Coloring photosensitive composition, cured product, and image display device including cured product

Abstract

To provide a coloring photosensitive composition which is excellent in dispersibility of a coloring agent or the like, and has good development characteristics even at a high coloring agent concentration, a coloring photosensitive composition which also has good heat resistance, and a cured product of them.SOLUTION: A coloring photosensitive composition contains: an unsaturated group-containing polycarboxylic acid resin (A) 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 obtained by reaction of alicyclic isocyanurate type polyisocyanate (a1) with an aromatic tricarboxylic acid anhydride (a2); a coloring agent (B); and a solvent (C).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a colored photosensitive composition, a cured product, and an image display device including the cured product. More specifically, the present invention relates to a photosensitive colored composition having excellent shielding properties and plate-making characteristics, and uses thereof. [Background technology]

[0002] Conventional displays often use color filters that form red, green, and blue pixels using organic pigments, colored spacers, and black matrices. In recent years, in order to reduce the power consumption and widen the color gamut of displays, color filters in which pixels are formed using luminescent nanocrystalline particles such as quantum dots have been studied. Specifically, color filters having red pixels containing red-luminescent nanocrystalline particles, green pixels containing green-luminescent nanocrystalline particles, and blue pixels that transmit blue light from a light source are known. There are two methods for manufacturing color filters: photolithography and inkjet printing, and the latter is known to be able to reduce the loss of ink material (Patent Document 1). When manufacturing a color filter containing luminescent nanocrystal particles by the inkjet method, ink is ejected into a region (pixel portion) surrounded by a partition wall prepared in advance to form pixels. This partition wall is required to prevent the inks from mixing with each other between adjacent pixel portions, and to have a highly precise pattern (fine pattern). In addition, it is known that a photosensitive composition containing a colorant (colored photosensitive composition) is used to form the partition wall by a photolithography method in order to have a light-shielding effect (Patent Document 2). In addition, there is also known an attempt to disperse carbon black or the like in an acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin as a basic skeleton and apply it to a cured product used in liquid crystal display panels or the like (Patent Document 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-086745 A [Patent Document 2] JP 2007-10795 A [Patent Document 3] JP 2005-055814 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, when the photosensitive composition of Patent Document 2 is used, there is a problem that the developability of the pattern obtained by the photolithography method is poor, and a pattern of a desired shape may not be obtained or may not be formed. In addition, in partition walls having a light-shielding effect, black matrices, colored spacers, and color resists, there is a need for colored photosensitive compositions that have good dispersibility even when further colorants are contained.

[0005] The present invention aims to improve the above-mentioned problems of the conventional art and to provide a colored photosensitive composition which has excellent dispersibility of colorants and the like and has good development properties even at a high colorant concentration, and further has good heat resistance, and a cured product thereof. [Means for solving the problem]

[0006] As a result of intensive efforts to solve the above-mentioned problems, the present inventors have found that a colored photosensitive composition containing an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an aromatic tricarboxylic acid anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule, a colored photosensitive composition containing a colorant (B) and a solvent (C), provides a colored photosensitive composition which is excellent in dispersibility of colorants, etc. and has good development properties even at a high colorant concentration, and in some cases has good heat resistance, as well as a cured product thereof.

[0007] That is, the present invention relates to the following [1] to

[11] . [1] A colored photosensitive composition comprising an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamide-imide resin (a3) ​​having terminal acid groups or acid anhydride groups, obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an aromatic tricarboxylic acid anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule, a colorant (B), and a solvent (C). [2] The photosensitive resin composition according to [1], wherein the molar ratio ((b) / (a2)) of the aromatic tricarboxylic anhydride (a2) to the epoxy group-containing (meth)acrylate compound (b) is 0.1 to 0.9. [3] The photosensitive resin composition according to claim 1 or 2, wherein the epoxy group of the (meth)acrylate compound (b) having an epoxy group in one molecule is an alicyclic epoxy. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the unsaturated group-containing polycarboxylic acid resin (A) has a molecular weight distribution (Mw / Mn) which is a ratio of the solid average molecular weight (Mn) to the weight average molecular weight (Mw) of 1.5 to 2.5. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the unsaturated group-containing polycarboxylic acid resin (A) has an acid value of 40 to 140 mg·KOH / g on solid content. [6] The colored photosensitive composition according to any one of [1] to [5], further comprising a crosslinking agent (D). [7] The colored photosensitive composition according to any one of [1] to [6], further comprising a photopolymerization initiator (E). [8] The colored photosensitive composition according to any one of [1] to [7], further comprising a curing agent (F). [9] The colored photosensitive composition according to any one of [1] to [8], wherein the colorant (B) contains a black pigment.

[10] A cured product comprising the colored photosensitive composition according to any one of [1] to [9].

[11] An image display device comprising the cured product according to

[10] . Effect of the Invention

[0008] The colored photosensitive composition of the present invention, which is characterized by containing the unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), and a solvent (C), has excellent photosensitivity, is dispersible even at a high colorant concentration, and has good developing properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] ≪Colored photosensitive composition≫ The colored photosensitive composition of the present invention contains an unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), and a solvent (C).

[0010] Essential and optional components contained in the colored photosensitive composition will be described below.

[0011] The colored photosensitive composition contains an unsaturated group-containing polycarboxylic acid resin (A). The unsaturated group-containing polycarboxylic acid resin (A) in the present invention is obtained by reacting a polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, which is obtained by reacting a cyclic isocyanurate-type polyisocyanate (a1) with an aromatic tricarboxylic acid anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule.

[0012] That is, the unsaturated group-containing polycarboxylic acid resin (A) in the present invention is produced by two reaction steps. First, an alicyclic isocyanurate-type polyisocyanate (a1) is reacted with an aromatic tricarboxylic anhydride (a2) to obtain a polyamide-imide resin (a3). In the present invention, this step is called an amide-imidization step. The next step is to react the resulting polyamideimide resin (a3) ​​with a (meth)acrylate compound (b) having an epoxy group in one molecule. In the present invention, this step is referred to as a carboxylation step.

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

[0014] Alicyclic in the present specification means, in the context of the present invention, a compound in which the carbon atoms are arranged in a ring (as already suggested by the identity of the two terms "aliphatic" and "cyclic" written together). Thus, alicyclic is also a synonym for cycloaliphatic. As a result, alicyclic compounds belong to the group of homocyclic compounds, which in this case include cycloalkanes, cycloalkenes and cycloalkynes. Aromatic and heterocyclic compounds, as well as saturated examples of heterocyclic compounds, are not considered to be alicyclic within the meaning of the present invention.

[0015] Examples of diisocyanates containing alicyclic diisocyanate compounds include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, norbornane diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0016] The trimerization catalyst is not particularly specified, and examples thereof include amine compounds such as 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, alkali metal salts of carboxylic acids having 2 to 12 carbon atoms such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate, and quaternary ammonium salts of carboxylic acids. Commercially available products include DAB CO P15 (manufactured by Sankyo Air Products), DABCO K15 (manufactured by Sankyo Air Products), PELCAT9540 (manufactured by Perlon), DABCO TMR (manufactured by Sankyo Air Products), TOYOCAT TR20 (manufactured by Tosoh), and U-CAT 18X ​​(manufactured by San-Apro).

