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

Abstract

Provided is a photosensitive resin composition having excellent low-temperature curability and capable of providing a cured resin film having sufficient solvent resistance or sufficient hardness. Also, provided are a color filter having excellent solvent resistance or excellent hardness, and an image display element having same. A photosensitive resin composition according to the present invention contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).　The copolymer (A) contains a structural unit (a), a structural unit (b), and a structural unit (c). The structural unit (a) has at least one selected from among an active methylene group having an alkoxycarbonyl group attached thereto, and an active methine group having an alkoxycarbonyl group attached thereto. The structural unit (c) has an acid group.

Description

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

[0001] The present disclosure relates to a photosensitive resin composition, a cured resin film, a color filter, and an image display device. This application claims priority based on Japanese Patent Application No. 2024-011275 filed on January 29, 2024, and Japanese Patent Application No. 2024-099982 filed on June 20, 2024, the contents of which are incorporated herein by reference.

[0002] Conventionally, some image display elements, such as displays, are equipped with color filters. Color filters are typically formed by baking and curing a resin composition on a substrate at a temperature exceeding 200°C. In recent years, with the trend toward more flexible and wearable displays, substrate materials have been increasingly switched from glass to organic materials such as resins. Furthermore, in order to realize image display elements with even higher brightness and contrast, colorants used in color filters have been increasingly switched from pigments to dyes and / or fluorescent compounds, quantum dots, and other materials.

[0003] Organic materials used as substrate materials have poorer heat resistance than glass. Furthermore, dyes used as colorants in color filters have poorer heat resistance than pigments. For these reasons, it is desirable to lower the heating temperature required for curing resin compositions used as color filter materials. Specifically, depending on the heat resistance of the substrate material and colorant materials, the heating temperature required for curing resin compositions used as color filter materials may be required to be 80 to 150°C, and in recent years, 80 to 100°C in particular. Furthermore, with growing awareness of environmental protection, a trend toward lowering heating temperatures is gaining attention, with the aim of reducing energy consumption during manufacturing.

[0004] If the heating temperature for curing the resin composition is low, it becomes difficult to obtain sufficient solvent resistance. In color filters provided in image display devices, the content of colorant in the resin composition used as the material for the color filter tends to be increased in order to improve color reproducibility. Furthermore, dyes have higher solubility in solvents than pigments. Therefore, if the solvent resistance of the color filter is insufficient, the dye contained in the color filter may dissolve in the solvent, causing a change in the chromaticity of the color filter.

[0005] Resin compositions capable of exhibiting these two contradictory properties are described, for example, in Patent Documents 1 to 3. Patent Documents 1 and 2 describe examples in which a copolymer having a thermal crosslinking mechanism derived from an inherent structure is given a characteristic as a condition necessary for providing a desired resin composition. Furthermore, Patent Document 3 describes an example in which a copolymer having a controlled glass transition temperature (Tg) is given a characteristic as a means for promoting the thermal crosslinking mechanism in order to provide a resin composition with the aim of further improving performance.

[0006] Patent No. 7189875 Patent No. 7306267 WO2022 / 138159

[0007] However, resin compositions using the copolymers described in Patent Documents 1 and 2 are unable to fully exhibit curability due to the characteristics of the thermal crosslinking mechanism of the copolymer, and are therefore unable to accommodate the low heating temperature range of 80 to 100°C that has become particularly popular in recent years. Furthermore, while resin compositions using the copolymers described in Patent Document 3 have demonstrated improved curability in low heating temperature ranges, the low glass transition temperature (Tg) can cause tackiness in the resin composition, potentially contaminating equipment and components that come into contact with the resin composition and adversely affecting processes during and after color filter production. Furthermore, in order to lower the glass transition temperature (Tg), an extreme use of specific monomers is required, which can have adverse effects on performance, such as the generation of haze and surface roughness due to poor compatibility with colorants, etc.

[0008] The present invention has been made in consideration of the above circumstances, and aims to provide a photosensitive resin composition and a photosensitive coloring composition that have excellent low-temperature curing properties and can form a cured resin film having sufficient solvent resistance. Another object of the present invention is to provide a photosensitive resin composition and a photosensitive coloring composition that can form a cured resin film having sufficient hardness. Another object of the present invention is to provide a cured resin film made of a cured product of the photosensitive resin composition of the present invention and having sufficient solvent resistance. Another object of the present invention is to provide a cured resin film made of a cured product of the photosensitive resin composition of the present invention and having sufficient hardness. Another object of the present invention is to provide a color filter having a color pattern made of a cured product of the photosensitive coloring composition of the present invention and having sufficient hardness and / or solvent resistance, and further to provide an image display element equipped with this color filter.

[0009] The present invention includes the following aspects. [1] A photosensitive resin composition containing a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A) contains structural units (a), (b), and (c), the structural unit (a) has one or more selected from an active methylene group having an alkoxycarbonyl group attached thereto and an active methine group having an alkoxycarbonyl group attached thereto, the structural unit (b) has a hydroxy group, and the structural unit (c) has an acid group. [2] The structural unit (a) has a group represented by the following formula (1) or (2), and the structural unit (b) has a —CH ２ The photosensitive resin composition according to [1], wherein the structural unit (c) has a group represented by —OH, the structural unit (c) is derived from acrylic acid, and the glass transition temperature (Tg) of the copolymer (A) is 20° C. or higher. (In formula (1), R １ and R ２ each independently represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site. (In formula (2), R ３represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site.) [3] The photosensitive resin composition according to [2], wherein the copolymer (A) further contains a structural unit (d) derived from an ethylenically unsaturated compound having an epoxy group or an oxetanyl group. [4] The photosensitive resin composition according to either [2] or [3], wherein the structural unit (a) in the copolymer (A) is a structural unit derived from a compound having a group represented by formula (1) or formula (2) and an acryloyloxy group. [5] The photosensitive resin composition according to [1], wherein the structural unit (a) has one or more selected from an active methylene group having a methoxycarbonyl group attached thereto and an active methine group having a methoxycarbonyl group attached thereto. [6] The photosensitive resin composition according to [5], wherein the structural unit (a) is a structural unit having one or more selected from the group consisting of a group represented by formula (i-1) below and a group represented by formula (ii-1) below: (In formula (i-1), n1 and n2 each independently represent an integer of 0 to 2. * represents a linking site.) (In formula (ii-1), n3 and n4 each independently represent an integer of 0 to 2. * represents a linking moiety.) [7] The photosensitive resin composition according to any one of [1] to [6], wherein the copolymer (A) further contains a structural unit (e) derived from a (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the copolymer (A) further contains a structural unit (f) derived from a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. [9] The photosensitive resin composition according to any one of [5] to [8], wherein the structural unit (a) of the copolymer (A) is a structural unit derived from a compound having an acryloyloxy group and one or more selected from the active methylene group having a methoxycarbonyl group attached and the active methine group having a methoxycarbonyl group attached.

[10] The structural unit (b) of the copolymer (A) is —(CH ２ ) ｎ Structural units having a group represented by —OH (n is an integer of 2 to 6) and —(O—C ｘ H ２ｘ ) ｍThe photosensitive resin composition according to any one of [1] to [9], wherein the reactive diluent (B) is at least one selected from the group consisting of structural units having a group represented by -OH (x is an integer of 2 to 4, and m is an integer of 2 to 6).

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

[10] , wherein the copolymer (A) has an acid value of 10 to 250 KOH mg / g.

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

[11] , wherein the copolymer (A) has a weight average molecular weight Mw of 3,000 to 50,000.

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

[12] , wherein the reactive diluent (B) is a compound having a plurality of ethylenically unsaturated groups.

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

[13] , wherein, when all structural units of the copolymer (A) are taken as 100 mol %, the copolymer (A) contains 1 to 40 mol % of the structural unit (a), 1 to 40 mol % of the structural unit (b), and 1 to 40 mol % of the structural unit (c).

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

[14] , wherein the solvent (D) is a glycol ether having a hydroxy group.

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

[15] , wherein the copolymer (A) is 10% by mass or more and less than 100% by mass, relative to 100% by mass of the total of the copolymer (A) and the reactive diluent (B), the reactive diluent (B) is more than 0% by mass and 90% by mass or less, the photopolymerization initiator (C) is 0.1 to 30 parts by mass, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B), and the solvent (D) is 30 to 1000 parts by mass, relative to 100 parts by mass of the total of the components excluding the solvent (D).

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

[16] , further containing a colorant (E).

[18] The photosensitive resin composition according to

[17] , wherein the colorant (E) includes a pigment.

[19] The photosensitive resin composition according to any one of [5] to

[18] , wherein the hardness of a cured resin film of the photosensitive resin composition is 3H or more, the hardness being the hardness measured in accordance with JIS K5600-5-4 when the cured resin film is formed on a glass substrate to a thickness of 2.5 μm.

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

[17] to

[19] .

[21] A color filter having a colored pattern made of a cured product of the photosensitive resin composition according to any one of

[17] to

[19] .

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

[21] .

[0010] According to the present disclosure, it is possible to provide a photosensitive resin composition that gives a cured resin film having solvent resistance or hardness, and also to provide a cured resin film having excellent solvent resistance or hardness obtained by curing the resin composition, and an image display element including the same.

[0011] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below. In this specification, the term "(meth)acryloyloxy group" refers to one or more groups selected from a methacryloyloxy group and an acryloyloxy group. The same applies to "(meth)acrylic acid" and "(meth)acrylate." In addition, in this specification, when "to" is used to describe a numerical range, the numerical values ​​at both ends are the upper and lower limits, respectively, and are included in the numerical range. When multiple upper or lower limits are listed, numerical ranges can be created from all combinations of the upper and lower limits. Similarly, when multiple numerical ranges are listed, separate numerical ranges can be created by individually selecting and combining upper and lower limits from those numerical ranges.

[0012] In this specification, the term "structural unit having an XYZ group" refers to a structural unit having the same structure as the monomer unit corresponding to the monomer in a polymer produced by addition polymerization of a compound having an XYZ group and an ethylenically unsaturated group as a monomer. For example, when the original monomer (compound having a hydroxy group and an ethylenically unsaturated group) is 2-hydroxyethyl methacrylate, the "structural unit having a hydroxy group" is "-C(CH ３ ) (COOC ２ H ４ OH)CH ２It should be noted that a unit obtained by first addition-polymerizing a compound having an ethylenically unsaturated group but not having an XYZ group as a monomer, and then introducing an XYZ group into the monomer unit, also falls under the category of a "structural unit having an XYZ group."

[0013] In this specification, "structural unit derived from an ethylenically unsaturated compound having an XYZ group" means a structural unit having the same structure as the monomer unit corresponding to the monomer in a polymer produced by addition polymerization of the ethylenically unsaturated compound as a monomer. For example, acrylic acid is a type of ethylenically unsaturated compound having a carboxy group. The structural unit derived from acrylic acid is "-CH(COOH)-CH ２ Note that a unit obtained by first addition-polymerizing a compound having an ethylenically unsaturated group but not having an XYZ group as a monomer and then introducing an XYZ group into the monomer unit also falls under the category of a "structural unit derived from an ethylenically unsaturated compound having an XYZ group."

[0014] <Photosensitive Resin Composition> [First Embodiment] The photosensitive resin composition of the first embodiment of the present invention contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The photosensitive resin composition of this embodiment contains a colorant (E) as needed. The photosensitive resin composition of this embodiment is polymerized and cured by light irradiation to form a cured resin film.

[0015] [Copolymer (A)] The copolymer (A) contains structural units (a), (b), and (c). The structural unit (a) has one or more selected from an active methylene group connected to an alkoxycarbonyl group and an active methine group connected to an alkoxycarbonyl group, the structural unit (b) has a hydroxy group, and the structural unit (c) has an acid group. When a resin composition containing the copolymer (A) is thermally cured, the alkoxycarbonyl group of the structural unit (a) in the copolymer (A) undergoes ester exchange with the hydroxy group of the structural unit (b) to form a crosslinked structure. Therefore, a resin composition containing the copolymer (A) can be cured at a low temperature of 50°C to 150°C to obtain a cured film with excellent solvent resistance and hardness. The alkoxy group of the alkoxycarbonyl group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms.

[0016] The active methylene group means a group in which an electron-withdrawing group is bonded to at least one side (preferably both sides) of a methylene group, and examples of the electron-withdrawing group include a carbonyl group, an ester group, a cyano group, a nitro group, a sulfonyl group, a sulfinyl group, and a phosphono group. As the active methylene group, a structure in which a carbonyl group or an ester group is bonded to both sides of a methylene group is preferred, and a group in which an ester group is bonded to both sides of a methylene group, i.e., -COO-CH ２ The structural unit (a) preferably has a group represented by the following formula (i) or (ii):

[0017] (In formula (i), R １ and R ２ each independently represents an alkyl group having 1 to 10 carbon atoms; n1 and n2 each independently represent an integer of 0 to 2; * represents a linking site. (In formula (ii), R ３represents an alkyl group having 1 to 10 carbon atoms. n3 and n4 each independently represent an integer of 0 to 2. * represents a linking moiety.) Examples of the photosensitive resin composition of the first embodiment include the photosensitive resin composition of the second embodiment or the photosensitive resin composition of the third embodiment described below.

[0018] [Second embodiment] The photosensitive resin composition of the second embodiment contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The photosensitive resin composition of this embodiment contains a colorant (E) as needed. The photosensitive resin composition of this embodiment is polymerized and cured by light irradiation to form a cured resin film. The copolymer (A) used in the photosensitive resin composition of this embodiment contains a structural unit (a) (hereinafter also simply referred to as "structural unit (a)") having a group represented by the following formula (1) or the following formula (2), and a -CH ２ It contains a structural unit (b) having a group represented by —OH (hereinafter also simply referred to as “structural unit (b)”) and a structural unit (c) derived from acrylic acid (hereinafter also simply referred to as “structural unit (c)”).

[0019] (In formula (1), R １ and R ２ each independently represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site.

[0020] (In formula (2), R ３ represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site.

[0021] Copolymer (A) of this embodiment may further contain, as necessary, a structural unit (d) (hereinafter also simply referred to as "structural unit (d)") derived from an ethylenically unsaturated compound having an epoxy group or an oxetanyl group. Copolymer (A) of this embodiment may further contain, as necessary, a structural unit (e) (hereinafter also simply referred to as "structural unit (e)") derived from a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. Copolymer (A) of this embodiment may further contain, as necessary, a structural unit (f) (hereinafter also simply referred to as "structural unit (f)") derived from a (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms.

[0022] "Structural unit (a)" The structural unit (a) having a group represented by formula (1) or formula (2) constituting the copolymer (A) is a structural unit derived from a monomer (m-a) having a group represented by formula (1) or formula (2) (hereinafter also simply referred to as "monomer (m-a)"). The group represented by formula (1) or formula (2) of the structural unit (a) contained in the copolymer (A) undergoes transesterification with the hydroxy group of the structural unit (b) to form a crosslinked structure by thermally curing a resin composition containing the copolymer (A). Therefore, a resin composition containing the copolymer (A) can produce a cured film with excellent solvent resistance even when cured at a low temperature of 50°C to 150°C.

[0023] R in the above formula (1) １ and R ２ are each independently an alkyl group having 1 to 10 carbon atoms. １ and R ２ are each independently preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and R １ and R ２ Most preferably, both of R are ethyl groups having 2 carbon atoms. １ and R ２ is an ethyl group, when the resin composition containing the copolymer (A) is thermally cured, R １ and R ２is transesterified with the hydroxy group of the structural unit (b) to produce ethanol. The ethanol produced during the thermal curing of the resin composition is preferred because it can be easily evaporated and removed by heating for thermal curing the resin composition.

