CN111812942A

CN111812942A - Photosensitive resin composition, cured film and display device

Info

Publication number: CN111812942A
Application number: CN202010265711.7A
Authority: CN
Inventors: 今野高志; 新名将司; 三浦慧
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2019-04-12
Filing date: 2020-04-07
Publication date: 2020-10-23
Also published as: JP2020173433A; KR20200120536A; TW202105061A

Abstract

The invention provides a photosensitive resin composition, a cured film formed by curing the photosensitive resin composition, and a display device having the cured film, wherein the photosensitive resin composition is suitable for a protection film with less gas generation, a coloring film of a shading film and the like. 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 the general formula (1), (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) a photopolymerization initiator, and (D) a solvent.

Description

Photosensitive resin composition, cured film and display device

Technical Field

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

Background

Conventionally, a transparent cured film (hereinafter, also referred to as a "protective film") has been formed as a protective layer on the surface of a color filter used for manufacturing a color Liquid Crystal Display (LCD). The purpose of forming the protective film of the color filter is to: flattening irregularities generated between pixels of the color filter; the durability of the color filter is improved relative to heat treatment and chemical treatment in the subsequent steps; the reliability of the color liquid crystal display is improved. As a protective film for a color filter, excellent transparency, chemical resistance, adhesion, hardness, flatness, heat resistance, electrical reliability, and the like are required.

On the other hand, as a method for forming the protective film, there are a method for forming a protective film on the front surface by thermal curing and a method for forming a protective film by photolithography. The method for forming the protective film can be selected according to the characteristics of the protective film and the requirement of patterning in the design process of the panel of the color filter and the design process of the processing procedure. Here, as the characteristics of the protective film to be regarded as important in the case of formation by the photolithography method, transparency, chemical resistance, adhesiveness, hardness, and electrical reliability are required on the premise that the protective film can have development characteristics capable of forming a desired protective film pattern.

For example, as the 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. The chemical resistance of the protective film is required to be stable against acids, bases, solvents, and the like used in the subsequent steps. In the case of manufacturing a liquid crystal display panel, adhesion is sometimes performed by bonding substrates to a protective film, and it is required that peeling does not occur even when the base of the protective film at the above-mentioned portion is a glass substrate, an Indium Tin Oxide (ITO) substrate, a molybdenum/aluminum/molybdenum (MAM) substrate, or the like. As the hardness, high hardness is required from the viewpoint of durability of the protective film. For electrical reliability, the protective film is required to maintain insulation properties, and impurities and the like contained in the protective film do not contaminate the liquid crystal.

Among the required characteristics of the protective film, a wide viewing angle and high-speed response are required along with the high functionality of the LCD panel, and the requirements are becoming more severe In the process of gradually using a display system similar to an In-plane Switching (IPS) mode. In a display mode such as the IPS mode, if a gaseous or liquid component or water generated or exuded from the color filter layer enters the liquid crystal layer through the protective layer, the concentration of moisture or ionic impurities in the liquid crystal layer increases, or bubbles are formed in the liquid crystal layer, which may cause display defects. Therefore, it is needless to say that the passage of the impurity components is prevented, and the gas generated from the protective film which is in direct contact with the liquid crystal layer is directly related to the display failure, and therefore, the low gas generation property is particularly important.

Further, after the protective film is formed, there are problems in the manufacturing process of the LCD panel such as photo-alignment treatment of the alignment film of the liquid crystal and problems in reducing the influence of external light in various display devices including organic Electroluminescence (EL). Therefore, in some cases, the protective film is required to have an ability to absorb ultraviolet light having a short wavelength that does not contribute to color display while ensuring transparency (high transmittance) as the protective film.

Disclosure of Invention

[ problems to be solved by the invention ]

A photosensitive resin composition capable of forming an appropriate protective film pattern by photolithography and sufficiently reducing gas generation that affects electrical reliability while sufficiently maintaining characteristics such as transparency, chemical resistance, adhesion, and hardness is desired. In addition, in color resists for forming Red Green Blue (RGB) pixels, black resists for forming light-shielding films, and the like, there are cases where a cured film excellent not only in required properties but also in low gas generation is desired.

The present invention has been made in view of the above problems, and an object thereof is to provide a photosensitive resin composition which can be applied to a protective film containing little gas generation, a colored film containing a light-shielding film, and the like, a cured film obtained by curing the photosensitive resin composition, and a display device having the cured film.

[ means for solving problems ]

The present inventors have conducted studies to solve the problems of the photosensitive resin composition for light-shielding film applications, and as a result, have found that a specific coloring material is preferable as a light-shielding component of the photosensitive resin composition for light-shielding film applications, and have 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 of the general formula (1); (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds; (C) a photopolymerization initiator; and (D) a solvent.

[ solution 1]

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

[ solution 2]

[ solution 3]

(in the formulae (2) and (3), R₂Is a hydrogen atom or a methyl group, R₃Is a C2-10 divalent alkylene or alkylarylene group, R₄Is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10. )

[ solution 4]

(in the 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 obtained by curing the photosensitive resin composition.

The display device of the invention is provided with the hardening film.

[ Effect of the invention ]

According to the present invention, there can be provided a photosensitive resin composition which can be suitably used for a protective film which generates little gas, a colored film of a light-shielding film, or the like, a cured film obtained by curing the photosensitive resin composition, and a display device having the cured film.

Detailed Description

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the embodiments below. In the present invention, when the first decimal place is 0, the content of each component may be omitted.

The polymerizable unsaturated group-containing alkali-soluble resin of the component (a) represented by the general formula (1) of the present invention is obtained by: reacting a reactant of an epoxy compound (a-1) having two glycidyl ether groups with a (meth) acrylic acid derivative with a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof and a tetracarboxylic acid or an acid dianhydride thereof (c).

Further, the polymerizable unsaturated group-containing alkali-soluble resin is characterized in that: as the epoxy compound used as a raw material, a compound containing a number of oxyalkylene groups in 1 molecule and having an aromatic hydrocarbon group of 6 to 14 carbon atoms as Ar in the general formula (1) is used.

Preferred examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a divalent naphthyl group and a phenylene group in which a part of hydrogen atoms may be substituted with an alkyl group or the like. In the alkali-soluble resin (a) containing a polymerizable unsaturated group according to the present invention, it is preferable that both of the two Ar groups bonded to the fluorenyl group in the general formula (1) are naphthyl groups (having a bisnaphthol fluorene skeleton) or phenylene groups (having a bisphenol fluorene skeleton), and it is more preferable that both of the two Ar groups bonded to the fluorenyl group are naphthyl groups. The reason for this is that: the cured film (coating film) obtained by curing the (a) polymerizable unsaturated group-containing alkali-soluble resin in which both Ar groups bonded to the fluorenyl group are naphthyl groups generates a small amount of gas when heated. In addition, "(meth) acrylic acid" is a generic term for acrylic acid and methacrylic acid, and means either one or both of them.

