15,000.

[0033] The content ratio of the unsaturated group-containing polycarboxylic acid resin (A) in the photosensitive coloring composition of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more in the total solid content, and is usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less. For example, it is 5 to 90% by mass, preferably 10 to 90% by mass, more preferably 15 to 90% by mass, still more preferably 15 to 80% by mass, and particularly preferably 15 to 70% by mass.

[0034] 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 colorants other than the light-shielding agent.

[0035] Examples of the light-shielding agent include various pigments regardless of whether they are organic or inorganic, such as lactam-based pigments, carbon black, dyes, perylene-based pigments, fine particles mainly composed of a silver tin (AgSn) alloy, titanium black, and metal oxides, composite oxides, metal sulfides, metal sulfates, or metal carbonates of metals such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver. A black pigment is preferred as the light-shielding agent.

[0036] ≪Carbon Black≫ As the carbon black, various carbon blacks conventionally used as light-shielding agents can be used. Specifically, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. Further, the carbon black may be one 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.

[0037] ≪Dye≫ The dye may be appropriately selected from known materials. Examples of dyes applicable to 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, phthalocyanine dyes, and the like. In addition, these dyes can be dispersed in an organic solvent or the like by lake formation (salification) and used as a light-shielding agent. In addition to these dyes, dyes described in, for example, JP-A No. 2013-225132, JP-A No. 2014-178477, JP-A No. 2013-137543, JP-A No. 2011-38085, JP-A No. 2014-197206, etc. can also be preferably used.

[0038] Specific examples of other colorants include compounds classified as Pigment in the Color Index (C.I.; published by The Society of Dyers and Colourists), specifically those with the following Color Index (C.I.) numbers.

[0039] C.I. Pigment Yellow 1 (hereinafter, the same shall apply to "C.I. Pigment Yellow", and only the numbers will be 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, the same shall apply to "C.I. Pigment Orange", and only the numbers will be listed), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; C.I. Pigment Violet 1 (hereinafter, the same shall apply to "C.I. Pigment Violet", and only the numbers will be listed), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; C.I. Pigment Red 1 (hereinafter, the same shall apply to "C.I. Pigment Red", and only the numbers will be listed), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; C.I. Pigment Blue 1 (hereinafter, the same shall apply to "C.I. Pigment Blue", and only the numbers will be 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.

[0040] In terms of good light-shielding properties, the ratio of the mass of carbon black to the total mass of the colorant (B) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0041] 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 as a dispersion. The colorant (B) is preferably used as a dispersion in the preparation of the colored photosensitive composition. As the dispersion, a dispersion containing two or more colorants (B) may be used. Also, two or more dispersions containing different types of colorants may be used.

[0042] 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, or water can be used.

[0043] In order to stabilize the dispersion of the colorant (B) in the dispersion and improve the dispersibility of the colorant (B) in the colored photosensitive composition, a dispersant may be added to the colorant (B). As the dispersant, it is preferable to use polymer dispersants such as polyethyleneimine-based dispersants, urethane-based dispersants, and acrylic resin-based dispersants. Among these dispersants, urethane-based dispersants are preferable in terms of the difficulty of generating residues after development. Also, a dispersion aid such as a copper compound may be used. Examples of the copper compound include copper phthalocyanine. In addition, corrosive gas may be generated from the cured film due to the dispersant. For this reason, it is also an example of a preferred embodiment that the colorant (B) is dispersion-treated 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.

[0044] The viscosity of the dispersion of the colorant (B) is not particularly limited. The viscosity of the dispersion is preferably 3 mPa·s or more and 200 mPa·s or less as measured at 25°C with a cone plate type viscometer.

[0045] The particle diameter of the colorant (B) in the dispersion is preferably 80 nm or more and 300 nm or less as the dispersion average particle diameter. The dispersion average particle diameter can be measured using a laser diffraction type particle size distribution system.

[0046] The content ratio of the colorant (B) to the total mass of the solid content of the colored photosensitive composition is not particularly limited, but the upper limit value of the total content of the colorant (B) may be 70% by mass or less, 65% by mass or less, or 60% by mass or less. The lower limit is usually 1% by mass or more in the total solid content, for example, 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more. In addition, in this specification, the amount of the above-mentioned colorant (B) can be defined as a value including the amount of the dispersant present together with the colorant (B).

[0047] The colored photosensitive composition contains a solvent (C). Examples of the solvent (C) were also given when synthesizing the unsaturated-containing polycarboxylic acid resin (A). For example, (poly)alkylene glycol monoalkyl ethers such as 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, propylene glycol mono - n - butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono - n - propyl ether, dipropylene glycol mono - n - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates 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, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2 - heptanone, 3 - heptanone; alkyl lactates such as methyl 2 - hydroxypropionate, ethyl 2 - hydroxypropionate;Other esters such as 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-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, 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, ethyl 2-oxobutanoate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc., and benzyl esters of aliphatic carboxylic acids such as benzyl acetate, benzyl propionate, benzyl butyrate, and benzyl pentanoate. These solvents may be used alone or in combination of two or more.;

[0048] 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) shown later. It is particularly preferred to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. Also, in terms of coatability and the like, the benzyl ester of the aliphatic carboxylic acid may be used in combination with the above preferred solvent. When the benzyl ester of the aliphatic carboxylic acid is included, the content of the benzyl ester of the aliphatic carboxylic acid is preferably 1% by mass or more and 10% by mass or less based on the total amount of the solvent (C). The content of the solvent (C) is not particularly limited, but an amount that makes the solid content concentration of the photosensitive composition 1% by mass or more and 80% by mass or less is preferred, and an amount that makes it 5% by mass or more and 70% by mass or less is more preferred.

