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

Abstract

A photosensitive resin composition according to one embodiment of the present disclosure contains a copolymer (A), a reactive monomer (B), a photopolymerization initiator (C), and a solvent (D). The copolymer (A) includes: a constitutional unit (a-1) having a heterocyclic ring with 5 or more ring members; a constitutional unit (a-2) having a blocked isocyanato group; a constitutional unit (a-3) having a hydroxy group; and a constitutional unit (a-4) having an acid group.

Description

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

[0001] This disclosure relates to a photosensitive resin composition, a cured resin film, a color filter, and an image display element.

[0002] In recent years, with the widespread adoption of liquid crystal displays, research has been conducted on color filters used as components of liquid crystal displays, overcoat films provided on color filters, interlayer insulating films, etc. (for example, Patent Document 1).

[0003] Japanese Patent Publication No. 2019-53266

[0004] The photosensitive resin composition used in color filters is required to form a resin cured film that has excellent developability and solvent resistance. This disclosure aims to provide a photosensitive resin composition that provides a resin cured film with good developability and excellent solvent resistance. This disclosure also aims to provide a color filter with excellent solvent resistance and an image display element equipped therewith.

[0005] The disclosure includes the following embodiments: [1] A photosensitive resin composition comprising a copolymer (A), a reactive monomer (B), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A) comprises a constituent unit (a-1) having a heterocycle with 5 or more members, a constituent unit (a-2) having a blocked isocyanate group, a constituent unit (a-3) having a hydroxyl group, and a constituent unit (a-4) having an acid group. [2] The photosensitive resin composition according to [1], wherein the heterocycle is at least one selected from the group consisting of cyclic ethers, cyclic esters, cyclic carbonates, cyclic amines, cyclic amides, and cyclic imides. [3] The photosensitive resin composition according to [1], wherein the heterocycle is a cyclic ether or a cyclic amine. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the blocking agent for the constituent unit (a-2) having the blocked isocyanate group is at least one selected from the group consisting of 3,5-dimethylpyrazole, methyl ethyl ketoxime, 4-hydroxybenzoate methyl, 2-hydroxybenzoate methyl, 3,5-xylenol, and compounds having an alkyloxycarbonyl group. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the copolymer (A) further comprises a constituent unit (a-5) having an aliphatic hydrocarbon group having 1 to 20 carbon atoms. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the acid value of the copolymer (A) is 5 to 250 mg KOH / g. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the weight-average molecular weight of the copolymer (A) is 3,000 to 50,000. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the reactive monomer (B) is a compound having two or more groups having ethylenically unsaturated bonds. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the copolymer (A) contains 1 to 40 mol% of the constituent unit (a-1), 1 to 40 mol% of the constituent unit (a-2), 1 to 40 mol% of the constituent unit (a-3), and 1 to 40 mol% of the constituent unit (a-4), based on the total constituent units derived from the monomer constituting the copolymer (A).

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the solvent (D) contains a glycol ether having a hydroxyl group.

[11] The photosensitive resin composition according to any one of [1] to

[10] , wherein the content of the copolymer (A) is 10 to 90 parts by mass per 100 parts by mass of the total of the copolymer (A) and the reactive monomer (B).

[12] The photosensitive resin composition according to any one of [1] to

[11] , further containing a coloring agent (E).

[13] A resin cured film comprising a cured product of the photosensitive resin composition according to any one of [1] to

[12] .

[14] A color filter having a color pattern comprising a cured product of the photosensitive resin composition according to

[12] .

[15] An image display element comprising the color filter according to

[14] .

[0006] According to this disclosure, it is possible to provide a photosensitive resin composition that yields a resin cured film with good developability and excellent solvent resistance, and to provide a color filter with excellent solvent resistance, and an image display element equipped therewith.

[0007] The embodiments of this disclosure will be described in detail below. However, this disclosure is not limited to the embodiments described below.

[0008] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. "A or greater" in a numerical range means A and the range exceeding A. "A or less" in a numerical range means A and the range less than A. In numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. In numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples.

[0009] In this specification, "A or B" means that either A or B may be included, or both may be included. Unless otherwise specified, the materials exemplified herein may be used individually or in combination of two or more. The content of each component in a composition means the total amount (sum) of the multiple substances corresponding to each component present in the composition, unless otherwise specified. The terms "layer" and "film" include not only structures that are formed on the entire surface when observed in a plan view, but also structures that are formed on only a part of it. The term "process" is included not only in the sense of an independent process, but also in the sense that the intended function of the process is achieved even if it cannot be clearly distinguished from other processes.

[0010] In this specification, "(meth)acryloyl" means at least one of "acryloyl" and its corresponding "methacryloyl," and the same applies to other similar expressions such as "(meth)acrylic acid" and "(meth)acrylate." Also, "room temperature" means around 25°C.

[0011] [Photosensitive resin composition] The photosensitive resin composition according to this embodiment contains a copolymer (A), a reactive monomer (B), a photopolymerization initiator (C), and a solvent (D).

[0012] <Copolymer (A)> Copolymer (A) comprises a constituent unit (a-1) having a heterocycle with 5 or more ring members, a constituent unit (a-2) having a blocked isocyanate group, a constituent unit (a-3) having a hydroxyl group, and a constituent unit (a-4) having an acid group.

[0013] A constituent unit (a-1) having a heterocycle with 5 or more ring members is a constituent unit derived from a heterocycle-containing monomer (ma-1). The monomer (ma-1) has a group having an ethylenically unsaturated bond and a heterocycle with 5 or more ring members. Examples of groups having an ethylenically unsaturated bond include vinyl groups and (meth)acryloyloxy groups. The monomer (ma-1) may be used alone or in combination of two or more types.

[0014] The copolymer (A) having a constituent unit (a-1) can improve developability and adhesion to fine lines.

[0015] The heterocycle may contain at least one heteroatom selected from the group consisting of oxygen, nitrogen, phosphorus, and sulfur atoms. The heterocycle may also be at least one selected from the group consisting of cyclic ethers, cyclic esters, cyclic carbonates, cyclic amines, cyclic amides, and cyclic imides. From the viewpoint of fine wire adhesion, the number of members in the heterocycle may be 5 to 8, and is preferably 5 or 6.

[0016] Examples of cyclic ethers include tetrahydrofuran rings, dioxolane rings, tetrahydropyran rings, dioxane rings, and oxepane rings. Examples of cyclic esters include lactone rings. Examples of cyclic amines include pyrrolidine rings, pyrazolidine rings, imidazolidine rings, piperidine rings, piperazine rings, morpholine rings, azepane rings, and pyridine rings. Examples of cyclic amides include γ-lactam rings, δ-lactam rings, and ε-caprolactam rings.

[0017] Examples of (meth)acrylates having a cyclic ether include tetrahydrofuran ring-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and γ-caprolactone-modified tetrahydrofurfuryl (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2,2-cyclohexyl-1,3 Examples include dioxolane ring-containing (meth)acrylates such as (-dioxolane-4-yl)methyl (meth)acrylate; tetrahydropyran ring-containing (meth)acrylates such as tetrahydropyranyl (meth)acrylate; and dioxane ring-containing (meth)acrylates such as dioxane glycol di(meth)acrylate, (5-ethyl-1,3-dioxane-5-yl)methyl (meth)acrylate, and cyclic trimethylolpropane formal (meth)acrylate.

[0018] Examples of (meth)acrylates having a cyclic amine include (meth)acryloylmorpholine, N-vinylpyrrolidone, and vinylpyridine.

[0019] The content of constituent units (a-1) in copolymer (A) may be 1 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, or 8 mol% or more, based on the total constituent units (100 mol%) derived from the monomers constituting copolymer (A), from the viewpoint of improving adhesion. The content of constituent units (a-1) in copolymer (A) may be 40 mol% or less, 35 mol% or less, 30 mol% or less, 25 mol% or less, or 20 mol% or less, from the viewpoint of solvent resistance and developability. From this viewpoint, the content of constituent units (a-1) in copolymer (A) may be 1 to 40 mol%, 3 to 35 mol%, 4 to 30 mol%, 5 to 25 mol%, or 8 to 20 mol%.