[0024] In addition, R in the above formula (2) ３ is an alkyl group having 1 to 10 carbon atoms. 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 having 2 carbon atoms. ３ is an ethyl group, when the resin composition containing the copolymer (A) is thermally cured, R ３ is transesterified with the hydroxy group of the structural unit (b) to produce ethanol. The ethanol produced during the thermal curing of the resin composition is preferred because it can be easily evaporated and removed by heating for thermal curing the resin composition.

[0025] The monomer (m-a) that provides the structural unit (a) is not particularly limited as long as it is a compound copolymerizable with the hydroxymethyl group-containing monomer (m-b) described below and acrylic acid. As the monomer (m-a), for example, from the viewpoint of reactivity when synthesizing the copolymer (A), a monomer having a group represented by the above formula (1) or (2) and an ethylenically unsaturated bond can be used. Specific examples of the group having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group. From the viewpoint of the degree of freedom in the monomer blending ratio, a (meth)acryloyloxy group is preferred, and from the viewpoint of the solvent resistance of the cured product of the photosensitive resin composition and the reduction of dye elution when a dye is used as the colorant (E), an acryloyloxy group is preferred.

[0026] Examples of the monomer (m-a) having a group represented by formula (1) or (2) and an ethylenically unsaturated bond include a reaction product of an ethylenically unsaturated group-containing isocyanate compound with a malonic acid diester or an acetoacetic acid ester. These monomers (m-a) may be used alone or in combination of two or more.

[0027] The ethylenically unsaturated group-containing isocyanate compound that produces the monomer (ma) is preferably a compound represented by the following formula (3):

[0028] (In formula (3), R ４ represents a hydrogen atom or a methyl group. ５ is -CO-, -COOR ６ - (where R ６ is an alkylene group having 1 to 6 carbon atoms, or —COO—R ７ O-CONH-R ８ - (where R ７ is an alkylene group having 2 to 6 carbon atoms. ８ represents an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have a substituent.

[0029] R in formula (3) ４ represents a hydrogen atom or a methyl group. From the viewpoint of the solvent resistance of the cured product of the photosensitive resin composition and the reduction of dye elution when a dye is used as the colorant (E), R ４ is preferably a hydrogen atom. ５ is -CO-, -COOR ６ -or-COO-R ７ O-CONH-R ８ - where R ６ is an alkylene group having 1 to 6 carbon atoms. ７ is an alkylene group having 2 to 6 carbon atoms. ８ is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have a substituent. ５ Is -COOR ６ - is preferred. ５ Ga-COOR ６ -, then R ６ is preferably an alkylene group having 1 to 4 carbon atoms.

[0030] Specific examples of the ethylenically unsaturated group-containing isocyanate compound represented by the above formula (3) 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, and (meth)acryloyl isocyanate.

[0031] Furthermore, the ethylenically unsaturated group-containing isocyanate compound represented by the above formula (3) can also be an equimolar (1 mole:1 mole) reaction product of a 2-hydroxyalkyl(meth)acrylate and a diisocyanate compound. The alkyl group contained in the above 2-hydroxyalkyl(meth)acrylate is preferably an ethyl group or an n-propyl group, and more preferably an ethyl group. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylene diisocyanate, 1,3- (or 1,4-) bis(isocyanatomethyl)cyclohexane, and lysine diisocyanate.

[0032] Among these ethylenically unsaturated group-containing isocyanate compounds, 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, and (meth)acryloyl isocyanate are preferred, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred. These ethylenically unsaturated group-containing isocyanate compounds may be used alone or in combination of two or more.

[0033] Examples of malonic acid diesters to be reacted with the ethylenically unsaturated group-containing isocyanate compound include dimethyl malonate, diethyl malonate, di(n-propyl) malonate, di(i-propyl) malonate, etc., with diethyl malonate or dimethyl malonate being preferred in terms of availability, cost, and quality. Examples of acetoacetic acid esters to be reacted with the ethylenically unsaturated group-containing isocyanate compound include methyl acetoacetate, ethyl acetoacetate, etc.

[0034] The reaction of an ethylenically unsaturated group-containing isocyanate compound with a malonic acid diester or an acetoacetic acid ester can be carried out regardless of the presence or absence of a solvent. When the reaction is carried out using a solvent, a solvent inactive to the isocyanato group is used. A catalyst such as an organic metal salt of tin, zinc, lead, or the like, or a tertiary amine, may be used during the reaction. The reaction can generally be carried out at a temperature of -20 to 150°C, preferably 25 to 130°C. A reaction temperature of -20°C or higher ensures a sufficient reaction rate. Furthermore, a reaction temperature of 150°C or lower can prevent the polymerization of a raw material having a C═C (double bond) and the resulting monomer (m-a) that provides the structural unit (a) after the reaction from gelling.

[0035] Specific examples of the monomer (m-a) include the following AOI-DEM, MOI-DEM, AOI-DMM, MOI-DMM, AOI-OBE, and MOI-OBE. AOI-DEM: Karenz (trademark) AOI-DEM, a reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (malonic acid-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, manufactured by Resonac Co., Ltd. MOI-DEM: Karenz (trademark) MOI-DEM, a reaction product of 2-isocyanatoethyl methacrylate and diethyl malonate (malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, manufactured by Resonac Co., Ltd. AOI-DMM: Karenz™ AOI-DMM, reaction product of 2-isocyanatoethyl acrylate and dimethyl malonate (malonic acid-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester, manufactured by Resonac Co., Ltd. MOI-DMM: Karenz™ MOI-DMM, reaction product of 2-isocyanatoethyl methacrylate and dimethyl malonate (malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester, manufactured by Resonac Co., Ltd. AOI-OBE: Karenz™ AOI-OBE, reaction product of 2-isocyanatoethyl acrylate and ethyl acetoacetate, manufactured by Resonac Co., Ltd. MOI-OBE: Karenz™ MOI-OBE, a reaction product of 2-isocyanatoethyl methacrylate and ethyl acetoacetate, manufactured by Resonac Corporation.

[0036] "Structural unit (b)" -CH ２ The structural unit (b) having a group represented by —OH does not have a group represented by the above formula (1) or (2), and is ２ The structural unit (b) has a group represented by —CH ２It is a structural unit derived from a monomer (mb) (hereinafter also referred to simply as "monomer (mb)") having a group represented by -OH. When a resin composition containing copolymer (A) is thermally cured, the hydroxy group of structural unit (b) contained in copolymer (A) undergoes transesterification with the group represented by formula (1) or formula (2) contained in structural unit (a), thereby forming a crosslinked structure.

[0037] From the viewpoint of low-temperature curing properties, the structural unit (b) is -(CH ２ ) ｎ Structural units having a group represented by —OH (n is an integer of 2 to 6) and —(O—C ｘ H ２ｘ ) ｍ It is more preferable that the structural unit is at least one selected from the group consisting of structural units having a group represented by —OH (where x is an integer of 2 to 4, and m is an integer of 2 to 10). ２ ) ｎ The value of n in the group represented by —OH is preferably 2 to 4, more preferably 2 and 4. —(O—C ｘ H ２ｘ ) ｍ In the group represented by —OH, x is preferably 2 to 3, more preferably 2. —(O—C ｘ H ２ｘ ) ｍ The value m in the group represented by —OH is preferably 2 to 6, more preferably 4 to 6.

[0038] The monomer (mb) that provides the structural unit (b) does not have a group represented by the above formula (1) or (2), and has an ethylenically unsaturated group and a —CH ２ There are no particular limitations on the monomer (mb) as long as it is a monomer having a group represented by —OH. Examples of the ethylenically unsaturated group contained in the monomer (mb) include a vinyl group and a (meth)acryloyloxy group. Examples of the monomer (mb) include a group represented by —CH ２and (meth)acrylic acid ester derivatives having a group represented by -OH. Specific examples of such monomers (m-b) 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. These monomers (m-b) may be used alone or in combination of two or more.

[0039] Of the above-mentioned monomers, hydroxyalkyl(meth)acrylate and polyalkylene glycol mono(meth)acrylate are preferred as the monomer (m-b) from the viewpoints of reactivity during synthesis of the copolymer (A), low-temperature curing properties of the resin composition containing the copolymer (A), and ease of availability. As the hydroxyalkyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate are preferred, and 2-hydroxyethyl(meth)acrylate is more preferred from the viewpoints of controlling the glass transition temperature of the copolymer (A) to a high level and obtaining solvent resistance as a cured product. As the polyalkylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate is preferred from the viewpoint of solvent resistance, and -(O-C ｘ H ２ｘ ) ｍ Polyethylene glycol mono(meth)acrylates in which x in —OH is 2 and m is 2 to 6 are more preferred.

[0040] "Structural unit (c)" The structural unit (c) is a structural unit derived from acrylic acid that constitutes the copolymer (A), and is represented by the formula "-CH(COOH)-CH ２-". When copolymer (A) contains structural unit (c), the ratio of acrylic-derived structures constituting the main chain of copolymer (A) increases and the ratio of methacrylic-derived structures decreases (the ratio of methyl groups bonded to carbon atoms constituting the main chain decreases) compared to when copolymer (A) contains structural units derived from methacrylic acid. This is thought to reduce steric hindrance near the main chain and increase the freedom of movement, such as rotation and bending, of the main chain, thereby increasing the efficiency of intermolecular crosslinking. Therefore, compared to when copolymer (A) contains structural units derived from methacrylic acid, good solvent resistance can be obtained even when a cured product is obtained under low temperature conditions, and even when a dye is used as the colorant (E), dye elution from the cured product can be reduced. Copolymer (A) of this embodiment can be used in combination with acid group-containing polymerizable monomers other than acrylic acid (e.g., methacrylic acid) as constituent monomers within a range that does not impair the effects of the present invention, but for the reasons mentioned above, it is preferable not to use such monomers.

[0041] "Structural unit (d)" The copolymer (A) of the present embodiment may further contain a structural unit (d) derived from an ethylenically unsaturated compound having an epoxy group or an oxetanyl group, as necessary. The structural unit (d) derived from an ethylenically unsaturated compound having an epoxy group or an oxetanyl group is a structural unit derived from a monomer (m-d) (hereinafter also simply referred to as "monomer (m-d)") that does not have a group represented by formula (1) or formula (2), a hydroxy group, or a carboxy group, and has an epoxy group or an oxetanyl group and an ethylenically unsaturated group. By having the structural unit (d) in the copolymer (A), the low-temperature curability of the photosensitive resin composition is improved, and a cured resin film with good solvent resistance can be obtained.

[0042] Specific examples of the polymerizable monomer (m-d) containing an epoxy group that provides the structural unit (d) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate having an alicyclic epoxy group and its lactone adduct (e.g., Cyclomer (registered trademark) A200, M100 manufactured by Daicel Corporation), mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxidized product of dicyclopentenyl (meth)acrylate, epoxidized product of dicyclopentenyloxyethyl (meth)acrylate, etc. Among these, from the viewpoints of availability and reactivity, epoxy group-containing (meth)acrylates are preferred, and glycidyl (meth)acrylate is more preferred. Specific examples of polymerizable monomers having an oxetanyl group include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, and 2-vinyl-2-methyloxetane. Among these, from the viewpoints of ease of availability and reactivity, oxetanyl group-containing (meth)acrylates are preferred, and (3-ethyloxetan-3-yl)methyl (meth)acrylate is more preferred. These polymerizable monomers may be used alone or in combination of two or more.

[0043] "Structural Unit (e)" The copolymer (A) of this embodiment may further contain a structural unit (e) derived from a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, if necessary. The structural unit (e) derived from a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is a structural unit derived from a monomer (me) (hereinafter also simply referred to as "monomer (me)") that does not have a group represented by formula (1) or (2), a hydroxy group, a carboxy group, an epoxy group, or an oxetanyl group, and that has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and ethylenic unsaturation. By including the structural unit (e) in the copolymer (A), the glass transition temperature of the copolymer (A) can be controlled to a high level, and the cured product can achieve solvent resistance and surface uniformity. Furthermore, when a dye is used as the colorant (E) in the photosensitive resin composition, appropriate voids can be created to confine the dye in the resin, thereby reducing dye elution from the cured product.

[0044] Specifically, the monomer (me) that provides the structural unit (e) is more preferably adamantyl (meth)acrylate or a (meth)acrylate having a structure represented by the following formula (5).

[0045]

[0046] In formula (5), R ７ ~R ９ R each independently represents a hydrogen atom or a methyl group. １０ and R １１ represents a hydrogen atom or a methyl group, or may be bonded to form a saturated or unsaturated ring. The ring is preferably a 5- or 6-membered ring. * represents a bond connected to the (meth)acryloyloxy group.

[0047] Specific examples of the (meth)acrylate having the structure represented by the above formula (5) include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate is particularly preferred from the viewpoint of being able to control the glass transition temperature of the copolymer (A) to a high level and having excellent heat resistance. These may be used alone or in combination of two or more.

[0048] "Structural Unit (f)" The copolymer (A) of the present embodiment may further contain a structural unit (f) derived from a (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms, as necessary. The structural unit (f) derived from a (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms is a structural unit derived from a monomer (m-f) (hereinafter also simply referred to as "monomer (m-f)") that does not have a group represented by formula (1) or (2), a hydroxy group, a carboxy group, an epoxy group, an oxetanyl group, or a cyclic hydrocarbon group, and that has a linear or branched alkyl group having 1 to 20 carbon atoms and ethylenic unsaturation. By including the structural unit (f) in the copolymer (A), it is possible to adjust the flexibility of the photosensitive resin composition and impart appropriate substrate adhesion.

[0049] Specific examples of the monomer (m-f) that provides the structural unit (f) include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and dodecyl (meth)acrylate. Among these, from the viewpoint of not inhibiting the thermosetting reaction of the copolymer (A) in terms of its stereostructure, alkyl (meth)acrylates having a linear alkyl group having 1 to 6 carbon atoms are preferred, and methyl (meth)acrylate and ethyl (meth)acrylate are preferred. Additionally, from the viewpoint of being able to appropriately adjust the substrate adhesion, alkyl(meth)acrylates having a branched alkyl group having 4 to 10 carbon atoms are preferred, and iso-butyl(meth)acrylate, tert-butyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate are more preferred. These may be used alone or in combination of two or more.

[0050] "Other Structural Units (g)" The copolymer (A) of this embodiment may contain a structural unit (g) other than the structural units (a) to (f) as needed. The other structural unit (g) is a structural unit derived from another monomer (m-g) (hereinafter simply referred to as "monomer (m-g)") that is copolymerizable with the monomers (m-a) to (m-f). Specific examples of the monomer (m-g) that provides the structural unit (g) include aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, (meth)acrylic acid anilides, (meth)acrylonitrile, and acrolein. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene. 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]hept-2-ene. ２，５ .1 ７，１０ ] dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ２，５ .1 ７，１０ ] dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ２，６ ]dec-8-ene, tricyclo[4.4.0.1 ２，５ ]undec-3-ene, tricyclo[6.2.1.0 １，８ ]undec-9-ene, tetracyclo[4.4.0.1 ２，５ .1 ７，１０ .0 １，６ ] dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ２，５ .1 ７，１２ ] dodec-3-ene, pentacyclo[6.5.1.1 ３，６ .0 ２，７ .0 ９，１３]pentadec-4-ene, etc. Examples of dienes include butadiene, isoprene, and chloroprene. Examples of (meth)acrylic acid esters include benzyl (meth)acrylate, tetrahydrofurfuryl (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. Examples of (meth)acrylic acid amides include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-di-isopropylamide, and (meth)acrylic acid anthracenylamide. Examples of vinyl compounds include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene. Examples of unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate. Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.

[0051] "Proportion of each structural unit" The content of the structural unit (a) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. The content of the structural unit (a) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (a) is 1 mol% or more, the amount of crosslinking by transesterification with the hydroxy group of the structural unit (c) can be sufficiently ensured, and the cured product has good solvent resistance even when the photosensitive resin composition is cured at low temperatures. When the content of the structural unit (a) is 40 mol% or less, the content of the structural unit (c) that is the crosslinking partner can be sufficiently ensured. Furthermore, the content of the structural unit (b) can be sufficiently ensured, and the developability of the photosensitive resin composition is good.