[0049] The above photosensitive resin composition may contain a crosslinking agent (D). Examples of the crosslinking agent (D) used in the above photosensitive resin composition include radical reaction type acrylates, cation reaction type epoxy compounds, vinyl compounds sensitive to both of them, and maleimide compounds.

[0050] Examples of the radical reaction type acrylates include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0051] 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, 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 phthalic acid derivatives. These monofunctional monomers can be used alone or in combination of two or more.

[0052] 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 ε-caprolactone adduct of hydroxybivalic acid neopentyl glycol, poly(meth)acrylate of reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethanolpropane 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-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 - hexanediol 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., the reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate, etc. and 2 - hydroxyethyl (meth)acrylate), methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, the condensate of polyhydric alcohol and N - methylol(meth)acrylamide, triacryl formal, 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. are mentioned.

[0053] Examples of cation-reactive epoxy compounds include compounds having an epoxy group, such as epoxy compound (i). Specific examples include glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (such as "Silacure UVR-6110" manufactured by Union Carbide Corporation), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide Corporation), limonene dioxide (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-dioxide, bis(3,4-epoxycyclohexyl)adipate (such as "Silacure UVR-6128" manufactured by Union Carbide Corporation), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, and the like.

[0054] Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and the like. Examples of the styrenes include styrene, methylstyrene, ethylstyrene, and the like. Examples of the other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, and the like.

[0055] The maleimide compounds are not particularly limited as long as they have one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidehexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimidoethane, 1,4-bismaleimidobutane, 1,5-bismaleimidopentane, 1,5-bismaleimido-2-methylpentane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 1,8-bismaleimido-3,6-dioxaoctane, 1,11-bismaleimido-3,6,9-trioxaundecane, 1,3-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,Maleimide compounds represented by formula (6) such as 5 - diethyl - 4 - citraconimidophenyl)methane, polyphenylmethane maleimide, polyphenylmethane maleimide, maleimide compounds represented by formula (7), fluorescein - 5 - maleimide, prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds, etc. may be mentioned.,

[0056] As the maleimide compound represented by the following formula (1), commercially available products can also be used. For example, BMI - 2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. may be mentioned. As the maleimide compound represented by formula (2), commercially available products can also be used. For example, MIR - 3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. may be mentioned. As the maleimide compound represented by formula (3), commercially available products can also be used. For example, MIR - 5000 (trade name) manufactured by Nippon Kayaku Co., Ltd. may be mentioned.,

[0057]

Chemical formula

[0058] In formula (1), each R1 independently represents a hydrogen atom or a methyl group. n1 represents an integer of 1 or more, preferably represents an integer of 1 to 10, and more preferably represents an integer of 1 to 5.,

[0059]

Chemical formula

[0060] In formula (2), each R2 independently represents a hydrogen atom or a methyl group. n2 represents an integer of 1 or more, preferably represents an integer of 1 to 5.,

[0061]

Chemical formula

[0062] In formula (3), each R3 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group; each l2 independently represents an integer of 1 to 3; and n3 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.

[0063] The crosslinking agent (D) can be used alone or in combination of two or more. The content of the crosslinking agent (D) in the colored photosensitive composition when containing the crosslinking agent (D) 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 it within the above range, the balance of sensitivity, developability, and resolution tends to be easily achieved.

[0064] The colored photosensitive composition can contain a photopolymerization initiator (E). The photopolymerization initiator (E) is not particularly limited, and a conventionally known photopolymerization initiator can be used.

[0065] Specific examples of the photoinitiator (E) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetoxyoxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylamino-2-isoamyl 4-dimethylaminobenzoate, 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-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 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’-bis-dimethylaminobenzophenone, 4,4’-bis-diethylaminobenzophenone, 4,4’-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxy triazine, 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-methoxystyryl)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxystyryl)phenyl-s-triazine, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, acetophenone dimethyl ketal, benzyldimethyl ketal, benzophenone, benzophenones such as 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bis(methylamino)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and the like can be mentioned. These photoinitiators can be used alone or in combination of two or more kinds.,

[0066] Among these, it is particularly preferable to use an oxime-based photoinitiator in terms of sensitivity. Among the oxime-based photoinitiators, particularly preferable ones include O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, ethanone, 1-[9-ethyl-6-(pyrrole-2-ylcarbonyl)-9H-carbazol-3-yl], 1-(O-acetoxyoxime), and 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone.

[0067] As described above, the colored photosensitive composition preferably contains an oxime ester compound as the photopolymerization initiator (E). The oxime ester compound is excellent in the ability to absorb ultraviolet rays and generate radicals. Therefore, the oxime ester compound has high sensitivity and can easily cure the colored photosensitive composition with a small exposure amount even when it contains a colorant (B) such as a high-concentration light-shielding agent. In the case of a colored photosensitive composition containing a large amount of the colorant (B), when the optical density of the film formed from the colored photosensitive composition is 3, the ultraviolet exposure amount in the deep layer is considerably smaller than the ultraviolet exposure amount in the surface layer (the outermost surface), but the oxime ester compound can generate radicals even with such a relatively small ultraviolet exposure amount and can cure the colored photosensitive composition well.

