Photosensitive resin composition, resin cured film, and image display element

Abstract

To provide a photosensitive resin composition which gives a resin cured film having good adhesion by reducing a low-molecular-weight component present in a cured product.SOLUTION: The photosensitive resin composition contains (A) an alkali-soluble resin, (B) a reactive diluent, (C) a photopolymerization initiator, and (D) a solvent and further contains (E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a cured resin film, a photosensitive coloring composition, a color filter, and an image display element. [Background technology]

[0002] Currently, from the viewpoint of resource and energy conservation, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in the fields of various coatings, printing, paints, adhesives, etc. In the field of electronic materials, photosensitive resin compositions are used as solder resists for printed wiring boards and the like, and color filter resists for displays such as liquid crystal and organic EL displays.

[0003] In recent years, photosensitive resin compositions have been proposed that have low-temperature curing properties and are compatible with components with low heat resistance, such as organic electroluminescence (EL) devices. For example, Patent Document 1 discloses an alkali-soluble resin that can give a cured product that has excellent solvent resistance and adhesion to substrates even under low-temperature curing conditions and that can be suitably used in applications such as color filters. The alkali-soluble resin has a structural unit (A) derived from an oxetanyl group-containing monomer, a structural unit (B) derived from an acid anhydride monomer, and a structural unit (C) derived from an acid group-containing compound adduct of a hydroxyl group-containing monomer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-14542 Summary of the Invention [Problem to be solved by the invention]

[0005] These photosensitive resin compositions are required to have curability that allows them to cure well under low temperature conditions without causing curing failure, and good adhesion that prevents the cured product from leaching or peeling from the substrate even when exposed to various solvents in the subsequent manufacturing process. Patent Document 1 describes how hydroxyl groups, which contribute to low-temperature curing, are capped with acid anhydrides to prevent them from crosslinking before the curing process, and then the acid anhydrides are eliminated by heating to form hydroxyl groups, thereby achieving low-temperature curing. However, this method raises concerns that the eliminated acid anhydrides may become liberated, adversely affecting the curing properties and the adhesion of the cured product.

[0006] Another approach is to introduce an ethylenically unsaturated group into an alkali-soluble resin to improve the photocurability of the photosensitive resin composition and thereby improve its low-temperature curability. However, this approach tends to cause gelation of the resin and a decrease in the storage stability of the photosensitive resin composition. To alleviate this, a polymerization inhibitor is often used. However, since the polymerization inhibitor also exists in a free state in the photosensitive resin composition, this can lead to poor curing of the photosensitive resin composition and a decrease in the solvent resistance and adhesion of the cured product.

[0007] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a photosensitive resin composition that reduces low-molecular-weight components present in the cured product and gives a cured resin film with good adhesion. Another object of the present invention is to provide an image display element having a cured resin film with excellent adhesion and a cured product of a photosensitive coloring composition containing the photosensitive resin composition and a colorant. [Means for solving the problem]

[0008] The present invention includes the following aspects. [1] (A) an alkali-soluble resin; (B) a reactive diluent; (C) a photopolymerization initiator; (D) a solvent; A photosensitive resin composition comprising: (E) A photosensitive resin composition further containing an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group. [2] (A) an alkali-soluble resin; (B) a reactive diluent; (C) a photopolymerization initiator; (D) a solvent; A photosensitive resin composition comprising: The photosensitive resin composition, wherein the alkali-soluble resin (A) is at least one selected from the group consisting of the alkali-soluble resin (A1) and the alkali-soluble resin (A2) described below. Alkali-soluble resin (A1): An adduct of an ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group to a copolymer (A1-0) containing a structural unit (ma-1) derived from an ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group and a structural unit (ma-2) derived from an ethylenically unsaturated group-containing compound (m-2) having a carboxy group. Alkali-soluble resin (A2): An adduct of a compound having an alkali-soluble functional group to an adduct of an ethylenically unsaturated group-containing compound (a-2) having a carboxy group to a copolymer (A2-0) containing a structural unit (ma-3) derived from an ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group and a structural unit (ma-4) derived from an ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group. [3] (A) an alkali-soluble resin; (B) a reactive diluent; (C) a photopolymerization initiator; (D) a solvent; A photosensitive resin composition comprising: (E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, The photosensitive resin composition, wherein the alkali-soluble resin (A) is at least one selected from the group consisting of the alkali-soluble resins (A3) and (A4) described below. Alkali-soluble resin (A3): An adduct of an ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group to a copolymer (A3-0) containing a structural unit (ma-5) derived from an ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group and a structural unit (ma-6) derived from an ethylenically unsaturated group-containing compound (m-6) having a carboxy group. Alkali-soluble resin (A4): An adduct of a compound having an alkali-soluble functional group to an adduct of an ethylenically unsaturated group-containing compound (a-4) having a carboxy group to a copolymer (A4-0) containing a structural unit (ma-7) derived from an ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group and a structural unit (ma-8) derived from an ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the ethylenically unsaturated group-containing compound having a phenolic hydroxyl group is an ethylenically unsaturated group-containing compound having one to three phenolic hydroxyl groups in the same aromatic ring. [5] The photosensitive resin composition according to [1] or [3], wherein the content of the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group is 0.01 to 10 millimoles per mole of the structural units of the (A) alkali-soluble resin. [6] A cured resin film obtained by curing the photosensitive resin composition according to any one of [1] to [5]. [7] A photosensitive coloring composition comprising the photosensitive resin composition according to any one of [1] to [5] and (F) a colorant. [8] A color filter comprising a cured product of the photosensitive coloring composition according to [7]. [9] [8] An image display device comprising the color filter according to [8]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a photosensitive resin composition that reduces low-molecular-weight components present in the cured product and gives a cured resin film with good adhesion. Furthermore, it is possible to provide an image display device that includes a cured resin film with excellent adhesion obtained by curing the photosensitive resin composition, and a cured product of a photosensitive coloring composition containing the photosensitive resin composition and a colorant. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the embodiments described below.

[0011] In this specification, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy.

[0012] In this specification, the acid value of the solid content of (A) alkali-soluble resin is a value measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K6901:2008 5.3. The acid value of the solid content of (A) alkali-soluble resin means the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of (A) alkali-soluble resin.

[0013] In this specification, the weight average molecular weight refers to a weight average molecular weight measured using gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene. Columns: Showdex (registered trademark) LF-G and LF-804 (both manufactured by Showa Denko KK) connected in series. Column temperature: 40℃ Sample: 0.2% tetrahydrofuran solution of the substance to be measured Developing solvent: tetrahydrofuran Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko K.K.) Flow rate: 1mL / min

[0014] In this specification, the ethylenically unsaturated group equivalent of (A) the alkali-soluble resin is a value calculated from the amounts of raw materials charged.

[0015] <Photosensitive Resin Composition: First Embodiment> The photosensitive resin composition in one embodiment contains (A) an alkali-soluble resin, (B) a reactive diluent, (C) a photopolymerization initiator, (D) a solvent, and (E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group.

[0016] [(A) Alkali-soluble resin] The alkali-soluble resin (A) used in the first embodiment is not particularly limited as long as it is a resin that has a phenolic hydroxyl group, does not have a structural unit derived from an ethylenically unsaturated group-containing compound, and is alkali-soluble, and any commonly used known alkali-soluble resin can be used without limitation. The alkali-soluble resin (A) may be used alone or in combination of two or more kinds.

[0017] The acid value of the solid content of the (A) alkali-soluble resin is preferably 10 to 300 mgKOH / g, more preferably 20 to 200 mgKOH / g, and even more preferably 30 to 150 mgKOH / g, from the viewpoint of improving the developability when developing the photosensitive resin composition after exposure. When the acid value of the solid content is 10 mgKOH / g or more, the alkali solubility of the photosensitive resin composition is sufficient, and therefore good developability can be obtained. When the acid value of the solid content is 300 mgKOH / g or less, the storage stability of the photosensitive resin composition is good.

[0018] The weight-average molecular weight of the (A) alkali-soluble resin is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and even more preferably 5,000 to 20,000. When the weight-average molecular weight is within this range, the viscosity of the photosensitive resin composition can be easily controlled, and good storage stability can be obtained.

[0019] The (A) alkali-soluble resin is preferably one into which an ethylenically unsaturated group is introduced, since this can be expected to maximize the effect of improving the photocurability of the photosensitive resin composition and the effect of suppressing crosslinking of the (A) alkali-soluble resin during storage by using the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, which will be described later.

[0020] When the (A) alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated group equivalent is preferably 100 to 900 g / mol, more preferably 150 to 800 g / mol, and even more preferably 200 to 700 g / mol. When the ethylenically unsaturated group equivalent is 100 g / mol or more, the photosensitive resin composition has good storage stability. When the ethylenically unsaturated group equivalent is 900 g / mol or less, the photosensitive resin composition has good curability, and therefore the cured product has good solvent resistance.

[0021] As the (A) alkali-soluble resin, it is preferable to use a (meth)acrylic resin, and it is more preferable to use a (meth)acrylic resin into which an ethylenically unsaturated group has been introduced, from the viewpoint of making the most of the effects of using an (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group as a photosensitive resin composition to suppress crosslinking during storage, the effects of improving low-temperature curing properties, and the effects of improving adhesion as a cured product.

[0022] The (meth)acrylic resin having an ethylenically unsaturated group introduced therein is preferably a (meth)acrylic resin selected from the following: (Meth)acrylic resin (1): An adduct of an ethylenically unsaturated group-containing compound (a-5) having an epoxy group or an oxetanyl group to a (meth)acrylic copolymer containing a structural unit (ma-9) derived from an ethylenically unsaturated group-containing compound (m-9) having a carboxy group. (Meth)acrylic resin (2): An adduct of a compound having an alkali-soluble functional group to an adduct of an ethylenically unsaturated group-containing compound (a-6) having a carboxy group to a (meth)acrylic copolymer containing a structural unit (ma-10) derived from an ethylenically unsaturated group-containing compound (m-10) having an epoxy group or an oxetanyl group.

[0023] (Meth)acrylic resin (1) The (meth)acrylic resin (1) is a (meth)acrylic resin in which an ethylenically unsaturated group is introduced by adding an ethylenically unsaturated group-containing compound (a-5) having an epoxy group or an oxetanyl group to a (meth)acrylic copolymer containing a structural unit (ma-9) derived from an ethylenically unsaturated group-containing compound (m-9) having a carboxy group, and optionally a structural unit (ma-11) other than the structural unit (ma-9) derived from another monomer (m-11).

[0024] <Ethylenically unsaturated group-containing compound (m-9) having a carboxy group> The ethylenically unsaturated group-containing compound (m-9) having a carboxy group is not particularly limited as long as it has an ethylenically unsaturated group and a carboxy group in one molecule and does not have a phenolic hydroxyl group. Among them, (meth)acrylic acid and its derivatives, and compounds having a (meth)acryloyloxy group and a carboxy group are preferred. Specific examples of the ethylenically unsaturated group-containing compound (m-9) having a carboxy group include (meth)acrylic acid; compounds having a (meth)acryloyloxy group and a carboxy group, such as 2-(meth)acryloyloxyethyl succinate and 2-(meth)acryloyloxyethyl hexahydrophthalic acid; derivatives of (meth)acrylic acid, such as α-bromo(meth)acrylic acid and β-furyl(meth)acrylic acid; crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate. The ethylenically unsaturated group-containing compound (m-9) having a carboxy group may be used alone or in combination of two or more kinds.

[0025] <Other Monomers (m-11)> The other monomer (m-11) is not particularly limited as long as it is a monomer that does not have a carboxy group, an epoxy group, an oxetanyl group, or a phenolic hydroxyl group and is copolymerizable with the ethylenically unsaturated group-containing compound (m-9) that has a carboxy group.

[0026] Other monomers (m-11) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate; adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, and cyclohexyl (Meth)acrylates containing an alicyclic hydrocarbon group having 6 to 20 carbon atoms, such as (meth)acrylate; hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate; phenyl (meth)acrylate, triphenylmethyl (meth)acrylate, naphthyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, biphenyloxyethyl (meth)acrylate, anthracene (meth)acrylate, benzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate aromatic hydrocarbon group-containing (meth)acrylates such as 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, and perfluoroisopropyl (meth)acrylate; conjugated diene compounds such as butadiene, isoprene, and chloroprene; (meth)acrylic acid ester compounds such as 3-(N,N-dimethylamino)propyl (meth)acrylate, cumyl (meth)acrylate, isoamyl acrylate, methoxytriethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate (for example, trade name: AM-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.), phenoxyethyl acrylate, and phenoxypolyethylene glycol acrylate (for example, trade name: LightAcrylate P-200A, manufactured by Kyoeisha Chemical Co., Ltd.);Examples of (meth)acrylic acid amide compounds include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide; (meth)acrylonitrile; vinyl compounds such as acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; unsaturated dicarboxylic acid diester compounds such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide; styrene; and styrene derivatives such as α-, o-, m-, and p-alkyl derivatives of styrene. Among these, from the viewpoints of curability and raw material procurement, (meth)acrylates containing an alicyclic hydrocarbon group having 6 to 20 carbon atoms, alkyl (meth)acrylates, and (meth)acrylates containing an aromatic hydrocarbon group are preferred, and benzyl (meth)acrylate and tricyclodecanyl (meth)acrylate are more preferred. The other monomers (m-11) may be used alone or in combination of two or more.