[0052] The content of the structural unit (b) is preferably 1 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. The content of the structural unit (b) is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and even more preferably 40 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (b) is 1 mol% or more, the developability of the photosensitive resin composition is good. When the content of the structural unit (b) is 70 mol% or less, it is easy to adjust the developability and storage stability of the photosensitive resin composition, and the amount of crosslinking between the structural unit (a) and the structural unit (c) can be sufficiently ensured, so that the low-temperature curing property of the photosensitive resin composition and the solvent resistance of the cured product are good.

[0053] The content of the structural unit (c) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. The content of the structural unit (c) is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and even more preferably 30 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (c) is 1 mol% or more, the amount of crosslinking by transesterification with the structural unit (a) can be sufficiently ensured, and the solvent resistance of the cured product is good even when the photosensitive resin composition is cured at low temperatures. In addition, the developability of the photosensitive resin composition can be adjusted to a desired range. When the content of the structural unit (c) is 70 mol% or less, the content of the crosslinking partner structural unit (a) can be sufficiently ensured. Furthermore, the content of the structural unit (b) can be sufficiently ensured, and the developability of the photosensitive resin composition is good.

[0054] When the copolymer (A) contains the structural unit (d), the content of the structural unit (d) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total of the structural units constituting the copolymer (A) is 100 mol%. The content of the structural unit (d) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less, when the total of the structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (d) is 1 mol% or more, crosslinking with the structural unit (b) is promoted, and the low-temperature curing property when formed into a photosensitive resin composition is good. When the content of the structural unit (d) is 40 mol% or less, the storage stability of the photosensitive resin composition is good.

[0055] When the copolymer (A) contains the structural unit (e), the content of the structural unit (e) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. The content of the structural unit (e) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (e) is 1 mol% or more, the properties derived from the structural unit (e) are well expressed. When the content of the structural unit (e) is 40 mol% or less, the contents of the structural units (a) to (c) can be sufficiently ensured, and the low-temperature curing properties of the photosensitive resin composition and the solvent resistance of the cured product are good.

[0056] When the copolymer (A) contains the structural unit (f), the content of the structural unit (f) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. The content of the structural unit (f) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (f) is 1 mol% or more, the properties derived from the structural unit (f) are well expressed. When the content of the structural unit (f) is 40 mol% or less, the contents of the structural units (a) to (c) can be sufficiently ensured, and the photosensitive resin composition has good low-temperature curability and good solvent resistance.

[0057] When the copolymer (A) contains the structural unit (g), the content of the structural unit (g) is preferably 0.5 to 25 mol % or more, more preferably 1 to 20 mol % or more, and even more preferably 5 to 15 mol % or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol %. When the content of the structural unit (g) is within the above range, the function of the structural unit (g) can be imparted to the photosensitive resin composition without impairing the functions of the structural units (a) to (c).

[0058] The acid value of the copolymer (A) is preferably 10 KOHmg / g or more, more preferably 15 KOHmg / g or more, and even more preferably 20 KOHmg / g or more. The acid value of the copolymer (A) is preferably 250 KOHmg / g or less, more preferably 200 KOHmg / g or less, even more preferably 150 KOHmg / g or less, and even more preferably 100 KOHmg / g or less. Any combination of these lower and upper limits may be used. When the acid value of the copolymer (A) is 10 KOHmg / g or more, the developability of the photosensitive resin composition when it is formed is good. When the acid value of the copolymer (A) is 250 KOHmg / g or less, the storage stability of the photosensitive resin composition is good.

[0059] The molecular weight of the copolymer (A) is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 6,000 or more. The weight-average molecular weight of the copolymer (A) is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. Any combination of these lower and upper limits may be used. When the weight-average molecular weight of the copolymer (A) is 3,000 or more, the copolymerization reaction of the copolymer (A) can be carried out stably, and a copolymer (A) with high reproducibility of physical properties can be provided. When the weight-average molecular weight of the copolymer (A) is 25,000 or less, the copolymerization reaction of the copolymer (A) can be carried out stably, and a copolymer (A) with high reproducibility of physical properties can be provided, and the developability when formed into a photosensitive resin composition is good. Insoluble matters in the photosensitive resin composition described below can be easily removed by filtration.

[0060] In this specification, the weight-average molecular weight refers to the weight-average molecular weight and number-average molecular weight in terms of standard polystyrene measured using gel permeation chromatography (GPC) under the following conditions: Column: Showdex (trademark) LF-804 + LF-804 (manufactured by Resonac Co., Ltd.) Column temperature: 40°C Sample: 0.2 mass% tetrahydrofuran solution of the object to be measured Developing solvent: tetrahydrofuran Detector: differential refractometer (Shodex (trademark) RI-71S) (manufactured by Resonac Co., Ltd.) Flow rate: 1 mL / min

[0061] The glass transition temperature of the copolymer (A) is 20°C or higher, preferably 25°C or higher, and more preferably 30°C or higher. The glass transition temperature of the copolymer (A) is preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 70°C or lower. Any combination of these lower and upper limits may be used. If the glass transition temperature of the copolymer (A) is lower than 20°C, tack may occur when the photosensitive resin composition is formed, contaminating equipment and components that come into contact with the resin composition, which may adversely affect processes during and after the production of a color filter. Furthermore, poor compatibility with colorants and the like may cause haze and surface roughness. If the glass transition temperature of the copolymer (A) is 90°C or lower, optimal substrate adhesion and pattern shape can be achieved when the photosensitive resin composition is cured and developed.

[0062] In this specification, the glass transition temperature is a value measured under the following conditions: using a DSC (differential scanning calorimeter, measuring instrument: Seiko DSC6200) in a nitrogen gas flow at a temperature increase rate of 10°C / min in accordance with JIS-K7121 (midpoint glass transition temperature: Tmg).

[0063] The content of copolymer (A) in the photosensitive resin composition of this embodiment is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total of the copolymer (A) and the reactive diluent (B). The content of reactive diluent (B) is preferably less than 100% by mass, more preferably 80% by mass or less, and even more preferably 60% by mass or less, based on 100% by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used. When the content of copolymer (A) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[0064] [Reactive Diluent (B)] The reactive diluent (B) contained in the photosensitive resin composition of this embodiment is not particularly limited as long as it is a low-molecular-weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloyloxy group. In order to improve the curability (reactivity) of the photosensitive composition, the reactive diluent (B) is preferably a reactive compound having a plurality of ethylenically unsaturated groups (a polyfunctional reactive diluent). Specific examples of the reactive diluent (B) include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; triallyl cyanurate, etc.

[0065] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate.

[0066] Specific 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.

[0067] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene 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 tris(hydroxyethyl)isocyanurate tri(meth)acrylate.

[0068] Among these, polyfunctional (meth)acrylates are preferred as the reactive diluent (B) in order to improve curability (reactivity), and dipentaerythritol penta(meth)acrylate and / or dipentaerythritol hexa(meth)acrylate are particularly preferred. These reactive diluents (B) may be used alone or in combination of two or more.

[0069] The content of the reactive diluent (B) in the photosensitive resin composition of this embodiment is preferably more than 0% by mass, more preferably 20% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total of the copolymer (A) and the reactive diluent (B). The content of the reactive diluent (B) is preferably 90% by mass or less, more preferably 75% by mass or less, and even more preferably 60% by mass or less, based on 100% by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used. When the content of the reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[0070] [Photopolymerization initiator (C)] The photopolymerization initiator (C) is not particularly limited, and examples thereof include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-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-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholino) Examples of the photopolymerization initiator (C) include anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; xanthone; 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 4-(1-t-butyldioxy-1-methylethyl)benzophenone and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and acylphosphine oxide photopolymerization initiators. The photopolymerization initiator (C) may be used alone or in combination of two or more.

[0071] The content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). The content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used. When the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, a photosensitive resin composition with good photocurability can be obtained. When the content of the photopolymerization initiator (C) is 30 parts by mass or less, it is possible to prevent the physical properties of the cured product of the photosensitive resin composition from being adversely affected by an excessive amount of the photopolymerization initiator (C).

[0072] [Solvent (D)] The solvent (D) is not particularly limited as long as it can dissolve the copolymer (A), the reactive diluent (B), and the photopolymerization initiator (C).Examples of the solvent (D) 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; hydroxy group-containing carboxylic acid esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutyrate; and hydroxy group-containing solvents such as diethylene glycol; and ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ... (Poly)alkylene glycol monoalkyl ether acetates such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and other ketones; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Examples of the solvent (D) include esters such as methylpropionate, 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-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. The solvent (D) may be used alone or in combination of two or more.

[0073] Among these solvents (D), from the viewpoints of availability, cost, and stability during resist preparation, it is preferable to use ethers, and specifically, it is preferable to use one or more selected from propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and 3-methoxy-1-butanol. More preferred are glycol ethers having a hydroxy group, and specifically, it is even more preferable to use one or more selected from propylene glycol monomethyl ether and ethylene glycol monomethyl ether.

[0074] The content of solvent (D) in the photosensitive resin composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, per 100 parts by mass of the total of all components excluding solvent (D). The content of solvent (D) in the photosensitive resin composition is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, per 100 parts by mass of the total of all components excluding solvent (D). Any combination of these lower and upper limits may be used. When the content of solvent (D) is 30 parts by mass or more, the viscosity of the photosensitive resin composition can be set within an appropriate range. When the content of solvent (D) is 1,000 parts by mass or less, the solvent (D) can be easily removed from a coating film formed by applying the photosensitive resin composition to a substrate.

[0075] [Colorant (E)] The photosensitive resin composition may contain a colorant (E) as needed. The photosensitive resin composition containing the colorant (E) can be used as a material for a color filter.

[0076] The colorant (E) is not particularly limited as long as it is soluble or dispersible in the solvent (D), and examples thereof include dyes and pigments.

[0077] As the dye, it is preferable to use an acid dye having an acid group such as a carboxy group or a sulfo group, a salt of an acid dye with a nitrogen compound, or a sulfonamide adduct of an acid dye, from the viewpoints of solubility in the solvent (D) and an alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc.

[0078] Examples of such 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; and acid red. 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114 ,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274;acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3 and derivatives thereof. Among these, azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dyes are preferred. The dyes can be used alone or in combination of two or more.

[0079] 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, and 214; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; Examples of suitable pigments include red pigments such as C.I. 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. The pigments may be used alone or in combination of two or more kinds.

[0080] The colorant (E) can be appropriately determined depending on, for example, the color of the intended colored pattern (black matrix and pixels). The colorant (E) may be used alone or in combination of two or more. When two or more types of colorants (E) are used, a dye and a pigment may be used in combination.

[0081] When a pigment is used as the colorant (E), a known dispersant may be blended into 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 BYK-Chemie), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Lubrizol Chemicals), may also be used. The content of the dispersant may be appropriately determined depending on the type and amount of the pigment used as the colorant (E).

[0082] The content of the colorant (E) in the photosensitive resin composition is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). The content of the colorant (E) in the photosensitive resin composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used. When the content of the colorant (E) is 3 parts by mass or more, the effect of containing the colorant (E) is significant, and a photosensitive resin composition suitable as a material for colored patterns in color filters can be obtained. When the content of the colorant (E) is 80 parts by mass or less, the colorant (E) does not interfere with the curing property of the photosensitive resin composition, and a photosensitive resin composition with good low-temperature curing properties can be obtained.

[0083] [Other Components] In addition to the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and the colorant (E) contained as needed, the photosensitive resin composition of one embodiment may contain known additives such as a coupling agent, a leveling agent, a thermal polymerization inhibitor, etc. The amount of the additives to be added is not particularly limited as long as it does not inhibit the effects of the present invention.

[0084] <Method for producing copolymer (A)> The proportions of the monomers used in the copolymerization reaction of copolymer (A) are not particularly limited. Preferably, the proportions are 1 to 40 mol% of monomer (m-a), 1 to 70 mol% of monomer (m-b), and 1 to 70 mol% of monomer (m-c), more preferably 5 to 30 mol% of monomer (m-a), 10 to 60 mol% of monomer (m-b), and 5 to 60 mol% of monomer (m-c), and even more preferably 5 to 25 mol% of monomer (m-a), 20 to 40 mol% of monomer (m-b), and 10 to 30 mol% of monomer (m-c). When the monomer (m-d) is further used, preferably, the monomer (m-a) is 1 to 40 mol%, the monomer (m-b) is 1 to 70 mol%, the monomer (m-c) is 5 to 70 mol%, and the monomer (m-d) is 1 to 40 mol%, more preferably, the monomer (m-a) is 5 to 40 mol%, the monomer (m-a) is 5 to 30 mol%, the monomer (m-b) is 10 to 60 mol%, the monomer (m-c) is 5 to 60 mol%, and the monomer (m-d) is 3 to 30 mol%, and even more preferably, the monomer (m-a) is 5 to 40 mol%, the monomer (m-a) is 5 to 25 mol%, the monomer (m-b) is 20 to 40 mol%, the monomer (m-c) is 10 to 30 mol%, and the monomer (m-d) is 5 to 20 mol%. When the monomer (me) and the monomer (m-f) are further used, preferably, the monomer (ma) is 1 to 40 mol%, the monomer (mb) is 1 to 70 mol%, the monomer (m-c) is 5 to 70 mol%, the monomer (m-d) is 1 to 40 mol%, the monomer (me) is 1 to 40 mol%, and the monomer (m-f) is 1 to 60 mol%, more preferably, the monomer (ma) is 5 to 30 mol%, the monomer (mb) is 10 to 60 mol%, The monomer (m-c) is 5 to 60 mol%, the monomer (m-d) is 3 to 30 mol%, the monomer (m-e) is 1 to 40 mol%, and the monomer (m-f) is 1 to 40 mol%, and more preferably the monomer (m-a) is 5 to 25 mol%, the monomer (m-b) is 20 to 40 mol%, the monomer (m-c) is 10 to 30 mol%, the monomer (m-d) is 5 to 20 mol%, the monomer (m-e) is 1 to 40 mol%, and the monomer (m-f) is 1 to 20 mol%.

[0085] The copolymerization reaction can be carried out in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art. From the viewpoint of preventing abnormal polymerization and enabling stable polymerization, it is preferable to carry out the copolymerization reaction in the presence of a hydroxyl-containing organic solvent, among the solvents (D) described above. By carrying out the copolymerization reaction in the presence of a hydroxyl-containing organic solvent, even if the group represented by formula (1) or (2) of monomer (m-a) dissociates to generate an isocyanato group, the isocyanato group reacts with the hydroxyl group of the hydroxyl-containing organic solvent, preventing abnormal polymerization. In the copolymer (A) thus obtained, it is believed that a portion of the blocking agent that blocked the isocyanato group has been replaced by the hydroxyl-containing organic solvent. For example, these monomers may be dissolved in a hydroxyl-containing organic solvent, and then a polymerization initiator may be added to the solution, followed by polymerization at 50 to 100°C for 1 to 20 hours. In this case, if the polymerization reaction is carried out at a temperature at which the group represented by the above formula (1) or (2) of the monomer (m-a) dissociates, the isocyanato group generated by dissociation of the group represented by the above formula (1) or (2) will react with the carboxy group of the acrylic acid to produce a gel. Therefore, it is preferable to carry out the polymerization at a temperature below the dissociation temperature of the group represented by the above formula (1) or (2), preferably at a temperature about 20 to 50° C. lower than the dissociation temperature of the group represented by the above formula (1) or (2).

[0086] The polymerization initiator that can be used in this copolymerization reaction is not particularly limited, but examples include azo-based thermal polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile; and peroxide-based thermal polymerization initiators such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used alone or in combination of two or more. The amount of polymerization initiator used is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass, relative to 100 parts by mass of the total amount of monomers charged.

