JP7568413B2 - Photosensitive resin composition, cured film obtained by curing the same, and display device having the cured film - Google Patents

Description

The present invention relates to a photosensitive resin composition containing an alkali-soluble resin containing a polymerizable unsaturated group having a specific structure, a cured film obtained by curing the photosensitive resin composition, and a touch panel and a color filter containing the cured film as a constituent component.

Conventionally, a transparent cured film (hereinafter also referred to as a "protective film") is formed as a protective layer on the surface of a color filter used in the manufacture of a color liquid crystal display (LCD). The protective film of a color filter is formed for the purposes of flattening the unevenness that occurs between the pixels of the color filter, improving the durability of the color filter against heat treatment and chemical treatment in the post-process, and improving the reliability of the color liquid crystal display. The protective film of a color filter is required to have excellent transparency, chemical resistance, adhesion, hardness, flatness, heat resistance, and electrical reliability.

Meanwhile, there are two methods for forming a protective film: one is to form a protective film on the front surface by thermal curing, and the other is to form a protective film by photolithography. The method for forming the protective film can be selected during the panel design and processing of the color filter, depending on the characteristics that the protective film should have and whether patterning is required. Here, when forming a protective film by photolithography, the characteristics that are important are transparency, chemical resistance, adhesion, hardness, and electrical reliability, assuming that the film has development characteristics that allow the desired protective film pattern to be formed.

For example, in terms of transparency, the protective film is required to have no absorption in the visible light wavelength range so as not to impair the color characteristics of the color filter. In terms of chemical resistance, the protective film is required to be stable against acids, alkalis, solvents, etc. used in later processes. In terms of adhesion, when a substrate is laminated on the protective film when manufacturing a liquid crystal display panel, the protective film in that area is required to not peel off even if the base is a glass substrate, an ITO substrate, a MAM substrate, etc. In terms of hardness, the protective film is required to have high hardness from the viewpoint of durability. In terms of electrical reliability, it is required that the insulating properties of the protective film be maintained and that impurities contained in the protective film do not contaminate the liquid crystal.

The requirements for the above protective film are becoming stricter as LCD panels become more sophisticated, requiring wider viewing angles and faster response times. In display methods such as IPS (In-plane Switching) mode, gaseous or liquid components or water generated or bleed-out from the color filter layer may enter the liquid crystal layer through the protective layer, increasing the concentration of moisture or ionic impurities in the liquid crystal layer or forming bubbles in the liquid crystal layer, causing display defects. For this reason, it is particularly important to prevent the passage of the above-mentioned impurities, as well as to have low gas generation properties, since gas generation from the protective film in direct contact with the liquid crystal layer directly leads to display defects.

Furthermore, there are issues in the LCD panel manufacturing process, such as photo-alignment treatment of the liquid crystal alignment film after the protective film is formed, and issues such as reducing the effects of external light, including various display devices such as organic electroluminescence. For this reason, there are cases where the protective film is required to have the ability to absorb short-wavelength ultraviolet light that does not contribute to color display, while still ensuring transparency (high transmittance) as a protective film.

It is desirable for the photosensitive resin composition to be capable of forming an appropriate protective film pattern by photolithography, and for the protective film pattern to be one that adequately retains properties such as transparency, chemical resistance, adhesion, and hardness, while also sufficiently reducing the gas generation that affects electrical reliability. Also, for color resists that form RGB pixels, black resists that form light-shielding films, and the like, there are cases in which a cured film that has excellent low gas generation properties in addition to the various required properties is desired.

The present invention has been made in consideration of these points, and aims to provide a photosensitive resin composition that can be used for protective films that generate little gas, colored films including light-shielding films, etc., a cured film obtained by curing the composition, and a display device having the cured film.

As a result of investigations conducted by the inventors to solve the problems with the photosensitive resin composition for the light-shielding film, they discovered that a specific colorant is suitable as a light-shielding component for the photosensitive resin composition for the light-shielding film, and thus completed the present invention.

The photosensitive resin composition of the present invention contains the following components (A) to (D) as essential components: (A) an alkali-soluble resin containing a polymerizable unsaturated group represented by general formula (1), (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) a photopolymerization initiator, and (D) a solvent.

(In formula (1), Ar's are each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each _{R 1} is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number from 0 to 3. Each G is independently a substituent represented by general formula (2) or general formula (3), and Y is a tetravalent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by general formula (4), and at least one Z is a substituent represented by general formula (4). n is a number having an average value of 1 to 20.)

(In formulas (2) and (3), _R2 is a hydrogen atom or a methyl group, _R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, _R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

The cured film of the present invention is formed by curing the above-mentioned photosensitive resin composition.

The display device of the present invention has the above-mentioned cured film.

The present invention provides a photosensitive resin composition that can be used for protective films that generate little gas, colored films including light-shielding films, etc., a cured film obtained by curing the composition, and a display device having the cured film.

The following describes an embodiment of the present invention, but the present invention is not limited to the following embodiment. Note that in the present invention, when the first decimal place of the content of each component is 0, the decimal point may be omitted.

The polymerizable unsaturated group-containing alkali-soluble resin of component (A) represented by general formula (1) of the present invention is obtained by reacting a reaction product of an epoxy compound (a-1) having two glycidyl ether groups and a (meth)acrylic acid derivative with a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof (b), and a tetracarboxylic acid or an acid dianhydride thereof (c). Note that "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and means either or both of these.

The above-mentioned polymerizable unsaturated group-containing alkali-soluble resin is characterized in that the epoxy compound used as the raw material is a compound in which Ar in the general formula (1) is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and may contain several oxyalkylene groups in one molecule.

Preferred examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a divalent naphthyl group and a phenylene group in which some of the hydrogen atoms may be substituted with an alkyl group or the like. Here, in the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention, it is preferable that both of the two Ars bonded to the fluorene group in the general formula (1) are naphthyl groups (having a bisnaphtholfluorene skeleton) or both are phenylene groups (having a bisphenolfluorene skeleton), and it is more preferable that both of the Ars bonded to the fluorene group are naphthyl groups. This is because the cured film (coating film) obtained by curing the (A) polymerizable unsaturated group-containing alkali-soluble resin in which both of the Ars bonded to the fluorene group are naphthyl groups generates a small amount of gas when heated.

(In formula (1), Ar is each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atom may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each R ₁ is each independently an alkylene group having 2 to 4 carbon atoms, each l is independently a number from 0 to 3, the average value of l in one molecule is also a number from 0 to 3, and the average value of l in the composition is also a number from 0 to 3. Each G is independently a substituent represented by general formula (2) or general formula (3), and Y is a tetravalent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by general formula (4), and at least one Z is a substituent represented by general formula (4). n is a number having an average value of 1 to 20.)

(In formulas (2) and (3), _R2 is a hydrogen atom or a methyl group, _R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, _R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is 0 to 10.)