[0020] Constituent unit (a-2) having a blocked isocyanate group Constituent unit (a-2) having a blocked isocyanate group has a structure in which the isocyanate group is blocked by the addition of a blocking agent. Constituent unit (a-2) is a constituent unit derived from a blocked isocyanate group-containing monomer (ma-2).

[0021] Because copolymer (A) has a constituent unit (a-2), crosslinking with the hydroxyl group-containing constituent unit (a-3) proceeds when the photosensitive resin composition is heated. As a result, the resulting cured product has good solvent resistance even under low-temperature curing conditions. Crosslinking is formed, for example, by the reaction of an isocyanate group generated by the dissociation of the blocking agent with a hydroxyl group. If the blocking agent is a compound having an alkyloxycarbonyl group, crosslinking can be formed by transesterification between the alkyl group of the alkyloxycarbonyl group and the hydroxyl group-containing constituent unit (a-3) even without dissociation of the blocking agent.

[0022] Monomer (ma-2) has a group having an ethylenically unsaturated bond and a blocked isocyanato group. Examples of the monomer (ma-2) include compounds obtained by blocking the isocyanato group of an isocyanate compound having a group having an ethylenically unsaturated bond and an isocyanato group with a blocking agent. Examples of the group having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group. Monomer (ma-2) does not have a heterocyclic ring, a hydroxy group, and an acid group. Monomer (ma-2) may be used alone or in combination of two or more kinds.

[0023] Examples of the isocyanate compound include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, (meth)acryloyl isocyanate, 1,1-bis(methacryloyloxymethyl)methyl isocyanate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 1,1-bis(acryloyloxymethyl)methyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0024] As the isocyanate compound, a reaction product obtained by reacting a hydroxyalkyl (meth)acrylate and a diisocyanate compound in equimolar amounts (hydroxyalkyl (meth)acrylate:diisocyanate compound = 1 mol:1 mol) may be used. The alkyl group of the hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, more preferably an ethyl group, from the viewpoints of the reactivity of the isocyanato group after deblocking and the simplicity of the reaction.

[0025] Examples of diisocyanate compounds include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, and lysine diisocyanate.

[0026] Examples of blocking agents include lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol compounds such as methanol, ethanol, propanol, 1-methoxy-2-propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenol compounds such as phenol, 2,6-dimethylphenol, cresol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrene-phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, 1-naphthol, p-nitrophenol, and p-chlorophenol; and active compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Methylene compounds; mercaptan compounds such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; amine compounds such as diisopropylamine, diphenylamine, phenylnaphthylamine, aniline, and carbazole; acid amide compounds such as acetanilide, acetanisidide, acetic acid amide, and benzamide; imide compounds such as succinimide and maleimide; imidazole compounds such as imidazole, 2-methylimidazole, and 2-ethylimidazole; pyrazole, 3,5 Examples include pyrazole compounds such as dimethylpyrazole; urea compounds such as urea, thiourea, and ethyleneurea; carbamic acid compounds such as phenyl N-phenylcarbamate and 2-oxazolidone; imine compounds such as ethyleneimine and polyethyleneimine; oxime compounds such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; and bisulfites such as sodium bisulfite and potassium bisulfite. The blocking agents may be used alone or in combination of two or more types.

[0027] From the viewpoint of the low-temperature curability of the photosensitive resin composition, the blocking agent may be a pyrazole compound, an oxime compound, or a phenol compound. As the blocking agent, at least one selected from the group consisting of 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 4-hydroxybenzoate, methyl 2-hydroxybenzoate, and 3,5-xylenol is preferable, at least one selected from the group consisting of 3,5-dimethylpyrazole, methyl 4-hydroxybenzoate, and methyl ethyl ketoxime is more preferable, and at least one selected from the group consisting of 3,5-dimethylpyrazole and methyl ethyl ketoxime is still more preferable.

[0028] By heating the photosensitive resin composition containing the copolymer containing the structural unit (a-2), the blocked isocyanato group of the structural unit (a-2) can be dissociated to regenerate the isocyanato group. The regenerated isocyanato group reacts with the reactive functional group contained in the copolymer to form a cured product having a high crosslink density. Examples of the reactive functional group contained in the copolymer include the hydroxy group of the structural unit (a-3), the acid group of the structural unit (a-4), and the amino group of other structural units.

[0029] In the structural unit (a-2), the dissociation rate of the blocked isocyanato group when heated at 100 ° C for 30 minutes may be 5 to 99%, 8 to 90%, 10 to 80%, 15 to 70%, 15 to 60%, or 30 to 50%. When the dissociation rate of the blocked isocyanato group of the structural unit (a-2) is 99% or less, the isocyanato group of the structural unit (a-2) is regenerated during the synthesis of the copolymer and during the storage of the photosensitive resin composition containing the copolymer, and an unintended crosslinking reaction can be suppressed, and the stability of the copolymer can be ensured. When the dissociation rate of the blocked isocyanato group of the structural unit (a-2) is 5% or more, good curability can be obtained even if the heating temperature for curing the photosensitive resin composition containing the copolymer is sufficiently low, and a cured product having more excellent solvent resistance can be obtained.

[0030] Examples of blocking agents that are suitable in terms of copolymer stability and low-temperature curability of the photosensitive resin composition, based on the dissociation rate of the blocked isocyanate group when heated at 100°C for 30 minutes, include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methyl ethyl ketoxime, and 3,5-dimethylpyrazole. Among these blocking agents, 3,5-dimethylpyrazole and methyl ethyl ketoxime are preferred from the viewpoint of low-temperature curability of the photosensitive resin composition containing the copolymer.

[0031] From the viewpoint of low-temperature curability of the photosensitive resin composition, a compound having an alkyloxycarbonyl group may be used as a blocking agent. In this case, the structural unit (a-2) having a blocked isocyanate group has an alkyloxycarbonyl group. By heating the photosensitive resin composition containing the copolymer, the alkyloxycarbonyl group undergoes transesterification with the structural unit (a-3) having a hydroxyl group, forming a crosslinked structure. Therefore, a photosensitive resin composition using a copolymer in which structural unit (a-2) has an alkyloxycarbonyl group can yield a cured film with excellent solvent resistance even when cured at low temperatures of 50°C to 150°C. As the compound having an alkyloxycarbonyl group, an activated methylene compound having an alkyloxycarbonyl group is preferred.

[0032] When an active methylene compound having an alkyloxycarbonyl group is used as a blocking agent, the blocking isocyanate group of the constituent unit (a-2) can be, for example, a constituent unit having a group represented by the following formula (1) or formula (2).

[0033]

[0034] In formula (1), R １ and R ２ Each of the following independently represents an alkyl group having 1 to 10 carbon atoms, n1 and n2 independently represent integers from 0 to 2, and * represents a linking site.

[0035]

[0036] In formula (2), R ３ and R４ Each independently represents an alkyl group having 1 to 10 carbon atoms, n3 and n4 each independently represent an integer of 0 to 2, and * represents a linking site.

[0037] When the constitutional unit (a-2) has a group represented by the formula (1) or the formula (2) as a blocked isocyanato group, when the photosensitive resin composition is cured at a low temperature of 50 ° C to 150 ° C, an ester exchange with the constitutional unit (a-3) having a hydroxy group occurs, generating a crosslinked structure. Therefore, even when the photosensitive resin composition is cured at 50 ° C to 150 ° C, a cured film excellent in solvent resistance can be provided.

[0038] R in the formula (1) １ and R ２ are preferably alkyl groups having 2 to 6 carbon atoms, more preferably alkyl groups having 2 to 3 carbon atoms, and even more preferably an ethyl group. R １ and R ２ When is an ethyl group, when the photosensitive resin composition is thermally cured, an ester exchange occurs with the constitutional unit (a-3) having a hydroxy group to generate ethanol. The generated ethanol can be easily evaporated and removed by heating for thermally curing the photosensitive resin composition.

