Alkali soluble resin, photosensitive resin composition, photosensitive colored composition and color filter

Abstract

Provided is an alkali soluble resin comprising a structural unit (a-1) that has a halogen-substituted phenyl group and is represented by formula (1) (wherein X is a hydrogen atom, an alkyl group having 1-4 carbon atoms, or a halogen atom; Y is a single bond or a divalent organic group; and R1, R2, R3, R4, and R5 are each independently H, Br, or I, provided that at least one of R1, R2, R3, R4, and R5 is Br or I). The alkali soluble resin has an acid value of 10-300 mg KOH / g.

Description

Alkali-soluble resin, photosensitive resin composition, photosensitive coloring composition, and color filter

[0001] The content of the present disclosure relates to an alkali-soluble resin, a photosensitive resin composition, a photosensitive coloring composition, a resin cured film, a color filter, and an image display element.

[0002] In recent years, with the spread of liquid crystal displays, extensive research has been conducted on color filters used as components of liquid crystal displays, overcoat layers provided on these color filters, interlayer insulating films, etc. (for example, Patent Document 1 and Patent Document 2). High refractive indices are often required for these materials.

[0003] Japanese Patent Application Laid-Open No. 2019-53266 Japanese Patent Application Laid-Open No. 2023-147017

[0004] However, further improvement has been demanded for materials that have both a high refractive index and developability.

[0005] An object of the present disclosure is to provide a resin capable of forming a cured film having a high refractive index and developability. Another object is to provide a photosensitive resin composition and a photosensitive coloring composition capable of obtaining a resin cured film having a high refractive index and developability. Furthermore, an object is to provide a resin cured film having a high refractive index and developability, a color filter including a cured product of the resin, and an image display element.

[0006] The content of the present disclosure includes the following aspects. [1] A structural unit (a-1) represented by formula (1) having a halogen-substituted phenyl group: (In the formula, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, Y is a single bond or a divalent organic group, and R １ R ２ R ３ R ４ R ５ are each independently H, Br, or I, provided that R １ R ２ R ３ R ４ R ５[1] An alkali-soluble resin having at least one of which is Br or I, and having an acid value of 10 to 300 mg KOH / g. [2] The alkali-soluble resin according to [1], wherein the halogen-substituted phenyl group equivalent is 400 to 1200 g / mol. [3] The alkali-soluble resin according to [1] or [2], wherein the refractive index is 1.55 or higher. [4] The alkali-soluble resin according to any one of [1] to [3], wherein the weight-average molecular weight is 1000 to 50000. [5] In formula (1), R １ , R ３ , and R ５ I is R ２ , and R ４ is H, or R １ , R ２ , R ３ , R ４ , and R ５[1] to [4] any one of the alkali-soluble resins, wherein is Br. [6] An alkali-soluble resin according to any one of the alkali-soluble resins, wherein it is a copolymer containing the structural unit (a-1) and a structural unit (a-2) having an acid group. [7] An alkali-soluble resin according to [6], wherein the content of the structural unit (a-1) is 10 to 95 mol% and the content of the structural unit (a-2) is 5 to 90 mol% based on 100 mol% of the total structural units. [8] An alkali-soluble resin according to any one of the alkali-soluble resins, wherein the alkali-soluble resin has a structure in which an ethylenically unsaturated compound (e) having a group that reacts with the acid group is added to a part of the acid group of an alkali-soluble resin precursor (PA1) containing the structural unit (a-1) and a structural unit (a-2) having an acid group. [9] The alkali-soluble resin according to [8], wherein, with respect to 100 mol% of the total structural units of the alkali-soluble resin precursor (PA1), the content of structural unit (a-1) is 10 to 95 mol%, the content of structural unit (a-2) is 5 to 90 mol%, the amount of ethylenically unsaturated compound (e) is 1 to 60 mol per 100 mol of structural units of the alkali-soluble resin precursor (PA1), and the amount of ethylenically unsaturated compound (e) added is 5 to 90 mol per 100 mol of structural unit (a-2) of the alkali-soluble resin precursor (PA1).

[10] The alkali-soluble resin according to any one of [1] to [7], wherein the alkali-soluble resin has a structure in which at least a portion of the epoxy group of an alkali-soluble resin precursor (PA2) containing the structural unit (a-1) and a structural unit having an epoxy group (a-3) is attached to an ethylenically unsaturated compound (f) having a group that is reactive with the epoxy group, and at least a portion of the hydroxyl group formed by ring-opening of the epoxy group is attached to a polybasic acid or polybasic anhydride (h).

[11] The alkali-soluble resin according to

[10] , wherein, with respect to 100 mol% of the total structural units of the alkali-soluble resin precursor (PA2), the content of structural unit (a-1) is 10 to 95 mol%, the content of structural unit (a-3) is 5 to 90 mol%, the amount of ethylenically unsaturated compound (f) is 5 to 90 mol per 100 mol of structural units of the alkali-soluble resin precursor (PA2), the amount of ethylenically unsaturated compound (f) added is 60 to 100 mol per 100 mol of structural unit (a-3) of the alkali-soluble resin precursor (PA2), the amount of polybasic acid or polybasic acid anhydride (h) is 5 to 50 mol per 100 mol of structural units of the alkali-soluble resin precursor (PA2), and the amount of polybasic acid or polybasic acid anhydride (h) added is 10 to 90 mol per 100 mol of ethylenically unsaturated compound (f).

[12] A photosensitive resin composition comprising: an alkali-soluble resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the alkali-soluble resin (A) is the alkali-soluble resin described in any of [1] to

[11] .

[13] The photosensitive resin composition according to

[12] , wherein the content of the alkali-soluble resin (A) is 10 to 99% by mass, the content of the reactive diluent (B) is 1 to 90% by mass, the content of the photopolymerization initiator (C) is 0.1 to 30 parts by mass, the content of the photopolymerization initiator (C) is 0.1 to 30 parts by mass, the content of the solvent (D) is 30 to 1000 parts by mass, the content of the solvent (D) is 30 to 1000 parts by mass, based on 100 parts by mass of the total of the alkali-soluble resin (A) and the reactive diluent (B).

[14] A photosensitive colored composition comprising the photosensitive resin composition described in

[12] or

[13] and a colorant (E).

[15] The photosensitive colored composition described in

[14] , 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 alkali-soluble resin (A) and the reactive diluent (B).

[16] A resin-cured film comprising a cured product of the photosensitive resin composition described in

[12] or

[13] .A resin cured film containing a cured product of the photosensitive coloring composition described in

[17] ,

[14] or

[15] . A resin cured film which is a cured product of the photosensitive resin composition described in

[12] or

[13] and has a pattern. A color filter which is a cured product of the photosensitive coloring composition described in

[14] or

[15] and has a colored pattern. An image display element including the color filter described in

[20] .

[0007] According to the present disclosure, it is possible to provide a resin capable of forming a cured film having a high refractive index and developability. Further, it is possible to provide a photosensitive resin composition and a photosensitive coloring composition capable of obtaining a resin cured film having a high refractive index and developability. Furthermore, it is possible to provide a resin cured film having a high refractive index and developability, a color filter including a cured product of the resin, and an image display element.

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

[0009] In the present disclosure, when "~" is used for a numerical range, the numerical values at both ends are respectively the upper limit value and the lower limit value and are included in the numerical range. When a plurality of upper limit values or lower limit values are described, a numerical range can be formed from all combinations of the upper limit value and the lower limit value. Similarly, when a plurality of numerical ranges are described, separate numerical ranges can be formed by individually selecting and combining the upper limit value and the lower limit value from those numerical ranges.

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

[0011] In this disclosure, "ethylenically unsaturated bond" means a double bond formed between carbon atoms excluding the carbon atoms forming the aromatic ring, "ethylenically unsaturated group" means a group having an ethylenically unsaturated bond, and "ethylenically unsaturated compound" means a compound having an ethylenically unsaturated bond.

[0012] In this disclosure, "structural unit" means a unit derived from the polymerizable compound used as a monomer, or a unit obtained by further modifying a unit derived from the polymerizable compound used as a monomer after polymerization.

[0013] <Alkali-soluble resin (A)> The alkali-soluble resin (A) of one embodiment is a structural unit (a-1) represented by formula (1) having a halogen-substituted phenyl group (also simply called "structural unit (a-1)"). The same applies to other structural units. (In the formula, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, Y is a single bond or a divalent organic group, R １ , R ２ , R ３ , R ４ , and R ５ Each of these is independently H, Br, or I, except R １ , R ２ , R ３ , R ４ , and R ５ The copolymer has at least one of which is Br or I, and has an acid value of 10 to 300 mg KOH / g. The alkali-soluble resin (A) may optionally contain a structural unit having an acid group (a-2), a structural unit having an epoxy group (a-3), other structural units other than structural units (a-1) to (a-3) (a-4), or a combination of two or more of these.

[0014] The alkali-soluble resin (A) may have a structure in which an ethylenically unsaturated compound (e) (also simply referred to as "ethylenically unsaturated compound (e)") having a group that reacts with the acid group is attached to a portion of the acid group of an alkali-soluble resin precursor (PA1) containing a structural unit (a-1), a structural unit having an acid group (a-2), and optionally other structural units (a-4). The structural unit having this structure imparts curability to the alkali-soluble resin (A).

