JP2021157176A - Photosensitive resin composition, cured film, substrate with cured film, method for producing substrate with cured film and display device - Google Patents

Abstract

To provide a photosensitive resin composition capable of forming a cured film having a light scattering function directly on the substrate regardless of the heat resistance temperature of a substrate.SOLUTION: There is provided a photosensitive resin composition which comprises (A) an alkali-soluble resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two ethylenic unsaturated bonds, (C) metal oxide particles having an average particle diameter of 40 nm or more and 600 nm or less and a refractive index of 1.2 or more and 1.5 or less or resin particles and (D) a photopolymerization initiator. The content of the component (D) is 10 mass% or more and 70 mass% or less based on the total mass of the solid content.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition, a cured film obtained by curing a photosensitive resin composition, a substrate with a cured film, a method for producing a substrate with a cured film, and a display device having a cured film or a substrate with a cured film.

In recent years, not only highly heat-resistant substrates such as glass substrates and silicon wafers that can be used at high temperatures of 200 ° C or higher, but also PET (polyethylene terephthalate) with low heat resistance has been used for the purpose of making devices flexible and one-chip. A pattern using a photosensitive resin composition having a light scattering function is formed on a plastic substrate (plastic film, resin film) such as PEN (polyethylene terephthalate), or a substrate with an organic device such as an organic EL device or an organic TFT. Consideration is being made to form it.

Here, when a photosensitive resin composition having a light scattering function for forming a pattern by high-temperature firing is formed by low-temperature firing according to the heat resistance of a substrate such as a plastic substrate and a substrate with an organic device, the above substrate is formed. The film strength of the pattern formed in the above becomes insufficient, and in the subsequent steps (for example, solvent resistance during resist application and alkali resistance during alkaline development), the film of the coating film is reduced, the surface is roughened, the pattern is peeled off, and the like. There was a problem that it was easy. Therefore, there is a demand for a photosensitive resin composition having light scattering properties that can be used for both high-temperature and low-temperature firing.

Further, in recent years, a photosensitive resin composition having a light scattering function is required to satisfy various required characteristics regarding optical characteristics such as a combination of light transmittance or cloudiness value (HAZE) and light scattering intensity. .. Further, in the development of a new display device, in order to improve functionality such as power saving and expansion of color gamut, it is required that the degree of freedom in designing the display device can be expanded by applying a light scattering layer having a specific function.

For example, Patent Document 1 describes _{a photosensitive composition for forming a pattern having a light scattering function, which is composed of a TiO 2} filler, a photopolymerizable monomer, an alkali-soluble resin, a photopolymerization initiator, and an organic solvent. It is disclosed. It is said that the photosensitive composition has photolithography characteristics suitable for use in a display device, and also has light scattering characteristics in which blue light is scattered at a wider angle than the incident angle by _{the TiO 2 filler.}

Further, Patent Document 2 includes at least one kind of resin (A) as a binder material, contains fluorine as light scattering particles (B), and includes ZrO ₂ and TiO _{2 as metal oxide fine particles (C).} A resin composition for a light scattering layer containing at least one selected metal oxide fine particles is disclosed. It is said that the resin composition for a light scattering layer can provide a resin composition for a light scattering layer that has a small wavelength dependence of light extraction efficiency and can be used in a wide wavelength range.

Japanese Unexamined Patent Publication No. 2013-156304 Japanese Unexamined Patent Publication No. 2015-022794

However, according to the findings of the present inventor, the photosensitive composition described in Patent Document 1 has low solvent resistance, and the resin composition for a light scattering layer described in Patent Document 2 has desired optical characteristics (transmittance, light). It was not possible to obtain a cured film pattern having (scattering property). Further, the photosensitive composition described in Patent Document 1 and the resin composition for a light scattering layer described in Patent Document 2 sufficiently satisfy the desired development characteristics (adhesion, linearity, fineness) of the cured film. I didn't.

