Photosensitive resin composition, photosensitive coloring composition, and color filter

Abstract

The present invention provides a photosensitive resin composition comprising a copolymer having a high refractive index. Also provided is a photosensitive resin composition from which a cured resin film having good light transmittance can be obtained. The present invention further provides a cured resin film having good light transmittance and a high refractive index, and an image display element comprising said cured resin film. The photosensitive resin composition contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A) contains a constitutional unit (a-1) derived from a naphthyl group-containing (meth)acrylate.

Description

Photosensitive resin composition, photosensitive coloring composition, and color filter

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive coloring composition, a cured resin film formed from the cured product of the composition, a color filter, and an image display device. This application claims priority based on Japanese Patent Application No. 2024-084358, filed on May 23, 2024, the contents of which are incorporated herein by reference.

[0002] In recent years, with the widespread use of liquid crystal displays, there has been active research into color filters used as components of liquid crystal displays, as well as overcoat layers and interlayer insulating films provided on these color filters (see, for example, Patent Documents 1 and 2). These materials are often required to have a high refractive index.

[0003] JP 2019-53266 A JP 2023-147017 A

[0004] However, further improvement is required as a material that combines a high refractive index and good light transmittance.

[0005] An object of the present invention is to provide a photosensitive resin composition containing a copolymer having a high refractive index. Another object is to provide a photosensitive resin composition from which a cured resin film having good light transmittance can be obtained. A further object is to provide a cured resin film having good light transmittance and a high refractive index, and an image display device comprising the cured resin film.

[0006] The present disclosure 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) is a copolymer containing a structural unit (a-1) derived from a naphthyl group-containing (meth)acrylate. [2] The photosensitive resin composition according to [1], wherein the copolymer (A) further contains a structural unit (a-2) having an acid group. [3] The photosensitive resin composition according to [2], wherein the acid value of the copolymer (A) is 10 to 300 KOH mg / g. [4] The photosensitive resin composition according to [2], wherein, of all structural units in the copolymer (A), the content of the structural unit (a-1) derived from a naphthyl group-containing (meth)acrylate is 5 to 95 mol %, and the content of the structural unit (a-2) having an acid group is 5 to 60 mol %. [5] The photosensitive resin composition according to any one of [1] to [5], wherein the copolymer precursor (PA1) is a copolymer containing a structural unit (a-1) derived from the naphthyl group-containing (meth)acrylate and a structural unit (a-2) having an acid group, the ethylenically unsaturated compound (e) is a compound having a functional group reactive with the acid group, and the copolymer (A) is a copolymer in which the ethylenically unsaturated compound (e) is added to some of the acid groups of the copolymer precursor (PA1). [6] The photosensitive resin composition according to [5], wherein the acid value of the copolymer (A) is 10 to 300 KOH mg / g. [7] The photosensitive resin composition according to [5], wherein, of all the structural units of the copolymer precursor (PA1), the content of the structural unit (a-1) derived from the naphthyl group-containing (meth)acrylate is 5 to 90 mol %, the content of the structural unit (a-2) having an acid group is 10 to 70 mol %, the amount of the ethylenically unsaturated compound (e) is 1 to 60 mol per 100 mol of the structural units of the copolymer precursor (PA1), and the amount of the ethylenically unsaturated compound (e) added is 5 to 90 mol per 100 mol of the structural unit (a-2) having an acid group of the copolymer precursor.[8] The photosensitive resin composition according to any one of [1] to [5], wherein the copolymer precursor (PA2) is a copolymer containing a structural unit (a-1) derived from the naphthyl group-containing (meth)acrylate and a structural unit (a-3) having an epoxy group, the ethylenically unsaturated compound (f) is a compound having a functional group reactive with the epoxy group, and the copolymer (A) is a copolymer in which the ethylenically unsaturated compound (f) adds to at least a portion of the epoxy groups of the copolymer precursor (PA2), and a polybasic acid or polybasic acid anhydride (h) adds to at least a portion of the hydroxy groups generated by ring-opening of the epoxy groups. [9] The photosensitive resin composition according to claim 8, wherein the acid value of the copolymer (A) is 10 to 300 KOH mg / g.

[10] The photosensitive resin composition according to [8], wherein, among all the structural units of the copolymer precursor (PA2), the content of the structural unit (a-1) derived from the naphthyl group-containing (meth)acrylate is 5 to 90 mol %, the content of the structural unit (a-3) having an epoxy group is 10 to 90 mol %, the amount of the ethylenically unsaturated compound (f) is 5 to 90 mol per 100 mol of the structural units of the copolymer precursor (PA2), the amount of the ethylenically unsaturated compound (f) added is 60 to 100 mol per 100 mol of the structural unit (a-3) having an epoxy group, the amount of the polybasic acid or polybasic acid anhydride is 5 to 50 mol per 100 mol of the structural units of the copolymer precursor (PA2), and the amount of the polybasic acid or polybasic acid anhydride (h) added is 10 to 90 mol per 100 mol of the ethylenically unsaturated compound (f).

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

[10] , wherein the content of the copolymer (A) is 10 to 95% by mass and the content of the reactive diluent (B) is 5 to 90% by mass relative to the total of the copolymer (A) and the reactive diluent (B), the content of 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 content of the solvent (D) is 30 to 1,000 parts by mass relative to 100 parts by mass of the total of the components excluding the solvent (D).

[12] A photosensitive coloring composition comprising the photosensitive resin composition according to any one of [1] to

[11] and a colorant (E).

[13] The photosensitive coloring composition according to

[12] , wherein the content of the colorant (E) is 0.1 to 80 parts by mass per 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).

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

[11] .

[15] A cured resin film comprising a cured product of the photosensitive coloring composition according to claim 12.

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

[11] , and having a pattern.

[17] A color filter comprising a cured product of the photosensitive coloring composition according to

[12] , and having a colored pattern.

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

[15] .

[0007] According to the present disclosure, it is possible to provide a photosensitive resin composition containing a copolymer having a high refractive index. It is also possible to provide a photosensitive resin composition that can yield a cured resin film with good light transmittance. Furthermore, it is also possible to provide a cured resin film with good light transmittance and a high refractive index, and an image display element including the cured resin film.

[0008] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the embodiments described below.

[0009] 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 using 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 the upper and lower limits from those numerical ranges.

[0010] In this specification, "(meth)acrylic acid" means methacrylic acid or acrylic acid, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy. In this specification, "(poly)alkylene glycol" means alkylene glycol or polyalkylene glycol.

[0011] As used herein, the term "ethylenically unsaturated bond" refers to a double bond formed between carbon atoms excluding carbon atoms forming an aromatic ring. The term "ethylenically unsaturated group" refers to a group having an ethylenically unsaturated bond. The term "ethylenically unsaturated compound" refers to a compound having an ethylenically unsaturated bond.

[0012] In this specification, the term "structural unit" refers to a unit derived from the polymerizable compound itself used as a monomer, or a unit obtained by further modifying a unit derived from the polymerizable compound itself used as a monomer after polymerization.

[0013] <Photosensitive Resin Composition> A photosensitive resin composition according to one 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 can be polymerized and cured by light irradiation to form a cured resin film.

[0014] [Copolymer (A)] Copolymer (A) is a copolymer containing a structural unit (a-1) (also simply referred to as "structural unit (a-1)") derived from a naphthyl group-containing (meth)acrylate. Copolymer (A) may, as necessary, contain a structural unit (a-2) (also simply referred to as "structural unit (a-2)") having an acid group, and / or a structural unit (a-4) (also simply referred to as "structural unit (a-4)") other than the structural units (a-1) and (a-2).

[0015] In another embodiment, when the copolymer (A) has the structural unit (a-2) having an acid group, the copolymer (A) may be a copolymer in which an ethylenically unsaturated compound (e) is added to a portion of the acid groups of a copolymer precursor (PA1). The copolymer precursor (PA1) contains a structural unit (a-1) derived from a naphthyl group-containing (meth)acrylate, a structural unit (a-2) having an acid group, and, as necessary, a structural unit (a-4) other than the structural units (a-1) and (a-2). The ethylenically unsaturated compound (e) is an ethylenically unsaturated compound (e) having a functional group reactive with the acid group (also simply referred to as "ethylenically unsaturated compound (e)").

[0016] In another embodiment, the copolymer (A) may be a copolymer in which an ethylenically unsaturated compound (f) is added to at least a portion of the epoxy groups of the copolymer precursor (PA2), and a polybasic acid or polybasic acid anhydride (h) is added to at least a portion of the hydroxy groups produced by ring-opening of the epoxy groups. The copolymer precursor (PA2) contains a structural unit (a-1) derived from a naphthyl group-containing (meth)acrylate, a structural unit (a-3) having an epoxy group (also simply referred to as "structural unit (a-3)"), and, if necessary, a structural unit (a-4) other than the structural units (a-1) to (a-3). The ethylenically unsaturated compound (f) is an ethylenically unsaturated compound (f) having a functional group reactive with the epoxy group (simply referred to as "ethylenically unsaturated compound (f)").