[0015] The alkali-soluble resin (A) may have a structure in which an ethylenically unsaturated compound (f) (also simply called "ethylenically unsaturated compound (f)") having a group that reacts with the epoxy group is added to at least a portion of the epoxy group of an alkali-soluble resin precursor (PA2) containing structural unit (a-1), structural unit having an epoxy group (a-3), and optionally other structural units (a-4), and a polybasic acid or polybasic acid anhydride (h) is further added to at least a portion of the hydroxyl group formed by ring-opening of the epoxy group. The structural unit having this structure is the structural unit having an acid group (a-2).

[0016] The acid value of the alkali-soluble resin (A) is 10 to 300 mg KOH / g. Preferably, the acid value of the alkali-soluble resin (A) is 20 mg KOH / g or more, more preferably 30 mg KOH / g or more. Preferably, the acid value of the alkali-soluble resin (A) is 200 mg KOH / g or less, more preferably 150 mg KOH / g or less. When the acid value of the alkali-soluble resin (A) is 10 mg KOH / g or more, the developability of the photosensitive resin composition or photosensitive colored composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. When the acid value of the alkali-soluble resin (A) is 300 mg KOH / g or less, the storage stability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. The acid value of the alkali-soluble resin (A) is preferably 20 to 200 KOH mg / g, more preferably 30 to 150 KOH mg / g.

[0017] The acid value of alkali-soluble resin (A) is measured according to JIS K 6901:2008 5.3. That is, the acid value represents the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of alkali-soluble resin (A).

[0018] The halogen-substituted phenyl group equivalent of alkali-soluble resin (A) is preferably 400 g / mol or more, more preferably 450 g / mol or more, and even more preferably 500 g / mol or more. The halogen-substituted phenyl group equivalent of alkali-soluble resin (A) is preferably 1200 g / mol or less, more preferably 1100 g / mol or less, and even more preferably 1000 g / mol or less. When the halogen-substituted phenyl group equivalent is 400 g / mol or more, a resin-cured film with desired developability can be obtained from alkali-soluble resin (A). When the halogen-substituted phenyl group equivalent is 1200 g / mol or less, a resin-cured film with high tropism can be obtained. The halogen-substituted phenyl group equivalent of alkali-soluble resin (A) is preferably 400 to 1200 g / mol, more preferably 450 to 1100 g / mol, and even more preferably 500 to 1000 g / mol.

[0019] The halogen-substituted phenyl group equivalent of alkali-soluble resin (A) is the mass of alkali-soluble resin (A) per mole of halogen-substituted phenyl groups in alkali-soluble resin (A). The halogen-substituted phenyl group equivalent is obtained by dividing the mass of alkali-soluble resin (A) by the number of halogen-substituted phenyl groups in alkali-soluble resin (A) (g / mol). In this disclosure, the halogen-substituted phenyl group equivalent of alkali-soluble resin (A) is a theoretical value calculated from the amount of raw materials used in the production of alkali-soluble resin (A).

[0020] The weight-average molecular weight (Mw) of the alkali-soluble resin (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 alkali-soluble resin (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 alkali-soluble resin (A) is 1,000 or more, the patterning properties of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) are good. When the weight-average molecular weight of the alkali-soluble resin (A) is 50,000 or less, the storage stability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. The weight-average molecular weight of the alkali-soluble resin (A) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 4,000 to 10,000.

[0021] The molecular weight distribution (Mw / Mn) of the alkali-soluble resin (A) is preferably 1.3 or higher, more preferably 1.5 or higher, even more preferably 1.7 or higher, and particularly preferably 1.9 or higher. The molecular weight distribution (Mw / Mn) of the alkali-soluble resin (A) is preferably 5.0 or lower, more preferably 4.0 or lower, and even more preferably 3.5 or lower. When the molecular weight distribution (Mw / Mn) of the alkali-soluble resin (A) is 1.3 or higher, it is easy to control the manufacturing conditions during the synthesis of the alkali-soluble resin (A). When the molecular weight distribution (Mw / Mn) of the alkali-soluble resin (A) is 5.0 or lower, the storage stability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good.

[0022] In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are measured using gel permeation chromatography (GPC) under the following conditions and obtained using a standard polystyrene calibration curve. Column: Two Showdex® LF-804 columns (Resonac Corporation) connected in series. Column temperature: 40°C. Sample: 0.2% by mass tetrahydrofuran solution of the substance to be measured. Developing solvent: Tetrahydrofuran. Detector: Differential refractometer (Showdex® RI-71S) (Resonac Corporation). Flow rate: 1 mL / min.

[0023] The refractive index of the alkali-soluble resin (A) is preferably 1.55 or higher, more preferably 1.58 or higher, and even more preferably 1.60 or higher. The refractive index of the alkali-soluble resin (A) may be 2.00 or lower, 1.80 or lower, or 1.75 or lower.

[0024] In this disclosure, the "refractive index" of the resin (polymer) alone is the value calculated by the following method. Specifically, the refractive index of a resin composition (sample) containing the resin and solvent is measured under the following conditions, and then the refractive index of the solvent is measured under the following conditions. Next, the resin content (solids) in the sample is measured according to JIS K 6901:2008 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) Measurement wavelength: 589 nm Measurement temperature: 25°C Refractive index of resin alone = (Refractive index of sample - Refractive index of solvent) ÷ Solids × 100 + Refractive index of solvent

[0025] In embodiments where the alkali-soluble resin (A) has ethylenically unsaturated groups, the equivalent amount of ethylenically unsaturated groups in the alkali-soluble resin (A) is preferably 100 g / mol or more, more preferably 500 g / mol or more, and even more preferably 1000 g / mol or more. The equivalent amount of ethylenically unsaturated groups in the alkali-soluble resin (A) is preferably 10000 g / mol or less, more preferably 8000 g / mol or less, and even more preferably 6000 g / mol or less. When the equivalent amount of ethylenically unsaturated groups is 100 g / mol or more, the content of structural unit (a-1) in the alkali-soluble resin (A) is ensured, a resin-cured film with high tropism can be obtained, and the storage stability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. When the equivalent amount of ethylenically unsaturated groups is 10000 g / mol or less, high curability is imparted to the alkali-soluble resin (A), and the solvent resistance of the cured product is improved. A resin-cured film having the desired hardness can be obtained. The ethylenically unsaturated group equivalent of the alkali-soluble resin (A) is preferably 100 to 10,000 g / mol, more preferably 500 to 8,000 g / mol, and even more preferably 1,000 to 6,000 g / mol.

[0026] The ethylenically unsaturated group equivalent of alkali-soluble resin (A) is the mass of alkali-soluble resin (A) per mole of ethylenically unsaturated groups in alkali-soluble resin (A). The ethylenically unsaturated group equivalent is obtained by dividing the mass of alkali-soluble resin (A) by the number of ethylenically unsaturated groups in alkali-soluble resin (A) (g / mol). In this disclosure, the ethylenically unsaturated group equivalent of alkali-soluble resin (A) is a theoretical value calculated from the amount of raw materials used in the production of alkali-soluble resin (A).

[0027] [Structural unit (a-1) represented by formula (1) having a halogen-substituted phenyl group] Structural unit (a-1) is represented by formula (1). In the formula, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, preferably a hydrogen atom or a methyl group. Y is a single bond or a divalent organic group. Examples of divalent organic groups represented by Y include an alkanediyl group having 1 to 20 carbon atoms, and a group having -O-, -(C=O)-, -(C=O)O-, -O(C=O)O-, -NH-, -C(=O)NH-, -NH(C=O)O-, -NH(C=O)NH- between the carbon-carbon bonds of the alkanediyl group having 1 to 20 carbon atoms, or between the alkanediyl group and the halogen-substituted phenyl group. Y is preferably a single bond or -R-NHC(=O)O-, and R is (CH ２ ) ｎ And n is an integer from 0 to 4. １ , R ２ , R ３ , R ４ , and R ５ Each of these is independently H, Br, or I, except R １ , R ２ , R ３ , R ４ , and R ５ At least one of them is Br or I. １ , R ２ , R ３ , R ４ , and R ５ Preferably, three or more of these are independently Br or I, and R １ , R ３ , and R ５ I is R ２ , and R ４ is H, or R １ , R ２ , R ３ , R ４ , and R ５ It is more preferable that it is Br. The structural unit (a-1) may be only one type or two or more types.

[0028] An example of a preferred structural unit (a-1) is shown below.

[0029] The structural unit (a-1) is derived from the monomer represented by formula (ma-1) (hereinafter also simply referred to as monomer (ma-1). The same applies to other monomers). In the formula, X, Y, R １ , R ２ , R ３ , R ４ , and R ５ This is as explained in equation (1).