Conventionally, in order to give a light scattering function to a cured film, metal oxide particles having a relatively large refractive index of 1.9 or more are often used, but the light transmittance or the cloudiness value (HAZE) is used. While various required characteristics related to optical characteristics such as combination with light scattering intensity are also required, even if metal oxide particles or resin particles having a refractive index of 1.2 or more and 1.5 or less are used. , There is a demand for a photosensitive resin composition capable of satisfying the required optical properties and other cured film properties.

Furthermore, in the development of a new display device, in order to improve the light extraction efficiency of a light emitting element such as an organic EL, a display using application to a light scattering layer in which diffusely transmitted light becomes stronger and light wavelength conversion of the light emitting element. In the apparatus, there is also a demand for a photosensitive resin composition that can be applied to a light scattering layer in which diffuse reflected light becomes strong.

The present invention has been made in view of the above points, and is a photosensitive resin composition capable of forming a cured film having good optical characteristics and good development characteristics regardless of the heat resistant temperature of the substrate. It is an object of the present invention to provide a cured film obtained by curing a resin composition, a substrate with a cured film, a method for producing a substrate with a cured film, and a display device having the cured film and the substrate with the cured film.

The photosensitive resin composition of the present invention comprises (A) an unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, and (C) an average particle size of 40 nm. It contains metal oxide particles or resin particles having a refractive index of 1.2 or more and 1.5 or less and (D) a photopolymerization initiator, and the content of the component (C) is solid. It is 10% by mass or more and 70% by mass or less with respect to the total mass of the particles.

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

The substrate with a cured film of the present invention has the above-mentioned cured film.

The display device of the present invention has the cured film or the substrate with the cured film.

The method for producing a substrate with a cured film of the present invention is a method for producing a substrate with a cured film by forming a cured film pattern having light scattering property on a substrate having a heat resistant temperature of 150 ° C. or lower, and the above-mentioned photosensitive resin. The composition is applied onto a substrate, exposed through a photomask, unexposed portions are removed by development, and heated at 150 ° C. or lower to form a predetermined cured film pattern.

Another method for producing a substrate with a cured film of the present invention is a method for producing a substrate with a cured film by forming a cured film pattern having photoscattering property on a substrate having a heat resistant temperature of more than 150 ° C. The photosensitive resin composition is applied onto a substrate, exposed through a photomask, unexposed portions are removed by development, and heated at over 150 ° C. to form a predetermined resin film pattern.

According to the present invention, a photosensitive resin composition capable of forming a cured film having good optical characteristics and good developing characteristics regardless of the heat resistant temperature of the substrate, and curing obtained by curing the photosensitive resin composition. It is possible to provide a film, a substrate with a cured film, a method for manufacturing a substrate with a cured film, and a display device having the cured film and the substrate with a cured film.

As a result, conventionally, in order to have a light scattering function, metal oxide particles having a relatively large refractive index of 1.9 or more and a relatively large particle size are often used, but light transmission is performed. While various required characteristics regarding optical characteristics such as a combination of rate or cloud value (HAZE) and light scattering intensity are also required, metal oxides having a refractive index of 1.2 or more and 1.5 or less are required. Alternatively, it is possible to provide a photosensitive resin composition capable of satisfying the required optical properties and other cured film properties even if resin particles are used.

Furthermore, in the development of a new display device, in order to improve the light extraction efficiency of a light emitting element such as an organic EL, a display using application to a light scattering layer in which diffusely transmitted light becomes stronger and light wavelength conversion of the light emitting element. In the apparatus, it is also possible to provide a photosensitive resin composition applicable to a light scattering layer in which diffuse reflected light is strengthened.

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

1. 1. Photosensitive Resin Composition The photosensitive resin composition according to the embodiment of the present invention has (A) an unsaturated group-containing alkali-soluble resin and (B) a photopolymerizable photopolymerizable bond having at least two ethylenically unsaturated bonds. It contains a monomer, (C) metal oxide particles or resin particles having an average particle diameter of 40 nm or more and 600 nm or less and a refractive index of 1.2 or more and 1.5 or less, and (D) a photopolymerization initiator.

