KR20230049564A - Colored photosensitive composition, cured product and image display device including the cured product - Google Patents

Abstract

The purpose of the present invention is to provide a colored photosensitive composition having excellent dispersibility of colorants and the like, and also having good developing properties even at a high colorant concentration, further, a colored photosensitive composition having good heat resistance, and a cured product thereof. The colored photosensitive composition comprises: a polycarboxylic acid resin (A) containing an unsaturated group obtained by making a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride, or aliphatic tricarboxylic anhydride (c) react with a polyamide imide resin (a3) having a terminal acid group or acid anhydride group obtained by making alicyclic isocyanurate type polyisocyanate (a1) react with alicyclic tricarboxylic acid anhydride (a2); a colorant (B); and a solvent (C).

Description

An image display device comprising a colored photosensitive composition, a cured product, and a cured product

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

In conventional displays, color filters, colored spacers, and black matrices in which red, green, and blue pixels using organic pigments are formed are frequently used.

In recent years, color filters in which pixels are formed using luminescent nanocrystal particles such as quantum dots have been studied for low power consumption and wide color gamut of displays. Specifically, it is known to have red pixels containing red luminescent nanocrystal particles, green pixels containing green luminescent nanocrystal particles, and blue pixels that transmit blue light from a light source.

As a manufacturing method of a color filter, there exist a photolithography method and an inkjet method, and it is known that the latter can reduce the loss of an ink material (patent document 1).

When a color filter containing luminescent nanocrystal particles is manufactured by an inkjet method, a pixel is formed by ejecting ink to a region (pixel portion) surrounded by a barrier rib prepared in advance. In addition to preventing mixing of inks between adjacent pixel portions, a high-definition pattern (fine pattern) is required for this barrier rib. Moreover, what is formed by the photolithography method using the photosensitive composition (coloring photosensitive composition) containing a coloring agent as what has a light-shielding effect is known (patent document 2).

In addition, an attempt to apply 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 is also known (Patent Document 3).

Japanese Unexamined Patent Publication No. 2019-086745 Japanese Unexamined Patent Publication No. 2007-10795 Japanese Unexamined Patent Publication No. 2005-055814

However, when the photosensitive composition of Patent Document 2 is used, there is a problem that developability of a pattern obtained by a photolithography method is poor, and a pattern having a desired shape cannot be obtained or cannot be formed. Moreover, in the barrier rib which has a light-shielding effect, a black matrix, a colored spacer, and a color resist, even if it contains an additional coloring agent, the coloring photosensitive composition with favorable dispersibility is required.

The present invention improves the above-described problems of the prior art, and provides a colored photosensitive composition having excellent dispersibility of a colorant and the like and having good development characteristics even at a high colorant concentration, and further, a colored photosensitive composition having good heat resistance, and their It is intended to provide cargo.

As a result of diligent efforts to solve the above problems, the inventors of the present invention have found a polyisocyanate (a1) and an alicyclic tricarboxylic acid anhydride (a2) having a terminal acid group or an acid anhydride group. An unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting an amidimide resin (a3) with a (meth)acrylate compound (b) having an epoxy group in one molecule and an aliphatic dicarboxylic acid anhydride (c), and a colorant (B); The coloring photosensitive composition containing the solvent (C) is excellent in the dispersibility of the coloring agent and the like, and also has good developing characteristics even at a high coloring agent concentration, and in some cases, the coloring photosensitive composition with good heat resistance, and their I found one that provides freight.

That is, the present invention relates to the following (1) to (7).

(1) An epoxy group in one molecule of a polyamideimide resin (a3) having a terminal acid group or an acid anhydride group obtained by reaction of an alicyclic isocyanurate type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2) (meth)acrylate compound (b) and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c) obtained by reacting an unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), and a solvent (C) It is a coloring photosensitive composition containing.

(2) It is the coloring photosensitive composition as described in (1) containing a crosslinking agent (D).

(3) It is the coloring photosensitive composition as described in (1) or (2) containing a photoinitiator (E).

(4) It is the coloring photosensitive composition as described in any one of (1)-(3) containing a hardening|curing agent (F).

(5) The said coloring agent (B) is the coloring photosensitive composition as described in any one of (1)-(4) containing a black pigment.

(6) It is a hardened|cured material of the coloring photosensitive composition in any one of (1)-(5).

(7) It is an image display apparatus provided with the hardened|cured material of (6).

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

(Mode for implementing the invention)

«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).

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

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 has a terminal acid group or an acid anhydride group obtained by reacting an alicyclic isocyanurate type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2). It is obtained by making polyamideimide resin (a3) react with the (meth)acrylate compound (b) which has an epoxy group in one molecule, and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c).

That is, the unsaturated group-containing polycarboxylic acid resin (A) in the present invention is produced with two reaction steps. First, it is a step of obtaining a polyamide-imide resin (a3) by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2). In the present invention, this step is referred to as an amide imidation step.

Next, it is a step of reacting the obtained polyamideimide resin (a3), the (meth)acrylate compound (b) having an epoxy group in one molecule, and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c). In the present invention, this step is referred to as a carboxylation step.

First, the amidimidization step will be described in detail.

The alicyclic isocyanurate-type polyisocyanate (a1) used in the production of the polyamideimide resin (a3) in the present invention is a diisocyanate compound containing an alicyclic diisocyanate compound in the presence or absence of a trimerization catalyst. It is obtained by isocyanurate-izing under.

In relation to the present invention, the alicyclic in the present specification means a compound in which carbon atoms are arranged in a ring (as already suggested by the same point as the two terms "aliphatic" and "cyclic" are described together) ). Therefore, alicyclic is also a synonym for cyclic aliphatic. Consequently, alicyclic compounds belong to the group of isocyclic compounds, and in this case include cycloalkanes, cycloalkenes, and cycloalkynes. Aromatic compounds and heterocyclic compounds, and examples of saturated compounds of heterocyclic compounds are not regarded as alicyclics within the meaning of the present invention.

As diisocyanate containing an alicyclic diisocyanate compound, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate etc. are mentioned, for example.

As the trimerization catalyst, for example, 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl) is not particularly specified. amine compounds such as hexahydro-S-triazine; alkali metal salts of carbonic acids having 2 to 12 carbon atoms such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate; and quaternary ammonium salts of carboxylic acids. As commercially available products, DABCO P15 (manufactured by Sankyo Air Products), DABCO K15 (manufactured by Sankyo Air Products), PELCAT9540 (manufactured by Pellon), DABCO TMR (manufactured by Sankyo Air Products), TOYOCAT TR20 (manufactured by Tosoh), U-CAT 18X (San-Apro) production), etc.

Examples of the alicyclic isocyanurate-type polyisocyanate (a1) include alicyclic isocyanurate-type triisocyanates synthesized from isophorone diisocyanate (including polymers such as pentamers), hydrogenated tolylene diisocyanate Alicyclic isocyanurate-type triisocyanate synthesized from (including polymers such as pentamers), alicyclic isocyanurate-type triisocyanates synthesized from hydrogenated xylene diisocyanate (including polymers such as pentamers) , isocyanurate-type triisocyanate synthesized from norbornane diisocyanate (including polymers such as pentamers), alicyclic isocyanurate-type triisocyanates synthesized from hydrogenated diphenylmethane diisocyanate (including pentamers, etc.) including polymers) and the like. Especially, the alicyclic isocyanurate type isocyanate synthesize|combined from isophorone diisocyanate is preferable. By using an alicyclic isocyanurate-type polyisocyanate synthesized from isophorone diisocyanate, tackiness and curing shrinkage are excellent.

As the alicyclic tricarboxylic acid anhydride (a2) used in the production of the polyamideimide resin (a3) in the present invention, 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, and the like are exemplified. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, which is excellent in tackiness and curing shrinkage, is preferable.