[0039] R in the formula (2) ３ is preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and even more preferably an ethyl group. R ３ When is an ethyl group, when the photosensitive resin composition is thermally cured, an ester exchange occurs with the constitutional unit (a-3) having a hydroxy group to generate ethanol. The generated ethanol can be easily evaporated and removed by heating for thermally curing the photosensitive resin composition.

[0040] The content of constituent units (a-2) in copolymer (A) may be 1 mol% or more, 5 mol% or more, 10 mol% or more, or 15 mol% or more, based on the total constituent units (100 mol%) derived from the monomers constituting copolymer (A), from the viewpoint of low-temperature curability of the photosensitive resin composition and solvent resistance of the cured product. The content of constituent units (a-2) in copolymer (A) may be 40 mol% or less, 35 mol% or less, 30 mol% or less, or 25 mol% or less, from the viewpoint of developability of the photosensitive resin composition. From this viewpoint, the content of constituent units (a-2) in copolymer (A) may be 1 to 40 mol%, 5 to 35 mol%, 10 to 30 mol%, or 15 to 25 mol%.

[0041] Constituent unit (a-3) having a hydroxyl group Constituent unit (a-3) is a constituent unit derived from monomer (ma-3) having a hydroxyl group. Monomer (ma-3) has a group having an ethylenically unsaturated bond and a hydroxyl group. Examples of groups having an ethylenically unsaturated bond include vinyl groups and (meth)acryloyloxy groups. Monomer (ma-3) does not have heterocyclic or acidic groups. Monomer (ma-3) may be used alone or in combination of two or more types.

[0042] The hydroxyl group of constituent unit (a-3) forms a crosslinked structure with the blocked isocyanate group of constituent unit (a-2) by thermal curing the resin composition containing copolymer (A).

[0043] The constituent unit (a-3) is -CH, from the viewpoint of low-temperature curing properties. ２ It is preferable to have a group represented by -OH, and -(CH ２ ) ｎ A constituent unit having a group represented by -OH (where n is an integer from 2 to 6) and -(O-C ｘ H ２ｘ ) ｍ It is more preferable that it be at least one selected from the group consisting of constituent units having a group represented by -OH (where x is an integer from 2 to 4 and m is an integer from 2 to 10). -(CH ２ ) ｎThe n of the group represented by -OH is preferably 2 to 4, more preferably 2 and 4. -(O-C ｘ H ２ｘ ) ｍ The x of the group represented by -OH is preferably 2 to 3, more preferably 2. -(O-C ｘ H ２ｘ ) ｍ The value of m in the group represented by -OH is preferably 2 to 6, more preferably 4 to 6.

[0044] Examples of monomers (ma-3) include (meth)acrylic acid ester derivatives having a hydroxyl group. Examples of such monomers (ma-3) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate.

[0045] As monomer (ma-3), hydroxyalkyl (meth)acrylate and polyalkylene glycol mono(meth)acrylate are preferred from the viewpoint of reactivity when synthesizing copolymer (A), low-temperature curability of the photosensitive resin composition, and ease of availability. As hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate may be used. As monomer (ma-3), 4-hydroxybutyl (meth)acrylate may be used from the viewpoint of obtaining solvent resistance of the cured product. As polyalkylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate is preferred from the viewpoint of solvent resistance, and polyethylene glycol mono(meth)acrylate having 2 to 6 oxyethylene units is more preferred.

[0046] The content of constituent unit (a-3) in copolymer (A) may be 1 mol% or more, 3 mol% or more, 5 mol% or more, or 10 mol% or more, based on the total constituent units (100 mol%) derived from the monomers constituting copolymer (A), from the viewpoint of developability and adhesion. The content of constituent unit (a-3) in copolymer (A) may be 40 mol% or less, 30 mol% or less, 25 mol% or less, or 20 mol% or less, based on the total constituent units (100 mol%) derived from the monomers constituting copolymer (A), from the viewpoint of reduced adhesion due to resin polarity. From this viewpoint, the content of constituent unit (a-3) in copolymer (A) may be 1 to 40 mol%, 3 to 30 mol%, 5 to 25 mol%, or 10 to 20 mol%.

[0047] Constituent unit having an acidic group (a-4) Constituent unit having an acidic group (a-4) is a constituent unit derived from monomer having an acidic group (ma-4). Monomer (ma-4) has a group having an ethylenically unsaturated bond and an acidic group. Examples of acidic groups include a carboxyl group, a sulfo group, and a phospho group. From the viewpoint of ease of availability, the carboxyl group is preferred as the acidic group. Examples of groups having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group. Monomer (ma-4) does not have a heterocycle. Monomer (ma-4) may be used alone or in combination of two or more types.

[0048] Since copolymer (A) has constituent units (a-4) having acid groups, the photosensitive resin composition has good alkali developability. Because such a photosensitive resin composition has excellent alkali developability, for example, by applying it to a substrate to form a coating film, exposing it through a photomask corresponding to a predetermined pattern shape, developing the unexposed areas with an alkaline aqueous solution, and then baking it at a sufficiently low temperature, a cured product with a predetermined pattern shape and excellent solvent resistance can be formed.

[0049] Examples of monomers having an acid group (ma-4) include unsaturated carboxylic acids or their anhydrides such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and p-styrenesulfonic acid; and unsaturated phosphonic acids such as vinylphosphonic acid.

[0050] The content of constituent unit (a-4) in copolymer (A) may be 1 mol% or more, 5 mol% or more, 8 mol% or more, or 10 mol% or more, based on the total constituent units (100 mol%) derived from the monomers constituting copolymer (A), from the viewpoint of development speed and fine line adhesion. The content of constituent unit (a-4) in copolymer (A) may be 40 mol% or less, 35 mol% or less, 30 mol% or less, or 25 mol% or less, based on the total constituent units (100 mol%) derived from the monomers constituting copolymer (A), from the viewpoint of development speed and fine line adhesion. From this viewpoint, the content of constituent unit (a-4) in copolymer (A) may be 1 to 40 mol%, 5 to 35 mol%, 8 to 30 mol%, or 10 to 25 mol%.

[0051] Constituent units (a-5) having aliphatic hydrocarbon groups having 1 to 20 carbon atoms The copolymer (A) according to this embodiment may further contain constituent units (a-5) having aliphatic hydrocarbon groups having 1 to 20 carbon atoms, if necessary. Constituent units (a-5) do not have heterocycles, blocked isocyanate groups, hydroxyl groups, or acid groups, and are derived from monomers (ma-5) having aliphatic hydrocarbon groups having 1 to 20 carbon atoms and groups having ethylenically unsaturated bonds. Monomers (ma-5) may be used alone or in combination of two or more types.

[0052] The copolymer (A) having constituent units (a-5) allows for adjustment of flexibility as a photosensitive resin composition and imparts appropriate substrate adhesion.

[0053] The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cross-linked cyclic hydrocarbon group having 10 to 20 carbon atoms. Examples of monomers (ma-5) include (meth)acrylates having a linear alkyl group having 1 to 20 carbon atoms, (meth)acrylates having a branched alkyl group having 3 to 20 carbon atoms, and (meth)acrylates having a cross-linked cyclic hydrocarbon group having 10 to 20 carbon atoms.

[0054] Examples of (meth)acrylates having a linear alkyl group with 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and dodecyl (meth)acrylate. From the viewpoint of suppressing the influence of the copolymer (A) on the thermosetting reaction in terms of stereostructure, (meth)acrylates having a linear alkyl group with 1 to 6 carbon atoms are preferred, and methyl (meth)acrylate and ethyl (meth)acrylate are preferred.

[0055] Examples of (meth)acrylates having branched alkyl groups with 3 to 20 carbon atoms include isopropyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. From the viewpoint of adhesion of the cured film, (meth)acrylates having branched alkyl groups with 4 to 10 carbon atoms are preferred, and isobutyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are more preferred.