[0068] Further, when the above-described colorant (B) is blended in the colored photosensitive composition at a high concentration, primary aggregates (aggregates) of the colorant (B) are inevitably generated in the coating film composed of the colored photosensitive composition. However, when a colored photosensitive composition containing an oxime ester compound as the photopolymerization initiator (E) is used, the photopolymerization initiator (E) generates radicals upon ultraviolet irradiation even in a slight gap where the aggregates overlap complexly. As a result, the cured product of the colored photosensitive composition is excellent not only in adhesion to the substrate and electrical resistivity (insulating property) under the environment of normal temperature, normal humidity, and atmospheric pressure, but also in adhesion to the substrate and electrical resistivity (insulating property) even when the cured product is exposed to a high-temperature, high-humidity, and high-pressure environment. The durability under a high-temperature, high-humidity, and high-pressure environment can be confirmed by a so-called PCT test (pressure cooker test). Therefore, the cured product (colored film) of the colored photosensitive composition containing an oxime ester compound is less likely to experience a performance decline even when the use environment is high-temperature and high-humidity.

[0069] As the photopolymerization initiator (E), an oxime ester compound and a photopolymerization initiator other than the oxime ester compound may be used in combination. In this case, the 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.

[0070] As a photopolymerization initiator other than the oxime ester compound, for example, an aminoalkylphenone-based photopolymerization initiator can be preferably used. Examples of aminoalkylphenone compounds include 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (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-butylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-isobutylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)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, 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, etc. may be mentioned., Among them, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpho linophenyl)butan-1-one is preferable.,

[0071] When an aminoalkylphenone-based photopolymerization initiator is combined with the oxime ester compound, it is easy to control the cross-sectional shape of the patterned colored film formed using the colored photosensitive composition., This is presumably because aminoalkylphenone-based photoinitiators tend to generate photopolymerization radicals in the surface layer portion (the surface facing the light to be exposed and its vicinity) of the colored photosensitive composition, while oxime ester compounds tend to generate photopolymerization radicals even in the deeper layer portion of the colored photosensitive composition. This tendency becomes more prominent as the film thickness of the colored photosensitive composition increases, but it can also be observed with a film thickness of 1 μm or less. In addition, as a secondary effect of using an aminoalkylphenone-based photoinitiator together with an oxime ester compound, the sensitivity is comprehensively improved, and a cured product of the colored photosensitive composition can be obtained with a small exposure amount. Furthermore, when an aminoalkylphenone-based photoinitiator 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 easier to form a patterned colored film with fewer pattern defects.

[0072] In the colored photosensitive composition, when the photoinitiator (E) contains an oxime ester compound and an aminoalkylphenone-based photoinitiator, the ratio of the mass of the aminoalkylphenone-based photoinitiator to the total of the mass of the oxime ester compound and the mass of the aminoalkylphenone-based photoinitiator 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.

[0073] The content of the photoinitiator (E) in the colored photosensitive composition is not particularly limited as long as it does not inhibit the object of the present invention. The content of the photoinitiator (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.

[0074] 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 the curing process to improve the subsequent heat resistance and is particularly preferably used when attempting to improve the thermal decomposition resistance by reacting with carboxyl groups and hydroxyl groups contained in the colored photosensitive composition by heating.

[0075] Specific examples of the epoxy compound as the curing agent (F) include phenol novolak type epoxy resin, cresol novolak type epoxy resin, tris(hydroxyphenyl)methane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin, bisphenol-A novolak type epoxy resin, glyoxal type epoxy resin, naphthalene skeleton-containing epoxy resin, cardo skeleton-containing epoxy resin, bisphenol fluorene type epoxy resin, heterocyclic epoxy resin, and the like.

[0076] Examples of the phenol novolak type epoxy resin include Epiklon N-770 (manufactured by DIC Corporation), D.E.N438 (manufactured by Dow Chemical Company), jER154 (manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201, RE-306 (all manufactured by Nippon Kayaku Co., Ltd.), and the like. Examples of the cresol novolak type epoxy resin include Epiklon 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), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

[0077] Examples of the tris(hydroxyphenyl)methane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Company), jER E1032H60 (manufactured by Japan Epoxy Resins Co., Ltd.), and the like. Examples of the dicyclopentadiene phenol type epoxy resin include Epiron EXA-7200 (manufactured by DIC Corporation), TACTIX-556 (manufactured by The Dow Chemical Company), and the like.

[0078] 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 The Dow Chemical Company), YD-8125 (manufactured by Tokyo Chemical Industry Co., Ltd.), NER-1202, NER-1302 (both manufactured by Nippon Kayaku Co., Ltd.), etc., bisphenol-F type epoxy resins such as UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (manufactured by Tokyo Chemical Industry Co., Ltd.), NER-7403, NER-7604 (both manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0079] Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000, NC-3000-H, NC-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), the bixylenol type epoxy resin of YX-4000 (manufactured by Japan Epoxy Resins Co., Ltd.), YL-6121 (manufactured by Japan Epoxy Resins Co., Ltd.), and the like. Examples of the bisphenol A novolak type epoxy resin include Epiron N-880 (manufactured by DIC Corporation), jER E157S75 (manufactured by Japan Epoxy Resins Co., Ltd.), and the like.

[0080] Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by DIC Corporation), and the like. Examples of the caldol skeleton-containing epoxy resin include PG-100, CG-500, EG-200, EG-280 (manufactured by Osaka Gas Chemical Co., Ltd.), and the like. Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Corporation). Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

[0081] Specific examples of the oxazine compound as the curing agent (F) include, for example, B-m type benzoxazine, P-a type benzoxazine, and B-a type benzoxazine (all manufactured by Shikoku Kasei Kogyo Co., Ltd.).