The reaction between the alicyclic isocyanurate-type polyisocyanate (a1) and the alicyclic tricarboxylic acid anhydride (a2) is an acid based on 1 mol of the isocyanate group of the alicyclic isocyanurate-type polyisocyanate (a1). The total of the anhydride group and the carboxylic acid is preferably 1.0 mol to 3.0 mol, more preferably 1.2 mol to 2.8 mol, still more preferably 1.4 mol to 2.6 mol. When the total amount of the acid anhydride group and the carboxylic acid is 1.0 mol or more, the remaining isocyanate group is prevented, the high molecular weight formation is suppressed, and the developability becomes good. When the total amount of the acid anhydride group and the carboxylic acid is 3.0 mol or less, the remaining of the alicyclic tricarboxylic acid anhydride can be prevented, and it can be suppressed from becoming a development residue.

The said amidimidation process uses the organic solvent which does not have a non-solvent or a hydroxyl group. Although specifically included in the solvent (C), for example, ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol dimethyl ether, ethylene glycol ethylene glycol dialkyl ethers such as 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 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 glycol monoalkyl ether acetates; 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 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. propylene glycol monoalkyl ether acetates; or dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers, and monoacetate monoalkyl ethers of copolymerized polyether glycols; or alkyl esters of these polyether glycols; Monoalkyl ester monoalkyl ethers of polyether glycol, and furthermore, a crosslinking agent (D) without a hydroxyl group among the crosslinking agents (D) described later can be reacted alone or in a mixed organic solvent.

In the amidimide reaction, at least one alicyclic isocyanurate-type polyisocyanate (a1) and at least one alicyclic tricarboxylic acid anhydride (a2) are mixed in a solvent or in the absence of a solvent, and stirring It is preferable to perform by raising the temperature while performing.

The reaction temperature of the amidimidation reaction is preferably in the range of 50°C to 250°C, particularly preferably in the range of 70°C to 180°C. By setting it as such a reaction temperature, it has the effect of accelerating the reaction rate. In the reaction, an anhydride group and an isocyanate group form an imide group, and a carboxylic acid group and an isocyanate form an amide group while accompanying decarboxylation. In the case of reaction, antioxidant, leveling agent, antifoaming agent, surfactant, etc. can be used as needed.

The progress of the amidimidation reaction can be tracked by analytical means such as infrared spectrum, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and quantification of isocyanate groups. . In the infrared spectrum, the characteristic absorption of the isocyanate group at 2270 cm ⁻¹ decreases along with the reaction, and the acid anhydride group having characteristic absorption at 1860 cm ⁻¹ and 850 cm ⁻¹ further decreases. On the other hand, absorption of ^the imide group increases at 1780 cm ⁻¹ and 1720 cm ⁻¹ . It is preferable to proceed the reaction until 2270 cm ⁻¹ , which is the characteristic absorption of the isocyanate group ^, is lost because it is easy to control the reaction.

As a preferable molecular weight range of the polyamideimide resin (a3) having a terminal acid group or an acid anhydride group obtained by the reaction of the alicyclic isocyanurate-type polyisocyanate (a1) with the alicyclic tricarboxylic acid anhydride (a2), GPC The polystyrene equivalent weight average molecular weight in the range is from 1000 to 20,000, more preferably from 1,500 to 15,000, and particularly preferably from 2000 to 10,000.

Next, the carboxylation step will be described in detail.

As the (meth)acrylate compound (b) having an epoxy group in one molecule used in the production of the unsaturated group-containing polycarboxylic acid resin (A), other specific structures as long as they have a (meth)acryloyl group and an epoxy group in the molecular structure is not particularly limited, and a wide variety of compounds can be used. Examples thereof include glycidyl group-containing (meth)acrylates such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate. acrylate monomer; Mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether etc. can be mentioned. These epoxy group-containing (meth)acrylate compounds may be used independently or may use 2 or more types together. Among these, from the viewpoint of easy control of the reaction, a (meth)acrylate compound having one epoxy group is preferable, and from the viewpoint of reactivity and curability, glycidyl methacrylate and epoxycyclohexylmethyl methacrylate are preferable. .

In addition, the molar ratio ((b)/(a2)) of the (meth)acrylate compound (b) having an epoxy group in one molecule and the alicyclic tricarboxylic acid anhydride (a2) is in the range of 0.8 to 2.0. It is preferable from the viewpoint of curing shrinkage and sensitivity. More preferably, it is 0.9 to 1.80, and it is still more preferable that it is 1.0 to 1.5.

Examples of the aliphatic dicarboxylic acid anhydride used in the production of the unsaturated group-containing polycarboxylic acid resin (A) or the aliphatic tricarboxylic acid anhydride (c) include succinic anhydride, 1,2-cyclopropanedicarboxylic acid anhydride, 2 ,2-dimethylsuccinic anhydride, charonic anhydride, 1,2-cyclohexanedicarboxylic anhydride, butylsuccinic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, n-octylsuccinic anhydride, decylsuccinic anhydride, dodecyl anhydride Silsuccinic acid anhydride etc. are mentioned. Moreover, as an aliphatic tricarboxylic acid anhydride, the tricarboxylic acid anhydride which has a linear aliphatic structure, the tricarboxylic acid anhydride which has an alicyclic structure, etc. are mentioned. As a tricarboxylic acid anhydride which has a linear aliphatic structure, propane tricarboxylic acid anhydride etc. are mentioned, for example. As a tricarboxylic acid anhydride which has an alicyclic structure, the thing similar to the compound illustrated for the said alicyclic tricarboxylic acid anhydride (a2) is mentioned, for example. Among these, aliphatic dicarboxylic acid anhydrides are preferable from the viewpoint of electrical properties. Further, tricarboxylic acid anhydrides having an alicyclic structure and the like are preferable from the viewpoints of aqueous alkali solution developability, heat resistance, hydrolysis resistance, and the like. Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is more preferred.

In addition, the molar ratio ((c)/(b)) of the aliphatic dicarboxylic acid anhydride or aliphatic tricarboxylic acid anhydride (c) and the (meth)acrylate compound (b) having an epoxy group in one molecule satisfies 0.05 to 1.5. It is preferable from a viewpoint of developability and storage stability that it is the range which does. More preferably, it is 0.1-1.2.

In the case of the reaction, it is preferable to add a thermal polymerization inhibitor in order to suppress the thermal polymerization reaction, and the amount of the thermal polymerization inhibitor used is to have an epoxy group in one molecule of the polyamideimide resin (a3) having a terminal acid group or an acid anhydride group. It is 0.05-10 mass parts with respect to 100 mass parts of total amounts of the (meth)acrylate compound (b), the aliphatic dicarboxylic acid anhydride, or the aliphatic tricarboxylic acid anhydride (c), and the solvent added. Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2,6-ditertiary butyl-p-cresol.

In the case of the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is (meth)acrylate having an epoxy group in one molecule of the polyamideimide resin (a3) having a terminal acid group or an acid anhydride group. It is 0.05-10 mass parts with respect to 100 mass parts of the total amount of the compound (b), the aliphatic dicarboxylic acid anhydride, or the aliphatic tricarboxylic acid anhydride (c), and the total amount of the reactants adding a solvent. The reaction temperature at that time is 60 to 150°C, and the reaction time is preferably 3 to 60 hours. As a catalyst used in this reaction, for example, dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, Methyltriphenylstibin, 2-ethylhexanoate chromium, octanoate chromium, 2-ethylhexanoate zinc, octanoate zinc, octanoate zirconium, dimethylsulfide, diphenylsulfide, etc. are mentioned.

The carboxylation process may be performed by diluting with no solvent or an organic solvent. As the said organic solvent, the thing similar to the solvent illustrated in the said amidimidization process is mentioned, for example.