[0027] <Ethylenically Unsaturated Group-Containing Compound (a-5) Having an Epoxy Group or an Oxetanyl Group> The ethylenically unsaturated group-containing compound (a-5) having an epoxy group or an oxetanyl group is not particularly limited as long as it does not have a carboxy group and has an ethylenically unsaturated group and an epoxy group or an oxetanyl group in one molecule. Specific examples of the ethylenically unsaturated group-containing compound having an epoxy group include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A200 and M100 manufactured by Daicel Corporation), mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, epoxidized dicyclopentenyl (meth)acrylate, and epoxidized dicyclopentenyloxyethyl (meth)acrylate. Specific examples of ethylenically unsaturated group-containing compounds having an oxetanyl group include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, and 2-vinyl-2-methyloxetane. Among these, epoxy group-containing (meth)acrylates are preferred, and glycidyl (meth)acrylate is more preferred. The ethylenically unsaturated group-containing compounds (a-5) having an epoxy group or an oxetanyl group may be used alone or in combination of two or more.

[0028] <Proportion of structural units of (meth)acrylic resin (1)>

[0029] The ethylenically unsaturated group-containing compound (m-9) having a carboxy group preferably accounts for 20 to 90 mol %, more preferably 30 to 80 mol %, and even more preferably 40 to 75 mol % of the total monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (1). When the ethylenically unsaturated group-containing compound (m-9) having a carboxy group is 20 mol % or more, alkaline developability is good. When the ethylenically unsaturated group-containing compound (m-9) having a carboxy group is 90 mol % or less, storage stability is good.

[0030] The other monomer (m-11) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 25 to 60 mol% of the total monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (1). When the other monomer (m-11) is 10 mol% or more, storage stability is good. When the other monomer (m-11) is 80 mol% or less, sufficient alkali developability and adhesion are obtained.

[0031] The amount of the ethylenically unsaturated group-containing compound (a-5) having an epoxy group or an oxetanyl group is preferably 10 to 90 moles, more preferably 20 to 70 moles, and even more preferably 30 to 50 moles, relative to a total of 100 moles of functional groups reactive with an epoxy group or an oxetanyl group possessed by the monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (1). When the amount of the ethylenically unsaturated group-containing compound (a-5) having an epoxy group or an oxetanyl group is 10 moles or more, good curability is achieved. When the amount of the ethylenically unsaturated group-containing compound (a-5) having an epoxy group or an oxetanyl group is 90 moles or less, good storage stability is achieved.

[0032] (Meth)acrylic resin (2) The (meth)acrylic resin (2) is a (meth)acrylic resin obtained by adding an ethylenically unsaturated group-containing compound (a-6) having a carboxy group to a (meth)acrylic copolymer containing a structural unit (ma-10) derived from an ethylenically unsaturated group-containing compound (m-10) having an epoxy group or an oxetanyl group, and optionally a structural unit (ma-12) other than the structural unit (ma-10) derived from another monomer (m-12), to introduce an ethylenically unsaturated group, and further adding a compound having an alkali-soluble functional group to introduce an alkali-soluble functional group. The compound having an alkali-soluble functional group is preferably a polybasic acid or polybasic acid anhydride (a-7). The compound having an alkali-soluble functional group can be added to the functional group of the (meth)acrylic copolymer having an ethylenically unsaturated group, and specific examples thereof include an epoxy group, an oxetanyl group, a hydroxy group, and an amino group.

[0033] <Ethylenically unsaturated group-containing compound (m-10) having an epoxy group or an oxetanyl group> The ethylenically unsaturated group-containing compound (m-10) having an epoxy group or an oxetanyl group is not particularly limited as long as it does not have a carboxy group or a phenolic hydroxyl group and has an ethylenically unsaturated group and an epoxy group or an oxetanyl group in one molecule. Specific examples and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (a-5) having an epoxy group or an oxetanyl group. The ethylenically unsaturated group-containing compound (m-10) having an epoxy group or an oxetanyl group may be used alone or in combination of two or more.

[0034] <Other Monomers (m-12)> The other monomer (m-12) is not particularly limited as long as it is a monomer that does not have a carboxy group, an epoxy group, an oxetanyl group, or a phenolic hydroxyl group and is copolymerizable with the ethylenically unsaturated group-containing compound (m-10) that has an epoxy group or an oxetanyl group. Specific examples and preferred examples are the same as those of the other monomer (m-11). The other monomer (m-12) may be used alone or in combination of two or more.

[0035] <Ethylenically unsaturated group-containing compound (a-6) having a carboxy group> The ethylenically unsaturated group-containing compound (a-6) having a carboxy group is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a carboxy group in one molecule. Specific examples and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (m-9) having a carboxy group. The ethylenically unsaturated group-containing compound (a-6) having a carboxy group may be used alone or in combination of two or more.

[0036] <Polybasic acid or polybasic acid anhydride (a-7)> By adding a polybasic acid or polybasic acid anhydride (a-7) to the (meth)acrylic resin (2) to introduce a carboxyl group, good alkaline developability can be obtained. Examples of polybasic acids include, but are not limited to, adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid. Examples of polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, and octenylsuccinic anhydride. The polybasic acids or polybasic acid anhydrides (a-7) may be used alone or in combination of two or more.

[0037] <Proportion of structural units of (meth)acrylic resin (2)> The ethylenically unsaturated group-containing compound (m-10) having an epoxy group or an oxetanyl group preferably accounts for 20 to 90 mol %, more preferably 30 to 80 mol %, and even more preferably 40 to 75 mol % of the total monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (2). When the ethylenically unsaturated group-containing compound (m-10) having an epoxy group or an oxetanyl group is 20 mol % or more, the curability is good. When the ethylenically unsaturated group-containing compound (m-10) having an epoxy group or an oxetanyl group is 90 mol % or less, the storage stability is good.

[0038] The other monomer (m-12) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 25 to 60 mol% of the total monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (2). When the other monomer (m-12) is 10 mol% or more, storage stability is good. When the other monomer (m-12) is 80 mol% or less, sufficient alkali developability and adhesion are obtained.

[0039] The amount of the ethylenically unsaturated group-containing compound (a-6) having a carboxy group is preferably 10 to 99 moles, more preferably 30 to 98 moles, and even more preferably 60 to 95 moles, relative to a total of 100 moles of functional groups reactive with a carboxy group possessed by the monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (2). When the amount of the ethylenically unsaturated group-containing compound (a-6) having a carboxy group is 10 moles or more, good curability is achieved. When the amount of the ethylenically unsaturated group-containing compound (a-6) having a carboxy group is 99 moles or less, good storage stability is achieved.

[0040] The amount of polybasic acid or polybasic acid anhydride (a-7) added when synthesizing the (meth)acrylic resin (2), i.e., relative to a total of 100 moles of hydroxy groups generated by ring-opening of the epoxy group or oxetanyl group derived from compound (m-10), is preferably 5 to 80 moles, more preferably 10 to 70 moles, and even more preferably 20 to 60 moles. When the amount of polybasic acid or polybasic acid anhydride (a-7) is 5 moles or more, alkaline developability is good. When the amount of polybasic acid or polybasic acid anhydride (a-7) is 80 moles or less, storage stability is good. When the polybasic acid or polybasic acid anhydride (a-7) is trifunctional, i.e., when it is a polybasic acid or polybasic acid anhydride having three carboxy groups, the upper limit of the number of moles of polybasic acid or polybasic acid anhydride (a-7) may be 40 moles or 30 moles.

[0041] [(B) Reactive diluent] The reactive diluent (B) is not particularly limited as long as it is a low-molecular-weight compound containing an ethylenically unsaturated double bond such as a vinyl group or a (meth)acryloyloxy group, but not containing a phenolic hydroxyl group. In this specification, a low-molecular-weight compound is a compound having a molecular weight of less than 1,000. Specific examples of the (B) reactive diluent include aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene; aromatic allyl compounds such as diallyl phthalate and diallylbenzene phosphonate; vinyl carboxylates such as vinyl acetate and vinyl adipate; (meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; and triallyl cyanurate. As the (B) reactive diluent, from the viewpoint of curability, a compound having a plurality of (meth)acryloyloxy groups is preferred, and a compound having three or more (meth)acryloyloxy groups such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc. is more preferred. The (B) reactive diluents may be used alone or in combination of two or more.

[0042] [(C) Photopolymerization initiator] The (C) photopolymerization initiator is preferably a photoradical generator, and specific examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4'-(1-t-butyldioxy-1-methylethyl)acetophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; acetophenone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; Examples of suitable photopolymerization initiators include ketal compounds such as phenone dimethyl ketal and benzil dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,-1-(O-acetyloxime); acylphosphine oxide photopolymerization initiators; and xanthone photopolymerization initiators. (C) Photopolymerization initiators may be used alone or in combination of two or more.

[0043] [(D) Solvent] The (D) solvent is not particularly limited as long as it does not react with the other components and can dissolve or disperse them. Specific examples of the (D) solvent include (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate; esters such as ethyl acetate, butyl acetate, and isopropyl acetate; (poly)alkylene glycol alkyl ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, and diethylene glycol monomethyl ether; and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Among these, (poly)alkylene glycol monoalkyl ether acetates and (poly)alkylene glycol alkyl ethers are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferred. The (D) solvent may be used alone or in combination of two or more kinds.

[0044] The solvent used in the synthesis of the alkali-soluble resin (A) may be used as is without removing it, or a new solvent may be added.

[0045] [(E) Ethylenically unsaturated group-containing compound having a phenolic hydroxyl group] The (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group is not particularly limited as long as it is a compound having a phenolic hydroxyl group and an ethylenically unsaturated group. The phenolic hydroxyl group is a hydroxyl group directly bonded to a benzene ring. Therefore, a monohydroxyphenyl group to a pentahydroxyphenyl group may be present. The number of phenolic hydroxyl groups in the compound is the sum of the numbers of hydroxyl groups bonded to each benzene ring. That is, if a compound contains one dihydroxyphenyl group and one monohydroxyphenyl group, the number of phenolic hydroxyl groups is four. The number of phenolic hydroxyl groups in the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group is not particularly limited, but may be 1 to 25, 1 to 15, 1 to 10, or 1 to 6. The inclusion of the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group in the photosensitive resin composition can improve the storage stability of the photosensitive resin composition and reduce unintended crosslinking of the ethylenically unsaturated group during storage. This reduces the use of polymerization inhibitors, and reduces the amount of low-molecular-weight components liberated in the cured product when the photosensitive resin composition is photocured to form a cured resin film. As a result, the adhesion of the cured resin film to the substrate can be improved. Since the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group contains an ethylenically unsaturated group, it is not liberated when the photosensitive resin composition is photocured to form a cured resin film. Instead, it undergoes radical polymerization with the ethylenically unsaturated groups of the alkali-soluble resin (A) and the reactive diluent (B) to be incorporated into the cured product. Furthermore, the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group not only inhibits polymerization but also improves adhesion by itself. In particular, when the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group has two or more phenolic hydroxyl groups in the same aromatic ring, the resin contains polyhydroxyphenyl groups, such as catechol structures, which are functional groups effective for adhesion and bonding, thereby further improving adhesion to the substrate.

[0046] Specific examples of (E) ethylenically unsaturated group-containing compounds having a phenolic hydroxyl group include ethylenically unsaturated group-containing compounds having a phenol structure such as hydroxyphenyl(meth)acrylate; ethylenically unsaturated group-containing compounds having a catechol structure such as dopamine(meth)acrylamide; ester compounds of ethylenically unsaturated group-containing compounds having a hydroxy group and gallic acid; ester compounds of ethylenically unsaturated group-containing compounds having an epoxy group and gallic acid or tannic acid; and ethylenically unsaturated group-containing compounds having a gallic acid-derived structure such as vinyl gallate and vinyl tannate. These are ethylenically unsaturated group-containing compounds having one to three phenolic hydroxyl groups in the same aromatic ring. Among these, from the viewpoints of suppressing crosslinking of the (A) alkali-soluble resin during storage, improving the storage stability of the photosensitive resin composition, and further improving the adhesion of the cured product, preferred are ethylenically unsaturated group-containing compounds having two or more phenolic hydroxyl groups in the same aromatic ring, and more preferred are ethylenically unsaturated group-containing compounds having two to three phenolic hydroxyl groups in the same aromatic ring. Preferred phenolic hydroxyl group-containing partial structures possessed by the (E) phenolic hydroxyl group-containing ethylenically unsaturated group-containing compound include a catechol structure and a gallic acid-derived structure. Preferred ethylenically unsaturated group-containing functional groups possessed by the (E) phenolic hydroxyl group-containing ethylenically unsaturated group-containing compound include a vinyl group and a (meth)acryloyloxy group.

[0047] The (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group may be used alone or in combination of two or more kinds.