[ solution 5]

[ solution 6]

[ solution 7]

[ solution 8]

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

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

[ solution 9]

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

[ solution 10]

[ solution 11]

(in the formulae (6) and (7), R₂Is a hydrogen atom or a methyl group, R₃Is a C2-10 divalent alkylene or alkylarylene group, R₄Is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atomsAnd p is a number of 0 to 10. )

The reaction of the epoxy compound (a-1) with the (meth) acrylic acid derivative can be carried out by a known method. For example, Japanese patent laid-open No. 4-355450 discloses the following: the diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth) acrylic acid per 1 mole of the epoxy compound having two epoxy groups. In the present invention, the compound obtained by the 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)").

[ solution 12]

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

[ solution 13]

[ solution 14]

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

Examples of the vehicle include: cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high boiling point ether-based or ester-based solvents such as diethylene glycol dimethyl ether (diglyme), ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; ketone solvents such as cyclohexanone and diisobutyl ketone. The reaction conditions of the solvent, catalyst, and the like used are not particularly limited, and for example, a solvent having no hydroxyl group and a boiling point higher than the reaction temperature is preferably used as the reaction solvent.

In addition, in the epoxy group and carboxyl or hydroxyl reaction preferably using a catalyst, in Japanese patent laid-open No. 9-325494 describes tetraethylammonium bromide, chloride three ethyl benzyl ammonium salt; 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) and the (meth) acrylic acid derivative, and the dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof, and the tetracarboxylic acid or acid dianhydride thereof (c) are reacted to obtain the alkali-soluble resin represented by the general formula (1) having a carboxyl group and a polymerizable unsaturated group in 1 molecule.

[ solution 15]

(in the formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of hydrogen atoms bonded to Ar may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group)₁Each independently an alkylene group having 2 to 4 carbon atoms, and l each independently a number of 0 to 3. G is a substituent represented by the general formula (2) or the general formula (3), and Y is a tetravalent carboxylic acid residue. Z is each independently a hydrogen atom or a substituent represented by the general formula (4), and one or more of Z are represented by the general formula(4) The substituents indicated. The average value of n is 1-20. )

[ solution 16]

[ solution 17]

[ solution 18]

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

The general formula (2), the general formula (3), the general formula (6) and the general formula (7) have a polymerizable unsaturated group and at least one ester bond.

[ solution 19]

[ solution 20]

[ solution 21]

[ solution 22]

R shown in general formula (2), general formula (3), general formula (6) and general formula (7)₂Is a hydrogen atom or a methyl group.

R in general formula (2), general formula (3), general formula (6) and general formula (7)₃Is a C2-10 divalent alkylene or alkylarylene group. The alkylene group may be any of linear or branched and is vinyl (ethylene), ethylene (ethylidene), vinylene (vinylene), vinylene (vinylidene), propenyl (propylene), trimethylene, propenyl (propenylene), isopropylidene, tetramethylene, and the like. The alkylarylene group may be an unsubstituted arylene group as long as it is within the carbon number range, and examples thereof include an o-phenylene group, an m-phenylene group, a p-phenylene group, a tolylene group, an ethylphenylene group, an n-propylphenylene group, an isopropylphenylene group, a linear or branched butylphenyl group, and a pentylphenylene group.

R in general formula (2), general formula (3), general formula (6) and general formula (7)₄Is a saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. The saturated and unsaturated aliphatic hydrocarbon groups may be linear or branched and include vinyl, ethylene, vinylene, propenyl, trimethylene, propenyl, isopropylidene, tetramethylene, and the like. The aromatic hydrocarbon group may be unsubstituted as long as it is within the carbon number range, and may be substituted with two to four substituents as long as it is within the carbon number range, for example, o-phenylene, m-phenylene, p-phenylene, tolylene, ethylphenylene, n-propylphenylene, isopropylphenylene, linear or branched butylphenyl, pentylphenylene, or the like. In addition, the aliphatic hydrocarbon group may be interrupted by an unsaturated bond, an ether bond, or an ester bond.

In addition, p is a number of 0 to 10, when synthesizing the alkali-soluble resin represented by the general formula (1), the average value of p is preferably a number of 0 to 5, and more preferably an average value of p is a number of 0 to 2. When the average value of p is in the above range, the distribution can be suppressed from becoming wide, and therefore sufficient hardenability as a cured film can be provided without degrading resin performance.

The acid component for synthesizing the alkali-soluble resin represented by the general formula (1) is a polybasic acid component which is reactive with the hydroxyl group in the molecule of the diol (d) represented by the general formula (8), and it is necessary to use a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride (b) thereof and a tetracarboxylic acid or an acid dianhydride thereof in combination. The carboxylic acid residue of the acid component may be any of a saturated hydrocarbon group or an unsaturated hydrocarbon group. The carboxylic acid residue may contain a bond containing a hetero element such as-O-, -S-, or a carbonyl group.

Examples of the dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) include: chain type hydrocarbon di-or tri-carboxylic acids, alicyclic hydrocarbon di-or tri-carboxylic acids, aromatic hydrocarbon di-or tri-carboxylic acids, or their acid mono-anhydrides, and the like.

Examples of acid monoanhydrides of chain hydrocarbon di-or tricarboxylic acids include: and 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, and the like, and monoanhydrides of dicarboxylic acids or tricarboxylic acids to which an arbitrary substituent is introduced, and the like. In addition, examples of the acid monoanhydride of the alicyclic dicarboxylic acid or tricarboxylic acid include: and acid monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids having an optional substituent introduced thereinto, and the like. In addition, examples of the acid monoanhydride of the aromatic dicarboxylic acid or tricarboxylic acid include: acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, and the like, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids having an optional substituent introduced thereto.

Among the acid monoanhydrides of the dicarboxylic acid or tricarboxylic acid, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferable, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferable. In addition, among the dicarboxylic acids or tricarboxylic acids, acid monoanhydrides thereof are preferably used. The acid monoanhydride of the dicarboxylic acid or tricarboxylic acid may be used alone, or two or more thereof may be used in combination.

In addition, examples of the tetracarboxylic acid or acid dianhydride thereof (c) include: chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or acid dianhydride thereof.

Examples of chain hydrocarbon tetracarboxylic acids include: butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acids into which a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group has been introduced. In addition, examples of the alicyclic tetracarboxylic acid include: cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornane-tetracarboxylic acid, alicyclic tetracarboxylic acids into which a substituent such as a chain hydrocarbon group or an unsaturated hydrocarbon group has been introduced, and the like. In addition, examples of the aromatic tetracarboxylic acid include: pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, naphthalene-1, 4,5, 8-tetracarboxylic acid, naphthalene-2, 3,6, 7-tetracarboxylic acid, and the like. In addition, the aryl esters of trimellitic anhydride can also be used. The bis-trimellitic anhydride aryl esters are, for example, a compound group produced by the method described in WO2010/074065, and structurally are acid dianhydrides in a form in which two hydroxyl groups of an aromatic diol (naphthalene diol, biphenol, terphenyl diol, etc.) react with 2 molecules of a carboxyl group of trimellitic anhydride and are ester-bonded. Hereinafter, the compound is described as a trimellitic anhydride ester of an aromatic diol.