The reaction temperature in the carboxylation step is preferably in the range of 60°C to 160°C, particularly preferably in the range of 70°C to 150°C, and the reaction time is preferably 3 to 60 hours.

The reaction of the carboxylation step is preferably carried out until the epoxy equivalent (solid epoxy equivalent) becomes 10,000 g/eq or more. The solid epoxy equivalent is measured by a normal neutralization titration method according to JIS K 7236. In addition, if the concentration of the resin in the solution is known, the solid epoxy equivalent can be calculated and obtained from the epoxy equivalent of the solution.

Unsaturated obtained by reacting a (meth)acrylate compound (b) having an epoxy group in one molecule with a polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group and an aliphatic dicarboxylic acid anhydride or an aliphatic tricarboxylic acid anhydride (c) As a preferable molecular weight range of the group-containing polycarboxylic acid resin (A), the weight average molecular weight in terms of polystyrene 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.

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 10% by mass or more, based on the total solid content. It is 15 mass % or more, and is usually 90 mass % or less, preferably 80 mass % or less, and more preferably 70 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, even more preferably 15 to 80% by mass, and particularly preferably 15 to 70% by mass.

The said coloring photosensitive composition contains coloring agents (B), such as a light-shielding agent.

As a coloring agent (B), a light-shielding agent and coloring agents other than a light-shielding agent are mentioned.

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

≪Carbon black≫

As carbon black, various carbon blacks conventionally used as a light-shielding agent can be used. As carbon black, specifically, well-known carbon blacks, such as channel black, furnace black, thermal black, and lamp black, can be used. Further, carbon black coated with an organic material such as resin, dye, or acidic group-containing compound may be used. Carbon black may be used individually by 1 type, and may be used in combination of 2 or more type.

≪Dye≫

What is necessary is just to select a dye suitably from well-known materials.

Examples of dyes applicable to the colored photosensitive composition include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and phthalocyanine dyes. etc. can be mentioned.

In addition, these dyes can be dispersed in an organic solvent or the like by raking (salting), and can be used as a light-shielding agent.

Other than these dyes, for example, Japanese Unexamined Patent Publication No. 2013-225132, Japanese Unexamined Patent Publication No. 2014-178477, Japanese Unexamined Patent Publication No. 2013-137543, Japanese Unexamined Patent Publication No. 2011-38085, Japanese Unexamined Patent Publication 2014- The dyes described in No. 197206 and the like can also be preferably used.

Specific examples of other colorants include compounds classified as pigments in the color index (C.I.; published by The Society of Dyers and Colourists), specifically, those with the following color index (C.I.) numbers attached. can hear

C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same, only numbers are written), 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 ; C.I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same, only numbers are written), 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 "C.I. Pigment Violet" is the same and only numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; C.I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same, only numbers are written), 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 ; , 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; C.I. Pigment Blue 1 (hereinafter "C.I. Pigment Blue" is the same and only numbers are described), 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.

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

The form of the coloring agent (B) used for preparation of a colored photosensitive composition is not specifically limited. The coloring agent (B) may be used as a powder or as a dispersion. A coloring agent (B) is preferably used as a dispersion liquid for preparation of a colored photosensitive composition.

As a dispersion liquid, you may use the dispersion liquid containing 2 or more types of colorants (B). Moreover, you may use 2 or more types of dispersion liquids each containing different types of colorants.

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

A dispersing agent may be added to the coloring agent (B) in order to stabilize the dispersion of the coloring agent (B) in the dispersion and improve the dispersibility of the coloring agent (B) in the colored photosensitive composition.

As the dispersing agent, it is preferable to use a polymeric dispersing agent such as a polyethyleneimine dispersing agent, a urethane dispersing agent, or an acrylic resin dispersing agent. Among these dispersants, urethane-based dispersants are preferred from the viewpoint of the difficulty in generating residues after development.

Moreover, you may use dispersion aids, such as a copper compound. As a copper compound, copper phthalocyanine is mentioned, for example.

In addition, corrosive gas resulting from the dispersant may be generated from the cured film. For this reason, it is also an example of a preferable aspect that the colorant (B) is subjected to dispersion treatment without using a dispersant.

The ratio of the dispersant in the coloring agent (B) in case the coloring agent (B) contains the dispersant is, for example, 5 mass% or more and 60 mass% or less, and 10 mass% or more and 50 mass% or less are preferable.

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 a value measured at 25° C. by a cone plate viscometer.

As for the particle diameter of the coloring agent (B) in a dispersion liquid, 80 nm or more and 300 nm or less are preferable as a dispersion average particle diameter. The average dispersion particle diameter can be measured using a laser diffraction type particle size distribution analyzer.

Although the content ratio of the coloring agent (B) with respect to the mass of the whole solid content of the coloring photosensitive composition is not specifically limited, The upper limit of the total amount of content of the coloring agent (B) should just be 70 mass % or less, and just 65 mass % or less, 60 It is good if it is 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, it can define as a value which includes the amount of the dispersing agent which exists together with a coloring agent (B) with respect to the amount of the coloring agent (B) mentioned above.

The coloring photosensitive composition contains a solvent (C). Examples of the solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, and 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, di (poly)alkylene glycol monoalkyl ethers such as propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-Hydroxy-2-methylethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyacetate ethyl, hydroxyacetate ethyl, 2 -Hydroxy-3-methylbutanoate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 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, other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc., benzyl esters of aliphatic carbon acids such as benzyl acetate, benzyl propionate, benzyl butanoate, and benzyl pentanoate can be heard These solvents may be used alone or in combination of two or more.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Methoxybutyl acetate is preferable since it shows excellent solubility with respect to the photoinitiator (E) shown later, and it is especially preferable to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. In addition, from the viewpoint of coating properties, etc., the above-mentioned preferable solvent may be used in combination with the above-mentioned benzyl ester of aliphatic carboxylic acid, and the content of the benzyl ester of aliphatic carboxylic acid in the case of containing the above-mentioned benzyl ester of aliphatic carboxylic acid is the solvent ( C) It is preferable that it is 1 mass % or more and 10 mass % or less with respect to the whole. The content of the solvent (C) is not particularly limited, but the solid content concentration of the photosensitive composition is preferably 1% by mass or more and 80% by mass or less, and more preferably 5% by mass or more and 70% by mass or less.

The said photosensitive resin composition may contain the crosslinking agent (D). Examples of the crosslinking agent (D) used in the photosensitive resin composition include compounds such as radical reactive acrylates, cation reactive epoxy compounds, vinyl compounds sensitive to both, and maleimide compounds.

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

Examples of the monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, and polyethylene glycol (meth)acrylate. rate, 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, butoxymethoxy Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, sheet Laconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2- Hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2 -Trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, half (meth)acrylate of a phthalic acid derivative, etc. are mentioned. These monofunctional monomers can be used alone or in combination of two or more.

Examples of the polyfunctional (meth)acrylates include butanedioldi(meth)acrylate, hexanedioldi(meth)acrylate, neopentylglycoldi(meth)acrylate, and nonanedioldi(meth)acrylate. , Decanedioldi(meth)acrylate, dodecanedioldi(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acrylate ) 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 Acrylate, bisphenol di(meth)acrylate, di(meth)acrylate which is a ε-caprolactone adduct of hydroxypivalic acid neopentyl glycol, poly(meth)acrylate which is a reaction product of dipentaerythritol and ε-caprolactone , dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tri(meth)acrylate or its Ethylene oxide adduct, pentaerythritol tetra(meth)acrylate or its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate or its ethylene oxide adduct, ethoxylated hexanediol di(meth)acrylate, tri Cyclodecanedimethanol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate Rate, tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, poly(ethylene-propylene) glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxy Hydrogenated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di( meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, glycerin di(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolye Toxyphenyl) propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di( meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate, trimethyl Hexamethylene diisocyanate, or a reaction product of hexamethylene diisocyanate and the like with 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, (meth)acrylamidemethylene ether, polyhydric alcohol and N-methylol ( Condensate with meth)acrylamide, triacrylformal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate and, 2,4 ,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol diacrylate etc. are mentioned.