[0017] Examples of the alicyclic isocyanurate polyisocyanate (a1) include alicyclic isocyanurate triisocyanate (including polymers such as pentamer) synthesized from isophorone diisocyanate, alicyclic isocyanurate triisocyanate (including polymers such as pentamer) synthesized from hydrogenated tolylene diisocyanate, alicyclic isocyanurate triisocyanate (including polymers such as pentamer) synthesized from hydrogenated xylene diisocyanate, isocyanurate triisocyanate (including polymers such as pentamer) synthesized from norbornane diisocyanate, and alicyclic isocyanurate triisocyanate (including polymers such as pentamer) synthesized from hydrogenated diphenylmethane diisocyanate. Among them, alicyclic isocyanurate isocyanate synthesized from isophorone diisocyanate is preferred. By using an alicyclic isocyanurate type polyisocyanate synthesized from isophorone diisocyanate, it has excellent tackiness and curing shrinkage.

[0018] Examples of the aromatic tricarboxylic anhydride (a2) used in the production of the polyamideimide resin (a3) ​​in the present invention include 1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride, 1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenylethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among these, trimellitic anhydride, which has excellent heat resistance and curing shrinkage, is preferred.

[0019] In the reaction between the alicyclic isocyanurate type polyisocyanate (a1) and the aromatic tricarboxylic anhydride (a2), the total of the acid anhydride group and the carboxylic acid is preferably 1.0 mol to 3.0 mol, more preferably 1.2 mol to 2.8 mol, and even more preferably 1.4 mol to 2.6 mol, per 1 mol of the isocyanate group of the alicyclic isocyanurate type polyisocyanate (a1). When the total of the acid anhydride group and the carboxylic acid exceeds 1.0 mol, the remaining of the isocyanate group is prevented, the polymerization is suppressed, and the developability is improved. When the total of the acid anhydride group and the carboxylic acid is lower than 3.0 mol, the remaining of the aromatic tricarboxylic anhydride is prevented, and the development residue can be suppressed.

[0020] The amide-imidization step uses a solvent-free or hydroxyl-free organic solvent.Specific examples of the solvent (C) include ethyl acetate, propyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and other ethylene glycol dialkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, and other polyethylene glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and other ethylene glycol monoalkyl ether acetates; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ... polyethylene glycol monoalkyl ether acetates such as glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and triethylene glycol monobutyl ether acetate; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether; polypropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate;Polypropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, and tripropylene glycol monobutyl ether acetate; or dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers, and monoacetate monoalkyl ethers of copolymerized polyether glycols; or alkyl esters of such polyether glycols; monoalkyl ester monoalkyl ethers of polyether glycols, and further crosslinking agents (D) not having a hydroxyl group among the crosslinking agents (D) described below, can be reacted alone or in a mixed organic solvent;

[0021] A catalyst may be used to promote the reaction during the reaction, and the amount of the catalyst used is 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of the reaction product including the alicyclic isocyanurate polyisocyanate (a1), the aromatic tricarboxylic anhydride (a2), and the solvent. Examples of the catalyst used in this reaction include diazabicycloundecene, tributylamine, triethylamine, tripropylamine, tetrabutylammonium chloride, tetrabutylammonium bromide, N,N-diisopropylethylamine, and triethylenediamine.

[0022] The amide-imidization reaction is preferably carried out by mixing one or more of the alicyclic isocyanurate polyisocyanates (a1) and one or more of the aromatic tricarboxylic acid anhydrides (a2) in a solvent or without a solvent, and raising the temperature while stirring.

[0023] The reaction temperature of the amide-imidization reaction is preferably in the range of 50°C to 250°C, and particularly preferably in the range of 70°C to 180°C. By setting the reaction temperature in this range, the reaction rate is increased. In the reaction, an anhydride group and an isocyanate group form an imide group accompanied by decarbonation, and a carboxylic acid group and an isocyanate group form an amide group. During the reaction, an antioxidant, a leveling agent, an antifoaming agent, a surfactant, etc. can be used as necessary.

[0024] The progress of the amide-imidization reaction can be monitored by analytical means such as infrared spectroscopy, acid value, gel permeation chromatography, liquid chromatography, gas chromatography, H-NMR, C-NMR, and quantification of isocyanate groups. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2270 cm -1 decreases with the reaction and further increases to 1860cm -1 and 850cm -1 The acid anhydride group, which has a characteristic absorption at 1780cm, is decreased. -1 and 1720cm -1 The absorption of the imide group increases at 2270 cm, which is the characteristic absorption of the isocyanate group. -1 It is preferable to allow the reaction to proceed until disappearance of the reaction product, since this makes it easier to control the reaction.

[0025] The polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group obtained by the reaction of the cyclic isocyanurate polyisocyanate (a1) with the aromatic tricarboxylic anhydride (a2) has a preferred molecular weight range, in terms of polystyrene, measured by GPC, of ​​800 to 10,000, more preferably 1,000 to 8,000, and particularly preferably 1,200 to 6,000.

[0026] Next, the carboxylation step will be described in detail. The (meth)acrylate (b) having epoxy in one molecule used for producing the unsaturated group-containing polycarboxylic acid resin (A) is not particularly limited in structure as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. Examples of such compounds include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate, mono(meth)acrylated products of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether, and mono(meth)acrylated products of bifunctional alicyclic epoxy compounds such as 1,2:5,6-diepoxyhexahydroindane, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate. These epoxy group-containing (meth)acrylate compounds can be used alone or in combination of two or more. Among these, alicyclic epoxy is preferred because of its good heat resistance, and (meth)acrylate compounds having one epoxy group are preferred because the reaction can be easily controlled, and 3,4-epoxycyclohexyl methacrylate is preferred from the viewpoints of reactivity and curability. From the viewpoint of cure shrinkage and developability, the molar ratio ((b) / (a2)) of the (meth)acrylate having an epoxy group in one molecule (b) to the aromatic tricarboxylic anhydride (a2) is preferably in the range of 0.1 to 0.9, more preferably 0.2 to 0.8.

[0027] During the reaction, it is preferable to add a thermal polymerization inhibitor to suppress the thermal polymerization reaction, and the amount of the thermal polymerization inhibitor is 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the reaction product obtained by adding the polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, the (meth)acrylate compound (b) having an epoxy group in one molecule, and the solvent. Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-tert-butyl-p-cresol.

[0028] In addition, it is preferable to use a catalyst during the reaction to promote the reaction, and the amount of the catalyst used is 0.05 to 10 parts by mass relative to 100 parts by mass of the total amount of the reaction product obtained by adding the polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, the (meth)acrylate compound (b) having an epoxy group in one molecule, and the solvent. Examples of the catalyst used in this reaction include dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium 2-ethylhexanoate, chromium octanoate, zinc 2-ethylhexanoate, zinc octanoate, zirconium octanoate, dimethylsulfide, and diphenylsulfide.

[0029] The carboxylation step can be carried out without a solvent or diluted with an organic solvent, for example, the same as the solvents exemplified in the amide-imidization step.

[0030] 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.

[0031] The reaction in the carboxylation step is preferably allowed to proceed until the epoxy equivalent (solid epoxy equivalent) is 30,000 g / eq or more. The solid epoxy equivalent is measured by a normal neutralization titration method in accordance with JIS K 7236. In addition, if the concentration of the resin in the solution is known, the solid epoxy equivalent can also be calculated from the epoxy equivalent of the solution.

[0032] The preferred molecular weight range of the unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group with a (meth)acrylate compound (b) having an epoxy group in one molecule is, in terms of polystyrene, a weight average molecular weight measured by GPC of 1,500 to 10,000, more preferably 2,000 to 8,000, and particularly preferably 2,500 to 7,000. Furthermore, the molecular weight distribution (Mw / Mn), which is the ratio of the number average molecular weight (Mn) to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC, is preferably in the range of 1.0 to 3.5, more preferably 1.3 to 3.0, and particularly preferably 1.5 to 2.5.