Among the tetracarboxylic acids or acid dianhydrides thereof, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, diphenyl ether tetracarboxylic acid are preferable, and biphenyltetracarboxylic acid and diphenyl ether tetracarboxylic acid are more preferable. Among tetracarboxylic acids or acid dianhydrides thereof, acid dianhydrides thereof are preferably used. Further, trimellitic anhydride ester of naphthalene diol can also be preferably used. The above tetracarboxylic acid or acid dianhydride thereof and the trimellitic anhydride ester of an aromatic diol may be used alone or in combination of two or more.

The reaction of the diol (d) represented by the general formula (8) with the acid component (b) and the acid component (c) is not particularly limited, and a known method can be employed. For example, Japanese patent application laid-open No. 9-325494 discloses a method of reacting an epoxy (meth) acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ℃.

Here, in order to form the carboxyl group at the terminal of the compound, it is preferable that the molar ratio of the diol (d), the dicarboxylic acid or the tricarboxylic acid represented by the general formula (8), or the acid monoanhydride (b) thereof, and the tetracarboxylic acid or the acid dianhydride thereof (c) is (d): (b) the method comprises the following steps (c) 1.0: 0.01-1.0: the reaction is carried out in a manner of 0.2 to 1.0.

For example, when the acid monoanhydride (b) and the acid dianhydride (c) are used, the reaction is preferably carried out so that the molar ratio [ (d)/[ (b)/2+ (c) ] of the amount of the acid component [ (b)/2+ (c) ] to the polymerizable unsaturated group-containing diol (d) is 0.5 to 1.0. Here, when the molar ratio is 1.0 or less, the content of unreacted diol containing a polymerizable unsaturated group is not increased, and therefore the stability of the alkali-soluble resin composition with time 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, and the increase in the content of unreacted acid dianhydride can be suppressed, whereby the stability of the alkali-soluble resin composition over time can be improved. The molar ratio of each component (b), (c), and (d) may be arbitrarily changed within the above range for the purpose of adjusting the acid value and the molecular weight of the alkali-soluble resin represented by the general formula (2).

The acid value of the alkali-soluble resin represented by the general formula (1) is preferably in the range of 20mgKOH/g to 180mgKOH/g, more preferably 40mgKOH/g to 120 mgKOH/g. When the acid value is not less than 20mgKOH/g, residue is not likely to remain during alkaline development, and when the acid value is not more than 180mgKOH/g, the permeation of the alkaline developer is not too fast, and thus the peeling phenomenon can be suppressed. The acid value can be determined by titration with 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Pongan industries, Ltd.).

The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) in terms of polystyrene measured by Gel Permeation Chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh corporation) is usually 1000 to 100000, preferably 2000 to 20000, and more preferably 2000 to 6000. When the weight average molecular weight is 1000 or more, the pattern adhesion in the alkali development can be suppressed from being lowered. When the weight average molecular weight (Mw) is less than 100000, the solution viscosity of the photosensitive resin composition preferable for coating can be easily adjusted, and the alkali development does not take an excessive time.

Next, a photosensitive resin composition using an alkali-soluble resin represented by general formula (1) of the present invention will be described.

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

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

(B) The content of the component (b) is preferably 5 to 200 parts by mass based on 100 parts by mass of the component (a), more preferably 10 to 80 parts by mass based on 100 parts by mass of the component (a), and still more preferably 10 to 60 parts by mass. When the content of the component (B) is 5 parts by mass or more based on 100 parts by mass of the component (a), the photoreactive functional group occupies a sufficient amount in the resin, and thus a sufficient crosslinked structure is formed. Further, since the acid value in the resin component is not excessively high, the solubility of the exposed portion in an alkaline developer is lowered, and thus the pattern formed can be suppressed from becoming thinner than the target line width, and the pattern defect can be suppressed. When the content of the component (B) is 200 parts by mass or less based on 100 parts by mass of the component (a), a cured film having sufficient hardenability can be obtained, and thus 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-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butyl acetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, p' -bisdimethylaminobenzophenone; benzoin ethers such as benzil, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like; biimidazole compounds such as 2- (o-chlorophenyl) -4, 5-phenylbiimidazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4, 5-diphenylbiimidazole, and 2,4, 5-triarylbiimidazole; halomethyl oxadiazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3, 4-oxadiazole, and 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole; 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, halogenated methyl-s-triazine compounds such as 3, 5-triazine, 2- (3,4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, and 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine; o-acyloxime-based compounds such as 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -,2- (O-benzoyloxime), 1- (4-phenylthiophenyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylthiophenyl) butane-1, 2-dione-2-oxime-O-acetate, and 1- (4-methylthiophenyl) butane-1-ketoxime-O-acetate; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothianthrone, 2, 4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, and 2, 3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, etc.; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; tertiary amines such as triethanolamine and triethylamine, and the like. In addition, the photopolymerization initiator may be used alone, or two or more kinds may be used in combination.

In particular, when a photosensitive resin composition containing a coloring material is used, O-acyloxime compounds (containing ketoxime) are preferably used. Specific examples of the compound group include O-acyloxime photopolymerization initiators represented by the general formula (9) or (10). In the above-mentioned compound group, when a coloring material is used at a high pigment concentration and when a light-shielding film pattern is formed, an O-acyloxime-based photopolymerization initiator having a molar absorption coefficient at 365nm of 10000L/mol cm or more is preferably used. In the present invention, the "photopolymerization initiator" is used as meaning including a sensitizer.

[ solution 23]

(in the formula (9), R₅、R₆Each 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, R₇The alkyl group has 1 to 15 carbon atoms, the aryl group has 6 to 18 carbon atoms, and the arylalkyl group has 7 to 20 carbon atoms. The alkyl and aryl groups 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 group may contain an unsaturated bond, an ether bond or a thioetherBond, ester bond. The alkyl group may be any of linear, branched, and cyclic alkyl groups. )

[ solution 24]

(in the formula (10), R₈And R₉Each independently is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl, cycloalkylalkyl or 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. R₁₀Each independently is a C2-10 linear or branched alkyl or alkenyl group, the alkyl or alkenyl group having a-CH₂Part of the-groups may be substituted by-O-groups. Further, said R₈～R₁₀A part of the hydrogen atoms in the group (2) may be substituted with halogen atoms. )

The content of the component (C) is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, based on 100 parts by mass of the total amount of the components (a) and (B). When the content of the component (C) is 0.1 parts by mass or more, the photopolymerization rate is moderate, and thus the decrease in sensitivity can be suppressed. When the content of the component (C) is 30 parts by mass or less, the line width faithful to the mask can be reproduced, and the pattern edge can be made sharp.

(D) Examples of the solvent 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, diacetone alcohol, etc.; terpenes such as α -terpineol and β -terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 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 these components, a uniform solution composition can be prepared. The solvents may be used alone or in combination of two or more in order to obtain the required properties such as coatability. The amount of the solvent varies depending on the target viscosity, but is preferably 60 to 90% by mass in the photosensitive resin composition solution.