[0082] The curing agent (F) can be used alone, or two or more thereof can be mixed and used. The content of the curing agent (F) is not particularly limited, but is preferably 0 to 40% by mass, more preferably 3 to 30% by mass, based on the mass of the solid content of the colored photosensitive composition. By setting the content of the polyfunctional crosslinkable compound (D) within the above range, it is easy to obtain a photosensitive resin composition capable of forming a cured film with high heat resistance.

[0083] By using the colored photosensitive composition containing the crosslinking agent (D), the photopolymerization initiator (E) in addition to the unsaturated group-containing polycarboxylic acid resin (A), the colorant (B), and the solvent (C), it can be dispersed even at a high photosensitivity and a high colorant concentration, and has good development characteristics. When necessary, by also containing the curing agent (F), the heat resistance can be improved well.

[0084] The colored photosensitive composition may contain, as other components (G), resins other than the unsaturated group-containing polycarboxylic acid (A), the crosslinking agent (D), and the curing agent (F), a surface conditioner, an adhesion improver, and various other additives, as long as the object of the present invention is not inhibited. The addition amount of the other component (G) is not particularly limited. The other component (G) in an amount within the range that does not inhibit the object of the present invention can be used.

[0085] ≪Surface conditioner≫ The surface conditioner suppresses the occurrence of surface defects and appearance defects (non-uniform distribution of colorants such as pigments) caused by non-uniform distribution of colorants such as surface tension reduction of the colored photosensitive composition. Specifically, polydimethylsiloxane, polyether-modified polysiloxane, polymethylalkylsiloxane, polysiloxane modified with an aralkyl group or a polyester chain, etc. can be preferably used.

[0086] ≪Adhesion improver≫ Known coupling agents such as silane coupling agents, titanate coupling agents, and aluminate coupling agents can be used. Among these, from the viewpoint of enhancing the adhesion to the glass substrate, a silane coupling agent can be preferably used.

[0087] The colored photosensitive composition may contain various additives other than those described above, if necessary. Specifically, examples include sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersion aids, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, thermal polymerization inhibitors, defoaming agents, surfactants, liquid repellents, chain transfer agents, photoinitiation aids, solvents, etc. Any additive can be a conventionally known one.

[0088] Examples of the surfactant include anionic compounds, cationic compounds, nonionic compounds, etc. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, etc. Examples of the defoaming agent include silicone-based compounds, fluorine-based compounds, etc. Examples of the chain transfer agent include mercaptan-based compounds, halogen-based compounds, quinone-based compounds, α-methylstyrene dimer, etc. By containing a chain transfer agent, the pattern shape (especially, CD change of the hole pattern, exposure margin) can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferable in that sublimates, coloring, and odor can be reduced in addition to the above effects. Examples of the photoinitiator aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 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 aids may be used alone or in combination of two or more.

[0089] Examples of the liquid repellent include fluorine atom-containing resins having a crosslinking group. Since it can impart ink repellency to the surface of the partition wall, it is considered that when the colored photosensitive composition is used to form the partition wall, it can prevent color mixing for each pixel. Examples of the crosslinking group include an epoxy group or an ethylenically unsaturated group. From the viewpoint of suppressing the outflow of the liquid repellent into the developer, an ethylenically unsaturated group is preferable. The fluorine atom-containing resin having a crosslinking group preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Examples of the perfluoroalkyl group include a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Examples of the perfluoroalkylene ether chain include -CF2-O-, -(CF2)2-O-, -(CF2)3-O-, -CF2-C(CF3)O-, -C(CF3)-CF2-O-, and divalent groups having these repeating units.

[0090] Specific examples of the fluorine atom-containing resin having a crosslinking group include, for example, an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, an epoxy a(meth)acrylate resin having an epoxy group and a perfluoroalkyl group, an epoxy a(meth)acrylate resin having an epoxy group and a perfluoroalkylene ether chain, an epoxy a(meth)acrylate resin having an ethylenically unsaturated group and a perfluoroalkyl group, an epoxy a(meth)acrylate resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, and the like. Among them, from the viewpoint of ink repellency, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, and an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable, and an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain is more preferable. As commercially available products of these fluorine atom-containing resins having a crosslinking group, "Megafac" (registered trademark, the same applies hereinafter) manufactured by DIC Corporation) "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", "Megafac RS304", "Megafac RS401", "Megafac RS402", "Megafac RS501", "Megafac RS502", "Megafac RS-72-K", "Megafac RS-78", "Megafac RS-90", "DEFENSA (registered trademark, the same hereinafter) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", "Florard FC430", "Florard FC431", "FC-4430", "FC4432" manufactured by 3M Japan Co., Ltd., "Asahi Guard (registered trademark) AG710", "Surflon (registered trademark, the same hereinafter) S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Surflon SC-106", etc. can be used as commercially available fluorine-containing organic compounds.

[0091] ≪Method for Preparing Colored Photosensitive Composition≫ The colored photosensitive composition is prepared, for example, by uniformly stirring and mixing the above components and uniformly dissolving and dispersing them. During mixing, a stirrer such as a roll mill, ball mill, or sand mill may be used for mixing. If necessary, it can be prepared by filtering with a filter such as a 2μm membrane filter.

[0092] ≪Colored Film and Patterned Colored Film≫ A colored film can be obtained by curing the above-described 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. The method for producing a patterned colored film includes a step of applying a colored photosensitive composition to form a coating film, a step of selectively exposing the coating film, and a step of developing the exposed coating film. By using the above-described colored photosensitive composition as a negative photosensitive composition, a highly detailed pattern with good straightness can be formed even if a high-concentration colorant is contained.