[0033] In the production of the unsaturated group-containing polycarboxylic acid resin (A), it is preferable not to contain a compound having an alcoholic hydroxyl group not directly bonded to the alicyclic skeleton. By making the unsaturated group-containing polycarboxylic acid resin (A) not react with a compound having an alcoholic hydroxyl group not directly bonded to the alicyclic skeleton, the solder heat resistance is improved.

[0034] The content of the unsaturated group-containing polycarboxylic acid resin (A) in the photosensitive coloring composition of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, based on the total solid content. For example, 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.

[0035] The colored photosensitive composition contains a colorant (B) such as a light-shielding agent. Examples of the colorant (B) include light-shielding agents and colorants other than light-shielding agents.

[0036] Examples of the light-shielding agent include various pigments, whether organic or inorganic, such as lactam pigments, carbon black, dyes, perylene pigments, fine particles mainly composed of silver-tin (AgSn) alloy, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, metal sulfates, and metal carbonates. As the light-shielding agent, black pigments are preferable.

[0037] Carbon black As the carbon black, various carbon blacks that have been used as light-shielding agents can be used. As the carbon black, specifically, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. In addition, the carbon black may be coated with an organic material such as a resin, a dye, or an acidic group-containing compound. The carbon black may be used alone or in combination of two or more kinds.

[0038] ≪Dye≫ The dye may be appropriately selected from among known materials. Examples of dyes that can be used in the colored photosensitive composition include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes. Furthermore, these dyes can be dispersed in organic solvents by forming lakes (chlorinating them) and used as light-shielding agents. In addition to these dyes, dyes described in, for example, JP-A-2013-225132, JP-A-2014-178477, JP-A-2013-137543, JP-A-2011-38085, JP-A-2014-197206, etc. can also be preferably used. do.

[0039] Specific examples of other colorants include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists), specifically, compounds having the following Color Index (CI) numbers:

[0040] CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same, and only the numbers are listed.), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185; CI Pigment Orange 1 (hereinafter, the same will be referred to as "CI Pigment Orange" and only the numbers will be listed), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; CI Pigment Violet 1 (hereinafter, the same will be referred to as "CI Pigment Violet" and only the numbers will be listed), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; CI Pigment Red 1 (hereinafter, the same applies to "CI Pigment Red", and only the numbers are listed.), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 1 01, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; CI Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same, and only the number will be stated.), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37; CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26, CI Pigment Brown 28; CI Pigment Black 1, CI Pigment Black 7.

[0041] In terms of good light-shielding properties, the ratio of the mass of carbon black to the total mass of the colorant (B) is preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 100 mass% or more.

[0042] The form of the colorant (B) used in the preparation of the colored photosensitive composition is not particularly limited. The colorant (B) may be used as a powder or as a dispersion. The colorant (B) is preferably used in the preparation of the colored photosensitive composition as a dispersion. The dispersion liquid may contain two or more kinds of colorants (B). Also, two or more kinds of dispersion liquids each containing a different kind of colorant may be used.

[0043] Examples of the dispersion medium that can be used include organic solvents such as propylene glycol monomethyl ether acetate, cellosolve acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxyethyl acetate 3-ethoxyethyl propionate, and propylene glycol monomethyl ether propionate, as well as water.

[0044] A dispersant may be added to the colorant (B) in order to stabilize the dispersion of the colorant (B) in the dispersion liquid and to improve the dispersibility of the colorant (B) in the colored photosensitive composition. As the dispersant, it is preferable to use a polymer dispersant such as a polyethyleneimine-based dispersant, a urethane-based dispersant, an acrylic resin-based dispersant, etc. Among these dispersants, a urethane-based dispersant is preferable from the viewpoint of less generation of residues after development. A dispersing agent such as a copper compound may also be used. An example of the copper compound is copper phthalocyanine. In addition, since corrosive gas caused by the dispersant may be generated from the cured film, one example of a preferred embodiment is that the colorant (B) is dispersed without using a dispersant. When the colorant (B) contains a dispersant, the proportion of the dispersant in the colorant (B) is, for example, from 5% by mass to 60% by mass, and preferably from 10% by mass to 50% by mass.

[0045] The viscosity of the dispersion of the colorant (B) is not particularly limited, but the viscosity of the dispersion is preferably 3 mPa·s or more and 200 mPa·s or less as measured at 25° C. using a cone-plate viscometer.

[0046] The particle size of the colorant (B) in the dispersion is preferably 80 nm or more and 300 nm or less in terms of the dispersion average particle size, which can be measured using a laser diffraction type particle size distribution system.

[0047] The content ratio of the colorant (B) relative to the total mass of the solid content of the colored photosensitive composition is not particularly limited, but the upper limit of the total content of the colorant (B) may be 70 mass% or less, 65 mass% or less, or 60 mass% or less. The lower limit is usually 1 mass% or more, for example, 10 mass% or more, preferably 20 mass% or more, and more preferably 30 mass% or more, based on the total solid content. In this specification, the amount of the colorant (B) can be defined as a value including the amount of the dispersant present together with the colorant (B).

[0048] The colored photosensitive composition contains a solvent (C). Examples of the solvent (C) are the same as those given when synthesizing the unsaturation-containing polycarboxylic acid resin (A), and include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n- (Poly)alkylene glycol monoalkyl ethers such as butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl esters of lactate such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, Examples of the solvent include other esters such as n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; and benzyl esters of aliphatic carboxylic acids such as benzyl acetate, benzyl propionate, benzyl butanoate, and benzyl pentanoate. These solvents may be used alone or in combination of two or more.

[0049] Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are preferred because they exhibit excellent solubility in the photopolymerization initiator (E) described below, and it is particularly preferred to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. In addition, in terms of coatability, the above preferred solvents may be used in combination with the benzyl ester of an aliphatic carboxylic acid, and when the benzyl ester of an aliphatic carboxylic acid is contained, the content of the benzyl ester of an aliphatic carboxylic acid is preferably 1% by mass or more and 10% by mass or less with respect to the entire solvent (C). The content of the solvent (C) is not particularly limited, but is preferably an amount that results in a solids concentration of the photosensitive composition of 1 mass % or more and 80 mass % or less, and more preferably an amount that results in a solids concentration of 5 mass % or more and 70 mass % or less.

[0050] The photosensitive resin composition may contain a crosslinking agent (D). Examples of the crosslinking agent (D) used in the photosensitive resin composition include radical reaction type acrylates, cationic reaction type epoxy compounds, vinyl compounds that react with both of them, maleimide compounds, and the like.

[0051] Examples of radical reaction type acrylates include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0052] Examples of the monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, Examples of the acrylic acid include leic acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylate of phthalic acid derivatives. These monofunctional monomers can be used alone or in combination of two or more kinds.

[0053] Examples of the polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene Glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of hydroxypivalic acid neopentyl glycol and ε-caprolactone adduct, poly(meth)acrylate of 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, tricyclodecane dimethanol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, p)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, poly(ethylene-propylene) glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate,Tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate Examples of the glycidyl ester di(meth)acrylate include glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, or the like with 2-hydroxyethyl (meth)acrylate), methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, a condensation product of a polyhydric alcohol with N-methylol (meth)acrylamide, triacrylformal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate, and 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol diacrylate.