The photosensitive resin composition contains a coloring material as the component (E). When used as a resist for a light-shielding film, the component (E) is one or more light-shielding components selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-shielding material, and is preferably a black organic pigment and/or a mixed-color organic pigment. The average secondary particle diameter of the black organic pigment and/or the mixed color organic pigment is preferably 20nm to 500 nm. The average secondary particle diameter of the black organic pigment and the mixed color organic pigment can be measured by a cumulative method using a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by tsukamur electronics ltd) by a dynamic light scattering method.

The content of the coloring material as the component (E) may be arbitrarily determined depending on the desired light-shielding degree, and 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 the black organic pigment as the (E) component include: perylene blacks, aniline blacks, cyanine blacks, lactam blacks, and the like. Examples of color-mixed organic pigments include: a pigment in which 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, vat (threne) pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments are mixed and pseudo-blackened. As the light-shielding material, carbon black, chromium oxide, iron oxide, titanium black, or the like is contained. The component (E) may be a pigment which is appropriately surface-treated depending on the function of the intended photosensitive resin composition. The component (E) may be used alone or in combination of two or more.

Examples of the organic pigment usable as the component (E) include, but are not limited to, pigments numbered below in the Color Index (Color Index) name.

Pigment Red (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, and the like

Pigment orange (pigment orange)5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81 and the like

Pigment yellow (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, and the like

The coloring material as the component (E) is preferably dispersed in the solvent (D) together with the dispersant (F) in advance to prepare a coloring material dispersion, and then blended into the photosensitive resin composition. Here, the solvent used for dispersion is a part of the component (D), and therefore, the solvent may be used as long as it is contained in the component (D). Among the above-mentioned components (D), propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butyl acetate and the like are preferable.

The content of the component (E) is preferably 1 to 80% by mass, more preferably 30 to 60% by mass, based on the total solid content of the photosensitive resin composition of the present invention. The solid component is a component other than the component (D) in the photosensitive resin composition. The solid component also includes a component (B) which becomes a solid component after photo-curing. When the component (E) is 1% by mass or more, the desired light-shielding property can be easily set. When the amount of the component (E) is 80% by mass or less, desired development characteristics and film forming ability can be obtained.

The dispersant (F) may be any known compound used for dispersing a coloring material (pigment) (e.g., a commercially available compound under the names of a dispersant, a dispersing wetting agent, and a dispersion accelerator).

Examples of the dispersant as the component (F) include: a cationic polymer dispersant, an anionic polymer dispersant, a nonionic polymer dispersant, and a pigment derivative type dispersant (dispersing aid). In particular, in terms of adsorption to a coloring material, the dispersant is preferably a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrole group, a pyridine group, a primary amino group, a secondary amino group or a tertiary amino group, and having an amine value of 1mgKOH/g to 100mgKOH/g and a number average molecular weight in the range of 1 thousand to 10 ten thousand. The amount of the dispersant to be blended is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, based on the coloring material. In addition, high-viscosity substances such as resins generally have an action of stabilizing dispersion, and substances having no dispersion-promoting ability are not regarded as dispersants. However, the use for the purpose of stabilizing the dispersion is not limited.

In addition, when the coloring material dispersion is prepared, not only the dispersant (F) but also a part of the alkali-soluble resin containing a polymerizable unsaturated group of the component (a) is co-dispersed, whereby a photosensitive resin composition which is easy to maintain high sensitivity in exposure, has good adhesion during development, and is less likely to cause a problem of residue can be obtained. The content of the component (a) in the coloring material dispersion is preferably 2 to 20% by mass, and more preferably 5 to 15% by mass. When the amount of the component (a) is 2% by mass or more, the effects after co-dispersion such as improvement in sensitivity, improvement in adhesion, and reduction in residue can be obtained. When the amount of the component (a) is 20% by mass or less, a cured film (coating film) in which the component (E) is uniformly dispersed can be obtained.

The colored material dispersion can be mixed with the component (a) (when the component (a) is co-dispersed in the preparation of the colored material dispersion, the remaining component (a), (B), (C), and the remaining component (E) to prepare a photosensitive resin composition for a light-shielding film.

In addition, the photosensitive resin composition of the present invention may be used in combination with other resin components that are polymerized or cured by light or heat as necessary. Examples of other resin components include: epoxy resins such as novolak epoxy resins derived from novolacs such as phenol novolak and cresol novolak, and bisphenol epoxy resins; and alkali-soluble resins obtained by reacting the epoxy resin with (meth) acrylic acid and an acid anhydride (excluding component (a)), copolymers with (meth) acrylic acid and/or (meth) acrylic esters, and alkali-soluble resins obtained by reacting carboxyl groups in the copolymers with epoxy group-containing (meth) acrylates.

The photosensitive resin composition of the present invention may contain additives such as a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, and a coupling agent, as required.

Examples of hardeners include: amine-based compounds, polycarboxylic acid-based compounds, phenol resins, amino resins, dicyanodiamine, lewis acid complex compounds, and the like, which contribute to the hardening of epoxy resins. Examples of the hardening accelerator include: tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, lewis acids, organometallic compounds, imidazoles, and the like, which contribute to accelerating the hardening of the epoxy resin. Examples of the thermal polymerization inhibitor and the antioxidant include: hydroquinone, hydroquinone monomethyl ether, pyrogallol (pyrogallol), t-butyl catechol, phenothiazine, hindered phenol compounds, and the like. Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler material include: glass fibers, silica, mica, alumina, and the like. Examples of defoaming or leveling agents include: silicone, fluorine, and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like. Examples of coupling agents include: 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.

The cured film (coating film) of the present invention can be formed by photolithography using the photosensitive resin composition of the present invention. The method comprises the following steps: first, a photosensitive resin composition solution is applied to a substrate surface, a solvent is dried (prebaked), a photomask is placed on the applied film, ultraviolet rays are irradiated to cure an exposed portion, an unexposed portion is developed using an alkaline aqueous solution to form a pattern, and post-baking is performed as post-curing. Here, examples of the substrate on which the photosensitive resin composition solution is applied include: glass, transparent films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.), and the like.

The substrate may be a transparent substrate, or may be a base material other than a transparent substrate. Examples of the transparent substrate on which the photosensitive resin composition is applied include not only a glass substrate but also a substrate on which a transparent electrode of ITO, gold, or the like is deposited or patterned on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, or the like).

As a method for coating the photosensitive resin composition solution on the substrate, not only a known solution dipping method or spraying method, but also a method using a roll coater, a disc coater (Land coater machine), a slit coater, a rotary coater, or the like can be used. After coating to a desired thickness by the above method, the coating film is formed by drying (prebaking) the solvent. Further, the prebaking is performed by heating with an oven, a hot plate, or the like. The heating temperature and the heating time in the prebaking may be appropriately selected depending on the solvent used, and for example, the heating may be carried out at a temperature of 60 to 110 ℃ for 1 to 3 minutes.

