Photosensitive resin composition and method for producing the photosensitive resin composition

Abstract

The photosensitive resin composition according to the present invention contains a resin (A), a reactive diluent (B), a solvent (C), a photopolymerization initiator (D), and a colorant (E). The resin (A) has a structural unit (a) having an aromatic ring skeleton, a structural unit (b) having a carboxy group, a structural unit (c), and a structural unit (d) having a bridging alicyclic hydrocarbon group having 7-20 carbon atoms, wherein the structural unit (c) is at least one unit selected from the group consisting of a structural unit (c-1) having a (meth) acryloyloxy group and a structural unit (c-2) having a functional group that reacts with a carboxy group. The photosensitive resin composition is characterized in that the content of the structural unit (a) having an aromatic ring skeleton is 5-50 mol% with respect to the total amount of the structural units of the resin (A).

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, an image display element, and a method for producing the photosensitive resin composition. This application claims priority based on Japanese Patent Application No. 2020-205539 filed in Japan on December 11, 2020, and incorporates its content herein.

Background Art

[0002] In recent years, from the viewpoints of resource saving and energy saving, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in various fields such as various coatings, printing, paints, and adhesives. The photosensitive resin composition is used for solder resists, resists for color filters, etc. in the field of electronic materials such as printed wiring boards.

[0003] A color filter generally has a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundaries of the pixels, and a protective film formed on the pixels and the black matrix. A color filter is usually manufactured by sequentially forming a black matrix, each pixel, and a protective film on a transparent substrate.

[0004] As methods for forming each pixel and the black matrix, various manufacturing methods have been proposed. Currently, a method using a photolithography method that repeatedly performs coating, exposure, development, and baking using a photosensitive resin composition as a resist has become mainstream as a method for forming each pixel and the black matrix. Each pixel and black matrix formed using this method are excellent in light resistance and heat resistance and have few defects such as pinholes.

[0005] Generally, the photosensitive resin composition used in the photolithography method contains a resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The photosensitive resin composition used in the photolithography method needs to have developability.

[0006] Conventionally, resins that are copolymers of unsaturated carboxylic acids and / or unsaturated carboxylic acid anhydrides, radical polymerizable compounds having epoxy groups, and other radical polymerizable compounds have been proposed as resins used in photosensitive resin compositions (see, for example, Patent Document 1). Furthermore, resin compositions have been proposed for use in photosensitive resin compositions, including copolymers synthesized using glycidyl (meth)acrylate, which do not have acid groups and have a weight-average molecular weight of 1,000 to 50,000 on a polystyrene basis, and copolymers which have acid groups and have a weight-average molecular weight of 1,000 to 50,000 on a polystyrene basis (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 06-043643 [Patent Document 2] Japanese Patent Publication No. 2015-222279 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] Recently, stricter dimensional accuracy is required for liquid crystal display elements and the components forming them. Therefore, photosensitive resin compositions used as materials for black matrices, color filters, and black column spacers require superior developability. Furthermore, to improve the display characteristics of liquid crystal display elements, the cured films obtained by curing the photosensitive resin compositions used in the above applications must have good colorant dispersibility. In addition, to prevent degradation of liquid crystal display elements, the cured films obtained by curing the photosensitive resin compositions used in the above applications are required to have a high elastic recovery rate.

[0009] The present invention was made to solve the above-mentioned problems, and aims to provide a photosensitive resin composition with excellent colorant dispersibility, developability, and elastic recovery rate. [Means for solving the problem]

[0010] The present invention includes the following embodiments. A first aspect of the present invention provides the following photosensitive resin composition: [1] resin (A) and Reactive diluent (B), Solvent (C) and, Photopolymerization initiator (D), Coloring agent (E), A photosensitive resin composition containing, The aforementioned resin (A) A constituent unit (a) having an aromatic ring skeleton, A constituent unit (b) having a carboxyl group, Constituent unit (c), A constituent unit (d) having a cross-linked alicyclic hydrocarbon group with 7 to 20 carbon atoms, It has, The aforementioned structural unit (c) is at least one selected from the group consisting of structural units having a (meth)acryloyloxy group (c-1) and structural units having a functional group that reacts with a carboxyl group (c-2), A photosensitive resin composition characterized in that the content of the constituent unit (a) having the aromatic ring skeleton is 5 to 50 mol% relative to the total amount of constituent units of the resin (A). The photosensitive resin composition of the first embodiment of the present invention preferably has the features described in [2] to [9] below. It is also preferable to combine two or more of the features described in [2] to [9] below. [2] The photosensitive resin composition according to [1], wherein the constituent unit (b) having a carboxyl group is one or more selected from the group consisting of constituent units derived from unsaturated carboxylic acids (b-1), constituent units derived from polybasic acids (b-2), and constituent units derived from polybasic acid anhydrides (b-3). [3] The photosensitive resin composition according to [1] or [2], wherein the resin (A) has a constituent unit (c-1) having a (meth)acryloyloxy group. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the constituent unit (a) having an aromatic ring skeleton is one or more selected from the group consisting of styrene-derived constituent units and benzyl (meth)acrylate-derived constituent units. [5] The resin (A) contains resin (A-1) and resin (A-2), The resin (A-1) contains 5 to 30 mol% of the constituent unit (a) having the aromatic ring skeleton, relative to the total amount of constituent units of the resin (A-1). The photosensitive resin composition according to any one of [1] to [4], wherein the resin (A-2) contains 35 mol% to 50 mol% of the constituent unit (a) having the aromatic ring skeleton, relative to the total amount of constituent units of the resin (A-2). [6] The resin (A) contains 10 to 90% by mass of the resin (A) and 10 to 90% by mass of the resin (A), The resin (A-1) is a resin in which a carboxyl group-containing (meth)acrylic compound is added to the epoxy group of a resin (A-1) precursor having an epoxy group, and further a polybasic acid or polybasic acid anhydride is added to the hydroxyl group formed by ring-opening of the epoxy group. The resin (A-2) is a resin in which epoxy group-containing (meth)acrylate or isocyanate group-containing (meth)acrylate is added to some of the carboxyl groups of a resin (A-2) precursor having carboxyl groups. The epoxy group-containing resin (A-1) precursor is a polymer of an aromatic ring-containing polymerizable monomer, an epoxy group-containing (meth)acrylate, and a polymerizable monomer having a crosslinked alicyclic hydrocarbon group with 7 to 20 carbon atoms. The photosensitive resin composition according to any one of [1] to [5], wherein the resin (A-2) precursor having a carboxyl group is a polymer of an aromatic ring-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, and a polymerizable monomer having a crosslinked alicyclic hydrocarbon group having 7 to 20 carbon atoms. [7] The photosensitive resin composition according to any one of [1] to [8], wherein the colorant (E) is an organic black pigment. [8] The photosensitive resin composition according to any one of [1] to [7], further containing a dispersant (F). [9] Containing 2 to 20% by mass of the resin (A), Containing 3 to 20% by mass of the reactive diluent (B), Containing 50 to 90% by mass of the solvent (C), and The photosensitive resin composition according to any one of [1] to [8], containing 3 to 30% by mass of the colorant (E). The second aspect of the present invention provides the following black column spacer.

[10] A black column spacer comprising a cured product of the photosensitive resin composition according to any one of [1] to [9]. The third aspect of the present invention provides the following image display element.

[11] An image display element comprising the black column spacer according to

[10] . The fourth aspect of the present invention provides the following method for producing a photosensitive resin composition.

[12] Step I: A step of mixing a resin (A1), a solvent (C1), a colorant (E), and an optional dispersant (F); Step II: A step of mixing a resin (A2), a reactive diluent (B), a solvent (C2), a photopolymerization initiator (D), and the mixture obtained in Step I; A method for producing a photosensitive resin composition having these steps in this order, wherein the resin (A1) and the resin (A2) each have A structural unit (a) having an aromatic ring skeleton, A structural unit (b) having a carboxy group, A structural unit (c), A structural unit (d) having a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms, and the structural unit (c) is at least one selected from the group consisting of a structural unit (c-1) having a (meth)acryloyloxy group and a structural unit (c-2) having a functional group that reacts with a carboxy group, A method for producing a photosensitive resin composition, characterized in that the resin (A1) and the resin (A2) each contain 5 to 60 mol% of the constituent unit (a) having the aromatic ring skeleton, relative to the total amount of constituent units. A fourth aspect of the present invention may also preferably have the following features.