[(A) component]
The unsaturated group-containing alkali-soluble resin as the component (A) preferably has a polymerizable unsaturated group and an acidic group for expressing alkali solubility in one molecule, and is preferably a polymerizable unsaturated group. It is more preferable to have both with a carboxy group. Any of the above resins can be used without particular limitation.

From the viewpoint of enhancing the adhesion to the substrate, the component (A) is preferably an unsaturated group-containing alkali-soluble resin represented by the following general formula (1) (hereinafter, also simply referred to as "alkali-soluble resin"). ..

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、それぞれ独立して、水素原子、炭素数が１〜５の直鎖または分岐鎖のアルキル基、ハロゲン原子またはフェニル基であり、Ｒ_５は、水素原子またはメチル基であり、Ｘは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、フルオレン−９，９−ジイル基または直結合であり、Ｙは４価のカルボン酸残基であり、Ｚは、それぞれ独立して、水素原子または一般式（２）で表される置換基であり、１個以上は一般式（２）で表される置換基である。ｎは平均値が１〜２０である。）

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently composed of a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group. Yes, R ₅ is a hydrogen atom or a methyl group, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH ₂ -,- C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, Z is a hydrogen atom or general, respectively. It is a substituent represented by the formula (2), and one or more is a substituent represented by the general formula (2). The average value of n is 1 to 20.)

（式（２）中、Ｗは２価または３価のカルボン酸残基であり、ｍは１または２である。）

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

Next, a method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail.

First, an unsaturated group is contained in an epoxy compound (a-1) having two epoxy groups in one molecule represented by the general formula (3) (hereinafter, also simply referred to as “epoxy compound (a-1)”). A monocarboxylic acid (eg, (meth) acrylic acid) is reacted to give an epoxy (meth) acrylate. In addition, "(meth) acrylic acid" is a general term for acrylic acid and methacrylic acid, and "(meth) acryloyl group" is a general term for acryloyl group and methacrylic acid group, and means one or both of them.

（式（３）中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、それぞれ独立して、水素原子、炭素数が１〜５の直鎖または分岐鎖のアルキル基、ハロゲン原子またはフェニル基であり、Ｘは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、フルオレン−９，９−ジイル基または直結合である。）

(In formula (3), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, linear or branched alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups. Yes, X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, Fluolene-9,9-diyl group or direct bond.)

The epoxy compound (a-1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin.

Examples of the above bisphenols include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, and bis (4-hydroxyphenyl) ketone. Hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy) -3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) ) Dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-Dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3) , 5-Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-Hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy) -3-Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy) -3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene. 4-Hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol and the like are included. Among these, bisphenols having a fluorene-9,9-diyl group are preferable from the viewpoint of further enhancing the adhesion. Only one of these may be used alone, or two or more thereof may be used in combination.

Examples of the unsaturated group-containing monocarboxylic acid compound include a compound obtained by reacting acrylic acid or methacrylic acid with an acid monoanhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride in addition to acrylic acid and methacrylic acid. Etc. are included.

A known method can be used for the reaction between the epoxy compound (a-1) and (meth) acrylic acid. For example, Japanese Patent Application Laid-Open No. 4-355450 describes a diol compound containing a polymerizable unsaturated group by using about 2 mol (meth) acrylic acid with respect to 1 mol of an epoxy compound having two epoxy groups. Is stated to be obtained. In the present invention, the compound obtained by the above reaction is a diol compound containing a polymerizable unsaturated group, and the diol (d) containing a polymerizable unsaturated group represented by the general formula (4) (hereinafter, simply referred to as "simply"). It is also referred to as "diol (d) represented by the general formula (4)").

（式（４）中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、それぞれ独立して、水素原子、炭素数が１〜５の直鎖または分岐鎖のアルキル基、ハロゲン原子またはフェニル基であり、Ｒ_５は、水素原子またはメチル基であり、Ｘは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、フルオレン−９，９−ジイル基または直結合である。）

(In formula (4), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, linear or branched alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups. Yes, R ₅ is a hydrogen atom or a methyl group, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH ₂ -,- C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond.)