[0030] The content of structural unit (a-1) in the alkali-soluble resin (A) can be appropriately determined depending on the application. The content of structural unit (a-1) is preferably 10 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 100 mol% of the total structural units of the alkali-soluble resin (A). The content of structural unit (a-1) is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less. When the content of structural unit (a-1) is 10 mol% or more, the refractive index of the alkali-soluble resin (A) is increased, and a resin-cured film with a high refractive index can be obtained. When the content of structural unit (a-1) is 95 mol% or less, the developability of the alkali-soluble resin (A) is ensured, and a resin-cured film with the desired developability can be obtained. The content of structural unit (a-1) in the alkali-soluble resin (A) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, even more preferably 30 to 80 mol%, and particularly preferably 40 to 80 mol%. In embodiments in which the alkali-soluble resin (A) has a structure to which an ethylenically unsaturated compound (e) is added, when the total structural units of the alkali-soluble resin precursor (PA1) are set to 100 mol%, the content of structural unit (a-1) in the alkali-soluble resin precursor (PA1) is the same as the above range. In embodiments in which the alkali-soluble resin (A) has a structure to which an ethylenically unsaturated compound (f) is added and a polybasic acid or polybasic acid anhydride (h) is further added, when the total structural units of the alkali-soluble resin precursor (PA2) are set to 100 mol%, the content of structural unit (a-1) in the alkali-soluble resin precursor (PA2) is the same as the above range.

[0031] [Structural unit having an acid group (a-2)] The alkali-soluble resin (A) is preferably a copolymer containing the structural unit (a-1) and the structural unit having an acid group (a-2). The structural unit having an acid group (a-2) is not particularly limited as long as it does not have a halogen-substituted phenyl group or an epoxy group and has an acid group. There may be only one type of structural unit (a-2) or two or more types. The structural unit (a-2) is a structural unit derived from an acid group-containing monomer (ma-2). By having structural unit (a-2) in the alkali-soluble resin (A), high developability can be imparted to the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A).

[0032] Examples of acidic groups that structural unit (a-2) may possess include carboxyl groups, sulfol groups, and phosphol groups. Among these acidic groups, carboxyl groups are preferred due to their availability.

[0033] Monomer (ma-2) is an ethylenically unsaturated compound that does not have a halogen-substituted phenyl group or epoxy group, but has an acid group. Examples of monomer (ma-2) include unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, and unsaturated phosphonic acids.

[0034] Examples of monomers (ma-2) include unsaturated carboxylic acids or their anhydrides 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. Monomers (ma-2) may be used alone or in combination of two or more types.

[0035] As the monomer (ma-2), an unsaturated carboxylic acid is preferred, and (meth)acrylic acid is more preferred, because it is readily available and can impart excellent alkali developability to a photosensitive resin composition or photosensitive colored composition containing an alkali-soluble resin (A).

[0036] When the total structural units of the alkali-soluble resin (A) are set to 100 mol%, the content of structural unit (a-2) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more. The content of structural unit (a-2) is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less. When the content of structural unit (a-2) is 5 mol% or more, the developability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. When the content of structural unit (a-2) is 90 mol% or less, the refractive index of the alkali-soluble resin (A) is increased, and a resin-cured film with a high refractive index can be obtained. The content of structural unit (a-2) in the alkali-soluble resin (A) is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, even more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol%.

[0037] [Structural unit having epoxy group (a-3)] The alkali-soluble resin (A) may contain structural units having epoxy groups (a-3). The structural unit having epoxy groups (a-3) is not particularly limited as long as it does not have halogen-substituted phenyl groups or acid groups and has epoxy groups. There may be only one type of structural unit (a-3) or two or more types. The structural unit (a-3) is a structural unit derived from an epoxy group-containing monomer (ma-3). By containing structural units (a-3) in the alkali-soluble resin (A), curability can be imparted to the alkali-soluble resin (A).

[0038] Monomer (ma-3) is an ethylenically unsaturated compound having an epoxy group and lacking a halogen-substituted phenyl group. Examples of ethylenically unsaturated compounds having an epoxy group include (meth)acrylic acid ester derivatives containing an epoxy group such as oxyranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxyranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, 4-glycidyloxybutyl (meth)acrylate, and glycidyloxyphenyl (meth)acrylate; and 3,4-epoxycyclohexyl (meth)acrylate. Examples include epoxy group-containing (meth)acrylates such as 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 epoxy group-containing alicyclic carbocyclic compounds such as 3,4-epoxycyclohexane rings; vinyl ether compounds containing epoxy groups; and allyl ether compounds containing epoxy groups. The monomer (ma-3) may be used alone or in combination of two or more types.

[0039] As monomers (ma-3), epoxy group-containing (meth)acrylates such as oxyranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxyranyl ethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 4-glycidyloxybutyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate are preferred from the viewpoint of polymerizability and ease of availability, and glycidyl (meth)acrylate, 4-glycidyloxybutyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate are more preferred.

[0040] In embodiments in which the alkali-soluble resin (A) contains structural unit (a-3), when the total structural units of the alkali-soluble resin (A) are set to 100 mol%, the content of structural unit (a-3) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. The content of structural unit (a-3) is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less. When the content of structural unit (a-3) is 5 mol% or more, the curability of the alkali-soluble resin (A) can be improved. When the content of structural unit (a-3) is 60 mol% or less, the refractive index of the alkali-soluble resin (A) can be increased, and a resin cured film with a high refractive index can be obtained.

[0041] [Introduction of ethylenically unsaturated groups using alkali-soluble resin precursor (PA1)] In some embodiments, alkali-soluble resin (A) can be obtained by adding an ethylenically unsaturated compound (e) to an acid group using an alkali-soluble resin precursor (PA1) containing structural units (a-1) and (a-2).

[0042] (Ethylene-unsaturated compound (e) having a group that reacts with an acid group) The ethylenically unsaturated compound (e) has a group that reacts with an acid group and an ethylenically unsaturated group. The ethylenically unsaturated compound (e) may be one type or two or more types. By adding the ethylenically unsaturated compound (e) to the alkali-soluble resin precursor (PA1), an ethylenically unsaturated group is introduced into the alkali-soluble resin (A). As a result, good photocurability is imparted to the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A), and the solvent resistance of the cured product is improved.

[0043] Examples of functional groups that react with acidic groups include epoxy groups, oxetanyl groups, hydroxyl groups, and isocyanate groups. Among these, epoxy groups are preferred from the viewpoint of ease of synthesis of alkali-soluble resin (A).

[0044] Examples of ethylenically unsaturated compounds having an epoxy group include compounds listed as epoxy group-containing monomers (ma-3) and a preferred range. The ethylenically unsaturated compound (e) may be used alone or in combination of two or more types.

[0045] When the total structural units of the alkali-soluble resin precursor (PA1) are set to 100 mol%, the content of structural unit (a-2) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more. The content of structural unit (a-2) is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less. When the content of structural unit (a-2) is 5 mol% or more, the developability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. When the content of structural unit (a-2) is 90 mol% or less, the refractive index of the alkali-soluble resin (A) is increased, and a resin cured film with a high refractive index can be obtained.

[0046] The amount of ethylenically unsaturated compound (e) is preferably 1 mole or more, more preferably 5 moles or more, and even more preferably 10 moles or more, per 100 moles of structural units of the alkali-soluble resin precursor (PA1). The amount of ethylenically unsaturated compound (e) is preferably 60 moles or less, more preferably 50 moles or less, and even more preferably 40 moles or less, per 100 moles of structural units of the alkali-soluble resin precursor (PA1). When the amount of ethylenically unsaturated compound (e) per 100 moles of structural units of the alkali-soluble resin precursor (PA1) is 1 mole or more, the photocurability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. When the amount of ethylenically unsaturated compound (e) per 100 moles of structural units of the alkali-soluble resin precursor (PA1) is 60 moles or less, the content of acid groups in the alkali-soluble resin (A) can be ensured, and good developability can be imparted to the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A).

[0047] The amount of 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 structural units (a-2) of the alkali-soluble resin precursor (PA1). The amount of 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 structural units (a-2) of the alkali-soluble resin precursor (PA1). When the amount of ethylenically unsaturated compound (e) added per 100 moles of structural units (a-2) is 5 moles or more, the photocurability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. When the amount of ethylenically unsaturated compound (e) added per 100 moles of structural units (a-2) is 90 moles or less, the content of acid groups in the alkali-soluble resin (A) can be ensured, and good developability can be imparted to the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A).

[0048] [Introduction of ethylenically unsaturated groups and acidic groups using alkali-soluble resin precursor (PA2)] In some embodiments, an alkali-soluble resin (A) having ethylenically unsaturated groups as curable groups and carboxyl groups as acidic groups can be obtained by using an alkali-soluble resin precursor (PA2) containing structural units (a-1) and (a-3), adding an ethylenically unsaturated compound (f) to at least a portion of the epoxy groups, and further adding a polybasic acid or polybasic acid anhydride (h) to at least a portion of the hydroxyl groups formed by ring-opening of the epoxy groups. A photosensitive resin composition or photosensitive colored composition containing this alkali-soluble resin (A) has photocurability and developability. In these embodiments, since it is easy to adjust the amount of carboxyl groups introduced by the polybasic acid or polybasic acid anhydride (h), the developability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) can be adjusted to a desired range.

[0049] (Ethylene-unsaturated compound (f) having a group reactive with epoxy groups) The ethylenically unsaturated compound (f) has a group reactive with epoxy groups and an ethylenically unsaturated group. The ethylenically unsaturated compound (f) may be one type or two or more types. By adding the ethylenically unsaturated compound (f) to the alkali-soluble resin precursor (PA2), an ethylenically unsaturated group is introduced into the alkali-soluble resin (A). A photosensitive resin composition or photosensitive colored composition containing such an alkali-soluble resin (A) has good photocurability and can form a cured product with excellent solvent resistance.

[0050] Acidic groups are preferred as functional groups that have reactivity with epoxy groups.