[13] The resin (A1) is either resin (A-1) or resin (A-2), The resin (A2) is the other of the resins (A-1) and (A-2) that is different from the resin (A1). The resin (A-1) contains 5 to 30 mol% of the constituent unit (a) having the aromatic ring skeleton, relative to the total amount of constituent units of the resin (A-1). The method for producing a photosensitive resin composition according to

[12] , wherein the resin (A-2) contains 35 mol% to 50 mol% of the constituent unit (a) having the aromatic ring skeleton, relative to the total amount of constituent units of the resin (A-2). [Effects of the Invention]

[0011] According to the present invention, a photosensitive resin composition with excellent colorant dispersibility, developability, and elastic recovery rate can be provided. The cured resin film obtained by curing the photosensitive resin composition of the present invention exhibits excellent colorant dispersibility and elastic recovery rate. [Modes for carrying out the invention]

[0012] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. For example, the present invention is not limited to the following examples, and additions, omissions, substitutions, or changes are possible regarding the number, quantity, ratio, composition, type, position, material, configuration, etc., without departing from the spirit of the present invention. In this specification, "(meth)acryloyloxy group" means at least one selected from acryloyloxy group and methacryloyloxy group, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid, and "(meth)acrylate" means at least one selected from acrylate and methacrylate. "Constituent units" refer to the monomer units that make up resin (A). "Constituent unit content" refers to the content (mol%) relative to the total number of moles of constituent monomers. A "monomer-derived constituent unit" is a constituent unit derived from a specific monomer among the monomers that make up resin (A).

[0013] <Photosensitive resin composition> The photosensitive resin composition of the present invention will be described in detail below. The photosensitive resin composition of this embodiment contains a resin (A), a reactive diluent (B), a solvent (C), a photopolymerization initiator (D), and a colorant (E). The photosensitive resin composition of this embodiment may optionally contain a dispersant (F).

[0014] [Resin (A)] The resin (A) of this embodiment comprises at least a constituent unit (a) having an aromatic ring skeleton (hereinafter also simply referred to as "constituent unit (a)"), a constituent unit (b) having a carboxyl group (hereinafter also simply referred to as "constituent unit (b)"), a constituent unit (c), and a constituent unit (d) having a crosslinked alicyclic hydrocarbon group having 7 to 20 carbon atoms (hereinafter also simply referred to as "constituent unit (d)"). The constituent unit (c) is at least one selected from the group consisting of a constituent unit (c-1) having a (meth)acryloyloxy group (hereinafter also simply referred to as "constituent unit (c-1)") and a constituent unit (c-2) having a functional group that reacts with a carboxyl group (hereinafter also simply referred to as "constituent unit (c-2)").

[0015] "Constituent unit (a)" The constituent unit (a) has an aromatic ring skeleton. The presence of constituent unit (a) in resin (A) results in a photosensitive resin composition with superior dispersibility of the colorant (E). In particular, when a pigment is used as the colorant (E), the improved dispersibility due to resin (A) having constituent unit (a) is significantly observed. Constituent unit (a) is introduced by using an aromatic ring-containing polymerizable monomer (m-1) as the polymerizable monomer used when producing resin (A) by copolymerization (it is derived from the aromatic ring-containing polymerizable monomer). Examples of aromatic ring-containing polymerizable monomers (m-1) include aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene; benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate (product name: Light Acrylate P-200A, manufactured by Kyoei Chemical Co., Ltd.), o-phenoxybenzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, and p-phenoxybenzyl (meth)acrylate. Among these, styrene and benzyl (meth)acrylate are preferred from the viewpoint of ease of acquisition and improved developability. These aromatic ring-containing polymerizable monomers (m-1) may be used individually or in combination of two or more. In other words, it is preferable that the constituent unit (a) having an aromatic ring skeleton is one or more selected from the group consisting of styrene-derived constituent units and benzyl (meth)acrylate-derived constituent units.

[0016] "Constituent unit (b)" The constituent unit (b) does not have an aromatic ring skeleton and has a carboxyl group. The carboxyl group may be present as an anhydride. It is preferable that the constituent unit (b) having a carboxyl group is one or more selected from the group consisting of constituent units derived from unsaturated carboxylic acids (b-1), constituent units derived from polybasic acids (b-2), and constituent units derived from polybasic acid anhydrides (b-3). Constituent unit (b) can generally be introduced into resin (A) by the following two methods.

[0017] The first method involves introducing a carboxyl group-containing polymerizable monomer (derived from a carboxyl group-containing polymerizable monomer) as the polymerizable monomer used when producing resin (A) by copolymerization. Examples of carboxyl group-containing polymerizable monomers (m-2) include unsaturated carboxylic acids such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, α-bromo(meth)acrylic acid, 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. These carboxyl group-containing polymerizable monomers may be used individually or in combination of two or more. Among these, (meth)acrylic acid is preferred from the viewpoint of availability and reactivity.

[0018] The second method involves using an epoxy group-containing (meth)acrylate (m-3) as the polymerizable monomer when producing a precursor of resin (A) by copolymerization. This method involves ring-opening the epoxy group by adding a carboxyl group of a carboxyl group-containing compound to the epoxy group, and then introducing a carboxyl group by adding a polybasic acid (n-1) or polybasic anhydride (n-2) to the resulting hydroxyl group.

[0019] Examples of epoxy group-containing (meth)acrylates (m-3) include glycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate having an alicyclic epoxy, its lactone adducts (e.g., Cyclomer® A200, M100 manufactured by Daicel Chemical Industries, Ltd.), mono(meth)acrylic acid esters of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxidized dicyclopentenyl (meth)acrylate, and epoxidized dicyclopentenyloxyethyl (meth)acrylate. These epoxy group-containing (meth)acrylates (m-3) may be used individually or in combination of two or more. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of availability and reactivity. As the carboxyl group-containing compound, the unsaturated carboxylic acids listed in the first method described above can be used. Among these, (meth)acrylic acid is preferred from the viewpoint of reactivity.

[0020] Examples of polybasic acids (n-1) include tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, and succinic acid. Examples of polybasic acid anhydrides (n-2) include the polybasic acid anhydrides mentioned above. These polybasic acids and polybasic acid anhydrides may be used individually or in combination of two or more types. Among these, tetrahydrophthalic acid anhydride is preferred from the viewpoint of improving developability.

[0021] In the second method, when adding the carboxyl group of a carboxyl group-containing compound to the epoxy group contained in the precursor, some of the epoxy group of the precursor can be left unreacted, thus remaining as a constituent unit (c-2) having a functional group that reacts with the carboxyl group. Alternatively, a constituent unit (c-1) having a (meth)acryloyloxy group can be introduced by adding a carboxyl group-containing compound having a (meth)acryloyloxy group to the epoxy group of the precursor.

[0022] "Constituent unit (c)" "Constituent unit (c-1)" The constituent unit (c-1) lacks an aromatic ring skeleton and a carboxyl group, but has a (meth)acryloyloxy group. The constituent unit (c-1) can generally be introduced into resin (A) by the following two methods.

[0023] The first method involves using an epoxy group-containing (meth)acrylate (m-3) as the polymerizable monomer when producing a precursor of resin (A) by copolymerization, and introducing a carboxyl group-containing (meth)acrylic compound by adding it to the epoxy group. The epoxy group-containing (meth)acrylate (m-3) can be the one described above. Examples of carboxyl group-containing (meth)acrylic compounds (m-2) include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, α-bromo(meth)acrylic acid, and β-furyl(meth)acrylic acid. Among these, (meth)acrylic acid is preferred from the viewpoint of reactivity and availability when synthesizing resin (A). These carboxyl group-containing (meth)acrylic compounds may be used individually or in combination of two or more.

[0024] The second method involves using a carboxyl group-containing monomer as the polymerizable monomer when producing a precursor of resin (A) by copolymerization, and introducing an epoxy group-containing (meth)acrylate (m-3) or an isocyanate group-containing (meth)acrylate (m-4) by adding it to the carboxyl group. As the carboxyl group-containing monomer, the unsaturated carboxylic acids listed above as carboxyl group-containing polymerizable monomers can be used. As the epoxy group-containing (meth)acrylate (m-3), the above-mentioned ones can be used. As the isocyanate group-containing (meth)acrylate (m-4), 2-isocyanatoethyl (meth)acrylate is an example.