[0048] [Polymerization inhibitor] In the first embodiment, known polymerization inhibitors having no ethylenically unsaturated group, such as BHT (dibutylhydroxytoluene), MEHQ (4-methoxyphenol), and methylhydroquinone, may be used in combination, provided that the effects of the present invention are not impaired. However, these polymerization inhibitors remain free in the cured resin film even after photocuring of the photosensitive resin composition and act to impair adhesion to the substrate. Therefore, it is preferable to reduce the content of these polymerization inhibitors, and more preferably not use them at all. The photosensitive resin composition contains, for example, 0.01 to 0.2 mass% of a polymerization inhibitor having no ethylenically unsaturated group. In one embodiment, the photosensitive resin composition does not contain a polymerization inhibitor having no ethylenically unsaturated group. The upper limit of the content of the polymerization inhibitor having no ethylenically unsaturated group in the photosensitive resin composition is, for example, 0.2 mass% or 0.1 mass%.

[0049] [Other ingredients] In addition to the above-described components, the photosensitive resin composition of the first embodiment may contain known additives such as a photoacid generator, a photobase generator, a coupling agent, a leveling agent, a colorant (F) described below, a filler, etc. in order to impart predetermined properties. The amounts of these components to be added are not particularly limited as long as they are within a range that does not impair the effects of the present invention.

[0050] [Composition ratio of each ingredient] The amount of the (A) component is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 75 parts by mass, relative to 100 parts by mass of the total of the (A) alkali-soluble resin (also referred to as the (A) component), the (B) reactive diluent (also referred to as the (B) component), the (C) photopolymerization initiator (also referred to as the (C) component), and the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group (also referred to as the (E) component). When the (A) component is 10 parts by mass or more, good curability is obtained. When the (A) component is 90 parts by mass or less, good storage stability is obtained.

[0051] The amount of component (B) is preferably 5 to 80 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (E). When component (B) is 5 parts by mass or more, good curability is obtained. When component (B) is 80 parts by mass or less, good storage stability is obtained.

[0052] The amount of component (C) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (E). When component (C) is 0.1 part by mass or more, good curability is obtained. When component (C) is 10 parts by mass or less, good adhesion is obtained.

[0053] The amount of component (E) is preferably 0.01 to 10 mmol, more preferably 0.1 to 5 mmol, and even more preferably 0.5 to 3.5 mmol, per mole of structural units contained in the alkali-soluble resin (A), i.e., per mole of the total monomers used in the radical polymerization of the alkali-soluble resin (A). When the amount of component (E) is 0.01 mmol or more, component (E) can be uniformly dispersed as an independent component (in a free state) in the photosensitive resin composition, reducing unintended crosslinking of ethylenically unsaturated groups during storage and improving the storage stability of the photosensitive resin composition. When the amount of component (E) is 10 mmol or less, good curability can be obtained without inhibiting the photocurability of the photosensitive resin composition.

[0054] In an embodiment in which the photosensitive resin composition contains a (F) colorant (also referred to as component (F)), the amount of component (A) is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 75 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (A) is 10 parts by mass or more, good curability is obtained. When component (A) is 90 parts by mass or less, good storage stability is obtained.

[0055] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of the component (B) is preferably 5 to 80 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total of the components (A), (B), (C), (E), and (F). When the amount of the component (B) is 5 parts by mass or more, good curability is obtained. When the amount of the component (B) is 80 parts by mass or less, good storage stability is obtained.

[0056] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of component (C) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (C) is 0.1 part by mass or more, good curability is obtained. When component (C) is 10 parts by mass or less, good adhesion is obtained.

[0057] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of the component (F) is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 9 to 25 parts by mass, relative to 100 parts by mass of the total of the components (A), (B), (C), (E), and (F). When the amount of the component (F) is 1 part by mass or more, the desired degree of coloring can be obtained. When the amount of the component (F) is 40 parts by mass or less, storage stability is good.

[0058] In an embodiment in which the photosensitive resin composition contains a (F) colorant, the amount of component (E) is preferably 0.01 to 10 mmol, more preferably 0.1 to 5 mmol, and even more preferably 0.5 to 3.5 mmol, per mole of the total monomers used in the radical polymerization of the (A) alkali-soluble resin. When the amount of component (E) is 0.01 mmol or more, component (E) can be uniformly dispersed as an independent component (in a free state) in the photosensitive resin composition, reducing unintended crosslinking of ethylenically unsaturated groups during storage and improving the storage stability of the photosensitive resin composition. When the amount of component (E) is 10 mmol or less, good curability can be obtained without inhibiting the photocurability of the photosensitive resin composition.

[0059] <Photosensitive Resin Composition: Second Embodiment> A photosensitive resin composition according to one embodiment of the present invention contains (A) an alkali-soluble resin, (B) a reactive diluent, (C) a photopolymerization initiator, and (D) a solvent.

[0060] [(A) Alkali-soluble resin] The alkali-soluble resin (A) used in the second embodiment is a resin having a structural unit derived from an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, and having alkali solubility. More specifically, the alkali-soluble resin (A) is one or more resins selected from the group consisting of the alkali-soluble resins (A1) and (A2) described below. Alkali-soluble resin (A1): An adduct of an ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group to a copolymer (A1-0) containing a structural unit (ma-1) derived from an ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group and a structural unit (ma-2) derived from an ethylenically unsaturated group-containing compound (m-2) having a carboxy group. Alkali-soluble resin (A2): An adduct of a compound having an alkali-soluble functional group to an adduct of an ethylenically unsaturated group-containing compound (a-2) having a carboxy group to a copolymer (A2-0) containing a structural unit (ma-3) derived from an ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group and a structural unit (ma-4) derived from an ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group.

[0061] The (A) alkali-soluble resin may be used alone or in combination of two or more kinds.

[0062] The acid value of the solid content of the (A) alkali-soluble resin is preferably 10 to 300 mgKOH / g, more preferably 20 to 200 mgKOH / g, and even more preferably 30 to 150 mgKOH / g, from the viewpoint of improving the developability when developing the photosensitive resin composition after exposure. When the acid value of the solid content is 10 mgKOH / g or more, the alkali solubility of the photosensitive resin composition is sufficient, and therefore good developability can be obtained. When the acid value of the solid content is 300 mgKOH / g or less, the storage stability of the photosensitive resin composition is good.

[0063] The weight-average molecular weight of the (A) alkali-soluble resin is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and even more preferably 5,000 to 20,000. When the weight-average molecular weight is within this range, the viscosity of the photosensitive resin composition can be easily controlled, and good storage stability can be obtained.

[0064] The ethylenically unsaturated group equivalent of the (A) alkali-soluble resin is preferably 100 to 900 g / mol, more preferably 150 to 800 g / mol, and even more preferably 200 to 700 g / mol. When the ethylenically unsaturated group equivalent is 100 g / mol or more, the photosensitive resin composition has good storage stability. When the ethylenically unsaturated group equivalent is 900 g / mol or less, the photosensitive resin composition has good curability, and therefore the cured product has good solvent resistance.

[0065] As the alkali-soluble resin (A), it is preferable to use a (meth)acrylic resin, from the viewpoint of making the most of the effect of suppressing an increase in molecular weight during synthesis of the alkali-soluble resin (A) due to the inclusion of a structural unit derived from an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, the effect of suppressing crosslinking formation during storage as a photosensitive resin composition, the effect of improving low-temperature curability, and the effect of improving adhesion as a cured product.

[0066] <Alkali-soluble resin (A1)> The alkali-soluble resin (A1) is an adduct of an ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group to a copolymer (A1-0) containing a structural unit (ma-1) derived from an ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group, a structural unit (ma-2) derived from an ethylenically unsaturated group-containing compound (m-2) having a carboxy group, and, optionally, a structural unit (ma-13) other than the structural units (ma-1) and (ma-2) derived from another monomer (m-13).

[0067] <Ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group> The ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group is not particularly limited as long as it is a compound having a phenolic hydroxyl group and an ethylenically unsaturated group. The number of phenolic hydroxyl groups in the ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group is not particularly limited, and may be 1 to 25, 1 to 15, 1 to 10, or 1 to 6. The number of phenolic hydroxyl groups is counted in the same manner as in the case of "(E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group." When the alkali-soluble resin (A1) contains a structural unit (ma-1) derived from the ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group, the storage stability of the photosensitive resin composition can be improved and unintended crosslinking of the ethylenically unsaturated group during storage can be reduced. In addition, when synthesizing the alkali-soluble resin (A1) by adding an ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group, excessive increase in the molecular weight of the alkali-soluble resin (A1) can be suppressed. This reduces the use of polymerization inhibitors, and when the photosensitive resin composition is photocured to form a cured resin film, the amount of low-molecular-weight components released in the cured product can be reduced. As a result, the adhesion of the cured resin film to the substrate can be improved. Furthermore, since the ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group contains an ethylenically unsaturated group, when the photosensitive resin composition is photocured to form a cured resin film, it is not released and is incorporated into the cured product by radical polymerization with the ethylenically unsaturated groups of the alkali-soluble resins (A) and (B) reactive diluents. Furthermore, the structural unit (ma-1) not only inhibits polymerization but also improves adhesion by itself. In particular, when the ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group has two or more phenolic hydroxyl groups in the same aromatic ring, the resin contains a polyhydroxyphenyl group such as a catechol structure, which is a functional group effective for adhesion and bonding, and therefore the adhesion to the substrate is further improved.

[0068] Specific examples of the ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group include ethylenically unsaturated group-containing compounds having a phenol structure such as hydroxyphenyl(meth)acrylate; ethylenically unsaturated group-containing compounds having a catechol structure such as dopamine(meth)acrylamide; ester compounds of an ethylenically unsaturated group-containing compound having a hydroxyl group and gallic acid; ester compounds of an ethylenically unsaturated group-containing compound having an epoxy group and gallic acid or tannic acid; and ethylenically unsaturated group-containing compounds having a gallic acid-derived structure such as vinyl gallate and vinyl tannate. These are ethylenically unsaturated group-containing compounds having one to three phenolic hydroxyl groups in the same aromatic ring. Among these, from the viewpoints of suppressing crosslinking of the alkali-soluble resin (A) during storage, improving the storage stability of the photosensitive resin composition, and further improving the adhesion of the cured product, preferred are ethylenically unsaturated group-containing compounds having two or more phenolic hydroxyl groups in the same aromatic ring, and more preferred are ethylenically unsaturated group-containing compounds having two to three phenolic hydroxyl groups in the same aromatic ring. Preferred phenolic hydroxyl group-containing partial structures of the ethylenically unsaturated group-containing compound (m-1) include a catechol structure and a gallic acid-derived structure. Preferred ethylenically unsaturated group-containing functional groups of the ethylenically unsaturated group-containing compound (m-1) include a vinyl group and a (meth)acryloyloxy group.

[0069] The ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group may be used alone or in combination of two or more kinds.

[0070] <Ethylenically unsaturated group-containing compound (m-2) having a carboxy group> The ethylenically unsaturated group-containing compound (m-2) having a carboxy group is not particularly limited as long as it has an ethylenically unsaturated group and a carboxy group in one molecule and does not have a phenolic hydroxyl group. Among them, (meth)acrylic acid and its derivatives, and compounds having a (meth)acryloyloxy group and a carboxy group are preferred. Specific examples of the ethylenically unsaturated group-containing compound (m-2) having a carboxy group include (meth)acrylic acid; compounds having a (meth)acryloyloxy group and a carboxy group, such as 2-(meth)acryloyloxyethyl succinic acid and 2-(meth)acryloyloxyethyl hexahydrophthalic acid; derivatives of (meth)acrylic acid, such as α-bromo(meth)acrylic acid and β-furyl(meth)acrylic acid; crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate. The ethylenically unsaturated group-containing compound (m-2) having a carboxy group may be used alone or in combination of two or more kinds.

[0071] <Other Monomers (m-13)> The other monomer (m-13) is not particularly limited as long as it is a monomer that does not have a carboxy group, an epoxy group, an oxetanyl group, or a phenolic hydroxyl group, and is copolymerizable with the ethylenically unsaturated group-containing compound (m-1) that has a phenolic hydroxyl group, and the ethylenically unsaturated group-containing compound (m-2) that has a carboxy group.

[0072] Other monomers (m-13) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate; adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, and cyclohexyl (Meth)acrylates containing an alicyclic hydrocarbon group having 6 to 20 carbon atoms, such as (meth)acrylate; hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate; phenyl (meth)acrylate, triphenylmethyl (meth)acrylate, naphthyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, biphenyloxyethyl (meth)acrylate, anthracene (meth)acrylate, benzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate aromatic hydrocarbon group-containing (meth)acrylates such as 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, and perfluoroisopropyl (meth)acrylate; conjugated diene compounds such as butadiene, isoprene, and chloroprene; (meth)acrylic acid ester compounds such as 3-(N,N-dimethylamino)propyl (meth)acrylate, cumyl (meth)acrylate, isoamyl acrylate, methoxytriethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate (for example, trade name: AM-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.), phenoxyethyl acrylate, and phenoxypolyethylene glycol acrylate (for example, trade name: LightAcrylate P-200A, manufactured by Kyoeisha Chemical Co., Ltd.);Examples of (meth)acrylic acid amide compounds include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide; (meth)acrylonitrile; vinyl compounds such as acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; unsaturated dicarboxylic acid diester compounds such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide; styrene; and styrene derivatives such as α-, o-, m-, and p-alkyl derivatives of styrene. Among these, from the viewpoints of curability and raw material availability, (meth)acrylates containing an alicyclic hydrocarbon group having 6 to 20 carbon atoms, alkyl (meth)acrylates, and (meth)acrylates containing an aromatic hydrocarbon group are preferred, and benzyl (meth)acrylate and tricyclodecanyl (meth)acrylate are more preferred. The other monomers (m-13) may be used alone or in combination of two or more.