The synthesis of the diol (d) represented by the general formula (4), the subsequent addition reaction of the polyvalent carboxylic acid or its anhydride, and the monofunctional epoxy having a polymerizable unsaturated group having reactivity with the carboxy group. In the production of the alkali-soluble resin represented by the general formula (1) by reacting a compound or the like, the reaction is usually carried out in a solvent using a catalyst as needed.

Examples of solvents include cellosolvent solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high boiling ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate; cyclohexanone, A ketone solvent such as diisobutyl ketone is included. The reaction conditions such as the solvent and the catalyst to be used are not particularly limited, but for example, it is preferable to use a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature as the reaction solvent.

Further, it is preferable to use a catalyst in the reaction between the carboxy group and the epoxy group. For example, Japanese Patent Application Laid-Open No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine and tris. Phosphines such as (2,6-dimethoxyphenyl) phosphine are described.

Next, the diol (d) represented by the general formula (4) obtained by the reaction of the epoxy compound (a-1) with the (meth) acrylic acid, and the dicarboxylic acid or tricarboxylic acid or its acid anhydride (b). , And tetracarboxylic acid or its acid dianhydride (c) can be reacted to obtain an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by the general formula (1). can.

（式（１）中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、それぞれ独立して、水素原子、炭素数が１〜５の直鎖または分岐鎖のアルキル基、ハロゲン原子またはフェニル基であり、Ｒ_５は、水素原子またはメチル基であり、Ｘは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、フルオレン−９，９−ジイル基または直結合であり、Ｙは４価のカルボン酸残基であり、Ｚは、それぞれ独立して、水素原子または一般式（２）で表される置換基であり、１個以上は一般式（２）で表される置換基である。ｎは平均値が１〜２０である。）

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently composed of a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group. Yes, R ₅ is a hydrogen atom or a methyl group, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH ₂ -,- C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, Z is a hydrogen atom or general, respectively. It is a substituent represented by the formula (2), and one or more is a substituent represented by the general formula (2). The average value of n is 1 to 20.)

（式（２）中、Ｗは２価または３価のカルボン酸残基であり、ｍは１または２である。）

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

The acid component used for synthesizing the alkali-soluble resin represented by the general formula (1) is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule represented by the general formula (4). Therefore, it is necessary to use dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) in combination with tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, these carboxylic acid residues may contain a bond containing a hetero element such as -O-, -S-, and a carbonyl group.

Examples of the dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) include chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, and the like. Alternatively, those acid monoanhydrides and the like can be used.

Examples of the acid monoanhydride of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralinic acid, malonic acid, glutaric acid and citric acid. , Tartrate acid, oxoglutaric acid, pimelli acid, sebacic acid, suberic acid, diglycolic acid and other acid monoanhydrides, and dicarboxylic acid or tricarboxylic acid monoan anhydride having an arbitrary substituent introduced therein.

Examples of acid monoanhydrides of alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methyl-3,6-end. Includes acid monoanhydrides such as methylenetetrahydrophthalic acid, norbornandicarboxylic acid, chlorendic acid, hexahydrotrimertic acid, and acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

Examples of acid unianhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid unianoxides such as phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and Includes acid monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituent has been introduced.

Among the acid monoanhydrides of 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 preferable. Is more preferable. Further, in the dicarboxylic acid or tricarboxylic acid, it is preferable to use those acid monoanhydrides. As the above-mentioned acid monoanhydride of dicarboxylic acid or tricarboxylic acid, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, and their acid dianhydride. Can be used.

Examples of chain hydrocarbon tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain type in which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups are introduced. Hydrocarbon tetracarboxylic acid and the like are included.

Examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptantetracarboxylic acid, norbornan tetracarboxylic acid, and chain hydrocarbon groups and unsaturated hydrocarbons. An alicyclic tetracarboxylic acid or the like into which a substituent such as a hydrogen group has been introduced is included.

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, naphthalene. -2,3,6,7-Tetracarboxylic acid and the like are included.