[0017] In an embodiment in which the copolymer (A) has the structural unit (a-2) or an embodiment in which the copolymer (A) is a copolymer to which a polybasic acid or a polybasic acid anhydride (h) is added, the acid value of the copolymer (A) is preferably 10 KOHmg / g or more, more preferably 20 KOHmg / g or more, and even more preferably 30 KOHmg / g or more. The acid value of the copolymer (A) is preferably 300 KOHmg / g or less, more preferably 200 KOHmg / g or less, and even more preferably 150 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 or the photosensitive coloring composition is good. When the acid value of the copolymer (A) is 300 KOHmg / g or less, the storage stability of the photosensitive resin composition or the photosensitive coloring composition is good.

[0018] The acid value of the copolymer (A) is the acid value of the curable polymer measured in accordance with JIS K6901:2008 5.3. That is, the acid value means the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer.

[0019] The weight average molecular weight (Mw) of the copolymer (A) is preferably 1,000 or more, more preferably 2,000 or more, and even more preferably 4,000 or more. The weight average molecular weight of the copolymer (A) is preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less. When the weight average molecular weight of the copolymer (A) is 1,000 or more, the patterning properties of the photosensitive resin composition or the photosensitive coloring composition are good. When the weight average molecular weight of the copolymer (A) is 50,000 or less, the storage stability of the photosensitive resin composition or the photosensitive coloring composition is good.

[0020] The molecular weight distribution (Mw / Mn) of the copolymer (A) is preferably 1.3 or more, more preferably 1.5 or more, even more preferably 1.7 or more, and particularly preferably 1.9 or more. The molecular weight distribution (Mw / Mn) of the copolymer (A) is preferably 5.0 or less, more preferably 4.5 or less, even more preferably 4.0 or less, and particularly preferably 3.5 or less. When the molecular weight distribution (Mw / Mn) of the copolymer (A) is 1.3 or more, it is easy to control the production conditions during synthesis of the copolymer (A). When the molecular weight distribution (Mw / Mn) of the copolymer (A) is 5.0 or less, storage stability is good.

[0021] In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) under the following conditions and determined using a standard polystyrene calibration curve. Column: Two Showdex (trademark) LF-804 (Resonac Corporation) connected in series. Column temperature: 40°C. Sample: 0.2% by mass solution of the object to be measured in tetrahydrofuran. Developing solvent: tetrahydrofuran. Detector: differential refractometer (Shodex (trademark) RI-71S) (Resonac Corporation). Flow rate: 1 mL / min.

[0022] The refractive index of the copolymer (A) is preferably 1.55 or more, more preferably 1.58 or more, and even more preferably 1.60 or more. The refractive index of the copolymer (A) may be 1.75 or less, 1.70 or less, or 1.65 or less.

[0023] In this specification, the "refractive index" of the resin (copolymer) alone is a value calculated by the following method. That is, the refractive index of a resin composition (sample) containing a resin and a solvent is measured under the following conditions, and then the refractive index of the solvent is measured under the following conditions. Next, the content (solid content) of the resin contained in the sample is measured in accordance with JIS K6901 5.11, and the refractive index of the resin alone contained in the sample is calculated using the following formula. Measuring instrument: J-357 Automatic Refractometer (Rudolph Research Analytical Co.) Measurement wavelength: 589 nm Measurement temperature: 25°C Refractive index of resin alone = (refractive index of sample - refractive index of solvent) ÷ solid content × 100 + refractive index of solvent

[0024] In an embodiment in which the copolymer (A) is a copolymer to which an ethylenically unsaturated compound (e) is added, or in an embodiment in which the copolymer (A) is a copolymer to which an ethylenically unsaturated compound (f) is added, the ethylenically unsaturated group equivalent of the copolymer (A) is preferably 100 g / mol or more, more preferably 200 g / mol or more, and even more preferably 300 g / mol or more. The ethylenically unsaturated group equivalent of the copolymer (A) is preferably 4,000 g / mol or less, more preferably 3,000 g / mol or less, and even more preferably 2,000 g / mol or less. When the ethylenically unsaturated group equivalent of the copolymer (A) is 100 g / mol or more, the storage stability of the photosensitive resin composition or the photosensitive coloring composition is good. When the ethylenically unsaturated group equivalent of the copolymer (A) is 4,000 g / mol or less, the solvent resistance of the cured product of the photosensitive resin composition or the photosensitive coloring composition is good.

[0025] The ethylenically unsaturated group equivalent is the mass of the copolymer (A) per mole of the ethylenically unsaturated group in the copolymer (A). The ethylenically unsaturated group equivalent can be determined by dividing the mass of the copolymer (A) by the number of ethylenically unsaturated groups in the copolymer (A) (g / mol). In this specification, the ethylenically unsaturated group equivalent of the copolymer (A) is a theoretical value calculated from the amounts of raw materials used in producing the copolymer (A).

[0026] The content of copolymer (A) in the photosensitive resin composition or photosensitive coloring composition is preferably 10% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more, based on the total of copolymer (A) and reactive diluent (B). The content of copolymer (A) is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, based on the total of copolymer (A) and reactive diluent (B). When the content of copolymer (A) is within the above range, the viscosity of the photosensitive resin composition or photosensitive coloring composition becomes a range suitable for handling, and in addition, the photocurability is also improved.

[0027] (Structural Unit (a-1) Derived from Naphthyl Group-Containing (Meth)acrylate) The structural unit (a-1) is a structural unit derived from a naphthyl group-containing (meth)acrylate (ma-1) (hereinafter also simply referred to as "monomer (ma-1)"). The structural unit (a-1) may be of only one type, or may be of two or more types. By including the structural unit (a-1) in the copolymer (A), the refractive index becomes high, and a cured resin film with a high refractive index can be obtained. Furthermore, a cured resin film with good light transmittance can be obtained. In other words, compared to when a high refractive index monomer other than the monomer (ma-1) is used, it is possible to achieve both a high refractive index and a high light transmittance.

[0028] Examples of naphthyl group-containing (meth)acrylates (ma-1) include naphthyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, etc. Among these, from the viewpoints of improving the refractive index of the resin and the light transmittance of the cured resin film, naphthylmethyl (meth)acrylate is preferred, and 1-naphthylmethyl (meth)acrylate is more preferred.

[0029] The content of the structural unit (a-1) in the copolymer (A) can be appropriately determined depending on the application. The content of the structural unit (a-1) is preferably 5 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the total structural units of the copolymer (A). The content of the structural unit (a-1) may be 95 mol% or less, 90 mol% or less, or even 80 mol% or less. When the content of the structural unit (a-1) is 20 mol% or more, the refractive index of the copolymer (A) becomes sufficiently high, and a cured resin film having a high refractive index is obtained. Furthermore, the light transmittance when formed into a cured resin film is good. In other words, a cured resin film that achieves both a high refractive index and a high light transmittance can be obtained. In applications where the developability of the photosensitive resin composition is not required, i.e., applications where patterning is not required for the cured resin film, the content of the structural unit (a-1) may be 100 mol%. When the structural unit (a-1) is 100 mol%, the copolymer (A) of the present invention is a polymer, but for the sake of simplicity, this distinction will not be made. In an embodiment in which an ethylenically unsaturated compound (e) is added, when the structural units of the copolymer precursor (PA1) are taken as 100 mol, the content of the structural unit (a-1) is the same as the above-mentioned range. In an embodiment in which an ethylenically unsaturated compound (f) is added, when the structural units of the copolymer precursor (PA2) are taken as 100 mol, the content of the structural unit (a-1) is the same as the above-mentioned range.

[0030] (Structural Unit (a-2) Having an Acid Group) The structural unit (a-2) having an acid group is not particularly limited, as long as it is a structural unit that does not have a naphthyl group or an epoxy group and has an acid group. The structural unit (a-2) may be of only one type, or of two or more types. The structural unit (a-2) is a structural unit derived from an acid group-containing monomer (ma-2) (hereinafter, also simply referred to as "monomer (ma-2)"). When the copolymer (A) has the structural unit (a-2), the photosensitive resin composition or photosensitive coloring composition has good developability.

[0031] Examples of the acid group contained in the structural unit (a-2) include a carboxy group, a sulfo group, a phospho group, etc. Of these acid groups, in terms of ease of availability, a carboxy group is preferred as the acid group contained in the structural unit (a-2).

[0032] Monomer (ma-2) is a monomer that does not have a naphthyl group or an epoxy group, but has an ethylenically unsaturated bond and an acid group. Examples of monomer (ma-2) include unsaturated carboxylic acids or anhydrides thereof, unsaturated sulfonic acids, and unsaturated phosphonic acids.