[0073] <Ethylenically Unsaturated Group-Containing Compound (a-1) Having an Epoxy Group or an Oxetanyl Group> The ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group is not particularly limited as long as it does not have a carboxy group and has an ethylenically unsaturated group and an epoxy group or an oxetanyl group in one molecule. Specific examples of the ethylenically unsaturated group-containing compound having an epoxy group include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A200 and M100 manufactured by Daicel Corporation), mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, epoxidized dicyclopentenyl (meth)acrylate, and epoxidized dicyclopentenyloxyethyl (meth)acrylate. Specific examples of ethylenically unsaturated group-containing compounds having an oxetanyl group include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, and 2-vinyl-2-methyloxetane. Among these, epoxy group-containing (meth)acrylates are preferred, and glycidyl (meth)acrylate is more preferred. The ethylenically unsaturated group-containing compounds (a-1) having an epoxy group or an oxetanyl group may be used alone or in combination of two or more.

[0074] <Proportion of structural units of alkali-soluble resin (A1)> The amount of the ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group relative to the total amount of monomers used in the radical polymerization for synthesizing the alkali-soluble resin (A1) is preferably 1 to 30 mol %, more preferably 3 to 20 mol %, and even more preferably 5 to 15 mol %. When the amount of the ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group is 1 to 30 mol %, it is possible to adjust the molecular weight of the alkali-soluble resin (A1) within an appropriate range, while also expecting improved adhesion of the cured product.

[0075] The content of the ethylenically unsaturated group-containing compound (m-2) having a carboxy group relative to the total amount of monomers used in the radical polymerization for synthesizing the alkali-soluble resin (A1) is preferably 15 to 90 mol %, more preferably 25 to 80 mol %, and even more preferably 35 to 75 mol %. When the content of the ethylenically unsaturated group-containing compound (m-2) having a carboxy group is 15 mol % or more, the alkali developability is good. When the content of the ethylenically unsaturated group-containing compound (m-2) having a carboxy group is 90 mol % or less, the storage stability is good.

[0076] The other monomer (m-13) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 15 to 60 mol% of the total monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A1). When the other monomer (m-13) is 5 mol% or more, storage stability is good. When the other monomer (m-13) is 80 mol% or less, sufficient alkali developability and adhesion are obtained.

[0077] The amount of the ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group is preferably 10 to 90 moles, more preferably 20 to 70 moles, and even more preferably 30 to 50 moles, relative to a total of 100 moles of functional groups reactive with an epoxy group or an oxetanyl group possessed by the monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A1). When the amount of the ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group is 10 moles or more, good curability is achieved. When the amount of the ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group is 90 moles or less, good storage stability is achieved.

[0078] <Alkali-soluble resin (A2)> The alkali-soluble resin (A2) is an adduct of a copolymer (A2-0) containing a structural unit (ma-3) derived from an ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group, a structural unit (ma-4) derived from an ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group, and optionally a structural unit (ma-14) other than the structural units (ma-3) and (ma-4) derived from another monomer (m-14), and an adduct of an ethylenically unsaturated group-containing compound (a-2) having a carboxyl group, and a compound having an alkali-soluble functional group. The compound having the alkali-soluble functional group is preferably a polybasic acid or polybasic acid anhydride (a-8). The compound having the alkali-soluble functional group can be added to the functional group of the copolymer having the carboxyl group introduced therein. Specific examples include a phenolic hydroxyl group, an epoxy group, an oxetanyl group, a hydroxy group, and an amino group.

[0079] <Ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group> The ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group is not particularly limited as long as it is a compound having a phenolic hydroxyl group and an ethylenically unsaturated group. Specific and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group. The ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group may be used alone or in combination of two or more. By including the structural unit (ma-3) derived from the ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group in the alkali-soluble resin (A2), the storage stability of the photosensitive resin composition can be improved and unintended crosslinking of the ethylenically unsaturated group during storage can be reduced. In addition, when synthesizing the alkali-soluble resin (A2) by adding the ethylenically unsaturated group-containing compound (a-2) having a carboxyl group, excessive increase in the molecular weight of the alkali-soluble resin (A2) can be suppressed. This reduces the use of polymerization inhibitors, and reduces the amount of low-molecular-weight components liberated in the cured product when the photosensitive resin composition is photocured to form a cured resin film. As a result, the adhesion of the cured resin film to the substrate can be improved. Furthermore, since the ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group contains an ethylenically unsaturated group, when the photosensitive resin composition is photocured to form a cured resin film, the ethylenically unsaturated group is not liberated but is incorporated into the cured product by radical polymerization with the ethylenically unsaturated groups of the alkali-soluble resin (A) and the reactive diluent (B). Furthermore, the structural unit (ma-3) not only inhibits polymerization but also improves adhesion by itself. In particular, when the ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group contains two or more phenolic hydroxyl groups in the same aromatic ring, the resin contains a polyhydroxyphenyl group, such as a catechol structure, which is a functional group effective for adhesion and bonding, thereby further improving adhesion to the substrate.

[0080] <Ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group> The ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group is not particularly limited as long as it does not have a carboxy group or a phenolic hydroxyl group and has an ethylenically unsaturated group and an epoxy group or an oxetanyl group in one molecule. Specific examples and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group. The ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group may be used alone or in combination of two or more.

[0081] <Other Monomers (m-14)> The other monomer (m-14) is not particularly limited as long as it is a monomer that does not have a carboxy group, an epoxy group, an oxetanyl group, or a phenolic hydroxyl group, and is copolymerizable with the ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group, and the ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group. Specific examples and preferred examples are the same as those of the other monomer (m-13). The other monomer (m-14) may be used alone or in combination of two or more.

[0082] <Ethylenically Unsaturated Group-Containing Compound (a-2) Having a Carboxy Group> The ethylenically unsaturated group-containing compound (a-2) having a carboxy group is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a carboxy group in one molecule. Specific examples and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (m-2) having a carboxy group. The ethylenically unsaturated group-containing compound (a-2) having a carboxy group may be used alone or in combination of two or more.

[0083] <Polybasic acid or polybasic acid anhydride (a-8)> By adding a polybasic acid or polybasic acid anhydride (a-8) to the alkali-soluble resin (A2) to introduce a carboxyl group, good alkaline developability can be achieved. Examples of polybasic acids include, but are not limited to, adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid. Examples of polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, and octenylsuccinic anhydride. The polybasic acids or polybasic acid anhydrides (a-8) may be used alone or in combination of two or more kinds.

[0084] <Proportion of structural units of alkali-soluble resin (A2)> The amount of the ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group relative to the total amount of monomers used in the radical polymerization for synthesizing the alkali-soluble resin (A2) is preferably 1 to 30 mol %, more preferably 3 to 20 mol %, and even more preferably 5 to 15 mol %. When the amount of the ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group is 1 to 30 mol %, it is possible to adjust the molecular weight of the alkali-soluble resin (A2) within an appropriate range, while also expecting improved adhesion of the cured product.

[0085] The ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group preferably accounts for 15 to 90 mol %, more preferably 25 to 80 mol %, and even more preferably 35 to 75 mol % of the total monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A2). When the ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group is 15 mol % or more, good curability is achieved. When the ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group is 90 mol % or less, good storage stability is achieved.

[0086] The other monomer (m-14) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 15 to 60 mol% of the total monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A2). When the other monomer (m-14) is 5 mol% or more, storage stability is good. When the other monomer (m-9) is 80 mol% or less, sufficient alkali developability and adhesion are obtained.

[0087] The amount of the ethylenically unsaturated group-containing compound (a-2) having a carboxy group is preferably 10 to 99 moles, more preferably 30 to 98 moles, and even more preferably 60 to 95 moles, relative to a total of 100 moles of functional groups reactive with a carboxy group possessed by the monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A2). When the amount of the ethylenically unsaturated group-containing compound (a-2) having a carboxy group is 10 moles or more, good curability is achieved. When the amount of the ethylenically unsaturated group-containing compound (a-2) having a carboxy group is 99 moles or less, good storage stability is achieved.

[0088] The amount of the polybasic acid or polybasic acid anhydride (a-8) added when synthesizing the alkali-soluble resin (A2), i.e., relative to a total of 100 moles of hydroxy groups generated by ring-opening of the epoxy group or oxetanyl group derived from the compound (m-4), is preferably 5 to 80 moles, more preferably 10 to 70 moles, and even more preferably 20 to 60 moles. When the amount of the polybasic acid or polybasic acid anhydride (a-8) is 5 moles or more, the alkali developability is good. When the amount of the polybasic acid or polybasic acid anhydride (a-8) is 80 moles or less, the storage stability is good. When the polybasic acid or polybasic acid anhydride (a-8) is trifunctional, i.e., when it is a polybasic acid or polybasic acid anhydride having three carboxy groups, the upper limit of the number of moles of the polybasic acid or polybasic acid anhydride (a-8) may be 40 moles or 30 moles.

[0089] [(B) Reactive diluent] The reactive diluent (B) is not particularly limited as long as it is a low molecular weight compound containing an ethylenically unsaturated double bond such as a vinyl group or a (meth)acryloyloxy group, but not containing a phenolic hydroxyl group. Specific examples of the (B) reactive diluent include aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene; aromatic allyl compounds such as diallyl phthalate and diallylbenzene phosphonate; vinyl carboxylates such as vinyl acetate and vinyl adipate; (meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; and triallyl cyanurate. As the (B) reactive diluent, from the viewpoint of curability, a compound having a plurality of (meth)acryloyloxy groups is preferred, and a compound having three or more (meth)acryloyloxy groups such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc. is more preferred. The (B) reactive diluents may be used alone or in combination of two or more.

[0090] [(C) Photopolymerization initiator] The (C) photopolymerization initiator is preferably a photoradical generator, and specific examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4'-(1-t-butyldioxy-1-methylethyl)acetophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; acetophenone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; Examples of suitable photopolymerization initiators include ketal compounds such as phenone dimethyl ketal and benzil dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,-1-(O-acetyloxime); acylphosphine oxide photopolymerization initiators; and xanthone photopolymerization initiators. (C) Photopolymerization initiators may be used alone or in combination of two or more.

[0091] [(D) Solvent] The (D) solvent is not particularly limited as long as it does not react with the other components and can dissolve or disperse them. Specific examples of the (D) solvent include (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate; esters such as ethyl acetate, butyl acetate, and isopropyl acetate; (poly)alkylene glycol alkyl ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, and diethylene glycol monomethyl ether; and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Among these, (poly)alkylene glycol monoalkyl ether acetates and (poly)alkylene glycol alkyl ethers are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferred. The (D) solvent may be used alone or in combination of two or more kinds.

[0092] The solvent used in the synthesis of the alkali-soluble resin (A) may be used as is without removing it, or a new solvent may be added.

[0093] [Polymerization inhibitor] In the second embodiment, known polymerization inhibitors having no ethylenically unsaturated group, such as MEHQ (4-methoxyphenol), BHT (dibutylhydroxytoluene), and methylhydroquinone, may be used in combination, provided that the effects of the present invention are not impaired. However, these polymerization inhibitors remain free in the cured resin film even after photocuring of the photosensitive resin composition and act to impair adhesion to the substrate. Therefore, it is preferable to reduce the content of these polymerization inhibitors, and more preferably not use them at all. The photosensitive resin composition contains, for example, 0.01 to 0.2 mass% of a polymerization inhibitor having no ethylenically unsaturated group. In one embodiment, the photosensitive resin composition does not contain a polymerization inhibitor having no ethylenically unsaturated group. The upper limit of the content of the polymerization inhibitor having no ethylenically unsaturated group in the photosensitive resin composition is, for example, 0.2 mass% or 0.1 mass%.

[0094] [Other ingredients] In addition to the above-described components, the photosensitive resin composition of the second embodiment may contain known additives such as a photoacid generator, a photobase generator, a coupling agent, a leveling agent, a colorant (F) described below, a filler, etc. in order to impart predetermined properties. The amounts of these components to be added are not particularly limited as long as they are within a range that does not impair the effects of the present invention.

[0095] [Composition ratio of each ingredient] The amount of the (A) component is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 75 parts by mass, relative to 100 parts by mass of the total of the (A) alkali-soluble resin (also referred to as the (A) component), the (B) reactive diluent (also referred to as the (B) component), and the (C) photopolymerization initiator (also referred to as the (C) component). When the (A) component is 10 parts by mass or more, good curability is obtained. When the (A) component is 90 parts by mass or less, good storage stability is obtained.

[0096] The amount of component (B) is preferably 5 to 80 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total of components (A), (B), and (C). When component (B) is 5 parts by mass or more, good curability is obtained. When component (B) is 80 parts by mass or less, good storage stability is obtained.