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

The method for producing the alkali-soluble resin containing a polymerizable unsaturated group represented by general formula (1) is described in detail below.

First, an epoxy compound (a-1) (hereinafter simply referred to as "epoxy compound (a-1)") having a bisnaphtholfluorene skeleton or a bisphenolfluorene skeleton, which may have several oxyalkylene groups in one molecule and is represented by general formula (5), is reacted with either or both of a (meth)acrylic acid derivative represented by general formula (6) or general formula (7) to obtain an epoxy (meth)acrylate.

(In formula (5), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each R ₁ is independently an alkylene group having 2 to 4 carbon atoms, and each 1 is independently a number from 0 to 3.)

(In formulas (6) and (7), _R2 is a hydrogen atom or a methyl group, _R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, _R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

The reaction between the epoxy compound (a-1) and the (meth)acrylic acid derivative can be carried out by a known method. For example, Japanese Patent Application Laid-Open No. 4-355450 describes that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth)acrylic acid per mole of an epoxy compound having two epoxy groups. In the present invention, the compound obtained by the above reaction is a diol (d) containing a polymerizable unsaturated group represented by formula (8) (hereinafter, also simply referred to as "diol (d) represented by general formula (8)").

(In formula (8), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atom may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each G is independently a substituent represented by general formula (2) or general formula (3), each R ₁ is independently an alkylene group having 2 to 4 carbon atoms, and each 1 is independently a number from 0 to 3.)

(In formulas (2) and (3), _R2 is a hydrogen atom or a methyl group, _R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, _R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

In the synthesis of diol (d) represented by general formula (8) and the subsequent reaction with a polycarboxylic acid or anhydride thereof to produce an alkali-soluble resin containing a polymerizable unsaturated group represented by general formula (1), the reaction is usually carried out in a solvent using a catalyst as necessary.

Examples of solvents include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone-based solvents such as cyclohexanone and diisobutyl ketone. There are no particular limitations on the reaction conditions, such as the solvent and catalyst used, but it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

In addition, it is preferable to use a catalyst in the reaction between an epoxy group and a carboxyl group or a hydroxyl group. JP-A-9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

Next, the diol (d) represented by the general formula (8) obtained by the reaction of the epoxy compound (a-1) with the (meth)acrylic acid derivative is reacted with a dicarboxylic acid or tricarboxylic acid or its acid anhydride (b) and a tetracarboxylic acid or its acid dianhydride (c) to obtain an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by the general formula (1).

(In formula (1), Ar's are each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each _{R 1} is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number from 0 to 3. Each G is independently a substituent represented by general formula (2) or general formula (3), and Y is a tetravalent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by general formula (4), and at least one Z is a substituent represented by general formula (4). n is a number having an average value of 1 to 20.)

(In formulas (2) and (3), _R2 is a hydrogen atom or a methyl group, _R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, _R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

Next, the substituents represented by general formula (2) or (3) derived from the (meth)acrylic acid derivatives represented by general formula (6) and general formula (7) constituting the alkali-soluble resin represented by general formula (1) will be described in detail.

General formulas (2), (3), (6) and (7) have a polymerizable unsaturated group and at least one ester bond.

In the general formulae (2), (3), (6) and (7), _R2 is a hydrogen atom or a methyl group.

In addition, in the general formulae (2), (3), (6) and (7), R ₃ is a divalent alkylene or alkylarylene group having 2 to 10 carbon atoms.

The alkylene group may be linear or branched, and may be, for example, an ethylene, ethylidene, vinylene, vinylidene, propylene, trimethylene, propenylene, isopropylidene, or tetramethylene group.

The alkylarylene group may be an unsubstituted arylene group within the range of carbon number, such as o-, m-, or p-phenylene, toluylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, or pentylphenylene.

In the general formulas (2), (3), (6) and (7), R ₄ is a saturated or unsaturated aliphatic or aromatic hydrocarbon group having 2 to 20 carbon atoms.

The above-mentioned saturated and unsaturated aliphatic hydrocarbon groups may be either linear or branched, and include ethylene, ethylidene, vinylene, vinylidene, propylene, trimethylene, propenylene, isopropylidene, and tetramethylene groups.

The aromatic hydrocarbon group may be unsubstituted within the range of the carbon number, for example, o-, m-, or p-phenylene, toluylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenylene, or pentylphenylene, and may be substituted with 2 to 4 substituents as long as the range of the carbon number is not exceeded. The aliphatic hydrocarbon group may be interrupted by an unsaturated bond, an ether bond, or an ester bond.

When the alkali-soluble resin represented by general formula (1) is synthesized, each p is independently a number from 0 to 10, but the average value of p in the resin is preferably a number from 0 to 5, and more preferably a number from 0 to 2. When the average value of p is within the above range, the distribution of the flexible structure, alkylene oxide, can be prevented from becoming wide, and sufficient curability can be imparted to the cured film without reducing the resin performance.

The acid component used to synthesize the alkali-soluble resin represented by general formula (1) is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule represented by general formula (8), and it is necessary to use a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof (b) in combination with a tetracarboxylic acid or an acid dianhydride thereof (c). The carboxylic acid residue of the acid component may be either a saturated or unsaturated hydrocarbon group. In addition, these carboxylic acid residues may contain bonds containing heteroatoms such as -O-, -S-, and carbonyl groups.

Examples of the dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b) include open-chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their monoanhydrides.

Examples of the acid monoanhydrides of the above-mentioned chain hydrocarbon dicarboxylic or tricarboxylic acids include acid monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, etc., and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

Examples of the above-mentioned alicyclic dicarboxylic or tricarboxylic acid monoanhydrides include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like, as well as dicarboxylic or tricarboxylic acid monoanhydrides having any substituent introduced therein.

Examples of the above aromatic dicarboxylic or tricarboxylic acid monoanhydrides include phthalic acid, isophthalic acid, trimellitic acid, and the like, and dicarboxylic or tricarboxylic acid monoanhydrides having any substituent introduced therein.

Among the above dicarboxylic or tricarboxylic acid monoanhydrides, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred.

In addition, in the case of dicarboxylic acids or tricarboxylic acids, it is preferable to use their acid monoanhydrides. The above-mentioned acid monoanhydrides of dicarboxylic acids or tricarboxylic acids may be used alone or in combination of two or more kinds.

Examples of the tetracarboxylic acid or its dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or their dianhydrides.

Examples of the above chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids having substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups.

Examples of the alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids having substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups.

Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

Bis(trimellitic anhydride) aryl esters can also be used. Bis(trimellitic anhydride) aryl esters are a group of compounds produced, for example, by the method described in International Publication No. 2010/074065, and are structurally dianhydrides formed by reacting two hydroxyl groups of an aromatic diol (naphthalenediol, biphenol, terphenyldiol, etc.) with the carboxyl groups of two molecules of trimellitic anhydride to form an ester bond. Hereinafter, these compounds will be referred to as bis(trimellitic anhydride) esters of aromatic diols.