[0054] The cationic reaction type epoxy compounds are not particularly limited as long as they are compounds having an epoxy group, including the epoxy compound (i). Examples of the epoxy compounds include glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol-A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (e.g., "Cyracure UVR-6110" manufactured by Union Carbide), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (e.g., "ELR-4206" manufactured by Union Carbide), limonene diamine, and the like. oxide (Daicel Chemical Industries, Ltd.'s "Celloxide 3000", etc.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl)adipate (Union Carbide Corporation's "Cyracure UVR-6128", etc.), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexyl)diethylsiloxane, and the like.

[0055] Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrenes include styrene, methylstyrene, and ethylstyrene. Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

[0056] The maleimide compounds are not particularly limited as long as they have one or more maleimide groups in the molecule, and specific examples thereof include N-phenylmaleimide, N-cyclohexylmaleimide, N-hydroxyphenylmaleimide, N-anilinophenylmaleimide, N-carboxyphenylmaleimide, N-(4-carboxy-3-hydroxyphenyl)maleimide, 6-maleimidohexanoic acid, 4-maleimidobutyric acid, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, 4,4-diphenylmethane bismaleimide, and bis(3,5-dimethyl-4-maleimidophenyl). Methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m-phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenyl Methane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,2-bismaleimide ethane, 1,4-bismaleimide butane, 1,5-bismaleimide pentane, 1,5-bismaleimide-2-methylpentane, 1,6-bismaleimide hexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,8-bismaleimide-3,6-dioxaoctane, 1,11-bismaleimide-3,6,9-trioxaundecane, 1,3-bis(maleimidemethyl)cyclohexane, 1,4-bis(maleimide) imidomethyl)cyclohexane, 4,4-diphenylether bismaleimide, 4,4-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 4,4-diphenylmethane biscitraconimide, 2,2-bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis(3,Examples of the maleimide compounds include those represented by formula (6) such as 5-diethyl-4-citraconimidophenyl)methane, polyphenylmethanemaleimide, and polyphenylmethanemaleimide, maleimide compounds represented by formula (7), fluorescein-5-maleimide, and prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds.

[0057] As the maleimide compound represented by the following formula (1), a commercially available product may be used, for example, BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd. As the maleimide compound represented by formula (2), a commercially available product may be used, for example, MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd. As the maleimide compound represented by formula (3), a commercially available product may be used, for example, MIR-5000 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0058] [ka]

[0059] In formula (1), R 1 Each independently represents a hydrogen atom or a methyl group. 1 represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

[0060] [ka]

[0061] In formula (2), R 2 Each independently represents a hydrogen atom or a methyl group. 2 represents an integer of 1 or more, and preferably an integer of 1 to 5.

[0062] [ka]

[0063] In formula (3), R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group; 2 Each independently represents an integer of 1 to 3, 5 represents an integer from 1 to 10. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and a neopentyl group.

[0064] The crosslinking agent (D) may be used alone or in combination of two or more kinds. The content of the crosslinking agent (D) in the colored photosensitive composition when the crosslinking agent (D) is not particularly limited, but is preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, based on the total mass of the solid content of the colored photosensitive composition. By setting the content in the above range, the sensitivity, developability, and resolution tend to be well balanced.

[0065] The colored photosensitive composition may contain a photopolymerization initiator (E). The photopolymerization initiator (E) is not particularly limited, and any conventionally known photopolymerization initiator may be used. can be done.

[0066] Specific examples of the photopolymerization initiator (E) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis( 4-Dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxy Shim, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetate thioxanthene, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, o-benzoylmethylbenzoate, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-Diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxy Benzophenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone acetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6- Bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine Examples of the benzophenones include nyl-s-triazine, 2-ethylanthraquinone, 2-tertiary butylanthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, acetophenone dimethyl ketal, benzyl dimethyl ketal, benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone, and other benzophenones, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. These photopolymerization initiators can be used alone or in combination of two or more kinds.

[0067] Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. Particularly preferable oxime-based photopolymerization initiators include O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, ethanone, 1-[9-ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazol-3-yl], 1-(O-acetyl oxime), and 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone.

[0068] As described above, the colored photosensitive composition preferably contains an oxime ester compound as the photopolymerization initiator (E). The oxime ester compound has an excellent ability to absorb ultraviolet light and generate radicals. Therefore, the oxime ester compound has high sensitivity, and even when a high concentration of a colorant (B) such as a light-shielding agent is contained, the colored photosensitive composition is likely to be sufficiently cured with a small amount of exposure. In the case of a colored photosensitive composition containing a large amount of colorant (B), it is possible to form the colored photosensitive composition. When the optical density of the film formed is 3, the amount of UV exposure in the deep layer is 1 / 1000 of the amount of UV exposure in the surface layer (top surface). Although the amount of UV radiation is considerably less than that of UV radiation, the oxime ester compounds react with such relatively little UV radiation. Even with a linear exposure dose, radicals are generated, and the colored photosensitive composition can be cured satisfactorily.

[0069] In addition, when the above-mentioned colorant (B) is blended in a high concentration in the colored photosensitive composition, In the coating film made of the composition, primary aggregates of the colorant (B) are inevitably generated. However, when a colored photosensitive composition containing an oxime ester compound is used as the photopolymerization initiator (E), the photopolymerization initiator (E) generates radicals when irradiated with ultraviolet light even in small gaps where aggregates are overlapped in a complex manner. As a result, the cured product of the colored photosensitive composition not only has excellent adhesion to a substrate and electrical resistivity (insulation properties) under an environment of normal temperature, normal humidity and atmospheric pressure, but also has excellent electrical resistivity (insulation properties) when exposed to a high-temperature, high-humidity and high-pressure environment. Even when exposed to heat, the adhesiveness to the substrate and electrical resistivity (insulation) are unlikely to decrease. Durability in high temperature, high humidity and high pressure environments can be confirmed by the so-called PCT test (pressure cooker test). For this reason, the performance of a cured product (colored film) of a colored photosensitive composition containing an oxime ester compound is unlikely to deteriorate even when used in a high-temperature or high-humidity environment.

[0070] As the photopolymerization initiator (E), an oxime ester compound may be used in combination with a photopolymerization initiator other than an oxime ester compound. In this case, the ratio of the mass of the oxime ester compound to the total mass of the photopolymerization initiator (E) is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more.

[0071] Examples of photopolymerization initiators other than the oxime ester compounds include aminoalkylpheno A photopolymerization initiator based on a silyl group can be preferably used. Examples of the aminoalkylphenone compound include 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., IRGACURE 369 manufactured by Ciba Specialty Chemicals), 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., IRGACURE 379 manufactured by Ciba Specialty Chemicals), 2-(4-ethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., IRGACURE 379 manufactured by Ciba Specialty Chemicals), and 2-(4-ethylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (e.g., IRGACURE 379 manufactured by Ciba Specialty Chemicals). 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- 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-morpholino phenyl)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 -one, 2-(4-n-butyloxybenzyl)-2-[(n-butyl)(methyl)amino]-1-(4-morpholinophenyl)pentan-1-one, 2-(4-methylbenzyl)-2-[di(n-octyl)amino]-1-(4-morpholinophenyl)hexan-1-one, and 2-(4-n-dodecylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)octan-1-one. Among them, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholino) phenyl)butan-1-one is preferred.

[0072] By combining an aminoalkylphenone-based photopolymerization initiator with an oxime ester compound, it becomes easier to control the cross-sectional shape of a patterned colored film formed using the colored photosensitive composition. This is believed to be because the aminoalkylphenone photopolymerization initiator tends to generate photopolymerization radicals relatively in the surface layer portion of the colored photosensitive composition (the surface facing the light to be exposed and its vicinity), while the oxime ester compound tends to generate photopolymerization radicals relatively in the deeper layer portion of the colored photosensitive composition. This tendency is more pronounced as the film thickness of the colored photosensitive composition increases, but is also observed in a film thickness of 1 μm or less. In addition, as a secondary effect of using an aminoalkylphenone-based photopolymerization initiator together with an oxime ester compound, the sensitivity is improved overall, and a cured product of the colored photosensitive composition can be obtained with a small amount of exposure. Furthermore, when an aminoalkylphenone-based photopolymerization initiator is used together with an oxime ester compound, the straightness of the line edge and the adhesion to the substrate are better, and it is easy to form a patterned colored film with fewer pattern defects.