[0087] As the solvent used in the copolymerization reaction, the same solvents as those described above as solvent (D) can be used. In addition, 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, C5-6 cycloalkanediol, C ５－６ Examples of the solvent include cycloalkane dimethanol, ethyl lactate, and diacetone alcohol. These solvents may be used alone or in combination of two or more.

[0088] <Method for producing photosensitive resin composition> The photosensitive resin composition of one embodiment can be produced by a method in which a known mixing device is used to mix the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and the colorant (E) that is contained as needed.

[0089] When producing a photosensitive resin composition, the reaction solution used in producing the copolymer (A) can be used as it is as a raw material. 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 or the photosensitive coloring composition.

[0090] The photosensitive resin composition comprises a structural unit (a) having a group represented by the above formula (1) or (2) and a —CH ２ Since the composition contains the copolymer (A) containing the structural unit (b) having a group represented by —OH, it has good low-temperature curing properties.

[0091] For this reason, when a cured product is formed using the photosensitive resin composition, it can be cured at a lower temperature than when a conventional resin composition is used. Therefore, when a baking treatment is performed after exposing a coating film formed on a substrate, the photosensitive resin composition can form a cured product having excellent solvent resistance because the crosslinking reaction proceeds sufficiently even if the baking temperature is low.

[0092] Therefore, when a cured product is formed using the photosensitive resin composition, less energy is required for heating for curing. In addition, by using the photosensitive resin composition, a cured product can be formed on a substrate with low heat resistance, such as a resin substrate, without causing any damage to the substrate. Furthermore, even when a colorant (E) with low heat resistance is used, a cured product can be formed that exhibits the inherent properties of the colorant (E).

[0093] The photosensitive resin composition can provide a cured product having excellent solvent resistance even when the baking temperature is low, and the colorant (E) is therefore less likely to be eluted from the cured product. Therefore, it is possible to increase the content of the colorant (E) in the photosensitive resin composition. A photosensitive resin composition having a high content of the colorant (E) can be used, for example, as a material for the color pattern of a color filter to form a color filter having excellent color reproducibility.

[0094] Since the copolymer (A) contained in the photosensitive resin composition has a structural unit (c) derived from acrylic acid, the photosensitive resin composition has good alkaline developability. Because such a photosensitive resin composition has excellent alkaline developability, it is possible to form a cured product having a predetermined pattern shape and excellent solvent resistance by, for example, applying the composition to a substrate to form a coating film, exposing the film through a photomask corresponding to a predetermined pattern shape, developing the unexposed portions with an alkaline aqueous solution, and then baking the resulting film at a sufficiently low temperature.

[0095] The photosensitive resin composition can be suitably used as a material for a color filter.

[0096] For these reasons, 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, protective films for color filters, photospacers, protrusions for liquid crystal alignment, microlenses, and insulating films for touch panels.

[0097] [Third Embodiment] The photosensitive resin composition of the third embodiment contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The photosensitive resin composition of the present embodiment contains a colorant (E) as needed. The photosensitive resin composition of the present embodiment is polymerized and cured by light irradiation to form a cured resin film.

[0098] [Copolymer (A)] The copolymer (A) used in the photosensitive resin composition of the present embodiment contains a structural unit (a) (hereinafter also simply referred to as "structural unit (a)") having one or more selected from an active methylene group having a methoxycarbonyl group attached thereto and an active methine group having a methoxycarbonyl group attached thereto, a structural unit (b) (hereinafter also simply referred to as "structural unit (b)") having a hydroxy group, and a structural unit (c) (hereinafter also simply referred to as "structural unit (c)") having an acid group.

[0099] Copolymer (A) of the present embodiment may further contain, as necessary, a structural unit (e) (hereinafter also simply referred to as "structural unit (e)") derived from a (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms. Copolymer (A) of the present embodiment may further contain, as necessary, a structural unit (f) (hereinafter also simply referred to as "structural unit (f)") derived from a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.

[0100] "Structural unit (a)" is a structural unit derived from a monomer (m-a) (hereinafter also referred to simply as "monomer (m-a)") having one or more selected from an active methylene group having a methoxycarbonyl group attached thereto and an active methine group having a methoxycarbonyl group attached thereto, which constitutes the copolymer (A). The methoxycarbonyl group of the structural unit (a) contained in the copolymer (A) undergoes transesterification with the hydroxy group of the structural unit (b) to form a crosslinked structure by thermally curing a resin composition containing the copolymer (A). Therefore, a resin composition containing the copolymer (A) can obtain a cured film with excellent solvent resistance and hardness even when cured at a low temperature of 50°C to 150°C. Furthermore, when the methoxycarbonyl group of the structural unit (a) contained in the copolymer (A) undergoes transesterification with the hydroxy group of the structural unit (b), methanol is produced. The methanol produced during thermal curing of the resin composition is easily evaporated and removed by the heating required for thermal curing the resin composition, which is preferred. When the alcohol produced by transesterification is methanol, evaporation and removal from the resin composition and curing of the resin composition proceed quickly, resulting in a cured resin film with sufficiently high hardness.

[0101] The active methylene group means a group in which an electron-withdrawing group is bonded to at least one side (preferably both sides) of a methylene group, and examples of the electron-withdrawing group include a carbonyl group, an ester group, a cyano group, a nitro group, a sulfonyl group, a sulfinyl group, and a phosphono group. As the active methylene group, a structure in which a carbonyl group or an ester group is bonded to both sides of a methylene group is preferred, and a group in which an ester group is bonded to both sides of a methylene group, i.e., -COO-CH ２ The —COO— structure is preferred.

[0102] The structural unit (a) is preferably a structural unit having at least one selected from the group consisting of a group represented by the following formula (i-1) and a group represented by the following formula (ii-1):

[0103]

[0104] (In formula (i-1), n1 and n2 each independently represent an integer of 0 to 2. * represents a linking site.)

[0105]

[0106] (In formula (ii-1), n3 and n4 each independently represent an integer of 0 to 2. * represents a linking site.)

[0107] In the formula (i-1) and formula (ii-1), n1 to n4 are each independently preferably 0 or 1, more preferably 0, from the viewpoint of further promoting transesterification and improving low-temperature curing properties.

[0108] The monomer (m-a) that provides the structural unit (a) is not particularly limited as long as it is a compound copolymerizable with the monomer (m-b) and monomer (m-c) described below. For example, from the viewpoint of reactivity when synthesizing the copolymer (A), a monomer having an ethylenically unsaturated bond and one or more selected from an active methylene group connected to a methoxycarbonyl group and an active methine group connected to a methoxycarbonyl group can be used as the monomer (m-a). Specific examples of the group having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group. From the viewpoint of the degree of freedom in the monomer blending ratio, a (meth)acryloyloxy group is preferred, and from the viewpoints of the solvent resistance and hardness of the cured product of the photosensitive resin composition and the reduction of dye elution when a dye is used as the colorant (E), an acryloyloxy group is preferred.

[0109] Examples of the monomer (m-a) having an ethylenically unsaturated bond and one or more selected from the group consisting of an active methylene group having a methoxycarbonyl group bonded thereto and an active methine group having a methoxycarbonyl group bonded thereto include a reaction product of an ethylenically unsaturated group-containing isocyanate compound with dimethyl malonate or methyl acetoacetate. These monomers (m-a) may be used alone or in combination of two or more.

[0110] The ethylenically unsaturated group-containing isocyanate compound that produces the monomer (ma) is preferably a compound represented by the following formula (3):

[0111] (In formula (3), R ４ represents a hydrogen atom or a methyl group.５ is -CO-, -COOR ６ - (where R ６ is an alkylene group having 1 to 6 carbon atoms, or —COO—R ７ O-CONH-R ８ - (where R ７ is an alkylene group having 2 to 6 carbon atoms. ８ represents an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have a substituent.

[0112] R in formula (3) ４ represents a hydrogen atom or a methyl group. From the viewpoint of the solvent resistance and hardness of the cured product of the photosensitive resin composition and the reduction of dye elution when a dye is used as the colorant (E), R ４ is preferably a hydrogen atom. ５ is -CO-, -COOR ６ -or-COO-R ７ O-CONH-R ８ - where R ６ is an alkylene group having 1 to 6 carbon atoms. ７ is an alkylene group having 2 to 6 carbon atoms. ８ is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have a substituent. ５ Is -COOR ６ - is preferred. ５ Ga-COOR ６ -, then R ６ is preferably an alkylene group having 1 to 4 carbon atoms.

[0113] Specific examples of the ethylenically unsaturated group-containing isocyanate compound represented by the above formula (3) 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, and (meth)acryloyl isocyanate.

[0114] Furthermore, the ethylenically unsaturated group-containing isocyanate compound represented by the above formula (3) can also be an equimolar (1 mole:1 mole) reaction product of a 2-hydroxyalkyl(meth)acrylate and a diisocyanate compound. The alkyl group contained in the above 2-hydroxyalkyl(meth)acrylate is preferably an ethyl group or an n-propyl group, and more preferably an ethyl group. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylene diisocyanate, 1,3- (or 1,4-) bis(isocyanatomethyl)cyclohexane, and lysine diisocyanate.

[0115] Among these ethylenically unsaturated group-containing isocyanate compounds, 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, and (meth)acryloyl isocyanate are preferred, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred. These ethylenically unsaturated group-containing isocyanate compounds may be used alone or in combination of two or more.

[0116] The reaction of an ethylenically unsaturated group-containing isocyanate compound with dimethyl malonate or methyl acetoacetate can be carried out regardless of the presence or absence of a solvent. When the reaction is carried out using a solvent, a solvent inactive to the isocyanato group is used. A catalyst such as an organic metal salt of tin, zinc, lead, or the like, or a tertiary amine, may be used during the reaction. The reaction can generally be carried out at a temperature of -20 to 150°C, preferably 25 to 130°C. A reaction temperature of -20°C or higher ensures a sufficient reaction rate. Furthermore, a reaction temperature of 150°C or lower can prevent the polymerization of a raw material having a C═C (double bond) and the resulting monomer (m-a) that provides the structural unit (a) after the reaction from gelling.

[0117] Specific examples of the monomer (ma) include the following AOI-DMM, MOI-DMM, AOI-OBM, and MOI-OBM. AOI-DMM: Karenz™ AOI-DMM, reaction product of 2-isocyanatoethyl acrylate and dimethyl malonate (malonic acid-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester, manufactured by Resonac Co., Ltd. MOI-DMM: Karenz™ MOI-DMM, reaction product of 2-isocyanatoethyl methacrylate and dimethyl malonate (malonic acid-2-[[[[2-[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester, manufactured by Resonac Co., Ltd. AOI-OBM: Karenz™ AOI-OBM, reaction product of 2-isocyanatoethyl acrylate and methyl acetoacetate, manufactured by Resonac Co., Ltd. MOI-OBM: Karenz™ MOI-OBM, a reaction product of 2-isocyanatoethyl methacrylate and methyl acetoacetate, manufactured by Resonac Corporation.

[0118] "Structural unit (b)" The structural unit (b) constituting the copolymer (A) is a structural unit derived from a monomer (mb) (hereinafter also simply referred to as "monomer (mb)") that does not have an active methylene group connected to a methoxycarbonyl group or an active methine group connected to a methoxycarbonyl group, but has a hydroxy group. When a resin composition containing the copolymer (A) is thermally cured, the hydroxy group of the structural unit (b) contained in the copolymer (A) undergoes transesterification with the methoxycarbonyl group of the structural unit (a), thereby forming a crosslinked structure.

[0119] Among these, the structural unit (b) is preferably —CH ２ It is preferable that the alkyl group has a group represented by —OH, and —(CH ２ ) ｎ Structural units having a group represented by —OH (n is an integer of 2 to 6) and —(O—C ｘ H ２ｘ ) ｍ It is more preferable that the structural unit is at least one selected from the group consisting of structural units having a group represented by —OH (where x is an integer of 2 to 4, and m is an integer of 2 to 10). ２ ) ｎ The value of n in the group represented by —OH is preferably 2 to 4, more preferably 2 and 4. —(O—C ｘ H ２ｘ ) ｍ In the group represented by —OH, x is preferably 2 to 3, more preferably 2. —(O—C ｘ H ２ｘ ) ｍ The value m in the group represented by —OH is preferably 2 to 6, more preferably 4 to 6.

[0120] The monomer (m-b) that provides the structural unit (b) is not particularly limited, as long as it does not have the active methylene group connected to a methoxycarbonyl group or the active methine group connected to a methoxycarbonyl group, and has an ethylenically unsaturated group and a hydroxy group. Examples of the ethylenically unsaturated group contained in the monomer (m-b) include a vinyl group and a (meth)acryloyloxy group. Examples of the monomer (m-b) include a (meth)acrylic acid ester derivative having a hydroxy group. Specific examples of such monomer (m-b) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and the like. These monomers (m-b) may be used alone or in combination of two or more.

[0121] Of the above-mentioned monomers, hydroxyalkyl(meth)acrylate and polyalkylene glycol mono(meth)acrylate are preferred as the monomer (m-b) from the viewpoints of reactivity during synthesis of the copolymer (A), low-temperature curing properties of the resin composition containing the copolymer (A), and ease of availability. As the hydroxyalkyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate and 4-hydroxybutyl(meth)acrylate are preferred, and from the viewpoint of obtaining solvent resistance as a cured product, 4-hydroxybutyl(meth)acrylate is more preferred. As the polyalkylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate is preferred from the viewpoint of solvent resistance, and -(O-C ｘ H ２ｘ ) ｍ Polyethylene glycol mono(meth)acrylates in which x in —OH is 2 and m is 2 to 6 are more preferred.

[0122] "Structural unit (c)" The structural unit (c) is a structural unit that does not have an active methylene group connected to a methoxycarbonyl group, an active methine group connected to a methoxycarbonyl group, or a hydroxy group, but has an acid group. Examples of the acid group include a carboxy group, a sulfo group, and a phospho group. Among these acid groups, a carboxy group is preferred in terms of availability. Examples of the monomer (m-c) that provides the structural unit (c) include unsaturated carboxylic acids or anhydrides thereof, unsaturated sulfonic acids, and unsaturated phosphonic acids. Specific examples include unsaturated carboxylic acids or anhydrides thereof 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. These monomers (m-c) may be used alone or in combination of two or more. Among these, (meth)acrylic acid is preferred from the viewpoint of developability as a photosensitive resin composition, and acrylic acid is more preferred from the viewpoint of solvent resistance.

[0123] "Structural Unit (e)" The copolymer (A) of this embodiment may further contain, as necessary, a structural unit (e) derived from a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. The structural unit (e) is the same as the structural unit (e) described in the second embodiment.

[0124] "Structural Unit (f)" The copolymer (A) of this embodiment may further contain, as necessary, a structural unit (f) derived from a (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms. The structural unit (f) is the same as the structural unit (f) described in the second embodiment.

[0125] "Other structural units (g)" The copolymer (A) of this embodiment may contain a structural unit (g) other than the structural units (a) to (e) as needed. The structural unit (g) is the same as the structural unit (g) described in the second embodiment.

[0126] "Proportion of each structural unit" The content of the structural unit (a) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. The content of the structural unit (a) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (a) is 1 mol% or more, the amount of crosslinking by transesterification with the hydroxy group of the structural unit (b) can be sufficiently ensured, and the hardness and solvent resistance of the cured product are good even when the photosensitive resin composition is cured at low temperatures. When the content of the structural unit (a) is 40 mol% or less, the content of the structural unit (b) that is the crosslinking partner can be sufficiently ensured. Furthermore, the content of the structural unit (c) can be sufficiently ensured, and the developability of the photosensitive resin composition is good.

