Photosensitive resin composition, cured product, black matrix, and image display device

Abstract

To provide a photosensitive resin composition that achieves formation of a cured product exhibiting low reflectance and superior light-shielding properties.SOLUTION: A photosensitive resin composition comprises (a) an alkali-soluble resin, (b) a photopolymerizable compound, (c) a photopolymerization initiator, (d) a light-shielding component, and (e) hollow polymer particles, the average particle diameter of the hollow polymer particles (e) being less than 110 nm, the content of the hollow polymer particles (e) being greater than 1 mass% relative to total solids of the photosensitive resin composition, and the optical density per 1.0 μm thickness upon curing of the photosensitive resin composition being 3.5 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a cured product, a black matrix (hereinafter sometimes abbreviated as "BM"), and an image display device. This application claims priority based on Japanese Patent Application No. 2024-038902, filed on March 13, 2024, the contents of which are incorporated herein by reference. [Background technology]

[0002] A color filter is usually formed by forming a black BM on the surface of a transparent substrate such as glass or plastic, and then forming pixels of three or more different colors such as red, green, and blue in sequence in a pattern such as a grid, stripe, or mosaic. The pattern size may vary depending on the application of the color filter and the individual colors, but is usually about 5 to 700 μm.

[0003] A typical method for producing color filters is currently known as a photolithography method using a photosensitive resin composition. In the photolithography method, for example, a photosensitive resin composition containing an alkali-soluble resin is applied to a transparent substrate, dried to form a photosensitive resin film, exposed to light in a predetermined pattern, developed with an alkali developer, and then cured by high-temperature treatment at 200°C or higher to form a pattern. When the photosensitive resin composition is used to form a BM, it contains a coloring material such as carbon black as a light-shielding component (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2022 / 124296 Summary of the Invention [Problem to be solved by the invention]

[0005] BMs are typically arranged in a grid, stripe, or mosaic pattern between red, green, and blue pixels, respectively, to improve contrast and prevent light leakage by suppressing color mixing between pixels. For this reason, BMs are required to have high light-blocking properties. Furthermore, the edges of the red, green, and blue pixels formed after BM formation partially overlap with the BM, resulting in the formation of a step at the overlapping area due to the influence of the BM film thickness. This overlapping area impairs pixel flatness, leading to uneven liquid crystal cell gaps and disturbed liquid crystal alignment, resulting in reduced display performance. Therefore, in recent years, there has been a demand for thinner BMs. To achieve sufficient light-blocking properties even with thinner BMs, the concentration of light-blocking components in the BM must be increased.

[0006] However, the refractive index of the light-blocking component tends to be higher than that of the alkali-soluble resin and other materials constituting the image display device. Therefore, increasing the concentration of the light-blocking component increases the difference in refractive index between the BM and other materials. As a result, the reflectance at the interface between the BM and other materials increases, impairing the visibility of the image.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition that can give a cured product having excellent light-shielding properties and low reflectance. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by incorporating hollow polymer particles into a photosensitive resin composition together with a light-shielding component, and have thus completed the present invention.

[0009] That is, the gist of the present invention is as follows. [1] A photosensitive resin composition comprising: (a) an alkali-soluble resin; (b) a photopolymerizable compound; (c) a photopolymerization initiator; (d) a light-shielding component; and (e) hollow polymer particles; The (e) hollow polymer particles have an average particle size of less than 110 nm, the content of the (e) hollow polymer particles is greater than 1% by mass based on the total solid content of the photosensitive resin composition, A photosensitive resin composition that, when cured, has an optical density per 1.0 μm thickness of 3.5 or more. [2] The photosensitive resin composition according to [1], wherein the (d) light-shielding component contains carbon black. [3] The photosensitive resin composition according to [1] or [2], wherein the hollow polymer particles (e) contain an acrylic resin. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the hollow polymer particles (e) have an average particle size of less than 70 nm. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of the (d) light-shielding component is 40% by mass or more and 55% by mass or less based on the total solid content of the photosensitive resin composition. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the content of the (e) hollow polymer particles is from 2% by mass to 10% by mass based on the total solid content of the photosensitive resin composition. [7] The photosensitive resin composition according to any one of [1] to [6], which has an optical density per 1.0 μm thickness of 3.7 or more when cured. [8] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [7]. [9][8] Black matrix made from the cured product.

[10] [9] An image display device having a black matrix. [Effects of the Invention]

[0010] According to the present invention, a photosensitive resin composition that can give a cured product with excellent light-shielding properties and low reflectance can be provided. Also, a cured product, a black matrix, and an image display device using the photosensitive resin composition that can give a cured product with excellent light-shielding properties and low reflectance can be provided. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element. DETAILED DESCRIPTION OF THE INVENTION

[0012] The following describes in detail the embodiments of the present invention, but the present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist thereof. In the present invention, the following terms have the following meanings: "(Meth)acrylic" means "either one or both of acrylic and methacrylic." The same applies to "(meth)acrylate" and "(meth)acryloyl." The term "acrylic resin" refers to a (co)polymer containing (meth)acrylic acid, or a (co)polymer containing a (meth)acrylic acid ester having a carboxy group. The "total solid content of the photosensitive resin composition" means all components other than the solvent in the photosensitive resin composition. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solid content. The term "(co)polymer" includes both homopolymers and copolymers, and the terms "acid (anhydride)" and "(anhydrous)...acid" include both acids and their anhydrides. The term "monomer" is the opposite of a so-called high molecular weight substance (polymer), and includes not only a monomer in the narrow sense, but also a dimer, trimer, and oligomer. The term "weight average molecular weight" refers to the weight average molecular weight (Mw) calculated as polystyrene by GPC (gel permeation chromatography). Unless otherwise specified, the "amine value" refers to the amine value converted into effective solid content, and is a value expressed as the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. The measurement method will be described later. Unless otherwise specified, the "acid value" refers to the acid value calculated as the effective solid content, and is calculated by neutralization titration. With respect to pigments, "CI" means Color Index. Percentages and parts expressed by "mass" are synonymous with percentages and parts expressed by "weight." "A and / or B" means "either one or both of A and B." A numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0013] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (a) an alkali-soluble resin, (b) a photopolymerizable compound, (c) a photopolymerization initiator, (d) a light-shielding component, and (e) hollow polymer particles.

[0014] <(a) Alkali-soluble resin> The (a) alkali-soluble resin is not particularly limited as long as it is an alkali-soluble resin, and examples thereof include resins containing a carboxy group or a hydroxyl group. More specifically, examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxy-containing epoxy resins, carboxy-containing urethane resins, novolac resins, and polyvinylphenol resins. In particular, (a1) epoxy (meth)acrylate resins and (a2) acrylic copolymer resins are preferably used from the viewpoint of excellent plate-making properties. These resins can be used alone or in combination of two or more.

[0015] <(a1) Epoxy (meth)acrylate resin> (a1) Epoxy (meth)acrylate resins are resins obtained by reacting an epoxy compound (epoxy resin) with an α,β-unsaturated monocarboxylic acid and / or an α,β-unsaturated monocarboxylic acid ester having a carboxy group in the ester moiety to generate hydroxyl groups, and then reacting the hydroxyl groups with a compound having two or more substituents capable of reacting with hydroxyl groups, such as a polybasic acid and / or anhydride thereof. The (a1) epoxy (meth)acrylate resin also includes a resin obtained by reacting a compound having two or more substituents capable of reacting with a hydroxyl group with a polybasic acid and / or anhydride thereof, and then reacting the compound with a polybasic acid and / or anhydride thereof. Resins obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a functional group that can further react are also included in (a1) epoxy (meth)acrylate resins. Epoxy (meth)acrylate resins have substantially no epoxy groups in their chemical structure, and are not limited to "(meth)acrylates." However, since epoxy compounds (epoxy resins) are used as raw materials and "(meth)acrylates" are a representative example, they are named as such according to convention.

[0016] As the (a1) epoxy(meth)acrylate resin, the following epoxy(meth)acrylate resin (a1-1) and / or epoxy(meth)acrylate resin (a1-2) (hereinafter sometimes referred to as "carboxy group-containing epoxy(meth)acrylate resin") are preferably used from the viewpoint of developability and reliability. As the (a1) epoxy (meth)acrylate resin, from the viewpoint of outgassing, it is more preferable to use one having an aromatic ring in the main chain.

[0017] Epoxy (meth)acrylate resin (a1-1): An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin, and then reacting the resulting resin with a polybasic acid and / or its anhydride. Epoxy (meth)acrylate resin (a1-2): An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin, and then reacting the resulting resin with a polyhydric alcohol and a polybasic acid and / or its anhydride.

[0018] Here, the term "epoxy resin" refers to raw material compounds before they are thermoset to form a resin, and the epoxy resin can be appropriately selected from known epoxy resins. Furthermore, the epoxy resin can be a compound obtained by reacting a phenolic compound with an epihalohydrin. The phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer. Suitable types of epoxy resins that can be used as raw materials include, for example, cresol novolac epoxy resins, phenol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, trisphenolmethane epoxy resins, biphenyl novolac epoxy resins, naphthalene novolac epoxy resins, epoxy resins that are reaction products of epihalohydrin with a polyaddition reaction product of dicyclopentadiene and phenol or cresol, adamantyl group-containing epoxy resins, and fluorene epoxy resins, and more preferably those that have an aromatic ring in the main chain.

[0019] Examples of epoxy resins include bisphenol A type epoxy resins (e.g., "jER (registered trademark, the same applies hereinafter) 828," "jER1001," "jER1002," and "jER1004" manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point: 76°C)), and bisphenol F type resins (e.g., "jER 807, "EP-4001", "EP-4002", "EP-4004", etc.), epoxy resins obtained by reacting the alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (for example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 350, softening point: 66°C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, "EPPN -201" manufactured by Mitsubishi Chemical Corporation, "EP-152" and "EP-154" manufactured by Dow Chemical Company, and "DEN-438" manufactured by Dow Chemical Company), (o, m, p-)cresol novolac type epoxy resins (for example, "EOCN (registered trademark, the same applies hereinafter)-102S", "EOCN-1020", and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resins (for example, "EPPN (registered trademark)" manufactured by Nippon Kayaku Co., Ltd.), Suitable epoxy resins that can be used include those represented by the following general formulas (B1) to (B4): cycloaliphatic epoxy resins (Daicel Corporation's "CELLOXIDE (registered trademark, the same applies hereinafter) 2021P" and "CELLOXIDE EHPE"); epoxy resins obtained by glycidylating phenolic resins obtained by reacting dicyclopentadiene with phenol (for example, DIC Corporation's "EXA-7200" and Nippon Kayaku Co., Ltd.'s "NC-7300"); and epoxy resins represented by the following general formulas (B1) to (B4).Specific examples include "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1); "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B2); "E-201" manufactured by Osaka Organic Chemical Industry Ltd. as an epoxy resin represented by the following general formula (B3); and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4).

[0020] [ka]

[0021] In formula (B1), a is an average value and represents a number from 0 to 10, and R 111 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 111 may be the same or different.

[0022] [ka]

[0023] In formula (B2), b1 and b2 each independently represent an average value and a number from 0 to 10; 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 121 may be the same or different.

[0024] [ka]

[0025] In formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), provided that the molecular structure contains one or more adamantane structures.

[0026] [ka]

[0027] In formulas (B3-1) and (B3-2), R 131 ~R 134 and R 135 ~R 137 each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bond.

[0028] [ka]

[0029] In formula (B4), p and q each independently represent an integer of 0 to 4; 141 and R 142 each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R 143 and R 144 each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or greater.

[0030] As the epoxy resin, it is preferable to use an epoxy resin represented by any one of formulas (B1) to (B4).

[0031] Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxy group include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro or cyano at the α-position; 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxyethyl methyl esters; Examples of the monomer include 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxybutyl succinate, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrophthalate, 2-(meth)acryloyloxybutyl phthalate, 2-(meth)acryloyloxybutyl maleate (meth), and a monomer obtained by adding a lactone such as ε-caprolactone, β-propiolactone, γ-butyrolactone, or δ-valerolactone to acrylic acid; or a monomer obtained by adding an acid (anhydride) such as succinic acid (anhydride), phthalic acid (anhydride), or maleic acid (anhydride) to hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate; and (meth)acrylic acid dimer. Of these, (meth)acrylic acid is preferred from the viewpoint of sensitivity.

[0032] A known method can be used to add an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150°C. Examples of the esterification catalyst that can be used here include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0033] The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may be used singly or in combination of two or more. The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group used is preferably 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1 equivalents, per equivalent of epoxy group in the epoxy resin. By using an amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group that is equal to or greater than the lower limit, it is possible to prevent a shortage of unsaturated groups from being introduced, and the subsequent reaction with the polybasic acid and / or its anhydride tends to be more satisfactory. By using an amount equal to or less than the upper limit, it is possible to prevent the remaining unreacted α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group, and it is possible to improve curing properties.