[0025] The constituent unit (c-2) does not have an aromatic ring skeleton, a carboxyl group, or a (meth)acryloyloxy group, but has a functional group that reacts with a carboxyl group. The functional group that reacts with the carboxyl group of constituent unit (c-2) is not particularly limited, but usually includes epoxy groups, oxetanyl groups, isocyanate groups, etc., with epoxy groups being particularly preferred. The constituent unit (c-2) is introduced by using a polymerizable monomer containing a functional group that reacts with a carboxyl group as the polymerizable monomer used when producing resin (A) by copolymerization (it is derived from a polymerizable monomer containing a functional group that reacts with a carboxyl group). In addition to the epoxy group-containing (meth)acrylate (m-3) mentioned above, polymerizable monomers containing functional groups that react with carboxyl groups include oxetanyl (meth)acrylate, (meth)acrylic acid (3-methyloxetan-3-yl)methyl, (meth)acrylic acid (3-ethyloxetan-3-yl)methyl, (meth)acrylic acid (3-methyloxetan-3-yl)ethyl, (meth)acrylic acid (3-ethyloxetan-3-yl)ethyl, (meth)acrylic acid (3-chloromethyloxetan-3-yl)methyl, and (meth)acrylic acid (oxetan-2-yl)methyl Examples include oxetanyl group-containing (meth)acrylates such as (2-methyloxetan-2-yl)methyl (meth)acrylate, (2-ethyloxetan-2-yl)methyl (meth)acrylate, (1-methyl-1-oxetanyl-2-phenyl)-3-(meth)acrylate, (1-methyl-1-oxetanyl)-2-trifluoromethyl-3-(meth)acrylate, and (1-methyl-1-oxetanyl)-4-trifluoromethyl-2-(meth)acrylate; and isocyanato group-containing (meth)acrylates such as 2-isocyanatoethyl (meth)acrylate. These polymerizable monomers containing functional groups that react with carboxyl groups may be used individually or in combination of two or more.

[0026] A method for introducing a constituent unit (b) having a carboxyl group, a constituent unit (c-1) having a (meth)acryloyloxy group, and a constituent unit (c-2) having a functional group that reacts with a carboxyl group into resin (A) can be achieved by appropriately combining the methods for introducing the above-described constituent units (b), (c-1), and (c-2). A preferred method involves using an epoxy group-containing (meth)acrylate (m-3) as the polymerizable monomer when producing a precursor of resin (A) by copolymerization, and opening the epoxy group by adding a carboxyl group-containing (meth)acrylic compound to a portion of the epoxy group, and then adding a polybasic acid anhydride to a portion of the hydroxyl group generated at that time. In other words, the constituent units introduced into resin (A) include a constituent unit having a carboxyl group (b) (a constituent unit derived from a polybasic acid anhydride), a constituent unit having a (meth)acryloyloxy group (c-1) (a constituent unit derived from a carboxyl group-containing (meth)acrylic compound (m-2)), and a constituent unit having a functional group that reacts with a carboxyl group (c-2) (a constituent unit derived from an epoxy group-containing (meth)acrylate in which unreacted epoxy groups remain). Alternatively, when producing a precursor of resin (A) by copolymerization, a carboxyl group-containing polymerizable monomer may be used as the polymerizable monomer, and an epoxy group-containing (meth)acrylate or an isocyanate group-containing (meth)acrylate may be added to some of the carboxyl groups derived from the carboxyl group-containing polymerizable monomer. In other words, the constituent units introduced into resin (A) include a constituent unit having a carboxyl group (b) and a constituent unit having a (meth)acryloyloxy group (c-1).

[0027] "Constituent unit (d)" The constituent unit (d) does not have an aromatic ring skeleton, a carboxyl group, a (meth)acryloyloxy group, or a functional group that reacts with a carboxyl group, but has a crosslinked alicyclic hydrocarbon group having 7 to 20 carbon atoms. By having constituent unit (d) in resin (A), a photosensitive resin composition can be obtained that gives a cured film with superior elastic recovery. Constituent unit (d) is introduced by using a polymerizable monomer (m-5) having a crosslinked alicyclic hydrocarbon group having 7 to 20 carbon atoms as the polymerizable monomer used when producing resin (A) by copolymerization (derived from a polymerizable monomer having a crosslinked alicyclic hydrocarbon group having 7 to 20 carbon atoms). Examples of polymerizable monomers (m-5) having a crosslinked alicyclic hydrocarbon group with 7 to 20 carbon atoms include dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, norbornene (bicyclo[2.2.1]hepto-2-ene), 5-methylbicyclo[2.2.1]hepto-2-ene, 5- Ethyl bicyclo[2.2.1]hepto-2-ene, tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]deca-8-ene, tricyclo[5. 2.1.02,6]deca-3-ene, tricyclo[4.4.0.12,5]undeca-3-ene, tricyclo[6.2.1.01,8]undeca-9-ene, tricyclo[6.2.1.01,8]undeca-4-ene, tetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3- Examples include ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,12]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadeca-4-ene, pentacyclo[7.4.0.12,5.19,12.08,13]pentadeca-3-ene, etc. Among these, tricyclodecanyl (meth)acrylate is preferred from the viewpoint of heat resistance. These polymerizable monomers having a cross-linked alicyclic hydrocarbon group with 7 to 20 carbon atoms may be used individually or in combination of two or more.

[0028] "Other constituent units (e)" The resin (A) of this embodiment may optionally have a constituent unit (e) derived from a radical polymerizable monomer (m-6) having an ethylenically active carbon-carbon double bond, other than the constituent units described above. Examples of radical polymerizable monomers (m-6) having an ethylenic carbon-carbon double bond include diene compounds such as butadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, cyclophosphate. Lopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth) (Meth)acrylic acid ester compounds such as acrylates, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-isopropyl (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, reaction products of (meth)acroyloxyethyl isocyanate (i.e., 2-isocyanatoethyl (meth)acrylate) with ε-caprolactam, and reaction products of (meth)acroyloxyethyl isocyanate with propylene glycol monomethyl ether;Examples include (meth)acrylamides such as (meth)acrylamide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N-diethylamide, (meth)acrylate N,N-dipropylamide, (meth)acrylate N,N-diisopropylamide, and (meth)acrylate anthracenylamide; vinyl compounds such as (meth)acrylate anilide, (meth)acrylonitrile, 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; and monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.

[0029] (Ratio of constituent units of resin (A)) The resin (A) used in this embodiment has a content of 5 to 50 mol% of the constituent unit (a) having the aromatic ring skeleton relative to the total amount of constituent units (total number of moles of constituent monomers). If the content of constituent unit (a) is 5 mol% or more, the photosensitive resin composition has good colorant dispersibility and good developability. If the content of constituent unit (a) is 50 mol% or less, the content of constituent unit (b), constituent unit (c), and constituent unit (d) can be sufficiently secured, so a photosensitive resin composition with a balanced set of necessary properties such as photocurability, developability, and elastic recovery rate as a cured product can be obtained. If necessary, the content of constituent unit (a) may be 5 to 10 mol%, 10 to 20 mol%, 20 to 30 mol%, 30 to 40 mol%, or 40 to 50 mol%.

[0030] In particular, the resin (A) used in this embodiment exhibits a synergistic effect by using two types of resins (A-1) and (A-2) with different content levels of the constituent units (a) having the aromatic ring skeleton, resulting in a cured film with improved elastic recovery, and a photosensitive resin composition with improved colorant dispersibility and developability. The content of the constituent units (a) having the aromatic ring skeleton in resin (A-1) is preferably 5 to 30 mol%, more preferably 5 to 25 mol%, relative to the total amount of constituent units in resin (A-1). The content may also be 5 to 8 mol%, 5 to 10 mol%, 5 to 15 mol%, or 10 to 20 mol%, as needed. The content of the constituent units (a) having the aromatic ring skeleton in resin (A-2) is preferably 35 to 50 mol%, more preferably 40 to 50 mol%, relative to the total amount of constituent units in resin (A-2). The aforementioned content may also preferably be 38-50 mol% or 42-45 mol% as needed.

[0031] When using two different types of resin (A) – resin (A-1) and resin (A-2) – as resin (A), the ratio of resin (A) to resin (A) is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and even more preferably 45 to 65% by mass. The ratio may also be 48 to 60% by mass, 50 to 58% by mass, etc. The ratio of resin (A) to resin (A) is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and even more preferably 35 to 55% by mass. The ratio may also be 38 to 53% by mass, 40 to 50% by mass, etc.