Among the above tetracarboxylic acids or their dianhydrides, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are more preferred. In addition, among the above tetracarboxylic acids or their dianhydrides, it is preferred to use the dianhydrides. Furthermore, bis(trimellitic anhydride) esters of naphthalenediol can also be preferably used. The above tetracarboxylic acids or their dianhydrides, and bis(trimellitic anhydride) esters of aromatic diols may be used alone or in combination of two or more.

The reaction between the diol (d) represented by the general formula (8) and the acid components (b) and (c) is not particularly limited, and any known method can be used. For example, JP-A-9-325494 describes a method in which an epoxy (meth)acrylate is reacted with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

It is preferable to react the compound with the epoxy (meth)acrylate (d), dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b), and tetracarboxylic dianhydride (c) in a molar ratio of (d):(b):(c) = 1.0:0.01-1.0:0.2-1.0 so that the terminals of the compound are carboxy groups.

For example, when an acid monoanhydride (b) and an acid dianhydride (c) are used, it is preferable to react them so that the molar ratio [(d)/[(b)/2+(c)]] of the amount of the acid component to the diol (d) containing a polymerizable unsaturated group [(b)/2+(c)] is 0.5 to 1.0. Here, when the molar ratio is 1.0 or less, the content of the diol containing an unreacted polymerizable unsaturated group is not increased, so the stability over time of the alkali-soluble resin composition can be improved. On the other hand, when the molar ratio exceeds 0.5, the terminal of the alkali-soluble resin represented by formula (2) does not become an acid anhydride, so that the content of the unreacted acid dianhydride can be prevented from increasing, and the stability over time of the alkali-soluble resin composition can be improved. In addition, in order to adjust the acid value and molecular weight of the alkali-soluble resin represented by general formula (2), the molar ratios of each component (b), (c) and (d) can be arbitrarily changed within the above-mentioned range.

The acid value of the alkali-soluble resin represented by formula (1) is preferably in the range of 20 to 180 mgKOH/g, and more preferably 40 mgKOH/g or more and 120 mgKOH/g or less. When the acid value is 20 mgKOH/g or more, residues are less likely to remain during alkaline development, and when the acid value is 180 mgKOH/g or less, the penetration of the alkaline developer does not become too rapid, so peeling development can be suppressed. The acid value can be determined by titration with a 1/10N aqueous KOH solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

The weight average molecular weight (Mw) of the alkali-soluble resin represented by general formula (1) in terms of polystyrene, as measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation), is usually 1,000 to 100,000, preferably 2,000 to 20,000, and more preferably 2,000 to 6,000. When the weight average molecular weight is 1,000 or more, it is possible to suppress a decrease in the adhesion of the pattern during alkaline development. Furthermore, when the weight average molecular weight (Mw) is less than 100,000, it is easy to adjust the solution viscosity of the photosensitive resin composition to a level suitable for application, and alkaline development does not require too much time.

Next, we will explain the photosensitive resin composition using the alkali-soluble resin represented by general formula (1) of the present invention.

In the photosensitive resin composition of the present invention, the content of component (A) is preferably 10 to 90% by mass based on the total mass of the solid content. The content of component (B) is preferably 5 to 200 parts by mass based on 100 parts by mass of component (A), and the content of component (C) is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total amount of components (A) and (B).

Examples of the photopolymerizable monomer (B) having at least three ethylenically unsaturated bonds in the photosensitive resin composition of the present invention include (meth)acrylic acid esters such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; dendrimer-type multifunctional acrylates. These photopolymerizable monomers may be used alone or in combination of two or more.

The content of the (B) component is preferably 5 to 200 parts by weight per 100 parts by weight of the (A) component, more preferably 10 to 80 parts by weight per 100 parts by weight of the (A) component, and even more preferably 10 to 60 parts by weight. When the content of the (B) component is 5 parts by weight or more per 100 parts by weight of the (A) component, the resin contains a sufficient number of photoreactive functional groups, so that a sufficient crosslinked structure is formed. In addition, the acid value of the resin component does not become too high, so that the solubility in an alkaline developer in the exposed area is reduced, so that the formed pattern is prevented from becoming thinner than the target line width, and pattern loss can be suppressed. In addition, when the content of the (B) component is 200 parts by weight or less per 100 parts by weight of the (A) component, a cured film having sufficient curability can be obtained, so that the pattern edges can be made sharp.

Examples of the photopolymerization initiator (C) in the photosensitive resin composition of the present invention include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzoin ethers such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, and 2-(o-fluorophenyl)-4,5-diphenylbiimidazole. , 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyldiazole compounds; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6 -Bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)- Halomethyl-s-triazine compounds such as 4,6-bis(trichloromethyl)-1,3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxy O-acyloxime compounds such as 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used alone or in combination of two or more.

In particular, when a photosensitive resin composition containing a colorant is to be prepared, it is preferable to use O-acyloxime compounds (including ketoximes). Specific compound groups include O-acyloxime photopolymerization initiators represented by general formula (9) or general formula (10). Among these, when a colorant is used at a high pigment concentration or when a light-shielding film pattern is to be formed, it is preferable to use an O-acyloxime photopolymerization initiator having a molar absorption coefficient at 365 nm of 10,000 L/mol cm or more. In the present invention, the term "photopolymerization initiator" is used to include sensitizers.

(In formula (9), R ₅ and R ₆ are each independently an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms; and R ₇ is an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. In addition, the alkyl group may be any of a linear, branched, and cyclic alkyl group.)

(In formula (10), R ₈ and R ₉ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. _{R 10} each independently represent a linear or branched alkyl group or alkenyl group having 2 to 10 carbon atoms, and some of the -CH ₂ - groups in the alkyl group or alkenyl group may be substituted with -O- groups. Furthermore, some of the hydrogen atoms in these R ₈ to R ₁₀ groups may be substituted with halogen atoms.)

The content of component (C) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 25 parts by mass, per 100 parts by mass of the total amount of components (A) and (B). When the content of component (C) is 0.1 parts by mass or more, the photopolymerization speed is appropriate, and a decrease in sensitivity can be suppressed. When the content is 30 parts by mass or less, the line width can be faithfully reproduced on the mask and the pattern edges can be sharpened.

(D) Examples of solvents contained in the photosensitive resin composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, and propylene glycol monomethyl ether. Examples of the solvent include glycol ethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing using these, a homogeneous solution-like composition can be obtained. These solvents may be used alone or in combination of two or more to obtain the required properties such as coatability. The amount of solvent varies depending on the target viscosity, but it is preferably 60 to 90% by mass in the photosensitive resin composition solution.