The cationic reaction type epoxy compounds are not particularly limited as long as they are compounds having an epoxy group including epoxy compounds, and examples thereof include glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, and butyl. Glycidyl ether, bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ("Cylacure UVR-6110" manufactured by Union Carbide, etc.), 3, 4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide ("ELR-4206" manufactured by Union Carbide, etc.), limonene dioxide ("Celoxide 3000" manufactured by Daicel Co., Ltd.), etc. ), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane- m-dioxane, bis(3,4-epoxycyclohexyl) adipate ("Cylacure UVR-6128" manufactured by Union Carbide, etc.), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3 , 4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, etc. are mentioned.

Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds.

Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether.

Examples of the styrenes include styrene, methyl styrene, and ethyl styrene.

As other vinyl compounds, triallyl isocyanurate, trimethylyl isocyanurate, etc. are mentioned, for example.

Maleimide compounds are not particularly limited as long as they are compounds having 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-hydride) oxyphenyl) maleimide, 6-maleimidehexanoic acid, 4-maleimidebutyric acid, bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5 -Diethyl-4-maleimidephenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebiscitraconimide , m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, 3,3-dimethyl-5, 5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,2-bismaleimideethane, 1,4-bismaleimidebutane, 1, 5-bismaleimide pentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimidehexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1, 8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecane, 1,3-bis(maleimidemethyl)cyclohexane, 1,4- Bis(maleimidemethyl)cyclohexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3- Bis(4-maleimidephenoxy)benzene, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3, 5-dimethyl-4-citraconimidephenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis(3,5-diethyl-4-citraconimidephenyl) ) Methane, polyphenylmethane maleimide, maleimide compounds represented by the following formula (1), (2) or (3), fluorescein-5-maleimide, prepolymers of these maleimide compounds, or maleimide compounds and prepolymers of amine compounds.

As a maleimide compound represented by following formula (1), a commercial item can also be used, For example, BMI-2300 (brand name) by Daiwa Chemical Industry Co., Ltd. is mentioned. As a maleimide compound represented by Formula (2), a commercial item can also be used, For example, Nippon Kayaku Co., Ltd. product MIR-3000 (brand name) is mentioned. As a maleimide compound represented by Formula (3), a commercial item can also be used, For example, Nippon Kayaku Co., Ltd. product MIR-5000 (brand name) is mentioned.

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

In Formula (2), R ₂ each independently represents a hydrogen atom or a methyl group. 1 each independently represents an integer of 1 to 3, n ₂ represents an integer of 1 or greater, preferably an integer of 1 to 5.

In formula (3), each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, l ₂ independently represents an integer of 1 to 3, and n ₃ represents 1 to 3; Represents an integer of 10.

Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, A neopentyl group is mentioned.

A crosslinking agent (D) may be used independently, and may mix and use 2 or more types. Although content in the coloring photosensitive composition of the crosslinking agent (D) in the case of containing a crosslinking agent (D) is not specifically limited, 1 mass % or more and 50 mass % or less are preferable with respect to the mass of the whole solid content of coloring photosensitive composition, and 5 mass % More than 40 mass % or less is more preferable. By setting it as the said range, there exists a tendency to balance sensitivity, developability, and resolution easily.

The colored photosensitive composition may contain a photopolymerization initiator (E).

It does not specifically limit as a photoinitiator (E), A conventionally well-known photoinitiator can be used.

Specifically as the photopolymerization initiator (E), 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy ) Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4- Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl) ketone, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one , O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3- yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1 -Octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyldimethylketal, 1-phenyl-1,2- Propanedione-2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thiocyanate Oxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2- Benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzooxazole, 2-mercaptobenzo Thiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone , 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone , dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro- 4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7 -Bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2 ,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2- yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s -triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4- Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)- s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2- Bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4 -Bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2 -Amylanthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, acetophenonedimethylketal, benzyldimethylketal, 4-benzoyl-4'-methyldiphenylsulphate feed, benzophenones such as 4,4'-bismethylaminobenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like. can These photoinitiators can be used individually or in combination of 2 or more types.

Among these, it is particularly preferable from the viewpoint of sensitivity to use an oxime-based photopolymerization initiator. Among the oxime photopolymerization initiators, particularly preferred are 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-acetyloxime) and, 2-(benzoyloxyimino)-1-[4 -(phenylthio)phenyl]-1-octanone.

As mentioned above, it is preferable that the colored photosensitive composition contains an oxime ester compound as a photoinitiator (E). An oxime ester compound is excellent in ability to generate radicals by absorbing ultraviolet rays. For this reason, even when an oxime ester compound is highly sensitive and contains coloring agents (B), such as a high-concentration light-shielding agent, it is easy to fully harden a coloring photosensitive composition with a small exposure amount. In the case of a coloring photosensitive composition containing a large amount of colorant (B), when the optical density of the film on which the colored photosensitive composition is formed is 3, the ultraviolet light exposure amount of the deep layer portion is considerably smaller than the ultraviolet light exposure amount of the surface layer portion (outmost surface), but the oxime ester compound, Radicals are generated even at such a relatively small amount of ultraviolet light exposure, and the colored photosensitive composition can be cured satisfactorily.

In addition, when the above-mentioned coloring agent (B) is blended in a high concentration in the coloring photosensitive composition, primary aggregates (aggregates) of the coloring agent (B) inevitably occur in the coating film composed of the coloring photosensitive composition. However, when using a colored photosensitive composition containing an oxime ester compound as the photopolymerization initiator (E), the photopolymerization initiator (E) generates radicals during ultraviolet irradiation even in a slight gap where the aggregates overlap each other in a complicated manner.

As a result, the cured product of the colored photosensitive composition has excellent adhesion to the substrate and electrical resistivity (insulation) in an environment of normal temperature, normal humidity and atmospheric pressure, and even when the cured product is exposed to a high-temperature, high-humidity, high-pressure environment, the substrate Adhesion to furnace and electric resistivity (insulation) are hard to fall. Durability in a high-temperature, high-humidity, high-pressure environment can be confirmed by a so-called PCT test (pressure cooker test).

For this reason, even if the hardened|cured material (colored film) of the coloring photosensitive composition containing an oxime ester compound is a high temperature and high humidity use environment, it is hard to produce a fall in performance.

As a photoinitiator (E), you may use combining an oxime ester compound and photoinitiators other than an oxime ester compound. In this case, the ratio of the mass of the oxime ester compound to the total mass of the photopolymerization initiator (E) is preferably 20 mass% or more, more preferably 30 mass% or more, and even more preferably 35 mass% or more, 40 mass % or more is especially preferable.

As photoinitiators other than an oxime ester compound, an aminoalkyl phenone type photoinitiator can be used suitably, for example.

Examples of aminoalkylphenone compounds include 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., IRGACURE369 manufactured by Ciba Specialty Chemicals); 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (for example, IRGACURE379 manufactured by Ciba Specialty Chemicals), 2-( 4-Ethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(4-isopropylbenzyl)-2-(dimethylamino)-1-(4 -Morpholinophenyl)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-morpholyl) Nophenyl)hexan-1-one, 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)octan-1-one, etc. are mentioned.

Especially, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one is preferable.

When an aminoalkyl phenone type photoinitiator is combined with an oxime ester compound, it is easy to control the cross-sectional shape of the patterned colored film formed using a colored photosensitive composition.

This is because the aminoalkylphenone-based photopolymerization initiator tends to generate photopolymerization radicals relatively to the surface layer portion (the surface facing the exposed light and its vicinity) of the colored photosensitive composition, and the oxime ester compound is relatively It is considered that this is because there is a tendency to generate photopolymerization radicals also in the deep layer portion of the colored photosensitive composition. Although this tendency appears more remarkably as the film thickness of the colored photosensitive composition is thicker, it is confirmed even in a thin film thickness of 1 µm or less.