[0073] In the colored photosensitive composition, when the photopolymerization initiator (E) contains an oxime ester compound and an aminoalkylphenone photopolymerization initiator, the ratio of the mass of the aminoalkylphenone photopolymerization initiator to the total mass of the oxime ester compound and the mass of the aminoalkylphenone photopolymerization initiator is preferably from 20% by mass to 75% by mass, more preferably from 25% by mass to 70% by mass, and particularly preferably from 30% by mass to 60% by mass.

[0074] The content of the photopolymerization initiator (E) in the colored photosensitive composition is not particularly limited as long as it does not impair the object of the present invention. The content of the photopolymerization initiator (E) is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.3% by mass or more and 20% by mass or less, and particularly preferably 0.5% by mass or more and 10% by mass or less, based on the mass of the solid content of the colored photosensitive composition.

[0075] 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, oxazine compounds, etc. The curing agent (F) can be added during and after the curing process to improve heat resistance, and is particularly preferably used when improving thermal decomposition resistance by reacting with carboxyl groups and hydroxyl groups contained in the colored photosensitive composition by heating.

[0076] Specific examples of epoxy compounds as the curing agent (F) include phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac type epoxy resins, glyoxal type epoxy resins, naphthalene skeleton-containing epoxy resins, cardo skeleton-containing epoxy resins, bisphenol fluorene type epoxy resins, heterocyclic epoxy resins, and the like.

[0077] Examples of the phenol novolac type epoxy resin include Epicron N-770 (manufactured by DIC Corporation), DEN438 (manufactured by Dow Chemical Company), jER154 (manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201, and RE-306 (all manufactured by Nippon Kayaku Co., Ltd.). Examples of the cresol novolac type epoxy resin include Epicron N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide Corporation), and ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.).

[0078] Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by The Dow Chemical Company), jER E1032H60 (manufactured by Japan Epoxy Resins Co., Ltd.), and the like. Examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 (manufactured by DIC Corporation) and TACTIX-556 (manufactured by The Dow Chemical Company).

[0079] Examples of the bisphenol type epoxy resin include bisphenol-A type epoxy resins such as jER828, jER1001 (both manufactured by Japan Epoxy Resins Co., Ltd.), UVR-6410 (manufactured by Union Carbide Corporation), DER-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.), NER-1202, NER-1302 (all manufactured by Nippon Kayaku Co., Ltd.), and bisphenol-F type epoxy resins such as UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (manufactured by Tohto Kasei Co., Ltd.), NER-7403, NER-7604 (all manufactured by Nippon Kayaku Co., Ltd.).

[0080] Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000, NC-3000-H, and NC-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), bixylenol type epoxy resins such as YX-4000 (manufactured by Japan Epoxy Resins Co., Ltd.), and YL-6121 (manufactured by Japan Epoxy Resins Co., Ltd.). Examples of the bisphenol A novolac type epoxy resin include Epicron N-880 (manufactured by DIC Corporation) and jER E157S75 (manufactured by Japan Epoxy Resins Co., Ltd.).

[0081] Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Corporation). Examples of the cardo skeleton-containing epoxy resin include PG-100, CG-500, EG-200, and EG-280 (manufactured by Osaka Gas Chemicals Co., Ltd.). An example of the glyoxal type epoxy resin is GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Corporation), etc. Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.), etc.

[0082] Specific examples of the oxazine compound as the curing agent (F) include Bm-type benzoxazine, Pa-type benzoxazine, and Ba-type benzoxazine (all manufactured by Shikoku Chemical Industry Co., Ltd.).

[0083] The curing agent (F) may be used alone or in combination of two or more kinds. The content of the curing agent (F) is not particularly limited, but is preferably 0 to 40 mass % and more preferably 3 to 30 mass % based on the mass of the solid content of the colored photosensitive composition. By setting the content of the polyfunctional crosslinking compound (D) within the above range, it is easy to obtain a photosensitive resin composition that can form a cured film with high heat resistance.

[0084] The colored photosensitive composition contains a crosslinking agent (D) and a photopolymerization initiator (E) in addition to the unsaturated group-containing polycarboxylic acid resin (A), a colorant (B), and a solvent (C), and thus has high photosensitivity, is dispersible even at a high colorant concentration, and has good development characteristics. In addition, by containing a curing agent (F) as necessary, the heat resistance can be improved.

[0085] The colored photosensitive composition may contain, as other components (G), resins other than the unsaturated group-containing polycarboxylic acid (A), the crosslinking agent (D), and the curing agent (F), surface conditioners, adhesion improvers, and other various additives, as long as the object of the present invention is not impaired. The amount of the other components (G) added is not particularly limited. The amount of the other components (G) that does not impair the object of the present invention can be used.

[0086] <Surface conditioner> The surface conditioner reduces the surface tension of the colored photosensitive composition, thereby preventing surface defects and poor appearance due to uneven distribution of colorants such as pigments (uneven distribution of colorants such as pigments). Specifically, polydimethylsiloxane, polyether-modified polysiloxane, polymethylalkylsiloxane, polysiloxane modified with an aralkyl group or polyester chain, etc. can be suitably used.

[0087] <Adhesion improver> Known coupling agents such as silane coupling agents, titanate coupling agents, aluminate coupling agents, etc. can be used. Among these, silane coupling agents are preferably used from the viewpoint of improving adhesion to the glass substrate.

[0088] The colored photosensitive composition may contain various additives other than those described above, if necessary.Specific examples include sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersion aids, fillers, antioxidants, UV absorbers, aggregation inhibitors, thermal polymerization inhibitors, defoamers, surfactants, liquid repellents, chain transfer agents, photoinitiation aids, solvents, etc.For any of the additives, conventionally known ones can be used.

[0089] Examples of the surfactant include anionic compounds, cationic compounds, and nonionic compounds. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Examples of the antifoaming agent include silicone-based compounds and fluorine-based compounds. Examples of the chain transfer agent include mercaptan compounds, halogen compounds, quinone compounds, and α-methylstyrene dimers. By including a chain transfer agent, the pattern shape (particularly, the CD change and exposure margin of the hole pattern) can be well controlled. Among them, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferable in that it can reduce sublimates, coloring, and odors in addition to the above effects. Examples of the photoinitiator assistant include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photoinitiator assistants may be used alone or in combination of two or more.

[0090] Examples of the liquid repellent include a fluorine atom-containing resin having a crosslinking group. Since the liquid repellent can impart ink repellency to the surface of the partition wall, it is considered that the liquid repellent can prevent color mixing between pixels when the colored photosensitive composition is used to form the partition wall. Examples of the crosslinking group include an epoxy group or an ethylenically unsaturated group, and from the viewpoint of suppressing the outflow of the liquid repellent into the developer, an ethylenically unsaturated group is preferred. The fluorine atom-containing resin having a crosslinking group preferably has either one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Examples of the perfluoroalkyl group include a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. Examples of the perfluoroalkylene ether chain include -CF 2 -O-, -(CF 2 ) 2 -O-, -(CF 2 )3-O-, -CF 2 -C(CF 3 )O-, -C(CF 3 )-CF 2 Examples of the repeating unit include -O- and divalent groups having these repeating units.