[0033] Specific examples of the monomer (ma-2) include unsaturated carboxylic acids or anhydrides thereof such as (meth)acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic 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. Monomer (ma-2) may be used alone or in combination of two or more.

[0034] Among these monomers, it is preferable to use an unsaturated carboxylic acid as the monomer (ma-2), and it is more preferable to use (meth)acrylic acid, because these monomers are easily available and the photosensitive resin composition or photosensitive coloring composition containing the copolymer (A) has excellent alkali developability.

[0035] The content of the structural unit (a-2) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on all structural units of the copolymer (A). The content of the structural unit (a-2) is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less, based on all structural units of the copolymer (A). When the content of the structural unit (a-2) is 5 mol% or more, the developability of the photosensitive resin composition or photosensitive coloring composition is good. When the content of the structural unit (a-2) is 60 mol% or less, the content of the structural unit (a-1) can be sufficiently ensured, and the refractive index of the resin becomes sufficiently high. In an embodiment in which an ethylenically unsaturated compound (e) is added, when the structural units of the copolymer precursor (PA1) are taken as 100 mol, the content of the structural unit (a-2) is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more. The content of the structural unit (a-2) is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, of all structural units of the copolymer (A). When the content of the structural unit (a-2) is 10 mol% or more, the developability of the photosensitive resin composition or photosensitive coloring composition is good. When the content of the structural unit (a-2) is 70 mol% or less, the content of the structural unit (a-1) can be sufficiently ensured, the refractive index of the resin is sufficiently high, and the refractive index and transparency of the photosensitive resin composition or photosensitive coloring composition are good.

[0036] (Ethylenically unsaturated compound (e) having a functional group reactive with an acid group) The ethylenically unsaturated compound (e) has a functional group reactive with an acid group and an ethylenically unsaturated group. The ethylenically unsaturated compound (e) may be of only one type, or of two or more types. By adding the ethylenically unsaturated compound (e) to the copolymer precursor (PA1), an ethylenically unsaturated group is introduced. As a result, the photosensitive resin composition or the photosensitive coloring composition has good photocurability, and the solvent resistance of the cured product is improved.

[0037] Examples of the functional group reactive with an acid group include an epoxy group, an oxetanyl group, a hydroxy group, an isocyanato group, etc. Among these, an epoxy group is preferred from the viewpoint of ease of synthesis of the copolymer (A).

[0038] Examples of the ethylenically unsaturated compound having an epoxy group include (meth)acrylic acid ester derivatives containing an epoxy group, such as oxiranyl(meth)acrylate, glycidyl(meth)acrylate, 2-methylglycidyl(meth)acrylate, 2-ethylglycidyl(meth)acrylate, 2-oxiranylethyl(meth)acrylate, 2-glycidyloxyethyl(meth)acrylate, 3-glycidyloxypropyl(meth)acrylate, 4-glycidyloxybutyl(meth)acrylate, and glycidyloxyphenyl(meth)acrylate; and 3,4-epoxycyclohexyl(meth)acrylate. ) acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, and other (meth)acrylate derivatives containing an epoxy group-containing alicyclic carbon ring such as a 3,4-epoxycyclohexane ring; vinyl ether compounds containing an epoxy group; and allyl ether compounds containing an epoxy group. Among these, from the viewpoints of polymerizability and ease of availability, epoxy group-containing (meth)acrylates such as oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 4-glycidyloxybutyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate are preferred, with glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 4-glycidyloxybutyl (meth)acrylate being more preferred.

[0039] The ethylenically unsaturated compound (e) may be used alone or in combination of two or more kinds.

[0040] The amount of the ethylenically unsaturated compound (e) is preferably 1 mol or more, more preferably 5 mol or more, and even more preferably 10 mol or more, relative to 100 mol of the structural units of the copolymer precursor. The amount of the ethylenically unsaturated compound (e) is preferably 60 mol or less, more preferably 50 mol or less, and even more preferably 40 mol or less, relative to 100 mol of the structural units of the copolymer precursor (PA1). When the amount of the ethylenically unsaturated compound (e) relative to 100 mol of the structural units of the copolymer precursor (PA1) is 1 mol or more, the photocurability of the photosensitive resin composition or photosensitive coloring composition is good. When the amount of the ethylenically unsaturated compound (e) relative to 100 mol of the structural units of the copolymer precursor is 60 mol or less, the acid group content of the structural unit (a-2) can be sufficiently ensured, and the developability of the photosensitive resin composition or photosensitive coloring composition is good.

[0041] The amount of the ethylenically unsaturated compound (e) added is preferably 5 moles or more, more preferably 10 moles or more, and even more preferably 20 moles or more, per 100 moles of the structural unit (a-2). The amount of the ethylenically unsaturated compound (e) added is preferably 90 moles or less, more preferably 80 moles or less, and even more preferably 70 moles or less, per 100 moles of the structural unit (a-2). When the amount of the ethylenically unsaturated compound (e) added per 100 moles of the structural unit (a-2) is 5 moles or more, the photocurability of the photosensitive resin composition or photosensitive coloring composition is good. When the amount of the ethylenically unsaturated compound (e) added per 100 moles of the structural unit (a-2) is 90 moles or less, the acid group content of the structural unit (a-2) can be sufficiently ensured, and the developability of the photosensitive resin composition or photosensitive coloring composition is good.

[0042] (Structural Unit (a-3) Having an Epoxy Group) The structural unit (a-3) having an epoxy group is not particularly limited as long as it does not have a naphthyl group or an acid group and has an epoxy group. The structural unit (a-3) may be of only one type, or may be of two or more types. The structural unit (a-3) is a structural unit derived from an epoxy group-containing monomer (ma-3) (hereinafter also simply referred to as "monomer (ma-3)"). When the copolymer precursor (PA2) has the structural unit (a-3), the epoxy group becomes a reaction site when the ethylenically unsaturated compound (f) is added to the copolymer (A), and photocurability is imparted to the photosensitive resin composition or photosensitive coloring composition. Furthermore, when the copolymer precursor (PA2) has the structural unit (a-3), the epoxy group becomes a reaction site when the polybasic acid or polybasic acid anhydride (h) is added, and developability is imparted to the photosensitive resin composition or photosensitive coloring composition.

[0043] Monomer (ma-3) is a monomer that does not have a naphthyl group or an acid group, but has an ethylenically unsaturated bond and an epoxy group.

[0044] Specifically, the monomer (ma-3) may be any of the ethylenically unsaturated compounds having an epoxy group exemplified as the ethylenically unsaturated compound (e) and a preferred range thereof. The monomer (ma-3) may be used alone or in combination of two or more.

[0045] The content of the structural unit (a-3), when the structural units of the copolymer precursor (PA2) are taken as 100 moles, is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more. The content of the structural unit (a-2), when the structural units of the copolymer precursor (PA2) are taken as 100 moles, is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less. When the content of the structural unit (a-3) is 10 mol% or more, sufficient reaction sites can be secured when adding the ethylenically unsaturated compound (f), polybasic acid or polybasic acid anhydride (h) to the copolymer precursor (PA2), and the photocurability and developability of the photosensitive resin composition or photosensitive coloring composition are good. When the content of the structural unit (a-2) is 90 mol% or less, the content of the structural unit (a-1) can be sufficiently ensured, the refractive index of the resin becomes sufficiently high, and the refractive index and transparency of the photosensitive resin composition or photosensitive coloring composition become good.

[0046] (Ethylenically unsaturated compound (f) having a functional group reactive with an epoxy group) The ethylenically unsaturated compound (f) has a functional group reactive with an epoxy group and an ethylenically unsaturated group. The ethylenically unsaturated compound (f) may be of only one type, or of two or more types. By adding the ethylenically unsaturated compound (f) to the copolymer precursor (PA2), an ethylenically unsaturated group is introduced. As a result, the photosensitive resin composition or the photosensitive coloring composition has good photocurability, and the solvent resistance of the cured product is improved.

[0047] The functional group reactive with an epoxy group is preferably an acid group.

[0048] As the ethylenically unsaturated compound having an acid group, for example, the compounds exemplified as the acid group-containing monomer (ma-2) and preferred ranges thereof can be used.

[0049] The ethylenically unsaturated compound (f) may be used alone or in combination of two or more kinds.

[0050] The amount of the ethylenically unsaturated compound (f) is preferably 5 moles or more, more preferably 15 moles or more, and even more preferably 25 moles or more, relative to 100 moles of the structural units of the copolymer precursor (PA2). The amount of the ethylenically unsaturated compound (f) is preferably 90 moles or less, more preferably 80 moles or less, and even more preferably 70 moles or less, relative to 100 moles of the structural units of the copolymer precursor (PA2). When the amount of the ethylenically unsaturated compound (f) is 5 moles or more relative to 100 moles of the structural units of the copolymer precursor (PA2), the photocurability of the photosensitive resin composition or the photosensitive coloring composition is good.