[0093] Hereinafter, each step will be described. Forming a coating film using a colored photosensitive composition is referred to as the "coating film forming step". Exposing the coating film is referred to as the "exposure step". Developing the exposed coating film is referred to as the "development step".

[0094] ≪Coating Film Forming Step≫ In the coating film forming step, the colored photosensitive composition is applied onto a substrate to form a coating film. The type of the 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 appropriately used. Examples of the substrate include quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, polymer substrates such as SOG (Spin On Glass), polyester film, polycarbonate film, and polyimide film, TFT array substrates, electrode plates of PDP, glass and transparent plastic substrates, conductive substrates such as ITO and metal, insulating substrates, and semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. Further, for example, when forming a laminated structure on a substrate, any layer that serves as a lower structure already formed on the substrate is also included in the concept of the substrate to which the colored photosensitive composition is applied. Also, the shape of the substrate is not particularly limited, and it may be plate-shaped or roll-shaped. The substrate may have unevenness on its surface depending on various patterns, for example. Also, as the above substrate, a light-transmissive or non-light-transmissive substrate can be selected.

[0095] In the coating film forming step, for example, using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, or a non-contact type coating device such as a spinner (rotary coating device), slit coater, or curtain flow coater, the colored photosensitive composition is applied onto the substrate, and if necessary, the solvent is removed by drying (pre-baking) to form a coating film.

[0096] The film thickness of the coating film is not particularly limited. As the thickness of the coating film, 0.05 μm or more is preferable, and 1 μm or more is more preferable. 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 for the thickness of the coating film, but it may be, for example, 50 μm or less, or 20 μm or less.

[0097] The coating film may be dried as necessary. The drying method is not particularly limited. Examples of the drying method include: (1) drying on a hot plate at a temperature of 80°C or higher and 120°C or lower, preferably 90°C or higher and 100°C or lower for 60 seconds or more and 120 seconds or less; (2) leaving it at room temperature for several hours to several days; (3) putting it in a hot air heater or an infrared heater for several tens of minutes to several hours to remove the solvent, etc.

[0098] ≪Exposure process≫ In the exposure process, the coating film formed in the coating film forming process is exposed. Thereby, a cured film (colored film) of the colored photosensitive composition is obtained. By selectively exposing and developing according to the pattern shape, a patterned cured film (colored film) is obtained.

[0099] In the exposure process, the coating film is exposed by irradiating the coating film with radiation or electromagnetic waves such as i-line, g-line, h-line, etc. When forming a patterned cured film (colored film), the exposure of the coating film is performed selectively by position through a negative mask. The exposure amount varies depending on the composition of the colored photosensitive composition, but is preferably about 5 mJ / cm 2 or more and 500 mJ / cm 2 or less. It is preferably about 10 mJ / cm 2 or more and 150 mJ / cm 2 or less.

[0100] The cured film cured by exposure may be heated. The temperature during heating is not particularly limited, preferably 180°C or higher and 280°C or lower, more preferably 200°C or higher and 260°C or lower, and particularly preferably 220°C or higher and 250°C or lower. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.

[0101] ≪Development process≫ In the development process, the coating film exposed in the exposure process is developed with an alkaline developer. In the development process, a cured film (colored film) patterned into a desired shape is formed by developing the exposed coating film with a developer. The development method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developer include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salts, and the like.

[0102] After development, post-baking may be performed as necessary. The temperature of the post-baking after development is preferably 80°C or higher and 250°C or lower, more preferably 100°C or higher and 230°C or lower. The time of the post-baking after development is preferably 5 minutes or longer and 60 minutes or shorter, more preferably 10 minutes or longer and 30 minutes or shorter.

[0103] By using the above-described colored photosensitive composition, as shown in the examples described later, a high-concentration colorant can be dispersed and a high-definition pattern can be formed. When it is desired to improve the heat resistance, a curing agent can be contained.

Examples

[0104] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, parts represent parts by weight unless otherwise specified.

[0105] The epoxy equivalent and acid value were measured under the following conditions. 1) Epoxy equivalent (WPE): Measured by a method in accordance with JIS K 7236:2001. 2) Acid value: Measured by 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