[0051] As the ethylenically unsaturated compound having an acid group, for example, compounds listed as acid group-containing monomer (ma-2) and a preferred range can be used. The ethylenically unsaturated compound (f) may be used alone or in combination of two or more types.

[0052] When the total structural units of the alkali-soluble resin precursor (PA2) are set to 100 mol%, the content of structural unit (a-3) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more. The content of structural unit (a-3) is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less. When the content of structural unit (a-3) is 5 mol% or more, it is possible to secure reaction sites when adding an ethylenically unsaturated compound (f) and a polybasic acid or polybasic acid anhydride (h) to the alkali-soluble resin precursor (PA2), and good photocurability and developability can be imparted to the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A). When the content of structural unit (a-3) is 90 mol% or less, the refractive index of the alkali-soluble resin (A) can be increased, and a resin-cured film with a high refractive index can be obtained.

[0053] The amount of ethylenically unsaturated compound (f) is preferably 5 moles or more, more preferably 10 moles or more, and even more preferably 20 moles or more, per 100 moles of structural units of alkali-soluble resin precursor (PA2). The amount of ethylenically unsaturated compound (f) is preferably 90 moles or less, more preferably 80 moles or less, even more preferably 70 moles or less, and particularly preferably 60 moles or less, per 100 moles of structural units of alkali-soluble resin precursor (PA2). When the amount of ethylenically unsaturated compound (f) is 5 moles or more, the curability of alkali-soluble resin (A) can be increased. When the amount of ethylenically unsaturated compound (f) is 90 moles or less, the refractive index of alkali-soluble resin (A) can be increased, and a resin-cured film with a high refractive index can be obtained.

[0054] The amount of 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 structural units (a-3) of the alkali-soluble resin precursor (PA2). The amount of ethylenically unsaturated compound (f) added is 100 moles or less, may be 99 moles or less, or 95 moles or less, per 100 moles of structural units (a-3) of the alkali-soluble resin precursor (PA2). When the amount of ethylenically unsaturated compound (f) added per 100 moles of structural units (a-3) of the alkali-soluble resin precursor (PA2) is 60 moles or more, the curability of the alkali-soluble resin (A) can be improved.

[0055] (Polybasic acid or polybasic anhydride (h)) A polybasic acid or polybasic anhydride (h) is a compound having two or more carboxyl groups or its anhydride. There may be only one polybasic acid or polybasic anhydride (h), or there may be two or more.

[0056] Examples of polybasic acids include adipic acid, itaconic acid, methylitaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, ethyl maleic acid, chlormaleic acid, citraconic acid, glutaric acid, tartaric acid, glutamic acid, sebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, 2-norvonene-5,6-dicarboxylic acid, 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic acid, and cyclohexanetricarboxylic acid. Examples of polybasic acid anhydrides include the anhydrides of the polybasic acids mentioned above. These compounds may be used individually or in combination of two or more. From the viewpoint of availability, itaconic anhydride, methylitaconic anhydride, succinic anhydride, maleic anhydride, ethyl maleic anhydride, chlormaleic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, 2-norvonene-5,6-dicarboxylic acid anhydride, 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride, and cyclohexanetricarboxylic acid anhydride are preferred. From the viewpoint of hardness of the cured resin film, polybasic acid anhydrides having an alicyclic structure are preferred. From the viewpoint of increasing the amount of carboxyl groups introduced and improving low-temperature curability, tetrahydrophthalic anhydride and cyclohexanetricarboxylic acid anhydride are more preferred.

[0057] 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 alkali-soluble resin precursor (PA2) are considered to be 100 moles. The amount of polybasic acid or polybasic acid anhydride (h) 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 alkali-soluble resin precursor (PA2) are considered to be 100 moles. When the amount of polybasic acid or polybasic acid anhydride (h) is 5 moles or more, the developability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. When the amount of polybasic acid or polybasic acid anhydride (h) is 50 moles or less, the storage stability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good.

[0058] 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 (h) 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 (h) added is 10 moles or more, the developability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good. When the amount of polybasic acid or polybasic acid anhydride (h) added is 90 moles or less, the storage stability of the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A) is good.

[0059] [Other structural units (a-4)] The alkali-soluble resin (A), alkali-soluble resin precursor (PA1), and alkali-soluble resin precursor (PA2) may, if necessary, have other structural units (a-4) other than structural units (a-1) to (a-3). The other structural units (a-4) do not have halogen-substituted phenyl groups, acid groups, or epoxy groups, and are structural units derived from other monomers (ma-4) that can copolymerize with monomers (ma-1) to (ma-3). The structural units (a-4) can be used to adjust the physical properties of the alkali-soluble resin (A) or to impart functionality to the alkali-soluble resin (A).

[0060] Examples of monomers (ma-4) include aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylic acid esters, (meth)acrylamides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, (meth)acrylamides, (meth)acrylonitriles, and acrolein.

[0061] 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.

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

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

[0064] Examples of (meth)acrylic acid esters include 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. Examples include acrylates, 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.

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

[0066] Examples of vinyl compounds include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene.

[0067] Examples of unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0068] Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide.

[0069] The monomer (ma-4) may be used alone or in combination of two or more types.

[0070] From the viewpoint of the refractive index of the alkali-soluble resin (A), the monomer (ma-4) is preferably a compound whose refractive index when formed as a homopolymer is 1.5 or higher, and more preferably a compound whose refractive index is 1.55 or higher. 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).

[0071] When the alkali-soluble resin (A), alkali-soluble resin precursor (PA1), or alkali-soluble resin precursor (PA2) contains structural unit (a-4), the content of structural unit (a-4) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, based on 100 mol% of the total structural units of the alkali-soluble resin (A), alkali-soluble resin precursor (PA1), or alkali-soluble resin precursor (PA2). The content of structural unit (a-4) is preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less, based on 100 mol% of the total structural units of the alkali-soluble resin (A), alkali-soluble resin precursor (PA1), or alkali-soluble resin precursor (PA2). When the content of structural unit (a-4) is 1 mol% or more, the desired function can be imparted to the photosensitive resin composition or photosensitive colored composition containing the alkali-soluble resin (A). If the content of structural unit (a-4) is 50 mol% or less, the content of structural units (a-1) to (a-3) can be ensured, so a resin cured film with a high refractive index can be obtained, and good developability can be imparted to a photosensitive resin composition or photosensitive colored composition containing alkali-soluble resin (A).

[0072] <Photosensitive Resin Composition and Photosensitive Colored Composition> The photosensitive resin composition of one embodiment contains the above-mentioned alkali-soluble resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The photosensitive resin composition can be cured by light irradiation to form a cured resin film. The photosensitive colored composition of one embodiment contains the above-mentioned photosensitive resin composition plus a colorant (E).

[0073] The content of alkali-soluble resin (A) in the photosensitive resin composition or photosensitive colored composition is preferably 10% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more, relative to the total of alkali-soluble resin (A) and reactive diluent (B). The content of alkali-soluble resin (A) is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, relative to the total of alkali-soluble resin (A) and reactive diluent (B). When the content of alkali-soluble resin (A) is within the above range, the viscosity of the photosensitive resin composition or photosensitive colored composition becomes within a range suitable for handling, and in addition, the photocurability is also improved. The content of alkali-soluble resin (A) in the photosensitive resin composition or photosensitive colored composition is preferably 10 to 99% by mass, more preferably 40 to 95% by mass, and even more preferably 60 to 90% by mass, relative to the total of alkali-soluble resin (A) and reactive diluent (B).

[0074] [Reactive Diluent (B)] The reactive diluent (B) may be any low molecular weight compound having at least one ethylenically unsaturated group, and is not particularly limited. In this disclosure, a low molecular weight compound is a compound with a molecular weight of less than 1000. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, and (meth)acryloyloxy groups. From the viewpoint of improving curability, 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 diallylbenzenephosphonate; vinyl carboxylates such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; and triallyl cyanurate.

[0075] Specific examples of aromatic vinyl compounds include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene.

[0076] 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.

[0077] 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 tri(meth)acrylate of tris(hydroxyethyl) isocyanurate.

[0078] For the reactive diluent (B), a polyfunctional (meth)acrylate is preferred to improve reactivity, and at least one selected from the group consisting of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate is more preferred.

[0079] The reactive diluent (B) may be used alone or in combination of two or more types.

[0080] The content of reactive diluent (B) in the photosensitive resin composition or photosensitive colored composition is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total of the alkali-soluble resin (A) and reactive diluent (B). The content of 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, relative to the total of the alkali-soluble resin (A) and reactive diluent (B). When the content of reactive diluent (B) is within the above range, the viscosity of the photosensitive resin composition or photosensitive colored composition becomes within a range suitable for handling, and in addition, the photocurability is also improved. The content of reactive diluent (B) in the photosensitive resin composition or photosensitive colored composition is preferably 1 to 90% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 40% by mass, relative to the total of the alkali-soluble resin (A) and reactive diluent (B).

[0081] [Photopolymerization initiator (C)] The photopolymerization initiator (C) is not particularly limited, but examples include: ethanolone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-,1-(O-acetyloxime); benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, and other benzoin and its alkyl ethers; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4'-(1-t-butyldioxy-1-methylethyl)acetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-benzyl-2-dimethylamino-1-(4-mol Examples include pholinophenyl)butanone-1; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; xanthones; thioxanthone compounds such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and acylphosphine oxide-based photopolymerization initiators. The photopolymerization initiator (C) may be used alone or in combination of two or more types.