[0034] Examples of polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof, and particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

[0035] The addition reaction of a polybasic acid and / or its anhydride can be carried out using known techniques, and the target product can be obtained by continuing the reaction under conditions similar to those of the addition reaction of an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin. The amount of polybasic acid and / or its anhydride component added is preferably such that the acid value of the resulting carboxy-containing epoxy (meth)acrylate resin is 10 to 150 mg KOH / g, more preferably 20 to 140 mg KOH / g. By adjusting the amount to be equal to or greater than the lower limit, alkaline developability tends to be improved. By adjusting the amount to be equal to or less than the upper limit, curing performance tends to be improved.

[0036] During the addition reaction of the polybasic acid and / or its anhydride, a polyfunctional alcohol (polyhydric alcohol) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, or 1,2,3-propanetriol may be added to introduce a multi-branched structure. In this case, there are no particular restrictions on the order in which the polybasic acid and / or its anhydride and the polyfunctional alcohol are mixed. By heating, the polybasic acid and / or its anhydride undergoes an addition reaction with any hydroxyl group present in the mixture of the reaction product of the epoxy resin with an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group and the polyfunctional alcohol.

[0037] The use of polyhydric alcohols increases the molecular weight of the (a1) epoxy (meth)acrylate resin, allows for the introduction of branching into the molecule, and tends to balance the molecular weight and viscosity. Furthermore, the introduction rate of acid groups into the molecule can be increased, which tends to make it easier to balance sensitivity, adhesion, and other properties.

[0038] In addition to the above-mentioned carboxyl group-containing epoxy (meth)acrylate resins, for example, resins described in Korean Patent Publication No. 10-2013-0022955 can be mentioned.

[0039] The weight-average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin, measured by gel permeation chromatography (GPC) in terms of polystyrene, is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, and particularly preferably 5,000 or more. It is also preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. By setting it to the lower limit or more, excessive solubility in the developer tends to be suppressed. By setting it to the upper limit or less, solubility in the developer tends to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 1,000 to 30,000, 1,500 to 20,000, 1,500 to 15,000, or 2,000 to 15,000.

[0040] The acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. It is also preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. By setting the acid value at or above the lower limit, the development solubility tends to be improved and the resolution tends to be good. By setting the acid value at or below the upper limit, the film remaining rate of the photosensitive resin composition tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 20 to 200 mgKOH / g, 60 to 150 mgKOH / g, 80 to 130 mgKOH / g, or 100 to 130 mgKOH / g.

[0041] The chemical structure of the epoxy(meth)acrylate resin is not particularly limited, but from the viewpoints of developability and reliability, it is preferable to contain an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (a1-I) (hereinafter may be abbreviated as "(a1-I) epoxy(meth)acrylate resin") and / or an epoxy(meth)acrylate resin having a partial structure represented by the following general formula (a1-II) (hereinafter may be abbreviated as "(a1-II) epoxy(meth)acrylate resin"):

[0042] [ka]

[0043] In formula (a1-I), R 11 represents a hydrogen atom or a methyl group, and R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (a1-I) may be further substituted with any substituent.

[0044] [ka]

[0045] In formula (a1-II), R 13 each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represents an integer of 0 to 2, and * represents a bond.

[0046] <(a1-I) Epoxy (meth)acrylate resin>

[0047] [ka]

[0048] In formula (a1-I), R 11 represents a hydrogen atom or a methyl group, and R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond. The benzene ring in formula (a1-I) may be further substituted with any substituent.

[0049] (R 12 ) In formula (a1-I), R 12 represents a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups are linked with one or more divalent aromatic ring groups.

[0050] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred. On the other hand, from the viewpoint of reducing penetration of the developer into the exposed area, cyclic aliphatic groups are preferred. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting it to the above lower limit or more, a strong film is easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting it to the above upper limit or less, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 20, 1 to 15, or 1 to 10.

[0051] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has, as a side chain, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 12 or less, more preferably 10 or less. By setting it to the lower limit or more, a strong film tends to be formed and substrate adhesion tends to be good. By setting it to the upper limit or less, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The upper and lower limits can be combined in any way. For example, the range may be 1 to 12, 1 to 10, or 2 to 10. Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a dicyclopentadiene ring, or a dicyclopentane ring. From the viewpoint of skeleton rigidity, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring are preferred.

[0052] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.

[0053] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. It is also preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting the number of carbon atoms at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development tends to be less likely to occur, and adhesion to the substrate tends to be good. By setting the number of carbon atoms at or below the upper limit, deterioration of sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 20, 5 to 15, or 6 to 10.

[0054] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each of which has two free valences. The aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has two free valences. From the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0055] Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of solubility in development, unsubstituted groups are preferred.

[0056] Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3. The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3.

[0057] Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include groups represented by the following formulae (a1-IA) to (a1-IF): From the viewpoints of skeleton rigidity and film hydrophobicity, the group represented by the following formula (a1-IA) is preferred.

[0058] [ka]

[0059] In formula (a1-I), k represents 1 or 2. From the viewpoint of adhesion and patterning properties, k is preferably 1. From the viewpoint of NMP resistance, k is preferably 2. Furthermore, the epoxy (meth)acrylate (a1-I) may contain both a partial structure where k is 1 and a partial structure where k is 2.

[0060] The benzene ring in formula (a1-I) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of the substituent is not particularly limited, and may be one or two or more. From the viewpoint of patterning properties, it is preferably unsubstituted.

[0061] From the viewpoint of ease of synthesis, the partial structure represented by formula (a1-I) is preferably a partial structure represented by the following general formula (a1-I-1).

[0062] [ka]

[0063] In formula (a1-I-1), R 11 , R 12 and k are defined as in formula (a1-I), and R X represents a hydrogen atom or a polybasic acid residue, and * represents a bond. The benzene ring in formula (a1-I-1) may be further substituted with any substituent.

[0064] The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

[0065] The benzene ring in formula (a1-I-1) may be further substituted with any substituent. As the substituent, those exemplified for the benzene ring in formula (a1-I) can be preferably used.

[0066] The partial structure represented by formula (a1-I-1) contained in one molecule of the epoxy (meth)acrylate resin (a1-I) may be one type or two or more types, and examples thereof include R X is a hydrogen atom, and R X However, polybasic acid residues may be present in the mixture.

[0067] The number of partial structures represented by formula (a1-I) contained in one molecule of the (a1-I) epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Also, it is preferably 20 or less, even more preferably 15 or less. By making it equal to or greater than the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By making it equal to or less than the upper limit, it is easy to suppress deterioration in sensitivity and film loss during development, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 20, 1 to 15, or 3 to 15.

[0068] The weight-average molecular weight (Mw) of the (a1-I) epoxy (meth)acrylate resin, measured by gel permeation chromatography (GPC) in terms of polystyrene, is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, and most preferably 5,000 or more, and is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. By setting the Mw to be equal to or greater than the lower limit, the residual film rate of the photosensitive resin composition tends to be good. By setting the Mw to be equal to or less than the upper limit, the solubility in the developer tends to be good. The upper and lower limits can be arbitrarily combined. For example, it may be 1,000 to 30,000, 1,500 to 2,000, 1,500 to 15,000, or 2,000 to 1,500.

[0069] The acid value of the (a1-I) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. By setting it to the above lower limit or more, the development solubility tends to be improved and the resolution tends to be good. By setting it to the above upper limit or less, the film remaining rate of the photosensitive resin composition tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 20 to 200 mgKOH / g, 60 to 150 mgKOH / g, 80 to 130 mgKOH / g, or 100 to 130 mgKOH / g.

[0070] Specific examples of (a1-I) epoxy (meth)acrylate resins are listed below. In the examples, * indicates a bond.

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] <(a1-II) Epoxy (meth)acrylate resin>

[0076] [ka]

[0077] In formula (a1-II), R 13 each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represents an integer of 0 to 2, and * represents a bond.

[0078] (R 14 ) In formula (a1-II), R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. The cyclic hydrocarbon group may be an aliphatic cyclic group or an aromatic cyclic group.

[0079] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. It is also preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3. The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. It is also preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. By setting it to the above-mentioned lower limit or more, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it to the above-mentioned upper limit or less, it is easy to suppress deterioration in sensitivity and film loss during development, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 40, 4 to 30, 6 to 20, or 8 to 15. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoints of the film remaining rate and resolution of the photosensitive resin composition, an adamantane ring is preferred.

[0080] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. It is also preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. The upper and lower limits above can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 4, 2 to 4, or 3 to 4. By setting it to the lower limit or more, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By setting it to the upper limit or less, it is easy to suppress deterioration in sensitivity and film loss during development, and resolution tends to be improved. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, and particularly preferably 12 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning properties tend to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 4 to 40, 6 to 40, 8 to 30, 10 to 20, or 12 to 15. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. From the viewpoint of patterning properties, a fluorene ring is preferred.

[0081] The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups.

[0082] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of solubility during development, linear aliphatic groups are preferred, while cyclic aliphatic groups are preferred from the viewpoint of reducing penetration of the developer into the exposed area. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, it is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. By setting the carbon atom number at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon atom number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 25, 3 to 20, or 6 to 15.

[0083] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group as a side chain. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. It is also preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film tends to be formed, and substrate adhesion tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3. Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoint of skeleton rigidity, groups in which two hydrogen atoms have been removed from an adamantane ring are preferred.

[0084] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.

[0085] Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. It is also preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting the number of carbon atoms at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development tends to be less likely to occur, and adhesion to the substrate tends to be good. By setting the number of carbon atoms at or below the upper limit, deterioration of sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 30, 5 to 20, or 6 to 15.

[0086] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each of which has two free valences. The aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has two free valences. From the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0087] Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of solubility in development, unsubstituted groups are preferred.

[0088] Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups. The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3. The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film is more likely to be obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the number at or below the upper limit, deterioration of sensitivity and film loss during development are more likely to be suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 10, 1 to 5, 1 to 3, or 2 to 3.

[0089] Examples of the group formed by linking one or more divalent aliphatic groups with one or more divalent aromatic ring groups include the groups represented by the above formulae (a1-IA) to (a1-IF). From the viewpoints of skeleton rigidity and film hydrophobicity, the group represented by formula (a1-IC) is preferred.

[0090] The bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but examples include a mode in which one hydrogen atom of an aliphatic group or aromatic ring group is substituted with the cyclic hydrocarbon group as a side chain, and a mode in which one carbon atom of an aliphatic group is included to form the cyclic hydrocarbon group as a side chain.

[0091] (R 15 , R 16 ) In formula (a1-II), R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent.

[0092] Examples of the divalent aliphatic group include linear, branched, and cyclic aliphatic groups. From the viewpoint of solubility during development, linear aliphatic groups are preferred, while cyclic aliphatic groups are preferred from the viewpoint of reducing penetration of the developer into the exposed area. The number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Also, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting the carbon atom number at or above the lower limit, a strong film tends to be easily obtained, surface roughness during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the carbon atom number at or below the upper limit, deterioration of sensitivity and film loss during development are easily suppressed, and resolution tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, it may be 1 to 20, 3 to 15, or 6 to 10.

[0093] Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred. Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has, as a side chain, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group. The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 12 or less, more preferably 10 or less. By setting it to the lower limit or more, a strong film tends to be formed and substrate adhesion tends to be good. By setting it to the upper limit or less, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The upper and lower limits can be combined arbitrarily. For example, the range may be 1 to 12, or 2 to 10. Examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms have been removed from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a dicyclopentadiene ring. From the viewpoint of skeleton rigidity, groups in which two hydrogen atoms have been removed from a dicyclopentadiene ring or an adamantane ring are preferred.

[0094] Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that the divalent aliphatic group is unsubstituted.

[0095] (m, n) In formula (a1-II), m and n each independently represent an integer of 0 to 2. By setting the m and n to be equal to or greater than the lower limit, patterning suitability is improved and surface roughness during development tends to be less likely to occur, while by setting the m and n to be equal to or less than the upper limit, developability tends to be improved. From the viewpoint of developability, m and n are preferably 0. From the viewpoint of patterning suitability and suppressing surface roughness during development, m and n are preferably 1 or greater.

[0096] The partial structure represented by formula (a1-II) is preferably a partial structure represented by the following general formula (a1-II-1) from the viewpoint of adhesion to a substrate.