[0051] The amount of the ethylenically unsaturated compound (f) added is preferably 60 moles or more, more preferably 70 moles or more, and even more preferably 90 moles or more, per 100 moles of the structural unit (a-3). The amount of the ethylenically unsaturated compound (f) added is 100 moles or less, alternatively 99 moles or less, or alternatively 95 moles or less, per 100 moles of the structural unit (a-3). When the amount of the ethylenically unsaturated compound (f) added per 100 moles of the structural unit (a-3) is 60 moles or more, the photocurability of the photosensitive resin composition or photosensitive coloring composition is good.

[0052] (Polybasic Acid or Polybasic Acid Anhydride (h)) The polybasic acid or polybasic acid anhydride (h) is a compound having two or more carboxy groups or an anhydride thereof. In the copolymer (A), an ethylenically unsaturated compound (f) having a functional group reactive with the epoxy group is added to the epoxy group of the structural unit (a-3), and a polybasic acid or polybasic acid anhydride (h) is further added to some of the hydroxy groups generated by ring-opening of the epoxy group to introduce a carboxy group. Since the amount of carboxy groups introduced by the polybasic acid or polybasic acid anhydride (h) can be adjusted in the copolymer (A), the developability of the photosensitive resin composition or photosensitive coloring composition can be adjusted to the desired range. Examples of polybasic acids include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid. Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, succinic anhydride, and cyclohexanetricarboxylic anhydride. These compounds may be used alone or in combination of two or more. Among these, from the viewpoint of the hardness of the cured film, polybasic acid anhydrides having an alicyclic structure are preferred, and maleic anhydride, itaconic anhydride, ethylmaleic anhydride, methylitaconic anhydride, chloromaleic anhydride, citraconic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and cyclohexanetricarboxylic anhydride are more preferred, and from the viewpoint of increasing the amount of carboxy groups introduced and improving low-temperature curing properties, tetrahydrophthalic anhydride and cyclohexanetricarboxylic anhydride are even more preferred.

[0053] The polybasic acids or polybasic acid anhydrides may be used alone or in combination of two or more kinds.

[0054] The amount of polybasic acid or polybasic acid anhydride (h) is preferably 5 moles or more, more preferably 10 moles or more, and even more preferably 15 moles or more, when the structural units of the copolymer precursor (PA2) are 100 moles. The amount of polybasic acid or polybasic acid anhydride is preferably 50 moles or less, more preferably 40 moles or less, and even more preferably 30 moles or less, when the structural units of the copolymer precursor (PA2) are 100 moles. When the amount of polybasic acid or polybasic acid anhydride is 5 moles or more, the developability of the photosensitive resin composition or photosensitive coloring composition is good. When the amount of polybasic acid or polybasic acid anhydride is 50 moles or more, the storage stability of the photosensitive resin composition or photosensitive coloring composition is good.

[0055] The amount of polybasic acid or polybasic acid anhydride (h) added is preferably 10 moles or more, more preferably 20 moles or more, and even more preferably 30 moles or more, when the ethylenically unsaturated compound (f) is 100 moles. The amount of polybasic acid or polybasic acid anhydride added is preferably 90 moles or less, more preferably 70 moles or less, and even more preferably 60 moles or less, when the ethylenically unsaturated compound (f) is 100 moles. When the amount of polybasic acid or polybasic acid anhydride added is 10 moles or more, the developability of the photosensitive resin composition or photosensitive coloring composition is good. When the amount of polybasic acid or polybasic acid anhydride added is 90 moles or less, the storage stability of the photosensitive resin composition or photosensitive coloring composition is good.

[0056] (Other structural unit (a-4)) The copolymer (A) or copolymer precursor may, if necessary, have a structural unit (a-4) other than the structural units (a-1) to (a-3). The other structural unit (a-4) is a structural unit derived from another monomer (ma-4) (hereinafter also simply referred to as "monomer (ma-4)") that does not have a naphthyl group, an acid group, or an epoxy group and is copolymerizable with the monomers (ma-1) to (ma-3). The structural unit (a-4) can adjust the physical properties required for the photosensitive resin composition or photosensitive coloring composition or can impart functions to the composition.

[0057] Specific examples of the monomer (ma-4) include aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, (meth)acrylic acid anilides, (meth)acrylonitrile, and acrolein.

[0058] 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.

[0059] 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, and the like.

[0060] Examples of dienes include butadiene, isoprene, and chloroprene.

[0061] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and tricyclodecanyl (meth)acrylate. acrylate, hydroxyethyl (meth)acrylate, hydroxybutyl (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, anthracene (meth)acrylate, and ethoxylated phenyl (meth)acrylate.

[0062] Examples of the (meth)acrylic acid amide include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide.

[0063] Examples of the vinyl compound include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene.

[0064] Examples of the unsaturated dicarboxylic acid diester include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0065] Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide.

[0066] The monomer (ma-4) may be used alone or in combination of two or more kinds.

[0067] Among these, from the viewpoint of the refractive index of the copolymer (A), compounds having a refractive index of 1.5 or more when made into a homopolymer are preferred, and compounds having a refractive index of 1.55 or more are more preferred. Specific examples of such compounds include vinyltoluene (refractive index of homopolymer: 1.58), styrene (refractive index of homopolymer: 1.58), and benzyl methacrylate (refractive index of homopolymer: 1.56).

[0068] When the copolymer (A), copolymer precursor (PA1), or copolymer precursor (PA2) contains the structural unit (a-4), the content of the structural unit (a-4) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, of the total structural units of the copolymer (A), copolymer precursor (PA1), or copolymer precursor (PA2). The content of the structural unit (a-4) is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less, of the total structural units of the copolymer (A), copolymer precursor (PA1), or copolymer precursor (PA2). When the content of the structural unit (a-4) is 1 mol% or more, it is possible to impart the necessary functions to the photosensitive resin composition or photosensitive coloring composition. When the content of the structural unit (a-4) is 50 mol% or less, the contents of the structural units (a-1) to (a-3) can be sufficiently ensured, and therefore the refractive index of the copolymer (A) or the cured resin film is sufficiently high, and the developability imparted to the photosensitive resin composition or photosensitive coloring composition as needed is good.

[0069] [Reactive Diluent (B)] The reactive diluent (B) is not particularly limited as long as it is a low-molecular-weight compound having at least one ethylenically unsaturated group. In this specification, a low-molecular-weight compound refers to a compound having a molecular weight of less than 1,000. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, and a (meth)acryloyloxy group. From the viewpoint of improving curing properties, a polyfunctional reactive diluent having multiple ethylenically unsaturated groups is preferred. Specific examples of the reactive diluent (B) include aromatic vinyl compounds; aromatic allyl compounds such as diallyl phthalate and diallyl benzene phosphonate; vinyl carboxylates such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; triallyl cyanurate, etc.

[0070] Specific examples of aromatic vinyl compounds include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene.

[0071] 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.

[0072] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate.

[0073] Among these, polyfunctional (meth)acrylates are preferred as the reactive diluent (B) in order to improve reactivity, and at least one selected from dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate is particularly preferred.

[0074] The reactive diluent (B) may be used alone or in combination of two or more kinds.

[0075] The content of the reactive diluent (B) in the photosensitive resin composition or the photosensitive coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on 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 60% by mass or less, and even more preferably 40% by mass or less, based on the total of the copolymer (A) and the reactive diluent (B). When the content of the reactive diluent (B) is within the above range, the viscosity of the photosensitive resin composition or the photosensitive coloring composition becomes a range suitable for handling, and in addition, the photocurability is also improved.

[0076] [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.

[0077] The content of the photopolymerization initiator (C) in the photosensitive resin composition or photosensitive coloring 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 or photosensitive coloring 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). When the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, a photosensitive resin composition or photosensitive coloring 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 or photosensitive coloring composition from being adversely affected by too much photopolymerization initiator (C).

[0078] [Solvent (D)] Examples of the solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol mono-n-butyl ether, propylene glycol monoalkyl ethers such as triethylene glycol monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, tripropylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether, (poly)alkylene glycol monoalkyl ethers such as 3-methoxy-1-butanol, hydroxy group-containing carboxylic acid esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutyrate, and diethylene glycol hydroxy group-containing organic solvents such as ethanol; and (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; methyl ethyl ketone, cyclohexanone, Ketones such as 2-heptanone and 3-heptanone; esters such as methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, i-propyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;Examples of the solvent (D) include aromatic hydrocarbons such as toluene and xylene, and hydroxy-free organic solvents such as 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.

[0079] Among these solvents (D), from the viewpoints of availability, cost, and stability during resist preparation, it is preferable to use a compound having an ether structure, and specifically, it is more preferable to use at least one 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.