Among the tetracarboxylic acids or acid dianhydrides thereof, biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid and diphenyl ether tetracarboxylic acid are preferable, and biphenyl tetracarboxylic acid and diphenyl ether tetracarboxylic acid are more preferable. Further, in the case of tetracarboxylic acid or its acid dianhydride, it is preferable to use the acid dianhydride. As the above-mentioned tetracarboxylic acid or acid dianhydride thereof, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

The reaction between the diol (d) represented by the general formula (4) and the acid components (b) and (c) is not particularly limited, and a known method can be adopted. For example, Japanese Patent Application Laid-Open No. 9-325494 describes a method for reacting an epoxy (meth) acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140 ° C.

Here, the diol (d) represented by the general formula (4), a dicarboxylic acid or a tricarboxylic acid or their acid monoanhydrides (b), and a tetracarboxylic acid dianhydride so that the end of the compound becomes a carboxy group. It is preferable to react so that the molar ratio with (c) is (d) :( b) :( c) = 1: 0.01 to 1.0: 0.2 to 1.0.

For example, when (b) acid monoanhydride and (c) acid dianhydride are used, the amount of the acid component with respect to the diol (d) represented by the general formula (4) [(b) / 2 + (c). ], It is preferable to react so that the molar ratio [(d) / [(b) / 2+ (c)]] is 0.5 to 1.0. Here, when the molar ratio exceeds 0.5, the terminal of the alkali-soluble resin represented by the general formula (1) does not become an acid anhydride, so that the content of the unreacted acid dianhydride increases. Therefore, the stability of the alkali-soluble resin composition over time can be improved. When the molar ratio is 1.0 or less, the content of the diol compound containing an unreacted polymerizable unsaturated group is not increased, so that the stability of the alkali-soluble resin composition over time can be improved. .. For the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the general formula (1), the molar ratio of each component of (d), (b) and (c) can be arbitrarily set within the above range. Can be changed.

The acid value of the alkali-soluble resin represented by the general formula (1) is preferably 20 mgKOH / g or more and 180 mgKOH / g or less, and more preferably 40 mgKOH / g or more and 140 mgKOH / g or less. More preferably, it is 80 mgKOH / g or more and 120 mgKOH / g or less. When the acid value is 20 mgKOH / g or more, the residue is 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 fast, so peeling development should be suppressed. Can be done. The acid value can be determined by titrating with a 1/10 N-KOH aqueous solution using, for example, a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (1) is preferably 1000 or more and 100,000 or less, more preferably 2000 or more and 20000 or less, and further preferably 2000 or more and 6000 or less. When the weight average molecular weight is 1000 or more, it is possible to suppress a decrease in pattern adhesion during alkaline development. Further, when the weight average molecular weight is 100,000 or less, it is easy to adjust the solution viscosity of the photosensitive resin composition suitable for coating, and it does not take too much time for alkaline development. The weight average molecular weight (Mw) can be determined in terms of polystyrene by using, for example, gel permeation chromatography (GPC) measurement (HLC-8220 GPC, manufactured by Tosoh Corporation).

Further, another example of a resin preferable as the component (A) includes a copolymer such as (meth) acrylic acid and (meth) acrylic acid ester, which has a (meth) acryloyl group and a carboxy group. Is done. In the above resin example, (meth) acrylic acid is reacted with a copolymer obtained by copolymerizing (meth) acrylic acid esters containing glycidyl (meth) acrylate in a solvent, and finally dicarboxylic acid. Alternatively, an unsaturated group-containing alkali-soluble resin obtained by reacting an anhydride of a tricarboxylic acid is included. The above-mentioned copolymer is a repeating unit of 20 to 90 mol% derived from a diesterglycerol in which the hydroxyl groups at both ends are esterified with (meth) acrylic acid, which is shown in JP-A-2014-111722, and the same copolymer thereof. A copolymer composed of 10 to 80 mol% repeating units derived from one or more polymerizable unsaturated compounds having a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 to 120 mgKOH / g. , And a unit derived from a (meth) acrylic acid ester compound, which is shown in JP-A-2018-141968, and a unit having a (meth) acryloyl group and a di or tricarboxylic acid residue, by weight average. An unsaturated group-containing alkali-soluble resin which is a polymer having a molecular weight (Mw) of 3000 to 50,000 and an acid value of 30 to 200 mgKOH / g can be referred to.