[0127] The content ratio of the structural unit (b) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%.The content ratio of the structural unit (b) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%.The combination of these lower limit and upper limit values ​​may be any combination.

[0128] When the content of the structural unit (b) is 1 mol% or more, the amount of crosslinking by transesterification with the structural unit (a) can be sufficiently ensured, and even when the photosensitive resin composition is cured at low temperatures, the hardness and solvent resistance of the cured product are good. Furthermore, the developability of the photosensitive resin composition can be adjusted to a desired range. When the content of the structural unit (b) is 40 mol% or less, the content of the crosslinking partner structural unit (a) can be sufficiently ensured. Furthermore, the content of the structural unit (c) can be sufficiently ensured, and the developability of the photosensitive resin composition is good.

[0129] The content of the structural unit (c) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total of the structural units constituting the copolymer (A) is 100 mol%. The content of the structural unit (c) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total of the structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (c) is 1 mol% or more, the developability of the photosensitive resin composition can be adjusted to the desired range. When the content of the structural unit (c) is 40 mol% or less, the content of the structural unit (a) and the structural unit (b) can be sufficiently ensured, and the amount of crosslinking by transesterification can be sufficiently ensured.

[0130] When the copolymer (A) contains the structural unit (e), the content of the structural unit (e) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. The content of the structural unit (e) is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (e) is 1 mol% or more, the properties derived from the structural unit (e) are well expressed. When the content of the structural unit (e) is 30 mol% or less, the contents of the structural units (a) to (c) can be sufficiently ensured, the low-temperature curing properties of the photosensitive resin composition are good, and the solvent resistance and hardness of the cured product are good.

[0131] When the copolymer (A) contains the structural unit (f), the content of the structural unit (f) is preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. The content of the structural unit (f) is preferably 95 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, when the total of the structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits may be used. When the content of the structural unit (f) is 10 mol% or more, the photosensitive resin composition can be imparted with desired properties such as flexibility and substrate adhesion. When the content of the structural unit (f) is 95 mol% or less, the content of the structural units (a) to (c) can be sufficiently ensured, the low-temperature curing property and developability of the photosensitive resin composition can be ensured, and the cured product has good solvent resistance and hardness.

[0132] When the copolymer (A) contains the structural unit (g), the content of the structural unit (g) is preferably 0.5 to 25 mol % or more, more preferably 1 to 20 mol % or more, and even more preferably 5 to 15 mol % or more, when the total of the structural units constituting the copolymer (A) is taken as 100 mol %. When the content of the structural unit (g) is within the above range, the function of the structural unit (g) can be imparted to the photosensitive resin composition without impairing the functions of the structural units (a) to (c).

[0133] "Acid value" The acid value of the copolymer (A) is preferably 10 KOHmg / g or more, more preferably 15 KOHmg / g or more, and even more preferably 20 KOHmg / g or more. The acid value of the copolymer (A) is preferably 250 KOHmg / g or less, more preferably 200 KOHmg / g or less, even more preferably 150 KOHmg / g or less, and even more preferably 100 KOHmg / g or less. When the acid value of the copolymer (A) is 10 KOHmg / g or more, the developability of the photosensitive resin composition is good. When the acid value of the copolymer (A) is 250 KOHmg / g or less, the storage stability of the photosensitive resin composition is good. The acid value of the copolymer (A) is the acid value of the curable polymer measured in accordance with JIS K6901 5.3. In other words, the acid value means the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer.

[0134] "Hydroxyl group equivalent" The hydroxyl group equivalent of the copolymer (A) is preferably 200 g / mol or more, more preferably 600 g / mol or more, and even more preferably 1000 g / mol or more. The hydroxyl group equivalent of the copolymer (A) is preferably 3000 g / mol or less, more preferably 2000 g / mol or less, and even more preferably 1600 g / mol or less. When the hydroxyl group equivalent of the copolymer (A) is 200 g / mol or more, the amount of the structural unit (a) and the structural unit (c) can be sufficiently ensured, and a photosensitive resin composition with excellent developability and low-temperature curing properties can be obtained. When the hydroxyl group equivalent of the copolymer (A) is 3000 g / mol or less, the amount of crosslinking with the structural unit (a) can be sufficiently ensured, and a cured resin film with excellent solvent resistance and hardness can be obtained. The hydroxyl group equivalent is the mass of the copolymer (A) per mole of hydroxy groups in the copolymer (A). The hydroxyl equivalent can be determined by dividing the mass of copolymer (A) by the number of hydroxy groups in the resin (g / mol). In this specification, the hydroxyl equivalent of copolymer (A) is a theoretical value calculated from the amounts of raw materials used to introduce hydroxy groups into the resin.

[0135] "Alkoxycarbonyl group equivalent" The alkoxycarbonyl group equivalent of the copolymer (A) is preferably 100 g / mol or more, more preferably 200 g / mol or more, and even more preferably 500 g / mol or more. The alkoxycarbonyl group equivalent of the copolymer (A) is preferably 5000 g / mol or less, more preferably 4000 g / mol or less, and even more preferably 3000 g / mol or less. When the alkoxycarbonyl group equivalent of the copolymer (A) is 100 g / mol or more, the storage stability of the photosensitive resin composition is good. When the alkoxycarbonyl group equivalent of the copolymer (A) is 5000 g / mol or less, the amount of crosslinking with the structural unit (b) can be sufficiently ensured, and a cured resin film with good solvent resistance and hardness can be obtained. The alkoxycarbonyl group equivalent is the mass of the copolymer (A) per mole of alkoxycarbonyl groups in the copolymer (A). The alkoxycarbonyl group equivalent can be determined by dividing the mass of the copolymer (A) by the number of alkoxycarbonyl groups in the resin (g / mol). In this specification, the alkoxycarbonyl group equivalent of the copolymer (A) is a theoretical value calculated from the amounts of raw materials used to introduce alkoxycarbonyl groups into the resin.

[0136] "Measurement of weight average molecular weight, number average molecular weight, and molecular weight distribution"

[0137] The weight-average molecular weight of the copolymer (A) is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 6,000 or more. The weight-average molecular weight of the copolymer (A) is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. When the weight-average molecular weight of the copolymer (A) is 3,000 or more, the copolymerization reaction of the copolymer (A) can be carried out stably, and a copolymer (A) with high reproducibility of physical properties can be provided. When the weight-average molecular weight of the copolymer (A) is 50,000 or less, the copolymerization reaction of the copolymer (A) can be carried out stably, and a copolymer (A) with high reproducibility of physical properties can be provided, and the developability when formed into a photosensitive resin composition is good. Insoluble matters in the photosensitive resin composition described below can be easily removed by filtration.

[0138] The number average molecular weight of the copolymer (A) is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 3,000 or more. The number average molecular weight of the copolymer (A) is preferably 25,000 or less, more preferably 15,000 or less, and even more preferably 10,000 or less. When the number average molecular weight of the copolymer (A) is 1,000 or more, the copolymerization reaction of the copolymer (A) can be carried out stably, and a copolymer (A) with high reproducibility of physical properties can be provided. When the number average molecular weight of the copolymer (A) is 25,000 or less, the copolymerization reaction of the copolymer (A) can be carried out stably, and a copolymer (A) with high reproducibility of physical properties can be provided, and the developability when formed into a photosensitive resin composition is good. Insoluble matters in the photosensitive resin composition described below can be easily removed by filtration.

[0139] The molecular weight distribution of the copolymer (A) is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.1 or more. The molecular weight distribution of the copolymer (A) is preferably 6.0 or less, more preferably 5.0 or less, and even more preferably 4.0 or less. When the molecular weight distribution of the copolymer (A) is 1.5 or more, the copolymerization reaction of the copolymer (A) can be stably carried out, and production control is easy. When the molecular weight distribution of the copolymer (A) is 6.0 or less, it is possible to provide a copolymer (A) with high reproducibility of physical properties, and when formed into a photosensitive resin composition, the developability is good.

[0140] The content of copolymer (A) in the photosensitive resin composition of this embodiment is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total of the copolymer (A) and the reactive diluent (B). The content of reactive diluent (B) is preferably less than 100% by mass, more preferably 80% by mass or less, and even more preferably 60% by mass or less, based on 100% by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used. When the content of copolymer (A) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[0141] [Reactive Diluent (B)] The reactive diluent (B) contained in the photosensitive resin composition of this embodiment is the same as the reactive diluent (B) contained in the photosensitive resin composition of the second embodiment.

[0142] The content of the reactive diluent (B) in the photosensitive resin composition of this embodiment is the same as the content of the reactive diluent (B) contained in the photosensitive resin composition of the second embodiment.

[0143] [Photopolymerization initiator (C)] The photopolymerization initiator (C) according to this embodiment is the same as the photopolymerization initiator (C) according to the second embodiment.

[0144] The content of the photopolymerization initiator (C) in the photosensitive resin composition of this embodiment is the same as the content of the photopolymerization initiator (C) in the photosensitive resin composition of the second embodiment.

[0145] [Solvent (D)] The solvent (D) in the photosensitive resin composition of this embodiment is the same as the solvent (D) in the photosensitive resin composition of the second embodiment.

[0146] The content of the solvent (D) in the photosensitive resin composition of this embodiment is the same as the content of the solvent (D) in the photosensitive resin composition of the second embodiment.

[0147] [Colorant (E)] The photosensitive resin composition may contain a colorant (E) as needed. A photosensitive resin composition containing the colorant (E) can be used as a material for a color filter. The colorant (E) in the photosensitive resin composition of this embodiment is the same as the colorant (E) in the photosensitive resin composition of the second embodiment.

[0148] When a pigment is used as the colorant (E), a known dispersant may be blended into the photosensitive resin composition in order to improve the dispersibility of the pigment. The dispersant is the same as the dispersant according to the second embodiment.

[0149] The content of the colorant (E) in the photosensitive resin composition of this embodiment is the same as the content of the colorant (E) in the photosensitive resin composition of the second embodiment.

[0150] [Other Components] In addition to the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and the colorant (E) contained as needed, the photosensitive resin composition of one embodiment may contain known additives such as a dispersant, a coupling agent, a leveling agent, a thermal polymerization inhibitor, etc. The amount of the additives to be added is not particularly limited as long as it does not inhibit the effects of the present invention.

[0151] <Method for producing copolymer (A)> The proportions of the monomers used in the copolymerization reaction of copolymer (A) are not particularly limited. Preferably, the proportions are 1 to 40 mol% of the monomer (m-a), 1 to 40 mol% of the monomer (m-b), and 1 to 40 mol% of the monomer (m-c), more preferably 5 to 30 mol% of the monomer (m-a), 5 to 30 mol% of the monomer (m-b), and 3 to 30 mol% of the monomer (m-c), and even more preferably 10 to 25 mol% of the monomer (m-a), 10 to 25 mol% of the monomer (m-b), and 5 to 25 mol% of the monomer (m-c). When the monomer (m-f) is further used, preferably, the monomer (m-a) is 1 to 40 mol%, the monomer (m-b) is 1 to 40 mol%, the monomer (m-c) is 1 to 40 mol%, and the monomer (m-f) is 10 to 95 mol%, more preferably, the monomer (m-a) is 5 to 30 mol%, the monomer (m-b) is 5 to 30 mol%, the monomer (m-c) is 3 to 30 mol%, and the monomer (m-f) is 30 to 90 mol%, and even more preferably, the monomer (m-a) is 10 to 25 mol%, the monomer (m-b) is 10 to 25 mol%, the monomer (m-c) is 5 to 25 mol%, and the monomer (m-f) is 50 to 80 mol%. When the monomer (me) is further used, preferably, the monomer (ma) is 1 to 40 mol%, the monomer (mb) is 1 to 40 mol%, the monomer (m-c) is 1 to 40 mol%, the monomer (m-f) is 10 to 95 mol%, and the monomer (me) is 1 to 30 mol%, more preferably, the monomer (ma) is 5 to 30 mol%, the monomer (mb) is 5 to 30 mol%, the monomer (m-c) is 3 to 30 mol%, the monomer (m-f) is 30 to 80 mol%, and the monomer (me) is 3 to 20 mol%, and even more preferably, the monomer (ma) is 10 to 25 mol%, the monomer (mb) is 10 to 25 mol%, the monomer (m-c) is 5 to 25 mol%, the monomer (m-f) is 50 to 70 mol%, and the monomer (me) is 5 to 10 mol%.

[0152] The copolymerization reaction can be carried out in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art. From the viewpoint of preventing abnormal polymerization and enabling stable polymerization, it is preferable to carry out the copolymerization reaction in the presence of a hydroxyl-containing organic solvent, among the aforementioned solvents (D). By carrying out the copolymerization reaction in the presence of a hydroxyl-containing organic solvent, even if the methoxycarbonyl group of the monomer (m-a) dissociates to generate an isocyanato group, the isocyanato group reacts with the hydroxyl group of the hydroxyl-containing organic solvent, preventing abnormal polymerization. In the copolymer (A) thus obtained, it is believed that a portion of the blocking agent that blocked the isocyanato group has been replaced with the hydroxyl-containing organic solvent. For example, these monomers may be dissolved in a hydroxyl-containing organic solvent, and then a polymerization initiator may be added to the solution, followed by polymerization 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 crosslinking due to transesterification between the methoxycarbonyl group of the monomer (m-a) and the monomer (m-b), are likely to proceed, resulting in gel formation. From the viewpoint of reducing gel, the temperature in the copolymerization reaction is preferably 80°C or lower, more preferably 70°C or lower.

[0153] Examples of polymerization initiators that can be used in this copolymerization reaction include azo-based thermal polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile, and peroxide-based thermal polymerization initiators such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used alone or in combination of two or more.

[0154] Among these, from the viewpoint of suppressing gel formation during the copolymerization reaction, it is preferable to use a polymerization initiator having a 10-hour half-life temperature of 50° C. or less, and it is more preferable to use a peroxide-based thermal polymerization initiator. Examples of such polymerization initiators include 1-methyl-1-phenylethyl 7,7-dimethylperoxyoctanoate and benzoyl peroxide, di(2-phenoxyethyl)peroxydicarbonate, cumyl peroxyneodecanoate (10-hour half-life temperature: 36.5°C), di(4-t-butylcyclohexyl)peroxydicarbonate (TCP (purity 90%) manufactured by NOF Corporation, 1-minute half-life temperature: 92.1°C, 1-hour half-life temperature: 57.5°C, 10-hour half-life temperature: 40.8°C), diisopropyl peroxydicarbonate (Peroyl IPP (purity 50%) manufactured by NOF Corporation, 1-minute half-life temperature: 88.3°C, 1-hour half-life temperature: 56.2°C, 10-hour half-life temperature: 40.5°C), Di(2-ethylhexyl) peroxydicarbonate (Perloyl OPP (purity 70%) manufactured by NOF Corporation, 1-minute half-life temperature: 90.6°C, 1-hour half-life temperature: 59.1°C, 10-hour half-life temperature: 43.6°C), di-sec-butyl peroxydicarbonate (Perloyl SBP (purity 50%) manufactured by NOF Corporation, 1-minute half-life temperature: 92.4°C, 1-hour half-life temperature: 57.4°C, 10-hour half-life temperature: 40.5°C), 3-hydroxy-1,1dimethylbutyl peroxyneodecanoate (10-hour half-life temperature T １０ : 37°C), diisobutyryl peroxide (manufactured by NOF Corporation, trade name: Perloyl IB, 10-hour half-life temperature 32.7°C), di-n-propyl peroxydicarbonate (manufactured by NOF Corporation, trade name: Perloyl NPP, 10-hour half-life temperature 40.3°C), etc.

[0155] The amount of the polymerization initiator used is generally 0.5 to 30 parts by mass, preferably 1 to 25 parts by mass, and more preferably 5 to 20 parts by mass, based on 100 parts by mass of the total amount of the monomers charged.