[0080] The content of the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, relative to 100 parts by mass of the total of the components excluding the solvent (D). The content of the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, relative to 100 parts by mass of the total of the components excluding the solvent (D). When the content of the solvent (D) is 30 parts by mass or more, the viscosity of the photosensitive resin composition or the photosensitive coloring composition can be set to an appropriate range. When the content of the solvent (D) is 1,000 parts by mass or less, when removing the solvent (D) in the coating film formed by applying the photosensitive resin composition or the photosensitive coloring composition to a substrate, the solvent (D) can be easily removed.

[0081] <Photosensitive Coloring Composition> The photosensitive coloring composition contains a colorant (E) in addition to the above-mentioned photosensitive resin composition.

[0082] [Colorant (E)] The photosensitive coloring composition containing the colorant (E) can be used as a material for a color filter.

[0083] 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.

[0084] As the dye, from the viewpoint of solubility in the solvent (D) and the alkaline developer, interaction with other components in the photosensitive coloring composition, heat resistance, etc., 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, a sulfonamide adduct of an acid dye, etc.

[0085] 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 may be used alone or in combination of two or more.

[0086] 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.

[0087] The colorant (E) can be appropriately determined depending on, for example, the desired color pattern, i.e., the color of the 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.

[0088] When a pigment is used as the colorant (E), a known dispersant may be blended into the photosensitive coloring composition to improve the dispersibility of the pigment. It is preferable to use a polymer dispersant that has excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. Commercially available polymer dispersants under trade names such as EFKA (EFKA CHEMICALS B.V.), Disperbyk (BYK), Disparlon (Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (Lubrizol Corporation) 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).

[0089] The content of the colorant (E) in the photosensitive coloring composition is preferably 0.1 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 the total 100 parts by mass of the copolymer (A) and the reactive diluent (B). The content of the colorant (E) in the photosensitive coloring 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 the total 100 parts by mass of the copolymer (A) and the reactive diluent (B). When the content of the colorant (E) is 0.1 parts by mass or more, the effect of containing the colorant (E) becomes significant, and a photosensitive coloring composition suitable as a material for the color pattern of a color filter 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 coloring composition, and a photosensitive coloring composition with good curing property can be obtained.

[0090] [Other Components] In addition to the copolymer (A), reactive diluent (B), photopolymerization initiator (C), solvent (D), and optionally contained colorant (E), the photosensitive resin composition or photosensitive coloring composition of one embodiment of the present invention may contain known additives such as coupling agents, leveling agents, and polymerization inhibitors as needed. The amount of additives added is not particularly limited as long as it does not impair the effects of the present invention. By containing the copolymer (A), the photosensitive resin composition or photosensitive coloring composition of one embodiment of the present invention can obtain a cured resin film having good light transmittance and a high refractive index. Therefore, a cured resin film having a high refractive index can be obtained without using inorganic particles other than the colorant (E) in combination to improve the refractive index of the cured resin film, or without using a dispersant to disperse the inorganic particles. From the viewpoint of ensuring particularly good light transmittance, the content of inorganic particles in the photosensitive resin composition is preferably 0% by mass relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). The content of the dispersant in the photosensitive resin composition is preferably 0% by mass relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). The content of inorganic particles other than the colorant (E) in the photosensitive coloring composition is preferably 0% by mass relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).

[0091] <Method for Producing Copolymer (A)> Copolymer (A) is obtained by copolymerizing monomer (ma-1), and, if necessary, monomer (ma-2), and other monomer (ma-4). In another embodiment, copolymer (A) can be produced by a method including the steps of: copolymerizing monomer (ma-1), monomer (ma-2), and, if necessary, other monomer (ma-4) to obtain copolymer precursor (PA1); and adding ethylenically unsaturated compound (e) to a portion of the acid groups of structural unit (a-2) of copolymer precursor (PA1) to obtain copolymer (A). In another embodiment, copolymer (A) can be produced by a method including the following steps: - A step of copolymerizing the monomer (ma-1), the monomer (ma-3), and, if necessary, another monomer (ma-4) to obtain the copolymer precursor (PA2); - A step of adding an ethylenically unsaturated compound (f) to at least a portion of the epoxy groups of the structural unit (a-3) of the copolymer precursor (PA2), and then adding a polybasic acid or a polybasic acid anhydride (h) to obtain the copolymer (A). The proportions of the structural units (a-1), (a-2), (a-3), and (a-4) contained in the copolymer (A), the copolymer precursor (PA1), or the copolymer precursor (PA2) are equivalent to the proportions of the respective monomers (ma-1), (ma-2), (ma-3), and (ma-4) in the total of all the monomers used as raw materials for the copolymer (A), the copolymer precursor (PA1), or the copolymer precursor (PA2).

[0092] The proportions of the monomers used in the copolymerization reaction to form the copolymer (A), the copolymer precursor (PA1), or the copolymer precursor (PA2) are not particularly limited. When the monomer (ma-2) is used, the proportions are preferably 5 to 95 mol % of the monomer (ma-1) and 5 to 95 mol % of the monomer (ma-2), more preferably 20 to 90 mol % of the monomer (ma-1) and 10 to 60 mol %, and even more preferably 30 to 80 mol % of the monomer (ma-1) and 15 to 50 mol % of the monomer (ma-2). When the monomer (ma-3) is used, the proportions are preferably 5 to 95 mol % of the monomer (ma-1) and 10 to 90 mol % of the monomer (ma-3), more preferably 20 to 90 mol % of the monomer (ma-1) and 20 to 80 mol % of the monomer (ma-3), and even more preferably 30 to 80 mol % of the monomer (ma-1) and 30 to 70 mol % of the monomer (ma-3).

[0093] The copolymerization reaction can be carried out in the presence or absence of a solvent according to a radical polymerization method known in the art. For example, the above-mentioned monomers may be dissolved in an organic solvent, a polymerization initiator may be added to the solution, and the polymerization reaction may be carried out at 50 to 100°C for 1 to 20 hours.

[0094] The solvent used in the copolymerization reaction can be the same as the solvent (D) described above. Other examples include hydroxy group-containing organic solvents such as 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, C5-6 cycloalkane dimethanol, ethyl lactate, and diacetone alcohol. Note that "C5-6 cycloalkane" means that the cycloalkyl group has 5 to 6 carbon atoms. The solvents may be used alone or in combination of two or more.

[0095] The polymerization initiator (i) that can be used in the copolymerization reaction is not particularly limited, but examples include azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate. The polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is generally 0.5 to 20 parts by mass, and preferably 1.0 to 18 parts by mass, per 100 parts by mass of the total amount of monomers charged.

[0096] Known addition reactions can be used as a method for adding an ethylenically unsaturated compound (e) to a portion of the acid groups of the structural unit (a-2) of the copolymer precursor (PA1), and adding an ethylenically unsaturated compound (f) to a portion of the epoxy groups of the structural unit (a-3) of the copolymer precursor (PA2), followed by adding a polybasic acid or polybasic acid anhydride (h). For example, a polymerization inhibitor and a catalyst are added to a reaction solution in which a copolymerization reaction has been carried out, and then the ethylenically unsaturated compound (e), the ethylenically unsaturated compound (f), and the polybasic acid or polybasic acid anhydride (h) are added as the compounds to be added, and the addition reaction is carried out under conditions of room temperature (23°C) to 150°C, preferably 50 to 120°C. The polymerization inhibitor is added to prevent side reactions of the introduced unsaturated groups.

[0097] Specific examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene.

[0098] Specific examples of the catalyst include quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine, tripartylphosphine, tricyclohexylphosphine, and tetraphenylphosphonium salts, and organometallic compounds containing metals such as chromium and tin. The amount of the catalyst used is preferably 0.5 to 12 parts by mass, and more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the total of the monomers and the ethylenically unsaturated compound (e) used in the copolymerization reaction of the copolymer precursor.

[0099] <Method for producing photosensitive resin composition and photosensitive coloring composition> The photosensitive resin composition of one embodiment of the present invention can be produced by a method of mixing the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), and the solvent (D) using a known mixing device. The photosensitive coloring composition of one embodiment of the present invention can be produced by a method of mixing the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and the coloring agent (E) using a known mixing device.

[0100] When producing a photosensitive resin composition or a photosensitive coloring 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 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.

[0101] When producing a photosensitive resin composition or a photosensitive coloring composition, the copolymer (A) isolated by a known method from a reaction solution containing the copolymer (A) may be used as a raw material.

[0102] The photosensitive resin composition or photosensitive coloring composition contains the copolymer (A) having a high refractive index, and therefore can form a cured resin film having a high refractive index.