[0032] A preferred configuration of resin (A-1) is a resin in which a carboxyl group-containing (meth)acrylic compound (m-2) is added to the epoxy group of a resin (A) precursor, which is a polymer of an aromatic ring-containing polymerizable monomer (m-1), an epoxy group-containing (meth)acrylate (m-3), and a polymerizable monomer (m-5) having a crosslinked alicyclic hydrocarbon group with 7 to 20 carbon atoms, and further a polybasic acid (n-2) or polybasic acid anhydride (n-3) is added to the hydroxyl group formed by ring-opening of the epoxy group. By giving resin (A-1) such a configuration, the content of the aromatic ring skeleton-containing constituent unit (a) can be controlled while balancing the content of other constituent units, thereby obtaining a photosensitive resin composition with excellent colorant dispersibility and developability, and a cured film with excellent elastic recovery rate.

[0033] A preferred configuration of resin (A-2) is a resin in which an epoxy group-containing (meth)acrylate (m-3) or an isocyanate group-containing (meth)acrylate (m-4) is added to some of the carboxyl groups of the resin (A) precursor, which is a polymer of an aromatic ring-containing polymerizable monomer (m-1), a carboxyl group-containing polymerizable monomer (m-2), and a polymerizable monomer (m-5) having a crosslinked alicyclic hydrocarbon group with 7 to 20 carbon atoms. By giving resin (A-2) such a configuration, the content of the aromatic ring skeleton-containing constituent unit (a) can be controlled while balancing the content of other constituent units, thereby obtaining a photosensitive resin composition with excellent colorant dispersibility and developability, and a cured film with excellent elastic recovery rate.

[0034] The content of the constituent unit (b) having a carboxyl group is preferably 5 to 50 mol%, more preferably 8 to 40 mol%, even more preferably 10 to 30 mol%, and particularly preferably 13 to 25 mol%, relative to the total amount of constituent units (total number of moles of constituent monomers). The amount may also be 15 to 23 mol% or 18 to 20 mol%. When the content of constituent unit (b) is 5 mol% or more, a photosensitive resin composition with good developability can be obtained. When the content of constituent unit (b) is 50 mol% or less, it is possible to prevent the exposed area from being washed away during development, which reduces the residual film rate.

[0035] The content of the constituent unit (c-1) having a (meth)acryloyloxy group is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and even more preferably 12 to 30 mol%, relative to the total amount of constituent units (total number of moles of constituent monomers). The amount is also preferably 15 to 28 mol% or 18 to 25 mol%. When the content of constituent unit (c-1) is 5 mol% or more, a photosensitive resin composition with good photocurability, solvent resistance, and developability can be obtained. When the content of constituent unit (c-1) is 50 mol% or less, the photocurability can be kept within an appropriate range, and the generation of residue in unexposed areas during development can be prevented. In the case of resin (A-1), the content of constituent unit (c-1) is particularly preferably 20 to 30 mol%, and in the case of resin (A-2), it is particularly preferably 10 to 20 mol%.

[0036] The content of the constituent unit (c-2) having a functional group that reacts with the carboxyl group is preferably 0 to 20 mol%, more preferably 0 to 15 mol%, even more preferably 0 to 10 mol%, and particularly preferably 0 to 5 mol%, relative to the total amount of constituent units (total number of moles of constituent monomers). When the content of constituent unit (c-2) is 20 mol% or less, a photosensitive resin composition with good developability can be obtained. The content of constituent unit (c-1) is particularly preferably 0.1 to 5 mol% in the case of resin (A-1), and particularly preferably 0 mol% in the case of resin (A-2).

[0037] The content of the constituent unit (d) having a cross-linked alicyclic hydrocarbon group with 7 to 20 carbon atoms is preferably 1 to 40 mol%, more preferably 3 to 35 mol%, and even more preferably 5 to 30 mol%, relative to the total amount of constituent units (total number of moles of constituent monomers). The amount may be 8 to 25 mol%, 10 to 20 mol%, 15 to 18 mol%, etc., as needed. When the content of constituent unit (d) is 1 mol% or more, a cured film with excellent elastic recovery rate is obtained. When the content of constituent unit (d) is 40 mol% or less, a photosensitive resin composition with excellent curability is obtained. In the case of resin (A-1), the content of constituent unit (d) is particularly preferably 10 to 30 mol%, and in the case of resin (A-2), it is particularly preferably 5 to 10 mol%.

[0038] The resin (A) may incorporate constituent units (a), (b), (c), and (d) other than constituent unit (e) as needed. When introducing a constituent unit (e) other than constituent unit (a), constituent unit (b), constituent unit (c), and constituent unit (d), it is preferable that the amount of constituent unit (e) is greater than 0 mol% and up to 60 mol%, and more preferably greater than 0 mol% and up to 50 mol%, relative to the total amount of constituent units (total number of moles of constituent monomers). Examples of introducing structural units (e) other than structural units (a) to (d) include synthesizing resin (A) using radical polymerizable monomers having ethylenic carbon-carbon double bonds other than those used for introducing structural units (a) to (d) as described above, as well as the following examples of introduction. For example, in the case of the preferred configuration of resin (A-1), when a carboxyl group-containing (meth)acrylic compound is added to the epoxy group of the resin (A) precursor, which is a polymer containing epoxy group-containing (meth)acrylate, structural units derived from epoxy group-containing (meth)acrylate with unreacted epoxy groups remaining are counted as structural units (c-2) having functional groups that react with carboxyl groups. Furthermore, structural units derived from epoxy group-containing (meth)acrylate in which the epoxy group has disappeared after the addition of the carboxyl group-containing (meth)acrylic compound are counted as structural units (e) other than structural units (a), structural units (b), structural units (c), and structural units (d).

[0039] (Method of manufacturing resin (A)) The reaction conditions for the copolymerization reaction to obtain resin (A) used in this embodiment, or for the copolymerization reaction to obtain a resin (A) precursor before the addition reaction, can be set appropriately according to conventional methods. For example, the copolymerization reaction can be carried out for about 1 to 12 hours at a temperature of preferably 50 to 150°C, more preferably 60 to 140°C, while adding a polymerizable monomer for copolymerization and a polymerization initiator dropwise into a solvent. For the addition reaction to the resin (A) precursor, the resin (A) precursor and the monomer for the addition reaction can be added to a solvent, and an addition reaction catalyst can be added further, and the reaction can be carried out for about 3 to 12 hours at a temperature of preferably 50 to 150°C, more preferably 80 to 130°C. It is not a problem if the solvent used in the copolymerization reaction to obtain the resin (A) precursor is present in this addition reaction. Therefore, after the copolymerization reaction to obtain the resin (A) precursor is completed, the addition reaction can be carried out immediately without removing the solvent.

[0040] The solvent that can be used in the copolymerization reaction is not particularly limited, and any known solvent can be used as appropriate. Specific examples of solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, and tripropylene (Poly)alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl-3-methoxybutyl acetate, methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-acetate Examples of solvents include ester compounds such as -propyl, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbon compounds such as toluene and xylene; and carboxylic acid amide compounds such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used individually or in combination of two or more.

[0041] Among these, (poly)alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, i.e., glycol ether-based solvents, are preferred.

[0042] The amount of solvent used for the copolymerization reaction is not particularly limited, but generally it is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, when the total amount of monomers charged is 100 parts by mass. Using 1000 parts by mass or less of solvent is preferable because it efficiently suppresses the decrease in molecular weight of resin (A) due to chain transfer and allows the viscosity of resin (A) to be controlled within an appropriate range. On the other hand, using 30 parts by mass or more of solvent is preferable because it prevents abnormalities from occurring in the copolymerization reaction and allows the copolymerization reaction to be carried out stably. It also prevents discoloration and gelation of resin (A).

[0043] The polymerization initiator that can be used in the copolymerization reaction is not particularly limited, and known ones can be used as appropriate. Specific examples of polymerization initiators include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used individually or in combination of two or more. The amount of polymerization initiator used is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 0.7 to 15 parts by mass, and more preferably 1 to 10 parts by mass, when the total amount of monomer charged is 100 parts by mass.

[0044] The type of addition catalyst used to add a monomer to the resin (A) precursor is not particularly limited and can be selected as needed. Examples of addition catalysts include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelate compounds. These addition catalysts may be used individually or in combination of two or more. The amount of addition catalyst used is not particularly limited, but is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass, when the amount of resin (A) precursor is 100 parts by mass.

[0045] When adding monomers to a resin (A) precursor, it is preferable to add a polymerization inhibitor to prevent gelation. The type of polymerization inhibitor is not particularly limited and is selected as needed. Examples of polymerization inhibitors include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene. These polymerization inhibitors may be used individually or in combination of two or more. The amount of polymerization inhibitor used is not particularly limited, but is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass, when the amount of resin (A) precursor is 100 parts by mass.