[0106] Production Example 1 Into a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen line, 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate-modified product of isophorone diisocyanate (manufactured by EVONIK, "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116 °C and reacted at the same temperature for 30 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1 which is the characteristic absorption of the isocyanate group completely disappeared. A solution of amide-imide resin (1) with a number average molecular weight of 1,250, a weight average molecular weight of 4,040, and a solid acid value of 164 mgKOH / g was obtained by gel permeation chromatography using polystyrene as a standard. After cooling to 60 °C, 494.5 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 154.0 g of hexahydrophthalic anhydride, and 2.27 g of dibutylhydroxytoluene were added and stirred, and then 2.27 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (I) with a solid acid value of 94.1 mgKOH / g, a (meth)acrylic equivalent of 629, a number average molecular weight of 1,870 by GPC, and a weight average molecular weight of 5,320. Also, when the epoxy equivalent was measured, it was 13,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0107] Production Example 2 Into a four-necked flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen line, 661.2 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 198.0 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116°C and reacted at the same temperature for 30 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1 which is the characteristic absorption of the isocyanate group completely disappeared. A solid content acid value of 155 mgKOH / g and an amidoimide resin (2) solution with a number average molecular weight of 1,290 and a weight average molecular weight of 3,590 based on polystyrene was obtained by gel permeation chromatography. After cooling to 60°C, 537.5 g of propylene glycol monomethyl ether acetate, 198.8 g of glycidyl methacrylate, 154.0 g of hexahydrophthalic anhydride, and 2.38 g of dibutylhydroxytoluene were added and stirred, and then 2.38 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (II) with a solid content acid value of 92.2 mgKOH / g, a (meth)acrylic equivalent of 629, a number average molecular weight of 1,710 by GPC, and a weight average molecular weight of 4,930. Also, when the epoxy equivalent was measured, it was 11,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0108] Production Example 3 Into a four-necked flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen line, 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 were added. While blowing nitrogen into the system, the temperature was raised to 116°C and reacted at the same temperature for 30 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1It was confirmed that the absorption had completely disappeared. A solid content acid value of 159 mgKOH / g of an amide imide resin (3) solution with 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 was obtained. After cooling to 60 °C, 448.0 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 123.2 g of hexahydrophthalic anhydride, and 2.17 g of dibutylhydroxytoluene were added and stirred, and then 2.17 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (III) with a solid content acid value of 85.9 mgKOH / 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. Also, when the epoxy equivalent was measured, it was 14,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0109] Production Example 4 Into a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate-modified product of isophorone diisocyanate (manufactured by EVONIK, "VESTANATT-1890 / 100", isocyanate group content 17.3 mass%), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116 °C and the reaction was carried out at the same temperature for 30 hours. The characteristic absorption of the isocyanate group at 2250 cm in the infrared spectrum -1It was confirmed that the absorption had completely disappeared. A solid content acid value of 151 mgKOH / g of an amide-imide resin (4) solution with 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 was obtained. After cooling to 60 °C, 494.8 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 154.0 g of hexahydro-4-methylphthalic anhydride, and 2.44 g of dibutylhydroxytoluene were added and stirred, and then 2.44 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (IV) with a solid content acid value of 95.8 mgKOH / 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. Also, when the epoxy equivalent was measured, it was 12,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0110] Production Example 5 Into a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate-modified product of isophorone diisocyanate (manufactured by EVONIK, "VESTANATT-1890 / 100", isocyanate group content 17.3 mass%), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116 °C and the reaction was carried out at the same temperature for 30 hours. The characteristic absorption of the isocyanate group at 2250 cm -1It was confirmed that the absorption had completely disappeared. A solid content acid value of 152 mgKOH / g amide-imide resin (5) solution with 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 was obtained. After cooling to 60 °C, 491.7 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 152.2 g of 1,2,3,6-tetrahydrophthalic anhydride, and 2.31 g of dibutylhydroxytoluene were added and stirred, and then 2.31 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (V) with a solid content acid value of 97.9 mgKOH / 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. Also, when the epoxy equivalent was measured, it was 14,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0111] Production Example 6 Into a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen line, 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate-modified product of isophorone diisocyanate (manufactured by EVONIK, "VESTANATT-1890 / 100", isocyanate group content 17.3 mass%), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. The characteristic absorption of the isocyanate group at 2250 cm in the infrared spectrum -1It was confirmed that the absorption had completely disappeared. A solid content acid value of 161 mgKOH / g amide-imide resin (6) solution with 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 was obtained. After cooling to 60°C, 261.9 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, and 1.90 g of dibutylhydroxytoluene were added and stirred, and then 1.90 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (I') with a solid content acid value of 19.2 mgKOH / g, a number average molecular weight of 1,740 by GPC, and a weight average molecular weight of 6,950. Also, when the epoxy equivalent was measured, it was 13,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0112] Production Example 7 Into a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen line, 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate-modified product of isophorone diisocyanate (manufactured by EVONIK, "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116°C and the reaction was carried out at the same temperature for 30 hours. The characteristic absorption of the isocyanate group at 2250 cm in the infrared spectrum -1It was confirmed that the absorption had completely disappeared. A solid content acid value of 154 mgKOH / g of an amide-imide resin (7) solution with 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 was obtained. After cooling to 60 °C, 494.5 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 148.1 g of phthalic anhydride, and 1.90 g of dibutylhydroxytoluene were added and stirred, and then 1.90 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (II') with a solid content acid value of 99.5 mgKOH / 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. Also, when the epoxy equivalent was measured, it was 14,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0113] Production Example 8 Into a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate-modified product of isophorone diisocyanate (manufactured by EVONIK, "VESTANATT-1890 / 100", isocyanate group content 17.3 mass%), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. 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. The characteristic absorption of the isocyanate group at 2250 cm -1It was confirmed that the absorption had completely disappeared. After cooling to 60°C, 97.58 g of pentaerythritol (tri / tetra) acrylate mixture ("PETRA" manufactured by Daicel Ornex Co., with a hydroxyl value of 115 mg KOH / g) was added, the temperature was raised to 116°C, and the reaction was carried out at the same temperature for 10 hours. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,070, and the weight average molecular weight was 3,080. An amide imide resin (8) solution with a solid acid value of 135 mg KOH / g was obtained. After cooling to 60°C, 494.8 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 154.0 g of hexahydro-4-methylphthalic anhydride, and 2.44 g of dibutylhydroxytoluene were added and stirred, and then 2.44 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (III') with a solid acid value of 82.1 mg KOH / g, 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. Also, when the epoxy equivalent was measured, it was 15,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0114] Production Example 9 Into a four-necked flask equipped with a stirring device, a thermometer and a condenser, 250.3 g of propylene glycol monomethyl ether acetate, 435.7 g of cresol novolak 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 temperature was raised to 116 °C, and the reaction was carried out at the same temperature for 12 hours to obtain a reactive carboxylate resin (9) solution having a solid acid value of 2.2 mg·KOH / g and an epoxy equivalent of 13 kg / eq. It 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 temperature was raised to 100 °C. The reaction was carried out at the same temperature for 5 hours to obtain an unsaturated group-containing polycarboxylic acid resin (IV') having a solid acid value of 61.2 mgKOH / g, a (meth)acrylic equivalent of 349, a number average molecular weight of 2058 by GPC, and a weight average molecular weight of 6420. Also, when the epoxy equivalent was measured, it was 13,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0115] Production Example 10 The resin described in Example 2-1 of Patent-6576161 was produced as described, and a reactive polycarboxylic acid compound (V') having a solid acid value of 61.5 mgKOH / g, a (meth)acrylic equivalent of 335, a number average molecular weight of 1830 by GPC, and a weight average molecular weight of 3520 was obtained.