[0103] The photosensitive resin composition or photosensitive coloring composition contains a copolymer (A) having an ethylenically unsaturated group introduced by the addition of an ethylenically unsaturated compound (e), a reactive diluent (B), and a photopolymerization initiator (C). Therefore, by irradiating with light, the reactive diluent (B) polymerizes together with the ethylenically unsaturated group contained in the copolymer (A), thereby exhibiting good photocurability. Similarly, in another embodiment, the photosensitive resin composition or photosensitive coloring composition contains a copolymer (A) having an ethylenically unsaturated group introduced by the addition of an ethylenically unsaturated compound (f), a reactive diluent (B), and a photopolymerization initiator (C). Therefore, by irradiating with light, the reactive diluent (B) polymerizes together with the ethylenically unsaturated group contained in the copolymer (A), thereby exhibiting good photocurability.

[0104] When the copolymer (A) contained in the photosensitive resin composition or the photosensitive coloring composition has an acid value, the photosensitive resin composition or the photosensitive coloring composition has good alkaline developability.Since such a photosensitive resin composition or the photosensitive coloring composition has excellent alkaline developability, for example, it is applied to a substrate to form a coating film, and exposed through a photomask corresponding to a predetermined pattern shape, and the unexposed part is developed with an alkaline aqueous solution, and then baked, thereby forming a cured product having a predetermined pattern shape.

[0105] The photosensitive resin composition and the photosensitive coloring composition can be suitably used as materials for color filters.

[0106] For these reasons, the photosensitive resin composition and the photosensitive coloring composition are extremely useful as materials for forming components of image display elements, such as pixels of color filters, black matrices, protective films for color filters, insulating films, photospacers, protrusions for liquid crystal alignment, microlenses, and insulating films for touch panels.

[0107] <Cured Resin Film> A cured resin film according to one embodiment of the present invention is a cured product of a photosensitive resin composition or a photosensitive coloring composition.

[0108] The cured resin film can be produced, for example, by a method in which a photosensitive resin composition or a photosensitive coloring 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.

[0109] When forming a cured resin film having a predetermined pattern shape, a copolymer (A) having an acid value can be used, for example, by the method shown below. That is, a photosensitive resin composition or a photosensitive coloring 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 to photocure the exposed portions. 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.

[0110] When producing a cured resin film, known methods can be used for applying the photosensitive resin composition or the photosensitive coloring composition, exposing the applied film, and developing the same.

[0111] The conditions for the baking treatment carried out when producing a cured resin film can be appropriately determined depending on the composition of the photosensitive resin composition or the photosensitive coloring composition, the film thickness of the coating film, the material of the substrate, etc. The baking treatment can be carried out at a temperature of, for example, 70°C to 250°C.

[0112] 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 or the photosensitive coloring composition, the temperature of the baking treatment, the film thickness of the coating film, etc. The cured resin film can be preferably used as a component of a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a microlens, a black matrix, a black column spacer, or a color filter.

[0113] <Color Filter> A color filter according to one embodiment of the present invention has a color pattern that is a cured product of a photosensitive coloring composition. The color filter preferably has a color pattern that is a cured product of a photosensitive coloring composition in which the content of copolymer (A) is 10 to 95% by mass, the content of reactive diluent (B) is 5 to 90% by mass, and the content of photopolymerization initiator (C) is 0.1 to 30 parts by mass, and the content of colorant (E) is 0.1 to 80 parts by mass, per 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B), and the content of solvent (D) is 30 to 1,000 parts by mass, per 100 parts by mass of the total of the components excluding solvent (D).

[0114] 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.

[0115] In the color filter, the pixels and the black matrix are color patterns formed from the cured product of the photosensitive coloring composition. In the color filter, known materials can be used for the components other than the materials of the pixels and the black matrix.

[0116] 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.

[0117] <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.

[0118] The colored pattern can be formed by photolithography. Specifically, a photosensitive colored 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.

[0119] The method for applying the photosensitive coloring composition is not particularly limited, but known methods such as screen printing, roll coating, curtain coating, spray coating, and spin coating can be used.

[0120] After the photosensitive coloring composition is applied to the substrate, the solvent (D) contained in the coating film may be volatilized and removed by heating the substrate using a heating means such as a circulation oven, an infrared heater, or a hot plate, as necessary. 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 coloring composition, the thickness of the coating film, etc. The substrate can be heated, for example, at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0121] 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 coloring composition, and may be, for example, 30 to 2000 mJ / cm. ２ The light source used for exposure is not particularly limited, but may be a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like.

[0122] 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.

[0123] 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.

[0124] The conditions for the baking treatment carried out when producing a color filter can be appropriately determined depending on the composition of the photosensitive coloring composition, the film thickness of the coating film, the material of the substrate, etc. The baking temperature can be, for example, 70°C to 230°C. When the baking temperature is 70°C or higher, good curability is obtained, and a cured product having excellent solvent resistance is obtained. The baking temperature is preferably 75°C or higher, and more preferably 80°C or higher.

[0125] 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 coloring composition, the temperature of the baking treatment, the film thickness of the coating film, etc.

[0126] 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).

[0127] The method for producing the protective film is not particularly limited, and the protective film may be formed using the photosensitive resin composition of this embodiment, or may be formed using known materials and known methods.

[0128] Through the above steps, a color filter is obtained.

[0129] Here, the case where a photosensitive coloring composition containing a photopolymerization initiator (C) is used and a colored pattern is produced using a method of photocuring the photosensitive coloring composition has been described as an example, but for example, instead of the photopolymerization initiator (C) contained in the photosensitive coloring composition, a photosensitive coloring composition containing a curing accelerator and a known epoxy resin is used, and after applying it on a substrate by an inkjet method, a colored pattern that is a cured product of the photosensitive coloring composition containing the copolymer (A) may also be formed using a method of heating.

[0130] <Image Display Element> The image display element according to one embodiment of the present invention includes a color filter. In the image display element, known components other than the color filter can 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.

[0131] 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.

[0132] The image display device has a color filter with excellent solvent resistance, and therefore, there is little color change.

[0133] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0134] A synthesis example of the copolymer (A) is shown below.

[0135] Synthesis Example 2 Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 191 g of propylene glycol monomethyl ether acetate as solvent (D) was placed, and the mixture was stirred while purging with nitrogen gas and heated to 120°C.

[0136] Next, 212 g (80 mol%) of monomer (ma-1), 18 g (20 mol%) of acrylic acid as monomer (ma-2), 130 g of propylene glycol monomethyl ether acetate as solvent (D), and 2.5 g (1 part by mass relative to 100 parts by mass of the total of the monomer components) of t-butylperoxy-2-ethylhexanoate as polymerization initiator (i) were mixed to prepare a raw material monomer solution.

[0137] The entire amount of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under a nitrogen gas atmosphere at normal pressure. After the addition was completed, the solution in the flask was stirred while undergoing a polymerization reaction at 120°C for 2 hours to obtain a liquid containing copolymer (A) and solvent (D) of Synthesis Example 1. The weight average molecular weight, molecular weight distribution, acid value, and refractive index of copolymer (A) were measured by the methods described above and are shown in Table 1.

[0138] To the reaction liquid containing the copolymer (A) and the solvent (D) thus obtained, 28 g of propylene glycol monomethyl ether acetate was added as the solvent (D) so that the content of components other than the solvent was 40 mass %, thereby obtaining a liquid containing the copolymer (A) of Synthesis Example 8.

[0139] [Synthesis Example 1, Synthesis Examples 3 to 7, Comparative Synthesis Examples 1 to 3] Liquids containing copolymers (A) of Synthesis Example 1 and Synthesis Examples 3 to 7, and liquids containing copolymers (cA) of Comparative Synthesis Examples 1 to 3, were obtained in the same manner as in Synthesis Example 2, except that the monomers, solvent (D), polymerization initiator (i), and their blending amounts shown in Tables 1 and 2 were used. The weight average molecular weights, molecular weight distributions, acid values, and refractive indices of copolymers (A) of Synthesis Examples 1 and 3 to 7, and copolymers (cA) of Comparative Synthesis Examples 1 to 3 were measured by the methods described above, and are shown in Tables 1 and 2.

[0140] Synthesis Example 8 Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 134 g of propylene glycol monomethyl ether acetate as solvent (D) was placed, and the mixture was stirred while purging with nitrogen gas and heated to 120°C.

[0141] Next, 157 g (60 mol%) of monomer (ma-1), 43 g (40 mol%) of methacrylic acid as monomer (ma-2), 80 g (40 parts by mass relative to 100 parts by mass of the total of the monomer components) of propylene glycol monomethyl ether acetate as solvent (D), and 14 g (7 parts by mass relative to 100 parts by mass of the total of the monomer components) of t-butylperoxy-2-ethylhexanoate as a polymerization initiator were mixed to prepare a raw material monomer solution.

[0142] The entire amount of the raw material monomer solution thus prepared was added dropwise to the solvent (D) in a flask under a nitrogen gas atmosphere at normal pressure using a dropping funnel over a period of 1 hour. After the dropwise addition was completed, the solution in the flask was stirred and subjected to a polymerization reaction at 120°C for 2 hours to obtain a liquid containing the copolymer precursor (PA1) and the solvent (D).