[0097] The amount of component (C) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of components (A), (B), and (C). When component (C) is 0.1 part by mass or more, good curability is obtained. When component (C) is 10 parts by mass or less, good adhesion is obtained.

[0098] In an embodiment in which the photosensitive resin composition contains a (F) colorant (also referred to as component (F)), the amount of component (A) is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 75 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (F). When component (A) is 10 parts by mass or more, good curability is obtained. When component (A) is 90 parts by mass or less, good storage stability is obtained.

[0099] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of the component (B) is preferably 5 to 80 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total of the components (A), (B), (C), and (F). When the amount of the component (B) is 5 parts by mass or more, good curability is obtained. When the amount of the component (B) is 80 parts by mass or less, good storage stability is obtained.

[0100] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of component (C) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (F). When component (C) is 0.1 part by mass or more, good curability is obtained. When component (C) is 10 parts by mass or less, good adhesion is obtained.

[0101] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of the component (F) is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 9 to 25 parts by mass, relative to 100 parts by mass of the total of the components (A), (B), (C), and (F). When the amount of the component (F) is 1 part by mass or more, the desired degree of coloring can be obtained. When the amount of the component (F) is 40 parts by mass or less, storage stability is good.

[0102] <Photosensitive Resin Composition: Third Embodiment> The photosensitive resin composition according to one embodiment of the present invention contains (A) an alkali-soluble resin, (B) a reactive diluent, (C) a photopolymerization initiator, (D) a solvent, and (E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group.

[0103] [(A) Alkali-soluble resin] The alkali-soluble resin (A) used in the third embodiment is a resin having a structural unit derived from an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, and having alkali solubility. More specifically, the alkali-soluble resin (A) is one or more resins selected from the group consisting of the alkali-soluble resins (A3) and (A4) described below. Alkali-soluble resin (A3): An adduct of an ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group to a copolymer (A3-0) containing a structural unit (ma-5) derived from an ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group and a structural unit (ma-6) derived from an ethylenically unsaturated group-containing compound (m-6) having a carboxy group. Alkali-soluble resin (A4): An adduct of a compound having an alkali-soluble functional group to an adduct of an ethylenically unsaturated group-containing compound (a-4) having a carboxy group to a copolymer (A4-0) containing a structural unit (ma-7) derived from an ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group and a structural unit (ma-8) derived from an ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group.

[0104] The (A) alkali-soluble resin may be used alone or in combination of two or more kinds.

[0105] The acid value of the solid content of the (A) alkali-soluble resin is preferably 10 to 300 mgKOH / g, more preferably 20 to 200 mgKOH / g, and even more preferably 30 to 150 mgKOH / g, from the viewpoint of improving the developability when developing the photosensitive resin composition after exposure. When the acid value of the solid content is 10 mgKOH / g or more, the alkali solubility of the photosensitive resin composition is sufficient, and therefore good developability can be obtained. When the acid value of the solid content is 300 mgKOH / g or less, the storage stability of the photosensitive resin composition is good.

[0106] The weight-average molecular weight of the (A) alkali-soluble resin is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and even more preferably 5,000 to 20,000. When the weight-average molecular weight is within this range, the viscosity of the photosensitive resin composition can be easily controlled, and good storage stability can be obtained.

[0107] The ethylenically unsaturated group equivalent of the (A) alkali-soluble resin is preferably 100 to 900 g / mol, more preferably 150 to 800 g / mol, and even more preferably 200 to 700 g / mol. When the ethylenically unsaturated group equivalent is 100 g / mol or more, the photosensitive resin composition has good storage stability. When the ethylenically unsaturated group equivalent is 900 g / mol or less, the photosensitive resin composition has good curability, and therefore the cured product has good solvent resistance.

[0108] As the alkali-soluble resin (A), it is preferable to use a (meth)acrylic resin, from the viewpoint of making the most of the effects of using an ethylenically unsaturated group-containing compound (E) having a phenolic hydroxyl group, and of utilizing to the fullest the effects of suppressing crosslinking formation during storage as a photosensitive resin composition, improving low-temperature curing properties, and improving adhesion as a cured product, which are achieved by including a structural unit derived from an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group.

[0109] <Alkali-soluble resin (A3)> The alkali-soluble resin (A3) is an adduct of an ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group to a copolymer (A3-0) containing a structural unit (ma-5) derived from an ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group, a structural unit (ma-6) derived from an ethylenically unsaturated group-containing compound (m-6) having a carboxy group, and, optionally, a structural unit (ma-15) other than the structural units (ma-5) and (ma-6) derived from another monomer (m-15).

[0110] <Ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group> The ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group is not particularly limited as long as it is a compound having a phenolic hydroxyl group and an ethylenically unsaturated group. The number of phenolic hydroxyl groups in the ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group is not particularly limited, and may be 1 to 25, 1 to 15, 1 to 10, or 1 to 6. When the alkali-soluble resin (A3) contains the structural unit (ma-5) derived from the ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group, the storage stability of the photosensitive resin composition can be improved and unintended crosslinking of the ethylenically unsaturated group during storage can be reduced. In addition, when synthesizing the alkali-soluble resin (A3) by adding the ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group, excessive increase in the molecular weight of the alkali-soluble resin (A3) can be suppressed. This reduces the need for polymerization inhibitors, and reduces the amount of low-molecular-weight components liberated in the cured product when the photosensitive resin composition is photocured to form a cured resin film. As a result, the adhesion of the cured resin film to the substrate can be improved. Since the ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group contains an ethylenically unsaturated group, it is not liberated when the photosensitive resin composition is photocured to form a cured resin film. Instead, it undergoes radical polymerization with the ethylenically unsaturated groups of the alkali-soluble resin (A) and the reactive diluent (B) to be incorporated into the cured product. Furthermore, the structural unit (ma-5) not only inhibits polymerization but also improves adhesion by itself. In particular, when the ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group contains two or more phenolic hydroxyl groups in the same aromatic ring, the resin contains a polyhydroxyphenyl group, such as a catechol structure, which is a functional group effective for adhesion and bonding, thereby further improving adhesion to the substrate.

[0111] Specific examples of the ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group include ethylenically unsaturated group-containing compounds having a phenol structure such as hydroxyphenyl(meth)acrylate; ethylenically unsaturated group-containing compounds having a catechol structure such as dopamine(meth)acrylamide; ester compounds of ethylenically unsaturated group-containing compounds having a hydroxy group and gallic acid; ester compounds of ethylenically unsaturated group-containing compounds having an epoxy group and gallic acid or tannic acid; and ethylenically unsaturated group-containing compounds having a gallic acid-derived structure such as vinyl gallate and vinyl tannate. These are ethylenically unsaturated group-containing compounds having one to three phenolic hydroxyl groups in the same aromatic ring. Among these, from the viewpoints of suppressing crosslinking of the alkali-soluble resin (A) during storage, improving the storage stability of the photosensitive resin composition, and further improving the adhesion of the cured product, preferred are ethylenically unsaturated group-containing compounds having two or more phenolic hydroxyl groups in the same aromatic ring, and more preferred are ethylenically unsaturated group-containing compounds having two to three phenolic hydroxyl groups in the same aromatic ring. Preferred phenolic hydroxyl group-containing partial structures of the ethylenically unsaturated group-containing compound (m-5) include a catechol structure and a gallic acid-derived structure. Preferred ethylenically unsaturated group-containing functional groups of the ethylenically unsaturated group-containing compound (m-5) include a vinyl group and a (meth)acryloyloxy group.

[0112] The ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group may be used alone or in combination of two or more kinds.

[0113] <Ethylenically unsaturated group-containing compound (m-6) having a carboxy group> The ethylenically unsaturated group-containing compound (m-6) having a carboxy group is not particularly limited as long as it has an ethylenically unsaturated group and a carboxy group in one molecule and does not have a phenolic hydroxyl group. Among them, (meth)acrylic acid and its derivatives, and compounds having a (meth)acryloyloxy group and a carboxy group are preferred. Specific examples of the ethylenically unsaturated group-containing compound (m-6) having a carboxy group include (meth)acrylic acid; compounds having a (meth)acryloyloxy group and a carboxy group, such as 2-(meth)acryloyloxyethyl succinate and 2-(meth)acryloyloxyethyl hexahydrophthalic acid; derivatives of (meth)acrylic acid, such as α-bromo(meth)acrylic acid and β-furyl(meth)acrylic acid; crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate. The ethylenically unsaturated group-containing compound (m-6) having a carboxy group may be used alone or in combination of two or more kinds.

[0114] <Other Monomers (m-15)> The other monomer (m-15) is not particularly limited as long as it is a monomer that does not have a carboxy group, an epoxy group, an oxetanyl group, or a phenolic hydroxyl group, and is copolymerizable with the ethylenically unsaturated group-containing compound (m-5) that has a phenolic hydroxyl group, and the ethylenically unsaturated group-containing compound (m-6) that has a carboxy group.

[0115] Other monomers (m-15) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate; adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, and cyclohexyl (Meth)acrylates containing an alicyclic hydrocarbon group having 6 to 20 carbon atoms, such as (meth)acrylate; hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate; phenyl (meth)acrylate, triphenylmethyl (meth)acrylate, naphthyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, biphenyloxyethyl (meth)acrylate, anthracene (meth)acrylate, benzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate aromatic hydrocarbon group-containing (meth)acrylates such as 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, and perfluoroisopropyl (meth)acrylate; conjugated diene compounds such as butadiene, isoprene, and chloroprene; (meth)acrylic acid ester compounds such as 3-(N,N-dimethylamino)propyl (meth)acrylate, cumyl (meth)acrylate, isoamyl acrylate, methoxytriethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate (for example, trade name: AM-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.), phenoxyethyl acrylate, and phenoxypolyethylene glycol acrylate (for example, trade name: LightAcrylate P-200A, manufactured by Kyoeisha Chemical Co., Ltd.);Examples of (meth)acrylic acid amide compounds include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide; (meth)acrylonitrile; vinyl compounds such as acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; unsaturated dicarboxylic acid diester compounds such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide; styrene; and styrene derivatives such as α-, o-, m-, and p-alkyl derivatives of styrene. Among these, from the viewpoints of curability and raw material availability, (meth)acrylates containing an alicyclic hydrocarbon group having 6 to 20 carbon atoms, alkyl (meth)acrylates, and (meth)acrylates containing an aromatic hydrocarbon group are preferred, and benzyl (meth)acrylate and tricyclodecanyl (meth)acrylate are more preferred. The other monomers (m-15) may be used alone or in combination of two or more.

[0116] <Ethylenically Unsaturated Group-Containing Compound (a-3) Having an Epoxy Group or an Oxetanyl Group> The ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group is not particularly limited as long as it does not have a carboxy group and has an ethylenically unsaturated group and an epoxy group or an oxetanyl group in one molecule. Specific examples of the ethylenically unsaturated group-containing compound having an epoxy group include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A200 and M100 manufactured by Daicel Corporation), mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, epoxidized product of dicyclopentenyl (meth)acrylate, and epoxidized product of dicyclopentenyloxyethyl (meth)acrylate. Specific examples of ethylenically unsaturated group-containing compounds having an oxetanyl group include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, and 2-vinyl-2-methyloxetane. Among these, epoxy group-containing (meth)acrylates are preferred, and glycidyl (meth)acrylate is more preferred. The ethylenically unsaturated group-containing compounds (a-3) having an epoxy group or an oxetanyl group may be used alone or in combination of two or more.

[0117] <Proportion of structural units of alkali-soluble resin (A3)> The amount of the ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group relative to the total amount of monomers used in the radical polymerization for synthesizing the alkali-soluble resin (A3) is preferably 1 to 30 mol %, more preferably 3 to 20 mol %, and even more preferably 5 to 15 mol %. When the amount of the ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group is 1 to 30 mol %, it is possible to adjust the molecular weight of the alkali-soluble resin (A3) within an appropriate range, while also expecting improved adhesion of the cured product.

[0118] The content of the ethylenically unsaturated group-containing compound (m-6) having a carboxy group relative to the total amount of monomers used in the radical polymerization for synthesizing the alkali-soluble resin (A3) is preferably 15 to 90 mol %, more preferably 25 to 80 mol %, and even more preferably 35 to 75 mol %. When the content of the ethylenically unsaturated group-containing compound (m-6) having a carboxy group is 15 mol % or more, the alkali developability is good. When the content of the ethylenically unsaturated group-containing compound (m-6) having a carboxy group is 90 mol % or less, the storage stability is good.

[0119] The other monomer (m-15) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 15 to 60 mol% of the total monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A3). When the other monomer (m-15) is 5 mol% or more, storage stability is good. When the other monomer (m-15) is 80 mol% or less, sufficient alkali developability and adhesion are obtained.

[0120] The amount of the ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group is preferably 10 to 90 moles, more preferably 20 to 70 moles, and even more preferably 30 to 50 moles, relative to a total of 100 moles of functional groups reactive with an epoxy group or an oxetanyl group possessed by the monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A3). When the amount of the ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group is 10 moles or more, good curability is achieved. When the amount of the ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group is 90 moles or less, good storage stability is achieved.