[0116] Production Example 11 Into a four-necked flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen line, 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate-modified isophorone diisocyanate (manufactured by EVONIK, "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116 °C and reacted at the same temperature for 30 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1 which is the characteristic absorption of the isocyanate group completely disappeared. A solid content acid value of 152 mgKOH / g and an amide imide resin (5) solution with a number average molecular weight of 1,310 and a weight average molecular weight of 3,810 based on polystyrene was obtained by gel permeation chromatography. After cooling to 60 °C, 338.6 g of propylene glycol monomethyl ether acetate, 142.0 g of glycidyl methacrylate, 79.2 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and 2.31 g of dibutylhydroxytoluene were added and stirred, and then 2.31 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (VI) with a solid content acid value of 87.1 mgKOH / g, a (meth)acrylic equivalent of 652, a number average molecular weight of 1,870 by GPC, and a weight average molecular weight of 6,010. Also, when the epoxy equivalent was measured, it was 16,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0117] Production Example 12 Into a four-necked flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen line, 646.3 g of propylene glycol monomethyl ether acetate, 242.8 g of an isocyanurate-modified isomer of isophorone diisocyanate (manufactured by Evonik, "VESTANATT-1890 / 100", isocyanate group content 17.3% by mass), and 188.1 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. While blowing nitrogen into the system, the temperature was raised to 116 °C and the reaction was carried out at the same temperature for 30 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1 corresponding to the characteristic absorption of isocyanate groups completely disappeared. A solid content acid of 156 mg KOH / g and an amidoimide resin (5) solution with a number average molecular weight of 1,260 and a weight average molecular weight of 3,600 were obtained by gel permeation chromatography using polystyrene as a standard. After cooling to 60 °C, 441.4 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 118.8 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, and 2.31 g of dibutylhydroxytoluene were added and stirred, and then 2.31 g of triphenylphosphine was added and the temperature was raised to 116 °C. The reaction was carried out at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (VII) with a solid content acid value of 80.6 mg KOH / g, a (meth)acrylic equivalent of 600, a number average molecular weight of 1,870 by GPC, and a weight average molecular weight of 6,010. Also, when the epoxy equivalent was measured, it was 14,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0118] [Example 1, Comparative Example 1] Preparation of colored photosensitive composition and evaluation of kneading dispersibility In Examples and Comparative Examples, 20 g of the unsaturated group-containing polycarboxylic acid resin obtained in Production Examples 1 to 10 was used, and Mitsubishi Carbon Black MA-100 (B1) was used as the colorant (B). As the solvent (C), propylene glycol monomethyl ether acetate (C1) was used, and it was kneaded with a bead mill, and the state after kneading was confirmed. The obtained colored photosensitive composition was marked as ○ if it was uniform, and × if it was non-uniform or gelation occurred due to the resin. Table 1 shows the evaluation results of the ratio of the colored photosensitive composition and the state after kneading.

[0119] [Table 1]

[0120] [Example 2, Comparative Example 2] Preparation of Colored Photosensitive Composition and Evaluation of Dispersibility of Colorant To the colored photosensitive compositions obtained in Example 1 and Comparative Example 1, as a crosslinking agent (D), DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.) (D1), and further 20 g of glass beads were added, and dispersion was carried out for 1 hour with a paint shaker. The dispersion liquid after the dispersion was coated on a polyethylene terephthalate film with a wire bar coater #2 and dried for 10 minutes with a hot air dryer at 80°C. The gloss of the coating film surface after drying was measured using a 60° reflection gloss meter (Horiba IG-331 gloss meter), and the dispersibility of carbon black was evaluated. The results are shown in Table 2. The higher the gloss value, the better the pigment dispersibility.

[0121] [Table 2]

[0122] [Example 3, Comparative Example 3] Preparation of Colored Photosensitive Composition and Evaluation of Developability The unsaturated group-containing polycarboxylic acid resin (A), colorant (B1), solvent (C1), crosslinking agent (D), and photopolymerization initiator (E) obtained in Production Examples 1 to 10 were uniformly dispersed in the formulations shown in Table 3 to obtain a resist resin composition. In the examples and comparative examples, as the crosslinking agent (D), DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.: ε-caprolactone-modified dipentaerythritol hexaacrylate) (D2), as the photopolymerization initiator (E), Irgacure 907 (manufactured by Ciba Specialty Chemicals) (E1) and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2), and as the curing agent (F), YD-134 (manufactured by Nippon Steel Chemical & Material Co., Ltd.: bisphenol-A type epoxy resin) (F1), and as the thermosetting catalyst (G), TPP (manufactured by Kitakyo Chemical Industry Co., Ltd.: triphenylphosphine) (G1) were used.

[0123] Each item of the evaluation items will be described in detail.