[0143] In a flask under normal pressure and nitrogen gas atmosphere, a liquid containing copolymer precursor (PA1) and solvent (D) was added 0.5 g (0.2 parts by weight relative to 100 parts by weight of the total of the monomer components) of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor, 0.7 g (0.3 parts by weight relative to 100 parts by weight of the total of the monomer components) of triphenylphosphine (TPP) as a catalyst, and 26 g of glycidyl methacrylate as an ethylenically unsaturated compound (e) was added, and the reaction was continued for 10 hours at 110 ° C. with stirring to obtain a reaction liquid containing copolymer (A) and solvent (D). The weight average molecular weight, molecular weight distribution, acid value, and refractive index of the copolymer (A) were measured using the methods described above and are listed in Tables 1 and 2.

[0144] To the reaction liquid containing the copolymer (A) and the solvent (D) thus obtained, 146 g of the solvent (D) (propylene glycol monomethyl ether acetate) was added so that the content of components other than the solvent was 40 mass %. Thus, a liquid containing the copolymer (A) of Synthesis Example 10 was obtained.

[0145] [Synthesis Example 9, Comparative Synthesis Example 5] A liquid containing the copolymer (A) of Synthesis Example 9 and a liquid containing the copolymer (cA) of Comparative Synthesis Example 5 were obtained in the same manner as in Synthesis Example 8, except that the monomers, solvent (D), polymerization initiators, and their blending amounts were used as shown in Tables 1 and 2. The weight average molecular weight, molecular weight distribution, acid value, and refractive index of the copolymer (A) of Synthesis Example 9 and the copolymer (cA) of Comparative Synthesis Example 5 were measured by the methods described above, and the results are shown in Tables 1 and 2.

[0146] Synthesis Example 10 98 g of propylene glycol monomethyl ether acetate as solvent (D) was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while purging with nitrogen gas and heated to 120°C.

[0147] Next, 81 g (40 mol%) of monomer (ma-1), 81 g (60 mol%) of glycidyl methacrylate as monomer (ma-3), 44 g of propylene glycol monomethyl ether acetate as solvent (D), and 11 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator were mixed to prepare a raw material monomer solution.

[0148] The entire amount of the raw material monomer solution thus prepared was added dropwise to the solvent (D) in a flask under a nitrogen gas atmosphere at normal pressure using a dropping funnel over a period of 1 hour. After completion of the addition, the solution in the flask was stirred and subjected to a polymerization reaction at 120°C for 2 hours to obtain a liquid containing the copolymer precursor (PA2) and the solvent (D).

[0149] A liquid containing copolymer precursor (PA2) and solvent (D) in a flask under normal pressure and nitrogen gas atmosphere was charged with 0.5 g (0.25 parts by weight per 100 parts by weight of the total of the monomer components) of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor, 0.8 g (0.4 parts by weight per 100 parts by weight of the total of the monomer components) of triphenylphosphine (TPP) as a catalyst, and 40 g of acrylic acid as an ethylenically unsaturated compound (f), and the reaction was continued for 10 hours at 110 ° C. with stirring. Next, 41 g of tetrahydrophthalic anhydride was added to the flask as a polybasic acid anhydride, and the reaction was continued for 3 hours at 110 ° C. to obtain a reaction liquid containing copolymer (A) and solvent (D). The weight average molecular weight, molecular weight distribution, acid value, and refractive index of the copolymer (A) were measured using the methods described above and are listed in Tables 1 and 2.

[0150] To the reaction liquid containing the copolymer (A) and the solvent (D) thus obtained, 240 g of the solvent (D) (propylene glycol monomethyl ether acetate) was added so that the components other than the solvent were 40 mass %. Thus, a liquid containing the copolymer (A) of Synthesis Example 10 was obtained.

[0151] [Synthesis Example 11, Comparative Synthesis Example 4] A liquid containing the copolymer (A) of Synthesis Example 11 and a liquid containing the copolymer (cA) of Comparative Synthesis Example 4 were obtained in the same manner as in Synthesis Example 10, except that the monomers, solvent (D), and polymerization initiators in the amounts thereof shown in Table 1 were used. The weight average molecular weights, molecular weight distributions, acid values, and refractive indices of the copolymer (A) of Synthesis Example 11 and the copolymer (cA) of Comparative Synthesis Example 4 were measured by the methods described above, and are shown in Tables 1 and 2.

[0152]

[0153]

[0154] In Tables 1 and 2, the meanings of each symbol are as follows: *: refractive index of homopolymer (ma-1): naphthyl group-containing (meth)acrylate (ma-2): acid group-containing monomer (ma-3): epoxy group-containing monomer (e): ethylenically unsaturated compound (f): ethylenically unsaturated compound (h): polybasic acid anhydride (i): polymerization initiator that can be used in copolymerization reaction

[0155] The compounds used in Tables 1 and 2 are as follows: Light acrylate NMT-A: 1-naphthylmethyl acrylate (Kyoeisha Chemical Co., Ltd.) AA: Acrylic acid (Tokyo Chemical Industry Co., Ltd.) MAA: Methacrylic acid (Kuraray Co., Ltd.) GMA: Glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.) TCDMA: Tricyclodecanyl methacrylate (Resonac Corporation) NVC: N-vinylcarbazole (Nissoku Techno Fine Chemical Co., Ltd.) 2VN: 2-vinylnaphthalene (Fujifilm Wako Pure Chemical Industries, Ltd.) VT: Vinyltoluene BZMA: Benzyl methacrylate (Tokyo Chemical Industry Co., Ltd.) SM: Styrene (Tokyo Chemical Industry Co., Ltd.) GMA: Glycidyl methacrylate THPA: Tetrahydrophthalic anhydride SA: Succinic anhydride TBO: t-butylperoxy-2-ethylhexanoate (NOF Corporation) MEHQ: Hydroquinone monomethyl ether TPP: Triphenylphosphine PGMEA: Propylene glycol monomethyl ether acetate (Kuraray Co., Ltd.)

[0156] [Examples 1 to 11, Comparative Examples 1 to 5] Copolymers (A) of Synthesis Examples 1 to 11 shown in Tables 3 and 4, or copolymers (cA) of Comparative Synthesis Examples 1 to 5, dipentaerythritol hexaacrylate (DPHA, product name: A-DPH, manufactured by Shin-Nakamura Kogyo Co., Ltd.) as the reactive diluent (B), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-, -1-(O-acetyloxime) (Ciba Japan Co., Ltd.) as the photopolymerization initiator (C), and propylene glycol monomethyl ether acetate as the solvent (D) were mixed in the proportions (units: parts by mass) shown in Tables 3 and 4, respectively, to prepare the photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 5. The blending amount of copolymer (A) or copolymer (cA) shown in Table 3 does not include the amount of solvent. The amount of solvent (D) shown in Tables 3 and 4 is the sum of the amount of solvent contained in the liquid containing copolymer (A) or copolymer (cA) obtained in the Synthesis Examples or Comparative Synthesis Examples and the amount of solvent added during the preparation of the photosensitive resin composition.

[0157] [Examples 12-13, Comparative Examples 6-7] Synthesis Examples 12-13 shown in Table 5, Comparative Examples 6-7 copolymer (A), reactive diluent (B) dipentaerythritol hexaacrylate (DPHA, product name: A-DPH, manufactured by Shin-Nakamura Kogyo Co., Ltd.), photopolymerization initiator (C) 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-, -1-(O-acetyloxime) (Ciba Japan Co., Ltd.), solvent (D) propylene glycol monomethyl ether acetate, and colorant (E) Valifast Blue 2620 (phthalocyanine dye, Orient Chemical Industry Co., Ltd.), were mixed in the proportions shown in Table 5, respectively, to prepare photosensitive colored compositions of Examples 12-13 and Comparative Examples 6-7. The blending amount of copolymer (A) or (cA) shown in Table 5 does not include the amount of solvent. The amount of solvent (D) shown in Table 5 is the sum of the amount of solvent contained in the liquid containing copolymer (A) or copolymer (cA) obtained in synthesis example or comparative synthesis example and the amount of solvent added when preparing the photosensitive coloring composition.

[0158]

[0159]

[0160]

[0161] In Tables 3 to 5, *1: Solid content of resins (A) and (cA) obtained in the synthesis examples *2: The solvent components of resin (A) and colorant (E) are included in solvent (B). The following compounds were used as compounds listed in Tables 3 to 5. THPA: Tetrahydrophthalic anhydride SA: Succinic anhydride Perbutyl O: t-butylperoxy-2-ethylhexanoate (NOF Corporation) PGMEA: Propylene glycol methyl ether acetate (Kuraray Co., Ltd.) DPHA: Dipentaerythritol hexaacrylate (product name: A-DPH, Shin-Nakamura Kogyo Co., Ltd.) Irgacure (registered trademark) OXE02: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-, 1-(O-acetyloxime) (BASF Japan Ltd.) PGMEA: Propylene glycol monomethyl ether acetate (Kuraray Co., Ltd.)