[0082] The content of the photopolymerization initiator (C) in the photosensitive resin composition or photosensitive colored 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 part by mass or more, based on 100 parts by mass of the total of the alkali-soluble resin (A) and the reactive diluent (B). The content of the photopolymerization initiator (C) in the photosensitive resin composition or photosensitive colored 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, based on 100 parts by mass of the total of the alkali-soluble resin (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 colored 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 adverse effects on the physical properties of the cured product of the photosensitive resin composition or photosensitive colored composition due to an excessive amount of the photopolymerization initiator (C).

[0083] [Solvent (D)] Examples of 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; triethylene glycol monomethyl ether; propylene glycol monoalkyl ethers such as 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; 3-methoxy-1-butanol; (poly)alkylene glycol monoalkyl ether; hydroxyl group-containing carboxylic acid esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate; and diethylene glycol Hydroxyl 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, 2 Ketones such as -heptanone and 3-heptanone; esters such as methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, methyl-3-methoxybutyl acetate, 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 include aromatic hydrocarbons such as toluene and xylene; and hydroxyl-free organic solvents such as carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Solvent (D) may be used alone or in combination of two or more.

[0084] Among these solvents (D), it is preferable to use compounds having an ether structure from the viewpoint of ease of availability, cost, and stability during resist preparation. More specifically, it is preferable to use at least one selected from the group consisting of propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and 3-methoxy-1-butanol.

[0085] The content of solvent (D) in the photosensitive resin composition or photosensitive colored composition is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more, based on 100 parts by mass of the total components excluding solvent (D). The content of solvent (D) in the photosensitive resin composition or photosensitive colored composition is preferably 1,000 parts by mass or less, and more preferably 800 parts by mass or less, based on 100 parts by mass of the total components excluding solvent (D). When the content of solvent (D) is 30 parts by mass or more, the viscosity of the photosensitive resin composition or photosensitive colored composition can be kept within an appropriate range. When the content of solvent (D) is 1,000 parts by mass or less, the solvent (D) can be easily removed from the coating film formed by applying the photosensitive resin composition or photosensitive colored composition to a substrate.

[0086] [Colorant (E)] A photosensitive colored composition containing a colorant (E) can be used as a material for a color filter. The colorant (E) is not particularly limited as long as it is soluble or dispersed in the solvent (D), and examples include dyes and pigments.

[0087] As dyes, it is preferable to use acidic dyes having acidic groups such as carboxyl groups and sulfo groups, salts of acidic dyes with nitrogen compounds, or sulfonamide adducts of acidic dyes, from the viewpoint of solubility in solvent (D) and alkaline developer, interaction with other components in the photosensitive coloring composition, and heat resistance.

[0088] Examples of dyes include: acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44, 70; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114 ,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274;acid violet 6B, 7, 9, 17, 19; acid yellow Examples include 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and their derivatives. Among these, azo, xanthene, anthraquinone, or phthalocyanine acid dyes are preferred. The dyes may be used individually or in combination of two or more.

[0089] Examples of pigments include yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Examples include red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as C.I. Pigment Green 7, 36, 58, and 59; brown pigments such as C.I. Pigment Brown 23 and 25; and black pigments such as C.I. Pigment Black 1 and 7, carbon black, titanium black, and iron oxide. Pigments may be used individually or in combination of two or more types.

[0090] The colorant (E) can be appropriately determined, for example, according to the desired coloring 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 types. When using two or more types of colorant (E), a combination of dyes and pigments may be used.

[0091] When a pigment is used as the coloring agent (E), a known dispersant may be added to the photosensitive coloring composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymeric dispersant that has excellent dispersion stability over time. Examples of polymeric dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified ester-based dispersants. As polymeric dispersants, commercially available products under trade names such as EFKA (EFKA Chemicals B.V.), Disperbyk (Vic Chemie), Disparon (Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (Lubrisol) may be used. The content of the dispersant can be appropriately set depending on the type and amount of pigment used as the coloring agent (E).

[0092] The content of the colorant (E) in the photosensitive colored 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, based on 100 parts by mass of the total of the alkali-soluble resin (A) and the reactive diluent (B). The content of the colorant (E) in the photosensitive colored 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, based on 100 parts by mass of the total of the alkali-soluble resin (A) and the reactive diluent (B). When the content of the colorant (E) is 0.1 parts by mass or more, the effect of including the colorant (E) becomes significant, and a photosensitive colored composition suitable as a material for the coloring 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 curability of the photosensitive colored composition, and a photosensitive colored composition with good curability can be obtained.

[0093] [Other Components] The photosensitive resin composition or photosensitive colored composition may contain an alkali-soluble resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and a colorant (E) as needed, as well as known additives such as curing aids, coupling agents, leveling agents, and polymerization inhibitors as needed. The amount of additives is not particularly limited, as long as it does not hinder the effects of the present invention.

[0094] In one embodiment, the photosensitive resin composition or photosensitive colored composition contains a polyfunctional thiol as an epoxy curing aid or a photoradical or thermal radical curing aid. Examples of polyfunctional thiols include pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinan-2,4,6-trione, and trimethylolpropane tris(3-mercaptobutyrate).

[0095] The photosensitive resin composition or photosensitive colored composition of one embodiment has excellent developability due to the inclusion of an alkali-soluble resin (A), and a resin-cured film with a high refractive index can be obtained. Therefore, a resin-cured film with a high refractive index can be obtained without the need to use inorganic particles in combination to improve the refractive index of the resin-cured film, or to use a dispersant in combination to disperse the inorganic particles. In one embodiment, the photosensitive resin composition or photosensitive colored composition is substantially free of inorganic particles or does not contain inorganic particles. "Substantially free" means that the inorganic particle content in the photosensitive resin composition or photosensitive colored composition is less than 1% by mass, less than 0.5% by mass, or less than 0.1% by mass.

[0096] <Method for producing alkali-soluble resin (A)> In one embodiment, alkali-soluble resin (A) can be produced by a method that includes the step of copolymerizing monomer (ma-1), monomer (ma-2), and, if necessary, other monomer (ma-4).

[0097] In another embodiment, the alkali-soluble resin (A) can be produced by a method comprising the steps of: copolymerizing monomer (ma-1), monomer (ma-2), and optionally other monomer (ma-4) to obtain an alkali-soluble resin precursor (PA1); and adding an ethylenically unsaturated compound (e) to a portion of the acid group of the structural unit (a-2) of the alkali-soluble resin precursor (PA1) to obtain the alkali-soluble resin (A).

[0098] In another embodiment, the alkali-soluble resin (A) can be produced by a method comprising the steps of: copolymerizing monomer (ma-1), monomer (ma-3), and optionally other monomer (ma-4) to obtain an alkali-soluble resin precursor (PA2); and adding an ethylenically unsaturated compound (f) to at least a portion of the epoxy group of structural unit (a-3) of the alkali-soluble resin precursor (PA2), and further adding a polybasic acid or polybasic acid anhydride (h) to at least a portion of the hydroxyl group formed by ring-opening of the epoxy group to obtain the alkali-soluble resin (A).

[0099] The proportions of structural units (a-1), (a-2), (a-3), and (a-4) contained in alkali-soluble resin (A), alkali-soluble resin precursor (PA1), or alkali-soluble resin precursor (PA2) are equivalent to the proportions of each monomer (ma-1), monomer (ma-2), monomer (ma-3), and monomer (ma-4) in the total amount of all monomers used as raw materials for alkali-soluble resin (A), alkali-soluble resin precursor (PA1), or alkali-soluble resin precursor (PA2).

[0100] The proportions of each monomer used in the copolymerization reaction to form the alkali-soluble resin (A), alkali-soluble resin precursor (PA1), or alkali-soluble resin precursor (PA2) are not particularly limited.

[0101] When monomer (ma-2) is used, preferably monomer (ma-1) is 10 to 95 mol% and monomer (ma-2) is 5 to 90 mol%, more preferably monomer (ma-1) is 20 to 90 mol% and monomer (ma-2) is 10 to 80 mol%, even more preferably monomer (ma-1) is 30 to 80 mol% and monomer (ma-2) is 20 to 70 mol%, and particularly preferably monomer (ma-1) is 40 to 80 mol% and monomer (ma-2) is 20 to 60 mol%.

[0102] When monomer (ma-3) is used, preferably monomer (ma-1) is 10 to 95 mol% and monomer (ma-3) is 5 to 90 mol%, more preferably monomer (ma-1) is 20 to 90 mol% and monomer (ma-3) is 10 to 80 mol%, even more preferably monomer (ma-1) is 30 to 80 mol% and monomer (ma-3) is 20 to 70 mol%, and particularly preferably monomer (ma-1) is 40 to 80 mol% and monomer (ma-3) is 20 to 60 mol%.

[0103] The copolymerization reaction can be carried out in or without a solvent according to radical polymerization methods known in the art. For example, the monomer can be dissolved in an organic solvent, a polymerization initiator (i) can be added to the solution, and the polymerization reaction can be carried out at 50 to 150°C for 1 to 20 hours.