The exposure after the prebaking is performed by an ultraviolet exposure apparatus, and exposure is performed through a photomask, thereby exposing only a portion of the resist corresponding to the pattern. The photosensitive resin composition in the coating film is photo-cured by exposure using a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far ultraviolet lamp, with the exposure apparatus and the exposure irradiation conditions appropriately selected.

As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like can be used, and the wavelength range of the radiation is preferably 250nm to 450 nm. As the developer suitable for the alkali development, for example, an aqueous solution of sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, or the like can be used. The developing solution may be appropriately selected depending on the characteristics of the resin layer, but it is also effective to add a surfactant as needed. The developing temperature is preferably 20 to 35 ℃, and a fine image can be formed precisely using a commercially available developing machine, ultrasonic cleaner, or the like. Further, after the alkaline development, water washing is usually performed. As the developing method, a shower developing method, a spray developing method, a dip (dip) developing method, a puddle (puddle) developing method, or the like can be applied.

The alkali development after the exposure is performed for the purpose of removing the photosensitive resin composition of the unexposed portion, and a desired pattern is formed by the development. Examples of the developer suitable for the alkali development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of a hydroxide of an alkali metal, and the like, and particularly, it is preferable to perform development at a temperature of 23 to 27 ℃ using a weakly alkaline aqueous solution containing 0.03 to 1 wt% of a carbonate of sodium carbonate, potassium carbonate, or the like, and to precisely form a fine image using a commercially available developing machine, an ultrasonic cleaning machine, or the like.

After the development in the above manner, heat treatment (post-baking) is performed at 180 to 250 ℃ for 20 to 100 minutes. However, when the heat resistance of a substrate or the like used for film formation is low, the formulation of the composition may be designed so that the post-baking conditions may be set to 80 to 180 ℃ for 30 to 100 minutes. The post-baking is performed for the purpose of improving adhesion between the patterned coating film and the substrate. This is performed by heating with an oven, a hot plate, or the like, as in the case of the prebaking. The patterned resin film of the present invention is formed through the above-described steps by photolithography.

[ examples ]

Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the examples and comparative examples.

First, a description will be given of a synthetic example of an alkali-soluble resin containing a polymerizable unsaturated group having a structure represented by general formula (1), and unless otherwise specified, evaluation of the resin in the synthetic example is performed as follows. When the same model is used for each measurement device, the device manufacturer name is omitted from the second place. In examples 1 and 2, the same treatment was applied to both of the glass substrates used for producing the substrates with the cured films for measurement.

[ solid content concentration ]

A glass filter was impregnated with 1g of the resin solution obtained in synthesis example [ weight: w₀(g) W middle and weight₁(g) Based on the weight [ W ] of the steel sheet after heating at 160 ℃ for 2 hours₂(g) And is obtained by the following equation (1).

The solid content concentration (wt%) was 100 × (W)₂-W₀)/(W₁-W₀) (1)

[ epoxy equivalent ]

The resin solution was dissolved in dioxane, and then an acetic acid solution of tetraethylammonium bromide was added thereto, and the solution was titrated with 1/10N-perchloric acid solution using a potential difference titrator "COM-1600" (manufactured by heimagama industries, ltd.).

[ acid value ]

The resin solution was dissolved in dioxane and was titrated with 1/10N-KOH aqueous solution using a potential difference titrator "COM-1600".

[ molecular weight ]

The weight average molecular weight (Mw) was determined by Gel Permeation Chromatography (GPC) "HLC-8220 GPC" (manufactured by Tosoh corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) column) + TSKgelSuperH-3000 (1) column) + TSKgelSuperH-4000 (1) column) + TSKgelSuperH-5000 (1) (manufactured by Tosoh corporation, temperature: 40 ℃ C., speed: 0.6ml/min) and converted to standard polystyrene (manufactured by Tosoh corporation, PS-oligomer set).

The abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

BPFE: bisphenol fluorene type epoxy resin

(epoxy resin of the general formula (5) wherein Ar is a benzene ring and l is 0, epoxy equivalent 256)

BNFE: bis-naphthol fluorene type epoxy resins

(epoxy resin of the general formula (5) wherein Ar is a naphthalene ring and l is 0, epoxy equivalent 281)

HOA-HH: 2-Acryloxyethylhexahydrophthalic acid

(Light Acrylate) HOA-HH (N) manufactured by Kyoeisha chemical Co., Ltd.)

BPDA: 3,3',4,4' -biphenyltetracarboxylic dianhydride

BTDA: benzophenone tetracarboxylic dianhydride

BTANE: trimellitic anhydride ester of naphthalene diol (DHN-D1, manufactured by Benzhou 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: methacrylic acid methyl ester

CHMA: cyclohexyl methacrylate

AIBN: azobisisobutyronitrile

GMA: glycidyl methacrylate

PGMEA: propylene glycol monomethyl ether acetate

[ Synthesis example 1]

BPFE (46.64g, 0.09mol), AA (13.12g, 0.18mol), TPP (0.24g), and PGMEA (40.00g) were put into a 250mL four-necked flask equipped with a reflux condenser, and stirred at 100 ℃ to 105 ℃ for 12 hours to obtain a reaction product. Then, PGMEA (20.00g) was charged to adjust the solid content to 50 mass%.

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

[ Synthesis example 2]

BNFE (47.60g, 0.08mol), AA (12.18g, 0.17mol), TPP (0.22g), and PGMEA (40.00g) were put into a 250mL four-necked flask equipped with a reflux condenser, and stirred at 100 ℃ to 105 ℃ for 12 hours to obtain a reaction product. Then, PGMEA (20.00g) was charged to adjust the solid content to 50 mass%.

Then, BPDA (12.49g, 0.04mol) and THPA (6.46g, 0.04mol) were added to the obtained reaction product, and the mixture was stirred at 115 ℃ to 120 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -2. The resin solution thus obtained had a solid content of 56.9% by mass, an acid value (in terms of solid content) of 90mgKOH/g, and Mw of 4000 as determined by GPC analysis.

[ Synthesis example 3]

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

[ Synthesis example 4]

Then, BPDA (16.49g, 0.06mol) and THPA (0.26g, 0.002mol) were added to the obtained reaction product, and the mixture was stirred at 115 ℃ to 120 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -4. The resin solution thus obtained had a solid content of 56.1% by mass, an acid value (in terms of solid content) of 83mgKOH/g, and Mw according to GPC analysis was 7000.

[ Synthesis example 5]

BNFE (30.53g, 0.05mol), HOA-HH (29.33g, 0.11mol), TPP (0.14g), and PGMEA (40.00g) were put into a 250mL four-necked flask equipped with a reflux condenser, and stirred at 100 ℃ to 105 ℃ for 12 hours to obtain a reaction product. Then, PGMEA (20.00g) was charged to adjust the solid content to 50 mass%.