[0091] Specific examples of the fluorine-containing resin having a crosslinking group include, for example, an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, an epoxy (meth)acrylate resin having an epoxy group and a perfluoroalkyl group, an epoxy (meth)acrylate resin having 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. Among them, from the viewpoint of ink repellency, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferred, and an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain is more preferred. Commercially available fluorine-containing resins having these crosslinking groups include "Megafac (registered trademark, the same applies below) F116", "Megafac F120", "Megafac F142D", "Megafac F144D", "Megafac F150", "Megafac F160", "Megafac F171", "Megafac F172", "Megafac F173", "Megafac F177", "Megafac F178A", "Megafac F178K", ​​"Megafac F179", "Megafac F183", "Megafac F184", "Megafac F191", "Megafac F812", and "Megafac F193". F815", "Megafac F824", "Megafac F833", "Megafac RS101", "Megafac RS102", "Megafac RS105", "Megafac RS201", "Megafac RS202", "Megafac RS301", "Megafac RS303", "Megafac RS304", "Megafac RS401", "Megafac RS402", "Megafac RS501", "Megafac RS502", "Megafac RS-72-K", "Megafac RS-78", "Megafac RS-90", "DEFENSA (registered trademark, the same applies below) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", 3M Japan Ltd.'s "Florald FC430", "Florald FC431", "F It is possible to use fluorine-containing organic compounds commercially available under trade names such as "C-4430", "FC4432", "Asahi Guard (registered trademark) AG710" manufactured by AGC, "Surflon (registered trademark, the same applies below) S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", and "Surflon SC-106".

[0092] <<Method for preparing colored photosensitive composition>> The colored photosensitive composition is prepared, for example, by uniformly stirring and mixing the above-mentioned components, and uniformly dissolving and dispersing them. The components may be mixed using a stirrer such as a roll mill, a ball mill, or a sand mill. If necessary, the composition may be prepared by filtering through a filter such as a 2 μm membrane filter.

[0093] <Colored film and patterned colored film> A colored film can be obtained by curing the colored photosensitive composition. The method for producing a colored film includes a step of applying a colored photosensitive composition to form a coating film, and a step of exposing the coating film to light. In addition, a method for producing a patterned colored film includes a step of forming a coating film by applying a colored photosensitive composition, a step of position-selectively exposing the coating film, and a step of developing the coating film after exposure. By using the above colored photosensitive composition as a negative-type photosensitive composition, a highly precise pattern having good linearity can be formed even if a high concentration of colorant is contained.

[0094] Each step will be described below. Forming a coating film using a colored photosensitive composition is referred to as a "coating film forming step." Exposing the coating film to light is referred to as an "exposure step." Developing the exposed coating film is referred to as a "development step."

[0095] <Coating film formation process> In the coating film forming step, the colored photosensitive composition is applied onto a substrate to form a coating film. The type of substrate is not particularly limited, and various substrates used in optical elements such as liquid crystal display elements, organic EL display elements, and organic TFT arrays can be used as appropriate. Examples of substrates include quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, SOG (Spin On Glass), polyester films, polycarbonate films, and polymer substrates such as polyimide films, TFT array substrates, electrode plates for PDPs, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, and semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. Furthermore, for example, when a laminated structure is formed on a substrate, any layer that becomes a lower structure already formed on the substrate is also included in the concept of the substrate to which the colored photosensitive composition is applied. The shape of the substrate is also not particularly limited, and may be a plate or a roll. The substrate may have unevenness on the surface due to various patterns, for example. As the substrate, a light-transmitting or light-non-transmitting substrate can be selected.

[0096] In the coating film forming step, for example, the colored photosensitive composition is applied onto a substrate using 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, and if necessary, the solvent is removed by drying (pre-baking) to form a coating film.

[0097] The thickness of the coating film is not particularly limited. The thickness of the coating film is preferably 0.05 μm or more, more preferably 1 μm or more. The thickness of the coating film may be, for example, 7 μm or more, or 10 μm or more. There is no particular upper limit to the thickness of the coating film, but it may be, for example, 50 μm or less, or 20 μm or less. The thickness of the coating film is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 2 μm or less. The thickness of the coating film is preferably in the range of 0.05 μm to 10 μm, more preferably 1 μm to 5 μm, and even more preferably 1 μm to 2 μm.

[0098] The coating film may be dried as necessary. The drying method is not particularly limited. Examples of the drying method include (1) drying on a hot plate at a temperature of 80° C. to 120° C., preferably 90° C. to 100° C., for 60 to 120 seconds, (2) leaving at room temperature for several hours to several days, and (3) placing in a hot air heater or infrared heater for several tens of minutes to several hours to remove the solvent.

[0099] <Exposure process> In the exposure step, the coating film formed in the coating film forming step is exposed to light. This results in a cured film (colored film) of the colored photosensitive composition. By selectively exposing and developing the film according to the pattern shape, a patterned cured film (colored film) is obtained.

[0100] In the exposure step, the coating film is exposed to radiation or electromagnetic waves such as i-rays, g-rays, or h-rays. When forming a patterned cured film (colored film), the coating film is exposed to light selectively through a negative mask. The exposure dose varies depending on the composition of the colored photosensitive composition, but is, for example, 5 mJ / cm. 2 More than 500mJ / cm 2 The preferred range is 10 mJ / cm or less. 2 More than 150mJ / cm 2 The following is preferable.

[0101] The cured film cured by exposure may be heated. The temperature at which the heating is performed is not particularly limited, and is preferably 180° C. to 280° C., more preferably 200° C. to 260° C., and particularly preferably 220° C. to 250° C. The heating time is typically preferably 1 minute to 60 minutes, more preferably 10 minutes to 50 minutes, and particularly preferably 20 minutes to 40 minutes.

[0102] ≪Development process≫ In the developing step, the coating film exposed in the exposing step is developed with an alkaline developer. In the development step, the exposed coating film is developed with a developer to form a cured film (colored film) patterned into a desired shape. The development method is not particularly limited, and a dipping method, a spray method, or the like can be used. Specific examples of the developer include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

[0103] After development, post-baking may be performed if necessary. The temperature of the post-baking after development is preferably from 80° C. to 250° C., more preferably from 100° C. to 230° C. The time of the post-baking after development is preferably from 5 minutes to 60 minutes, more preferably from 10 minutes to 30 minutes.

[0104] By using the above-mentioned colored photosensitive composition, as shown in the examples described later, it is possible to disperse a colorant at a high concentration and form a high-definition pattern, and if it is desired to improve heat resistance, a curing agent can be contained. EXAMPLES

[0105] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, parts are by weight unless otherwise specified.