[0056] By having constituent units derived from (meth)acrylate having cross-linked cyclic hydrocarbon groups with 10 to 20 carbon atoms, the glass transition temperature of copolymer (A) can be controlled to a high level, thereby obtaining solvent resistance and surface uniformity of the cured product. Furthermore, when the photosensitive resin composition contains a dye as a colorant (E), it is possible to create appropriate voids to confine the dye within the resin, thereby reducing the elution of the dye from the cured product.

[0057] Examples of cross-linked cyclic hydrocarbon groups having 10 to 20 carbon atoms include adamantyl, dicyclopentanyl, dicyclopentenyl, and isobornyl groups. Examples of (meth)acrylates having cross-linked cyclic hydrocarbon groups having 10 to 20 carbon atoms include adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate. Dicyclopentanyl (meth)acrylate is preferred from the viewpoint of being able to control the glass transition temperature of copolymer (A) to a high degree and having excellent heat resistance.

[0058] The content of constituent unit (a-5) in copolymer (A) may be 1 mol% or more, 10 mol% or more, 20 mol% or more, or 25 mol% or more, based on the total constituent units (100 mol%) derived from the monomers constituting copolymer (A), from the viewpoint of fine wire adhesion and solvent resistance. The content of constituent unit (a-5) in copolymer (A) may be 70 mol% or less, 60 mol% or less, 55 mol% or less, or 50 mol% or less, based on the total constituent units (100 mol%) derived from the monomers constituting copolymer (A), from the viewpoint of fine wire adhesion and solvent resistance. From this viewpoint, the content of constituent unit (a-5) in copolymer (A) may be 1 to 70 mol%, 1 to 60 mol%, 20 to 55 mol%, or 25 to 50 mol%.

[0059] Other constituent units (a-6) Copolymer (A) may optionally contain other constituent units (a-6) other than the above constituent units (a-1) to (a-5). Other constituent units (a-6) are constituent units derived from other monomers (ma-6) that can copolymerize with monomers (ma-1) to (ma-5).

[0060] Examples of monomers (ma-6) include vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylamides, (meth)acrylic acid esters, unsaturated dicarboxylic acid diesters, monomaleimides, (meth)acrylamides, (meth)acrylonitriles, and acrolein. Monomers (ma-6) may be used alone or in combination of two or more.

[0061] Examples of vinyl compounds include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene.

[0062] Examples of cyclic olefins having a norbornene structure include norbornene(bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, and tetracyclo[4.4.0.1 ２，５ 1. ７，１０ ] Dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 ２，５ 1. ７，１０ ] Dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ２，６ Deca-8-en, tricyclo[4.4.0.1 ２，５ ]Undeca-3-ene, tricyclo[6.2.1.0 １，８ ]Undeka-9-ene, tetracyclo[4.4.0.1 ２，５ 1. ７，１０ . 0 １，６ ] Dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ２，５ 1. ７，１２] Dodeca-3-ene and pentacyclo[6.5.1.1 ３，６ . 0 ２，７ . 0 ９，１３ ] Pentadeca-4-ene is one example.

[0063] Examples of dienes include butadiene, isoprene, and chloroprene.

[0064] Examples of (meth)acrylic acid esters include benzyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol mono (meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, and ethoxylated phenyl (meth)acrylate.

[0065] Examples of (meth)acrylamides include (meth)acrylamide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N-diisopropylamide, and (meth)acrylate anthracenylamide.

[0066] Examples of unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0067] Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.

[0068] Copolymer (A) can be produced by copolymerizing the monomers described above. The copolymerization reaction can be carried out in or out of the presence of a solvent according to radical polymerization methods known in the art. For example, the monomers can be dissolved in a solvent, a polymerization initiator can be added to the solution, and the polymerization reaction can be carried out at 40 to 100°C for 1 to 20 hours. In this case, the higher the polymerization temperature, the more likely unintended side reactions such as dissociation and crosslinking of the block isocyanate group of the constituent unit (a-2) will occur. Therefore, the temperature in the copolymerization reaction is preferably 80°C or lower, and more preferably 70°C or lower.

[0069] The solvent used in the copolymerization reaction can be the same as solvent (D) described later. Other solvents include, for example, propylene glycol monoaryl ether, 1,3-propanediol monoalkyl ether, 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerin monoalkyl ether, glycerin dialkyl ether, methanol, ethanol, propanol, cyclopentanediol, cyclohexanediol, cyclopentanedimethanol, cyclohexanedimethanol, ethyl lactate, and diacetone alcohol. The solvents may be used individually or in combination of two or more.

[0070] From the viewpoint of preventing abnormal polymerization and ensuring a stable polymerization reaction, copolymerization is preferably carried out in the presence of a hydroxyl group-containing solvent (for example, a glycol ether containing hydroxyl groups). By carrying out copolymerization in the presence of a hydroxyl group-containing solvent, even if the blocked isocyanate group dissociates and an isocyanate group is formed, the isocyanate group reacts with the hydroxyl group of the hydroxyl group-containing solvent, preventing abnormal polymerization. In copolymer (A) thus obtained, it is considered that a portion of the blocking agent that was blocking the isocyanate group is replaced by the hydroxyl group-containing solvent.

[0071] Examples of polymerization initiators include azo-based thermal polymerization initiators such as azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl; and peroxide-based thermal polymerization initiators such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. Polymerization initiators may be used individually or in combination of two or more.

[0072] The amount of polymerization initiator used may be 0.5 to 30 parts by mass, 1 to 25 parts by mass, or 5 to 20 parts by mass per 100 parts by mass of the total amount of monomer charged.

[0073] During the copolymerization reaction, a peroxide-based thermal polymerization initiator may be used, and a polymerization accelerator may be used in combination. Examples of polymerization accelerators include aliphatic amines, aromatic amines, sulfinic acid derivatives, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, borate compounds, barbituric acid derivatives, triazine compounds, and halogen compounds. Among these, aromatic amines are preferred from the viewpoint of the progress of the redox reaction with the peroxide-based polymerization initiator.

[0074] Examples of aromatic amine compounds include 2,2-[3-(methylphenyl)imino]bisethanolacetate, 1,1-[(4-methylphenyl)imino]bis(2-propanol), p-tolyldiethanolamine, N,N-bis(2,2,2-trifluoroethyl)-p-toluidine, N,N-di(1-hydroxyethyl)-p-toluidine, N,N-di(2-hydroxypropyl)-p-toluidine, N-(1-cyanoethyl)-N-(1-acetoxyethyl)-m-toluidine, N,N-di(1-chloroethyl)-p-toluidine, N,N-dimethyl-p-toluidine, N-ethyl-N-methylaniline, N,N-dimethylaniline, N,N-dipropyl-o-toluidine, N,N-dipropyl-m-toluidine, N,N-dipropyl-p-toluidine, and ethyl 4-dimethylaminobenzoate. From the viewpoint of reducing the copolymerization reaction temperature, 1,1-[(4-methylphenyl)imino]bis(2-propanol), N,N-dimethylaniline, and N,N-dimethyl-p-toluidine are preferred.

[0075] The amount of polymerization accelerator used may be 0.001 to 10 parts by mass or 0.01 to 5 parts by mass per 100 parts by mass of the total amount of monomer charged.

[0076] The weight-average molecular weight (Mw) of copolymer (A) may be 3000 or more, 4000 or more, 5000 or more, 6000 or more, or 6400 or more, from the viewpoint of storage stability of the photosensitive resin composition. The Mw of copolymer (A) may be 50000 or less, 30000 or less, 20000 or less, 15000 or less, or 13000 or less, from the viewpoint of curability of the photosensitive resin composition and solvent resistance of the cured product. From this viewpoint, the Mw of copolymer (A) may be 3000 to 50000, 4000 to 30000, 5000 to 20000, 6000 to 15000, or 6400 to 13000.