[0097] [ka]

[0098] In formula (a1-II-1), R 13 , R 15 , R 16 , m and n are defined as in formula (a1-II), and R α represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer of 1 or greater, and * represents a bond. The benzene ring in formula (a1-II-1) may be further substituted with any substituent.

[0099] (R α ) In formula (a1-II-1), R α represents an optionally substituted monovalent cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aliphatic cyclic group or an aromatic cyclic group.

[0100] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning properties tend to be good. The upper and lower limits can be combined arbitrarily. For example, it may be 1 to 6, 1 to 4, 1 to 3, or 2 to 3. The number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. By setting it to the above-mentioned lower limit or more, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it to the above-mentioned upper limit or less, patterning characteristics tend to be good. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 40, 4 to 30, 6 to 20, or 8 to 15. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoint of strong film properties, an adamantane ring is preferred.

[0101] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and more preferably 3 or more. Also, it is preferably 10 or less, and more preferably 5 or less. By making it equal to or greater than the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By making it equal to or less than the upper limit, patterning properties tend to be improved. The upper and lower limits can be combined in any way. For example, the range may be 1-10, 1-5, 2-5, or 3-5. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. The number is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning properties tend to be good. The upper and lower limits can be combined arbitrarily. For example, it may be 4 to 30, 5 to 20, or 6 to 15. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of solubility in development, a fluorene ring is preferred.

[0102] Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxy. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0103] p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 is preferred, and 2 to 3 is more preferred. By setting it to the lower limit or more, the film hardness and film remaining rate tend to be good. By setting it to the upper limit or less, the developability tends to be good.

[0104] From the viewpoint of strong film hardness, R α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

[0105] The benzene ring in formula (a1-II-1) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and may be one or two or more. From the viewpoint of patterning properties, it is preferably unsubstituted.

[0106] Specific examples of the partial structure represented by formula (a1-II-1) are listed below.

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] The partial structure represented by formula (a1-II) is preferably a partial structure represented by the following general formula (a1-II-2) from the viewpoints of skeleton rigidity and film hydrophobicity.

[0113] [ka]

[0114] In formula (a1-II-2), R 13 , R 15 , R 16 , m and n are defined as in formula (a1-II), and R β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a bond. The benzene ring in formula (a1-II-2) may be further substituted with any substituent.

[0115] (R β ) In formula (a1-II-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent. The cyclic hydrocarbon group may be an aliphatic cyclic group or an aromatic cyclic group.

[0116] The number of rings in the aliphatic cyclic group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Also, it is preferably 10 or less, more preferably 5 or less. By making the number equal to or greater than the lower limit, a strong film tends to be obtained, and surface roughness during development tends to be less likely to occur. By making the number equal to or less than the upper limit, deterioration in sensitivity and film loss during development tend to be easily suppressed, and resolution tends to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 1 to 10, or 2 to 5. The number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. It is also preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. By setting it to the above lower limit or more, roughening of the film surface during development tends to be suppressed. By setting it to the above upper limit or less, deterioration of sensitivity and film loss during development tend to be suppressed, and resolution tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 40, 6 to 35, or 8 to 30. Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. From the viewpoints of film loss during development and resolution, an adamantane ring is preferred.

[0117] The number of rings in the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Also, it is preferably 10 or less, more preferably 5 or less. By making it equal to or greater than the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By making it equal to or less than the upper limit, it is easy to suppress deterioration in sensitivity and film loss, and resolution tends to be improved. The upper and lower limits can be combined in any way. For example, the range may be 1-10, 1-5, 2-5, or 3-5. Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and even more preferably 10 or more. It is also preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. By setting it to the above-mentioned lower limit or more, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it to the above-mentioned upper limit or less, it is easy to suppress deterioration in sensitivity and film loss, and resolution tends to be improved. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it may be 4 to 40, 6 to 30, 8 to 20, or 10 to 15. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of developability, a fluorene ring is preferred.

[0118] Examples of the substituent that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, and isoamyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl; nitro; cyano; and carboxy. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0119] From the viewpoint of suppressing film loss and improving resolution, R β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

[0120] The benzene ring in formula (a1-II-2) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and may be one or two or more. In addition, the two benzene rings in formula (a1-II-2) are R β In addition, they may be linked via a substituent to form a tricyclic structure. In this case, examples of the substituent include divalent groups such as -O-, -S-, -NH-, and -CH2-. For example, the formation of a tricyclic structure by linking via -O- means that R β This means that the carbon atoms at the ortho positions of the carbon atom bonded to the carbon atom bonded to the xanthene skeleton are linked via -O-. From the viewpoint of patterning properties, it is preferably unsubstituted, and from the viewpoint of preventing film loss and the like, it is preferably substituted with a methyl group.

[0121] Specific examples of the partial structure represented by formula (a1-II-2) are shown below. In the examples, * indicates a bond.

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] The partial structure represented by formula (a1-II) is preferably a partial structure represented by the following general formula (a1-II-3) from the viewpoint of the coating film remaining rate and patterning characteristics.

[0127] [ka]

[0128] In formula (a1-II-3), R 13 , R 14 , R 15 , R 16 , m and n are defined as in formula (a1-II), and R Z represents a hydrogen atom or a polybasic acid residue.

[0129] The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid. In addition, when another OH group is removed, the R Z It may be shared with R ZA plurality of formula (a1-II-3) may be linked via the following. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.

[0130] The partial structure represented by formula (a1-II-3) contained in one molecule of the epoxy (meth)acrylate resin (a1-II) may be one type or two or more types, and examples thereof include R Z is the partial structure of a hydrogen atom, and R Z However, partial structures of polybasic acid residues may be mixed.

[0131] The number of partial structures represented by formula (a1-II) contained in one molecule of the (a1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. It is also preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By ensuring that the number is equal to or greater than the lower limit, a strong film tends to be easily obtained, and surface roughness during development tends to be less likely to occur. By ensuring that the number is equal to or less than the upper limit, deterioration in sensitivity and film loss tend to be easily suppressed, and resolution tends to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 1 to 20, 1 to 15, or 3 to 10.

[0132] The weight-average molecular weight (Mw) of the (a1-II) epoxy (meth)acrylate resin, measured by gel permeation chromatography (GPC) in terms of polystyrene, is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, and particularly preferably 5,000 or more. It is also preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less. By setting it to the above lower limit or more, the film remaining rate of the photosensitive resin composition tends to be good. By setting it to the above upper limit or less, the solubility in the developer tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 1,000 to 10,000, 1,500 to 10,000, 1,500 to 8,000, 2,000 to 8,000, or 2,000 to 7,000.

[0133] The acid value of the (a1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, even more preferably 60 mgKOH / g or more, even more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. By setting it to the above lower limit or more, the development solubility tends to be improved and the resolution tends to be good. By setting it to the above upper limit or less, the film remaining rate of the photosensitive resin composition tends to be good. The above upper and lower limits can be arbitrarily combined. For example, it may be 20 to 200 mgKOH / g, 60 to 150 mgKOH / g, 80 to 130 mgKOH / g, or 100 to 120 mgKOH / g.

[0134] The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more resins. Furthermore, a portion of the carboxyl group-containing epoxy (meth)acrylate resin may be replaced with another binder resin. That is, the carboxyl group-containing epoxy (meth)acrylate resin may be used in combination with another binder resin. In this case, the proportion of the carboxyl group-containing epoxy (meth)acrylate resin in the alkali-soluble resin (a) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, and may be 100% by mass or less.

[0135] <(a2) Acrylic copolymer resin> As the alkali-soluble resin (a), from the viewpoint of compatibility with pigments, dispersants, etc., it is preferable to use an acrylic copolymer resin (a2), and the resins described in JP 2014-137466 A can be preferably used.

[0136] Examples of the (a2) acrylic copolymer resin include a copolymer of an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as "unsaturated monomer (a2-1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (a2-2)").

[0137] Examples of the unsaturated monomer (a2-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl]; mono(meth)acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid. These unsaturated monomers (a2-1) can be used alone or in combination of two or more.

[0138] Examples of the unsaturated monomer (a2-2) include: N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene; Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0] 2,6 ] (meth)acrylic acid esters such as decan-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of para-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane; Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 ] Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane; Examples include macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane. These unsaturated monomers (a2-2) can be used alone or in combination of two or more.

[0139] In the copolymer of the unsaturated monomer (a2-1) and the unsaturated monomer (a2-2), the copolymerization ratio of the unsaturated monomer (a2-1) is preferably 5 to 50 mass %, more preferably 10 to 40 mass %. By copolymerizing the unsaturated monomer (a2-1) in such a range, a photosensitive resin composition excellent in alkali developability and storage stability tends to be obtained.

[0140] Examples of the copolymer of the unsaturated monomer (a2-1) and the unsaturated monomer (a2-2) include the copolymers disclosed in Japanese Patent Application Laid-Open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728. The copolymer of the unsaturated monomer (a2-1) and the unsaturated monomer (a2-2) can be produced by known methods. For example, the structure, Mw, and Mw / Mn (Mn is the number average molecular weight) can be controlled by the methods disclosed in JP 2003-222717 A, JP 2006-259680 A, and WO 2007 / 029871 A.

[0141] Resins described in WO 2016 / 194619 and WO 2017 / 154439 may also be used.

[0142] The content of (a) alkali-soluble resin is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total solid content of the photosensitive resin composition, and is preferably less than 45% by mass, more preferably 40% by mass or less, and even more preferably 35% by mass or less. If the content of (a) alkali-soluble resin is equal to or more than the lower limit, the alkali development solubility of the unexposed areas tends to be better, and if it is equal to or less than the upper limit, the alkali dissolution time of the unexposed areas tends to be appropriate, and a good image tends to be obtained. The upper and lower limits can be combined in any way, and may be, for example, 10% by mass or more but less than 45% by mass, 15 to 40% by mass, or 20 to 35% by mass.

[0143] <(b) Photopolymerizable compound> The photosensitive resin composition of the present invention contains (b) a photopolymerizable compound from the viewpoint of sensitivity and the like. (b) Examples of photopolymerizable compounds include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, sometimes referred to as "ethylenic monomers"). Specific examples include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, and esters of carboxylic acids having one ethylenically unsaturated bond with polyhydric or monohydric alcohols.

[0144] As the (b) photopolymerizable compound, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, particularly preferably 6 or more, and preferably 10 or less, more preferably 8 or less. By setting the number to be equal to or greater than the lower limit, the photosensitive resin composition tends to have high sensitivity, and by setting the number to be equal to or less than the upper limit, curing shrinkage during polymerization tends to be small. The above upper and lower limits can be combined in any way, for example, 2 to 10, 3 to 10, 4 to 10, 5 to 8, or 6 to 8. Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification reactions of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

[0145] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic acid esters in which the acrylate of these exemplary compounds is replaced with methacrylate; and similarly, itaconic acid esters in which itaconate is replaced with itaconate, crotonate esters in which cronate is replaced with cronate, or maleate esters in which maleate is replaced with cronate.

[0146] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. Esters obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound are not necessarily single compounds, but examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

[0147] Other useful polyfunctional ethylenic monomers for use in the present invention include, for example, urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester; epoxy acrylates such as the addition reaction product of a polyfunctional epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. These may be used alone or in combination of two or more.

[0148] The content of the (b) photopolymerizable compound is preferably 3% by mass or more, more preferably 4% by mass or more, and preferably 18% by mass or less, more preferably 16% by mass or less, even more preferably 13% by mass or less, and particularly preferably 10% by mass or less, based on the total solids content of the photosensitive resin composition. If the content of the (b) photopolymerizable compound is at least the above-mentioned lower limit, photocuring by ultraviolet irradiation tends to be improved and alkaline developability also tends to be good. If the content of the (b) photopolymerizable compound is at most the above-mentioned upper limit, the permeability of the developer into the exposed area tends to be appropriate, and a good image tends to be obtained. The upper and lower limits can be combined arbitrarily, for example, 3 to 18 mass %, 3 to 16 mass %, 4 to 13 mass %, or 4 to 10 mass %.

[0149] <(c) Photopolymerization initiator> The photosensitive resin composition of the present invention contains (c) a photopolymerization initiator. (c) The photopolymerization initiator is a component that directly absorbs light, causes a decomposition reaction or a hydrogen abstraction reaction, and generates polymerization-active radicals. If necessary, an additive such as a sensitizing dye may be added.

[0150] Examples of the (c) photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118; radical activators and α-aminoalkylphenone derivatives such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters described in JP-A-10-39503; and oxime ester derivatives described in JP-A-2000-80068 and JP-A-2006-36750.