[0106] The epoxy equivalent and acid value were measured under the following conditions. 1) Epoxy equivalent (WPE): Measured according to a method in accordance with JIS K 7236:2001. 2) Acid value: Measured according to the method of JIS K 0070:1992. 3) The measurement conditions for gel permeation chromatography (GPC) are as follows. Model: TOSOH HLC-8220GPC Column: TSKGEL Super HZM-N Eluent: THF (tetrahydrofuran); 0.35 ml / min, temperature 40°C Detector: Differential refractometer Molecular weight standards: polystyrene

[0107] Manufacturing Example 1 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 147.4 g of propylene glycol monomethyl ether acetate, 84.2 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANAT T-1890 / 100", isocyanate group content 17.3% by mass), and 63.3 g of trimellitic anhydride were added. The temperature was raised to 122°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 48 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1 It was confirmed that the absorption of 1,070 mgKOH / g had disappeared completely. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,070, the weight average molecular weight was 2,560, and the solid acid value was 135 mgKOH / g. The solution was cooled to 60°C, and 27.2 g of propylene glycol monomethyl ether acetate, 27.2 g of 3,4-epoxycyclohexylmethyl methacrylate, and 0.35 g of dibutylhydroxytoluene were added and stirred, and then 0.70 g of triphenylphosphine was added and heated to 116°C. The reaction was continued at the same temperature for 20 hours, and an unsaturated group-containing polycarboxylic acid resin (I) was obtained with a solid acid value of 85.1 mgKOH / g, a (meth)acrylic equivalent of 1259, a number average molecular weight by GPC of 1,910, a weight average molecular weight of 3,830, and a molecular weight distribution of 2.0. The epoxy equivalent was measured to be 44,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0108] Manufacturing Example 2 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 131.1 g of propylene glycol monomethyl ether acetate, 67.2 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANAT T-1890 / 100", isocyanate group content 17.3% by mass), and 63.9 g of trimellitic anhydride were added. The temperature was raised to 122°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 48 hours. Infrared spectroscopy confirmed that the absorption at 2250 cm-1, which is the characteristic absorption of the isocyanate group, had completely disappeared. An amide-imide resin (2) solution was obtained, which had a number average molecular weight of 780, a weight average molecular weight of 1,830, and a solid acid value of 165 mgKOH / g, as measured by gel permeation chromatography using polystyrene as a standard. The mixture was cooled to 60°C, and 43.5g of propylene glycol monomethyl ether acetate, 43.5g of 3,4-epoxycyclohexylmethyl methacrylate, and 0.35g of dibutylhydroxytoluene were added and stirred. Then, 0.70g of triphenylphosphine was added and the temperature was raised to 116°C. The mixture was reacted at the same temperature for 20 hours to obtain an unsaturated group-containing polycarboxylic acid resin (II) with a solid acid value of 65.2mgKOH / g, a (meth)acrylic equivalent of 788, a number average molecular weight by GPC of 2,160, a weight average molecular weight of 4,130, and a molecular weight distribution of 1.9. The epoxy equivalent was also measured to be 37,000kg / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0109] Manufacturing Example 3-1 127.0g of 1,2:5,6-diepoxyhexahydroindane (epoxy equivalent 76.5g / eq) and 0.60g of dibutylhydroxytoluene were added to a four-neck flask equipped with a stirrer, thermometer, condenser, and nitrogen line and stirred at 80°C. Then, 71.8g of methacrylic acid and 0.60g of tetrabutylammonium bromide were added and heated to 116°C. The mixture was allowed to react at the same temperature for 8 hours to obtain a methacrylate compound (b1) with an epoxy group in one molecule and a solid acid value of 0.8mg KOH / g.

[0110] Manufacturing Example 3-2 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 142.2 g of propylene glycol monomethyl ether acetate, 81.2 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANAT T-1890 / 100", isocyanate group content 17.3% by mass), and 61.0 g of trimellitic anhydride were added. The temperature was raised to 122°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 48 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1 It was confirmed that the absorption of α-aminobutyric acid had completely disappeared. An amide-imide resin (3) solution was obtained with a number average molecular weight of 1,100 and a weight average molecular weight of 2,590 by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 137 mgKOH / g. The solution was cooled to 60°C, and 31.9 g of propylene glycol monomethyl ether acetate, 31.9 g of the methacrylate compound (b1) having an epoxy group in one molecule obtained in Production Example 3-2, and 0.35 g of dibutylhydroxytoluene were added and stirred, and then 0.70 g of triphenylphosphine was added and the temperature was raised to 116°C. The reaction was continued at the same temperature for 20 hours, and an unsaturated group-containing polycarboxylic acid resin (III) was obtained with a solid acid value of 82.9 mgKOH / g, a (meth)acrylic equivalent of 1302, a number average molecular weight of 1,950 by GPC, a weight average molecular weight of 4,300, and a molecular weight distribution of 2.2. In addition, the epoxy equivalent was measured to be 43,000 kg / eq, confirming that the epoxy groups had reacted sufficiently.

[0111] Production Example 4 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 174.2 g of propylene glycol monomethyl ether acetate, 83.2 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANAT T-1890 / 100", isocyanate group content 17.3% by mass), and 64.5 g of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride were added. The temperature was raised to 116°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 30 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 1,250 mgKOH / g was completely disappeared. The number average molecular weight by gel permeation chromatography using polystyrene as a standard was 1,250, the weight average molecular weight was 3,680, and the solid acid value was 161 mgKOH / g. The solution was cooled to 60°C, and 26.9 g of propylene glycol monomethyl ether acetate, 26.9 g of 3,4-epoxycyclohexylmethyl methacrylate, and 0.35 g of dibutylhydroxytoluene were added and stirred, and then 0.7 g of triphenylphosphine was added and heated to 116°C. The reaction was continued at the same temperature for 20 hours, and an unsaturated group-containing polycarboxylic acid resin (I') was obtained with a solid acid value of 79.2 mgKOH / g, a (meth)acrylic equivalent of 1273, a number average molecular weight by GPC of 1,640, a weight average molecular weight of 5,950, and a molecular weight distribution of 3.6. The epoxy equivalent was also measured to be 38,000 kg / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0112] Production Example 5 Into a four-neck flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen line, 150.1 g of propylene glycol monomethyl ether acetate, 76.0 g of an isocyanurate modified product of isophorone diisocyanate (EVONIK's "VESTANAT T-1890 / 100", isocyanate group content 17.3% by mass), and 58.9 g of citrimellitic anhydride were added. The temperature was raised to 122°C while blowing nitrogen into the system, and the reaction was carried out at the same temperature for 48 hours. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2250 cm was observed. -1It was confirmed that the absorption of 111 mgKOH / g had completely disappeared. The mixture was cooled to 60°C, and 15.3 g of a mixture of pentaerythritol (tri / tetra)acrylate (Daicel-Allnex Corporation's "PETRA", hydroxyl value 115 mgKOH / g) was added. The mixture was heated to 116°C and reacted at the same temperature for 10 hours to obtain an amide-imide resin (5) solution with a number average molecular weight of 1,250 and a weight average molecular weight of 3,050 measured by gel permeation chromatography using polystyrene as a standard, and a solid acid value of 111 mgKOH / g. The mixture was cooled to 60°C, and 24.6 g of propylene glycol monomethyl ether acetate, 24.6 g of 3,4-epoxycyclohexylmethyl methacrylate, and 0.35 g of dibutylhydroxytoluene were added and stirred, and then 0.70 g of triphenylphosphine was added and the temperature was raised to 116°C. After reacting at the same temperature for 20 hours, an unsaturated group-containing polycarboxylic acid resin (II') was obtained with a solid acid value of 57.1 mgKOH / g, a number average molecular weight by GPC of 1,720, a weight average molecular weight of 4,490, and a molecular weight distribution of 2.6. The epoxy equivalent was measured to be 55,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0113] Production Example 6 In a four-neck flask equipped with a stirrer, thermometer, and condenser, 250.3g of propylene glycol monomethyl ether acetate, 435.7g of cresol novolac epoxy resin ("EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 218g / eq), and 1.75g ​​of dibutylhydroxytoluene were added and stirred at 80℃ to dissolve the epoxy resin. Then, 148.4g of acrylic acid and 1.75g ​​of triphenylphosphine were added and the mixture was heated to 116℃, and reacted at the same temperature for 12 hours to obtain a reactive epoxide carboxylate resin (1) solution with a solid acid value of 2.2mg·KOH / g and an epoxy equivalent of 13kg / eq. The mixture was cooled to 60℃, and 48.6g of propylene glycol monomethyl ether acetate and 113.5g of 1,2,3,6-tetrahydrophthalic anhydride were added and the mixture was heated to 100℃. The reaction was continued at the same temperature for 5 hours to obtain an unsaturated group-containing polycarboxylic acid resin (III') having a solid acid value of 61.2 mgKOH / g, a (meth)acrylic equivalent of 349, a number average molecular weight by GPC of 2060, a weight average molecular weight of 6420, and a molecular weight distribution of 3.2. The epoxy equivalent was measured to be 13,000 g / eq, and it was also confirmed that the epoxy groups had reacted sufficiently.