[0121] <Alkali-soluble resin (A4)> The alkali-soluble resin (A4) is an adduct of a copolymer (A4-0) containing a structural unit (ma-7) derived from an ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group, a structural unit (ma-8) derived from an ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group, and optionally a structural unit (ma-16) other than the structural units (ma-7) and (ma-8) derived from another monomer (m-16), and an adduct of an ethylenically unsaturated group-containing compound (a-4) having a carboxyl group, and a compound having an alkali-soluble functional group. The compound having an alkali-soluble functional group is preferably a polybasic acid or polybasic acid anhydride (a-9). The compound having an alkali-soluble functional group can be added to the functional group of the copolymer having the carboxyl group introduced therein. Specific examples include a phenolic hydroxyl group, an epoxy group, an oxetanyl group, a hydroxy group, and an amino group.

[0122] <Ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group> The ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group is not particularly limited as long as it is a compound having a phenolic hydroxyl group and an ethylenically unsaturated group. Specific and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group. The ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group may be used alone or in combination of two or more. By including the structural unit (ma-7) derived from the ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group in the alkali-soluble resin (A4), the storage stability of the photosensitive resin composition can be improved and unintended crosslinking of the ethylenically unsaturated group during storage can be reduced. In addition, when synthesizing the alkali-soluble resin (A4) by adding the ethylenically unsaturated group-containing compound (a-4) having a carboxy group, excessive increase in the molecular weight of the alkali-soluble resin (A4) can be suppressed. This reduces the need for polymerization inhibitors, and reduces the amount of low-molecular-weight components liberated in the cured product when the photosensitive resin composition is photocured to form a cured resin film. As a result, the adhesion of the cured resin film to the substrate can be improved. Since the ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group contains an ethylenically unsaturated group, it is incorporated into the cured product by radical polymerization with the ethylenically unsaturated groups of the alkali-soluble resin (A) and the reactive diluent (B) without liberating when the photosensitive resin composition is photocured to form a cured resin film. Furthermore, the structural unit (ma-7) not only inhibits polymerization but also improves adhesion by itself. In particular, when the ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group contains two or more phenolic hydroxyl groups in the same aromatic ring, the resin contains a polyhydroxyphenyl group, such as a catechol structure, which is a functional group effective for adhesion and bonding, thereby further improving adhesion to the substrate.

[0123] <Ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group> The ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group is not particularly limited as long as it does not have a carboxy group or a phenolic hydroxyl group and has an ethylenically unsaturated group and an epoxy group or an oxetanyl group in one molecule. Specific examples and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group. The ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group may be used alone or in combination of two or more.

[0124] Other Monomers (m-16) The other monomer (m-16) is not particularly limited as long as it is a monomer that does not have a carboxy group, an epoxy group, an oxetanyl group, or a phenolic hydroxyl group and is copolymerizable with the ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group and the ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group. Specific examples and preferred examples are the same as those of the other monomer (m-15). The other monomer (m-16) may be used alone or in combination of two or more.

[0125] <<Ethylenically Unsaturated Group-Containing Compound (a-4) Having a Carboxy Group>> The ethylenically unsaturated group-containing compound (a-4) having a carboxy group is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a carboxy group in one molecule. Specific examples and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (m-6) having a carboxy group. The ethylenically unsaturated group-containing compound (a-4) having a carboxy group may be used alone or in combination of two or more.

[0126] <Polybasic acid or polybasic acid anhydride (a-9)> By adding a polybasic acid or polybasic acid anhydride (a-9) to the alkali-soluble resin (A4) to introduce a carboxyl group, good alkaline developability can be obtained. Examples of polybasic acids include, but are not limited to, adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid. Examples of polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, and octenylsuccinic anhydride. The polybasic acids or polybasic acid anhydrides (a-9) may be used alone or in combination of two or more kinds.

[0127] <Proportion of structural units of alkali-soluble resin (A4)> The amount of the ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group relative to the total amount of monomers used in the radical polymerization for synthesizing the alkali-soluble resin (A4) is preferably 1 to 30 mol %, more preferably 3 to 20 mol %, and even more preferably 5 to 15 mol %. When the amount of the ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group is 1 to 30 mol %, the molecular weight of the alkali-soluble resin (A4) can be adjusted within an appropriate range, and improved adhesion of the cured product can also be expected.

[0128] The ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group preferably accounts for 15 to 90 mol %, more preferably 25 to 80 mol %, and even more preferably 35 to 75 mol % of the total monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A4). When the ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group is 15 mol % or more, good curability is achieved. When the ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group is 90 mol % or less, good storage stability is achieved.

[0129] The other monomer (m-16) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 15 to 60 mol% of the total monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A4). When the other monomer (m-16) is 5 mol% or more, the storage stability is good. When the other monomer (m-16) is 80 mol% or less, sufficient alkali developability and adhesion are obtained.

[0130] The amount of the ethylenically unsaturated group-containing compound (a-4) having a carboxy group is preferably 10 to 99 moles, more preferably 30 to 98 moles, and even more preferably 60 to 95 moles, relative to a total of 100 moles of functional groups reactive with a carboxy group possessed by the monomers used in the radical polymerization when synthesizing the alkali-soluble resin (A4). When the amount of the ethylenically unsaturated group-containing compound (a-4) having a carboxy group is 10 moles or more, good curability is achieved. When the amount of the ethylenically unsaturated group-containing compound (a-4) having a carboxy group is 99 moles or less, good storage stability is achieved.

[0131] The amount of the polybasic acid or polybasic acid anhydride (a-9) added when synthesizing the alkali-soluble resin (A4), i.e., relative to a total of 100 moles of hydroxy groups generated by ring-opening of the epoxy group or oxetanyl group derived from the compound (m-8), is preferably 5 to 80 moles, more preferably 10 to 70 moles, and even more preferably 20 to 60 moles. When the amount of the polybasic acid or polybasic acid anhydride (a-9) is 5 moles or more, the alkali developability is good. When the amount of the polybasic acid or polybasic acid anhydride (a-9) is 80 moles or less, the storage stability is good. When the polybasic acid or polybasic acid anhydride (a-9) is trifunctional, i.e., when it is a polybasic acid or polybasic acid anhydride having three carboxy groups, the upper limit of the number of moles of the polybasic acid or polybasic acid anhydride (a-9) may be 40 moles or 30 moles.

[0132] [(B) Reactive diluent] The reactive diluent (B) is not particularly limited as long as it is a low molecular weight compound containing an ethylenically unsaturated double bond such as a vinyl group or a (meth)acryloyloxy group, but not containing a phenolic hydroxyl group. Specific examples of the (B) reactive diluent include aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene; aromatic allyl compounds such as diallyl phthalate and diallylbenzene phosphonate; vinyl carboxylates such as vinyl acetate and vinyl adipate; (meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; and triallyl cyanurate. As the (B) reactive diluent, from the viewpoint of curability, a compound having a plurality of (meth)acryloyloxy groups is preferred, and a compound having three or more (meth)acryloyloxy groups such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc. is more preferred. The (B) reactive diluents may be used alone or in combination of two or more.

[0133] [(C) Photopolymerization initiator] The (C) photopolymerization initiator is preferably a photoradical generator, and specific examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4'-(1-t-butyldioxy-1-methylethyl)acetophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; acetophenone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; Examples of suitable photopolymerization initiators include ketal compounds such as phenone dimethyl ketal and benzil dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,-1-(O-acetyloxime); acylphosphine oxide photopolymerization initiators; and xanthone photopolymerization initiators. (C) Photopolymerization initiators may be used alone or in combination of two or more.

[0134] [(D) Solvent] The (D) solvent is not particularly limited as long as it does not react with the other components and can dissolve or disperse them. Specific examples of the (D) solvent include (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate; esters such as ethyl acetate, butyl acetate, and isopropyl acetate; (poly)alkylene glycol alkyl ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, and diethylene glycol monomethyl ether; and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Among these, (poly)alkylene glycol monoalkyl ether acetates and (poly)alkylene glycol alkyl ethers are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferred. The (D) solvent may be used alone or in combination of two or more kinds.

[0135] The solvent used in the synthesis of the alkali-soluble resin (A) may be used as is without removing it, or a new solvent may be added.

[0136] [(E) Ethylenically unsaturated group-containing compound having a phenolic hydroxyl group] The (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group is not particularly limited as long as it is a compound having a phenolic hydroxyl group and an ethylenically unsaturated group. The number of phenolic hydroxyl groups in the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group is not particularly limited, but may be 1 to 25, 1 to 15, 1 to 10, or 1 to 6. By including the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group in the photosensitive resin composition, the storage stability of the photosensitive resin composition can be improved and unintended crosslinking of ethylenically unsaturated groups during storage can be reduced. This reduces the use of polymerization inhibitors, and when the photosensitive resin composition is photocured to form a cured resin film, the amount of low-molecular-weight components liberated in the cured product can be reduced. As a result, the adhesion of the cured resin film to the substrate can be improved. Furthermore, since the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group contains an ethylenically unsaturated group, when the photosensitive resin composition is photocured to form a cured resin film, it is not liberated but is incorporated into the cured product by radical polymerization with the ethylenically unsaturated groups of the alkali-soluble resin (A) and the reactive diluent (B). Furthermore, the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group not only inhibits polymerization but also improves adhesion by itself. In particular, when the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group has two or more phenolic hydroxyl groups in the same aromatic ring, the resin contains a polyhydroxyphenyl group such as a catechol structure, which is a functional group effective for adhesion and bonding, thereby further improving adhesion to the substrate.

[0137] Specific examples of (E) ethylenically unsaturated group-containing compounds having a phenolic hydroxyl group include ethylenically unsaturated group-containing compounds having a phenol structure such as hydroxyphenyl(meth)acrylate; ethylenically unsaturated group-containing compounds having a catechol structure such as dopamine(meth)acrylamide; ester compounds of ethylenically unsaturated group-containing compounds having a hydroxy group and gallic acid; ester compounds of ethylenically unsaturated group-containing compounds having an epoxy group and gallic acid or tannic acid; and ethylenically unsaturated group-containing compounds having a gallic acid-derived structure such as vinyl gallate and vinyl tannate. These are ethylenically unsaturated group-containing compounds having one to three phenolic hydroxyl groups in the same aromatic ring. Among these, from the viewpoints of suppressing crosslinking of the (A) alkali-soluble resin during storage, improving the storage stability of the photosensitive resin composition, and further improving the adhesion of the cured product, preferred are ethylenically unsaturated group-containing compounds having two or more phenolic hydroxyl groups in the same aromatic ring, and more preferred are ethylenically unsaturated group-containing compounds having two to three phenolic hydroxyl groups in the same aromatic ring. Preferred phenolic hydroxyl group-containing partial structures possessed by the (E) phenolic hydroxyl group-containing ethylenically unsaturated group-containing compound include a catechol structure and a gallic acid-derived structure. Preferred ethylenically unsaturated group-containing functional groups possessed by the (E) phenolic hydroxyl group-containing ethylenically unsaturated group-containing compound include a vinyl group and a (meth)acryloyloxy group.

[0138] The (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group may be used alone or in combination of two or more kinds.

[0139] [Polymerization inhibitor] In the third embodiment, known polymerization inhibitors having no ethylenically unsaturated group, such as MEHQ (4-methoxyphenol), BHT (dibutylhydroxytoluene), and methylhydroquinone, may be used in combination, provided that the effects of the present invention are not impaired. However, these polymerization inhibitors remain free in the cured resin film even after photocuring of the photosensitive resin composition and act to impair adhesion to the substrate. Therefore, it is preferable to reduce the content of these polymerization inhibitors, and more preferably not use them at all. The photosensitive resin composition contains, for example, 0.01 to 0.2 mass% of a polymerization inhibitor having no ethylenically unsaturated group. In one embodiment, the photosensitive resin composition does not contain a polymerization inhibitor having no ethylenically unsaturated group. The upper limit of the content of the polymerization inhibitor having no ethylenically unsaturated group in the photosensitive resin composition is, for example, 0.2 mass% or 0.1 mass%.

[0140] [Other ingredients] In addition to the above-described components, the photosensitive resin composition of the third embodiment may contain known additives such as a photoacid generator, a photobase generator, a coupling agent, a leveling agent, a colorant (F) described below, a filler, etc. in order to impart predetermined properties. The amounts of these components to be added are not particularly limited as long as they are within a range that does not impair the effects of the present invention.

[0141] [Composition ratio of each ingredient] The amount of the (A) component is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 75 parts by mass, relative to 100 parts by mass of the total of the (A) alkali-soluble resin (also referred to as the (A) component), the (B) reactive diluent (also referred to as the (B) component), the (C) photopolymerization initiator (also referred to as the (C) component), and the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group (also referred to as the (E) component). When the (A) component is 10 parts by mass or more, good curability is obtained. When the (A) component is 90 parts by mass or less, good storage stability is obtained.

[0142] The amount of component (B) is preferably 5 to 80 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (E). When component (B) is 5 parts by mass or more, good curability is obtained. When component (B) is 80 parts by mass or less, good storage stability is obtained.