[0162] <Formation of cured resin film using photosensitive resin composition or photosensitive coloring composition (without development)> Each photosensitive resin composition or each photosensitive coloring composition was spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) so that the average thickness of the final cured coating film was 2.0 μm, and then heated at 100° C. for 3 minutes to volatilize the solvent. Next, the entire coating film was exposed (exposure amount 200 mJ / cm 2 ) and photocured, and then further baked at 230° C. for 30 minutes to obtain a cured resin film.

[0163] [Evaluation of transmittance] Measurement was performed using a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). Measurement object: the above-mentioned cured resin film Measurement conditions: measurement wavelength (wavelength range) 380 to 780 nm The transmittance of the cured resin film of the photosensitive resin composition R1 of Example 1 was 97%. The transmittances of the cured resin films of the photosensitive resin compositions or photosensitive coloring compositions R2 to R13 of Examples 2 to 13 and the photosensitive resin compositions or photosensitive coloring compositions cR1 to cR7 of Comparative Examples 1 to 7 are shown in Tables 6 and 7.

[0164] <Pattern formation using photosensitive resin composition or photosensitive coloring composition (with development)> Each photosensitive resin composition or photosensitive coloring composition was spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) so that the average thickness of the final cured coating film would be 2.0 μm, and then heated at 100° C. for 3 minutes to volatilize the solvent. Next, the composition was exposed to light (exposure amount 200 mJ / cm ) through a photomask. ２ ), photocuring, and then baking at 230°C for 30 minutes to obtain a cured resin film having a line and space pattern. [Evaluation of Developability] The developability was evaluated according to the following criteria. A: Development was successful after 30 seconds of dipping in TMAH (tetramethylammonium hydroxide). B: Development was not successful after 30 seconds of dipping in TMAH (tetramethylammonium hydroxide).

[0165] The photosensitive coloring compositions prepared in Examples 1 to 13 and Comparative Examples 1 to 7 were each coated on a 5 cm square alkali-free glass substrate by spin coating so that the thickness after exposure was 2.0 μm (coating process). The glass substrate coated with the photosensitive coloring composition was heated at 100 ° C. for 3 minutes to volatilize the solvent, and the coating film was dried (pre-baking process).

[0166] Next, an ultra-high pressure mercury lamp was used to irradiate 100 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, the film was developed by immersing it in a 2.38% aqueous tetramethylammonium hydroxide solution at 23°C for 10 to 180 seconds, and the unexposed areas were removed (development step). The glass substrate with the coating film after the development step was placed in a dryer at 100°C for 30 minutes to thermally cure the coating film (post-bake step), thereby obtaining a pattern. The pattern thus obtained was observed using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The evaluation results of the developability of the photosensitive resin compositions or photosensitive coloring compositions R2 to R13 of Examples 2 to 13 and the photosensitive resin compositions or photosensitive coloring compositions cR1 to cR7 of Comparative Examples 1 to 7 are shown in Tables 6 and 7.

[0167] <Method for measuring refractive index> The refractive index refers to the refractive index of copolymer (A) measured using a refractometer. The refractive index of a resin composition (sample) containing copolymer (A) of the present invention and solvent (D) is measured under the following conditions, and then the refractive index of solvent (D) is measured under the following conditions. Next, the content (solid content) of copolymer (A) contained in the sample is measured in accordance with JIS K6901 5.11, and the refractive index of copolymer (A) alone contained in the sample is calculated using the following formula. Measuring device: J-357 Automatic Refractometer (Rudolph Research Analytical Co.) Measurement wavelength: 589 nm Measurement temperature: 25°C Refractive index of copolymer (A) alone = (refractive index of sample - refractive index of solvent (D)) ÷ solid content × 100 + refractive index of solvent (D) The refractive index of copolymer P1 in Example 1 was 1.64. The refractive indices of copolymers P2 to P10 of Examples 2 to 13 and copolymers cP1 to cP5 of Comparative Examples 1 to 7 are shown in Tables 6 and 7.

[0168] <Method for Measuring Solid Content> The samples obtained in the following synthesis examples were heated at 130° C. for 2 hours, and the heating residue was measured.

[0169]

[0170]

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) is a copolymer containing a structural unit (a-1) derived from a naphthyl group-containing (meth)acrylate.

2. The photosensitive resin composition according to claim 1, wherein the copolymer (A) is a copolymer further containing a structural unit (a-2) having an acid group.

3. The photosensitive resin composition according to claim 2, wherein the copolymer (A) has an acid value of 10 to 300 KOH mg / g.

4. The photosensitive resin composition according to claim 2, wherein, of all structural units of said copolymer (A), the content of structural units (a-1) derived from a naphthyl group-containing (meth)acrylate is 5 to 95 mol %, and the content of structural units (a-2) having an acid group is 5 to 60 mol %.

5. The photosensitive resin composition according to claim 1, wherein the copolymer precursor (PA1) is a copolymer containing a structural unit (a-1) derived from the naphthyl group-containing (meth)acrylate and a structural unit (a-2) having an acid group, the ethylenically unsaturated compound (e) is a compound having a functional group reactive with the acid group, and the copolymer (A) is a copolymer in which the ethylenically unsaturated compound (e) is added to a portion of the acid groups of the copolymer precursor (PA1).

6. The photosensitive resin composition according to claim 5, wherein the copolymer (A) has an acid value of 10 to 300 KOH mg / g.

7. The photosensitive resin composition according to claim 5, wherein, of all structural units of said copolymer precursor (PA1), the content of structural units (a-1) derived from said naphthyl group-containing (meth)acrylate is 5 to 90 mol %, the content of structural units (a-2) having an acid group is 10 to 70 mol %, the amount of said ethylenically unsaturated compound (e) is 1 to 60 mol per 100 mol of structural units of said copolymer precursor (PA1), and the amount of said ethylenically unsaturated compound (e) added is 5 to 90 mol per 100 mol of structural units (a-2) having an acid group of said copolymer precursor.

8. The photosensitive resin composition according to claim 1, wherein the copolymer precursor (PA2) is a copolymer containing a structural unit (a-1) derived from the naphthyl group-containing (meth)acrylate and a structural unit (a-3) having an epoxy group, the ethylenically unsaturated compound (f) is a compound having a functional group reactive with the epoxy group, and the copolymer (A) is a copolymer in which the ethylenically unsaturated compound (f) is added to at least a portion of the epoxy groups of the copolymer precursor (PA2), and a polybasic acid or polybasic acid anhydride (h) is added to at least a portion of the hydroxy groups produced by ring-opening of the epoxy groups.

9. The photosensitive resin composition according to claim 8, wherein the acid value of the copolymer (A) is 10 to 300 KOH mg / g.

10. The photosensitive resin composition according to claim 8, wherein, of all structural units of said copolymer precursor (PA2), the content of said structural unit (a-1) derived from said naphthyl group-containing (meth)acrylate is 5 to 90 mol %, the content of said structural unit (a-3) having an epoxy group is 10 to 90 mol %, the amount of said ethylenically unsaturated compound (f) is 5 to 90 mol per 100 mol of structural units of said copolymer precursor (PA2), the amount of said ethylenically unsaturated compound (f) added is 60 to 100 mol per 100 mol of said structural unit (a-3) having an epoxy group, the amount of said polybasic acid or polybasic acid anhydride is 5 to 50 mol per 100 mol of structural units of said copolymer precursor (PA2), and the amount of said polybasic acid or polybasic acid anhydride added is 10 to 90 mol per 100 mol of said ethylenically unsaturated compound (f).

11. The photosensitive resin composition according to claim 1, wherein the content of said copolymer (A) is 10 to 95 mass% and the content of said reactive diluent (B) is 5 to 90 mass% relative to the total of said copolymer (A) and said reactive diluent (B); the content of said photopolymerization initiator (C) is 0.1 to 30 mass parts relative to 100 parts by mass of the total of said copolymer (A) and said reactive diluent (B); and the content of said solvent (D) is 30 to 1,000 mass parts relative to 100 parts by mass of the total of the components excluding said solvent (D).

12. A photosensitive coloring composition comprising the photosensitive resin composition according to any one of claims 1 to 11 and a colorant (E).

13. The photosensitive coloring composition according to claim 12, wherein the content of the colorant (E) is 0.1 to 80 parts by mass per 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).

14. A cured resin film comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 11.

15. A cured resin film comprising the cured product of the photosensitive coloring composition according to claim 12.

16. A cured resin film having a pattern, which is a cured product of the photosensitive resin composition according to any one of claims 1 to 11.

17. A color filter having a color pattern, which is a cured product of the photosensitive coloring composition according to claim 12.

18. An image display device comprising the color filter according to claim 17.

Images