[0046] (Properties of resin (A)) The resin (A) used in the present invention preferably has a weight-average molecular weight obtained by gel permeation chromatography (GPC) in terms of polystyrene equivalent of 1,000 to 50,000, more preferably 3,000 to 40,000, and even more preferably 5,000 to 20,000. A weight-average molecular weight of 1,000 or more is preferable because it prevents pattern defects from occurring after alkaline development. On the other hand, a weight-average molecular weight of 50,000 or less is preferable because it results in a suitable development time, making it practical for use.

[0047] The acid value (JIS K6901 5.3) of resin (A) used in the present invention is not limited as long as it achieves the desired effects of the present invention, but is usually 20 to 300 KOH mg / g, preferably 30 to 200 KOH mg / g. An acid value of 20 KOH mg / g or higher is preferable because it results in good developability. On the other hand, an acid value of 300 KOH mg / g or lower is preferable because the exposed portion (photocured portion) becomes less soluble in alkaline developer.

[0048] The unsaturated group equivalent of resin (A) used in the present invention is not limited as long as it achieves the desired effects of the present invention, but is usually 100 to 4000 g / mol, preferably 200 to 2000 g / mol, and more preferably 300 to 500 g / mol. An unsaturated group equivalent of 100 g / mol or more is preferable because it is effective in improving the physical properties of the coating film and alkali developability. On the other hand, an unsaturated group equivalent of 4000 g / mol or less is preferable because it is effective in further improving sensitivity. The unsaturated group equivalent is the mass of resin (A) per mole of unsaturated bonds (ethylenically active carbon-carbon double bonds) in resin (A). The unsaturated group equivalent can be determined by dividing the mass of resin (A) by the number of unsaturated groups in resin (A) (g / mol). In this specification, the unsaturated group equivalent is a theoretical value calculated from the amount of raw material used to introduce the unsaturated groups.

[0049] The epoxy equivalent of resin (A) used in the present invention is not limited as long as it achieves the desired effects of the present invention, but is usually 100 to 4000 g / mol, preferably 200 to 2000 g / mol, and more preferably 300 to 500 g / mol. An epoxy equivalent of 100 g / mol or more is effective and preferable for improving the physical properties of the coating film and storage stability. Conversely, an epoxy equivalent of 4000 g / mol or less is effective for further improving solvent resistance. The epoxy equivalent refers to the mass of polymer per mole of epoxy groups of the polymer. This value can be obtained by dividing the mass of the polymer by the amount of epoxy groups of the polymer (g / mol). In this specification, "epoxy equivalent" is a theoretical value calculated from the amount of raw materials used to introduce epoxy groups.

[0050] (Amount of resin (A)) The amount of resin (A) is not particularly limited, but is preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass, per 100 parts by mass of the total amount of the photosensitive resin composition excluding solvent (C). If the amount of resin (A) is 5% by mass or more, it is preferable because it has good curability. On the other hand, if the amount of resin (A) is 40 parts by mass or less, it is preferable because it has good coatability.

[0051] [Reactive Diluent (B)] The reactive diluent (B) used in this embodiment is a compound having at least one ethylenically unsaturated group in its molecule. Compounds having multiple ethylenically unsaturated groups are preferred. By using the reactive diluent (B), the strength of the cured film and its adhesion to the substrate can be improved.

[0052] Examples of monofunctional monomers used as reactive diluents (B) include (meth)acrylamide, methylol(meth)acrylamide, methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, and 2-phenoxy-2-hydroxypropyl(meth)acrylate. Examples include (meth)acrylate compounds such as roxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylates of phthalic acid derivatives; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate. These monofunctional monomers may be used individually or in combination of two or more.

[0053] Examples of polyfunctional monomers used as reactive diluents (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylol glycol di(meth)acrylate, and trimethylol glycol di(meth)acrylate. Pantri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl( Examples include (meth)acrylate compounds such as meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), reaction products of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate, and tri(meth)acrylate of tris(hydroxyethyl) isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; dicarboxylic acid ester compounds such as divinyl adipate; triallyl cyanurate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohols with N-methylol(meth)acrylamide. These polyfunctional monomers may be used individually or in combination of two or more.

[0054] Among these, dipentaerythritol hexa(meth)acrylate is preferred from the viewpoint of adhesion.

[0055] The amount of reactive diluent (B) is not particularly limited, but is preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass, per 100 parts by mass of the total amount of the photosensitive resin composition excluding solvent (C). If the amount of reactive diluent (B) is 10 parts by mass or more, it is preferable because the photosensitive resin composition has good photocurability. If the amount of reactive diluent (B) is 40 parts by mass or less, it is preferable because residue of unexposed areas is less likely to occur after exposure and development of the coating film of the photosensitive resin composition.

[0056] [Solvent (C)] The solvent (C) used in this embodiment is not particularly limited as long as it is an inert solvent that can dissolve the resin (A) and does not react with the resin (A), and can be arbitrarily selected. Furthermore, it is preferable that the solvent (C) is compatible with the reactive diluent (B) described above. The same solvent that can be used when manufacturing the resin (A) can be used as the solvent (C). As the solvent (C), (poly)alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate are preferred.

[0057] Solvent (C) can be added as appropriate to the isolated resin (A) after the copolymerization reaction has been completed, by isolating the target resin (A) from the resin (A) solution. However, it is not always necessary to isolate the target resin (A) from the resin solution. The solvent contained in the resin (A) solution at the end of the copolymerization reaction can be used as solvent (C) without separating it from the resin (A) solution. If necessary, other solvents may be added to the resin (A) solution. Alternatively, solvents contained in other components used in preparing the photosensitive resin composition may be used as solvent (C).

[0058] The amount of solvent (C) is not particularly limited, but it is preferably 150 to 300 parts by mass, and more preferably 200 to 250 parts by mass, per 100 parts by mass of the total amount of the photosensitive resin composition excluding solvent (C). If the amount of solvent (C) is 150 parts by mass or more, the photosensitive resin composition has good coatability, which is preferable. On the other hand, if the amount of solvent (C) is 300 parts by mass or less, the coating film can have a sufficient thickness, which is preferable.

[0059] [Photopolymerization initiator (D)] The photopolymerization initiator (D) used in this embodiment is not particularly limited, but examples include benzoin compounds 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, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; and 2-methylanthraquinone. Examples include anthraquinone compounds such as 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; xanthone compounds such as xanthone, 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. These photopolymerization initiators may be used individually or in combination of two or more.

[0060] The amount of photopolymerization initiator (D) is not particularly limited, but is preferably 0.03 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.3 to 6 parts by mass, per 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). The above amount may be 0.5 to 8 parts by mass or 1 to 5 parts by mass, as needed. An amount of photopolymerization initiator (D) of 0.03 parts by mass or more is preferable because the photosensitive resin composition has sufficient photocurability. On the other hand, an amount of photopolymerization initiator (D) of 15 parts by mass or less is preferable because it is less likely to produce residue in the unexposed areas after development.

[0061] [Coloring agent (E)] The colorant (E) is not particularly limited as long as it is soluble or dispersed in the solvent (C). Examples of colorants (E) include dyes and pigments. As the colorant (E), only dyes may be used, only pigments may be used, or a combination of dyes and pigments may be used. When the resin-cured film of the photosensitive resin composition of this embodiment is used as a black matrix, a color filter, or a black column spacer, the above-mentioned colorant (E) can be used alone or in combination of two or more types, depending on the purpose of the component formed by the resin-cured film. For example, if a black colorant (E) is used, the resin-cured film of the photosensitive resin composition becomes suitable as a black matrix and a black column spacer.

[0062] Examples of dyes include, for example, 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; acid red1, 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, 11 4,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274;acid violet 6B, 7, 9, 17, 19;acid Examples include 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 and its derivatives.

[0063] Among these dyes, it is preferable to use azo, xanthene, anthraquinone, or phthalocyanine-based acid dyes. These dyes may be used individually or in mixtures of two or more.

[0064] Examples of pigments include, for example, 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, 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; and CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192. Examples include red pigments such as 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, and 58; brown pigments such as CI Pigment Brown 23 and 25; and black pigments such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, and iron oxide.

[0065] These pigments may be used individually or in mixtures of two or more. As for the black pigment, an organic black pigment is preferred, and lactam-based organic black is more preferred, from the viewpoint of the optical density of the image display element having a resin-cured film of the photosensitive resin composition of this embodiment.