The photosensitive resin composition described above contains a colorant as component (E). When used as a resist for a light-shielding film, component (E) is one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials, and is preferably a black organic pigment and/or a mixed-color organic pigment. The average secondary particle size of the black organic pigment and/or the mixed-color organic pigment is preferably 20 to 500 nm. The average secondary particle size of the black organic pigment and the mixed-color organic pigment can be measured by the cumulant method using a dynamic light scattering particle size distribution meter "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.).

The content of the colorant, which is component (E), can be determined arbitrarily depending on the desired degree of light blocking, but is preferably 1 to 80% by mass relative to the solid content in the photosensitive resin composition, and more preferably 20 to 60% by mass when an organic pigment or a carbon-based inorganic pigment is used.

Examples of black organic pigments, component (E), include perylene black, aniline black, cyanine black, lactam black, etc.

Examples of mixed-color organic pigments, which are component (E), include pseudo-black pigments obtained by mixing at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments.

Examples of the light-shielding material (E) include carbon black, chromium oxide, iron oxide, and titanium black. These (E) components may be surface-treated as appropriate depending on the intended function of the photosensitive resin composition. These (E) components may be used alone or in combination of two or more.

Examples of organic pigments that can be used as component (E) include, but are not limited to, those having the following Color Index numbers:
Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

It is also preferable that the colorant (E) is dispersed in advance in the (D) solvent together with the (F) dispersant to form a colorant dispersion, which is then blended into the photosensitive resin composition. The solvent used for dispersion becomes part of the (D) component, and can be any solvent that is included in the above-mentioned (D) component. Among the above-mentioned (D) components, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butyl acetate, etc. are preferable.

The content of component (E) is preferably 1 to 80% by mass, and more preferably 30 to 60% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The above solid content refers to the components of the photosensitive resin composition excluding component (D). The above solid content also includes component (B), which becomes a solid content after photocuring. When component (E) is 1% by mass or more, it is easy to set the desired light blocking properties. When it is 80% by mass or less, the desired development characteristics and film forming ability are obtained.

The dispersant (F) can be any known compound used to disperse colorants (pigments) without any particular restrictions (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion promoters, etc.).

Examples of the dispersant that is the component (F) include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative dispersants (dispersion aids). In particular, the dispersant is preferably a cationic polymer dispersant that has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, or a primary, secondary, or tertiary amino group as an adsorption point to the colorant, has an amine value of 1 to 100 mgKOH/g, and has a number average molecular weight in the range of 1,000 to 100,000. The blending amount of this dispersant is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, relative to the colorant. Note that, although high-viscosity substances such as resins generally have the effect of stabilizing dispersion, those that do not have the ability to promote dispersion are not treated as dispersants. However, there is no restriction on using them for the purpose of stabilizing dispersion.

When preparing the colorant dispersion, by co-dispersing a part of the polymerizable unsaturated group-containing alkali-soluble resin of component (A) in addition to the dispersant (F), it is possible to obtain a photosensitive resin composition that is easy to maintain high exposure sensitivity, has good adhesion during development, and is less likely to cause residue problems. The content of component (A) in the colorant dispersion is preferably 2 to 20% by mass, and more preferably 5 to 15% by mass. When component (A) is 2% by mass or more, the effects of co-dispersion such as improved sensitivity, improved adhesion, and reduced residue can be obtained. When component (A) is 20% by mass or less, a cured film (coating film) in which component (E) is uniformly dispersed can be obtained.

The colorant dispersion can be mixed with component (A) (if component (A) is co-dispersed when preparing the colorant dispersion, the remaining component (A)), component (B), component (C), and the remaining component (E) to form a photosensitive resin composition for a light-shielding film.

The photosensitive resin composition of the present invention may be used in combination with other resin components that polymerize or harden by light or heat, if necessary. Examples of other resin components include novolac epoxy resins derived from novolacs such as phenol novolac and cresol novolac, epoxy resins such as bisphenol-type epoxy resins, and alkali-soluble resins (excluding component (A)) obtained by reacting the epoxy resins with (meth)acrylic acid and acid anhydrides, copolymers with (meth)acrylic acid and/or (meth)acrylic acid esters, and alkali-soluble resins obtained by reacting the carboxy groups in the copolymers with epoxy group-containing (meth)acrylates.

The photosensitive resin composition of the present invention can contain additives such as curing agents, curing accelerators, thermal polymerization inhibitors and antioxidants, plasticizers, fillers, leveling agents, defoamers, surfactants, and coupling agents, as necessary.

Examples of curing agents include amine compounds, polyvalent carboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc., which contribute to the curing of epoxy resins. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to the curing acceleration of epoxy resins. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, silica, mica, alumina, etc. Examples of defoamers and leveling agents include silicone-based, fluorine-based, and acrylic compounds. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

The cured film (coating) of the present invention can be formed by photolithography using the photosensitive resin composition of the present invention. In the above method, first, a solution of the photosensitive resin composition is applied to the surface of a substrate, the solvent is dried (prebaked), a photomask is placed on the coating, and the exposed areas are cured by irradiating with ultraviolet light. A pattern is formed by developing the unexposed areas using an alkaline aqueous solution, and then post-baking is performed as a post-curing step. Examples of substrates onto which the photosensitive resin composition solution is applied include glass and transparent films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.).

The substrate may be a transparent substrate or a substrate other than a transparent substrate. Examples of transparent substrates onto which the photosensitive resin composition is applied include glass substrates and transparent films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.) on which transparent electrodes such as ITO or gold are vapor-deposited or patterned.

Methods for applying the photosensitive resin composition solution onto the substrate include the well-known solution immersion method, spray method, and methods using a roller coater, land coater, slit coater, or spinner. After applying the solution to the desired thickness using the above method, the solvent is dried (prebaked) to form a coating. Prebaking is performed by heating in an oven, hot plate, or the like. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 60 to 110°C for 1 to 3 minutes.

The exposure performed after pre-baking is performed using an ultraviolet exposure device, and only the resist in the area corresponding to the pattern is exposed by exposing through a photomask. The exposure device and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, or far ultraviolet lamp, to photocure the photosensitive resin composition in the coating film.

Radiation used for exposure can be, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc., but the wavelength range of the radiation is preferably 250 to 450 nm. In addition, as a developer suitable for this alkaline development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used. These developers can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant as necessary. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using a commercially available developing machine, ultrasonic cleaner, etc. Note that after alkaline development, the film is usually washed with water. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid puddle) development method, etc. can be applied.

After exposure, alkaline development is carried out for the purpose of removing the photosensitive resin composition from the unexposed areas, and the desired pattern is formed by this development. Examples of developers suitable for this alkaline development include aqueous solutions of carbonates of alkali metals or alkaline earth metals, and aqueous solutions of hydroxides of alkali metals. In particular, it is preferable to use a weakly alkaline aqueous solution containing 0.03 to 1% by weight of carbonates such as sodium carbonate or potassium carbonate at a temperature of 23 to 27°C, and fine images can be precisely formed using a commercially available developing machine or ultrasonic cleaner.