In addition, as a secondary effect of using an aminoalkylphenone-based photopolymerization initiator together with an oxime ester compound, the sensitivity is improved comprehensively, and a cured product of the colored photosensitive composition can be obtained with a small exposure amount. Moreover, when using an aminoalkyl phenone type photoinitiator together with an oxime ester compound, the linearity of a line edge and the adhesiveness to a board|substrate are more favorable, and it is easy to form a patterned colored film with few pattern defects.

Colored photosensitive composition WHEREIN: When a photoinitiator (E) contains an oxime ester compound and an aminoalkyl phenone type photoinitiator, the total of the mass of the oxime ester compound and the mass of an aminoalkyl phenone type photoinitiator The mass ratio of the aminoalkylphenone-based photopolymerization initiator is preferably 20% by mass or more and 75% by mass or less, more preferably 25% by mass or more and 70% by mass or less, and 30% by mass or more and 60% by mass or less. particularly preferred.

Content of the photoinitiator (E) in a colored photosensitive composition is not specifically limited in the range which does not impair the objective of this invention. 0.1 mass % or more and 30 mass % or less are preferable with respect to the mass of the solid content of a colored photosensitive composition, and, as for content of a photoinitiator (E), 0.3 mass % or more and 20 mass % or less are more preferable, and 0.5 mass % or more 10 In terms of mass%, the following is particularly preferred.

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 to improve heat resistance thereafter during the curing treatment, and is particularly preferably used when thermal decomposition resistance is improved by reacting with a carboxyl group or a hydroxyl group contained in the colored photosensitive composition by heating. do.

Specific examples of the epoxy compound as the curing agent (F) include phenol novolak type epoxy resins, cresol novolak type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol-A type epoxy resins, 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, alicyclic An epoxy resin, a heterocyclic epoxy resin, etc. are mentioned.

Examples of the phenol novolac type epoxy resin include Epiclon N-770 (manufactured by DIC Corporation), D.E.N438 (manufactured by Dow Chemical Co., Ltd.), jER154 (manufactured by Japan Epoxy Resin Co., Ltd.), and EPPN-201. , RE-306 (both manufactured by Nippon Gayaku Co., Ltd.), and the like.

Examples of the cresol novolak type epoxy resin include Epiclon N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, and EOCN-104S (both manufactured by Nippon Gayaku Co., Ltd.), UVR- 6650 (made by Union Carbide Co., Ltd.), ESCN-195 (made by Sumitomo Chemical Co., Ltd.), etc. are mentioned.

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Gayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), and jER E1032H60. (Japan Epoxy Resin Co., Ltd. product) etc. are mentioned.

Examples of the dicyclopentadiene phenol type epoxy resin include Epiclon EXA-7200 (manufactured by DIC Corporation) and TACTIX-556 (manufactured by Dow Chemical Co., Ltd.).

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

As the said biphenol type epoxy resin, biphenol type epoxy resins, such as NC-3000, NC-3000-H, NC-3000-L (all Nippon Kayaku Co., Ltd. product), YX-4000 (Japan), for example Non-ylenol type epoxy resin of Epoxy Resin Co., Ltd.), YL-6121 (product of Japan Epoxy Resin Co., Ltd.), etc. are mentioned.

Examples of the bisphenol A novolac type epoxy resin include Epiclon N-880 (manufactured by DIC Corporation) and jER E157S75 (manufactured by Japan Epoxy Resin Co., Ltd.).

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Gayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Corporation).

As the said cardo skeleton containing epoxy resin, PG-100, CG-500, EG-200, EG-280 (Osaka Gas Chemicals Co., Ltd. product) etc. are mentioned, for example.

As the said glyoxal type epoxy resin, GTR-1800 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As the said alicyclic epoxy resin, EHPE-3150 (made by Daicel Co., Ltd.) etc. are mentioned, for example. As the said heterocyclic epoxy resin, TEPIC (made by Nissan Chemical Industries, Ltd.) etc. are mentioned, for example.

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

The curing agent (F) may be used alone or in combination of two or more.

Although content of a hardening|curing agent (F) is not specifically limited, It is preferable that it is 0-40 mass % with respect to the mass of solid content of a coloring photosensitive composition, and it is more preferable that it is 3-30 mass %. By making content of a hardening|curing agent (F) into said range, it is easy to obtain the photosensitive resin composition which can form a cured film with high heat resistance.

The coloring photosensitive composition is a coloring photosensitive composition containing an unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), and a solvent (C), as well as a crosslinking agent (D) and a photopolymerization initiator (E). While being photosensitive and dispersible even at a high colorant concentration, and having good development characteristics, heat resistance can be improved by containing a curing agent (F) if necessary.

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

≪Surface conditioner≫

The surface conditioner suppresses surface defects and appearance defects (uneven distribution of coloring agents such as pigments) caused by uneven distribution of coloring agents such as pigments by reducing the surface tension of the colored photosensitive composition. Specifically, polydimethylsiloxane, polyether-modified polysiloxane, polymethylalkylsiloxane, polysiloxane modified with an aralkyl group or polyester chain, and the like can be suitably used.

≪Adhesion improver≫

Known coupling agents such as silane coupling agents, titanate coupling agents, and aluminate coupling agents can be used. Among these, a silane coupling agent can be suitably used from a viewpoint of improving adhesiveness with a glass substrate.

The coloring photosensitive composition may contain various additives other than the above as needed. Specifically, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersing aid, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, a surfactant, a liquid repellent, a chain transfer agent, and a light initiation aid , solvents, etc. are exemplified. As any additive, a conventionally well-known thing can be used.

As surfactant, anionic compounds, cationic compounds, nonionic compounds, etc. are mentioned, for example.

As a thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example.

As an antifoamer, a silicone type compound, a fluorine type compound, etc. are mentioned, for example.

Examples of the chain transfer agent include mercaptan-based compounds, halogen-based compounds, quinone-based compounds, and α-methylstyrene dimer. By containing a chain transfer agent, the pattern shape (particularly, the CD change of the hole pattern and the exposure margin) can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (?-methylstyrene dimer) is preferable in that it can reduce sublimation, coloration, and odor in addition to the above effects.

Examples of photoinitiating aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Ethylhexyl, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzo phenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. You may use these photoinitiation adjuvant 1 type or in combination of 2 or more types.

Examples of the liquid repellent include fluorine atom-containing resins having a crosslinking group. From the point which ink repellency can be provided to the surface of a partition, when using a colored photosensitive composition for formation of a partition, it is thought that it can prevent color mixture for every pixel.

As a crosslinking group, an epoxy group or an ethylenically unsaturated group is mentioned, and an ethylenically unsaturated group is preferable from a viewpoint of suppressing the outflow of a liquid repellent agent to a developing solution. Further, the fluorine atom-containing resin having a crosslinking group preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. As a perfluoroalkyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, etc. are mentioned. As the perfluoroalkylene ether chain, -CF ₂ -O-, -(CF ₂ ) ₂ -O-, -(CF ₂ ) ₃ -O-, -CF ₂ -C(CF ₃ )O-, -C (CF ₃ )-CF ₂ -O- and divalent groups having repeating units thereof.