[0151] Examples of titanocene derivatives include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl), dicyclopentadienyltitanium di(2,6-difluorophenyl), dicyclopentadienyltitanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), and dicyclopentadienyltitanium[2,6-difluoro-3-(pyrro-1-yl)phenyl].

[0152] Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0153] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

[0154] Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0155] Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0156] As the (c) photopolymerization initiator, oxime derivatives (oxime ester compounds and ketoxime ester compounds) are preferred in terms of sensitivity. Among oxime derivatives, oxime ester compounds are preferred in terms of adhesion to the substrate. When an alkali-soluble resin containing a phenolic hydroxyl group is used, it may be disadvantageous in terms of sensitivity. Oxime ester-based photopolymerization initiators possess a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals. Therefore, they are highly sensitive even in small amounts and are stable against thermal reactions, making it possible to design highly sensitive photosensitive resin compositions with small amounts. In particular, from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, oxime ester-based compounds containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring) are more preferred because they exhibit this structural characteristic well. Currently, the market demands thin black matrices with high light blocking properties, and pigment concentrations are also increasing. Under these circumstances, these compounds are particularly effective.

[0157] The oxime ester compound includes a compound containing a structural moiety represented by the following formula (22), and preferably includes an oxime ester compound represented by the following formula (23).

[0158] [ka]

[0159] In formula (22), R 22represents an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminoalkylcarbonyl group having 2 to 10 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, each of which may be substituted.

[0160] [ka]

[0161] In formula (23), R 21a represents hydrogen, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms, each of which may be substituted. R 21b represents any substituent containing an aromatic ring or heteroaromatic ring.

[0162] R 21a is R 21b and the linking group may be an alkylene group having 1 to 10 carbon atoms, a polyethylene group (-(CH=CH) r -), polyethynylene group (-(C≡C) r-) or a group formed by combining these (wherein r is an integer of 0 to 3). R 22a is R in equation (22) 22 represents a group similar to the above. R in equation (22) 22 and R in Eq. (23) 22a As the alkanoyl group, preferred examples include an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms.

[0163] R in equation (23) 21a Preferred examples of the alkyl group include unsubstituted straight-chain alkyl groups or cycloalkylalkyl groups such as methyl, ethyl, and propyl groups, and propyl groups substituted with an N-acetyl-N-acetoxyamino group. R in equation (23) 21b Preferred examples of the group include an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenyl sulfide group.

[0164] The photopolymerization initiator of the oxime ester compound is R 21b For the reasons mentioned above, compounds in which the group is an optionally substituted carbazolyl group are more preferred. Furthermore, a carbazole group having at least one group selected from the group consisting of an optionally substituted aryl group having 6 to 25 carbon atoms, an optionally substituted arylcarbonyl group having 7 to 25 carbon atoms, an optionally substituted heteroaryl group having 5 to 25 carbon atoms, an optionally substituted heteroarylcarbonyl group having 6 to 25 carbon atoms, and a nitro group are preferred. In particular, a carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferred. Furthermore, it is desirable that these groups be bonded to the 3-position of the carbazolyl group.

[0165] Commercially available photopolymerization initiators of such oxime ester compounds include, for example, OXE-02 manufactured by BASF, and TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Strong Electronics Co., Ltd.

[0166] Suitable oxime ester-based photopolymerization initiators include, for example, the following compounds, but are not limited to these compounds.

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] Examples of the ketoxime ester compound include compounds containing a structural moiety represented by the following formula (24), and preferably, the ketoxime ester compound represented by the following formula (25).

[0171] [ka]

[0172] In equation (24), R 24 is R in the formula (22) 22 is synonymous with.

[0173] [ka]

[0174] In equation (25), R 23arepresents a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms, each of which may be substituted.

[0175] R 23b represents any substituent containing an aromatic ring or heteroaromatic ring. R 23a is R 23b and the linking group may be an alkylene group having 1 to 10 carbon atoms, a polyethylene group (-(CH=CH) r -), polyethynylene group (-(C≡C) r -) or a group formed by combining these (wherein r is an integer of 0 to 3).

[0176] R 24a represents an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, each of which may be substituted. R in equation (24) 24 and R in Eq. (25) 24aPreferred examples of the alkanoyl group include an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and an aryloyl group having 7 to 20 carbon atoms.

[0177] R in equation (25) 23a Preferred examples of the alkyl group include an unsubstituted ethyl group, a propyl group, and a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group. R in equation (25) 23b Preferred examples of the alkyl group include an optionally substituted carbazoyl group and an optionally substituted phenyl sulfide group. Examples of ketoxime ester compounds suitable for the present invention include, but are not limited to, the following compounds:

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181] Commercially available photopolymerization initiators of such ketoxime ester compounds include, for example, OXE-01 manufactured by BASF and TR-PBG-305 manufactured by Changzhou Strong Electronics Co., Ltd.

[0182] These oxime and ketoxime ester compounds are known per se and are described, for example, in Japanese Patent Application Laid-Open Nos. 2000-80068 and 2006-36750.

[0183] Other examples include benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropyl phenyl)propanone, and the like. acetophenone derivatives such as 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone. As the photopolymerization initiator, oxime ester derivatives are particularly preferred for the reasons mentioned above. The photopolymerization initiator may be used alone or in combination of two or more kinds.

[0184] The content of (c) photopolymerization initiator is preferably 1.5% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, particularly preferably 4% by mass or more, based on the total solid content of the photosensitive resin composition, and is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, particularly preferably 6% by mass or less. If the content of (c) photopolymerization initiator is equal to or greater than the lower limit, sensitivity tends to improve, and if it is equal to or less than the upper limit, the solubility of the unexposed portion in a developer tends to improve. The upper and lower limits can be combined in any way, for example, 1.5 to 15 mass %, 2 to 10 mass %, 3 to 7 mass %, or 4 to 6 mass %.

[0185] <(d) Light blocking component> The photosensitive resin composition of the present invention contains (d) a light-shielding component. By containing (d) a light-shielding component, a cured product having light-shielding properties can be obtained. (d) Examples of the light-shielding component include coloring materials. Coloring materials refer to components that color the photosensitive resin composition. Examples of coloring materials include pigments and dyes. In terms of heat resistance and light resistance, pigments are preferred.

[0186] Pigments of various colors can be used, such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, black pigments, etc. In terms of structure, organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments, as well as various inorganic pigments can also be used.

[0187] Specific examples of pigments that can be used in the present invention are shown below by pigment number. Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, and 53:3. :3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 288, 289, 290, 300, 301, 302, 303, 304, 305, 306, 307, 35, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, and 276. Preferred examples include CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, and 254, and more preferred examples include CI Pigment Red 177, 209, 224, and 254.

[0188] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Preferred examples include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60, and more preferred examples include CI Pigment Blue 15:6 and 60.

[0189] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, and 58. Preferred examples include CI Pigment Green 7, 36, and 58.

[0190] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, and 134. , 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Preferred are CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185, and more preferred are CI Pigment Yellow 83, 138, 139, 150, and 180.

[0191] Examples of orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. Preferred examples include CI Pigment Orange 38, 64, and 71.

[0192] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Preferred examples include CI Pigment Violet 19, 23, and 29, and more preferred examples include CI Pigment Violet 23 and 29.

[0193] When the photosensitive resin composition is a photosensitive resin composition for a black matrix, a black coloring material can be used as the (d) light-shielding component. The black coloring material may be a single black coloring material or a mixture of red, green, blue, etc. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes. Examples of colorants that can be mixed to prepare black colorants include Victoria Pure Blue (42595), Auramine O (41000), Catilon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK 70:100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), and Shimla First Yellow. -8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla First Red 4015 (12355), Lionor Red 7B4401 (15850), Firstgen Blue TGR-L (74160), Lionor Blue SM (26150), Lionor Blue ES (Pigment Blue 15:6), Lionor Red GD (Pigment Red 168), and Lionor Green 2YS (Pigment Green 36) (Note: The numbers in parentheses above refer to the Color Index (CI)).

[0194] Other pigments that can be mixed are listed by CI number, for example, CI Yellow Pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI Orange Pigments 36, 43, 51, 55, 59, 61, 64; CI Red Pigments 9, 97, 122, 123, 149, 168 , 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; CI Violet Pigment 19, 23, 29, 30, 37, 40, 50; CI Blue Pigment 15, 15:1, 15:4, 22, 60, 64; CI Green Pigment 7; CI Brown Pigment 23, 25, 26.

[0195] Examples of black coloring materials that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black. When a black coloring material is used among these (d) light-shielding components, carbon black is preferred from the viewpoint of light-shielding rate and image characteristics. Examples of carbon black include the following:

[0196] Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, # 960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Manufactured by Degussa: Printex (registered trademark. The same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170 Cabot Corporation: Monarch (registered trademark; the same applies hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark; the same applies hereinafter) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark)-8 Biller: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

[0197] Other black pigments that can be used include, for example, titanium black, aniline black, iron oxide black pigments, and a mixture of three organic pigments of red, green, and blue.

[0198] Examples of pigments that can be used include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide. These pigments can also be used in combination. For example, to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a purple pigment can be used in combination.

[0199] The average particle size of the pigment used in the photosensitive resin composition may be any size that allows the desired color to be developed when used in a colored layer of a color filter, and although it varies depending on the type of pigment used, it is preferably 10 to 100 nm, more preferably 10 to 70 nm. When the average particle size of the pigment is within the above range, the color characteristics of a liquid crystal display device manufactured using the photosensitive resin composition tend to be of high quality. When the pigment is carbon black, the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more. By setting the average particle size to the upper limit or less, scattering tends to be reduced, and deterioration of color properties such as light-blocking ability and contrast tends to be suppressed. Furthermore, by setting the average particle size to the lower limit or more, the amount of dispersant does not need to be excessively large, and dispersibility tends to be good. The upper and lower limits can be combined arbitrarily. For example, the thickness is preferably 20 to 60 nm, and more preferably 20 to 50 nm. The average particle size of a pigment can be determined by directly measuring the size of primary particles from an electron microscope photograph. Specifically, the minor and major axis diameters of each primary particle are measured, and the average is taken as the particle size of that particle. Next, the volume (mass) of each of 100 or more particles is calculated by approximating it to a rectangular parallelepiped of the calculated particle size, and the volume-average particle size is calculated, which is then taken as the average particle size. The same results can be obtained using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

[0200] The photosensitive resin composition preferably contains at least a pigment as the light-shielding component (d), but may also contain a dye in combination as long as it does not affect the effects of the present invention. Examples of dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

[0201] Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0202] Examples of anthraquinone dyes include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0203] An example of the phthalocyanine dye is CI Pad Blue 5. Examples of quinoneimine dyes include CI Basic Blue 3 and CI Basic Blue 9. Examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64. Examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0204] As described above, the photosensitive resin composition of the present invention can be used for various applications. However, its excellent image forming properties are particularly effective when used to form a black matrix for a color filter. When used to form a black matrix, the light-shielding component (d) may be a black colorant such as the aforementioned carbon black or titanium black, or a mixture of multiple non-black colorants may be used to adjust the color to black. Among these, the use of carbon black is particularly preferred from the viewpoints of dispersion stability and light-shielding properties.

[0205] The content of the (d) light-shielding component is preferably 40% by mass or more, more preferably 43% by mass or more, and even more preferably 45% by mass or more, based on the total solid content of the photosensitive resin composition, and is preferably 55% by mass or less, more preferably 50% by mass or less. If the content of the (d) light-shielding component is equal to or greater than the above lower limit, a cured product with high light-shielding properties (optical density) can be obtained. Specifically, by setting the content of the (d) light-shielding component to 40 mass% or more relative to the total solid content of the photosensitive resin composition, the optical density per 1.0 μm thickness (hereinafter also referred to as unit OD value) when the photosensitive resin composition is cured can be set to a value of 3.5 or more. If the content of the (d) light-shielding component is equal to or less than the above upper limit, the image forming performance is better. The upper and lower limits can be combined in any way, for example, 40 to 55 mass %, 43 to 55 mass %, 45 to 55 mass %, or 45 to 50 mass %.

[0206] (d) When the light-shielding component contains carbon black, the content of carbon black is preferably 40% by mass or more, more preferably 43% by mass or more, and even more preferably 45% by mass or more, relative to the total solid content of the photosensitive resin composition, from the viewpoint of obtaining a cured product with high light-shielding properties, and is preferably 55% by mass or less, more preferably 53% by mass or less. The upper and lower limits can be combined in any way, for example, 40 to 55 mass %, 43 to 55 mass %, 45 to 55 mass %, or 45 to 50 mass %.

[0207] The content of carbon black relative to the total mass of the (d) light-shielding component is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 100% by mass.