Then, BPDA (8.00g, 0.03mol) and THPA (4.14g, 0.03mol) were put into the obtained reaction product, and the mixture was stirred at 115 ℃ to 120 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -5. The resin solution thus obtained had a solid content of 54.6% by mass, an acid value (in terms of solid content) of 63mgKOH/g, and Mw, as determined by GPC analysis, of 5300.

[ Synthesis example 6]

Then, BTDA (13.68g, 0.04mol) and THPA (6.46g, 0.04mol) were added to the obtained reaction product, and the mixture was stirred at 115 ℃ to 120 ℃ for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -6. The resin solution thus obtained had a solid content of 54.6% by mass, an acid value (in terms of solid content) of 92mgKOH/g, and Mw according to GPC analysis of 4100.

[ Synthesis example 7]

Then, BTANE (21.58g, 0.04mol) and THPA (6.46g, 0.04mol) were put into the obtained reaction product, and the mixture was stirred at 115 ℃ to 120 ℃ for 7 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -7. The resin solution thus obtained had a solid content of 54.6% by mass, an acid value (in terms of solid content) of 91mgKOH/g, and Mw, as determined by GPC analysis, of 5000.

[ Synthesis example 8]

A1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube was charged with MAA (51.65g, 0.60 mol), MMA (36.04g, 0.36 mol), CHMA (40.38g, 0.24 mol), AIBN (5.91g), and PGMEA (360g), and the mixture was stirred at 80 to 85 ℃ for 8 hours under a nitrogen stream to carry out polymerization. GMA (61.41g, 0.43 mol), TPP (2.27g) and TBPC (0.086g) were further charged into the flask, and the mixture was stirred at 80 to 85 ℃ for 16 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin solution (A) -8. The resin solution thus obtained had a solid content of 35.7% by mass, an acid value (in terms of solid content) of 50mgKOH/g, and Mw according to GPC analysis was 19600.

(alkali soluble resin solution)

(A) -1: the alkali-soluble resin solution obtained in Synthesis example 1

(A) -2: the alkali-soluble resin solution obtained in Synthesis example 2

(A) -3: the alkali-soluble resin solution obtained in Synthesis example 3

(A) -4: the alkali-soluble resin solution obtained in Synthesis example 4

(A) -5: the alkali-soluble resin solution obtained in Synthesis example 5

(A) -6: the alkali-soluble resin solution obtained in Synthesis example 6

(A) -7: the alkali-soluble resin solution obtained in Synthesis example 7

(A) -8: the alkali-soluble resin solution obtained in Synthesis example 8

(photopolymerizable monomer)

(B) The method comprises the following steps DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon chemical Co., Ltd.)

(photopolymerization initiator)

(C) The method comprises the following steps Brilliant (Irgacure) OXE-02 (ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), manufactured by BASF corporation, "Brilliant (Irgacure)" is a registered trademark of this corporation)

(solvent)

(D) -1: propylene glycol monomethyl ether acetate

(D) -2: 3-methoxy-3-methyl-1-butyl acetate

(surfactant)

Ppgmea solution of Pico (BYK) -330 (solid content 1.0%) (manufactured by Pico chemical (BYK-Chemie) Co., Ltd.)

[ example 1]

Photosensitive resin compositions of examples 1 to 10, comparative examples 1 and 2 were prepared by blending the blending components (A) to (F) in the proportions shown in Table 1. In the column of the solvent, (D) -1 represents the amount of PGMEA (same as (D) -1) in the resin solution containing no unsaturated group (polymerizable unsaturated group-containing alkali-soluble resin solution), the solvent in the light-shielding pigment dispersion, and the solvent in the surfactant. In addition, the numerical values in table 1 all represent mass%.

[ evaluation ]

The photosensitive resin compositions of examples 1 to 10 and comparative examples 1 and 2 were used to perform the following evaluations.

(preparation of cured film (coating film))

Using a spin coater, the photosensitive resin compositions shown in Table 1 were applied to a film having a thickness of 1.5 μm after heat curing so as to give a film having an illuminance of 1000mJ/cm at a wavelength of 254nm by irradiation with a low-pressure mercury lamp²The coated plate was prepared by pre-baking a 50mm × 50mm glass substrate "EAGLE XG" (manufactured by Corning corporation) (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") with a hot plate at 90 ℃ for 1 minute. Then, the illuminance at a wavelength of 365nm was 30mW/cm²Is irradiated by a high pressure mercury lamp at a concentration of 100mJ/cm²The ultraviolet ray of (2) to perform a photo-curing reaction. Then, the cured films (coating films) of examples 1 to 10 and comparative examples 1 and 2 were obtained by curing the coating film at 230 ℃ for 30 minutes using a hot air dryer.

The cured films (coating films) containing the photosensitive resin compositions of examples 1 to 10 and comparative examples 1 and 2 obtained as described above were evaluated for the following items, and the results are shown in table 2. The evaluation methods were carried out as follows. Further, regarding the high temperature and high humidity resistance adhesion and the chemical resistance adhesion, not only the cured film (coating film) on the glass substrate but also the cured films (coating films) formed on the ITO substrate and the MAM substrate were evaluated.

(measurement of film thickness)

The thickness of the cured film (coating film) in examples 1 to 10, comparative examples 1 and 2 was measured by using a stylus type step shape measuring apparatus "P-17" (manufactured by KLA-Tencor Co., Ltd.).

[ high temperature and high humidity resistance adhesion ]

(evaluation method)

The cured films (coating films) formed on the glass substrate, the ITO substrate, and the MAM substrate were allowed to stand at a temperature of 121 ℃, a humidity of 100%, and an atmospheric pressure of 2atm for 5 hours. Then, a cross cut peeling test was performed, in which a substrate was cut with a cut using a Super Cutter Guide (manufactured by tai sai machine materials ltd) to form 100 square grids of 1mm × 1mm, and a cellophane tape (manufactured by Nichiban) was attached to the grids and then peeled off.

(evaluation criteria)

O: the cured film (coating film) in the mesh was not peeled off

And (delta): less than 1/3 of the hardened film (coating film) in the mesh was peeled off

X: 1/3 above

[ chemical resistance adhesion ]

(evaluation method)

The cured film (coating film) formed on the glass substrate, ITO substrate, and MAM substrate was immersed in a petri dish containing N-methyl-2-pyrrolidone at 60 ℃ for 2 minutes, and then washed with pure water to remove water. Then, a cross-cut peel test was performed, in which a substrate was cut into a slit using a Super Cutter Guide (Super Cutter Guide) to form 100 square grids of 1mm × 1mm, and a cellophane tape was attached to the grids and then peeled off.

(evaluation criteria)

O: the cured film (coating film) in the mesh was not peeled off

X: 1/3 above

[ coating film hardness 1]

(evaluation method)

The cured film (coating film) produced on the glass substrate was subjected to a load of 750g using a pencil hardness tester according to the test method of Japanese Industrial Standards (JIS) -K5600-5-4, and the maximum pencil hardness was represented by the maximum pencil hardness at which no damage was caused in the cured film (coating film). The pencil used was "Mitsubishi Youyini (HI-Uni)" (manufactured by Mitsubishi Pencil Co., Ltd.). The present evaluation was carried out as an index of the resistance of the coating film surface to a force (scratch) in the transverse direction.