[0104] As the solvent used in the copolymerization reaction, the same solvent as solvent (D) described above can be used. Other examples include 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 cycloalkanol, C5-6 cycloalkanediol, C5-6 cycloalkanedimethanol, ethyl lactate, and diacetone alcohol, which are hydroxyl group-containing organic solvents. "C5-6 cycloalkane" means that the cycloalkyl group has 5-6 carbon atoms. The solvents may be used individually or in combination of two or more.

[0105] 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 initiator (i) may be used alone or in combination of two or more. The amount of polymerization initiator (i) used is generally 0.5 to 20 parts by mass, preferably 1.0 to 18 parts by mass, per 100 parts by mass of the total amount of monomer charged. A chain transfer agent (n), such as thioglycolic acid, may also be used in combination in the copolymerization reaction.

[0106] As a method for adding an ethylenically unsaturated compound (e) to a portion of the acid groups of an alkali-soluble resin precursor (PA1), and a method for adding an ethylenically unsaturated compound (f) to at least a portion of the epoxy groups of an alkali-soluble resin precursor (PA2), and further adding a polybasic acid or polybasic acid anhydride (h), known addition reactions can be used. For example, after adding a polymerization inhibitor (j) and a catalyst (k) to the reaction solution in which the copolymerization reaction has been carried out, an ethylenically unsaturated compound (e), an ethylenically unsaturated compound (f), a polybasic acid or polybasic acid anhydride (h) can be added as the compound to be added, and the addition reaction can be carried out under conditions of room temperature (23°C) to 150°C, preferably 50 to 120°C.

[0107] Polymerization inhibitors (j) are added to prevent side reactions of the introduced ethylenically unsaturated groups. Examples of polymerization inhibitors (j) include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene.

[0108] Examples of catalysts (k) include quaternary ammonium salts such as triethylbenzylammonium chloride; phosphorus compounds such as triphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine, triparathylphosphine, tricyclohexylphosphine, and tetraphenylphosphonium salts; and organometallic compounds containing metals such as chromium and tin. The amount of catalyst (k) used is preferably 0.1 to 12 parts by mass, and more preferably 0.2 to 6.0 parts by mass, per 100 parts by mass of the total amount of monomers used in the copolymerization reaction of the alkali-soluble resin precursor (PA1) or alkali-soluble resin precursor (PA2), as well as the ethylenically unsaturated compound (e) and the ethylenically unsaturated compound (f).

[0109] <Methods for producing photosensitive resin composition and photosensitive colored composition> The photosensitive resin composition of one embodiment can be produced by mixing an alkali-soluble resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and additives as needed, using a known mixing apparatus. The photosensitive colored composition of one embodiment can be produced by mixing an alkali-soluble resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), a colorant (E), and additives as needed, using a known mixing apparatus.

[0110] When manufacturing a photosensitive resin composition or a photosensitive colored composition, the reaction solution used to manufacture the alkali-soluble resin (A) can be used 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 colored composition.

[0111] When producing a photosensitive resin composition or a photosensitive colored composition, alkali-soluble resin (A) isolated from a reaction solution containing alkali-soluble resin (A) by a known method may be used as a raw material.

[0112] Since the photosensitive resin composition or photosensitive colored composition contains an alkali-soluble resin (A) having a high refractive index, it can form a resin cured film having a high refractive index.

[0113] Since the alkali-soluble resin (A) contained in the photosensitive resin composition or photosensitive colored composition has an acid value, the photosensitive resin composition or photosensitive colored composition has good alkali developability. Because such a photosensitive resin composition or photosensitive colored composition has excellent alkali developability, for example, it can be applied to a substrate to form a coating film, exposed through a photomask corresponding to a predetermined pattern shape, developed in an alkaline aqueous solution for the unexposed areas, and then baked to form a resin cured product having a predetermined pattern shape.

[0114] In embodiments in which the alkali-soluble resin (A) has ethylenically unsaturated groups, the photosensitive resin composition or photosensitive colored composition contains the alkali-soluble resin (A), a reactive diluent (B), and a photopolymerization initiator (C). Therefore, upon irradiation with light, the ethylenically unsaturated groups contained in the alkali-soluble resin (A) and the reactive diluent (B) react or polymerize, resulting in good photocurability.

[0115] The photosensitive resin composition and the photosensitive colored composition can be suitably used as materials for color filters.

[0116] The photosensitive resin composition and the photosensitive colored composition are extremely useful as materials for forming components of image display elements, such as pixels of color filters, black matrices, color filter protective films, insulating films, photospacers, liquid crystal alignment protrusions, microlenses, and insulating films for touch panels.

[0117] <Resin-cured film> The resin-cured film of one embodiment is a cured product of the above-mentioned photosensitive resin composition or photosensitive colored composition.

[0118] A resin-cured film can be manufactured, for example, by applying a photosensitive resin composition or a photosensitive colored composition onto a substrate, volatilizing and removing the solvent (D) to form a coating film, exposing the coating film to light-curing, and then performing a baking treatment.

[0119] When forming a resin-cured film having a predetermined pattern shape, for example, the following method can be used. That is, a photosensitive resin composition or a photosensitive colored composition is applied to a substrate, and the solvent (D) is evaporated and removed to form a coating film. Next, the coating film is exposed to light through a photomask having a predetermined pattern shape to photocur the exposed portion. Then, the unexposed portion of the coating film is developed with an alkaline aqueous solution. After that, the developed coating film is subjected to a baking treatment to form a resin-cured film having a predetermined pattern shape.

[0120] When manufacturing a cured resin film, known methods can be used for applying the photosensitive resin composition or photosensitive colored composition, for exposing the applied film to light, and for developing the film.

[0121] The baking conditions performed when manufacturing the cured resin film can be appropriately determined according to the composition of the photosensitive resin composition or photosensitive coloring composition, the film thickness of the coating, the material of the substrate, etc. The baking process can be carried out at a temperature of, for example, 70°C to 250°C.

[0122] The baking process performed when manufacturing the resin-cured 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 photosensitive coloring composition, the baking temperature, the film thickness of the coated film, etc.

[0123] The resin-cured film can preferably be used as a component of a transparent film, protective film, insulating film, overcoat, photospacer, microlens, black matrix, black column spacer, or color filter.

[0124] <Color Filter> A color filter in one embodiment comprises a colored pattern which is a cured product of a photosensitive colored composition.

[0125] A color filter may include, for example, a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix.

[0126] In a color filter, the pixels and black matrix are colored patterns that are cured products of the above-mentioned photosensitive colored composition. Other components of the color filter, besides the materials of the pixels and black matrix, can be those of known origin.

[0127] The substrate used in the color filter is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide-imide substrates, polyimide substrates, aluminum substrates, printed circuit boards, array substrates, etc., can be used as appropriate depending on the application.

[0128] <Method for Manufacturing Color Filters> An example method for manufacturing color filters is described below. First, a color pattern is formed on a substrate. Specifically, a color pattern that will become the black matrix formed at the boundary of each pixel, and a color pattern that will become each RGB pixel are sequentially formed on the substrate by the method shown below.

[0129] The colored pattern can be formed by photolithography. Specifically, a photosensitive colored composition is applied to a substrate to form a coating film. Then, the coating film is exposed to light through a photomask having a predetermined pattern shape, and the exposed areas are photocured. Next, the unexposed areas of the coating film are developed with an alkaline aqueous solution. After that, the developed coating film is subjected to a baking treatment to form a colored pattern having a predetermined pattern shape.

[0130] The method for applying the photosensitive colored composition is not particularly limited, but known methods such as screen printing, roll coating, curtain coating, spray coating, and spin coating can be used.

[0131] After applying the photosensitive coloring composition to the substrate, the substrate may be heated using a heating means such as a circulating oven, infrared heater, or hot plate, if necessary, to volatilize and remove the solvent (D) contained in the coating film. The conditions for heating the substrate to remove the solvent (D) are not particularly limited and can be appropriately set depending on the substrate material, the composition of the photosensitive coloring composition, the thickness of the coating film, etc. For example, the substrate can be heated at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0132] Next, the coated film formed in this manner is irradiated with an active energy ray, such as ultraviolet light or excimer laser light, through a negative-type photomask to partially expose it and photo-cure the exposed portion. The amount of active energy irradiated onto the coated film can be appropriately selected according to the composition of the photosensitive coloring composition, for example, 30 to 2000 mJ / cm². ２ This can be done. The light source used for exposure is not particularly limited, but low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc., can be used.

[0133] The alkaline aqueous solution used for developing the coating film is not particularly limited, but can be used: aqueous solutions of inorganic alkali 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 their salts such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochloride, or p-toluenesulfonate; and aqueous solutions of p-phenylenediamine compounds and their salts. Additives such as defoamers and surfactants may be added to the alkaline aqueous solution as needed.

[0134] After developing the coating film using the above-mentioned alkaline aqueous solution, it is preferable to wash the coating film with water and dry it.

[0135] The baking conditions performed when manufacturing color filters can be appropriately determined according to the composition of the photosensitive coloring composition, the 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 curing properties are obtained, and a cured product with excellent solvent resistance is obtained. The baking temperature is preferably 75°C or higher, and more preferably 80°C or higher.

[0136] The baking time performed when manufacturing color filters can be, 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 baking temperature, the film thickness of the coating, etc.