[0124] Developability evaluation (abbreviation in the table: developability) The colored photosensitive composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) to a thickness of 20 μm using an applicator, and the coating film was dried for 30 minutes with a hot air dryer at 80 °C. For the dried coating film, through a mask with an opening of 50 μm, using an ultraviolet irradiator (USHIO, ultra-high pressure mercury lamp), curing was performed at an irradiation dose of 150 mJ / cm 2 Then, spray development was performed using a 1% aqueous sodium carbonate solution as the developer. The time until the coating film in the unexposed area was completely dissolved, that is, the so-called break time, was used as the evaluation of developability (unit: seconds). △ ·· Film reduction × ·· Pattern straightness ×× ·· Swelling and peeling;

[0125] Regarding "film reduction", it was obtained from the film thickness of the coating film before development and the height of the cross-section of the pattern after development. When there was film reduction, it was evaluated as △ instead of the break time. (Using an electron microscope) Regarding "pattern straightness", when it was bent, it was evaluated as ×. When there was no pattern straightness and it could not be formed neatly, it was evaluated as × instead of the break time. (Using an electron microscope) Regarding "swelling and peeling", when the coating film swelled and peeled instead of dissolving and developing during development, it was evaluated as ×× instead of the break time.

[0126] Thermal decomposition resistance evaluation (abbreviation in the table: thermal decomposition resistance) The colored photosensitive composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) to a thickness of 20 μm using an applicator, and after the coating film was dried for 30 minutes with a hot air dryer at 80 °C, using an ultraviolet irradiator (GS YUASA, CS 30L-1), 500 mJ / cm 2It was irradiated with ultraviolet rays using the energy of . Next, it was cured at 150 °C for 30 minutes in an oven to obtain a cured product. The copper foil was removed with iron(III) chloride 45° Pome (manufactured by Junsei Chemical Co., Ltd.). 3 mg of the sample prepared from the cured product was measured for the temperature at which the weight decreased by 5% using TGA / DSC1 manufactured by METTLER in an air flow of 100 ml per minute.

[0127] [Table 3]

[0128] From the above results, it can be confirmed that the coating film obtained from the colored photosensitive composition of the present invention has excellent dispersibility of the colorant, high developability, and the cured product is also excellent in thermal decomposition resistance.

[0129] [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 was used, and Mitsubishi Carbon Black MA-100 (B1) was used as the colorant (B). It was kneaded with a bead mill, and the state after kneading was confirmed. The obtained colored photosensitive composition was marked as ○ if it was uniform, and × if it was non-uniform or gelation occurred due to the resin.

[0130] [Table 4]

[0131] [Example 5] Preparation of colored photosensitive composition and evaluation of colorant dispersibility To the colored photosensitive compositions obtained in Examples 4-1, 4-2, and 4-3, as a crosslinking agent (D), DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.) (D1) was added, and further 20 g of glass beads were added, followed by dispersion with a paint shaker for 1 hour. The dispersion liquid after the dispersion was applied onto a polyethylene terephthalate film using a wire bar coater #2 and dried with a hot air dryer at 80 °C for 10 minutes. The gloss of the surface of the coating film after drying was measured using a 60° reflection gloss meter (HORIBA IG-331 gloss meter), and the dispersibility of carbon black was evaluated. The results are shown in Table 5. The higher the gloss value, the better the pigment dispersibility.

[0132] [Table 5]

[0133] [Example 6] Preparation and developability evaluation of colored photosensitive composition The unsaturated group-containing polycarboxylic acid resin (A), colorant (B1), solvent (C1), crosslinking agent (D), and photopolymerization initiator (E) obtained in Production Examples 11 and 12 were uniformly dispersed according to the formulations shown in Table 3 to obtain a resist resin composition. In the examples, as the crosslinking agent (D), DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.: ε-caprolactone-modified dipentaerythritol hexaacrylate) (D2) was used, as the photopolymerization initiator (E), Irgacure 907 (manufactured by Ciba Specialty Chemicals) (E1) and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2) were used, and as the curing agent (F), YD-134 (manufactured by Nippon Steel Chemical & Material Co., Ltd.: bisphenol-A type epoxy resin) (F1) was used, and as the thermosetting catalyst (G), TPP (manufactured by Hokko Chemical Industry Co., Ltd.: triphenylphosphine) (G1) was used.

[0134] For each of the evaluation items, it was the same as in Example 3. The evaluation results of each evaluation item are shown in Table 6.

[0135] [Table 6]

[0136] 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 its cured product is also excellent in thermal decomposition resistance.

[0137] As described above, since the coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility, high developability, and its cured product is also excellent in heat resistance, it is suitable for a partition wall having a light-shielding effect for an image display device, a black matrix, a colored spacer, and a color resist.

Claims

1. 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 acid anhydride group, which is obtained by reacting an alicyclic isocyanurate type polyisocyanate (a1) and an alicyclic tricarboxylic anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule and only an aliphatic dicarboxylic anhydride or an aliphatic tricarboxylic anhydride (c), a colorant (B), and a solvent (C).

2. The colored photosensitive composition according to Claim 1, containing a crosslinking agent (D).

3. The colored photosensitive composition according to Claim 1, further containing a photopolymerization initiator (E).

4. The colored photosensitive composition according to Claim 1, further containing a curing agent (F).

5. The colored photosensitive composition according to Claim 1, wherein the colorant (B) contains a black pigment.

6. A cured product of the colored photosensitive composition according to any one of Claims 1 to 5.

7. An image display device including the cured product according to Claim 6.

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