[0156] During the copolymerization reaction, a peroxide-based thermal polymerization initiator may be used in combination with a polymerization accelerator. Examples of the polymerization accelerator include aliphatic amines, aromatic amines, sulfinic acid derivatives, sulfur-containing reductive inorganic compounds, nitrogen-containing reductive inorganic compounds, borate compounds, barbituric acid derivatives, triazine compounds, and halogen compounds, as described in JP-A-2021-054814. Among these, aromatic amines are preferred from the viewpoint of the ease with which the oxidation-reduction reaction with the peroxide-based polymerization initiator proceeds. Examples of the aromatic amine compound include 2,2-[3-(methylphenyl)imino]bisethanol acetate, 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-dimethyl-aniline, N,N-dipropyl-o-toluidine, N,N-dipropyl-m-toluidine, N,N-dipropyl-p-toluidine, and ethyl 4-dimethylaminobenzoate. Among these, 1,1-[(4-methylphenyl)imino]bis(2-propanol), N,N-dimethyl-aniline, and N,N-dimethyl-p-toluidine are preferred from the viewpoint of reducing the copolymerization reaction temperature. The amount of the polymerization accelerator used is generally 0.001 to 10 parts by mass, and preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the total amount of the monomers charged.

[0157] As the solvent used in the copolymerization reaction, the same solvents as those described above as solvent (D) can be used. In addition, 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, C5-6 cycloalkanediol, C ５－６Examples of the solvent include cycloalkane dimethanol, ethyl lactate, and diacetone alcohol. These solvents may be used alone or in combination of two or more.

[0158] <Hardness of cured resin film of photosensitive resin composition> In one embodiment, the hardness of the cured resin film of the photosensitive resin composition is preferably 3H or more, and more preferably 4H or more. The hardness is measured according to JIS K5600-5-4 when a cured resin film having a thickness of 2.5 μm is formed on a glass substrate. The hardness may also be evaluated using the following method. (I) Preparation of cured resin film for evaluation The photosensitive resin composition is applied to a glass substrate and heated at 70°C for 3 minutes to volatilize the solvent, forming a coating film. Next, the coating film is irradiated with light having a wavelength of 365 nm at an exposure dose of 200 mJ / cm. ２ The glass substrate having the photocured coating film is then placed in a dryer at 85°C for 30 minutes to thermally cure the coating film, thereby obtaining a cured resin film having a thickness of 2.5 µm. (II) Measurement of Hardness The hardness of the cured resin film thus produced is measured in accordance with JIS K5600-5-4 using a pencil hardness tester (e.g., No. 553-M, manufactured by Yasuda Seiki Seisakusho).

[0159] <Method for producing photosensitive resin composition> The photosensitive resin composition of one embodiment can be produced by a method in which a known mixing device is used to mix the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and the colorant (E) that is contained as needed.

[0160] When producing a photosensitive resin composition, the reaction solution used in producing the copolymer (A) can be used as it is as a raw material. 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 or the photosensitive coloring composition.

[0161] The photosensitive resin composition has good low-temperature curability because it contains the copolymer (A) containing the structural unit (a) having a methoxycarbonyl group and the structural unit (b) having a hydroxy group.

[0162] For this reason, when a cured product is formed using the photosensitive resin composition, it can be cured at a lower temperature than when a conventional resin composition is used. Therefore, when a baking treatment is performed after exposing a coating film formed on a substrate, the photosensitive resin composition allows the crosslinking reaction to proceed sufficiently even if the baking temperature is low, so that a cured product having excellent solvent resistance and hardness can be formed.

[0163] Therefore, when a cured product is formed using the photosensitive resin composition, less energy is required for heating for curing. In addition, by using the photosensitive resin composition, a cured product can be formed on a substrate with low heat resistance, such as a resin substrate, without causing any damage to the substrate. Furthermore, even when a colorant (E) with low heat resistance is used, a cured product can be formed that exhibits the inherent properties of the colorant (E).

[0164] The photosensitive resin composition can provide a cured product having excellent solvent resistance and hardness even when the baking temperature is low, and therefore the colorant (E) is less likely to leach out from the cured product. Therefore, it is possible to increase the content of the colorant (E) in the photosensitive resin composition. A photosensitive resin composition having a high content of the colorant (E) can be used, for example, as a material for the color pattern of a color filter to form a color filter having excellent color reproducibility.

[0165] Since the copolymer (A) contained in the photosensitive resin composition has a structural unit (c) having an acid group, the photosensitive resin composition has good alkaline developability. Because such a photosensitive resin composition has excellent alkaline developability, it is possible to form a cured product having a predetermined pattern shape and excellent solvent resistance by, for example, applying the composition to a substrate to form a coating film, exposing the film through a photomask corresponding to a predetermined pattern shape, developing the unexposed portions with an alkaline aqueous solution, and then baking the resulting film at a sufficiently low temperature.

[0166] The photosensitive resin composition can be suitably used as a material for a color filter.

[0167] For these reasons, 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, protective films for color filters, photospacers, protrusions for liquid crystal alignment, microlenses, and insulating films for touch panels.

[0168] <Cured Resin Film> A cured resin film according to one embodiment of the present invention (sometimes referred to as the "cured resin film of this embodiment") comprises a cured product of a photosensitive resin composition.

[0169] The cured resin film can be produced, for example, by a method in which the photosensitive resin composition is applied to a substrate, the solvent (D) is removed by volatilization to form a coating film, the coating film is exposed to light to photocure it, and then a baking treatment is performed.

[0170] When forming a cured resin film having a predetermined pattern shape, for example, the following method can be used. That is, a photosensitive resin composition is applied to a substrate, and the solvent (D) is removed by volatilization to form a coating film. Next, the coating film is exposed to light through a photomask having a predetermined pattern shape, and the exposed portions are photocured. Next, the unexposed portions of the coating film are developed with an alkaline aqueous solution. Thereafter, the developed coating film is subjected to a baking treatment to form a cured resin film having a predetermined pattern shape.

[0171] When producing a cured resin film, known methods can be used for applying the photosensitive resin composition, exposing the applied film, and developing the film.

[0172] The conditions for the baking treatment performed when producing a cured resin film can be appropriately determined depending on the composition of the photosensitive resin composition, the thickness of the coating film, the material of the substrate, and the like. Baking can be performed, for example, at a temperature of 70°C to 250°C. Baking temperatures of 70°C or higher result in crosslinking via transesterification between the methoxycarbonyl group of the structural unit (a) contained in the copolymer (A) in the photosensitive resin composition and the hydroxy group of the structural unit (b). As a result, a good degree of curing is achieved, resulting in a cured product with excellent solvent resistance and hardness. The structural unit (a) can undergo both a deblocking reaction, in which it dissociates to produce an isocyanato group, and a transesterification reaction. By adjusting the baking temperature, either reaction can be prioritized. The baking temperature is preferably 75°C or higher, more preferably 80°C or higher. A baking temperature of 250°C or lower is preferable because it is a temperature that can be tolerated by materials with low heat resistance and can suppress discoloration of the photosensitive resin composition. The photosensitive resin composition has good low-temperature curing properties, and therefore the baking temperature can be set to 160°C or lower depending on the heat resistance of the substrate on which the cured resin film is formed. For example, when a resin substrate is used as the substrate, the baking temperature may be set to 150°C or lower, 120°C or lower, or 100°C or lower.

[0173] The baking treatment carried out when producing a cured resin film can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive resin composition, the temperature of the baking treatment, the film thickness of the coating film, etc.

[0174] The cured resin film is made of a cured product of a photosensitive resin composition, and therefore can be produced by a baking process at a low temperature and has excellent solvent resistance.

[0175] <Color Filter> A color filter according to one embodiment of the present invention (sometimes referred to as the "color filter of the present embodiment") has a colored pattern made of a cured product of a photosensitive resin composition. The color filter preferably has a colored pattern made of a cured product of a photosensitive resin composition containing 10 to 100% by mass of copolymer (A), more than 0 to 90% by mass of reactive diluent (B) relative to 100% by mass of the total of copolymer (A) and reactive diluent (B), 0.1 to 30 parts by mass of photopolymerization initiator (C), 3 to 80 parts by mass of colorant (E), and 30 to 1,000 parts by mass of solvent (D) relative to 100 parts by mass of the total of components excluding solvent (D).

[0176] The color filter may include, for example, a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries of each pixel, and a protective film formed on the pixels and the black matrix.

[0177] In the color filter, the pixels and black matrix are colored patterns formed from the cured product of the photosensitive resin composition. In the color filter, known materials can be used for the components other than the materials for the pixels and black matrix.

[0178] The substrate used for the color filter is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, an array substrate, or the like can be used as appropriate depending on the application.

[0179] <Method for Manufacturing Color Filter> Next, an exemplary method for manufacturing a color filter will be described. First, a colored pattern is formed on a substrate. Specifically, a colored pattern that will become a black matrix formed at the boundaries of each pixel, and a colored pattern that will become each of the RGB pixels are sequentially formed on the substrate by the method described below.

[0180] The colored pattern can be formed by photolithography. Specifically, a photosensitive resin composition is applied to a substrate to form a coating film. The coating film is then exposed to light through a photomask having a predetermined pattern shape, causing the exposed portions to photocure. The unexposed portions of the coating film are then developed with an alkaline aqueous solution. The developed coating film is then subjected to a baking treatment, thereby forming a colored pattern having a predetermined pattern shape.

[0181] The method for applying the photosensitive resin composition is not particularly limited, but known methods such as screen printing, roll coating, curtain coating, spray coating, and spin coating can be used.

[0182] After the photosensitive resin composition is applied to the substrate, the substrate may be heated using a heating means such as a circulation oven, an infrared heater, or a hot plate, as necessary, to volatilize and remove the solvent (D) contained in the coating film. The conditions for heating the substrate to remove the solvent (D) are not particularly limited and may be appropriately set depending on the material of the substrate, the composition of the photosensitive resin composition, the thickness of the coating film, and the like. The substrate may be heated, for example, at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0183] Next, the coating film thus formed is partially exposed to active energy rays such as ultraviolet rays or excimer laser light through a negative photomask, and the exposed portions are photocured. The amount of active energy rays irradiated onto the coating film may be appropriately selected depending on the composition of the photosensitive resin composition, and may be, for example, 30 to 2000 mJ / cm. ２ The light source used for exposure is not particularly limited, but may be a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like.

[0184] The alkaline aqueous solution used for developing the coating film is not particularly limited, but examples thereof include aqueous solutions of inorganic alkaline compounds such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; aqueous solutions of aniline compounds and salts thereof such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, and 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates; and aqueous solutions of p-phenylenediamine compounds and salts thereof. Additives such as antifoaming agents and surfactants may be added to the alkaline aqueous solution as needed.

[0185] After the coating film is developed using the above-mentioned aqueous alkaline solution, it is preferable to wash the coating film with water and dry it.

[0186] The conditions for the baking treatment carried out when producing a color filter can be appropriately determined depending on the composition of the photosensitive resin composition, the film thickness of the coating film, the material of the substrate, etc. The baking temperature can be, for example, 70°C to 210°C. When the baking temperature is 70°C or higher, good curing properties are obtained, and a cured product having excellent solvent resistance and hardness is obtained. The baking temperature is preferably 75°C or higher, and more preferably 80°C or higher. When the baking temperature is 210°C or lower, it is preferable because low-heat-resistant materials, such as low-heat-resistant substrates, can be used as materials for the color filter.

[0187] When a colored pattern of a color filter is formed using a conventional photosensitive resin composition, if the baking temperature is set to 200°C or less, the hardness of the colored pattern is insufficient. In contrast, the photosensitive resin composition of one embodiment has good low-temperature curing properties, and therefore the baking temperature can be lowered compared to when using a conventional photosensitive resin composition while ensuring the hardness of the colored pattern. Specifically, the baking temperature can be set to 160°C or less depending on the heat resistance of the substrate on which the cured resin film is formed. For example, when a colored pattern is formed using a resin substrate as the substrate, the baking temperature may be set to 150°C or less, 120°C or less, or 100°C or less.

[0188] The baking treatment carried out when producing a color filter can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive resin composition, the temperature of the baking treatment, the film thickness of the coating film, etc.

[0189] The photosensitive resin composition has good photocurability and low-temperature curability. Therefore, when a colored pattern is formed using the photosensitive resin composition of one embodiment, the baking time can be shortened and a color filter can be efficiently formed, provided that the baking temperature is the same as when a colored pattern is formed using a conventional photosensitive resin composition.

[0190] Using the above-described method for manufacturing a colored pattern, a colored pattern that will become each of the RGB pixels and a colored pattern that will become a black matrix formed at the boundaries of each pixel are formed, and then a protective film is formed on the colored pattern (each of the RGB pixels and the black matrix).

[0191] The method for producing the protective film is not particularly limited, and the protective film may be formed using the photosensitive resin composition of one embodiment, or may be formed using known materials and known methods.

[0192] Through the above steps, a color filter is obtained.

[0193] The color filter has a colored pattern made of the cured product of the photosensitive resin composition described above. Therefore, the colored pattern in the color filter can be formed by a method of performing a baking treatment at a low temperature. Therefore, the energy required for the baking treatment can be reduced.

[0194] In addition, a colorant (E) having low heat resistance can be used as the colorant (E) contained in the photosensitive resin composition used as a material for the color filter. This allows for a wider range of options for the colorant (E). Therefore, for example, it is possible to form a color filter containing a colorant (E) having low heat resistance and having a color pattern that exhibits the inherent properties of the colorant (E).

[0195] Furthermore, the colored pattern in the color filter can be formed on a substrate with low heat resistance, such as a resin substrate, without damaging the substrate. This increases the options for usable substrates. Specifically, for example, since a color filter can be formed on a substrate with low heat resistance, such as a resin substrate, the display can be made flexible. In addition, the colored pattern in the color filter has excellent solvent resistance and hardness, so there is little color change.

[0196] Here, an example has been described in which a photosensitive resin composition containing a photopolymerization initiator (C) is used to produce a colored pattern by a method of photocuring the photosensitive resin composition. However, for example, a photosensitive resin composition containing a curing accelerator and a known epoxy resin may be used instead of the photopolymerization initiator (C) contained in the photosensitive resin composition, and a colored pattern made of a cured product of the photosensitive resin composition containing the copolymer (A) may be formed by applying the composition to a substrate by an inkjet method and then heating the composition.

[0197] <Image Display Element> An image display element according to an embodiment includes a color filter. In the image display element, known components other than the color filter may be used. Specific examples of the image display element include a liquid crystal display element, an organic EL display element, and a solid-state imaging element such as a CCD element or a CMOS element.

[0198] Components other than the color filter in the image display element can be manufactured by known methods. For example, when manufacturing a liquid crystal display element as the 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 formed sequentially on the substrate having the color filter. Next, electrodes, etc. are formed on another substrate, and the substrate having the color filter is placed opposite and bonded to it. Then, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0199] The image display device has a color filter having excellent solvent resistance and hardness, and therefore exhibits little color change.

[0200] 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. The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In these examples, parts and percentages are all by mass unless otherwise specified.

[0201] <Method for measuring weight-average molecular weight> The weight-average molecular weight described below means a weight-average molecular weight calculated as standard polystyrene, measured using gel permeation chromatography (GPC) under the following conditions: Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Resonac Corporation) Column temperature: 40°C Sample: 0.2% by mass solution of copolymer (A) in tetrahydrofuran Developing solvent: tetrahydrofuran Detector: differential refractometer (Shodex RI-71S) (manufactured by Showa Denko K.K.) Flow rate: 1 mL / min

[0202] <Method for measuring acid value> The number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the solid content of copolymer (A) was measured according to JIS K6901 5.3.2. Measuring device: 776 Dosimat (Metrohm) Mixed indicator: mixed indicator of bromothymol blue and phenol red

[0203] <Method for Measuring Glass Transition Temperature (Tg)> Solutions of copolymers (A) obtained in Synthesis Examples A1 to A13 and copolymers (A') obtained in Comparative Synthesis Examples A1 to A6 were applied to a glass substrate and dried at 50°C for 24 hours under reduced pressure. The solutions were then redissolved in acetone and dried again at 50°C for 24 hours under reduced pressure to remove volatile components. The glass transition temperature (Tg) of the copolymers (A) and (A') was measured in accordance with JIS-K7121 using a DSC (differential scanning calorimeter, measuring device: Seiko DSC6200) under a nitrogen gas flow at a heating rate of 10°C / min (midpoint glass transition temperature: Tgm). The obtained result was taken as the glass transition temperature (Tg) of the copolymers (A) and (A').