[0066] The amount of colorant (E) is not particularly limited, but is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, and even more preferably 20 to 40 parts by mass, per 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). The above amount may be 25 to 45 parts by mass or 30 to 35 parts by mass, etc., as needed. If the amount of colorant (E) is 10 parts by mass or more, the cured film will have sufficient color reproducibility, and if a black pigment is used as the colorant (E), it will have sufficient light-shielding properties, which is preferable. On the other hand, if the amount of colorant (E) is 50 parts by mass or less, it is preferable because residue of unexposed areas is less likely to occur after development.

[0067] [Dispersant (F)] The photosensitive resin composition of this embodiment may contain a dispersant (F). Any known dispersant can be used as the dispersant (F) without particular limitation. Using a dispersant (F) improves the dispersibility of the colorant, especially when a pigment is used as the colorant (E). As the dispersant (F), a polymeric dispersant is preferable due to its excellent dispersion stability over time. Any polymeric dispersant can be selected, but examples 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. Such polymeric dispersants may be commercially available under trade names such as EFKA (registered trademark, manufactured by BASF Japan), Disperbyk (registered trademark, manufactured by Bic Chemie), Disparon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (registered trademark, manufactured by Zeneca). The amount of dispersant should be appropriately set according to the type of pigment used.

[0068] The amount of dispersant (F) is not particularly limited, but is preferably 0.03 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.3 to 6 parts by mass, per 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent (C). The above amount may be 1 to 8 parts by mass, 2 to 5 parts by mass, etc., as needed. An amount of dispersant (F) of 0.03 parts by mass or more is preferable because it further enhances dispersibility. On the other hand, an amount of dispersant (F) of 15 parts by mass or less is preferable because it reduces the likelihood of unexposed residue after development.

[0069] The photosensitive resin composition of this embodiment may contain known additives such as coupling agents, leveling agents, and thermal polymerization inhibitors, as long as they do not impair the effects of the present invention. The amount of these additives is not particularly limited, as long as it does not impair the effects of the present invention.

[0070] <Method for producing a photosensitive resin composition> The photosensitive resin composition of this embodiment can be manufactured by mixing the above-mentioned components using a known mixing apparatus.

[0071] One embodiment of a method for producing a photosensitive resin composition is a method comprising the following steps I and II in that order. Step I: A step of mixing resin (A1), solvent (C1), colorant (E), and a dispersant of any component (F). Step II: A step of mixing the resin (A2), reactive diluent (B), solvent (C2), photopolymerization initiator (D), and the mixture obtained in Step I.

[0072] The solvent (C1) in step I and the solvent (C2) in step II, which are mixed as solvent (C) in the photosensitive resin composition, may be of the same type or different types. Furthermore, the solvent (C1) or solvent (C2) used in each step may be the aforementioned solvent (C) used alone or two or more types may be used.

[0073] Similarly, the resin (A1) in step I and the resin (A2) in step II, which are mixed as resin (A) in the photosensitive resin composition, may be the same type of resin or different types of resin. Furthermore, the resin (A1) or resin (A2) used in each step may be the same resin (A) as described above, or two or more types may be used.

[0074] In order to further improve the balance of all properties of the photosensitive resin composition, such as the colorant dispersibility, development time, and elastic recovery rate of the cured product, it is preferable to use different types of resin (A) for resin (A1) in step I and resin (A2) in step II. The combination of different types of resin (A) used for resin (A1) and resin (A2) is not particularly limited, but a synergistic effect is achieved by using two types of resin (A-1) and resin (A-2) with different content of the constituent unit (a) having the aromatic ring skeleton in the photosensitive resin composition. As described above, the content of the constituent unit (a) having the aromatic ring skeleton in resin (A-1) is preferably 5 to 30 mol%, more preferably 5 to 25 mol%, relative to the total amount of constituent units in resin (A-1). The resin (A-2) contains a constituent unit (a) having the aromatic ring skeleton, preferably in an amount of 35 mol% to 50 mol%, and more preferably 40 to 50 mol%, relative to the total amount of constituent units in the resin (A-2).

[0075] <Cured resin film> The resin-cured film of this embodiment is a resin-cured film obtained by photocuring the photosensitive resin composition of this embodiment. The resin-cured film of this embodiment is suitable as a black matrix, color filter, black column spacer, and BPDL, which are components of an image display element, because it has good colorant dispersibility, solvent resistance, and elastic recovery rate.

[0076] <Method for manufacturing hardened resin film> The resin cured film of this embodiment can be manufactured, for example, by the method shown below. First, a photosensitive resin composition is applied to the surface to be formed on the resin-cured film to create a resin layer (coating). Next, the resin layer is exposed to light through a mask with a predetermined pattern, and the exposed portion is photocured. Then, the unexposed portion of the resin layer is developed with a developer to create a resin-cured film with a predetermined pattern. After that, if necessary, the resin-cured film is post-baked (heat treated). When exposing the resin layer, a halftone mask with a predetermined pattern may be used. In this case, the unexposed and partially exposed areas are developed with a developer to obtain a resin-cured film having the predetermined pattern.

[0077] The substrate material is not particularly limited, but examples include glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide-imide substrates, polyimide substrates, aluminum substrates, printed circuit boards, array substrates, and the like.

[0078] The method for applying the photosensitive resin composition is not particularly limited, but examples include screen printing, roll coating, curtain coating, spray coating, and spin coating. After applying the photosensitive resin composition, the solvent (C) contained in the resin layer may be volatilized by heating using a heating means such as a circulating oven, infrared heater, or hot plate, if necessary. The heating conditions after application are not particularly limited and can be set appropriately according to the composition of the photosensitive resin composition. For example, the heating temperature after application can be 50°C to 120°C, and the heating time can be 30 seconds to 30 minutes.

[0079] The method for exposing the resin layer is not particularly limited, but examples include irradiation with active energy rays such as ultraviolet light and excimer laser light. The amount of energy irradiated can be appropriately set according to the composition of the photosensitive resin composition. For example, 30 to 2000 mJ / cm². 2 It is preferable that this be the case, but the range is not limited to this. The light source used for exposure is not particularly limited, but low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc., can be arbitrarily selected and used.

[0080] The alkaline developer used for developing is not particularly limited and includes, for example, aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; and aqueous solutions of p-phenylenediamine compounds such as tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates. Antifoaming agents, surfactants, etc., may be added to these alkaline developers as needed. Furthermore, it is preferable to wash with water and dry after developing with the alkaline developer.

[0081] The curing of the resin can be further advanced by post-baking the resin-cured film formed by alkaline development. The post-baking conditions are not particularly limited and can be arbitrarily selected. Depending on the composition of the photosensitive resin composition, preferred conditions can be selected and the heat treatment performed. For example, heating may be performed at a temperature of 130°C to 250°C for 10 minutes to 4 hours, more preferably for 20 minutes to 2 hours.

[0082] The resin-cured film produced in this manner exhibits excellent colorant dispersibility and elastic recovery.

[0083] <Image display element> Specific examples of image display elements include liquid crystal display elements and organic EL display elements. There are no restrictions on the manufacturing of image display elements, and they can be manufactured according to conventional methods. [Examples]

[0084] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0085] An example of resin (A) synthesis is shown below. [Synthesis Example 1] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 140 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while purging nitrogen gas into the flask, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 68.0 g (molar ratio 0.3), 11.0 g (molar ratio 0.1), and 88.0 g (molar ratio 0.6) tricyclodecanyl methacrylate was prepared separately by adding 18.4 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 2 hours. After the addition was complete, the mixture was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and produce a precursor of resin (A-1). Subsequently, the flask was purged with air, and 43.4 g (molar ratio 0.58), 1.1 g (catalyst), and 0.1 g (polymerization inhibitor) acrylic acid, methylhydroquinone were added to the above resin (A-1) precursor solution. The reaction was then continued at 110°C for 10 hours. Next, 61.0 g of tetrahydrophthalic anhydride (molar ratio 0.39) was added to the flask, and the reaction was continued at 110°C for 3 hours to obtain a solution of resin (A-1) (resin sample No. p1). The acid value of resin (A-1) contained in this resin solution was 79 KOH mg / g, the weight-average molecular weight was 8300, and the unsaturated group equivalent was 480. Propylene glycol monomethyl ether acetate was further added to this resin solution to prepare the resin (A-1) solution (solid content concentration 44% by mass) of Synthesis Example 1. The solid content refers to the residue after heating the resin solution at 130°C for 2 hours, and consists mainly of resin (A-1) and polymerization initiator.