After development in this manner, a heat treatment (post-baking) is performed at 180-250°C for 20-100 minutes. However, if the heat resistance of the substrate on which the film is to be formed is low, the composition can be designed so that the post-baking conditions are 80-180°C for 30-100 minutes. This post-baking is performed for the purpose of increasing the adhesion between the patterned coating film and the substrate, etc., as in the pre-baking, by heating in an oven, hot plate, etc. The patterned cured film of the present invention is formed through each of the steps of the photolithography method described above.

The following describes the embodiments of the present invention in detail based on examples and comparative examples, but the present invention is not limited to these.

First, synthesis examples of alkali-soluble resins containing polymerizable unsaturated groups, including a structure represented by general formula (1), will be described. The resins in these synthesis examples were evaluated as follows unless otherwise noted. When the same model of measuring equipment was used, the name of the equipment manufacturer is omitted from the second position onwards. In addition, in Examples 1 and 2, the glass substrates used to prepare the substrates with cured films for measurement were all glass substrates that had been subjected to the same treatment.

[Solid content]
1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter (weight: _W0 (g)), weighed ( _W1 (g)), and the weight after heating at 160°C for 2 hours ( _W2 (g)) was calculated from the following formula (1).
Solid content concentration (wt%) = 100 x (W ₂ - W ₀ )/(W ₁ - W ₀ ) (1)

[Epoxy equivalent]
The resin solution was dissolved in dioxane, and then a solution of tetraethylammonium bromide in acetic acid was added. The content was determined by titration with a 1/10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[Acid value]
The resin solution was dissolved in dioxane, and titrated with a 1/10N KOH aqueous solution using a potentiometric titrator "COM-1600" to determine the content.

[Molecular weight]
Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuperH-2000 (2 columns) + TSKgelSuperH-3000 (1 column) + TSKgelSuperH-4000 (1 column) + TSKgelSuperH-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, speed: 0.6 ml/min), and the weight average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

The abbreviations used in the Synthesis Examples and Comparative Synthesis Examples are as follows.
BPFE: Bisphenol fluorene type epoxy resin
(Epoxy resin of general formula (5) where Ar is a benzene ring and l is 0, epoxy equivalent 256)
BNFE: Bisnaphthol fluorene type epoxy resin
(Epoxy resin of general formula (5) where Ar is a naphthalene ring and l is 0, epoxy equivalent 281)
HOA-HH: 2-acryloyloxyethylhexahydrophthalic acid
(Light Acrylate HOA-HH(N), manufactured by Kyoeisha Chemical Co., Ltd.)
BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride BTDA: Benzophenonetetracarboxylic dianhydride BTANE: Bis(trimellitic anhydride) ester of naphthalenediol
(DHN-D1, manufactured by Honshu Chemical Industry Co., Ltd.)
THPA: 1,2,3,6-tetrahydrophthalic anhydride TPP: triphenylphosphine TBPC: 2,6-di-tert-butyl-p-cresol AA: acrylic acid MAA: methacrylic acid MMA: methyl methacrylate CHMA: cyclohexyl methacrylate AIBN: azobisisobutyronitrile GMA: glycidyl methacrylate PGMEA: propylene glycol monomethyl ether acetate

[Synthesis Example 1]
In a 250 mL four-neck flask equipped with a reflux condenser, BPFE (46.64 g, 0.09 mol), AA (13.12 g, 0.18 mol), TPP (0.24 g), and PGMEA (40.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (20.00 g) was charged and adjusted so that the solid content was 50% by mass.

Then, BPDA (13.45 g, 0.05 mol) and THPA (6.96 g, 0.05 mol) were added to the obtained reaction product and stirred at 115 to 120°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-1. The solids concentration of the obtained resin solution was 57.3 mass%, the acid value (solids equivalent) was 96 mgKOH/g, and the Mw by GPC analysis was 3600.

[Synthesis Example 2]
In a 250 mL four-neck flask equipped with a reflux condenser, BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (20.00 g) was charged and adjusted so that the solid content was 50% by mass.

Then, BPDA (12.49 g, 0.04 mol) and THPA (6.46 g, 0.04 mol) were added to the obtained reaction product and stirred at 115 to 120°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-2. The solids concentration of the obtained resin solution was 56.9 mass%, the acid value (solids equivalent) was 90 mgKOH/g, and the Mw by GPC analysis was 4000.

[Synthesis Example 3]
In a 250 mL four-neck flask equipped with a reflux condenser, BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (20.00 g) was charged and adjusted so that the solid content was 50% by mass.

Then, BPDA (8.74 g, 0.03 mol) and THPA (10.34 g, 0.07 mol) were added to the obtained reaction product and stirred at 115 to 120°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-3. The solids concentration of the obtained resin solution was 56.9 mass%, the acid value (solids equivalent) was 90 mgKOH/g, and the Mw by GPC analysis was 2600.

[Synthesis Example 4]
In a 250 mL four-neck flask equipped with a reflux condenser, BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (20.00 g) was charged and adjusted so that the solid content was 50% by mass.

Then, BPDA (16.49 g, 0.06 mol) and THPA (0.26 g, 0.002 mol) were added to the obtained reaction product and stirred at 115 to 120°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-4. The solids concentration of the obtained resin solution was 56.1% by mass, the acid value (solids equivalent) was 83 mgKOH/g, and the Mw by GPC analysis was 7000.

[Synthesis Example 5]
In a 250 mL four-neck flask equipped with a reflux condenser, BNFE (30.53 g, 0.05 mol), HOA-HH (29.33 g, 0.11 mol), TPP (0.14 g), and PGMEA (40.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (20.00 g) was charged and adjusted so that the solid content was 50% by mass.

Then, BPDA (8.00 g, 0.03 mol) and THPA (4.14 g, 0.03 mol) were added to the obtained reaction product and stirred at 115 to 120°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-5. The solids concentration of the obtained resin solution was 54.6 mass%, the acid value (solids equivalent) was 63 mgKOH/g, and the Mw by GPC analysis was 5,300.

[Synthesis Example 6]
In a 250 mL four-neck flask equipped with a reflux condenser, BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (20.00 g) was charged and adjusted so that the solid content was 50% by mass.

Then, BTDA (13.68 g, 0.04 mol) and THPA (6.46 g, 0.04 mol) were added to the resulting reaction product and stirred at 115 to 120°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-6. The solids concentration of the resulting resin solution was 54.6% by mass, the acid value (solids equivalent) was 92 mg KOH/g, and the Mw by GPC analysis was 4100.

[Synthesis Example 7]
In a 250 mL four-neck flask equipped with a reflux condenser, BNFE (47.60 g, 0.08 mol), AA (12.18 g, 0.17 mol), TPP (0.22 g), and PGMEA (40.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (20.00 g) was charged and adjusted so that the solid content was 50% by mass.