[0204] <Method for Measuring Exothermic Peak Temperature of Copolymer (A)> A solution containing 75 parts by mass (solids) of the copolymer (A) obtained in Synthesis Examples A1 to A13 or the copolymer (A') obtained in Comparative Synthesis Examples A1 to A6 and 25 parts by mass of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) was mixed and several drops were dropped into an aluminum cup. The mixture was then dried under reduced pressure at 40°C for 30 minutes to remove volatile components such as the polymerization solvent. This sample was measured using a DSC (differential scanning calorimeter, measuring device: TA Instruments DSC250) in a nitrogen stream at a heating rate of 2°C / min over a range of 50 to 120°C. The measurement results were plotted with temperature on the horizontal axis and heat flow on the vertical axis. The maximum value of the heat flow was considered to be the exothermic peak resulting from the reaction of the copolymer (A) or copolymer (A') with dipentaerythritol hexaacrylate, and the temperature of that peak was read.

[0205] <Alkoxycarbonyl Group Equivalent> A theoretical value calculated from the amounts of the monomers (ma) to (me) and the polymerization initiator used in producing the copolymer is used.

[0206] <Hydroxyl Group Equivalent> A theoretical value calculated from the amounts of the monomers (ma) to (me) and the polymerization initiator used in producing the copolymer is used.

[0207] A synthesis example of the copolymer (A) or copolymer (A') according to the photosensitive resin composition of the second embodiment will be shown below.

[0208] Synthesis Example A1: 278.4 g of propylene glycol monomethyl ether was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube as solvent (D). The mixture was then stirred while purging with nitrogen gas and heated to 78°C. Next, 50.0 g (15 mol%) of the reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (malonic acid-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester) (m-a), 21.6 g (15 mol%) of 2-hydroxyethyl methacrylate (m-b), 21.5 g (27 mol%) of acrylic acid (m-c), and 31.5 g (20 mol%) of glycidyl methacrylate (m-d) were added. A monomer mixture consisting of 36.5 g (15 mol%) of dicyclopentanyl methacrylate (me), and 8.9 g (8 mol%) of methyl methacrylate (mf) was added with 28.9 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65B, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (17.0 parts by mass relative to a total of 100 parts by mass of the monomer mixture) as a polymerization initiator, and the resulting mixture was added dropwise from the dropping funnel to the flask over 1 hour. After completion of the dropwise addition, the mixture was stirred at 78°C for 3 hours to carry out a copolymerization reaction, and finally, propylene glycol monomethyl ether acetate was added as solvent (D) so that the content of components other than the solvent was 35% by mass, thereby obtaining a mixture containing copolymer (A) (sample number P1) and solvent (D). The composition of solvent (D) was such that propylene glycol monomethyl ether accounted for 49% by mass of the 65% by mass of the solvent component, and propylene glycol monomethyl ether acetate accounted for 16% by mass of the 65% by mass of the solvent component. Table 1 shows the blending ratio of each monomer when the total monomer mixture is converted to 100 mol %, as well as the glass transition temperature (Tg), acid value, weight average molecular weight, and exothermic peak temperature (°C) of copolymer (A).

[0209] Synthesis Examples A2 to A6, A9 to A11, Comparative Synthesis Examples A1 to A5 Mixtures containing each of the copolymers (A) of the Examples (sample numbers P1 to P6, P9 to P11, respectively) and the copolymer (A') of the Comparative Examples (sample numbers cP1 to cP5, respectively) and solvent (D) were obtained in the same manner as in Synthesis Example 1, except that the monomer blending ratios were as shown in Table 1. The amount of polymerization initiator added was adjusted according to the desired weight-average molecular weight. Table 1 shows the blending ratio of each monomer, as well as the glass transition temperature (Tg), acid value, weight-average molecular weight, and exothermic peak temperature (°C) of each copolymer (A) or copolymer (A').

[0210] Synthesis Examples A7 to A8 Mixtures containing each copolymer (A) (sample numbers P7 to P8, respectively) and solvent (D) were obtained in the same manner as in Synthesis Example 1, except that the monomer blending ratios shown in Table 1 were used and that propylene glycol monomethyl ether was replaced with 3-methoxy-1-butanol as solvent (D). The amount of polymerization initiator added was adjusted according to the desired weight-average molecular weight. Table 1 shows the blending ratio of each monomer, as well as the glass transition temperature (Tg), acid value, weight-average molecular weight, and exothermic peak temperature (°C) of each copolymer (A).

[0211] Synthesis Examples A12 and A13 Mixtures containing copolymer (A) (sample numbers P12 and P13) and solvent (D) were obtained in the same manner as in Synthesis Example 1, except that the monomers were used in the proportions shown in Table 1 and the amount of polymerization initiator added, relative to 100 parts by mass of the total monomer mixture, was 25.0 parts by mass in Synthesis Example 12 and 5.0 parts by mass in Synthesis Example 13. Table 1 shows the proportions of the monomers used, and the glass transition temperature (Tg), acid value, weight-average molecular weight, and exothermic peak temperature (°C) of copolymer (A).

[0212] The following compounds were used as compounds shown in Table 1. AOI-DEM: Karenz™ AOI-DEM, a reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (malonic acid-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, manufactured by Resonac Corporation. 2HEMA: 2-hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.). 2HEA: 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.). 4HBA: 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd.). PE-200: polyethylene glycol monomethacrylate (manufactured by NOF Corporation). GLM: glycerin monomethacrylate (manufactured by NOF Corporation). 2HPA: 2-hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd.). AA: methacrylic acid (manufactured by Nippon Shokubai Co., Ltd.). MAA: methacrylic acid (manufactured by Kuraray Co., Ltd.). GMA: glycidyl methacrylate (manufactured by NOF Corporation) TCDMA: tricyclodecanyl methacrylate (manufactured by Resonac Co., Ltd.) MMA: methyl methacrylate (manufactured by Mitsubishi Chemical Corporation) 2EHA: 2-ethylhexyl acrylate (manufactured by Toagosei Co., Ltd.)

[0213] A production example of the photosensitive resin composition of the second embodiment will be described below.

[0214] Examples A1 to A13, Comparative Examples A1 to A5 A mixture containing 60 parts by mass (solid content) of copolymer (A) obtained in Synthesis Examples A1 to A13, copolymer (A′) obtained in Comparative Synthesis Examples A1 to A5 (sample numbers: P1 to P13, cP1 to cP5, respectively), and solvent (D), 20 parts by mass of dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.) as reactive diluent (B), 2 parts by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyloxime) (IRGACURE OXE02: manufactured by BASF) as photopolymerization initiator (C), and blue dye (VALIFAST BLUE: manufactured by Orient Chemical Industries Co., Ltd.) as colorant (E) was added. 20 parts by mass of propylene glycol monomethyl ether (2620) was mixed, and propylene glycol monomethyl ether was added as solvent (D) so that the total solids content was 30%, followed by filtration through a 1 μm mesh membrane filter to prepare photosensitive coloring compositions No. 1 to 19. However, photosensitive coloring composition No. 19 could not be filtered through a filter, so it was prepared without filtration. The blending amounts of each component relative to 100% by mass of the total solids content of copolymer (A) or copolymer (A') and reactive diluent (B) were: 75% by mass of the solids content of copolymer (A) or copolymer (A'), 25% by mass of the reactive diluent (B), 2.5% by mass of the photopolymerization initiator (C), and 25% by mass of the colorant (E). The blending ratios are shown in Table 2. The obtained photosensitive resin compositions (respective sample numbers: R1 to R13, cR1 to cR5) are shown in Table 3.

[0215]

[0216] <Preparation of Color Resist 1> The photosensitive coloring compositions (sample numbers: R1 to R13, cR1 to 5) were spin-coated onto 5 cm square glass substrates (alkali-free glass substrates) so that the average thickness after the development process described below would be 2.2 μm. The appearance of the glass substrate after spin-coating was observed visually and by touch, and the appearance was evaluated on a four-point scale of ○ to ×, with ○ being considered acceptable. The evaluation results are shown in Table 3.

[0217] A: Good appearance B: Poor appearance (surface roughness, haze, and tack observed)

[0218] <Preparation of Color Resist 2> After the spin coating, the substrates with good appearance were selected and heated at 70°C for 1 minute to volatilize the solvent, forming a coating film (pre-baking step). Next, a photomask (having a 30 μm-wide line and space pattern) was placed on the coating film at a distance of 100 μm from the coating film, and a 200 mJ / cm irradiance was applied from above using an ultra-high pressure mercury lamp. ２ The unexposed areas were then removed by spraying 100-fold diluted Semiclean DL-A10 developer (manufactured by Yokohama Yushi Kogyo Co., Ltd.) (0.05% aqueous KOH solution) onto the surface of the coating film for 60 seconds at a temperature of 23°C and a discharge pressure of 0.1 MPa (development step). Finally, the glass substrate with the coating film after the development step was left to stand in a dryer at 85°C or 95°C for 30 minutes to thermally cure the coating film (post-bake step), thereby obtaining a color resist having a color pattern.

[0219] <Measurement of Residual Film Ratio of Coating Film> The color resist was immersed in propylene glycol monomethyl ether at 23°C for 5 minutes. The coating film was then removed and dried in air at room temperature, and the thickness of the dried coating film was measured. The relative value when the thickness of the coating film after the development process was taken as 100% was calculated as the residual film ratio. The calculation results of the residual film ratio when the post-bake process was performed at 85°C and 95°C are shown in Table 3.

[0220] <Evaluation of Dye Elution from Coating Film> The color resist was left to stand in propylene glycol monomethyl ether at 23°C for 5 minutes, and the degree of collapse of the colored pattern upon immersion was visually observed, and the dye elution from the colored pattern was evaluated as follows. Evaluation was made on a four-point scale of ◎, ○, △, ×, with ◎ and ○ being considered acceptable. The evaluation results are shown in Table 3. A: The pattern does not fade and remains firmly. B: The pattern fades but remains without disappearing. C: Part of the pattern disappears. D: The entire pattern disappears.

[0221]

[0222] (Discussion) The copolymers (A) obtained in Synthesis Examples A1 to A13 and the copolymer obtained in Comparative Synthesis Example A2 exhibited exothermic peak temperatures detected at lower temperatures relative to 100°C, whereas the copolymers (A') obtained in Comparative Synthesis Example A1 and Comparative Synthesis Examples A3 to A5 all exhibited high exothermic peak temperatures of 100°C or higher. Compared with Comparative Synthesis Example A1, Comparative Synthesis Example A3, and Comparative Synthesis Example A4, it was suggested that the introduction of the structural unit (c) derived from acrylic acid imparts flexibility that allows the copolymer to satisfactorily undergo crosslinking reaction at low temperatures even when the glass transition temperature is 20°C or higher. Furthermore, compared with Comparative Synthesis Example A5, the introduction of the structural unit (c) derived from acrylic acid imparts flexibility that allows the copolymer to satisfactorily undergo crosslinking reaction at low temperatures. ２ It was suggested that by introducing the structural unit (b) represented by -OH, i.e., a primary hydroxyl group, it is possible to obtain a cured product which, unlike a secondary or tertiary hydroxyl group, has high crosslinking reactivity and exhibits satisfactory curability and solvent resistance at low temperatures.

[0223] It has become clear that this phenomenon also affects the performance of films coated with the photosensitive coloring composition. Comparing the film retention rate and dye elution from the coated film, the resists of Examples A1 to A13, which used the copolymer (A) obtained in Synthesis Examples A1 to A13, exhibited higher film retention rates and higher dye elution resistance than the resists of Comparative Examples A3 to A5, which used the copolymer (A') obtained in Comparative Synthesis Examples A3 to A5. In all cases, the crosslinking reaction of the copolymer occurred satisfactorily in environments at 85°C and 95°C, imparting sufficient curability to the photosensitive coloring composition, and the dye being robustly encapsulated in this cured photosensitive coloring composition, making it less susceptible to external erosion by organic solvents. Additionally, the inclusion of the structural unit (e) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms appropriately formed a space encapsulating the dye, further suggesting improved dye elution resistance. On the other hand, in Comparative Synthesis Examples A1 and A2, the copolymer (A') having a low glass transition temperature of 20°C or less was used, so that the film coated with the photosensitive coloring composition became extremely soft, and poor appearance such as surface roughness, haze, and tack occurred. Furthermore, since there was a risk that the occurrence of tack would contaminate an evaluation device such as a palpator for measuring the film thickness, it was not possible to proceed to the color resist preparation process, and it became clear that there would be significant industrial constraints on production on an actual line.

[0224] A synthesis example of the copolymer (A) or copolymer (A') according to the photosensitive resin composition of the third embodiment will be shown below.

[0225] Synthesis Example B1 Synthesis of Copolymer (A) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 243.0 g of propylene glycol monomethyl ether as solvent (D) was placed, and the mixture was stirred while purging with nitrogen and heated to 65°C.

[0226] Next, 88.5 g (18 mol%) of AOI-DMM as the monomer (m-a), 32.8 g (14 mol%) of 2-hydroxyethyl methacrylate as the monomer (m-b), 17.0 g (11 mol%) of methacrylic acid as the monomer (m-c), 155.7 g (47 mol%) of 2-ethylhexyl acrylate and 18.0 g (10 mol%) of methyl methacrylate as the monomer (m-e), 38.1 g of Percumyl ND (polymerization initiator) as a polymerization initiator (12.2 parts by mass relative to a total of 100 parts by mass of the monomer components), and 140.4 g of propylene glycol monomethyl ether acetate and 118.5 g of propylene glycol monomethyl ether as the solvent (D) were mixed to prepare a raw material monomer solution.

[0227] The entire amount of the prepared raw material monomer solution was added dropwise to the solvent (D) in a flask under normal pressure and a nitrogen gas atmosphere using a dropping funnel over 1 hour. After the dropwise addition, the solution in the flask was stirred and polymerized at 65 ° C for 2 hours to obtain a liquid containing the copolymer (A) and the solvent (D). To the reaction liquid containing the copolymer (A) and the solvent (D) obtained in this way, propylene glycol monomethyl ether acetate was added as the solvent (D) so that the components other than the solvent were 35 mass %. A liquid (resin composition) containing the copolymer (A) of Synthesis Example B1 was obtained.

[0228] [Synthesis Examples B2 to B13] Mixtures containing each copolymer (A) (respective sample numbers P1 to P13) of the Synthesis Examples and solvent (D) were obtained in the same manner as Synthesis Example B1, except that the monomer blending ratios shown in Table 4 were used. The amount of polymerization initiator added was adjusted according to the desired weight-average molecular weight. Furthermore, a chain transfer agent was added to Synthesis Example B4, and a reducing agent was added to Synthesis Examples B12 and B13, in the amounts shown in Table 4 (parts by mass relative to 100 parts by mass of the total of the monomer components), together with the polymerization initiator. The blending ratio of each monomer, as well as the weight-average molecular weight, number-average molecular weight, molecular weight distribution, acid value, alkoxycarbonyl group equivalent, and hydroxyl group equivalent of each copolymer (A) are shown in Table 4.