[0077] The molecular weight distribution (Mw / Mn) of copolymer (A) may be 1.1 or higher, 1.3 or higher, 1.5 or higher, or 2.0 or higher, from the viewpoint of facilitating control of reaction conditions during synthesis. The Mw / Mn of copolymer (A) may be 4.0 or lower, 3.5 or lower, 3.0 or lower, or 2.5 or lower, from the viewpoint of storage stability and solvent resistance of the photosensitive resin composition. From this viewpoint, the Mw / Mn of copolymer (A) may be 1.1 to 4.0, 1.3 to 3.5, 1.5 to 3.0, or 2.0 to 2.5.

[0078] In this specification, Mw and Mn can be obtained by measuring them by gel permeation chromatography (GPC) under the following conditions and converting them using a calibration curve for standard polystyrene. Measuring device: SHOWDEX® GPC-101 (manufactured by RESONAC Corporation) Detector: Differential refractometer SHOWDEX RI-71S (manufactured by RESONAC Corporation) Column: SHOWDEX LF-804 + LF-804 (manufactured by RESONAC Corporation) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Sample concentration: 0.2% by mass THF solution Flow rate: 1 mL / min

[0079] The acid value of copolymer (A) may be 5 mg KOH / g or more, 10 mg KOH / g or more, 20 mg KOH / g or more, or 25 mg KOH / g or more, from the viewpoint of the storage stability of the photosensitive resin composition. The acid value of copolymer (A) may be 250 mg KOH / g or less, 150 mg KOH / g or less, 100 mg KOH / g or less, or 80 mg KOH / g or less, from the viewpoint of the solvent resistance of the cured product of the photosensitive resin composition. From this viewpoint, the acid value of copolymer (A) may be 5 to 250 mg KOH / g, 10 to 150 mg KOH / g, 20 to 100 mg KOH / g, or 25 to 80 mg KOH / g. The acid value can be measured according to JIS K6901:2008 5.3.

[0080] The block isocyanate group equivalent of copolymer (A) may be 200 g / mol or more, 300 g / mol or more, 400 g / mol or more, or 500 g / mol or more, from the viewpoint of storage stability. The block isocyanate group equivalent of copolymer (A) may be 3000 g / mol or less, 2000 g / mol or less, 1500 g / mol or less, or 1200 g / mol or less, from the viewpoint of solvent resistance. From this viewpoint, the block isocyanate group equivalent of copolymer (A) may be 200 to 3000 g / mol, 300 to 2000 g / mol, 400 to 1500 g / mol, or 500 to 1200 g / mol.

[0081] The block isocyanate group equivalent is the mass of copolymer (A) per mole of block isocyanate groups in copolymer (A). The block isocyanate group equivalent can be determined by dividing the mass of copolymer (A) by the number of moles of block isocyanate groups in copolymer (A). In this specification, the block isocyanate group equivalent of copolymer (A) is a theoretical value calculated from the amount of monomer (ma-2) used to introduce block isocyanate groups into copolymer (A).

[0082] The hydroxyl group equivalent of copolymer (A) may be 100 g / mol or more, 200 g / mol or more, 300 g / mol or more, 500 g / mol or more, or 1000 g / mol or more, from the viewpoint of storage stability. The hydroxyl group equivalent of copolymer (A) may be 5000 g / mol or less, 4000 g / mol or less, 3000 g / mol or less, 2000 g / mol or less, or 1600 g / mol or less, from the viewpoint of solvent resistance. From this viewpoint, the hydroxyl group equivalent of copolymer (A) may be 100 to 5000 g / mol, 200 to 4000 g / mol, 300 to 3000 g / mol, 500 to 2000 g / mol, or 1000 to 1600 g / mol.

[0083] The hydroxyl group equivalent is the mass of copolymer (A) per mole of hydroxyl groups in copolymer (A), and can be determined by dividing the mass of copolymer (A) by the number of moles of hydroxyl groups in copolymer (A). In this specification, the hydroxyl group equivalent is a theoretical value calculated from the amount of monomer (ma-3) used to introduce hydroxyl groups into copolymer (A).

[0084] The heterocyclic equivalent of copolymer (A) may be 300 g / mol or more, 500 g / mol or more, 600 g / mol or more, or 800 g / mol or more, from the viewpoint of storage stability. The heterocyclic equivalent of copolymer (A) may be 5000 g / mol or less, 4800 g / mol or less, 4600 g / mol or less, or 4400 g / mol or less, from the viewpoint of solvent resistance. From this viewpoint, the heterocyclic equivalent of copolymer (A) may be 300 to 5000 g / mol, 500 to 4800 g / mol, 600 to 4600 g / mol, or 800 to 4400 g / mol.

[0085] The heterocyclic equivalent is the mass of copolymer (A) per mole of heterocyclic ring in copolymer (A), and can be determined by dividing the mass of copolymer (A) by the number of moles of heterocyclic ring in copolymer (A). In this specification, the heterocyclic equivalent of copolymer (A) is a theoretical value calculated from the amount of monomer (ma-1) used to introduce heterocyclic rings into copolymer (A).

[0086] The content of copolymer (A) in the photosensitive resin composition may be 10 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more, or 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, based on 100 parts by mass of the total of copolymer (A) and reactive monomer (B), from the viewpoint of handling and photocurability of the photosensitive resin composition. The content of copolymer (A) may be 10 to 90 parts by mass, 25 to 80 parts by mass, 30 to 70 parts by mass, or 40 to 60 parts by mass, based on 100 parts by mass of the total of copolymer (A) and reactive monomer (B).

[0087] <Reactive Monomer (B)> Reactive monomer (B) is not particularly limited and may be any compound having at least one group having a reactive ethylenically unsaturated bond. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, and (meth)acryloyloxy groups. To improve the curability (reactivity) of the photosensitive resin composition, reactive monomer (B) is preferably a compound having two or more groups having ethylenically unsaturated bonds (polyfunctional reactive monomer). Examples of reactive monomer (B) include aromatic vinyl compounds, vinyl ester compounds, allyl compounds, monofunctional (meth)acrylates, and polyfunctional (meth)acrylates. Reactive monomer (B) may be used alone or in combination of two or more types.

[0088] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene. Examples of vinyl ester compounds include vinyl acetate and divinyl adipate.

[0089] Examples of allyl compounds include diallyl phthalate, diallylbenzenephosphonate, triallyl isocyanurate, and diallyl isocyanurate.

[0090] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0091] Examples of polyfunctional (meth)acrylates include 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 penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(meth)acrylate of tris(hydroxyethyl) isocyanurate.

[0092] Among these, as the reactive monomer (B), polyfunctional (meth)acrylates are preferred for improved curability (reactivity), and in particular, dipentaerythritol penta(meth)acrylate and / or dipentaerythritol hexa(meth)acrylate are preferred.

[0093] The content of reactive monomer (B) in the photosensitive resin composition may be 10 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more, or 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, based on 100 parts by mass of the total of copolymer (A) and reactive monomer (B), from the viewpoint of handling and photocurability of the photosensitive resin composition. The content of reactive monomer (B) may be 10 to 90 parts by mass, 25 to 80 parts by mass, 30 to 70 parts by mass, or 40 to 60 parts by mass, based on 100 parts by mass of the total of copolymer (A) and reactive monomer (B).

[0094] <Photopolymerization Initiator (C)> The photopolymerization initiator (C) is not particularly limited, but examples include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]ethanone, 1-(O-acetyloxime); benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4'-(1-t-butyldioxy-1-methylethyl)acetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-benzyl-2-dimethylamino-1-(4-methylthiophenyl) Examples include anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; xanthones; thioxanthone compounds such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and acylphosphine oxide compounds. The photopolymerization initiator (C) may be used alone or in combination of two or more types.

[0095] From the viewpoint of photocurability, the content of the photopolymerization initiator (C) in the photosensitive resin composition may be 0.1 parts by mass or more, 0.5 parts by mass or more, or 1.0 part by mass or more, per 100 parts by mass of the total of the copolymer (A) and the reactive monomer (B). From the viewpoint of the physical properties of the cured product of the photosensitive resin composition, the content of the photopolymerization initiator (C) may be 10 parts by mass or less, 8 parts by mass or less, or 5 parts by mass or less, per 100 parts by mass of the total of the copolymer (A) and the reactive monomer (B). From this viewpoint, the content of the photopolymerization initiator (C) may be 0.1 to 10 parts by mass, 0.5 to 8 parts by mass, or 1.0 to 5 parts by mass, per 100 parts by mass of the total of the copolymer (A) and the reactive monomer (B).