Then, BTANE (21.58 g, 0.04 mol) and THPA (6.46 g, 0.04 mol) were added to the obtained reaction product and stirred at 115 to 120°C for 7 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-7. The solids concentration of the obtained resin solution was 54.6 mass%, the acid value (solids equivalent) was 91 mgKOH/g, and the Mw by GPC analysis was 5000.

[Synthesis Example 8]
MAA (51.65 g, 0.60 mol), MMA (36.04 g, 0.36 mol), CHMA (40.38 g, 0.24 mol), AIBN (5.91 g), and PGMEA (360 g) were charged into a 1000 ml four-neck flask equipped with a nitrogen inlet tube and a reflux condenser, and the mixture was polymerized by stirring for 8 hours under a nitrogen stream at 80 to 85 ° C. Further, GMA (61.41 g, 0.43 mol), TPP (2.27 g) and TBPC (0.086 g) were charged into the flask, and the mixture was stirred for 16 hours at 80 to 85 ° C. to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A)-8. The solid content concentration of the obtained resin solution was 35.7% by mass, the acid value (solid content equivalent) was 50 mg KOH / g, and the Mw by GPC analysis was 19,600.

(Alkali-soluble resin solution)
(A)-1: Alkali-soluble resin solution obtained in Synthesis Example 1 (A)-2: Alkali-soluble resin solution obtained in Synthesis Example 2 (A)-3: Alkali-soluble resin solution obtained in Synthesis Example 3 (A)-4: Alkali-soluble resin solution obtained in Synthesis Example 4 (A)-5: Alkali-soluble resin solution obtained in Synthesis Example 5 (A)-6: Alkali-soluble resin solution obtained in Synthesis Example 6 (A)-7: Alkali-soluble resin solution obtained in Synthesis Example 7 (A)-8: Alkali-soluble resin solution obtained in Synthesis Example 8

(Photopolymerizable Monomer)
(B): DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)

(Photopolymerization initiator)
(C): Irgacure OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), manufactured by BASF Corporation; "Irgacure" is a registered trademark of the company)

(solvent)
(D)-1: Propylene glycol monomethyl ether acetate (D)-2: 3-methoxy-3-methyl-1-butyl acetate

(Surfactant)
PGMEA solution of BYK-330 (solid content 1.0%) (manufactured by BYK-Chemie)

[Example 1]
Photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2 were prepared by mixing the components (A) to (D) and the surfactant in the ratios shown in Table 1. (D)-1 in the solvent column is the amount excluding PGMEA (the same as (D)-1) in the unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution), the solvent in the light-shielding pigment dispersion, and the solvent in the surfactant. All values in Table 1 are in mass %.

[evaluation]
The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2 were used to carry out the following evaluations.

(Preparation of cured film (coating film))
The photosensitive resin composition shown in Table 1 was applied to a 50 mm x 50 mm glass substrate "EAGLEXG" (manufactured by Corning) (hereinafter referred to as "glass substrate"), an indium-tin oxide vapor-deposited glass substrate (hereinafter referred to as "ITO substrate ^" ), and a molybdenum-aluminum alloy vapor-deposited substrate (hereinafter referred to as "MAM substrate"), the surface of which had been cleaned by irradiating with ultraviolet light having a wavelength of 254 nm and an illuminance of 1000 mJ/cm 2 using a low-pressure mercury lamp, so that the film thickness after heat curing treatment would be 1.5 μm, using a spin coater, and pre-baked at 90 ° C. for 1 minute using a hot plate to prepare a coated plate. Next, a photocuring reaction was performed by irradiating with ultraviolet light having a wavelength of 365 nm and an illuminance of 30 mW/cm ² at 100 mJ/cm ^2. Thereafter, a curing treatment was performed for 30 minutes at 230 ° C. using a hot air dryer to obtain cured films (coating films) according to Examples 1 to 10 and Comparative Examples 1 and 2.

The results of evaluation of the following items for the cured films (coatings) made of the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 and 2 obtained above are shown in Table 2. These evaluation methods were performed as follows. Note that the high temperature and high humidity resistance adhesion and chemical resistance adhesion were evaluated not only for the cured films (coatings) on the glass substrate, but also for the cured films (coatings) prepared on the ITO substrate and MAM substrate.

(Film thickness measurement)
The thickness of the cured films (coating films) of Examples 1 to 10 and Comparative Examples 1 and 2 was measured using a stylus-type step shape measuring device "P-17" (manufactured by KLA Tencol Corporation).

[High temperature and humidity resistance and adhesion]
(Evaluation Method)
The cured films (coating films) prepared on the glass substrate, ITO substrate, and MAM substrate were left to stand for 5 hours under conditions of a temperature of 121° C., humidity of 100%, and atmospheric pressure of 2 atm. Then, a cross-cut peeling test was performed in which the substrate was cut using a SuperCutterGuide (manufactured by Taiyu Kizai Co., Ltd.) so that 100 squares of 1 mm×1 mm were formed, and cellophane tape (manufactured by Nichiban Co., Ltd.) was applied on the squares and then peeled off.

(Evaluation Criteria)
○: The cured film (coating film) in the square has not peeled off at all. △: Less than 1/3 of the cured film (coating film) in the square has peeled off. ×: 1/3 or more has peeled off.

[Chemical resistance and adhesion]
(Evaluation Method)
The cured films (coatings) prepared on the glass substrate, ITO substrate, and MAM substrate were immersed in a petri dish containing N-methyl-2-pyrrolidone at 60°C for 2 minutes, washed with pure water, and wiped to remove moisture. Then, a cross-cut peeling test was performed in which the substrate was cut using a SuperCutterGuide to form 100 squares of 1 mm x 1 mm, and cellophane tape was applied to the squares and then peeled off.

(Evaluation Criteria)
○: The cured film (coating film) in the square has not peeled off at all. △: Less than 1/3 of the cured film (coating film) in the square has peeled off. ×: 1/3 or more has peeled off.

[Coating film hardness 1]
(Evaluation Method)
A load of 750 g was applied to the cured film (coating film) formed on the glass substrate using a pencil hardness tester in accordance with the test method of JIS-K5600-5-4, and the highest pencil hardness that did not scratch the cured film (coating film) was indicated. The pencil used was "Mitsubishi Hi-Uni" (manufactured by Mitsubishi Pencil Co., Ltd.). This evaluation was carried out as an index of resistance to lateral forces (scratching) on the coating film surface.

(Evaluation Criteria)
○: 3H or more △: 2H
×: H or less

[Coating film hardness 2]
(Evaluation Method)
The hardness of the cured film (coating film) formed on the glass substrate was measured using a microfilm hardness tester "HM2000" (manufactured by Fisher Instruments). A Vickers indenter was used to apply a load of 5 mN/ ^μm2 at a loading rate of 0.25 mN/sec, and the load was removed after holding for 1 second to measure the Martens hardness (in accordance with ISO14577). This evaluation was carried out as an index of resistance to vertical force (indentation) on the surface of the cured film (coating film). The "Martens hardness" is the hardness calculated from the load-penetration depth curve.