(evaluation criteria)

O: over 3H

△：2H

X: h or less

[ coating film hardness 2]

(evaluation method)

The cured film (coating film) formed on the glass substrate was measured using a microfilm hardness tester "HM 2000" (manufactured by Fischer Instruments). The indenter was a Vickers indenter loaded at a load rate of 0.25mN/sec with a load of 5mN/μm²The load of (2) was maintained for 1 second, and then the load was removed to measure the Martens hardness (according to International Organization for Standardization (ISO)) 14577. This evaluation was performed as an index of the resistance of the surface of the cured film (coating film) against the force (press-in) in the longitudinal direction. The "mahalanobis hardness" refers to a hardness calculated from a load-penetration depth curve.

(evaluation criteria)

○：65N/mm²The above

△：60N/mm²More than and less than 65N/mm²

X: less than 60N/mm²

[ transmittance 1]

(evaluation method)

The transmittance of a cured film (coating film) formed on a glass substrate "EAGLE (EAGLE) XG" in a thickness of 2 μm was measured using a transmittance meter "spectrophotometer (spectrum PHOTOMETER) SD 5000" (manufactured by japan electro-chromatic industries, ltd.).

(evaluation criteria)

O: a transmittance at a wavelength of 400nm of 95% or more

And (delta): the transmittance at wavelength of 400nm is more than 90% and less than 95%

X: less than 90 percent

[ transmittance 2]

The transmittance of a cured film (coating film) formed on a glass substrate "EAGLE (EAGLE) XG" in a film thickness of 3 μm was measured using a transmittance meter "spectrophotometer (spectra PHOTOMETER) SD 5000".

(evaluation criteria)

O: the transmittance at the wavelength of 340nm is less than 20 percent

And (delta): the transmittance at wavelength of 340nm is more than 20% and less than 65%

X: over 65 percent

[ gas Generation Property ]

(evaluation method)

The hardened film (coating film) formed on the glass substrate "EAGLE (EAGLE) XG" was ground with a squeegee (scraper) or the like, and a thermogravimetric loss of 10mg of the obtained powdery hardened film (coating film) was measured using a thermogravimetric Analysis-thermogravimetric Analysis (TG/DTA)) "eastma (star) 6000" (manufactured by Hitachi High-Tech Science, ltd). The measurement conditions were such that the pretreatment was carried out at 120 ℃ for 30 minutes under the atmospheric air, and then the reaction mixture was held at 230 ℃ for 3 hours. The gas generation performance was evaluated by the weight loss rate calculated from the weight loss before and after heating at 230 ℃.

(evaluation criteria)

Very good: the weight reduction rate is less than 3 percent

O: the weight reduction rate is more than 3 percent and less than 7 percent

And (delta): the weight reduction rate is more than 7 percent and less than 15 percent

X: the weight reduction rate is more than 15 percent

[ Water absorption ]

(evaluation method)

The hardened film (coating film) produced on the glass substrate "EAGLE (EAGLE) XG" was left to stand at a constant temperature and humidity of 40 ℃ and a humidity of 90% for 24 hours, and then ground with a blade or the like, and the obtained powdery hardened film (coating film) was measured for a thermal weight loss of 10mg using a differential thermal analysis-thermal weight measuring apparatus (TG/DTA) "Eastma (EXSTAR) 6000". The measurement conditions were set such that the temperature was increased to 120 ℃ at 10 ℃/min under a nitrogen atmosphere and maintained for 1 hour. The water absorption was evaluated by the weight loss ratio.

(evaluation criteria)

O: the weight reduction rate is less than 2 percent

And (delta): the weight reduction rate is more than 2 percent and less than 5 percent

X: the weight loss rate is more than 5%

[ developing characteristics ]

(preparation of evaluation sample)

The photosensitive resin compositions shown in table 1 were applied onto a 125mm × 125mm glass substrate "EAGLE (EAGLE) XG" using a spin coater so that the film thickness after the heat curing treatment was 1.5 μm, and were prebaked at 90 ℃ for 1 minute using a hot plate. Then, the photomask was set to an exposure gap of 150 μm and an illuminance of 30mW/cm at a wavelength of 365nm²Is irradiated by a high pressure mercury lamp at a concentration of 100mJ/cm²The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.

Then, the cured film (coating film) after the exposure was developed at a pressure of 0.1MPa for 60 seconds using a 0.05% potassium hydroxide aqueous solution or a 0.2% sodium carbonate aqueous solution at 23 ℃, and then washed with water to remove the unexposed portion of the cured film (coating film). Then, the cured films (patterns) of examples 1 to 10 and comparative examples 1 and 2 were obtained by heat-curing treatment at 230 ℃ for 30 minutes using a hot air dryer.

(evaluation method and evaluation criteria)

The formation of fine lines in the obtained pattern was confirmed by an optical microscope, and evaluated in the following three stages.

O: a pattern having an L/S of 15 μm/15 μm or more is formed without leaving any residue

And (delta): a pattern having an L/S of 30 μm/30 μm or more is formed without leaving any residue

X: no pattern with L/S less than 50 μm/50 μm is formed, or no curling or residue of the pattern is formed

[ example 2]

Photosensitive resin compositions containing light-shielding pigment dispersions of examples 11 to 16 and comparative examples 11 to 13 were prepared by blending the blending components (a) to (F) in the proportions shown in table 3. In the column of the solvent, (D) -1 represents the amount of PGMEA (same as (D) -1) in the resin solution containing no unsaturated group (polymerizable unsaturated group-containing alkali-soluble resin solution), the solvent in the light-shielding pigment dispersion, and the solvent in the surfactant. In addition, the numerical values in table 3 all represent mass%.

(light-shielding pigment dispersion liquid)

(E) -1: PGMEA dispersion (solid content: 19.5%) containing 15.0% by mass of lactam-based black pigment and 4.5% by mass of polymer dispersant

(E) -2: PGMEA dispersion (solid content: 30.0%) containing 25.0 mass% of resin-coated carbon-based black pigment and 5.0 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.

[ measurement of optical Density ]

The photosensitive resin compositions shown in Table 3 were applied onto a 125mm × 125mm glass substrate using a spin coater so that the film thickness after the heat curing treatment was 1.1 μm, and prebaked at 90 ℃ for 1 minute. Then, the cured films (coating films) of examples 11 to 16 and comparative examples 11 to 13 were obtained by heat-curing treatment at 230 ℃ for 30 minutes using a hot air dryer. Next, the Optical Density (OD) of the obtained cured film (coating film) was measured using a Macbeth transmission densitometer, and evaluated by 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 glass substrate of 100mm × 100mm, on which Cr was deposited, and which had a thickness of 1.2mm, except for the electrodes, so that the film thickness after the heat curing treatment was 3.5 μm, using a spin coater, and was prebaked at 90 ℃ for 1 minute. Then, the cured films (coating films) of examples 11 to 16 and comparative examples 11 to 13 were obtained by heat-curing treatment at 230 ℃ for 30 minutes using a hot air dryer. Then, an aluminum electrode was formed on the cured film (coating film) to prepare a substrate for measuring volume resistivity. Next, volume resistivity was measured from 1V to 10V using an electrometer (model 6517A) (manufactured by Keithley) in the measurement. Further, the measurement was performed under the condition that each applied voltage was held for 60 seconds at 1V step (step).