[0096] <Solvent (D)> Solvent (D) is not particularly limited as long as it can dissolve the copolymer (A), the reactive monomer (B), and the photopolymerization initiator (C). Examples of solvent (D) include hydroxyl group-containing solvents and hydroxyl group-free solvents. Solvent (D) may be used alone or in combination of two or more types.

[0097] Examples of hydroxyl group-containing solvents include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and 3-methoxy-1-butanol; hydroxyl group-containing carboxylic acid esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutyrate; and diethylene glycol.

[0098] Examples of hydroxyl group-free solvents include (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; and methyl 3-methoxypropionate and 3-ethoxypropyl ester. Examples include esters such as methyl cypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, i-propyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and carboxylic acid amides such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0099] From the viewpoint of ease of availability, cost, and storage stability of the photosensitive resin composition, it is preferable to use ethers such as propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and 3-methoxy-1-butanol as the solvent (D), and it is more preferable to use glycol ethers having a hydroxyl group such as propylene glycol monomethyl ether and ethylene glycol monomethyl ether.

[0100] The content of solvent (D) in the photosensitive resin composition may be 30 parts by mass or more, 50 parts by mass or more, or 100 parts by mass or more, per 100 parts by mass of the total components excluding solvent (D), from the viewpoint of maintaining an appropriate viscosity range for the photosensitive resin composition. The content of solvent (D) may be 1,000 parts by mass or less, 800 parts by mass or less, 500 parts by mass or less, or 300 parts by mass or less, per 100 parts by mass of the total components excluding solvent (D), from the viewpoint of the ease of removing solvent (D) from the coated film.

[0101] <Colorant (E)> The photosensitive resin composition may further contain a colorant (E). A photosensitive resin composition containing a colorant (E) can be used as a material for a color filter. The colorant (E) is not particularly limited as long as it is soluble or dispersed in the solvent (D), and examples include dyes and pigments.

[0102] The colorant (E) can be appropriately determined according to the desired color pattern (black matrix and pixels). The colorant (E) may be used alone or in combination of two or more types. When using two or more types of colorant (E), dyes and pigments may be used in combination.

[0103] As dyes, from the viewpoint of solubility in solvent (D) and alkaline developer, interaction with other components, and heat resistance, acidic dyes having acidic groups such as carboxyl groups and sulfo groups, salts of acidic dyes with nitrogen compounds, or sulfonamide adducts of acidic dyes may be used.

[0104] Examples of dyes include: 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; solvent blue 38, 44, 70; 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; 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;acid violet 6B, 7, 9, 17, 19; acid yellow Examples include 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 and their derivatives. Among these, azo, xanthene, anthraquinone, or phthalocyanine acid dyes are preferred. The dyes can be used individually or in combination of two or more.

[0105] Examples of pigments include yellow pigments such as C.I. 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, 214; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Examples of pigments include red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as C.I. Pigment Green 7, 36, 58, and 59; brown pigments such as C.I. Pigment Brown 23 and 25; and black pigments such as C.I. Pigment Black 1 and 7, carbon black, titanium black, and iron oxide. Pigments can be used individually or in combination of two or more types.

[0106] When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive resin composition to improve the dispersibility of the pigment. It is preferable to use a polymeric dispersant that exhibits excellent dispersion stability over time. Examples of polymeric 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 polymeric dispersants such as EFKA (manufactured by EFKA CHEMICALS B.V.), Disperbyk (manufactured by Bic Chemie), Disparon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Lubrizol) may also be used. The dispersant content should be appropriately set according to the type and amount of pigment used as the colorant (E).

[0107] The content of the colorant (E) in the photosensitive resin composition may be 3 parts by mass or more, 5 parts by mass or more, or 10 parts by mass or more, based on 100 parts by mass of the total of the copolymer (A) and the reactive monomer (B), from the viewpoint of obtaining a photosensitive resin composition suitable as a material for the coloring pattern of a color filter. The content of the colorant (E) may be 50 parts by mass or less, 40 parts by mass or less, or 30 parts by mass or less, based on 100 parts by mass of the total of the copolymer (A) and the reactive monomer (B), from the viewpoint of the low-temperature curability of the photosensitive resin composition.

[0108] The photosensitive resin composition may optionally contain known additives such as dispersants, coupling agents, leveling agents, and thermal polymerization inhibitors. The amount of additives is not particularly limited as long as it does not impair the effects of this disclosure.

[0109] A photosensitive resin composition can be prepared by mixing a copolymer (A), a reactive monomer (B), a photopolymerization initiator (C), a solvent (D), and a colorant (E) as needed, using a known mixing apparatus.

[0110] When preparing a photosensitive resin composition, the reaction solution used to prepare copolymer (A) can be used as is. In this case, the solvent (D) contained in the reaction solution can be used as part or all of the solvent (D) contained in the photosensitive resin composition.

[0111] When forming a cured product using the photosensitive resin composition according to this embodiment, curing can be performed at a lower temperature compared to conventional resin compositions. For example, when a coating film formed on a substrate is exposed to light and then subjected to a baking treatment, the crosslinking reaction proceeds sufficiently even at a lower baking temperature, resulting in the formation of a cured product with excellent solvent resistance and hardness. Furthermore, when forming a cured product using the photosensitive resin composition, less energy is required for heating during curing.

[0112] By using the photosensitive resin composition according to this embodiment, a cured product can be formed on a substrate with low heat resistance, such as a resin substrate, without damaging the substrate. Even when a colorant (E) with low heat resistance is used, a cured product can be formed that exhibits the original properties of the colorant (E).

[0113] The photosensitive resin composition yields a cured product with excellent solvent resistance and hardness even at low baking temperatures, so the colorant (E) is less likely to leach out of the cured product. Therefore, it is possible to increase the colorant (E) content in the photosensitive resin composition. A photosensitive resin composition with a high colorant (E) content can be used, for example, as a material for the coloring pattern of a color filter to form a color filter with excellent color reproduction.

[0114] The photosensitive resin composition according to this embodiment can be suitably used as a material for color filters. The photosensitive resin composition is extremely useful as a material for forming components of image display elements, such as pixels of color filters, black matrices, color filter protective films, photospacers, liquid crystal alignment protrusions, microlenses, and insulating films for touch panels.

[0115] [Cured Resin Film] The cured resin film according to this embodiment includes a cured product of the photosensitive resin composition described above. The cured resin film can be produced, for example, by applying the photosensitive resin composition to a substrate, evaporating and removing the solvent to form a coating film, exposing the coating film to light-curing, and then performing a baking treatment. Known methods can be used for the method of applying the photosensitive resin composition, the method of exposing the coating film, and the method of developing when producing the cured resin film.

[0116] When forming a resin-cured film having a predetermined pattern shape, for example, the following method can be used. First, a photosensitive resin composition is applied to a substrate, and the solvent is evaporated and removed to form a coating film. Next, the coating film is exposed to light through a photomask having a predetermined pattern shape, and the exposed portion is photocured. Then, the unexposed portion of the coating film is developed with an alkaline aqueous solution. After that, the developed coating film is subjected to a baking treatment to form a resin-cured film having a predetermined pattern shape.

[0117] The baking conditions can be appropriately determined according to the composition of the photosensitive resin composition, the film thickness of the coating, the material of the substrate, etc. The baking treatment can be carried out at a temperature of, for example, 70°C to 250°C. When the baking temperature is 70°C or higher, cross-linking occurs through transesterification between the blocked isocyanate group of constituent unit (a-2) contained in copolymer (A) and the hydroxyl group of constituent unit (a-3). As a result, a good degree of curing is obtained, and a cured product with excellent solvent resistance and hardness is obtained. Constituent unit (a-2) can undergo both a deblocking reaction to generate an isocyanate group and a transesterification reaction, but by adjusting the baking temperature, one of the reactions can be preferentially promoted. The baking temperature may be 75°C or higher or 80°C or higher.