(Evaluation Criteria)
○: 65 N/mm2 or ^more △: 60 N/mm2 or ^more and less than 65 N/ ^mm2 ×: ^Less than 60 N/mm2

[Transmittance 1]
(Evaluation Method)
The transmittance of a cured film (coating film) formed on a glass substrate "EAGLE XG" with a thickness of 2 μm was measured using a transmittance meter "SPECTRO PHOTOMETER SD5000" (manufactured by Nippon Denshoku Industries Co., Ltd.).

(Evaluation Criteria)
◯: Transmittance at a wavelength of 400 nm is 95% or more △: Transmittance at a wavelength of 400 nm is 90% or more but less than 95% ×: Transmittance at a wavelength of 400 nm is less than 90%

[Transmittance 2]
The transmittance of a cured film (coating film) formed on a glass substrate "EAGLE XG" with a thickness of 3 μm was measured using a transmittance meter "SPECTRO PHOTOMETER SD5000."

(Evaluation Criteria)
◯: The transmittance at a wavelength of 340 nm is less than 20%. △: The transmittance at a wavelength of 340 nm is 20% or more and less than 65%. ×: The transmittance at a wavelength of 340 nm is 65% or more.

[Gas generation]
(Evaluation Method)
The cured film (coating) prepared on the glass substrate "EAGLE XG" was scraped off with a scraper or the like, and the thermal weight loss of 10 mg of the resulting powdery cured film (coating) was measured using a differential thermal analyzer (TG/DTA) "EXSTAR6000" (manufactured by Hitachi High-Tech Science Corporation). The measurement conditions were as follows: pretreatment was performed at 120°C for 30 minutes in air, followed by holding at 230°C for 3 hours. The gas generation property was evaluated from the weight loss rate, which was calculated from the weight loss before and after heating at 230°C.

(Evaluation Criteria)
◎: Weight loss rate is less than 3%. ○: Weight loss rate is 3% or more and less than 7%. △: Weight loss rate is 7% or more and less than 15%. ×: Weight loss rate is 15% or more.

[Water absorbency]
(Evaluation Method)
The cured film (coating film) prepared on the glass substrate "EAGLE XG" was left to stand for 24 hours under constant temperature and humidity conditions of 40°C and 90%, and then scraped off with a scraper or the like, and the thermal weight loss of 10 mg of the resulting powdery cured film (coating film) was measured using a differential thermal analyzer (TG/DTA) "EXSTAR6000". The measurement conditions were as follows: under a nitrogen atmosphere, the temperature was raised to 120°C at 10°C/min, and held for 1 hour. The water absorption was evaluated from the weight loss rate.

(Evaluation Criteria)
○: Weight loss rate is less than 2% △: Weight loss rate is 2% or more and less than 5% ×: Weight loss rate is 5% or more

[Development characteristics]
(Preparation of evaluation samples)
The photosensitive resin composition shown in Table 1 was applied to a 125 mm x 125 mm glass substrate "EAGLE XG" using a spin coater so that the film thickness after heat curing treatment would be 1.5 μm, and the substrate was pre-baked for 1 minute at 90° C. using a hot plate. After that, a photomask was placed so that the exposure gap was 150 μm, and ultraviolet rays of 100 mJ/cm ² were irradiated from a high-pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to cause a photocuring reaction of the photosensitive portion.

Next, this exposed cured film (coating film) was developed for 60 seconds at a pressure of 0.1 MPa using a 0.05% aqueous potassium hydroxide solution or a 0.2% aqueous sodium carbonate solution at 23°C, and then washed with water to remove the unexposed areas of the cured film (coating film). After that, a heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer, and the cured films (patterns) according to Examples 1 to 10 and Comparative Examples 1 and 2 were obtained.

(Evaluation method and criteria)
The formation of fine lines in the obtained pattern was confirmed by an optical microscope and evaluated according to the following three levels.
◯: A pattern with an L/S of 15 μm/15 μm or more is formed without any residue. △: A pattern with an L/S of 30 μm/30 μm or more is formed without any residue. ×: A pattern with an L/S of less than 50 μm/50 μm is not formed, or the pattern has noticeable footing or residue.

[Example 2]
Photosensitive resin compositions containing light-shielding pigment dispersions of Examples 11 to 16 and Comparative Examples 11 to 13 were prepared by mixing the components (A) to (E) and the surfactant in the ratios shown in Table 3. (D)-1 in the solvent column is the amount excluding PGMEA (the same as (D)-1) in the unsaturated group-containing resin solution (polymerizable unsaturated group-containing alkali-soluble resin solution), the solvent in the light-shielding pigment dispersion, and the solvent in the surfactant. All values in Table 3 are in mass %.

(Light-blocking pigment dispersion)
(E)-1: PGMEA dispersion of 15.0% by mass of lactam black pigment and 4.5% by mass of polymer dispersant (solid content 19.5%)
(E)-2: PGMEA dispersion (solid content 30.0%) of 25.0% by mass of resin-coated carbon-based black pigment and 5.0% by mass of polymer dispersant

[evaluation]
The following evaluations were carried out using the photosensitive resin compositions of Examples 11 to 16 and Comparative Examples 11 to 13. The evaluation results are shown in Table 4.

[Optical Density Measurement]
The photosensitive resin composition shown in Table 3 was applied onto a 125 mm x 125 mm glass substrate using a spin coater so that the film thickness after heat curing treatment would be 1.1 μm, and the substrate was prebaked at 90° C. for 1 minute. Then, a heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer, to obtain cured films (coating films) according to Examples 11 to 16 and Comparative Examples 11 to 13. Next, the optical density (OD) of the obtained cured films (coating films) was measured using a Macbeth transmission densitometer, and evaluated as the optical density per unit film thickness.

[Measurement of volume resistivity]
(Measurement method)
Each photosensitive resin composition shown in Table 3 was applied to a portion of a 100 mm x 100 mm Cr-deposited glass substrate with a thickness of 1.2 mm, excluding the electrodes, using a spin coater so that the film thickness after heat curing treatment would be 3.5 μm, and pre-baked at 90 ° C. for 1 minute. Then, a heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer to obtain cured films (coating films) according to Examples 11 to 16 and Comparative Examples 11 to 13. Then, an aluminum electrode was formed on the cured film (coating film) to prepare a substrate for measuring volume resistivity. Next, the volume resistivity was measured at applied voltages of 1 V to 10 V using an electrometer "6517A type" (manufactured by Keithley). The measurement was performed under conditions in which the voltage was held for 60 seconds at each applied voltage in 1 V steps.