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 ethylenically unsaturated group and a perfluoroalkyl group. An acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, an epoxy (meth)acrylate resin having an epoxy group and a perfluoroalkyl group, an epoxy group and a perfluoroalkylene ether chain An epoxy (meth)acrylate resin having an ethylenically unsaturated group and a perfluoroalkyl group, an epoxy (meth)acrylate resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, etc. can be mentioned. 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 ethylenically unsaturated group and a purple An acrylic copolymer resin having a fluoroalkylene ether chain is more preferred. Examples of commercially available fluorine atom-containing resins having these crosslinking groups include “Megapack (registered trademark, hereinafter the same) F116”, “Megapack F120”, “Megapack F142D”, “Megapack F144D” and “Megapack F150” manufactured by DIC. ”, “Megapack F160”, “Megapack F171”, “Megapack F172”, “Megapack F173”, “Megapack F177”, “Megapack F178A”, “Megapack F178K”, “Megapack F179”, “Megapack F183”, “Megapack F184”, “Megapack F191”, “Megapack F812”, “Megapack F815”, “Megapack F824”, “Megapack F833”, “Megapack RS101”, “Megapack RS101” “Megapack RS102”, “Megapack RS105”, “Megapack RS201”, “Megapack RS202”, “Megapack RS301”, “Megapack RS303”, “Megapack RS304”, “Megapack RS401”, “Megapack RS402”, "Megapack RS501", "Megapack RS502", "Megapack RS-72-K", "Megapack RS-78", "Megapack RS-90", "DEFENSA (registered trademark) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", "Florad FC430", "Florad FC431", "FC-4430", "FC4432" manufactured by 3M Japan, "Asahi Guard (registered)" manufactured by AGC Trademark) AG710”, “Saffron (registered trademark, the same hereinafter) S-382”, “Saffron SC-101”, “Saffron SC-102”, “Saffron SC-103”, “Saffron SC-104” ”, “Saffron SC-105”, “Saffron SC-106” and other commercially available fluorine-containing organic compounds can be used.

<<Preparation method of colored photosensitive composition>>

The coloring photosensitive composition is prepared by, for example, uniformly stirring and mixing each of the above components, dissolving and dispersing them uniformly. In the case of mixing, you may mix with a stirrer, such as a roll mill, a ball mill, and a sand mill. It can prepare by filtering with a filter, such as a 2 micrometer membrane filter, as needed.

≪Colored film and patterned colored film≫

A colored film can be obtained by hardening the said coloring photosensitive composition.

The manufacturing method of a colored film includes the process of apply|coating a colored photosensitive composition and forming a coating film, and the process of exposing a coating film.

Further, the method for producing a patterned colored film includes a step of forming a coated film by applying a colored photosensitive composition, a step of positionally selectively exposing the coated film, and a step of developing the coated film after exposure.

By using the said coloring photosensitive composition as a negative photosensitive composition, even if a high-concentration coloring agent is contained, it can form a high-definition pattern with good linearity.

Hereinafter, each process is demonstrated. Forming a coating film using the colored photosensitive composition is described as a "coating film formation step". Exposing the coating film is described as an "exposure step". Developing the exposed coating film is described as a "development step".

≪Coating film formation process≫

In the coating film formation step, the colored photosensitive composition is applied onto a substrate to form a coating film.

The type of substrate is not particularly limited, and various substrates used for optical elements such as liquid crystal display elements, organic EL display elements, and organic TFT arrays can be suitably used. As the substrate, for example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, SOG (Spin On Glass), polyester film, polycarbonate film , polymer substrates such as polyimide films, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metal, insulating substrates, semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon A production board|substrate etc. are mentioned. Further, for example, in the case of forming a laminated structure on a substrate, any layer that becomes a lower structure already formed on the substrate is included in the concept as a base material to which the colored photosensitive composition is applied. Also, the shape of the substrate is not particularly limited, and may be in a plate shape or in a roll shape. The base material may have unevenness on the surface by, for example, various patterns. In addition, as the substrate, a light-transmitting or non-light-transmitting substrate can be selected.

In the coating film forming step, for example, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device), a slit coater, or a curtain flow coater is used to form a color photosensitive coating. The composition is applied on a substrate and, if necessary, the solvent is removed by drying (prebaking) to form a coating film.

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

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

≪Exposure process≫

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

In the exposure step, the coating film is exposed to radiation or electromagnetic waves, such as i-line, g-line, or h-line, for example. In the case of forming a patterned cured film (colored film), exposure to be a coated film is performed positionally 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, for example. About 10 mJ/cm<2> or more and 150 mJ/cm<2> or less is more preferable.

You may heat with respect to the cured film hardened|cured by exposure. The temperature at the time of heating is not particularly limited, and is preferably 180°C or more and 280°C or less, more preferably 200°C or more and 260°C or less, and particularly preferably 220°C or more and 250°C or less. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.

≪Development process≫

In the developing step, the coating film exposed in the exposure step is developed with an alkaline developer.

In the developing step, a cured film (colored film) patterned into a desired shape is formed by developing the exposed coating film with a developing solution. The developing method is not particularly limited, and an immersion method, a spray method, or the like can be used. As a specific example of a developing solution, aqueous solutions, such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt, are mentioned.

After development, you may perform post-baking as needed. The post-baking temperature after development is preferably 80°C or more and 250°C or less, more preferably 100°C or more and 230°C or less. 5 minutes or more and 60 minutes or less are preferable, and, as for the time of post-baking after image development, 10 minutes or more and 30 minutes or less are more preferable.

By using the colored photosensitive composition, as shown in Examples to be described later, a high-concentration colorant can be dispersed and a high-definition pattern can be formed, and a curing agent can be contained when it is desired to improve heat resistance. there is.

[Example]

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

Epoxy equivalent and acid value were measured under the following conditions.

1) Epoxy equivalent weight (WPE): measured according to JIS K 7236:2001.

2) Acid value: measured according to JIS K 0070:1992.

3) The measurement conditions of gel permeation chromatography (GPC) are as follows.

Model: TOSOH HLC-8220GPC

Column: TSKGEL Super HZM-N

Eluent: THF (tetrahydrofuran); 0.35ml/min, temperature 40℃

Detector: Differential Refractometer

Molecular Weight Standard: Polystyrene

Preparation Example 1

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of group content 17.3 mass %) and 188.1 g of cyclohexane- 1,3,4- tricarboxylic acid- 3,4- anhydride were added. It heated up to 116 degreeC, blowing nitrogen into the system, and was made to react at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. An amideimide resin (1) solution having a number average molecular weight of 1,250 and a weight average molecular weight of 4,040 and a solid acid value of 164 mgKOH/g was obtained by gel permeation pressure chromatography using polystyrene as a standard. After cooling to 60 ° C., adding 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 and stirring, 2.27 g of triphenylphosphine was added and the temperature was raised to 116°C. It was made to react at the same temperature for 20 hours, and the solid content acid value of 94.1 mgKOH/g, the (meth)acrylic equivalent weight of 629, the number average molecular weight by GPC of 1,870, and the unsaturated group-containing polycarboxylic acid resin (I) of weight average molecular weight of 5,320 were obtained. In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 13,000 g/eq.

Preparation Example 2

In a four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 661.2 g of propylene glycol monomethyl ether acetate and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of group content 17.3 mass %) and 198.0 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. An amideimide resin (2) solution having a number average molecular weight of 1,290 and a weight average molecular weight of 3,590 and a solid acid value of 155 mgKOH/g was obtained by gel osmosis chromatography using polystyrene as a standard. After cooling to 60 ° C., adding 537.5 g of propylene glycol monomethyl ether acetate, 198.8 g of glycidyl methacrylate, 154.0 g of hexahydrophthalic anhydride, and 2.38 g of dibutylhydroxytoluene and stirring, 2.38 g of triphenylphosphine was added and the temperature was raised to 116°C. It was made to react at the same temperature for 20 hours, and the solid content acid value of 92.2 mgKOH/g, the (meth)acryl equivalent weight of 629, the number average molecular weight by GPC of 1,710, and the unsaturated group-containing polycarboxylic acid resin (II) of weight average molecular weight of 4,930 were obtained. In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 11,000 g/eq.