[0137] Using the method for manufacturing the colored patterns described above, a colored pattern is formed to represent each RGB pixel, and a colored pattern is formed to represent the black matrix at the boundary of each pixel. Then, a protective film is formed on the colored patterns (each RGB pixel and the black matrix).

[0138] The method for manufacturing the protective film is not particularly limited and may be formed using the photosensitive resin composition of this disclosure, or using known materials and known methods.

[0139] A color filter can be obtained through the above process.

[0140] Here, we have described an example in which a colored pattern is produced using a photosensitive colored composition containing a photopolymerization initiator (C) and a method of photocuring the photosensitive colored composition. However, for example, instead of the photopolymerization initiator (C) contained in the photosensitive colored composition, a photosensitive colored composition containing a curing accelerator and a known epoxy resin may be used, and a colored pattern, which is a cured product of the photosensitive colored composition containing an alkali-soluble resin (A), may be formed by applying it to a substrate by an inkjet method and then heating it.

[0141] <Image Display Element> An image display element in one embodiment includes a color filter. Other components of the image display element can be those known to exist. Specific examples of image display elements include solid-state image sensors such as liquid crystal display elements, organic EL display elements, CCD elements, and CMOS elements.

[0142] Components of an image display element other than the color filter can be manufactured by known methods. For example, when manufacturing a liquid crystal display element as an image display element, it can be manufactured using the method shown below. First, a color filter is formed on a substrate using the method described above. Then, electrodes, spacers, etc., are sequentially formed on the substrate having the color filter. Next, electrodes, etc., are formed on another substrate and bonded together with the substrate having the color filter, facing each other. Then, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0143] The image display element is equipped with a color filter that has excellent solvent resistance, resulting in minimal color distortion.

[0144] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0145] The materials used in the examples are as follows: TIPA: 2,4,6-triiodophenyl acrylate TIPA: 2,4,6-triiodophenyl methacrylate PBrPA: 2,3,4,5,6-pentabromopenylate AA: Acrylic acid (Tokyo Chemical Industries, Ltd.) MAA: Methacrylic acid (Kuraray Co., Ltd.) HOA-MS: 2-acryloyloxyethyl succinic acid (Kyoeisha Chemical Co., Ltd.) GMA: Glycidyl methacrylate (Tokyo Chemical Industries, Ltd.) PQMA: 4-hydroxyphenyl methacrylate (Resonac Co., Ltd.) Light acrylate NMT-A: 1-naphthylmethyl acrylate (Kyoeisha Chemical Co., Ltd.) NVC: N-vinylcarbazole (Nisshoku Techno Fine Chemical Co., Ltd.) EEA: 2-(2-ethoxyethoxy)ethyl acrylic acid (Osaka Organic Chemical Industry Co., Ltd.) St: Styrene (Tokyo Chemical Industries, Ltd.) TCDMA: Tricyclodecanyl methacrylate (Resonac Co., Ltd.) BZMA: Benzyl methacrylate (Tokyo Chemical Industries, Ltd.) THPA: Tetrahydrophthalic anhydride SA: Succinic anhydride V-601: 2,2'-Azobis(2-methylpropionic acid)dimethyl (NOF Corporation) TBO: t-Butyl peroxy-2-ethylhexanoate (NOF Corporation) MEHQ: Hydroquinone monomethyl ether TPP: Triphenylphosphine TGA: Thioglycolic acid CyP: Cyclopentanol DPHA: Dipentaerythritol hexaacrylate (Product name: A-DPH, Shin Nakamura Kogyo Co., Ltd.) Irgacure™ OXE02: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-,1-(O-acetyloxime) (BASF Japan Ltd.) PGMEA: Propylene glycol monomethyl ether acetate (Kuraray Co., Ltd.)

[0146] An example of the synthesis of alkali-soluble resin (A) is shown below.

[0147] [Example 1] 105.8 g of cyclopentanol as solvent (D) was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while purging with nitrogen gas, and the temperature was raised to 98°C.

[0148] Next, a raw material monomer solution was prepared by mixing 183.4 g (70 mol%) of TIPA as monomer (ma-1), 10.8 g (30 mol%) of acrylic acid as monomer (ma-2), 194.2 g of cyclopentanol as solvent (D), and 5.8 g (3 parts by mass per 100 parts by mass of the total monomer components) of 2,2'-azobis(2-methylpropionic acid)dimethyl as polymerization initiator (i).

[0149] The entire volume of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was polymerized at 98°C for 5 hours while stirring to obtain a liquid containing alkali-soluble resin (A) and solvent (D). The acid value, weight-average molecular weight, molecular weight distribution, ethylenically unsaturated group equivalent, and halogen-substituted phenyl group equivalent of alkali-soluble resin (A) were determined by the method described above. The results are shown in Table 1.

[0150] [Examples 2 to 8, Example 11, Comparative Examples 1 to 3] Liquids containing alkali-soluble resin (A) or (cA) and solvent (D) were obtained using the same procedure as in Example 1, except that the types and compositions of monomers were changed as shown in Table 1 or Table 2. In Example 8, 2 parts by mass of thioglycolic acid was used as a chain transfer agent (n) during polymerization, per 100 parts by mass of the total monomer components. The results are shown in Tables 1 and 2.

[0151] [Example 9] 101.6 g of cyclopentanol as solvent (D) was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while purging with nitrogen gas, and the temperature was raised to 98°C.

[0152] Next, a raw material monomer solution was prepared by mixing 168.1 g (60 mol%) of TIPA as monomer (ma-1), 18.3 g (40 mol%) of methacrylic acid as monomer (ma-2), 186.4 g of cyclopentanol as solvent (D), and 5.6 g (3 parts by mass per 100 parts by mass of the total monomer components) of 2,2'-azobis(2-methylpropionic acid)dimethyl as polymerization initiator (i).

[0153] The entire volume of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was stirred and polymerized at 98°C for 5 hours to obtain a liquid containing alkali-soluble resin precursor (PA1) and solvent (D).

[0154] In a flask at atmospheric pressure under a nitrogen gas atmosphere, a liquid containing an alkali-soluble resin precursor (PA1) and solvent (D) was mixed with 0.6 g of hydroquinone monomethyl ether as a polymerization inhibitor (j) (0.3 parts by mass per 100 parts by mass of the total monomer component and ethylenically unsaturated compound (e)), 0.6 g of triphenylphosphine as a catalyst (k) (0.3 parts by mass per 100 parts by mass of the total monomer component and ethylenically unsaturated compound (e)), and 7.6 g of glycidyl methacrylate as the ethylenically unsaturated compound (e). The mixture was reacted at 110°C for 5 hours with stirring to obtain a liquid containing alkali-soluble resin (A) and solvent (D). To this liquid, 11.3 g of cyclopentanol was added to prepare a solution of alkali-soluble resin (A) with a solid content of 40%. The results are shown in Table 1.

[0155] [Example 10] 122.0 g of cyclopentanol as solvent (D) was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while purging with nitrogen gas, and the temperature was raised to 98°C.

[0156] Next, a raw material monomer solution was prepared by mixing 95.9 g (40 mol%) of TIPA as monomer (ma-1), 38.8 g (60 mol%) of glycidyl methacrylate as monomer (ma-3), 94.3 g of cyclopentanol as solvent (D), and 9.4 g (7 parts by mass per 100 parts by mass of the total monomer components) of 2,2'-azobis(2-methylpropionic acid)dimethyl as polymerization initiator (i).

[0157] The entire volume of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was stirred and polymerized at 98°C for 5 hours to obtain a liquid containing alkali-soluble resin precursor (PA2) and solvent (D).

[0158] To a liquid containing an alkali-soluble resin precursor (PA2) and a solvent (D) in a flask at atmospheric pressure under a nitrogen gas atmosphere, 0.5 g of hydroquinone monomethyl ether as a polymerization inhibitor (j) (0.3 parts by mass per 100 parts by mass of the total monomer component and ethylenically unsaturated compound (f)), 0.5 g of triphenylphosphine as a catalyst (k) (0.3 parts by mass per 100 parts by mass of the total monomer component and ethylenically unsaturated compound (f)), and 38.1 g of acrylic acid as the ethylenically unsaturated compound (f) were added, and the reaction was continued at 110°C for 10 hours with stirring.

[0159] Next, 17.3 g of tetrahydrophthalic anhydride was added to the flask as polybasic acid anhydride (h), and the mixture was reacted at 110°C for 3 hours to obtain a liquid containing alkali-soluble resin (A) and solvent (D). To this liquid, 83.1 g of cyclopentanol was added to prepare a solution of alkali-soluble resin (A) with a solid content of 40%. The results are shown in Table 1.

[0160] [Comparative Example 4] A liquid containing an alkali-soluble resin (cA) and a solvent (D) was obtained using the same procedure as in Example 10, except that the types and compositions of the monomer, ethylenically unsaturated compound (f), and polybasic acid anhydride (h) were changed as shown in Table 2. The results are shown in Table 2.

[0161] [Comparative Example 5] A liquid containing an alkali-soluble resin (cA) and a solvent (D) was obtained using the same procedure as in Example 9, except that the type and composition of the monomer and the ethylenically unsaturated compound (e) were changed as shown in Table 2. The results are shown in Table 2.