[0118] When the baking temperature is 250°C or lower, it is a condition that materials with low heat resistance can withstand, and discoloration of the photosensitive resin composition can be suppressed. Since the photosensitive resin composition according to this embodiment has good low-temperature curing properties, the baking temperature can be set to 160°C or lower, depending on the heat resistance of the substrate on which the resin-cured film is formed. When a resin substrate is used as the base material, the baking temperature may be 150°C or lower, 120°C or lower, or 100°C or lower. The resin-cured film can be produced using a baking method at a low temperature and has excellent solvent resistance.

[0119] The baking time can be appropriately determined depending on the composition of the photosensitive resin composition, the baking temperature, the film thickness of the coating, etc. For example, the baking time can be 10 minutes to 4 hours, or 20 minutes to 2 hours.

[0120] [Color Filter] The color filter according to this embodiment has a colored pattern including a cured product of a photosensitive resin composition. The photosensitive resin composition contains a copolymer (A), a reactive monomer (B), a photopolymerization initiator (C), a colorant (E), and a solvent (D), wherein the copolymer (A) includes a constituent unit (a-1) having a heterocycle with 5 or more ring members, a constituent unit (a-2) having a blocked isocyanate group, a constituent unit (a-3) having a hydroxyl group, and a constituent unit (a-4) having an acid group.

[0121] The color filter may have a colored pattern made of a cured product of a photosensitive resin composition containing, for a total of 100 parts by mass of copolymer (A) and reactive monomer (B), 10 to 90 parts by mass of copolymer (A), 10 to 90 parts by mass of reactive monomer (B), 0.1 to 30 parts by mass of photopolymerization initiator (C), 3 to 80 parts by mass of colorant (E), and 30 to 1000 parts by mass of solvent (D) for a total of 100 parts by mass of components excluding solvent (D).

[0122] A color filter may include, for example, a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix. In a color filter, the pixels and the black matrix are a colored pattern including a cured product of the above-mentioned photosensitive resin composition. In a color filter, components other than the materials of the pixels and the black matrix can be those of known origin.

[0123] The substrate used in the color filter is not particularly limited. Examples of substrates include glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide-imide substrates, polyimide substrates, aluminum substrates, printed circuit boards, and array substrates, which can be used as appropriate depending on the application.

[0124] Next, an exemplary method for manufacturing a color filter will be described. First, a color pattern is formed on the substrate. Specifically, a color pattern that will become the black matrix formed at the boundary of each pixel, and a color pattern that will become each RGB pixel are sequentially formed on the substrate by the method described below.

[0125] The colored pattern can be formed by photolithography. Specifically, a photosensitive resin composition is applied to a substrate to form a coating film. Then, the coating film is exposed to light through a photomask having a predetermined pattern shape, and the exposed areas are photocured. Next, the unexposed areas of the coating film are developed with an alkaline aqueous solution. After that, a baking treatment is performed on the developed coating film to form a colored pattern having a predetermined pattern shape.

[0126] The photosensitive resin composition has good photocurability and low-temperature curability. Therefore, when forming a colored pattern using the photosensitive resin composition of one embodiment, if the baking temperature is the same as when forming a colored pattern using a conventional photosensitive resin composition, the baking time can be shortened, and a color filter can be formed efficiently.

[0127] After forming color patterns that will become each RGB pixel and a color pattern that will become the black matrix formed at the boundary of each pixel using the color pattern manufacturing method described above, a protective film is formed on the color patterns (each RGB pixel and the black matrix). The method for manufacturing the protective film is not particularly limited and may be formed using the photosensitive resin composition of one embodiment, or using known materials and known methods.

[0128] The color filter has a colored pattern containing a cured product of the photosensitive resin composition described above. Therefore, the colored pattern in the color filter can be formed by a baking process at a low temperature. Consequently, the energy required for the baking process can be reduced.

[0129] It is possible to use a colorant (E) with low heat resistance as the colorant (E) contained in the photosensitive resin composition used as a material for color filters. This increases the number of usable colorants (E). Therefore, for example, it is possible to form a color filter that contains a colorant (E) with low heat resistance and has a coloring pattern that exhibits the inherent properties of the colorant (E) with low heat resistance.

[0130] The colored patterns in color filters can be formed on substrates with low heat resistance, such as resin substrates, without damaging the substrate itself. Therefore, the range of usable substrates can be increased. Specifically, for example, since color filters can be formed on substrates with low heat resistance, such as resin substrates, flexible displays are possible. In addition, the colored patterns in color filters have excellent solvent resistance and hardness, resulting in minimal color change.

[0131] The explanation described an example in which a colored pattern is produced using a photosensitive resin composition containing a photopolymerization initiator (C) and a method of photocuring the photosensitive resin composition. However, for example, instead of the photopolymerization initiator (C) contained in the photosensitive resin composition, a photosensitive resin composition containing a curing accelerator and a known epoxy resin may be used, and a colored pattern consisting of a cured product of the photosensitive resin composition containing copolymer (A) may be formed by applying it to a substrate using an inkjet method and then heating it.

[0132] [Image Display Element] The image display element according to this embodiment includes a color filter. Other components of the image display element can be those known to be used. Examples of image display elements include liquid crystal display elements, organic EL display elements, CCD elements, and solid-state image sensors such as CMOS elements.

[0133] The components of an image display element other than the color filter can be manufactured by known methods. For example, when manufacturing a liquid crystal display element as an image display element, it can be manufactured using the method shown below. First, a color filter is formed on a substrate using the method described above. Then, electrodes, spacers, etc., are sequentially formed on the substrate having the color filter. Next, electrodes, etc., are formed on another substrate and bonded together with the substrate having the color filter, facing each other. Then, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0134] The image display element according to this embodiment is equipped with a color filter that has excellent solvent resistance and hardness, resulting in minimal color change.

[0135] The present disclosure will be described in detail below with reference to examples and comparative examples. The following examples are provided to facilitate understanding of the contents of this disclosure. This disclosure is not limited to these examples.

[0136] (Synthesis of Copolymers) The following monomers were prepared to synthesize copolymers. (Monomer ma-1) IPGMA: (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate (Tokyo Chemical Industries, Ltd.) THFA: Tetrahydrofurfuryl acrylate (Osaka Organic Chemical Industry Co., Ltd., trade name "Viscote #150") THPMA: Tetrahydropyranyl methacrylate (Kyoeisha Chemical Co., Ltd., trade name "Light Ester THF") CTFA: Cyclic trimethylolpropane formal acrylate (Osaka Organic Chemical Industry Co., Ltd., trade name "Viscote #200") ACMO: Acryloylmorpholine (KJ Chemicals Co., Ltd., trade name "ACMO") (Monomer ma-2) AOI-DEM: Malonic acid-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester (reaction product of 2-isocyanatoethyl acrylate and diethyl malonate, Resona Corporation, product name "Karenz AOI-DEM") MOI-BP: 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (reaction product of 2-isocyanatoethyl methacrylate and 3,5-dimethylpyrazole, Resona Corporation, product name "Karenz MOI-BP") (monomer ma-3) HEMA: 2-hydroxyethyl methacrylate (Nippon Shokubai Co., Ltd.) (monomer ma-4) MAA: Methacrylic acid (Kuraray Co., Ltd.) (monomer ma-5) 2EHA: 2-ethylhexyl acrylate (Toagosei Co., Ltd.) TCDMA: Dicyclopentanyl methacrylate (Resonac Corporation, product name "FA-513M")

[0137] (Synthesis Example 1) Mixture (x) was prepared by mixing the monomers IPGMA 20.0 g (0.100 mol), AOI-DEM 95.3 g (0.191 mol), HEMA 19.4 g (0.149 mol), MAA 10.1 g (0.117 mol), and 2EHA 81.6 g (0.443 mol) with the polymerization initiator 2,2'-azobis(isobutyrate)dimethyl 37.8 g and the solvents propylene glycol monomethyl ether acetate (PGMEA) 143.6 g and propylene glycol monomethyl ether (PGME) 112.4 g.