[ measurement of dielectric constant ]

(measurement method)

Each photosensitive resin composition shown in table 3 was applied to a glass substrate of 100mm × 100mm, on which Cr was deposited, and which had a thickness of 1.2mm, except for the electrodes, so that the film thickness after the heat curing treatment was 3.5 μm, using a spin coater, and was prebaked at 90 ℃ for 1 minute. Then, the cured films (coating films) of examples 11 to 16 and comparative examples 11 to 13 were obtained by heat-curing treatment at 230 ℃ for 30 minutes using a hot air dryer. Then, an aluminum electrode was formed on the coating film to prepare a substrate for measuring dielectric constant. Next, the capacitance was measured from 1Hz to 100000Hz using an electrometer (model 6517A) and the dielectric constant was calculated from the capacitance.

[ gas Generation Property ]

(evaluation method)

The hardened film (coating film) formed on the glass substrate "EAGLE (EAGLE) XG" was ground with a blade or the like, and the obtained powdery hardened film (coating film) was measured for a thermal weight loss of 10mg using a differential thermal analysis-thermal weight measuring apparatus (TG/DTA) "Easta (EXSTAR) 6000". The measurement conditions were such that the pretreatment was carried out at 120 ℃ for 30 minutes under the atmospheric air, and then the reaction mixture was held at 230 ℃ for 3 hours.

(evaluation criteria)

Very good: the weight reduction rate is less than 3 percent

O: the weight reduction rate is more than 3 percent and less than 7 percent

And (delta): the weight reduction rate is more than 7 percent and less than 10 percent

X: the weight reduction rate is more than 10%

[ measurement of elastic recovery Rate of spacer ]

(measurement method)

Each photosensitive resin composition shown in table 3 was applied onto a 125mm × 125mm glass substrate "EAGLE (EAGLE) XG" using a spin coater so that the film thickness after the heat curing treatment was 3.0 μm, and was prebaked at 90 ℃ for 1 minute. Then, the film was brought into close contact with a photomask having a dot pattern and the film was irradiated with 30mW/cm of illumination having a wavelength of 365nm²Is irradiated by a high pressure mercury lamp at a concentration of 100mJ/cm²The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.

Subsequently, the exposed glass substrate was developed with a 0.05% aqueous solution of potassium hydroxide at 24 ℃ and a pressure of 0.1MPa for 60 seconds to remove the unexposed portion of the cured film (coating film). Then, the cured films (coating films) of examples 1 to 6 and comparative examples 1 to 3 were obtained by heat-curing treatment at 230 ℃ for 30 minutes using a hot air dryer. The interval characteristics of the obtained hardened film (coat film) pattern were evaluated using an ultra-fine durometer "Fischer science HM2000 xpp" (manufactured by Fischer Instruments). A displacement curve was prepared by applying a 100 μm square plane indenter at a load rate of 5.0 mN/sec, unloading the indenter at an unloading rate of 5.0 mN/sec after a load of 50mN is applied.

The elastic recovery rate was calculated from the following equation (2) with the displacement amount at 50mN under load being L1 and the displacement amount at unloading being L2.

Elastic recovery (%) - (L1-L2)/L1X 100(2)

[ developing characteristics ]

(preparation of evaluation sample)

The photosensitive resin compositions shown in table 3 were applied to a 125mm × 125mm glass substrate "EAGLE (EAGLE) XG" by using a spin coater so that the film thickness after the heat curing treatment was 1.5 μm, and were prebaked at 90 ℃ for 1 minute by using a hot plate. Then, the photomask was set to an exposure gap of 150 μm and an illuminance of 30mW/cm at a wavelength of 365nm²Is irradiated by a high pressure mercury lamp at a concentration of 100mJ/cm²The ultraviolet ray of (2) to perform a photo-curing reaction of the photosensitive portion.

Then, the cured film (coating film) after the exposure was developed at a pressure of 0.1MPa for 60 seconds using a 0.05% potassium hydroxide aqueous solution or a 0.2% sodium carbonate aqueous solution at 23 ℃, and then washed with water to remove the unexposed portion of the cured film (coating film). Then, the cured films (patterns) of examples 11 to 16 and comparative examples 11 to 13 were obtained by heat-curing treatment at 230 ℃ for 30 minutes using a hot air dryer.

(evaluation method and evaluation criteria)

The invention can obtain a light-shielding and insulating material with high light-shielding performance; excellent adhesion to the substrate; a photosensitive resin composition for a cured film which is excellent in elastic modulus, deformation amount, and elastic recovery rate.

[ Industrial Applicability ]

The cured film of the photosensitive resin composition of the present invention can be very effectively used as a component of a color filter including an organic EL device, a quantum dot display, a TFT array, a wavelength conversion device, and the like. The resin composition having a dinaphthofluorene skeleton functions as a light transmission control layer for cutting off ultraviolet light in a specific range, and is therefore useful.

Claims

1. A photosensitive resin composition comprising the following components (A) to (D) as essential components:

(A) an alkali-soluble resin containing a polymerizable unsaturated group of the general formula (1);

(B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds;

(C) a photopolymerization initiator; and

(D) a solvent, a water-soluble organic solvent,

in the formula (1), Ar is an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a part of hydrogen atoms bonded to Ar may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group; r₁Each independently an alkylene group having 2 to 4 carbon atoms, and l each independently a number of 0 to 3; g is a substituent represented by the general formula (2) or the general formula (3), and Y is a tetravalent carboxylic acid residue; each Z is independently a hydrogen atom or a substituent represented by the general formula (4), and one or more substituents are represented by the general formula (4); n is a number having an average value of 1 to 20;

in the formulae (2) and (3), R₂Is a hydrogen atom or a methyl group, R₃Is a C2-10 divalent alkylene or alkylarylene group, R₄Is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10;

in the 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, which comprises (E) a coloring material.

3. The photosensitive resin composition according to claim 2, wherein the coloring material (E) is one or more light-shielding components selected from the group consisting of a black organic pigment, a mixed color organic pigment and a light-shielding material.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the component (A) is a compound in which Ar in the general formula (1) contains a naphthalene skeleton.

5. The photosensitive resin composition according to claim 1, wherein the content of the component (A) is 10 to 90% by mass based on the total mass of the solid components, the content of the component (B) is 5 to 200 parts by mass based on 100 parts by mass of the component (A), and the content of the component (C) is 0.1 to 30 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (B).

6. The photosensitive resin composition according to claim 2, wherein the content of the coloring material (E) is 1 to 80% by mass based on the total mass of the solid components of the photosensitive resin composition.

7. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 6.

8. A display device having the cured film according to claim 7.