[0208] <(e) Hollow polymer particles> (e) Hollow polymer particles are hollow particles having a shell layer containing a polymer. (e) Hollow polymer particles have a space (hereinafter also referred to as a hollow portion) surrounded by the shell layer inside. (e) Hollow polymer particles typically have one hollow portion. From the viewpoint of preventing the components of the photosensitive resin composition from entering the hollow portion, it is preferable that the shell layer does not have holes penetrating the shell layer that are large enough to allow the components of the photosensitive resin composition to enter.

[0209] The polymer constituting the shell layer is not particularly limited and may be any polymer used in known hollow polymer particles. Examples include polymers having units based on monomers having ethylenically unsaturated bonds, such as (meth)acrylate, (meth)acrylic acid, and styrene. The polymer may be a homopolymer or a copolymer. Two or more types of polymers may be used in combination. (e) The hollow polymer particles may contain an acrylic resin.

[0210] The average particle diameter of the (e) hollow polymer particles is, for example, 110 nm or less, preferably less than 100 nm, more preferably less than 70 nm, even more preferably less than 69 nm, and particularly preferably less than 65 nm. The lower limit of the average particle diameter of the (e) hollow polymer particles is not particularly limited, but is, for example, 50 nm or more. If the average particle diameter of the (e) hollow polymer particles is less than 70 nm, the refractive index of the cured product can be further reduced. In addition, the generation of foreign matter during curing can be suppressed. The average particle size of the hollow polymer particles is determined by taking a photograph using an electron microscope at a magnification that allows at least 300 particles to be captured, measuring the longest and shortest diameters of the particles captured in the photograph, averaging these values ​​as the particle size of each particle, and then calculating the average particle size of each particle.

[0211] The hollow ratio of the (e) hollow polymer particles is preferably 80 to 20% by volume, more preferably 60 to 30% by volume. When the hollow ratio of the (e) hollow polymer particles is equal to or greater than the lower limit, the cured product can have a lower refractive index. When the hollow ratio of the (e) hollow polymer particles is equal to or less than the upper limit, the strength of the hollow polymer particles is superior. The hollowness of hollow polymer particles can be expressed as the ratio of the hollow volume (V2) to the particle volume (V1). When hollow polymer particles are photographed using a transmission electron microscope, the hollows can be seen as areas with low contrast. The longest and shortest diameters of the hollows are measured, and their average value is taken as the diameter of the hollows. V1 is calculated from the particle diameter, and V2 is calculated from the diameter of the hollows.

[0212] (e) The hollow polymer particles may be commercially available products, or hollow polymer particles produced by a known method may be used.

[0213] The content of the (e) hollow polymer particles is, for example, 1% by mass or more, preferably 2% by mass or more, more preferably 2.4% by mass or more, even more preferably 2.8% by mass or more, particularly preferably 3% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 6% by mass or less, even more preferably 5% by mass or less, and particularly preferably 4% by mass or less, based on the total solid content of the photosensitive resin composition. If the content of the (e) hollow polymer particles is equal to or greater than the above-mentioned lower limit, the refractive index of the cured product can be made lower. If the content of the (e) hollow polymer particles is equal to or less than the above-mentioned upper limit, the developability of the resist is improved. The above lower and upper limits can be combined in any manner, and may be, for example, 2 to 10 mass %, 2 to 7 mass %, 2.4 to 7 mass %, 2.8 to 5 mass %, or 3.0 to 4 mass %.

[0214] <Solvent> The photosensitive resin composition may contain a solvent, which makes it easier to apply. The photosensitive resin composition is used in a state where, for example, (a) an alkali-soluble resin, (b) a photopolymerizable compound, (c) a photopolymerization initiator, (d) a light-shielding component, (e) hollow polymer particles, and various other materials that are blended as needed are dissolved or dispersed in a solvent. As the solvent, an organic solvent is preferred from the viewpoint of dispersibility and coating properties.

[0215] The organic solvent is preferably an organic solvent having a boiling point of 100 to 300° C., more preferably an organic solvent having a boiling point of 120 to 280° C. Here, the boiling point is the value at a pressure of 1013.25 hPa. The same applies to all boiling points hereinafter.

[0216] Examples of organic solvents having a boiling point of 100 to 300°C include the following: glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0217] glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0218] glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

[0219] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile.

[0220] Examples of commercially available organic solvents that fall under the above category include mineral spirits, Balsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve" is a registered trademark; the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all of which are trade names). These organic solvents may be used alone or in combination of two or more.

[0221] When the photosensitive resin composition is used to form pixels or a black matrix of a color filter by photolithography, the organic solvent preferably has a boiling point of 100 to 250°C, more preferably 120 to 230°C.

[0222] As the organic solvent, glycol alkyl ether acetates are preferred because they have a good balance of coatability, surface tension, etc., and have a relatively high solubility of the components in the photosensitive resin composition. One type of glycol alkyl ether acetate may be used alone, or two or more types may be used in combination. Glycol alkyl ether acetates may be used alone, or may be used in combination with other organic solvents. As the other organic solvent, glycol monoalkyl ethers are preferred, and among them, propylene glycol monomethyl ether is preferred in view of the solubility of the components in the photosensitive resin composition. Glycol monoalkyl ethers have high polarity, and if added in an excessive amount, the pigment tends to aggregate, and the storage stability tends to decrease, such as the viscosity of the photosensitive resin composition obtained later increasing, etc. Therefore, when the organic solvent contains glycol monoalkyl ethers, the content of the glycol monoalkyl ethers is preferably 5 to 30 mass %, more preferably 5 to 20 mass %, relative to the total mass of the organic solvent.

[0223] Glycol alkyl ether acetates may be used in combination with organic solvents having a boiling point of 200°C or higher (hereinafter sometimes referred to as "high-boiling solvents"). The use of such high-boiling solvents makes the photosensitive resin composition less likely to dry, but also has the effect of preventing the uniform dispersion of the pigment in the composition from being destroyed by rapid drying. In other words, it has the effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of pigments, etc., at the tip of a slit nozzle, for example. The upper limit of the boiling point of the high-boiling solvent is not particularly limited, but is, for example, 300°C or lower. In view of the high effects as described above, the high-boiling point solvents preferably include dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, triacetin, and 1,6-hexanediol diacetate. These high boiling point solvents may be used alone or in combination of two or more.

[0224] The content of the high-boiling point solvent is preferably 0 to 50% by mass, more preferably 0.5 to 40% by mass, and even more preferably 1 to 30% by mass, based on the total mass of the organic solvent. When the content of the high-boiling point solvent is equal to or less than the upper limit, the time required for drying the composition can be appropriately reduced, which tends to prevent problems such as poor tact time in the reduced-pressure drying process and pin marks during pre-baking in the color filter manufacturing process. When the content of the high-boiling point solvent is 0.5% by mass or more, it tends to prevent the precipitation and solidification of pigments, etc., at the tip of a slit nozzle, which can cause foreign matter defects.

[0225] The content of the solvent in the photosensitive resin composition can be appropriately selected taking into consideration the content of the total solid content of the photosensitive resin composition. When the photosensitive resin composition contains a solvent, the content ratio of all solids relative to the total mass of the photosensitive resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The upper and lower limits can be combined in any way, for example, 5 to 40 mass %, 5 to 30 mass %, 8 to 25 mass %, or 10 to 20 mass %.

[0226] <Other ingredients> In addition to the above-mentioned components, the photosensitive resin composition of the present invention may appropriately contain dispersants, dispersion aids, thiols, adhesion improvers, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, etc.

[0227] (dispersant) The photosensitive coloring composition preferably contains a dispersant for the purpose of finely dispersing the (d) light-shielding component and stabilizing the dispersed state to ensure the stability of quality. As the dispersant, a polymer dispersant having a functional group is preferred, and further, from the viewpoint of dispersion stability, a polymer dispersant having a functional group such as a carboxyl group; a phosphate group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group; a quaternary ammonium base; or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferred. A polymer dispersant having a basic functional group such as a primary, secondary, or tertiary amino group; a quaternary ammonium base; or a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is particularly preferred. The use of a polymer dispersant having such a basic functional group tends to improve dispersibility.

[0228] Examples of polymer dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of a monomer having an amino group and a macromonomer, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants.

[0229] Examples of the dispersant, by trade name, include EFKA (registered trademark, manufactured by EFKA Chemicals BV), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow or Florene (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Fine-Techno Co., Inc.). These polymer dispersants may be used alone or in combination of two or more.

[0230] In terms of adhesion and linearity, the dispersant is preferably a urethane-based polymer dispersant and / or an acrylic-based polymer dispersant having a basic functional group, and a urethane-based polymer dispersant is more preferred in terms of adhesion. In another embodiment, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester and / or polyether bond is preferred.

[0231] The weight average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1000 or more, and is preferably 100000 or less, more preferably 50000 or less, and even more preferably 30000 or less. By ensuring that the Mw is equal to or less than the upper limit, alkaline developability tends to be good even when the pigment concentration is high. The upper and lower limits can be combined in any way, for example, 700 to 100,000, 700 to 50,000, or 1,000 to 30,000.

[0232] Examples of urethane-based or acrylic polymer dispersants include DISPERBYK 160 to 167, 182 series (all urethane-based), and DISPERBYK 2000 and 2001 (all acrylic-based) (all manufactured by BYK-Chemie). Particularly preferred examples of urethane-based or acrylic polymer dispersants having a basic functional group and a polyester and / or polyether bond and a weight-average molecular weight of 30,000 or less include DISPERBYK 167 and 182.

[0233] Examples of urethane-based polymer dispersants include dispersion resins with a weight-average molecular weight of 1,000 to 200,000, which are obtained by reacting a polyisocyanate compound with a compound having one or two hydroxyl groups in the molecule and a number-average molecular weight of 300 to 10,000, and a compound having active hydrogen and a tertiary amino group in the same molecule.

[0234] Examples of polyisocyanate compounds include aromatic diisocyanates such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and ω,ω'-diisocyanate dimethyl cycloisocyanate; Examples of suitable polyisocyanates include alicyclic diisocyanates such as hexane; aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate; triisocyanates such as lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), and tris(isocyanatophenyl)thiophosphate, as well as trimers, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, with trimers of tolylene diisocyanate and isophorone diisocyanate being more preferred. These may be used alone or in combination.

[0235] Examples of methods for producing an isocyanate trimer include a method in which a polyisocyanate compound is subjected to partial trimerization of the isocyanate groups using an appropriate trimerization catalyst, such as a tertiary amine, a phosphine, an alkoxide, a metal oxide, or a carboxylate, and the trimerization is terminated by adding a catalyst poison. Thereafter, the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

[0236] Examples of compounds having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

[0237] Examples of polyether glycols include polyether diols and polyether ester diols. Examples of polyether diols include compounds obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylene glycol.

[0238] Examples of polyetherester diols include those obtained by reacting an ether group-containing diol or a mixture thereof with another glycol with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, such as poly(polyoxytetramethylene) adipate. Preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

[0239] Examples of polyester glycols include dicarboxylic acids (e.g., succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, Examples of suitable polyester glycols include compounds obtained by polycondensation of aliphatic glycols such as 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, and 1,9-nonanediol; alicyclic glycols such as bishydroxymethylcyclohexane; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene; and N-alkyldialkanolamines such as N-methyldiethanolamine, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, and polyethylene / propylene adipate. Other examples include polylactone diols and polylactone monools obtained using glycols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol and polymethylvalerolactone. Polycaprolactone glycol and polycaprolactones using alcohols having 1 to 25 carbon atoms as initiators are preferred.

[0240] Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. These may be used alone or in combination of two or more.

[0241] The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is preferably 300 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 4,000. In a compound having active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, i.e., the hydrogen atom directly bonded to an oxygen atom, nitrogen atom, or sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, or a thiol group, and among these, a hydrogen atom in an amino group, particularly a primary amino group, is preferred.

[0242] The tertiary amino group in a compound having active hydrogen and a tertiary amino group in the same molecule may be, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure such as an imidazole ring or a triazole ring. Examples of compounds having an active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, and N,N-dibutyl-1,4-butanediamine.

[0243] When the tertiary amino group has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include a 5-membered nitrogen-containing heterocyclic ring such as a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, a benzothiazole ring, and a benzothiadiazole ring; and a 6-membered nitrogen-containing heterocyclic ring such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring, and an isoquinoline ring, with an imidazole ring and a triazole ring being preferred.

[0244] Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole. Examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, and 3-amino-1-benzyl-1H-2,4-triazole. Preferred compounds having an active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole. These may be used alone or in combination of two or more.