[0143] The amount of component (C) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (E). When component (C) is 0.1 part by mass or more, good curability is obtained. When component (C) is 10 parts by mass or less, good adhesion is obtained.

[0144] The amount of component (E) is preferably 0.01 to 10 mmol, more preferably 0.1 to 5 mmol, and even more preferably 0.5 to 3.5 mmol, per mole of structural units contained in the alkali-soluble resin (A), i.e., per mole of the total monomers used in the radical polymerization of the alkali-soluble resin (A). When the amount of component (E) is 0.01 mmol or more, component (E) can be uniformly dispersed as an independent component (in a free state) in the photosensitive resin composition, reducing unintended crosslinking of ethylenically unsaturated groups during storage and improving the storage stability of the photosensitive resin composition. When the amount of component (E) is 10 mmol or less, good curability can be obtained without inhibiting the photocurability of the photosensitive resin composition.

[0145] In an embodiment in which the photosensitive resin composition contains a (F) colorant (also referred to as component (F)), the amount of component (A) is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 75 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (A) is 10 parts by mass or more, good curability is obtained. When component (A) is 90 parts by mass or less, good storage stability is obtained.

[0146] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of the component (B) is preferably 5 to 80 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total of the components (A), (B), (C), (E), and (F). When the amount of the component (B) is 5 parts by mass or more, good curability is obtained. When the amount of the component (B) is 80 parts by mass or less, good storage stability is obtained.

[0147] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of component (C) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (C) is 0.1 part by mass or more, good curability is obtained. When component (C) is 10 parts by mass or less, good adhesion is obtained.

[0148] In an embodiment in which the photosensitive resin composition contains a colorant (F), the amount of the component (F) is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 9 to 25 parts by mass, relative to 100 parts by mass of the total of the components (A), (B), (C), (E), and (F). When the amount of the component (F) is 1 part by mass or more, the desired degree of coloring can be obtained. When the amount of the component (F) is 40 parts by mass or less, storage stability is good.

[0149] In an embodiment in which the photosensitive resin composition contains a (F) colorant, the amount of component (E) is preferably 0.01 to 10 mmol, more preferably 0.05 to 5 mmol, and even more preferably 0.07 to 3.5 mmol, per mole of the total monomers used in the radical polymerization of the (A) alkali-soluble resin. When the amount of component (E) is 0.01 mmol or more, component (E) can be uniformly dispersed as an independent component (in a free state) in the photosensitive resin composition, reducing unintended crosslinking of ethylenically unsaturated groups during storage and improving the storage stability of the photosensitive resin composition. When the amount of component (E) is 10 mmol or less, good curability can be obtained without inhibiting the photocurability of the photosensitive resin composition.

[0150] <Photosensitive coloring composition> The photosensitive coloring composition according to one embodiment of the present invention contains a photosensitive resin composition and a colorant (F).

[0151] [(F) Colorant] The (F) colorant used is one that is soluble or dispersible in a solvent, and examples thereof include dyes and pigments. The (F) colorant may be, for example, a dye alone, a pigment alone, or a combination of a dye and a pigment, depending on the color of the pixel to be produced using the photosensitive coloring composition. When the photosensitive coloring composition is used as a material for a color filter, it is preferable to use a dye as the (F) colorant for the following reasons. Pigments are particles, while dyes are molecules. For this reason, when a dye is used as a colorant, light scattering in the color filter is suppressed compared to when a pigment is used, and the brightness of an image display device equipped with the color filter is increased.

[0152] As the dye, from the viewpoint of solubility in solvents and alkaline developers, interaction with other components in the photosensitive coloring composition, heat resistance of the photosensitive coloring composition, etc., it is preferable to use an acid dye having an acidic group such as a carboxylic acid or sulfonic acid, a salt of an acid dye with a nitrogen compound, a sulfonamide adduct of an acid dye, etc. In particular, it is preferable to use an anthraquinone-based, azo-based, xanthene-based, or phthalocyanine-based dye as the dye. Among them, it is preferable to use one or both of an anthraquinone-based dye and a xanthene-based dye, since a photosensitive coloring composition can be obtained that can produce a resin cured film with high transmittance.

[0153] Specifically, the dyes are: acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; and acid red. 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274, 289, Rhodamine B; acid violet 6B; 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3, VALIFAST (trademark) BLUE 1603, 1605, 1621, 2606, 2620, 2670, and derivatives thereof. The dyes can be used alone or in combination of two or more types depending on, for example, the color of the desired pixel.

[0154] Pigments include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 154, 166, 168, and 173. Examples of suitable pigments include red pigments such as 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as CI Pigment Green 7, 36, 58, 59, and 62; brown pigments such as CI Pigment Brown 23 and 25; and black pigments such as CI Pigment Black 1, 7, carbon black, titanium black, and iron oxide. Pigments can be used alone or in combination depending on the desired pixel color, for example.

[0155] When a pigment is used as the (F) colorant, a known dispersant may be contained in the photosensitive coloring composition to improve the dispersibility of the pigment. It is preferable to use a polymer dispersant that has excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. Commercially available polymer dispersants, such as EFKA (manufactured by EFKA CHEMICALS BV), Disperbyk (manufactured by BYK), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Lubrizol Corporation), may also be used.

[0156] <(A) Method for producing alkali-soluble resin> [Method for producing alkali-soluble resin (A) of the first embodiment] In the first embodiment, the alkali-soluble resin (A) can be produced, for example, by the following production method. That is, a monomer, a polymerization solvent, and a radical polymerization initiator are mixed together and radically polymerized in a nitrogen gas atmosphere, typically at 70°C to 130°C, to obtain a copolymer. When introducing functional groups such as ethylenically unsaturated groups and carboxy groups into the obtained copolymer, a catalyst is added as needed in a dry air atmosphere, and an addition reaction is carried out typically at 70°C to 130°C, to obtain the alkali-soluble resin (A).

[0157] In the first and third embodiments, the addition reaction may be carried out in the presence of (E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, which reduces unintended crosslinking of the ethylenically unsaturated group and prevents the molecular weight of (A) the alkali-soluble resin from increasing excessively.

[0158] <Polymerization solvent> The polymerization solvent is not particularly limited as long as it is a solvent inert to the copolymerization reaction of the raw material monomers. As the polymerization solvent, those exemplified as the (D) solvent can be used. From the viewpoint of handling, it is preferable to use a (poly)alkylene glycol monoalkyl ether acetate as the polymerization solvent, and it is particularly preferable to use propylene glycol monomethyl ether acetate.

[0159] The amount of the polymerization solvent used is not particularly limited, but is preferably 30 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass, per 100 parts by mass of the raw material monomers. When the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw material monomers can be carried out stably, and coloration and gelation of the copolymer can be prevented. When the amount of the polymerization solvent used is 1,000 parts by mass or less, a decrease in the molecular weight of the copolymer due to chain transfer can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

[0160] <Radical Polymerization Initiator> The radical polymerization initiator that can be used in the copolymerization reaction of the raw material monomers is not particularly limited, and examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyrate) dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. The radical polymerization initiators may be used alone or in combination of two or more.

[0161] The amount of radical polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 16 parts by mass, relative to 100 parts by mass of the raw material monomer.

[0162] [Method for producing alkali-soluble resin (A) of the second embodiment] In the second embodiment, the alkali-soluble resin (A) can be produced in the same manner as in the first embodiment. In the second embodiment, the alkali-soluble resin (A) has a structural unit derived from an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, thereby reducing unintended crosslinking of the ethylenically unsaturated group during synthesis of the alkali-soluble resin (A), and preventing the molecular weight of the alkali-soluble resin (A) from increasing excessively.

[0163] For example, the alkali-soluble resin (A) can be produced by copolymerizing p-hydroxyphenyl methacrylate and acrylic acid to obtain a copolymer, and then adding glycidyl methacrylate to the carboxyl groups derived from acrylic acid contained in the copolymer. The presence of structural units derived from p-hydroxyphenyl methacrylate in the copolymer suppresses crosslinking via the methacryloyl groups of glycidyl methacrylate during the addition reaction.

[0164] For example, p-hydroxyphenyl methacrylate and glycidyl methacrylate are copolymerized to obtain a copolymer, and acrylic acid is added to the glycidyl groups derived from glycidyl methacrylate contained in the obtained copolymer (first addition reaction). Succinic anhydride is then added to the resulting adduct (second addition reaction), thereby producing (A) an alkali-soluble resin. The presence of structural units derived from p-hydroxyphenyl methacrylate in the copolymer suppresses crosslinking via the acryloyl groups derived from acrylic acid during the first and second addition reactions.

[0165] [Method for producing alkali-soluble resin (A) of the third embodiment] In the third embodiment, the alkali-soluble resin (A) can be produced in the same manner as in the first embodiment. In the third embodiment, the alkali-soluble resin (A) contains a structural unit derived from an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, thereby reducing unintended crosslinking of ethylenically unsaturated groups during synthesis of the alkali-soluble resin (A), and preventing the molecular weight of the alkali-soluble resin (A) from increasing excessively. In addition, when the addition reaction is carried out in the presence of an ethylenically unsaturated group-containing compound (E) having a phenolic hydroxyl group, the molecular weight suppression effect can be further enhanced.

[0166] <Method for producing photosensitive resin composition> The photosensitive resin composition can be produced by mixing the above-mentioned components using a known mixing device. For example, it can be produced by sequentially mixing (A) an alkali-soluble resin, (B) a reactive diluent, (C) a photopolymerization initiator, (D) a solvent, etc. If necessary, a colorant (F) may be added. In the first and third embodiments, (E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group may be mixed before the addition reaction for introducing functional groups such as ethylenically unsaturated groups and carboxyl groups when producing the alkali-soluble resin (A), or may be newly added when mixing the components (A) to (D). From the viewpoints of reducing unintended crosslinking of ethylenically unsaturated groups during the synthesis of the alkali-soluble resin (A) and suppressing excessive increases in the molecular weight of the alkali-soluble resin (A), it is preferable to mix (E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group before the addition reaction when producing the alkali-soluble resin (A).

[0167] The photosensitive resin composition obtained as described above has excellent storage stability and can exhibit various excellent resist properties such as excellent solvent resistance, pattern adhesion, and developability, and can form a pattern with excellent reliability.By using a photosensitive coloring composition in which a colorant (F) is blended with the photosensitive resin composition, a color filter with excellent reliability can be provided.

[0168] <Cured resin film> A cured resin film can be obtained by irradiating a photosensitive resin composition with active energy rays to cure it. Specifically, the cured resin film can be produced by the following method. A photosensitive resin composition or a photosensitive coloring composition is applied to a substrate such as glass so that the average thickness of the final cured coating film is a predetermined value depending on the purpose, and then the coating film is heated, for example, at 50 to 150°C for 1 to 50 minutes to volatilize the solvent. Next, the entire surface of the coating film is exposed to light (for example, using a lamp USH-250BY manufactured by Ushio Inc., with an exposure dose of 40 mJ / cm). 2) and then baking, for example, at 50 to 200°C for 10 to 180 minutes to obtain a cured coating film. After volatilizing the solvent, the coating film is exposed to light through a photomask and developed with an alkaline developer to obtain a cured coating film having a predetermined pattern.

[0169] <Color filter> A color filter according to one embodiment has a cured product of a photosensitive coloring composition. The color filter has a color pattern formed using the photosensitive coloring composition. A color filter typically comprises a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries between the pixels, and a protective film formed on the pixels and the black matrix. In this configuration, known substrates and protective films can be used.

[0170] A color filter can be manufactured, for example, by the following method. First, a colored pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, printed wiring boards, array substrates, etc. can be used as appropriate.

[0171] The colored pattern can be formed by photolithography. Specifically, a photosensitive colored composition is applied to a substrate to form a coating film, and then the coating film is exposed to light through a photomask with a predetermined pattern to photocure the exposed portions. The unexposed portions are then developed with an alkaline aqueous solution and baked to form the desired colored pattern.

[0172] The method for applying the photosensitive coloring composition is not particularly limited, and can be screen printing, roll coating, curtain coating, spray coating, spin coating, or the like. After applying the photosensitive coloring composition, the solvent (D) may be evaporated by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate, if necessary. The heating conditions are not particularly limited and may be appropriately set depending on the type of photosensitive coloring composition used. Generally, heating at a temperature of 50°C to 120°C for 30 seconds to 30 minutes is sufficient.

[0173] Next, the formed coating film is partially exposed by irradiating it with active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The amount of energy radiation to be irradiated may be appropriately selected depending on the composition of the photosensitive coloring composition, and may be, for example, 30 to 2000 mJ / cm. 2 The light source used for exposure is not particularly limited, but may be a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like.

[0174] The alkaline aqueous solution used for development is not particularly limited, but may include aqueous solutions of inorganic alkaline compounds such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amines such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; aqueous solutions of aniline compounds and their salts such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, and 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates; and aqueous solutions of p-phenylenediamine compounds and their salts. Additives such as antifoaming agents and surfactants may also be added to these aqueous solutions as needed. After development with the alkaline aqueous solution, the cured coating film is preferably washed with water and dried.

[0175] The baking conditions are not particularly limited, and the heat treatment may be carried out depending on the type of photosensitive coloring composition used. Generally, the heating may be carried out at 80 to 250° C. for 10 to 60 minutes.