[0162]

[0163]

[0164] [Examples 12-22, Comparative Examples 6-10] The alkali-soluble resin (A) from Examples 1-11, or the alkali-soluble resin (cA) from Comparative Examples 1-5, dipentaerythritol hexaacrylate as a reactive diluent (B), Irgacure™ OXE02 as a photopolymerization initiator (C), and propylene glycol monomethyl ether acetate as a solvent (D) were mixed in the compositions shown in Table 3 (unit: parts by mass) to prepare the photosensitive resin compositions of Examples 12-22 and Comparative Examples 6-10.

[0165] [Examples 23-24, Comparative Examples 11-12] The alkali-soluble resin (A) from Example 1 or Example 8, or the alkali-soluble resin (cA) from Comparative Example 2 or Comparative Example 4, dipentaerythritol hexaacrylate as a reactive diluent (B), Irgacure™ OXE02 as a photopolymerization initiator (C), propylene glycol monomethyl ether acetate as a solvent (D), and Valifast Blue 2620 (phthalocyanine dye, Orient Chemical Co., Ltd.) as a colorant (E) were mixed in the compositions shown in Table 4 (unit: parts by mass) to prepare the photosensitive colored compositions of Examples 23-24 and Comparative Examples 11-12.

[0166] The amounts of alkali-soluble resin (A) or (cA) shown in Tables 3 and 4 do not include the amount of solvent (D). The amounts of solvent (D) shown in Tables 3 and 4 are the sum of the amount of solvent (D) contained in the liquid containing alkali-soluble resin (A) or (cA) obtained in Examples 1 to 11 or Comparative Examples 1 to 5, and the amount of solvent (D) added during the preparation of the photosensitive resin composition.

[0167] (1) Evaluation of transmittance Each photosensitive resin composition was spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) so that the average thickness of the cured resin film was 2.0 μm. The solvent was then evaporated by heating at 100°C for 3 minutes to form a coated film. Next, the entire coated film was exposed to light (wavelength 365 nm, exposure dose 200 mJ / cm²). ２ After photocuring, a resin-cured film was obtained by baking at 230°C for 30 minutes.

[0168] Measurements were taken using a UV-1650PC spectrophotometer (Shimadzu Corporation). Measurement target: The above-mentioned cured resin film. Measurement conditions: Measurement wavelength (wavelength range) 380-780 nm.

[0169] (2) Each developable photosensitive resin composition or photosensitive colored composition was spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) to a thickness of 2.0 μm after exposure, and then heated at 100°C for 3 minutes to evaporate the solvent and form a coated film.

[0170] Next, using an ultra-high pressure mercury lamp, 100 mJ / cm² ２ Light was shone onto the surface of the dried coating film via a photomask. Exposure was performed with the photomask positioned 100 μm away from the coating film. A photomask with a line-and-space pattern having a width of 3 to 100 μm was used. Next, the unexposed areas were removed by developing the surface by immersing it in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C for 30 seconds. The glass substrate with the developed coating film was then left to stand in a 100°C dryer for 30 minutes to heat-cur the coating film and obtain a pattern. The pattern thus obtained was observed using an electron microscope S-3400 (manufactured by Hitachi High-Technologies Corporation).

[0171] Developability was evaluated according to the following criteria: A: A pattern is formed after development. B: The pattern is not fully formed after development, or residue is observed between the patterns after development.

[0172] (3) Refractive index: The refractive index refers to the refractive index of the alkali-soluble resin (A) or (cA) measured using a refractometer. The refractive index of a resin composition (sample) containing alkali-soluble resin (A) or (cA) 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 (solids) of alkali-soluble resin (A) or (cA) contained in the sample is measured in accordance with JIS K 6901:2008 5.11, and the refractive index of alkali-soluble resin (A) or (cA) alone contained in the sample is calculated using the following formula. Measuring instrument: J-357 Automatic Refractometer (Rudolph Research Analytical) Measurement wavelength: 589 nm Measurement temperature: 25°C Refractive index of alkali-soluble resin (A) or (cA) alone = (Refractive index of sample - Refractive index of solvent (D)) ÷ Solids content × 100 + Refractive index of solvent (D)

[0173] (4) Overall evaluation The photosensitive resin composition or photosensitive colored composition was comprehensively evaluated according to the following criteria: A: Developability is A and refractive index is 1.55 or higher B: Developability is B or refractive index is less than 1.55

[0174] The results are shown in Tables 3 and 4.

[0175]

[0176]

Claims

1. A structural unit (a-1) represented by formula (1) having a halogen-substituted phenyl group: (In the formula, X is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, Y is a single bond or a divalent organic group, and R １ , R ２ , R ３ , R ４ , and R ５ are each independently H, Br, or I, provided that at least one of R １ , R ２ , R ３ , R ４ , and R ５ is Br or I.) having an acid value of 10 to 300 mgKOH / g, an alkali-soluble resin.

2. The alkali-soluble resin according to claim 1, wherein the halogen-substituted phenyl group equivalent is 400 to 1200 g / mol.

3. The alkali-soluble resin according to claim 1 or 2, wherein the refractive index is 1.55 or higher.

4. The alkali-soluble resin according to claim 1 or 2, wherein the weight-average molecular weight is 1,000 to 50,000.

5. In equation (1), R １ , R ３ , and R ５ I is R ２ , and R ４ is H, or R １ , R ２ , R ３ , R ４ , and R ５ The alkali-soluble resin according to claim 1 or 2, wherein is Br.

6. The alkali-soluble resin according to claim 1 or 2, which is a copolymer containing the structural unit (a-1) and the structural unit (a-2) having an acid group.

7. The alkali-soluble resin according to claim 6, wherein, with respect to 100 mol% of all structural units, the content of structural unit (a-1) is 10 to 95 mol%, and the content of structural unit (a-2) is 5 to 90 mol%.

8. The alkali-soluble resin according to claim 1 or 2, wherein the alkali-soluble resin has a structure in which an ethylenically unsaturated compound (e) having a group that is reactive with the acid group is attached to a part of the acid group of an alkali-soluble resin precursor (PA1) containing the structural unit (a-1) and a structural unit (a-2) having an acid group.

9. The alkali-soluble resin according to claim 8, wherein, with respect to 100 mol% of the total structural units of the alkali-soluble resin precursor (PA1), the content of structural unit (a-1) is 10 to 95 mol%, the content of structural unit (a-2) is 5 to 90 mol%, the amount of ethylenically unsaturated compound (e) is 1 to 60 mol per 100 mol of structural units of the alkali-soluble resin precursor (PA1), and the amount of ethylenically unsaturated compound (e) added is 5 to 90 mol per 100 mol of structural unit (a-2) of the alkali-soluble resin precursor (PA1).

10. The alkali-soluble resin according to claim 1 or 2, wherein the alkali-soluble resin has a structure in which at least a portion of the epoxy group of an alkali-soluble resin precursor (PA2) containing the structural unit (a-1) and a structural unit (a-3) having an epoxy group is attached to an ethylenically unsaturated compound (f) having a group reactive with the epoxy group, and at least a portion of the hydroxyl group formed by ring-opening of the epoxy group is attached to a polybasic acid or polybasic acid anhydride (h).

11. The alkali-soluble resin according to claim 10, wherein, with respect to 100 mol% of the total structural units of the alkali-soluble resin precursor (PA2), the content of structural unit (a-1) is 10 to 95 mol%, the content of structural unit (a-3) is 5 to 90 mol%, the amount of ethylenically unsaturated compound (f) is 5 to 90 moles per 100 moles of structural units of the alkali-soluble resin precursor (PA2), the amount of ethylenically unsaturated compound (f) added is 60 to 100 moles per 100 moles of structural unit (a-3) of the alkali-soluble resin precursor (PA2), the amount of polybasic acid or polybasic acid anhydride (h) is 5 to 50 moles per 100 moles of structural units of the alkali-soluble resin precursor (PA2), and the amount of polybasic acid or polybasic acid anhydride (h) added is 10 to 90 moles per 100 moles of ethylenically unsaturated compound (f).

12. A photosensitive resin composition comprising an alkali-soluble resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the alkali-soluble resin (A) is the alkali-soluble resin described in claim 1 or 2.

13. The photosensitive resin composition according to claim 12, wherein, with respect to 100% by mass of the total of the alkali-soluble resin (A) and the reactive diluent (B), the content of the alkali-soluble resin (A) is 10 to 99% by mass, the content of the reactive diluent (B) is 1 to 90% by mass, the content of the photopolymerization initiator (C) is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total of the alkali-soluble resin (A) and the reactive diluent (B), and the content of the solvent (D) is 30 to 1000 parts by mass with respect to 100 parts by mass of the total of the components excluding the solvent (D).

14. A photosensitive colored composition comprising the photosensitive resin composition described in claim 12 and a colorant (E).

15. The photosensitive colored composition according to claim 14, wherein the content of the coloring agent (E) is 0.1 to 80 parts by mass per 100 parts by mass of the total of the alkali-soluble resin (A) and the reactive diluent (B).

16. A resin-cured film comprising a cured product of the photosensitive resin composition according to claim 12.

17. A resin-cured film comprising a cured product of the photosensitive coloring composition according to claim 14.

18. A cured resin film having a pattern, which is a cured product of the photosensitive resin composition according to claim 12.

19. A color filter having a colored pattern, which is a cured product of the photosensitive colored composition according to claim 14.

20. An image display element comprising the color filter described in claim 19.

Images