[0245] The preferred blending ratio of raw materials when producing a urethane polymer dispersant is 100 parts by mass of polyisocyanate compound, 10 to 200 parts by mass, preferably 20 to 190 parts by mass, and more preferably 30 to 180 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of a compound having an active hydrogen and a tertiary amino group in the same molecule. The blending ratios above can be combined as desired. For example, per 100 parts by mass of polyisocyanate compound, preferably 10 to 200 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.2 to 25 parts by mass of a compound having active hydrogen and a tertiary amino group in the same molecule; more preferably 20 to 190 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.2 to 25 parts by mass of a compound having active hydrogen and a tertiary amino group in the same molecule; and even more preferably 30 to 180 parts by mass of a compound having one or two hydroxyl groups in the same molecule and a number average molecular weight of 300 to 10,000, and 0.3 to 24 parts by mass of a compound having active hydrogen and a tertiary amino group in the same molecule.

[0246] The production of urethane polymer dispersants is carried out according to known methods for producing polyurethane resins. Examples of solvents used in the production include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; hydrocarbons such as benzene, toluene, xylene, and hexane; alcohols such as diacetone alcohol, isopropanol, sec-butanol, and tert-butanol; chlorides such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; and aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.

[0247] A urethane-based polymer dispersant may be produced using a urethane-forming reaction catalyst, such as tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; and tertiary amine-based catalysts such as triethylamine and triethylenediamine.

[0248] The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule introduced is preferably controlled to an amine value after the reaction of 1 to 100 mg KOH / g, more preferably 5 to 95 mg KOH / g. By controlling the amine value to be equal to or greater than the lower limit, dispersibility tends to be improved. On the other hand, by controlling the amine value to be equal to or less than the upper limit, developability tends to be improved.

[0249] The amine value is expressed as the mass of KOH equivalent to the amount of base per gram of solids excluding the solvent in the sample, and can be measured by the following method. Accurately weigh out 0.5-1.5 g of sample into a 100 mL beaker and dissolve in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, neutralize this solution with a 0.1 mol / L HClO4 (perchloric acid) acetic acid solution. The inflection point on the titration pH curve is used as the endpoint, and the amine value is calculated using the following formula. Amine value [mgKOH / g] = (561 × V) / (W × S) (where W is the weight of the dispersant sample [g], V is the titration amount at the end of the titration [mL], and S is the solids concentration of the dispersant sample [% by mass]).

[0250] When isocyanate groups remain in the polymer dispersant, it is preferable to consume the isocyanate groups with an alcohol or an amino compound, since this increases the stability of the product over time.

[0251] The weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 50,000. The upper limit is particularly preferably 30,000 or less. When Mw is equal to or greater than the lower limit, dispersibility and dispersion stability tend to be good, and when Mw is equal to or less than the upper limit, solubility tends to be good. The upper and lower limits can be combined in any way, for example, 1,000 to 30,000, 2,000 to 30,000, or 3,000 to 30,000. In particular, alkaline developability tends to be good even when the pigment concentration is high when Mw is 30000 or less. Examples of such commercially available urethane dispersants include DISPERBYK 167 and 182 (BYK-Chemie).

[0252] When the photosensitive resin composition contains a dispersant, the content of the dispersant is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, and is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, and particularly preferably 10% by mass or more, based on the total solid content of the photosensitive resin composition. The upper and lower limits can be combined in any manner, for example, 1 to 50 mass %, 3 to 50 mass %, 5 to 30 mass %, 7 to 30 mass %, or 10 to 20 mass %.

[0253] When the photosensitive resin composition contains a dispersant, the content of the dispersant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of the (d) light-shielding component, and is preferably 200 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 50 parts by mass or less. By setting the content at or above the lower limit, sufficient dispersibility tends to be easily ensured. By setting the content at or below the upper limit, sufficient unit OD value, sensitivity, film-forming properties, etc. tend to be easily achieved without reducing the proportions of other components. The upper and lower limits can be combined in any way, and may be, for example, 5 to 200 parts by mass, 10 to 80 parts by mass, or 15 to 50 parts by mass.

[0254] (Dispersion aid) The photosensitive resin composition preferably contains a dispersion aid to improve the dispersion stability of the (d) light-shielding component. Examples of the dispersing aid include pigment derivatives, such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolopyrrole-based, and dioxazine-based derivatives, with phthalocyanine-based and quinophthalone-based derivatives being preferred.

[0255] Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and its quaternary salts, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc., which are bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc., and preferably a sulfonic acid group. Furthermore, a single pigment skeleton may be substituted with a plurality of these substituents. Examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.

[0256] When the photosensitive resin composition contains a dispersing aid, the content of the dispersing aid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the photosensitive resin composition. When the content of the dispersing aid is equal to or greater than the lower limit, the dispersion stability tends to be better. When the content of the dispersing aid is equal to or less than the upper limit, the developability tends to be stable and the substrate adhesion tends to be good. The upper and lower limits can be combined in any way, for example, 0.1 to 10 mass %, 0.5 to 10 mass %, or 1 to 5 mass %.

[0257] (thiols) The photosensitive resin composition may contain thiols to improve sensitivity and adhesion to the substrate. Examples of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane; (trade name: Karenz MT) BD1, manufactured by Showa Denko K.K.), butanediol trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate); (trade name: Karenz MT PE1, manufactured by Showa Denko K.K.), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptobutyrate) (TPMB), trimethylolpropane tris(2-mercaptoisobutyrate) (TPMIB), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko K.K. These can be used alone or in combination of two or more. As the thiols, polyfunctional thiol compounds such as PGMB, TPMB, TPMIB, KarenzMT BD1, KarenzMT PE1, and KarenzMT NR1 are preferred, and among these, KarenzMT BD1, KarenzMT PE1, and KarenzMT NR1 are more preferred, and KarenzMT PE1 is particularly preferred.

[0258] When the photosensitive resin composition contains thiols, the content of the thiols is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the total solid content of the photosensitive resin composition, and is preferably 10% by mass or less, more preferably 5% by mass or less. If the content ratio of the thiols is equal to or greater than the lower limit, there is a tendency that a decrease in sensitivity can be suppressed, and if it is equal to or less than the upper limit, there is a tendency that storage stability can be improved. The upper and lower limits can be combined in any way, and may be, for example, 0.1 to 10 mass %, 0.3 to 10 mass %, or 0.5 to 5 mass %.

[0259] (adhesion improver) The photosensitive resin composition may contain an adhesion promoter to improve adhesion to the substrate. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent, with the silane coupling agent being particularly preferred. Examples of silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, and X-12-1050 (manufactured by Shin-Etsu Silicones Co., Ltd.), and Z-6040, Z-6043, and Z-6062 (manufactured by Dow Corning Toray Co., Ltd.). One type of silane coupling agent may be used alone, or two or more types may be used in combination.

[0260] The photosensitive resin composition may contain an adhesion improver other than the silane coupling agent and the titanium coupling agent. Examples of the adhesion improver other than the silane coupling agent and the titanium coupling agent include a phosphoric acid-based adhesion improver and other adhesion improvers. As the phosphoric acid-based adhesion improver, (meth)acryloyloxy group-containing phosphates are preferred, and among them, compounds represented by the following general formulas (g1), (g2) and (g3) are preferred.

[0261] [ka]

[0262] In formulas (g1), (g2), and (g3), R 51 each independently represents a hydrogen atom or a methyl group; l and l' each independently represents an integer of 1 to 10; and m each independently represents 1, 2, or 3. Other adhesion improvers include, for example, TEGO*Add Bond LTH (manufactured by Evonik Co., Ltd.) These phosphate group-containing compounds and other adhesion improvers may be used alone or in combination of two or more.

[0263] When the photosensitive resin composition contains an adhesion improver, the content of the adhesion improver in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less, relative to the total solid content of the photosensitive resin composition. If the content ratio of the adhesion improver is equal to or greater than the lower limit, adhesion tends to be improved, and if it is equal to or less than the upper limit, developability tends to be good. The upper and lower limits can be combined in any way, and may be, for example, 0.01 to 5 mass%, 0.01 to 3 mass%, 0.1 to 2 mass%, or 0.5 to 1.5 mass%.

[0264] (Coating improver) The photosensitive resin composition may contain a coatability improver to improve coatability. Examples of the coatability improver include surfactants. Examples of usable surfactants include anionic, cationic, nonionic, and amphoteric surfactants. Among these, nonionic surfactants are preferred because they are less likely to adversely affect various properties, and fluorine-based or silicone-based surfactants are particularly effective in terms of coatability.

[0265] Examples of surfactants that can be used as application improvers include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicones), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar Co., Ltd.), and FC4430 (manufactured by 3M Japan). The coatability improver may be used alone or in combination of two or more kinds.

[0266] When the photosensitive resin composition contains a coatability improver, the content of the coatability improver in the photosensitive resin composition is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and is preferably 1% by mass or less, more preferably 0.7% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, relative to the total solid content of the photosensitive resin composition. If the content of the coatability improver is equal to or greater than the lower limit, coating uniformity tends to improve, and if it is equal to or less than the upper limit, resist sensitivity tends not to decrease. The upper and lower limits can be combined arbitrarily, and may be, for example, 0.01 to 1 mass %, 0.01 to 0.7 mass %, 0.05 to 0.5 mass %, or 0.05 to 0.3 mass %.

[0267] <Physical properties of photosensitive resin composition> The optical density (unit OD value) per 1.0 μm thickness when the photosensitive resin composition of the present invention is cured is 3.5 or more, preferably 3.6 or more, more preferably 3.7 or more, and even more preferably 3.8 or more. When the unit OD value is equal to or more than the lower limit, the photosensitive resin composition is useful for forming a black matrix of a color filter. The higher the unit OD value, the more preferable, and there is no particular upper limit, but it is, for example, 6.0. The unit OD value may be, for example, 3.5 to 6.0, 3.6 to 6.0, 3.7 to 6.0, or 3.8 to 6.0. The unit OD value can be adjusted by the type and content of (d) the light-blocking component. The photosensitive resin composition of the present invention can be suitably used for forming a black matrix, and from this viewpoint, it is preferable that the composition exhibits a black color.

[0268] <Method for producing photosensitive resin composition> The photosensitive resin composition of the present invention is produced by a conventional method. The (d) light-shielding component is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. The dispersion process microparticulates the (d) light-shielding component, improving the coating properties of the photosensitive resin composition. When a black coloring material is used as the (d) light-shielding component, this contributes to improving the light-shielding ability.

[0269] It is preferable to carry out a dispersion treatment in a system in which (d) a light-shielding component, a solvent, and, if necessary, a dispersant, and part or all of (a) an alkali-soluble resin are used in combination (hereinafter, the mixture to be subjected to the dispersion treatment and the mixture obtained by the dispersion treatment may be referred to as an "ink" or a "pigment dispersion.") In particular, using a polymer dispersant as a dispersant is preferable because the resulting ink and photosensitive resin composition have excellent dispersion stability and are prevented from thickening over time. When a dispersion treatment is performed on a liquid containing all the components to be blended into the photosensitive resin composition, the heat generated during the dispersion treatment may cause denaturation of highly reactive components. In such cases, therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

[0270] When dispersing the (d) light-shielding component using a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is preferably in the range of 0°C to 100°C, more preferably room temperature to 80°C. The dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment device, and other factors, and should be adjusted as appropriate. The standard for dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 100 to 200. When the gloss of the photosensitive resin composition is low, the dispersion treatment is often insufficient, leaving coarse pigment (colorant) particles, which can result in insufficient developability, adhesion, resolution, and other properties. If the dispersion treatment is performed until the gloss value exceeds the above range, the pigment will be crushed, producing a large number of ultrafine particles, which tends to actually impair dispersion stability.

[0271] Next, the ink obtained by the dispersion treatment is mixed with the other components contained in the photosensitive resin composition to form a homogeneous solution. In order to remove fine dust particles that may have been mixed in during the manufacturing process, the obtained photosensitive resin composition is preferably filtered using a filter or the like.

[0272] <Application> The photosensitive resin composition of the present invention can be used as a resist for components constituting a color filter, such as pixels, black matrices, etc. When the photosensitive resin composition of the present invention is for a black matrix, it contains a black color material such as a black pigment. The photosensitive resin composition of the present invention can also be used as a resist for colored spacers. The photosensitive resin composition of the present invention can also be used to form partition walls, particularly partition walls for separating organic layers of organic electroluminescent devices. Examples of the organic layer of an organic electroluminescent device include organic layers used as a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer, as described in JP 2016-165396 A.

[0273] [Cured product] The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. Alternatively, the cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. The cured product of the present invention can be suitably used as a component of a color filter, such as a pixel or a black matrix. The cured product of the present invention can also be used as a colored spacer. The cured product of the present invention can also be used as a partition wall, particularly a partition wall for separating organic layers of an organic electroluminescent device.