[0176] The above-mentioned coating, exposure, development, and baking processes can be repeated in sequence using the photosensitive coloring composition for the black matrix and the photosensitive coloring compositions for the red, green, and blue pixels to form a desired color pattern. Thereafter, a protective film is formed on the color pattern (each of the RGB pixels and the black matrix). The protective film is not particularly limited, and any known film may be used.

[0177] The color filter produced in this manner is expected to have excellent solvent resistance and adhesion, and to suppress the bleeding out of low molecular weight components such as polymerization inhibitors.

[0178] <Image display element> An image display element according to one embodiment is an image display element equipped with a color filter, and specific examples thereof include liquid crystal display elements, organic EL display elements, and solid-state imaging elements such as CCD elements and CMOS elements. The image display element may be manufactured according to a conventional method. For example, when manufacturing a liquid crystal display element, a color filter is formed on a substrate, and then electrodes, spacers, and the like are formed in sequence. Then, electrodes, etc. are formed on another substrate, and the two are bonded together, after which a predetermined amount of liquid crystal is injected and sealed. [Example]

[0179] 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.

[0180] (A) The raw materials used in the synthesis of the alkali-soluble resin are listed below. PQMA: 4-hydroxyphenyl methacrylate, manufactured by Showa Denko K.K., number of phenolic hydroxyl groups: 1 DA-AA: Dopamine acrylamide (condensation compound of dopamine and acrylic acid chloride), synthesized by the applicant, number of phenolic hydroxyl groups: 2 GA-GMA: ester compound of glycidyl methacrylate (GMA) and gallic acid, synthesized by the applicant, number of phenolic hydroxyl groups: 3 AA: Acrylic acid, manufactured by Nippon Shokubai Co., Ltd. GMA: Glycidyl methacrylate, manufactured by Mitsubishi Gas Chemical Company, Inc. BZMA: Benzyl methacrylate, manufactured by Mitsubishi Gas Chemical Company, Inc. TCDMA: Tricyclodecanyl methacrylate, manufactured by Showa Denko Materials Co., Ltd. MEHQ: 4-Methoxyphenol, manufactured by Tokyo Chemical Industry Co., Ltd. GA-GMA-OMe3: A compound in which the three phenolic hydroxyl groups of GA-GMA are methoxylated, synthesized by the applicant SA (Rikacid SA): Succinic anhydride, manufactured by New Japan Chemical Co., Ltd.

[0181] An example of synthesis of the alkali-soluble resin (A) is shown below.

[0182] [Synthesis Example 1] (First stage: copolymerization reaction) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 188 g of propylene glycol monomethyl ether acetate, and the mixture was stirred while purging with nitrogen gas and heated to 120°C. Next, a mixture of 44.0 g of tricyclodecanyl methacrylate, 17.6 g of benzyl methacrylate, and 50.4 g of acrylic acid, to which 11.2 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator had been added, was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 120°C for 2 hours to carry out the copolymerization reaction. (Second step: First addition reaction) Next, after replacing the air inside the flask with dry air, 42.6 g of glycidyl methacrylate, 0.45 g of triphenylphosphine as a catalyst, and 0.45 g of PQMA as an ethylenically unsaturated group-containing compound (E) having a phenolic hydroxyl group were added, and the reaction was carried out at 120°C for 5 hours. After that, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40 mass%, and a solution containing alkali-soluble resin PD1 was obtained.

[0183] [Synthesis Examples 2 and 3, Comparative Synthesis Examples 1 to 3] Solutions containing alkali-soluble resins PD2, PD3, and cPD1 to cPD3 were obtained in the same manner as in Synthesis Example 1, except that the amounts of raw materials used were changed as shown in Table 1. [Synthesis Example 4] (First stage: copolymerization reaction) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 188 g of propylene glycol monomethyl ether acetate, and the mixture was stirred while purging with nitrogen gas and heated to 120°C. Next, a mixture of 44.0 g of tricyclodecanyl methacrylate, 17.8 g of PQMA, and 50.4 g of acrylic acid, to which 11.2 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was added, was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 120°C for 2 hours to carry out the copolymerization reaction. (Second step: First addition reaction) Next, the air inside the flask was replaced with dry air, and then 42.6 g of glycidyl methacrylate, 0.45 g of triphenylphosphine as a catalyst, and 0.3 g of MEHQ as a polymerization inhibitor were added, and the reaction was carried out at 120°C for 5 hours. After that, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40 mass%, and a solution containing alkali-soluble resin PD4 was obtained. [Synthesis Examples 5 to 10] Solutions containing alkali-soluble resins PD5 to PD10 were obtained in the same manner as in Synthesis Example 4, except that the amounts of raw materials used were changed as shown in Table 1. [Synthesis Example 11] (First stage: copolymerization reaction) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 188 g of propylene glycol monomethyl ether acetate, and the mixture was stirred while purging with nitrogen gas and heated to 120°C. Next, a mixture of 44.0 g of tricyclodecanyl methacrylate, 17.8 g of PQMA, and 50.4 g of acrylic acid, to which 11.2 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was added, was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 120°C for 2 hours to carry out the copolymerization reaction. (Second step: First addition reaction) Next, after replacing the air inside the flask with dry air, 42.6 g of glycidyl methacrylate, 0.45 g of triphenylphosphine as a catalyst, and 0.02 g of PQMA as an ethylenically unsaturated group-containing compound (E) having a phenolic hydroxyl group were added, and the reaction was carried out at 120°C for 5 hours. After that, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40 mass%, and a solution containing alkali-soluble resin PD11 was obtained. [Synthesis Examples 12 and 13] Solutions containing alkali-soluble resins PD12 and PD13 were obtained in the same manner as in Synthesis Example 11, except that the amounts of raw materials used were changed as shown in Table 1.

[0184] [Synthesis Example 14] (First stage: copolymerization reaction) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 188 g of propylene glycol monomethyl ether acetate, and the mixture was stirred while purging with nitrogen gas and heated to 120°C. Next, a mixture of a monomer mixture consisting of 44.0 g of tricyclodecanyl methacrylate, 17.6 g of benzyl methacrylate, and 99.4 g of glycidyl methacrylate, to which 11.2 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was added, was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 120°C for 2 hours to carry out a copolymerization reaction. (Second step: First addition reaction) Next, the atmosphere in the flask was replaced with dry air, and then 46.8 g of acrylic acid, 0.45 g of triphenylphosphine as a catalyst, and 0.25 g of GA-GMA as an ethylenically unsaturated group-containing compound having (E) a phenolic hydroxyl group were added, followed by reaction at 120°C for 10 hours. (Third step: Second addition reaction) Next, while the air in the flask was replaced with dry air, 30 g of Rikacid (trademark) SA was added and the reaction was carried out at 115°C for 2 hours. After that, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40% by mass, and a solution containing alkali-soluble resin PD14 was obtained.

[0185] [Synthesis Examples 15 and 16, Comparative Synthesis Examples 4 to 6] Solutions containing alkali-soluble resins PD15, 16, and cPD4 to cPD6 were obtained in the same manner as in Synthesis Example 14, except that the amounts of raw materials used were changed as shown in Table 1.

[0186] [Example 1: Preparation of photosensitive coloring composition RPD1] 150 parts by mass of the alkali-soluble resin PD1 obtained in Synthesis Example 1 as solid content, (B) 50 parts by mass of dipentaerythritol hexaacrylate as a reactive diluent, (C) 5 parts by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyloxime) as a photopolymerization initiator, and (F) 50 parts by mass of VALIFAST (trademark) BLUE 2620 as a colorant were mixed, and propylene glycol monomethyl ether acetate was added as a solvent so that the total solid content was 30% by mass, and mixed to prepare a photosensitive coloring composition RPD1. [Examples 2 to 16, Comparative Examples 1 to 6] Photosensitive coloring compositions RPD2 to 16 and cRPD1 to 6 were obtained in the same manner as in Example 1, except that the alkali-soluble resins shown in Table 2 were used instead of the alkali-soluble resin PD1.

[0187] <Preparation of cured resin film for adhesion evaluation> Using the photosensitive coloring composition obtained by the above method, a resin cured film for adhesiveness evaluation was prepared by the following procedure. The photosensitive coloring composition was applied to a glass substrate so that the final cured coating film had an average thickness of 2.0 μm, and then heated at 100° C. for 3 minutes to volatilize the solvent. Next, the coating film was exposed to light through a photomask (using a lamp USH-250BY manufactured by Ushio Inc., exposure dose 40 mJ / cm ). 2 The coating was then developed with an alkaline developer (a solution prepared by diluting Semiclean DL-A10 (manufactured by Yokohama Yushi Kogyo Co., Ltd.) 75 times) to obtain a cured coating film having a predetermined dot pattern (70 dots), which was then baked at 100°C for 30 minutes to obtain a cured resin film for adhesion evaluation.

[0188] <Adhesion evaluation> The cured resin film obtained by the above method was used to evaluate the adhesion of the cured resin film. After immersing the cured resin film in propylene glycol monomethyl ether (PGME) at room temperature for 3 minutes, the solvent was dried, and the dot pattern was observed under a microscope and evaluated on a 6-point scale according to the following criteria. The results are shown in Table 2. 6: Remaining dot count 50 or more 5: Remaining dots 40-49 4: Remaining dots 30-39 3: Remaining dots 20-29 2: Remaining dots 10-19 1: Remaining dots 9 or less

[0189] [Table 1-1] [Table 1-2]

[0190] [Table 2] [Industrial Applicability]

[0191] According to the present invention, a photosensitive resin composition is provided that gives a cured resin film with good adhesion and has excellent storage stability. Also provided are a cured resin film with excellent adhesion, a color filter having a cured product of a photosensitive coloring composition with excellent adhesion, and an image display device including the same. The photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, and a resist for a color filter.

Claims

1. (A) an alkali-soluble resin; (B) a reactive diluent; and (C) a photopolymerization initiator; (D) a solvent; A photosensitive resin composition comprising: (E) A photosensitive resin composition further containing an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group.

2. (A) an alkali-soluble resin; (B) a reactive diluent; and (C) a photopolymerization initiator; (D) a solvent; A photosensitive resin composition comprising: The photosensitive resin composition, wherein the alkali-soluble resin (A) is at least one selected from the group consisting of the alkali-soluble resin (A1) and the alkali-soluble resin (A2) described below. Alkali-soluble resin (A1): An adduct of an ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group to a copolymer (A1-0) containing a structural unit (ma-1) derived from an ethylenically unsaturated group-containing compound (m-1) having a phenolic hydroxyl group and a structural unit (ma-2) derived from an ethylenically unsaturated group-containing compound (m-2) having a carboxy group. Alkali-soluble resin (A2): An adduct of a compound having an alkali-soluble functional group to an adduct of an ethylenically unsaturated group-containing compound (a-2) having a carboxy group to a copolymer (A2-0) containing a structural unit (ma-3) derived from an ethylenically unsaturated group-containing compound (m-3) having a phenolic hydroxyl group, and a structural unit (ma-4) derived from an ethylenically unsaturated group-containing compound (m-4) having an epoxy group or an oxetanyl group.

3. (A) an alkali-soluble resin; (B) a reactive diluent; and (C) a photopolymerization initiator; (D) a solvent; A photosensitive resin composition comprising: (E) an ethylenically unsaturated group-containing compound having a phenolic hydroxyl group, The photosensitive resin composition, wherein the alkali-soluble resin (A) is at least one selected from the group consisting of the alkali-soluble resins (A3) and (A4) described below. Alkali-soluble resin (A3): An adduct of an ethylenically unsaturated group-containing compound (a-3) having an epoxy group or an oxetanyl group to a copolymer (A3-0) containing a structural unit (ma-5) derived from an ethylenically unsaturated group-containing compound (m-5) having a phenolic hydroxyl group, and a structural unit (ma-6) derived from an ethylenically unsaturated group-containing compound (m-6) having a carboxy group. Alkali-soluble resin (A4): An adduct of a compound having an alkali-soluble functional group to an adduct of an ethylenically unsaturated group-containing compound (a-4) having a carboxy group to a copolymer (A4-0) containing a structural unit (ma-7) derived from an ethylenically unsaturated group-containing compound (m-7) having a phenolic hydroxyl group, and a structural unit (ma-8) derived from an ethylenically unsaturated group-containing compound (m-8) having an epoxy group or an oxetanyl group.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the ethylenically unsaturated group-containing compound having a phenolic hydroxyl group is an ethylenically unsaturated group-containing compound having one to three phenolic hydroxyl groups in the same aromatic ring.

5. 4. The photosensitive resin composition according to claim 1, wherein the content of the (E) ethylenically unsaturated group-containing compound having a phenolic hydroxyl group is 0.01 to 10 millimoles per mole of the structural units of the (A) alkali-soluble resin.

6. A cured resin film obtained by curing the photosensitive resin composition according to any one of claims 1 to 3.

7. A photosensitive coloring composition comprising the photosensitive resin composition according to any one of claims 1 to 3 and (F) a colorant.

8. A color filter comprising a cured product of the photosensitive coloring composition according to claim 7.

9. An image display device comprising the color filter according to claim 8.

Images