[Measurement of dielectric constant]
(Measurement method)
Each photosensitive resin composition shown in Table 3 was applied to a portion of a 100 mm x 100 mm Cr-deposited glass substrate having a thickness of 1.2 mm, excluding the electrodes, using a spin coater so that the film thickness after heat curing treatment would be 3.5 μm, and the coating was prebaked at 90° C. for 1 minute. Then, a heat curing treatment was performed at 230° C. for 30 minutes using a hot air dryer, to obtain cured films (coating films) according to Examples 11 to 16 and Comparative Examples 11 to 13. Then, an aluminum electrode was formed on the coating film to prepare a substrate for measuring the dielectric constant. Next, an electrometer "6517A type" was used to measure the electric capacitance at frequencies from 1 Hz to 100,000 Hz, and the dielectric constant was calculated from the electric capacitance.

[Gas generation]
(Evaluation Method)
The cured film (coating) formed on the glass substrate "EAGLE XG" was scraped off with a scraper or the like, and the thermal weight loss of 10 mg of the resulting powdery cured film (coating) was measured using a differential thermal analyzer (TG/DTA) "EXSTAR6000". The measurement conditions were as follows: pretreatment was performed at 120°C for 30 minutes in air, followed by holding at 230°C for 3 hours.

(Evaluation Criteria)
◎: Weight loss rate is less than 3%. ○: Weight loss rate is 3% or more and less than 7%. △: Weight loss rate is 7% or more and less than 10%. ×: Weight loss rate is 10% or more.

[Measurement of Elastic Recovery Rate of Spacer]
(Measurement method)
Each photosensitive resin composition shown in Table 3 was applied onto a 125 mm x 125 mm glass substrate "EAGLE XG" using a spin coater so that the film thickness after heat curing treatment would be 3.0 μm, and the substrate was prebaked at 90° C. for 1 minute. Thereafter, a photomask having a dot pattern was attached to the substrate, and ultraviolet rays of 100 mJ/cm ² were irradiated from an ultra-high pressure mercury lamp with an illuminance of 30 mW/cm ² and a wavelength of 365 nm using a 500 W high pressure mercury lamp, to cause a photocuring reaction of the photosensitive portion.

Next, the exposed glass substrate was developed using a 0.05% potassium hydroxide aqueous solution at 24°C and 0.1 MPa for 60 seconds to remove the unexposed portions of the cured film (coating). After that, a heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer to obtain the cured films (coatings) of Examples 11 to 16 and Comparative Examples 11 to 13. The spacer characteristics of the obtained cured film (coating) patterns were evaluated using an ultra-microhardness tester "Fisherscope HM2000Xyp" (manufactured by Fisher Instruments). A 100 μm square flat indenter was pressed at a loading speed of 5.0 mN/sec, a load of up to 50 mN was applied, and then the load was removed at a loading speed of 5.0 mN/sec to create a displacement curve.

The elastic recovery rate was calculated from the following formula (2) using the displacement amount at a load of 50 mN when loaded as L1 and the displacement amount at the time of unloading as L2.
Elastic recovery rate (%) = (L1 - L2) / L1 × 100 (2)

[Development characteristics]
(Preparation of evaluation samples)
The photosensitive resin composition shown in Table 3 was applied to a 125 mm x 125 mm glass substrate "EAGLE XG" using a spin coater so that the film thickness after heat curing treatment would be 1.5 μm, and the substrate was pre-baked for 1 minute at 90° C. using a hot plate. After that, a photomask was placed so that the exposure gap was 150 μm, and ultraviolet rays of 100 mJ/cm ² were irradiated from a high-pressure mercury lamp with a wavelength of 365 nm and an illuminance of 30 mW/cm ² to cause a photocuring reaction of the photosensitive portion.

Next, this exposed cured film (coating film) was developed for 60 seconds at a pressure of 0.1 MPa using a 0.05% aqueous potassium hydroxide solution or a 0.2% aqueous sodium carbonate solution at 23°C, and then washed with water to remove the unexposed areas of the cured film (coating film). After that, a heat curing treatment was performed at 230°C for 30 minutes using a hot air dryer, and the cured films (patterns) of Examples 11 to 16 and Comparative Examples 11 to 13 were obtained.

(Evaluation method and criteria)
The formation of fine lines in the obtained pattern was confirmed by an optical microscope and evaluated according to the following three levels.
◯: A pattern with an L/S of 15 μm/15 μm or more is formed without any residue. △: A pattern with an L/S of 30 μm/30 μm or more is formed without any residue. ×: A pattern with an L/S of less than 50 μm/50 μm is not formed, or the pattern has noticeable footing or residue.

We were able to obtain a photosensitive resin composition that can provide a cured film that has high light-blocking and insulating properties, excellent adhesion to the substrate, and excellent elastic modulus, deformation amount, and elastic recovery rate.

The cured film of the photosensitive resin composition of the present invention is extremely useful as a component of color filters including organic EL elements, quantum dot displays, TFT arrays, and wavelength conversion elements. In addition, resin compositions having a bisnaphtholfluorene skeleton are useful because they function as a light transmission control layer that blocks ultraviolet light in a specific range.

Claims (7)

The following components (A) to (D):
(A) a polymerizable unsaturated group-containing alkali-soluble resin represented by general formula (1),
(B) a (meth)acrylic acid ester selected from the group consisting of trimethylolpropane trimethacrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate;
(C) a photopolymerization initiator; and
(D) a solvent;
as an essential component, with the proviso that no o-naphthoquinone diazide sulfonic acid ester is contained , and the component (A) is a compound in which Ar in general formula (1) contains a naphthalene skeleton .

(In formula (1), Ar's are each independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group. Each _{R 1} is independently an alkylene group having 2 to 4 carbon atoms, and each l is independently a number from 0 to 3. Each G is independently a substituent represented by general formula (2) or general formula (3), and Y is a tetravalent carboxylic acid residue. Each Z is independently a hydrogen atom or a substituent represented by general formula (4), and at least one Z is a substituent represented by general formula (4). n is a number having an average value of 1 to 20.)

(In formulas (2) and (3), _R2 is a hydrogen atom or a methyl group, _R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, _R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10.)

(In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.) 2. The photosensitive resin composition according to claim 1, wherein a content of the component (A) is 10 to 90% by mass based on the total mass of the solid contents, a content of the component (B) is 5 to 200 parts by mass based on 100 parts by mass of the component (A), and a content of the component (C) is 0.1 to 30 parts by mass based on 100 parts by mass of the combined amount of the component (A) and the component ( B) . The photosensitive resin composition according to claim 1 , further comprising (E) a colorant. 4. The photosensitive resin composition according to claim 3 , wherein the colorant (E) is one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials. 5. The photosensitive resin composition according to claim 3 , wherein the content of the component (E) is 1 to 80 mass % based on the total mass of the solid content of the photosensitive resin composition. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 5 . A display device comprising the cured film according to claim 6 .