[0274] [Black Matrix] The black matrix made of the cured product of the present invention will be described in accordance with its manufacturing method. A black matrix made of the cured product of the present invention can be formed, for example, by applying the photosensitive resin composition of the present invention to a support on which the black matrix is ​​to be provided, drying the composition, placing a photomask on the dried coating film, exposing the composition to light (imagewise exposure) through the photomask, developing the composition, and optionally curing the composition.

[0275] (1) Support The material of the support for forming the black matrix is ​​not particularly limited as long as it has an appropriate strength, and a transparent substrate is mainly used. Examples of materials for the transparent substrate include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic resin, and various types of glass. Glass and heat-resistant resins are preferred from the viewpoint of heat resistance. A transparent electrode such as ITO or IZO may also be formed on the surface of the transparent substrate. The black matrix can also be formed on a support other than a transparent substrate, for example, a TFT array. In order to improve surface properties such as adhesiveness, the support may be subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, or thin film formation treatment using a silane coupling agent or various resins such as urethane resins, as necessary. The thickness of the transparent substrate is preferably in the range of 0.05 to 10 mm, more preferably 0.1 to 7 mm. When a thin film of various resins is formed, the thickness is preferably in the range of 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[0276] (2) Formation of black matrix (2-1) Application of photosensitive resin composition The photosensitive resin composition for a black matrix can be applied to a support by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, etc. Among these, the die coating method is preferred from an overall viewpoint, since it significantly reduces the amount of coating solution used, is completely free from the influence of mist and the like that adheres when using a spin coating method, and suppresses the generation of foreign matter.

[0277] The thickness of the coating film after drying is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm, and even more preferably 1 to 4 μm. By setting it to the upper limit or less, pattern development tends to be easy, and gap adjustment in the liquid crystal cell formation process also tends to be easy. By setting it to the lower limit or more, desired color expression tends to be easy.

[0278] (2-2) Drying of the coating After applying the photosensitive resin composition to the support, the coating is preferably dried using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected depending on the type of liquid medium (organic solvent, water) contained in the photosensitive resin composition, the performance of the dryer used, and other factors. For example, the drying time is selected from the range of 15 seconds to 5 minutes at a temperature of 40 to 200°C, preferably 30 seconds to 3 minutes at a temperature of 50 to 130°C. The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate, but if the temperature is too high, the alkali-soluble resin may decompose, inducing thermal polymerization and resulting in poor development. The drying process of this coating film may also be a reduced-pressure drying method in which drying is carried out in a reduced-pressure chamber without increasing the temperature.

[0279] (2-3) Exposure Imagewise exposure is carried out by placing a photomask on a coating film of the photosensitive resin composition and irradiating the coating film with light having a wavelength ranging from the ultraviolet region to the visible region through the photomask. A negative mask pattern is typically used as the photomask. If necessary, an oxygen-blocking layer such as a polyvinyl alcohol layer may be formed on the coating film before exposure in order to prevent a decrease in the sensitivity of the coating film due to oxygen. The light source used for imagewise exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arc lamps. When using light of a specific wavelength, an optical filter can also be used.

[0280] (2-4) Development Development is carried out using an organic solvent or an aqueous solution containing an alkaline compound and a surfactant, which may further contain organic solvents, buffers, complexing agents, dyes or pigments.

[0281] Examples of alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be used alone or in combination.

[0282] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinate salts; and amphoteric surfactants such as alkylbetaines and amino acids.

[0283] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.

[0284] There are no particular restrictions on the conditions for the development process. The development temperature is preferably 10 to 50° C., more preferably 15 to 45° C., and even more preferably 20 to 40° C. The development method can be any of immersion development, spray development, brush development, ultrasonic development, etc.

[0285] (2-5) Hardening treatment Examples of the curing treatment include heat curing treatment and light curing treatment, with heat curing treatment being preferred. The heat curing conditions are such that the temperature is selected from the range of 100 to 280°C, preferably from the range of 150 to 250°C, and the time is selected from the range of 5 to 60 minutes.

[0286] The height of the black matrix formed as described above is preferably 0.5 to 5 μm, more preferably 0.8 to 4 μm. The optical density (OD value) per 1 μm of thickness of the black matrix is ​​3.5 or more, preferably 3.6 or more, more preferably 3.7 or more, and even more preferably 3.8 or more. The higher the OD value, the better. There is no particular upper limit, but it is, for example, 6.0.

[0287] [Color filter] A photosensitive resin composition containing a colorant of one of red (R), green (G), and blue (B) colors is applied to a transparent substrate provided with a black matrix using the same processes as those described above in (2-1) to (2-5). After drying, a photomask is placed on the coating film, and a pixel image is formed by imagewise exposure through the photomask, development, and, if necessary, heat curing or photocuring to form a colored layer. This process is repeated for each of the photosensitive resin compositions of the three colors R, G, and B, thereby forming a color filter. The order of these processes is not limited to the above.

[0288] (2-6) Formation of transparent electrodes The color filter can be used as a part of a color display, a liquid crystal display device, etc. by forming a transparent electrode such as ITO on the image in this state. To improve surface smoothness and durability, a topcoat layer of polyamide, polyimide, etc. can be formed on the image as needed. In some applications, such as those using a planar alignment driving system (IPS mode), a transparent electrode may not be formed.

[0289] [Colored spacer] When spacers are used in TFT-type LCDs, light incident on the TFTs can cause the TFTs to malfunction as switching elements, and colored spacers are used to prevent this. For example, Japanese Patent Application Laid-Open No. 8-234212 describes making spacers light-blocking. The colored spacers made of the cured product of the present invention can be formed in the same manner as the above-mentioned black matrix, except that a mask for the colored spacers is used.

[0290] [Bulkhead] The partition walls made of the cured product of the present invention will be described in accordance with the method for producing them. The partition walls made of the cured product of the present invention can be formed, for example, by a method in which the photosensitive resin composition of the present invention is applied to a support on which the partition walls are to be provided, dried, a photomask is placed on the dried coating film, exposure (imagewise exposure) is performed through the photomask, development is performed, and, if necessary, curing treatment is performed.

[0291] (3-1) Support As the support for forming the partition walls, the same support as the support for forming the black matrix described above can be used.

[0292] (3-2) Formation of partition walls In the method for forming the partition walls, the specific methods for applying the photosensitive resin composition to the support, drying, exposing, developing and curing can be the same as those used in the formation of the black matrix described above.

[0293] The size and shape of the partition wall are adjusted as appropriate depending on the specifications of the organic electroluminescent device to which it is applied, but the height of the partition wall formed from the photosensitive resin composition is preferably about 0.5 to 10 μm.

[0294] [Organic electroluminescent device] Various organic electroluminescent devices are manufactured using a support provided with the partition walls manufactured by the above-described method. For example, the method for forming an organic electroluminescent element is not particularly limited, but preferably, after forming a partition wall on a support by the above-described method, an organic layer such as a pixel is formed, thereby manufacturing the organic electroluminescent element. Methods for forming the organic layer include a vapor deposition method in which a functional material is sublimated in a vacuum and deposited in an area surrounded by a partition on a substrate to form a film, and wet processes such as a casting method, a spin coating method, and an inkjet printing method.

[0295] The types of organic electroluminescent devices include bottom emission types and top emission types. A bottom-emission type is fabricated, for example, by forming a partition wall on a glass substrate on which a transparent electrode is laminated, and then laminating a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in an opening surrounded by the partition wall, whereas a top-emission type is fabricated, for example, by forming a partition wall on a glass substrate on which a metal electrode layer is laminated, and then laminating an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in an opening surrounded by the partition wall. Examples of the light-emitting layer include organic electroluminescent layers such as those described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[0296] The layer structure is not limited to this, and for example, each of the hole transport layer and the electron transport layer may have a laminate structure consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is preferably 1 to 500 nm from the viewpoint of luminous efficiency and brightness.

[0297] The organic electroluminescent element may be formed with each RGB color separated for each opening, or two or more colors may be laminated in one opening. The organic electroluminescent element may have a sealing layer to improve reliability. The sealing layer has the function of preventing moisture in the air from being adsorbed onto the organic electroluminescent element and reducing luminous efficiency. The organic electroluminescent element may have a low-reflection film at the interface with air to improve light extraction efficiency. By disposing the low-reflection film at the interface between air and the element, it is expected that the refractive index gap will be reduced and reflection at the interface will be suppressed. For example, moth-eye structure and super multilayer film technology can be applied to such a low-reflection film.

[0298] When the organic electroluminescent element is used as a pixel of an image display device, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent element in order to prevent light from the light-emitting layer of one pixel from leaking to other pixels and, further, to prevent deterioration in image quality due to reflection of external light when the electrodes or the like are made of metal. In an organic electroluminescent device, since electrodes are provided on the upper and lower surfaces of the partition walls, the partition walls preferably have high resistance and low dielectric constant from the viewpoint of insulation. Therefore, when a colorant is used to impart light-shielding properties to the partition walls, it is preferable to use the organic pigment having high resistance and low dielectric constant.

[0299] [Image display device] The image display device of the present invention has the black matrix of the present invention. In another embodiment, the image display device of the present invention includes the cured product of the present invention. The image display device of the present invention may be, for example, an image display device provided with the above-mentioned black matrix or partition wall. The image display device is not particularly limited as long as it is a device that displays images or videos, and examples thereof include a liquid crystal display device and an organic EL display, which will be described later.

[0300] [Liquid crystal display device] The liquid crystal display device of the present invention can be produced, for example, by using a color filter having the above-mentioned black matrix. The order and position of forming the color pixels and the black matrix are not particularly limited.

[0301] Liquid crystal display devices are typically manufactured by forming an alignment film on a color filter, dispersing spacers on the alignment film, and then bonding it to an opposing substrate to form a liquid crystal cell. Liquid crystal is then injected into the formed liquid crystal cell, and the cell is then connected to the opposing electrode. A resin film such as polyimide is suitable for the alignment film. Gravure printing and / or flexographic printing are typically used to form the alignment film, with a thickness of several tens of nanometers. After curing the alignment film by thermal baking, the surface is treated with ultraviolet light or a rubbing cloth to create a surface that allows adjustment of the tilt of the liquid crystal.

[0302] The spacer used should be of a size that corresponds to the gap (gap) with the opposing substrate, with 2 to 8 μm being preferred. A transparent resin film photospacer (PS) can be formed on the color filter substrate by photolithography and used instead of the spacer. An array substrate is usually used as the opposing substrate, with a TFT (thin film transistor) substrate being particularly preferred.

[0303] The gap between the opposing substrate and the substrate is preferably in the range of 2 to 8 μm, although it varies depending on the application of the liquid crystal display device. After bonding with the opposing substrate, the area other than the liquid crystal injection port is sealed with a sealant such as epoxy resin. The sealant is hardened by UV irradiation and / or heating, sealing the periphery of the liquid crystal cell. The liquid crystal cell with its periphery sealed is cut into panel units, and then the pressure is reduced in a vacuum chamber. After the liquid crystal injection port is immersed in the liquid crystal, the liquid crystal is injected into the liquid crystal cell by leaking the chamber. The degree of pressure reduction inside the liquid crystal cell is 1 x 10 -7 ~1×10 -2 Pa is preferred, 1×10 -6 ~1×10 -3Pa is more preferable. Furthermore, it is preferable to heat the liquid crystal cell during decompression, and the heating temperature is preferably 30 to 100°C, more preferably 50 to 90°C. The heating is preferably maintained for 10 to 60 minutes during decompression. Thereafter, the liquid crystal cell is immersed in liquid crystal. The liquid crystal cell into which the liquid crystal has been injected is sealed at the liquid crystal injection port by curing a UV curable resin, thereby completing a liquid crystal display device (panel).

[0304] The type of liquid crystal is not particularly limited, and may be any conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, for example, a lyotropic liquid crystal, or a thermotropic liquid crystal. Known thermotropic liquid crystals include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals, and any of these may be used.

[0305] [OLED display] The organic EL display of the present invention can be produced using, for example, a color filter having the above-mentioned black matrix or an organic electroluminescent element having the above-mentioned partition wall.