[0229] Comparative Synthesis Example B1 Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 237.6 g of propylene glycol monomethyl ether as solvent (D) was placed, and the mixture was stirred while purging with nitrogen and heated to 78°C.

[0230] Next, 90.6 g (18 mol%) of AOI-DEM as the monomer (m-a'), 30.4 g (14 mol%) of 2-hydroxyethyl methacrylate as the monomer (m-b), 15.8 g (11 mol%) of methacrylic acid as the monomer (m-c), 175.4 g (57 mol%) of 2-ethylhexyl acrylate as the monomer (m-e), 37.8 g (12.1 parts by mass relative to a total of 100 parts by mass of the monomer components) of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) as a polymerization initiator, 143.6 g of propylene glycol monomethyl ether acetate as the solvent (D), and 112.4 g of propylene glycol monomethyl ether were mixed to prepare a raw material monomer solution.

[0231] The entire amount of the prepared raw material monomer solution was added dropwise to the solvent (D) in a flask under nitrogen gas atmosphere at normal pressure using a dropping funnel over 1 hour. After the dropwise addition, the solution in the flask was stirred and subjected to a polymerization reaction at 78 ° C for 3 hours to obtain a liquid containing the copolymer (A) and the solvent (D). To the reaction liquid containing the copolymer (A) and the solvent (D) thus obtained, propylene glycol monomethyl ether acetate was added as the solvent (D) so that the components other than the solvent were 35 mass %. A liquid (resin composition) containing the copolymer (A) of Comparative Synthesis Example B1 was obtained.

[0232] Comparative Synthesis Example B2 Copolymer cP2 of Comparative Synthesis Example B2 was obtained in the same manner as in Comparative Synthesis Example B1, except that the raw materials shown in Table 5 were used in the proportions shown in Table 5. The results are shown in Table 5.

[0233] Comparative Synthesis Example B3 Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 242.9 g of propylene glycol monomethyl ether as solvent (D) was placed, and the mixture was stirred while purging with nitrogen and heated to 78°C.

[0234] Next, 88.5 g (18 mol%) of AOI-DMM as the monomer (m-a), 32.8 g (14 mol%) of 2-hydroxyethyl methacrylate as the monomer (m-b), 17.1 g (11 mol%) of methacrylic acid as the monomer (m-c), 155.8 g (47 mol%) of 2-ethylhexyl acrylate as the monomer (m-e), 37.8 g (12.1 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) as a polymerization initiator (100 parts by mass of the total of the monomer components), 140.5 g of propylene glycol monomethyl ether acetate as the solvent (D), and 118.6 g of propylene glycol monomethyl ether were mixed to prepare a raw material monomer solution.

[0235] The entire amount of the raw material monomer solution thus prepared was added dropwise using a dropping funnel over 1 hour to the solvent (D) in a flask under nitrogen gas atmosphere at normal pressure, but gelation occurred.

[0236] The weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, methoxycarbonyl group equivalent, and hydroxyl group equivalent were determined for each of the copolymers cP1 to cP3 thus obtained in Comparative Synthesis Examples B1 to B3. The results are shown in Table 5.

[0237]

[0238]

[0239] The following compounds were used as compounds shown in Tables 4 and 5. AOI-DMM: Karenz™ AOI-DMM, a reaction product of isocyanatoethyl acrylate and dimethyl malonate, (malonic acid-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 dimethyl ester, manufactured by Resonac Co., Ltd. MOI-DMM: Karenz™ MOI-DMM, a reaction product of isocyanatoethyl methacrylate and dimethyl malonate, (malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 dimethyl ester, manufactured by Resonac Co., Ltd. AOI-DEM: Karenz™ AOI-DEM, reaction product of isocyanatoethyl acrylate and diethyl malonate (malonic acid-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, manufactured by Resonac Corporation; 2-hydroxyethyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd.; 4-hydroxybutyl acrylate: manufactured by Tokyo Chemical Industry Co., Ltd.; methacrylic acid: manufactured by Tokyo Chemical Industry Co., Ltd.; acrylic acid: manufactured by Tokyo Chemical Industry Co., Ltd.; 2-ethylhexyl acrylate: manufactured by Tokyo Chemical Industry Co., Ltd.; methyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd.; dicyclopentanyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd.; propylene glycol monomethyl ether acetate: manufactured by Tokyo Chemical Industry Co., Ltd.; propylene glycol monomethyl ether: manufactured by Tokyo Chemical Industry Co., Ltd.; 3-methoxy-1-butanol: manufactured by Tokyo Chemical Industry Co., Ltd.; thioglycolic acid: manufactured by Tokyo Chemical Industry Co., Ltd. Cobalt octylate: manufactured by Nippon Chemical Industry Co., Ltd. Accelerator A: 1,1-[(4-methylphenyl)imino]bis(2-propanol) (manufactured by Wako Pure Chemical Industries, Ltd.) Percumyl ND: cumyl peroxyneodecanoate (manufactured by NOF Corporation) V65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0240] Examples of the photosensitive resin composition of the third embodiment are shown below. <Preparation of photosensitive coloring composition> [Examples B1 to B13, Comparative Examples B1 to B2] As the copolymer (A), the copolymers P1 to P13, cP1 to cP2 of Examples B1 to B13 and Comparative Examples B1 to B2 and the (B), (C), and (E) components shown in Table 6 were mixed in the ratios shown in Table 6 to prepare photosensitive coloring compositions R1 to R13 and cR1 to cR2 of Examples B1 to B13 and Comparative Examples B1 to B2, respectively.

[0241] In addition, the blending amount of copolymer (A) in the resin composition in Table 6 does not include the polymerization solvent used when synthesizing copolymer (A). In addition, the blending amount of solvent (D) in Table 6 is the total amount of the polymerization solvent used when synthesizing copolymer (A) in the photosensitive colored resin composition and the solvent added when preparing the photosensitive colored resin composition.

[0242]

[0243] <Evaluation of Photosensitive Coloring Composition> The photosensitive coloring compositions R1 to R13 and cR1 to cR2 of Examples B1 to B13 and Comparative Examples B1 to B2 were evaluated by the following methods.

[0244] (1) Developability By spin coating method, the photosensitive coloring compositions R1 to R13 and cR1 to cR2 prepared in Examples B1 to B13 and Comparative Examples B1 to B2 were each coated on a 5 cm square glass substrate (alkali-free glass substrate) (coating process) so that the thickness after exposure was 2.5 μm. The glass substrate coated with the photosensitive coloring composition was heated at 70 ° C. for 3 minutes to volatilize the solvent, and the coating film was dried (pre-bake process).

[0245] Next, an ultra-high pressure mercury lamp was used to irradiate 200 mJ / cm ２The surface of the dried coating film was irradiated with light through a photomask (exposure step). The exposure step was performed by placing the photomask 100 μm away from the coating film. The photomask used had a line and space pattern with a width of 3 to 100 μm. Next, Semiclean DL-A10 developer (manufactured by Yokohama Yushi Kogyo Co., Ltd.) (5-fold diluted) was sprayed onto the surface of the coating film for 60 seconds under conditions of a temperature of 23°C and a pressure of 0.1 MPa, thereby removing the unexposed areas (development step). The glass substrate with the coating film after the development step was left standing in a dryer at 85°C for 30 minutes to thermally cure the coating film (post-bake step), thereby obtaining a colored pattern.

[0246] The colored patterns thus obtained were observed using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation, and the minimum line width (minimum development dimension) that could be developed and the presence or absence of residues in the unexposed areas between the developed patterns were evaluated. The presence or absence of residues was evaluated according to the following criteria. The results are shown in Table 7 or Table 8. "Residue Evaluation Criteria" ○: No residues in the unexposed areas between the developed patterns ×: Residues present in the unexposed areas between the developed patterns

[0247] (2) Pencil Hardness The photosensitive coloring compositions R1 to R13 and cR1 to cR2 prepared in Examples B1 to B13 and Comparative Examples B1 to B2 were applied by spin coating onto a square glass substrate (alkali-free glass substrate) measuring 5 cm in length and 5 cm in width, and heated at 70°C for 3 minutes to volatilize the solvent, forming a coating film. Next, the coating film was irradiated with light of 365 nm wavelength at an exposure dose of 200 mJ / cm. ２ The glass substrate having the photocured coating film was then placed in a dryer at 85°C for 30 minutes to thermally cure the coating film (post-baking step), thereby obtaining a cured resin film having a thickness of 2.5 µm.

[0248] The pencil hardness of the cured resin film thus produced was measured using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho) in accordance with JIS K5600-5-4, and evaluated according to the following criteria. The results are shown in Table 7 or Table 8. "Evaluation criteria for pencil hardness" ○: Pencil hardness of 3H or more ×: Pencil hardness less than 3H

[0249] (4) Overall Judgment The cured resin films made of the cured products of the photosensitive coloring compositions R1 to R13 and cR1 to cR2 prepared in Examples B1 to B13 and Comparative Examples B1 and B2 were evaluated according to the following criteria. The results are shown in Table 7 or Table 8.

[0250] "Evaluation Criteria" ◯: All of the following items are met: (1) The minimum development dimension is 15 μm or less, and there is no residue in the unexposed areas between the developed patterns. (2) The pencil hardness of the resin cured film is 3H or more. ×: One or more of the above ◯ items are not met.

[0251]

[0252]

[0253] (Discussion) As shown in Table 7, the resin cured film made of the cured product obtained by photocuring the coating film formed using the photosensitive coloring compositions R1 to R13 of Examples B1 to B13 and then heat-curing at a low temperature of 85 ° C. had a pencil hardness of 3H or more, and had excellent hardness. Moreover, the solvent resistance of the above-mentioned resin cured film was evaluated as ○, and it was confirmed that it had excellent solvent resistance.

[0254] In contrast, as shown in Table 8, the photosensitive coloring compositions cR1 and cR2 of Comparative Examples B1 and B2 were insufficient in pencil hardness or solvent resistance.

[0255] More specifically, the copolymers cP1 and cP2 of Comparative Synthesis Examples B1 and B2 contained in the photosensitive coloring compositions cR1 and cR2 of Comparative Examples B1 and B2 undergo transesterification with hydroxyl groups to produce ethanol. However, the reaction proceeds slowly at a curing temperature of 85°C. This resulted in poor hardness and solvent resistance.

[0256] According to one embodiment of the present invention, a photosensitive resin composition and a photosensitive coloring composition are provided that have excellent low-temperature curing properties and can form a cured resin film having sufficient hardness and solvent resistance. Also provided is a cured resin film having sufficient hardness and solvent resistance, which is made from a cured product of the photosensitive resin composition of the present invention, and an image display device comprising the same. The photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, or a resist for a color filter.

[0257] According to another embodiment of the present invention, there is provided a photosensitive resin composition that provides a cured resin film having excellent solvent resistance and hardness and has good developability. Also provided is a cured resin film having excellent solvent resistance, and an image display device comprising the same. The photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, or a resist for a color filter.

Claims

1. A photosensitive resin composition comprising: a copolymer (A); a reactive diluent (B); a photopolymerization initiator (C); and a solvent (D), wherein the copolymer (A) comprises structural units (a), (b), and (c), the structural unit (a) has one or more selected from an active methylene group having an alkoxycarbonyl group attached thereto and an active methine group having an alkoxycarbonyl group attached thereto, the structural unit (b) has a hydroxy group, and the structural unit (c) has an acid group.

2. The structural unit (a) has a group represented by the following formula (1) or (2), and the structural unit (b) has a —CH ２ 2. The photosensitive resin composition according to claim 1, wherein the structural unit (c) has a group represented by —OH, the structural unit (c) is derived from acrylic acid, and the glass transition temperature (Tg) of the copolymer (A) is 20° C. or higher. (In formula (1), R １ and R ２ each independently represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site. (In formula (2), R ３ represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site.

3. The photosensitive resin composition according to claim 2, wherein the copolymer (A) further contains a structural unit (d) derived from an ethylenically unsaturated compound having an epoxy group or an oxetanyl group.

4. The photosensitive resin composition according to claim 2, wherein the structural unit (a) of the copolymer (A) is a structural unit derived from a compound having a group represented by formula (1) or formula (2) and an acryloyloxy group.

5. The photosensitive resin composition according to claim 1, wherein the structural unit (a) has at least one selected from an active methylene group having a methoxycarbonyl group attached thereto and an active methine group having a methoxycarbonyl group attached thereto.

6. The photosensitive resin composition according to claim 5, wherein the structural unit (a) is a structural unit having at least one selected from the group consisting of a group represented by the following formula (i-1) and a group represented by the following formula (ii-1): (In formula (i-1), n1 and n2 each independently represent an integer of 0 to 2. * represents a linking site.) (In formula (ii-1), n3 and n4 each independently represent an integer of 0 to 2. * represents a linking site.) 7. The photosensitive resin composition according to any one of claims 1, 2, and 5, wherein the copolymer (A) further contains a structural unit (e) derived from a (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms.

8. The photosensitive resin composition according to any one of claims 1, 2, and 5, wherein the copolymer (A) further contains a structural unit (f) derived from a (meth)acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms.

9. The photosensitive resin composition according to claim 5, wherein the structural unit (a) of the copolymer (A) is a structural unit derived from a compound having an acryloyloxy group and one or more selected from the group consisting of an active methylene group having a methoxycarbonyl group attached thereto and an active methine group having a methoxycarbonyl group attached thereto.

10. The structural unit (b) of the copolymer (A) is —(CH ２ ) ｎ Structural units having a group represented by —OH (n is an integer of 2 to 6) and —(O—C ｘ H ２ｘ ) ｍ The photosensitive resin composition according to any one of claims 1 to 5, wherein the structural unit is at least one selected from the group consisting of structural units having a group represented by -OH (where x is an integer of 2 to 4, and m is an integer of 2 to 6).

11. The photosensitive resin composition according to any one of claims 1, 2 and 5, wherein the acid value of the copolymer (A) is 10 to 250 KOHmg / g.

12. The photosensitive resin composition according to any one of claims 1, 2 and 5, wherein the weight average molecular weight Mw of the copolymer (A) is 3,000 to 50,000.

13. The photosensitive resin composition according to any one of claims 1, 2 and 5, wherein the reactive diluent (B) is a compound having a plurality of ethylenically unsaturated groups.

14. The photosensitive resin composition according to any one of claims 1, 2, and 5, wherein, when all structural units of said copolymer (A) are taken as 100 mol %, said copolymer (A) contains 1 to 40 mol % of said structural unit (a), 1 to 40 mol % of said structural unit (b), and 1 to 40 mol % of said structural unit (c).

15. The photosensitive resin composition according to any one of claims 1, 2 and 5, wherein the solvent (D) is a glycol ether having a hydroxy group.

16. The photosensitive resin composition according to any one of claims 1, 2, and 5, wherein, relative to 100 mass% of the total of the copolymer (A) and the reactive diluent (B), the copolymer (A) is 10 mass% or more and less than 100 mass%, the reactive diluent (B) is more than 0 mass% and 90 mass% or less, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B), the photopolymerization initiator (C) is 0.1 to 30 parts by mass relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B), and the solvent (D) is 30 to 1000 parts by mass relative to 100 parts by mass of the total of the components excluding the solvent (D).

17. The photosensitive resin composition according to any one of claims 1, 2 and 5, further comprising a colorant (E).

18. The photosensitive resin composition according to claim 17, wherein the colorant (E) comprises a pigment.

19. The photosensitive resin composition according to claim 17, wherein the hardness of a cured resin film of the photosensitive resin composition is 3H or more, the hardness being measured in accordance with JIS K5600-5-4 when a cured resin film having a thickness of 2.5 μm is formed on a glass substrate.

20. A cured resin film comprising the cured product of the photosensitive resin composition according to claim 17.

21. A color filter having a colored pattern made of a cured product of the photosensitive resin composition according to claim 17.

22. An image display device comprising the color filter according to claim 21.

Images