[0086] [Synthesis Examples 2-5, Comparative Synthesis Example 1] Except for using the materials in Table 1, solutions of resin (A-1) (resin samples No. p2-5, No. cp1) from Synthesis Examples 2-5 and Comparative Synthesis Example 1 were obtained in the same manner as in Synthesis Example 1. Propylene glycol monomethyl ether acetate was further added to these resin solutions to prepare resin (A-1) solutions (solid content concentration 44% by mass) from Synthesis Examples 2-5 and Comparative Synthesis Example 1. Table 1 shows the acid value, weight-average molecular weight, and unsaturated group equivalent for each resin (A-1) (resin samples No. p2~5, No. cp1).

[0087] [Synthesis Example 6] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 140 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while purging nitrogen gas into the flask, and the temperature was raised to 120°C. Next, a monomer mixture consisting of 24.9 g (molar ratio 0.1), 99.6 g (molar ratio 0.5), and 38.9 g (molar ratio 0.4) of tricyclodecanyl methacrylate was prepared separately by adding 4.3 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O). This monomer and polymerization initiator mixture was added dropwise to the flask from a dropping funnel over a period of 2 hours. After the addition was complete, the mixture was stirred at 120°C for a further 2 hours to carry out the copolymerization reaction and synthesize the precursor of resin (A-2). Subsequently, the flask was purged with air, and 24.1 g (molar ratio 0.15), 1.8 g (catalyst) of triphenylphosphine, and 1.0 g (polymerization inhibitor) of methylhydroquinone were added to the above resin (A-2) precursor solution. The reaction was then continued at 110°C for 10 hours to obtain a solution of resin (A-2). The acid value of resin (A-2) contained in this solution was 80 KOH mg / g, the weight-average molecular weight was 9000, and the unsaturated group equivalent was 1200. Propylene glycol monomethyl ether acetate was further added to this resin solution to prepare a solution of resin (A-2) (resin sample No. p6) from Synthesis Example 6 (solid content concentration 40% by mass).

[0088] [Synthesis Example 7, Comparative Synthesis Example 2] A solution of resin (A-2) was obtained in the same manner as in Synthesis Example 6, except that the materials in Table 1 were used. Propylene glycol monomethyl ether acetate was further added to this resin solution to prepare solutions of resin (A-2) (resin samples No. p7, No. cp2) (solid content concentration 40% by mass) for Synthesis Example 7 and Comparative Synthesis Example 2. Table 1 shows the acid value, weight-average molecular weight, and unsaturated group equivalent for each resin (A-2) (resin samples No. p1~p7, mp1, mp2).

[0089] [Table 1]

[0090] <Method for measuring physical properties> The acid value, unsaturated group equivalent, and weight-average molecular weight listed in the synthesis examples are values ​​obtained by the method described below. (1) Acid value: This is the acid value of resin (A) measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K6901 5.3.2. It represents the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of resin (A). (2) Unsaturated group equivalent: This is the mass of polymer per mole of polymerizable unsaturated bonds, and is a calculated value based on the amount of monomer used. (3) Weight-average molecular weight (Mw): This refers to the weight-average molecular weight converted to standard polystyrene, measured using gel permeation chromatography (GPC) under the following conditions. Column: Showdex® LF-804 + LF-804 (manufactured by Showa Denko K.K.) Column temperature: 40℃ Sample: 0.2% tetrahydrofuran solution of copolymer Developing solvent: tetrahydrofuran Detector: Differential refractometer (Showdex® RI-71S) (manufactured by Showa Denko Corporation) Flow rate: 1mL / min

[0091] An example of preparing a colorant dispersion (mill base) by mixing resin (A1), solvent (C1), colorant (E), and dispersant (F) is shown below.

[0092] [Example 1] Mill base (sample No. m1) was prepared by mixing 10.7 parts by mass of resin (A-1) (resin sample No. p1) from synthesis example 1 as resin (A1) on a solid content basis, 200 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as solvent (C1), 35.7 parts by mass of 3,7-bis(2-oxo-1H-indole3(2H)-ylidene)benzo[1,2-b:4,5-b']difuran-2,6-(3H,7H)-dione (IBS0100CF, product name: Irgaphor Black S 0100CF, manufactured by BASF) as colorant (E), and 3.7 parts by mass of Azispar PB822 (PB822, manufactured by Ajinomoto Fine Techno Co., Ltd.) as dispersant (F) in a paint shaker for 3 hours. The amount of solvent contained in the resin (A-1) solution of Synthesis Example 1 is added to the amount of solvent (C1) as a compounding component.

[0093] [Examples 2-4, 6, 7; comparative examples 1, 2] Mill bases (samples No. m2-m4, m6, m7, cm1, cm2) for Preparation Examples 2-4, 6, 7 and Comparative Preparation Examples 1, 2 were prepared in the same manner as Preparation Example 1, except that the formulations (based on parts by mass) listed in Table 2 below were used.

[0094] [Table 2]

[0095] Examples of photosensitive resin compositions prepared by mixing resin (A2), reactive diluent (B), solvent (C2), photopolymerization initiator (D), and the mill base from the above-mentioned example are shown below.

[0096] [Example 1] As resin (A2), 9.3 parts by mass of resin (A-1) (resin sample No. p1) from synthesis example 1 was used on a solid content basis; as reactive diluent (B), 37 parts by mass of dipentaerythritol hexaacrylate (DPHA, product name: A-DPH, manufactured by Shin Nakamura Kogyo Co., Ltd.) was used; as solvent (C2), 33 parts by mass of propylene glycol monomethyl ether acetate was used; and as photopolymerization initiator (D), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetyloxime) (OXE 02, product name: IRGACURE OXE) was used. A photosensitive resin composition was prepared by mixing 3.7 parts by mass of 02 (BASF) and the mill base from Preparation Example 1 (a mixture of mill base sample No. m1, 10.7 parts by mass of resin (A-1) (resin sample No. 1) from Synthesis Example 1 on a solid content basis, 200 parts by mass of PGMEA, 35.7 parts by mass of IBS0100CF, and 3.7 parts by mass of Adisper PB822). In the formulations shown in Table 3, 10.7 parts by mass of resin (A1) contained in the mill base (marked with "*1" in Table 3, meaning that it was a resin contained in the mill base) and 9.3 parts by mass of newly added resin (A2) (resin sample No. p1) are listed as components of resin (A) on a solid content basis. The amount of solvent contained in the resin (A-1) solution from Synthesis Example 1 is included in solvent (C) as a component of the formulation. Furthermore, the 200 parts by mass of solvent (C1) that was included in the mill base and the 33 parts by mass of solvent (C2) that was newly added are listed together as solvent (C) component.

[0097] [Examples 2-17, Comparative Examples 1-8] The photosensitive resin compositions for Examples 2-17 and Comparative Examples 1-8 were prepared in the same manner as in Example 1, except that the formulations shown in Tables 3-5 were used.

[0098] [Table 3]

[0099] [Table 4]

[0100] [Table 5]

[0101] <Evaluation of colorant dispersibility> The dispersibility of the colorant in the photosensitive resin composition was evaluated by the method described below. First, the photosensitive resin compositions of Examples 1-17 and Comparative Examples 1-8 were spin-coated onto a 10cm x 10cm IZO substrate to a coating thickness of 1.5μm. Afterward, the solvent was evaporated by heating at 90°C for 3 minutes. Next, the entire surface of the coating was exposed to light using a Ushio Inc. Multi-Light ML-251D / B and illumination optical unit PM25C-100 (exposure dose 50mJ / cm²). 2 The material was then photocured. Subsequently, it was developed with a 0.2% by mass potassium hydroxide aqueous solution for 120 seconds, and then post-baked at 230°C for 30 minutes to obtain the desired cured coating film. The optical density (OD) of the 1 μm thick cured coating film was measured using a transmission densitometer (361T, X-lite). The results are shown in Tables 6-8. A higher optical density indicates better dispersibility of the colorant.

[0102] <Evaluation of elastic recovery rate> A 2.5 μm coating film was prepared on a substrate using the same method as for optical density, and the compressive displacement and elastic recovery rate were measured at 25°C using an elasticity measuring device (DUH-W201S, Shimadzu Corporation) according to the following measurement conditions. A flat pressing body with a diameter of 50 μm was used as the pressing body to press the pattern, and the load was applied and unloaded using a loading-unloading method. The elastic recovery rate was measured in a test in which a load of 300 mN was applied to obtain distinguishable results between the groups being compared. A loading rate of 3 gf / sec and a holding time of 3 seconds were kept constant. Regarding the elastic recovery rate, a constant load was applied to the flat pressing body for 3 seconds, and then the actual elastic recovery rate of the pattern before and after loading was measured using a three-dimensional thickness measuring device. The elastic recovery rate is the ratio of the distance recovered after a recovery time of 10 minutes to the distance compressed when a constant force was applied (compression displacement), and it is expressed by the following formula. Elastic recovery rate (%) = [(Recovery distance / Compression displacement) × 100] The results are shown in 6-8.