Preparation Example 3

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. An amide-imide resin (3) solution having a number average molecular weight of 1,260 and a weight average molecular weight of 4,120 and a solid acid value of 159 mgKOH/g by gel osmosis chromatography using polystyrene as a standard was obtained. After cooling to 60 ° C., adding 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 and stirring, 2.17 g of triphenylphosphine was added and the temperature was raised to 116°C. It was made to react at the same temperature for 20 hours, and the solid content acid value of 85.9 mgKOH/g, (meth)acrylic equivalent weight of 604, the number average molecular weight by GPC of 1,750, and the unsaturated group-containing polycarboxylic acid resin (III) of weight average molecular weight of 5,500 were obtained. In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 14,000 g/eq.

Production Example 4

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. An amide-imide resin (4) solution having a number average molecular weight of 1,190 and a weight average molecular weight of 3,850 and a solid acid value of 151 mgKOH/g by gel osmosis chromatography using polystyrene as a standard was obtained. After cooling to 60 ° C., adding 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 and stirring, triphenyl 2.44 g of phosphine was added and the temperature was raised to 116°C. It was made to react at the same temperature for 20 hours, and polycarboxylic acid resin (IV) containing an unsaturated group with a solid acid value of 95.8 mgKOH/g, a (meth)acryl equivalent of 641, a number average molecular weight by GPC of 1,640, and a weight average molecular weight of 4,790 was obtained. In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 12,000 g/eq.

Preparation Example 5

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. An amideimide resin (5) solution having a number average molecular weight of 1,300 and a weight average molecular weight of 3,690 and a solid acid value of 152 mgKOH/g was obtained by gel osmosis chromatography using polystyrene as a standard. 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. After that, 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. It was made to react at the same temperature for 20 hours, and polycarboxylic acid resin (V) containing an unsaturated group with a solid acid value of 97.9 mgKOH/g, a (meth)acrylic equivalent of 628, and a number average molecular weight by GPC of 1,690 and a weight average molecular weight of 4,980 was obtained. In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 14,000 g/eq.

Preparation Example 6

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. An amide-imide resin (6) solution having a number average molecular weight of 1,250 and a weight average molecular weight of 3,680 and a solid acid value of 161 mgKOH/g by gel osmosis chromatography using polystyrene as a standard was obtained. After cooling to 60 ° C., adding 261.9 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, and 1.90 g of dibutylhydroxytoluene and stirring, 1.90 g of triphenylphosphine was added and the temperature was raised to 116 ° C. . It was made to react at the same temperature for 20 hours, and polycarboxylic acid resin (I') containing an unsaturated group having a solid content acid value of 19.2 mgKOH/g, a number average molecular weight by GPC of 1,740, and a weight average molecular weight of 6,950 was obtained. In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 13,000 g/eq.

Preparation Example 7

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ⁻¹ , which is the characteristic absorption of an isocyanate group, completely disappeared. An amideimide resin (7) solution having a number average molecular weight of 1,180 and a weight average molecular weight of 3,860 and a solid acid value of 154 mgKOH/g was obtained by gel osmosis chromatography using polystyrene as a standard. After cooling to 60°C, 494.5 g of propylene glycol monomethyl ether acetate, 170.4 g of glycidyl methacrylate, 148.1 g of phthalic anhydride, and 1.90 g of dibutylhydroxytoluene were added and stirred, then 1.90 g of triphenylphosphine was added. The temperature was raised to 116°C. It was made to react at the same temperature for 20 hours, and polycarboxylic acid resin (II') containing an unsaturated group having a solid 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 was obtained. . In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 14,000 g/eq.

Preparation Example 8

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. Cool to 60°C, add 97.58 g of a pentaerythritol (tri/tetra)acrylate mixture ("PETRA" manufactured by Daicel Allnex, hydroxyl value: 115 mgKOH/g), and raise the temperature to 116°C, the same temperature was reacted for 10 hours to obtain an amideimide resin (8) solution having a number average molecular weight of 1,070 and a weight average molecular weight of 3,080 and a solid acid value of 135 mgKOH/g by gel osmosis pressure chromatography using polystyrene as a standard. After cooling to 60 ° C., adding 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 and stirring, triphenyl 2.44 g of phosphine was added and the temperature was raised to 116°C. It was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (III') having a solid acid value of 82.1 mgKOH/g, a (meth)acrylic equivalent of 395, a number average molecular weight of 1,370 by GPC, and a weight average molecular weight of 3,700. . In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 15,000 g/eq.

Preparation Example 9

In a four-necked flask equipped with a stirring device, a thermometer and a condenser, 250.3 g of propylene glycol monomethyl ether acetate and a cresol novolac type epoxy resin (“EOCN-104S” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 218 g/eq) 435.7 g and 1.75 g of dibutylhydroxytoluene were added, and the mixture was stirred at 80°C to dissolve the epoxy resin. Thereafter, 148.4 g of acrylic acid and 1.75 g of triphenylphosphine were added, the temperature was raised to 116° C., and the reaction was carried out at the same temperature for 12 hours to obtain a reactive epoxy carboxylate having a solid acid value of 2.2 mg KOH/g and an epoxy equivalent of 13 kg/eq. A resin (9) solution was obtained. After cooling to 60°C, 48.6 g of propylene glycol monomethyl ether acetate and 113.5 g of 1,2,3,6-tetrahydrophthalic anhydride were added, and the temperature was raised to 100°C. It was reacted 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. . In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 13,000 g/eq.

Preparation Example 10

The resin described in Example 2-1 of Japanese Patent-6576161 was prepared as described, and had a solid content acid value of 61.5 mgKOH/g, a (meth)acrylic equivalent of 335, a number average molecular weight by GPC of 1830, and a weight average molecular weight of 3520. A reactive polycarboxylic acid compound (V') was obtained.

Preparation Example 11

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. An amideimide resin (5) solution having a number average molecular weight of 1,310 and a weight average molecular weight of 3,810 and a solid acid value of 152 mgKOH/g was obtained by gel osmosis chromatography using polystyrene as a standard. Cool 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, dibutylhydroxytoluene After adding 2.31 g and stirring, 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. It was made to react at the same temperature for 20 hours, and the solid content acid value of 87.1 mgKOH/g, the (meth)acryl equivalent weight of 652, the number average molecular weight by GPC of 1,870, and the unsaturated group containing polycarboxylic acid resin (VI) of weight average molecular weight of 6,010 were obtained. In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 16,000 g/eq.

Preparation Example 12

In 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 and a modified isocyanurate of isophorone diisocyanate ("VESTANATT-1890/100" manufactured by EVONIK, isocyanate 242.8 g of 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 mixture was reacted at the same temperature for 30 hours. In the infrared spectrum, it was confirmed that absorption at 2250 cm ^{−1 ,} which is the characteristic absorption of an isocyanate group, completely disappeared. An amideimide resin (5) solution having a number average molecular weight of 1,260 and a weight average molecular weight of 3,600 and a solid acid value of 156 mgKOH/g was obtained by gel osmosis chromatography using polystyrene as a standard. Cool 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, dibutylhydroxytoluene After adding 2.31 g and stirring, 2.31 g of triphenylphosphine was added and the temperature was raised to 116°C. It was made to react at the same temperature for 20 hours, and polycarboxylic acid resin (VII) containing an unsaturated group having a solid acid value of 80.6 mgKOH/g, a (meth)acryl equivalent of 600, a number average molecular weight by GPC of 1,870, and a weight average molecular weight of 6,010 was obtained. In addition, as a result of measuring the epoxy equivalent, it was also confirmed that the epoxy group was sufficiently reacting at 14,000 g/eq.