[0114] Production Example 7 The resin described in Example 2-1 of Patent-6576161 was produced as described, and a reactive polycarboxylic acid compound (IV') was obtained having a solid acid value of 61.5 mg KOH / g, a (meth)acrylic equivalent of 335, a number average molecular weight of 1830 by GPC, and a weight average molecular weight of 3520.

[0115] [Example 1, Comparative Example 1] Preparation of colored photosensitive composition and evaluation of kneading dispersibility In the examples and comparative examples, 20 g of the unsaturated group-containing polycarboxylic acid resin obtained in Production Examples 1 to 7 and Mitsubishi Carbon Black MA-100 (B1) were used as the colorant (B). As the solvent (C), propylene glycol monomethyl ether acetate (C1) was used so that the mass ratio of the components other than the organic solvent was 60 mass% solid content, and the mixture was kneaded with a bead mill and the state after kneading was confirmed. The colored photosensitive composition obtained was marked as ◯ when it was uniform, and marked as × when it was non-uniform or gelation occurred due to the resin. [Table 1]

[0116] [Example 2, Comparative Example 2] Preparation of colored photosensitive composition and evaluation of colorant dispersibility The colored photosensitive compositions obtained in Example 1 and Comparative Example 1 were mixed with DPHA (trade name: manufactured by Nippon Kayaku Co., Ltd.) (D1) as a crosslinking agent (D) and 20 g of glass beads, and dispersed for 1 hour using a paint shaker. The dispersion after dispersion was applied to a polyethylene terephthalate film using a wire bar coater #2, and dried for 10 minutes using a hot air dryer at 80°C. The gloss of the coating surface after drying was measured using a 60° reflection gloss meter (Horiba Ltd. IG-331 gloss meter) to evaluate the dispersibility of carbon black. The results are shown in Table 2. The higher the gloss value, the better the pigment dispersibility.

[0117] [Table 2]

[0118] [Example 3, Comparative Example 3] Preparation of colored photosensitive composition and evaluation of developability The unsaturated group-containing polycarboxylic acid resins (A) obtained in Production Examples 1 to 7, the colorant (B1), the solvent (C1), the crosslinking agent (D), and the photopolymerization initiator (E) were uniformly dispersed in the formulation shown in Table 3 to obtain resist resin compositions. In the examples and comparative examples, DPHA (product name: manufactured by Nippon Kayaku Co., Ltd.) (D1) was used as the crosslinking agent (D), and Irgacure 907 (manufactured by Chiba Specialty Chemicals) (E1) and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (E2) were used as the photopolymerization initiator (E).

[0119] Each evaluation item will be described in detail.

[0120] Developability evaluation (abbreviation in table: developability) The colored photosensitive composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) with an applicator to a thickness of 20 μm, and the coating was dried for 30 minutes in a hot air dryer at 80° C. The dried coating film was irradiated with 150 mJ / cm 2 using an ultraviolet irradiator (USHIO (ultra-high pressure mercury lamp)) through a mask with a 50 μm opening. 2 The coating was cured at an irradiation dose of 100 nm. Thereafter, spray development was performed using a 1% aqueous solution of sodium carbonate as a developer. The developability was evaluated based on the time it took for the coating film in the unexposed area to completely dissolve, that is, the so-called break time. ○ 60 seconds or less △ 61 seconds or more × Unable to develop

[0121] Residual evaluation (abbreviation in table: residual) The resist resin composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Co., Ltd.) with an applicator to a thickness of 20 μm, and the coating film was dried for 30 minutes in a hot air dryer at 80° C. The composition film obtained above was irradiated with 500 mJ / cm 2 using an ultraviolet irradiator (CS 30L-1, manufactured by GS YUASA) through a mask with a line width of 100 μm. 2 The pattern was then developed by spraying a 1% aqueous solution of sodium carbonate as a developer, and the residue in the unexposed areas was examined using a microscope for evaluation. ○ No residuals × Residuals present

[0122] Thermal decomposition resistance evaluation (abbreviation in table: thermal decomposition resistance) The colored photosensitive composition was applied to rolled copper foil BHY-82F-HA-V2 (manufactured by JX Metals Corporation) with an applicator to a thickness of 20 μm, and the coating was dried for 30 minutes in a hot air dryer at 80°C. After that, it was irradiated with 500 mJ / cm using an ultraviolet irradiator (GS YUASA: CS 30L-1). 2 The cured product was then cured in an oven at 150°C for 30 minutes to obtain a cured product. The copper foil was removed using ferric chloride (III) 45° Pomer (Junsei Chemical Co., Ltd.). A 3 mg sample of the cured product was placed in an air flow of 100 ml per minute and the temperature at which the weight decreased by 5% was measured using a METTLER TGA / DSC1.

[0123] [Table 3]

[0124] From the above results, it can be confirmed that the coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility, high developability, and the cured product thereof also has excellent resistance to thermal decomposition.

[0125] As described above, a coating film obtained from the colored photosensitive composition of the present invention has excellent colorant dispersibility and high developability, and the cured product also has excellent heat resistance, making it suitable for use in black matrices, colored spacers, and color resists.

Claims

1. A colored photosensitive composition comprising an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a polyamideimide resin (a3) ​​having a terminal acid group or an acid anhydride group, obtained by reacting an alicyclic isocyanurate-type polyisocyanate (a1) with an aromatic tricarboxylic acid anhydride (a2), with a (meth)acrylate compound (b) having an epoxy group in one molecule, a colorant (B), and a solvent (C).

2. 2. The photosensitive resin composition according to claim 1, wherein the molar ratio ((b) / (a2)) of the aromatic tricarboxylic anhydride (a2) to the epoxy group-containing (meth)acrylate compound (b) is 0.1 to 0.

9.

3. 2. The photosensitive resin composition according to claim 1, wherein the epoxy group of the (meth)acrylate compound (b) having an epoxy group in one molecule is an alicyclic epoxy group.

4. The photosensitive resin composition according to claim 1, wherein the unsaturated group-containing polycarboxylic acid resin (A) has a molecular weight distribution (Mw / Mn) which is a ratio of the solid average molecular weight (Mn) to the weight average molecular weight (Mw) of 1.5 to 2.

5.

5. 2. The photosensitive resin composition according to claim 1, wherein the unsaturated group-containing polycarboxylic acid resin (A) has an acid value of 40 to 140 mg·KOH / g on solid content.

6. The colored photosensitive composition according to claim 1 , further comprising a crosslinking agent (D).

7. The colored photosensitive composition according to claim 1 , further comprising a photopolymerization initiator (E).

8. The colored photosensitive composition according to claim 1 , further comprising a curing agent (F).

9. 2. The colored photosensitive composition of claim 1, wherein the colorant (B) comprises a black pigment.

10. A cured product comprising the colored photosensitive composition according to any one of claims 1 to 9.

11. An image display device comprising the cured product according to claim 10.

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