[0103] <Evaluation of developability> The photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 to 8 were spin-coated onto a 10 cm x 10 cm IZO substrate (a substrate with an IZO wiring pattern formed on its surface) to a coating thickness of 1.5 μm. The solvent was then evaporated by heating the IZO substrate at 90°C for 3 minutes. Next, a pattern mask was placed on the coating, and the mask was exposed using a Ushio Inc. Multi-Light ML-251D / B and illumination optical unit PM25C-100 (exposure dose 120 mJ / cm²). 2 The film was then photocured. Afterwards, it was developed with a 0.2% by mass potassium hydroxide aqueous solution, and the development time (the time from when the unexposed areas began to be washed away until the pattern change disappeared) and the development form were confirmed. There are two types of development: peeling, where the unexposed areas are washed away as they peel off, and dissolution, where the unexposed areas are washed away as they dissolve. Dissolution is preferable because peeling can lead to display defects. Powder dissolution refers to a form in which the unexposed areas dissolve while a small amount of powder remains. The results are shown in 6-8. ◎(Excellent): Development time is 10-40 seconds and development method is complete dissolution. ○ (Acceptable): Development time is 10-40 seconds and development method is powder dissolution. × (Not acceptable): Development time of 41 seconds or longer, and development method of complete peeling or powder peeling.

[0104] [Table 6]

[0105] [Table 7]

[0106] [Table 8]

[0107] From the above results, the photosensitive resin compositions of Examples 1 to 17 exhibited excellent colorant dispersibility, developability, and elastic recovery rate. On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 8 were inferior in their evaluation of colorant dispersibility, developability, and elastic recovery rate. [Industrial applicability]

[0108] The present invention provides a photosensitive resin composition that exhibits excellent colorant dispersibility, developability, and elastic recovery rate. The photosensitive resin composition of the present invention exhibits excellent colorant dispersibility, developability, and elastic recovery rate. Therefore, the cured resin film obtained by curing the photosensitive resin composition of the present invention also exhibits excellent colorant dispersibility and elastic recovery rate. Such a cured resin film is suitable as a black matrix, color filter, black column spacer, and BPDL, which are components of image display elements.

Claims

1. Resin (A) and Reactive diluent (B), Solvent (C) and Photopolymerization initiator (D), Coloring agent (E), A photosensitive resin composition containing, The aforementioned resin (A) A constituent unit (a) having an aromatic ring skeleton, A constituent unit (b) having a carboxyl group, A constituent unit (c-1) having a (meth)acryloyloxy group, A constituent unit (d) having a cross-linked alicyclic hydrocarbon group with 7 to 20 carbon atoms, It has, The resin (A) contains resin (A-1) and resin (A-2), The resin (A-1) is a resin in which a carboxyl group-containing (meth)acrylic compound is added to the epoxy group of a resin (A-1) precursor having an epoxy group, and further a polybasic acid or polybasic acid anhydride is added to the hydroxyl group generated by ring-opening of the epoxy group. The resin (A-2) is a resin in which epoxy group-containing (meth)acrylate or isocyanate group-containing (meth)acrylate is added to a portion of the carboxyl groups of a resin (A-2) precursor having carboxyl groups. The epoxy group-containing resin (A-1) precursor is a polymer of an aromatic ring-containing polymerizable monomer, an epoxy group-containing (meth)acrylate, and a polymerizable monomer having a crosslinked alicyclic hydrocarbon group with 7 to 20 carbon atoms. The resin precursor (A-2) having a carboxyl group is a polymer of an aromatic ring-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, and a polymerizable monomer having a crosslinked alicyclic hydrocarbon group with 7 to 20 carbon atoms. The constituent unit (a) having an aromatic ring skeleton contained in the resin (A-1) is a constituent unit derived from styrene, and the content of the constituent unit (a) having an aromatic ring skeleton in the resin (A-1) is 5 to 30 mol% of the total amount of constituent units in the resin (A-1). A photosensitive resin composition characterized in that the constituent unit (a) having an aromatic ring skeleton contained in the resin (A-2) is a constituent unit derived from benzyl (meth)acrylate, and the content of the constituent unit (a) having an aromatic ring skeleton in the resin (A-2) is 35 mol% to 50 mol% of the total amount of constituent units in the resin (A-2).

2. The photosensitive resin composition according to claim 1, wherein the constituent unit (b) having a carboxyl group is one or more selected from the group consisting of a constituent unit derived from an unsaturated carboxylic acid (b-1), a constituent unit derived from a polybasic acid (b-2), and a constituent unit derived from a polybasic acid anhydride (b-3).

3. The photosensitive resin composition according to claim 1 or 2, wherein the resin (A-1) further comprises a constituent unit (c-2) having a functional group that reacts with a carboxyl group.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the constituent unit (a) having an aromatic ring skeleton is one or more selected from the group consisting of styrene-derived constituent units and benzyl (meth)acrylate-derived constituent units.

5. A photosensitive resin composition according to any one of claims 1 to 4, wherein the total amount of resin (A) contains 10 to 90% by mass of resin (A-1) and 10 to 90% by mass of resin (A-2).

6. The photosensitive resin composition according to claim 5, wherein the resin (A-1) is contained in an amount of 45 to 65% by mass and the resin (A-2) is contained in an amount of 35 to 55% by mass, based on the total amount of the resin (A).

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the coloring agent (E) is an organic black pigment.

8. A photosensitive resin composition according to any one of claims 1 to 7, further comprising a dispersant (F).

9. The aforementioned resin (A) is contained in an amount of 2 to 20% by mass. The reactive diluent (B) is contained in an amount of 3 to 20% by mass. The solvent (C) is contained in an amount of 50 to 90% by mass, and The photosensitive resin composition according to any one of claims 1 to 8, comprising 3 to 30% by mass of the coloring agent (E).

10. A black column spacer comprising a cured product of a photosensitive resin composition according to any one of claims 1 to 9.

11. An image display element characterized by comprising the black column spacer described in claim 10.

12. Step I: A step of mixing resin (A1), solvent (C1), colorant (E), and a dispersant of any component (F), Step II: A step of mixing the resin (A2), reactive diluent (B), solvent (C2), photopolymerization initiator (D), and the mixture obtained in Step I. A method for producing a photosensitive resin composition having the following in this order: The resin (A1) and the resin (A2) are, respectively, A constituent unit (a) having an aromatic ring skeleton, A constituent unit (b) having a carboxyl group, A constituent unit (c-1) having a (meth)acryloyloxy group, A constituent unit (d) having a cross-linked alicyclic hydrocarbon group with 7 to 20 carbon atoms and It has, The resin (A1) is either resin (A-1) or resin (A-2), The resin (A2) is the other of the resins (A-1) and (A-2) that is different from the resin (A1). The resin (A-1) is a resin in which a carboxyl group-containing (meth)acrylic compound is added to the epoxy group of a resin (A-1) precursor having an epoxy group, and further a polybasic acid or polybasic acid anhydride is added to the hydroxyl group generated by ring-opening of the epoxy group. The resin (A-2) is a resin in which epoxy group-containing (meth)acrylate or isocyanate group-containing (meth)acrylate is added to a portion of the carboxyl groups of a resin (A-2) precursor having carboxyl groups. The epoxy group-containing resin (A-1) precursor is a polymer of an aromatic ring-containing polymerizable monomer, an epoxy group-containing (meth)acrylate, and a polymerizable monomer having a crosslinked alicyclic hydrocarbon group with 7 to 20 carbon atoms. The resin precursor (A-2) having a carboxyl group is a polymer of an aromatic ring-containing polymerizable monomer, a carboxyl group-containing polymerizable monomer, and a polymerizable monomer having a crosslinked alicyclic hydrocarbon group with 7 to 20 carbon atoms. The constituent unit (a) having an aromatic ring skeleton contained in the resin (A-1) is a constituent unit derived from styrene, and the content of the constituent unit (a) having an aromatic ring skeleton in the resin (A-1) is 5 to 30 mol% of the total amount of constituent units in the resin (A-1). A method for producing a photosensitive resin composition, characterized in that the constituent unit (a) having an aromatic ring skeleton contained in the resin (A-2) is a constituent unit derived from benzyl (meth)acrylate, and the content of the constituent unit (a) having an aromatic ring skeleton in the resin (A-2) is 35 mol% to 50 mol% of the total amount of constituent units in the resin (A-2).

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