[0138] 237.6 g of PGME was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 78°C. Next, the mixture (x) was added dropwise to the flask from the dropping funnel over 3 hours to carry out the copolymerization reaction. After the reaction, 156.4 g of PGMEA was added to obtain a solution of copolymer P1.

[0139] (Synthesis Examples 2-7) Solutions of copolymers P2-P7 of Synthesis Examples 2-7 were obtained in the same manner as in Synthesis Example 1, except that the type and amount of monomers in the mixed solution (x) were changed to the monomers and molar ratios shown in Table 1.

[0140] (Synthesis Examples 8-14) Solutions of copolymers P8-P14 of Synthesis Examples 8-14 were obtained in the same manner as in Synthesis Example 1, except that the type and amount of monomers in the mixed solution (x) were changed to the monomers and molar ratios shown in Table 2.

[0141] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the copolymer were calculated by GPC measurement. The acid value of the copolymer was measured by neutralization titration in accordance with JIS K6901:2008 5.3.2. The equivalent amounts of blocked isocyanate groups, hydroxyl groups, and heterocyclic rings were calculated from the amounts of monomers and polymerization initiators used in the production of the copolymer.

[0142]

[0143]

[0144] [Photosensitive Resin Composition] (Example 1) A photosensitive resin composition was prepared by mixing 15.7 parts by mass of copolymer P1, 15.7 parts by mass of a mixture of reactive monomers dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD DPHA"), 0.8 parts by mass of photopolymerization initiator ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], 1-(O-acetyloxime) (manufactured by BASF Japan Ltd., trade name "Irgacure OXE02"), 60.0 parts by mass of a mixture of solvents PGMEA and PGME, and 7.8 parts by mass of a colorant phthalocyanine dye (manufactured by Orient Chemical Industry Co., Ltd., trade name "VALIFAST BLUE 2620"). The solvent content is the total amount of solvent used in synthesizing the copolymer in the resin composition and any additional solvent added during the preparation of the resin composition.

[0145] (Examples 2-11) The photosensitive resin compositions of Examples 2-11 were prepared in the same manner as in Example 1, except that copolymer P1 was changed to copolymers P2-P11 shown in Tables 1 and 2.

[0146] (Comparative Examples 1-3) Photosensitive resin compositions of Comparative Examples 1-3 were prepared in the same manner as in Example 1, except that copolymer P1 was changed to copolymers P12-P14 shown in Table 2.

[0147] [Evaluation] The developability and solvent resistance of the photosensitive resin compositions of the examples and comparative examples were evaluated. The results are shown in Tables 3 and 4.

[0148] (Developability) A photosensitive resin composition was spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) to a thickness of 2.5 μm after exposure (coating step), and the solvent was evaporated by heating at 100°C for 3 minutes to form a coated film on the glass substrate (pre-bake step).

[0149] Next, using an ultra-high pressure mercury lamp, 200 mJ / cm² was measured. ２Light was shone onto the surface of the coated film via a photomask (exposure step). The exposure step was performed with the photomask positioned 100 μm away from the coated film. The photomask used had a line and space pattern with a width of 3 to 100 μm. Next, semi-clean DL-A10 developer (manufactured by Yokohama Oil & Fat Industry Co., Ltd.) (5-fold dilution) was sprayed onto the surface of the coated film for 60 seconds at a temperature of 23°C and a pressure of 0.1 MPa to remove the unexposed areas (development step). The glass substrate with the developed coated film was left to stand in a 100°C dryer for 30 minutes to heat-cur the coated film (post-bake step) and obtain a colored pattern.

[0150] The colored patterns were observed using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation, and the developability was evaluated based on the minimum line width (minimum development dimension) that could be developed and the presence or absence of residue in the unexposed areas between the developed patterns. For residue, it was determined as "A" if there was no residue in the unexposed areas between the developed patterns, and as "B" if there was residue in the unexposed areas between the developed patterns.

[0151] (Solvent Resistance) A photosensitive resin composition was spin-coated onto a 5 cm x 5 cm square glass substrate (alkali-free glass substrate), and heated at 100°C for 3 minutes to form a coated film. The coated film was exposed to light with a wavelength of 365 nm at an exposure dose of 200 mJ / cm². ２ After photocuring by irradiation, the coated film was heat-cured by heating at 100°C for 30 minutes, forming a 2.5 μm thick resin-cured film on a glass substrate.

[0152] The absorption spectrum of the cured resin film was measured using a spectrophotometer (Shimadzu Corporation, product name "UV-1650PC"). Additionally, 200 mL of PGMEA was placed in a 500 mL glass bottle with a lid and left standing at 23°C. A glass substrate with the cured resin film was then placed in this bottle and immersed in the PGMEA at 23°C for 15 minutes. Afterward, the glass substrate with the cured resin film was removed, and the absorption spectrum of the cured resin film was measured using a spectrophotometer.

[0153] Color change of the resin cured film before and after immersion in PGMEA (ΔE ＊The solvent resistance of the resin-cured film was evaluated by calculating ab). A smaller value indicates better solvent resistance.

[0154]

[0155]

[0156] The photosensitive resin compositions of Examples 1 to 11 were found to have excellent alkali developability and to be able to form resin-cured films with excellent solvent resistance.

Claims

1. A photosensitive resin composition comprising a copolymer (A), a reactive monomer (B), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A) comprises a constituent unit (a-1) having a heterocycle with 5 or more members, a constituent unit (a-2) having a blocked isocyanate group, a constituent unit (a-3) having a hydroxyl group, and a constituent unit (a-4) having an acid group.

2. The photosensitive resin composition according to claim 1, wherein the heterocycle is at least one selected from the group consisting of cyclic ethers, cyclic esters, cyclic carbonates, cyclic amines, cyclic amides, and cyclic imides.

3. The photosensitive resin composition according to claim 1, wherein the heterocycle is a cyclic ether or a cyclic amine.

4. The photosensitive resin composition according to claim 1, wherein the blocking agent of the constituent unit (a-2) having the blocked isocyanate group is at least one selected from the group consisting of 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 4-hydroxybenzoate, methyl 2-hydroxybenzoate, 3,5-xylenol, and compounds having an alkyloxycarbonyl group.

5. The photosensitive resin composition according to claim 1, wherein the copolymer (A) further comprises a constituent unit (a-5) having an aliphatic hydrocarbon group having 1 to 20 carbon atoms.

6. The photosensitive resin composition according to claim 1, wherein the acid value of the copolymer (A) is 5 to 250 mg KOH / g.

7. The photosensitive resin composition according to claim 1, wherein the weight-average molecular weight of the copolymer (A) is 3,000 to 50,000.

8. The photosensitive resin composition according to claim 1, wherein the reactive monomer (B) is a compound having two or more groups having ethylenically unsaturated bonds.

9. The photosensitive resin composition according to claim 1, wherein the copolymer (A) contains 1 to 40 mol% of the constituent unit (a-1), 1 to 40 mol% of the constituent unit (a-2), 1 to 40 mol% of the constituent unit (a-3), and 1 to 40 mol% of the constituent unit (a-4), based on the total constituent units derived from the monomers constituting the copolymer (A).

10. The photosensitive resin composition according to claim 1, wherein the solvent (D) comprises a glycol ether having a hydroxyl group.

11. The photosensitive resin composition according to claim 1, wherein the content of the copolymer (A) is 10 to 90 parts by mass per 100 parts by mass of the total of the copolymer (A) and the reactive monomer (B).

12. The photosensitive resin composition according to claim 1, further comprising a coloring agent (E).

13. A resin-cured film comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 12.

14. A color filter having a colored pattern comprising a cured product of the photosensitive resin composition described in claim 12.

15. An image display element comprising the color filter described in claim 14.

Images