[0306] When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1 , a color filter having a pattern (i.e., pixels 20 and a black matrix (not shown) provided between adjacent pixels 20) formed from a photosensitive resin composition is first produced on a transparent support substrate 10, and an organic light-emitting element 500 is then laminated on the color filter via an organic protective layer 30 and an inorganic oxide film 40, thereby producing an organic EL element 100. Note that at least one of the pixels 20 and the black matrix is ​​produced using the photosensitive resin composition of the present invention. Examples of methods for laminating the organic light-emitting element 500 include a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the top surface of the color filter, and a method of laminating the organic light-emitting element 500 formed on a separate substrate onto the inorganic oxide film 40. Using the organic EL element 100 thus produced, an organic EL display can be produced by, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Light Emitting, by Shizuo Tokito, Chinaya Adachi, and Hideyuki Murata). The color filter of the present invention can be applied to both passively driven organic EL displays and actively driven organic EL displays.

[0307] [Reasons why the invention is effective] By using the photosensitive resin composition of the present invention, a cured product having excellent light-shielding properties and low reflectance can be obtained. Although the reason why the present invention is effective is not clear, it is presumed that when a cured product is produced from the photosensitive resin composition of the present invention, the (e) hollow polymer particles, which have a relatively low reflectance, are unevenly distributed on the coated glass substrate side due to the surface properties of the (e) hollow polymer particles and other components, and similarly, the surface properties of the (e) hollow polymer particles and other components prevent the components from agglomerating as foreign matter, thereby realizing light-blocking properties and low reflectance. [Example]

[0308] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. The components of the photosensitive resin compositions used in the following examples and comparative examples are as follows:

[0309] <Alkali-soluble resin> Alkali-soluble resin I: The alkali-soluble resin obtained in Synthesis Example 1 described below. Alkali-soluble resin II: The alkali-soluble resin obtained in Synthesis Example 2 described below.

[0310] <Synthesis Example 1: Synthesis of alkali-soluble resin I>

[0311] [ka]

[0312] 240 parts by mass of the epoxy compound (epoxy equivalent 249) of the above structure, 68.3 parts by mass of acrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of 2,6-di-tert-butyl-4-cresol (BHT) were placed in a flask equipped with a thermometer, a stirrer, and a condenser, and reacted with stirring at 90°C for 12 hours until the acid value reached 5 mgKOH / g or less. Next, the reaction liquid obtained by the above reaction, 100.0 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 68.9 parts by mass of tetrahydrophthalic anhydride (THPA) were placed in a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was slowly raised to 105°C while stirring to allow the reaction to occur, thereby obtaining an alkali-soluble resin I having a solid acid value of 105 mgKOH / g and a weight average molecular weight (Mw) of 6900 in terms of polystyrene as measured by GPC.

[0313] <Synthesis Example 2: Synthesis of alkali-soluble resin II>

[0314] [ka]

[0315] 240 parts by mass of the epoxy compound (epoxy equivalent weight 264) having the above structure, 81.6 parts by mass of methacrylic acid, 263.1 parts by mass of methoxybutyl acetate, 6.4 parts by mass of triphenylphosphine, and 0.16 parts by mass of paramethoxyphenol were placed in a flask equipped with a thermometer, a stirrer, and a condenser, and reacted with stirring at 90°C for 12 hours until the acid value reached 5 mgKOH / g or less. Next, the reaction liquid obtained by the above reaction, 8.3 parts by mass of trimethylolpropane (TMP), 80.7 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 51.6 parts by mass of tetrahydrophthalic anhydride (THPA) were placed in a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was slowly raised to 105°C while stirring to allow the reaction to occur, yielding an alkali-soluble resin II having a solid acid value of 112 mgKOH / g and a weight average molecular weight (Mw) of 2500 in terms of polystyrene as measured by GPC.

[0316] <Photopolymerizable compound> DPHA: "KAYARAD DPHA" (multifunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.

[0317] <Photopolymerization initiator> TR-PBG-304: "TR-PBG-304" manufactured by Changzhou Strong Electronic New Materials Co., Ltd. (oxime ester having a carbazole skeleton. The structure is as follows).

[0318] [ka]

[0319] <Surfactant> F-554: DIC's "Megafac F554" (fluorine-based surfactant).

[0320] <Adhesion improver> X-12-1048: "X-12-1048" (multifunctional acrylic silane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0321] <Hollow polymer particles> Hollow polymer a: Sekisui Plastics Co., Ltd., propylene glycol monomethyl ether (PGME) dispersion of hollow polymer microparticles made from acrylic resin, average particle diameter 65 nm. Hollow polymer b: Sekisui Plastics Co., Ltd., PGME dispersion of hollow polymer microparticles, average particle diameter 120 nm.

[0322] <Silica particles> Amorphous silica: Nissan Chemical's "PMA-ST", average particle size 10-15 nm. <Hollow silica particles> Hollow silica: "Sururia 4330" manufactured by JGC Catalyst Chemicals, PGME dispersion with an average particle size of 60 nm.

[0323] <Production Example 1: Preparation of CB1> Coated carbon black (hereinafter also referred to as CB1) was prepared by the method described in Production Example 1 of JP 2013-195538 A. In preparing CB1, MA77 (Carbon Black, manufactured by Mitsubishi Chemical Corporation) was used as the carbon black.

[0324] <Production Example 2: Preparation of CB Ink 1> Using the CB1, a coated carbon black ink (hereinafter also referred to as CB ink 1) having a solid content of 25% by mass was prepared according to the method described in Production Example 2 of JP 2013-195538 A. The dispersant used was DISPERBYK-167 (a basic urethane dispersant manufactured by BYK-Chemie). The mass ratio of each component of the resulting CB ink 1 is as follows: Pigment (MA77 (Mitsubishi Chemical Corporation, carbon black)): 18.0 parts by mass. Coating resin (jER (registered trademark) 828 (manufactured by Mitsubishi Chemical Corporation, epoxy resin)): 2.0 parts by mass. Dispersant (DISPERBYK-167 (manufactured by BYK-Chemie, basic urethane dispersant)): 4.4 parts by mass. Dispersing aid (pigment derivative, Solsperse 12000 (manufactured by Lubrizol Corporation, a phthalocyanine pigment derivative having an acidic group)): 1.0 part by mass. Solvent (propylene glycol monomethyl ether acetate (PGMEA)): 76.2 parts by mass.

[0325] <Production Example 3: Preparation of CB Ink 2> A carbon black ink (hereinafter also referred to as CB ink 2) was prepared in the same manner as in Production Example 2, except that 18.0 parts by mass of MA77 (carbon black, manufactured by Mitsubishi Chemical Corporation) was used instead of 20.0 parts by mass of CB1 (18.0 parts by mass of carbon black and 2.0 parts by mass of coating resin).

[0326] [Preparation of Photosensitive Resin Composition (Resist)] <Examples 1 to 5, Comparative Examples 1 to 4> Each component was added so that the ratio of the solid content of each component to the total solid content was the ratio shown in Table 1, and propylene glycol monomethyl ether acetate (PGMEA), 3-methoxybutyl acetate (MBA), and diethylene glycol monoethyl ether acetate (EDGAC) were further added so that the ratio of the total solid content to the total mass of the photosensitive resin composition was 13.5 mass% and the mass ratio of PGMEA / MBA / EDGAC was 75 / 23 / 2, and the mixture was stirred and dissolved to prepare a photosensitive resin composition.

[0327] [Evaluation of Photosensitive Resin Composition] <Measurement of optical density (unit: OD value) per 1.0 μm thickness> The photosensitive resin composition was applied to a glass substrate (AGC, thickness 0.5 mm) using a spin coater so that the film thickness after heat curing would be 1.15 μm, and then dried under reduced pressure at 100 Pa for 30 seconds, followed by drying on a hot plate at 110°C for 120 seconds. The resulting coating film was then heated without a mask to an intensity of 45 mW / cm at a wavelength of 365 nm. 2 The exposure dose was 50 mJ / cm 2 The entire surface was exposed to light so that Next, using a developer consisting of a 0.04% by mass aqueous solution of potassium hydroxide (KOH), shower development was performed at 23°C under a water pressure of 0.05 MPa for 80 seconds, after which the development was stopped with pure water and the substrate was washed with a water spray.The substrate was then heat-cured (post-baked) in an oven at 230°C for 30 minutes to form a cured film, and a substrate for optical density measurement was obtained. The optical density (OD) of the optical density measurement substrate was measured using a transmission densitometer (361T(V) manufactured by X-Rite), and the film thickness of the cured film was measured using a scanning white light interference microscope (VS1530 manufactured by Hitachi High-Technologies Corporation). The optical density (OD value) per unit thickness (1.0 μm) was calculated from the optical density (OD) and film thickness. The results are shown in Table 1. The OD value is a value that indicates the light-blocking ability, with a larger value indicating a higher light-blocking ability.

[0328] <Reflectance evaluation> A substrate for measuring reflectance was obtained in the same manner as for the substrate for measuring optical density in measuring the unit OD value. Using a spectrophotometer (U-3900H manufactured by Hitachi High-Tech Science Corporation), the reflectance obtained when the glass substrate side surface of the reflectance measurement substrate was irradiated with light having a wavelength of 550 nm at an incident angle of 5° was measured. Similarly, the reflectance of the coating film side, which is the opposite side to the glass substrate side, was also measured. The results are shown in Table 1.

[0329] <Evaluation of foreign matter> The photosensitive coloring composition was applied to a glass substrate using a spin coater so that the film thickness after heat curing would be 1.15 μm, and after drying under reduced pressure at 100 Pa for 30 seconds, it was dried on a hot plate at 110° C. for 120 seconds. The substrate was then heat cured (post-baked) at 230° C. for 30 minutes in an oven to form a cured film, and a substrate for evaluating foreign matter was obtained. The surface of the cured film side of the foreign matter evaluation substrate was observed using an optical microscope to check for the presence or absence of protruding foreign matter. The number of foreign matters in an area of ​​7 cm x 1 mm in the center of the evaluation substrate was counted, and the results were evaluated as follows. The results are shown in Table 1. A: More than 30 pieces. B: 15 or more but less than 30. C: Less than 15 pieces.

[0330] [Table 1]

[0331] The cured products of the photosensitive resin compositions of Examples 1 to 5 had unit OD values ​​of 3.5 or more, but had lower reflectance than Comparative Examples 1 and 4, which did not contain hollow polymer particles. Furthermore, in Examples 1 to 4, which used hollow polymer particles with an average particle size of less than 70 μm, the generation of foreign matter was suppressed. Comparative Example 2, in which the CB content was reduced compared to Comparative Example 1, had a low unit OD value. Comparative Example 3, in which silica particles were used instead of hollow polymer particles, did not show much effect in reducing reflectance, and a large amount of foreign matter was generated. Comparing the reflectance from the coating film side of Example 1 and Comparative Example 1, Example 1 exhibits a value equivalent to or slightly higher than that of Comparative Example 1. This is presumably because the hollow polymer particles are unevenly distributed on the glass substrate side, causing other components that increase reflectance to be unevenly distributed on the coating film side, resulting in an ideal reflectance on the coating film side. In Comparative Example 5, in which hollow silica particles were used instead of hollow polymer particles, the reflectance reduction effect was smaller than that of the hollow polymer particles, and a large amount of foreign matter was generated. Furthermore, the reflectance of the coating film side was lower than that of Example 1 and Comparative Example 1, resulting in a decrease in light blocking performance. This is presumably because the hollow silica particles, unlike the hollow polymer particles, are uniformly dispersed in the film. [Explanation of symbols]

[0332] 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light-emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic Light Emitting Materials

Claims

1. A photosensitive resin composition comprising: (a) an alkali-soluble resin; (b) a photopolymerizable compound; (c) a photopolymerization initiator; (d) a light-shielding component; and (e) hollow polymer particles; The (e) hollow polymer particles have an average particle size of less than 110 nm, the content of the (e) hollow polymer particles is greater than 1 mass% based on the total solid content of the photosensitive resin composition, A photosensitive resin composition having an optical density of 3.5 or more per 1.0 μm thickness when cured.

2. 2. The photosensitive resin composition according to claim 1, wherein the light-shielding component (d) comprises carbon black.

3. 3. The photosensitive resin composition according to claim 1, wherein the hollow polymer particles (e) contain an acrylic resin.

4. 3. The photosensitive resin composition according to claim 1, wherein the hollow polymer particles (e) have an average particle size of less than 70 nm.

5. 3. The photosensitive resin composition according to claim 1, wherein the content of the light-shielding component (d) is 40% by mass or more and 55% by mass or less based on the total solid content of the photosensitive resin composition.

6. 3. The photosensitive resin composition according to claim 1, wherein the content of the hollow polymer particles (e) is 2% by mass or more and 10% by mass or less based on the total solid content of the photosensitive resin composition.

7. 3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has an optical density of 3.7 or more per 1.0 μm thickness when cured.

8. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2.

9. A black matrix comprising the cured product according to claim 8.

10. An image display device comprising the black matrix according to claim 9.

Images