[Example 1, Comparative Example 1] Preparation of colored photosensitive composition and evaluation of kneading dispersibility

Mitsubishi Carbon Black MA-100 (B1) was used as a colorant (B) in 20 g of the unsaturated group-containing polycarboxylic acid resins obtained in Production Examples 1 to 10, Examples and Comparative Examples. As the solvent (C), propylene glycol monomethyl ether acetate (C1) was used and kneaded in a bead mill, and the state after kneading was confirmed. What the obtained colored photosensitive composition was uniform was rated as (circle), and what gelation by non-uniformity and resin occurred was rated as x. Table 1 shows the evaluation results of the ratio of the colored photosensitive composition and the state after kneading.

[Example 2, Comparative Example 2] Preparation of colored photosensitive composition and evaluation of colorant dispersibility

To the colored photosensitive composition obtained in Example 1 and Comparative Example 1, as a crosslinking agent (D), DPHA (trade name: manufactured by Nippon Gayaku Co., Ltd.) (D1) and further 20 g of glass beads were added, and the mixture was stirred in a paint shaker for 1 hour. dispersion was carried out. After completion of the dispersion, the dispersion was coated on a polyethylene terephthalate film with a wire bar coater #2, and dried for 10 minutes with a warm air dryer at 80°C. The gloss of the coating film surface after completion of drying was measured using a 60° reflective gloss meter (Horiba Seisakusho IG-331 gloss meter) to evaluate the carbon black dispersibility. Table 2 shows the results. The higher the gloss value, the better the pigment dispersibility.

[Example 3, Comparative Example 3] Preparation of colored photosensitive composition and evaluation of developability

The unsaturated group-containing polycarboxylic acid resin (A) obtained in Production Examples 1 to 10, the colorant (B1), the solvent (C1), the crosslinking agent (D), and the photopolymerization initiator (E) are uniformly formulated in the formulations shown in Table 3. and dispersed to obtain a resist resin composition.

In Examples and Comparative Examples, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.: ε-caprolactone-modified dipentaerythritol hexaacrylate) (D2) as a crosslinking agent (D), and as a photopolymerization initiator (E) Gacur 907 (manufactured by Chiba Specialty Chemicals) (E1) and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2) and, as a curing agent (F), YD-134 (Nittetsu Chemical & Material ( Note) Production: bisphenol-A type epoxy resin) (F1) and TPP (Hokkyo Chemical Industry Co., Ltd.: triphenylphosphine) (G1) were used as the thermal curing catalyst (G).

Each item of the evaluation item is described in detail.

Developability evaluation (abbreviation in the table: developability)

The colored photosensitive composition was applied to a rolled copper foil BHY-82F-HA-V2 (manufactured by JX Kinzoku Co., Ltd.) with an applicator to a thickness of 20 μm, and the coated film was dried with a hot air dryer at 80° C. for 30 minutes. The coated film after drying was cured with an irradiation amount of 150 mJ/cm 2 using an ultraviolet irradiator (manufactured by USHIO (ultra-high pressure mercury lamp)) through a mask with a 50 μm opening. Then, spray development was performed using a 1% sodium carbonate aqueous solution as a developing solution. It was set as the developability evaluation with the time until the coating film of an unexposed area melt|dissolves completely, so-called break time (unit: second).

△ .. membrane reduction

× ... pattern straightness

×× Swelling peeling

Regarding "film shrinkage", 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, and when there was film reduction, it was evaluated as △, not the break time (using an electron microscope). Regarding "pattern straightness", the case where it was curved was evaluated as x. When there was no linearity of the pattern and it was not formed neatly, it was set as x evaluation instead of break time (using an electron microscope). About "swelling peeling", it was not a dissolution phenomenon at the time of development, and when the coating film swelled and peeled, it was set as xx evaluation, not break time.

Thermal degradation resistance evaluation (abbreviation in the table: thermal degradation resistance)

The colored photosensitive composition was applied to a rolled copper foil BHY-82F-HA-V2 (manufactured by JX Kinzoku Co., Ltd.) with an applicator to a thickness of 20 µm, and the coated film was dried with a hot air dryer at 80 ° C. for 30 minutes, followed by an ultraviolet irradiation machine. (Product made by GS YUASA: CS 30L-1) was used, and ultraviolet rays were irradiated with an energy of 500 mJ/cm 2 . Subsequently, it was made to harden at 150 degreeC for 30 minutes in oven, and the hardened|cured material was obtained. The copper foil was removed with an iron (III) chloride 45° Baume (manufactured by Junsei Chemical Co., Ltd.). The temperature at which the weight decreases by 5% was measured for a sample of 3 mg of the produced cured product using a TGA/DSC1 manufactured by METTLER in an air stream of 100 ml per minute.

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

[Example 4] Preparation of colored photosensitive composition and evaluation of kneading dispersibility

20 g of the unsaturated group-containing polycarboxylic acid resin obtained in Production Examples 11 and 12 and Mitsubishi Carbon Black MA-100 (B1) were used as the colorant (B). It was kneaded with a bead mill, and the state after kneading was confirmed. What the obtained colored photosensitive composition was uniform was rated as (circle), and what gelation by non-uniformity and resin occurred was rated as x.

[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 Gayaku Co., Ltd.) (D1) and further 20 g of glass beads were added , and dispersion was performed for 1 hour with a paint shaker. After completion of the dispersion, the dispersion was coated on a polyethylene terephthalate film with a wire bar coater #2, and dried for 10 minutes with a warm air dryer at 80°C. The gloss of the coating film surface after completion of drying was measured using a 60° reflective gloss meter (Horiba Seisakusho IG-331 gloss meter) to evaluate the dispersibility of the carbon black. Table 5 shows the results. The higher the gloss value, the better the pigment dispersibility.

[Example 6] Preparation of colored photosensitive composition and evaluation of developability

The unsaturated group-containing polycarboxylic acid resin (A) obtained in Production Examples 11 and 12, the colorant (B1), the solvent (C1), the crosslinking agent (D), and the photopolymerization initiator (E) are uniformly formulated as shown in Table 6. and dispersed to obtain a resist resin composition.

In Examples, DPCA-20 (Nippon Kayaku Co., Ltd.: ε-caprolactone-modified dipentaerythritol hexaacrylate) (D2) as a crosslinking agent (D), Irgacure 907 as a photopolymerization initiator (E) (Chiba Specialty Chemicals) (E1) and Kayacure DETX-S (Nippon Kayaku Co., Ltd.) (E2) and, as a curing agent (F), YD-134 (Nittetsu Chemical & Materials Co., Ltd.) : Bisphenol-A type epoxy resin) (F1) and TPP (Hokkyo Chemical Industry Co., Ltd. triphenylphosphine) (G1) were used as the thermal curing catalyst (G).

About each item of evaluation criteria, it is the same as Example 3. The evaluation result of each evaluation item is shown in Table 6.

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

From the above, the coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility and high developability, and a cured product thereof is also excellent in heat resistance, so that a barrier rib having a light-shielding effect for an image display device, a black matrix, and coloring Suitable for spacers and color resists.

Claims (7)

Polyamide-imide resin (a3) having a terminal acid group or an acid anhydride group obtained by reaction of an alicyclic isocyanurate type polyisocyanate (a1) with an alicyclic tricarboxylic acid anhydride (a2) has an epoxy group in one molecule (meta) ) Coloring containing an acrylate compound (b) and an aliphatic dicarboxylic acid anhydride or an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting an aliphatic tricarboxylic acid anhydride (c) with a coloring agent (B) and a solvent (C) photosensitive composition. According to claim 1,
A colored photosensitive composition containing a crosslinking agent (D). According to claim 1,
The coloring photosensitive composition which further contains a photoinitiator (E). According to claim 1,
The coloring photosensitive composition which further contains a hardening|curing agent (F). According to claim 1,
The coloring photosensitive composition in which the said coloring agent (B) contains a black pigment. A cured product of the colored photosensitive composition according to any one of claims 1 to 5. An image display device comprising the cured product according to claim 6.