As for the unsaturated group-containing alkali-soluble resin of the component (A), only one type may be used alone, or two or more types may be used in combination.

Among these resins, resins having a highly aromatic skeleton generally tend to have a higher specific gravity than aliphatic resins, and when solutions having the same resin concentration are used, the specific gravity of the resin solution is increased. It can be made larger. It is presumed that this makes it possible to improve the dispersion stability of the metal oxide particles having a higher specific density than the resin. Therefore, by using the alkali-soluble resin represented by the general formula (1), a photosensitive resin composition having sufficient dispersion stability of the metal oxide particles can be obtained. In particular, when X represented by the general formula (1) uses an unsaturated group-containing alkali-soluble resin (cardo resin) having a polycyclic aromatic skeleton such as a fluorene-9,9-diyl group, the effect is effective. As the size increases, it is expected that the dispersion stability of the metal oxide particles will be further improved. By including the cardo resin as the component (A) in the photosensitive resin composition of the present invention, it is possible to enhance the light scattering property of the cured product obtained by curing the photosensitive resin composition. In addition, cardo resin has a property of excellent adhesion during development when pattern formation is performed by photolithography, and this property is also effective when an inorganic filler such as a metal oxide coexists. It is presumed that it can be utilized in.

The content of the component (A) is preferably 25% by mass or more and 70% by mass or less with respect to the total mass of the solid content.

Here, when the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150 ° C. or lower, the content of the component (A) is 25% by mass or more and 60% by mass with respect to the total mass of the solid content. It is preferably mass% or less. When a cardo resin is used as the component (A), it is preferably 30% by mass or more and 55% by mass or less. When another resin such as an acrylic copolymer system is used as the component (A), it is preferably 25% by mass or more and 50% by mass or less. When the content of the component (A) is 25% by mass or more, good developability can be obtained even if the metal oxide particles or resin particles having a refractive index of 1.2 or more and 1.5 or less are contained, which is desirable. Pattern can be obtained without residue. When the content of the component (A) is 60% by mass or less, the suitability of the production process at the time of alkaline development is improved, and the photocurability can be sufficiently ensured.

When the photosensitive resin composition of the present invention is a composition that is fired at a high temperature of more than 150 ° C., the content of the component (A) is 40% by mass or more and 70% by mass with respect to the total mass of the solid content. % Or less is preferable. When a cardo resin is used as the component (A), it is preferably 45% by mass or more and 60% by mass or less. When another resin such as an acrylic copolymer system is used as the component (A), it is preferably 40% by mass or more and 60% by mass or less. When the content of the component (A) is 40% by mass or more, good developability can be obtained even if the metal oxide particles or resin particles having a refractive index of 1.2 or more and 1.5 or less are contained. The desired pattern can be obtained without residue. When the content of the component (A) is 70% by mass or less, the suitability of the production process at the time of alkaline development is improved, and the photocurability can be sufficiently ensured.

Next, the components (B) to (F) contained in the photosensitive resin composition according to the embodiment of the present invention will be described.

[(B) component]
The component (B) is a photopolymerizable monomer having at least two ethylenically unsaturated bonds. The component (B) can have higher adhesion of the cured product, and can obtain good development characteristics (pattern adhesion, pattern linearity, pattern definition) of the exposed portion.

Examples of the component (B) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tetramethylene glycol di (meth) acrylate. , Glyoxide di (meth) acrylate, trimethylolpropantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene (Meta) acrylic acid esters such as alkylene oxide-modified hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and dendritic polymers having (meth) acryloyl group as compounds having an ethylenic double bond. included. It should be noted that these may be used alone or in combination of two or more.

Examples of the dendritic polymer include a dendritic polymer obtained by adding a polyvalent mercapto compound to a part of carbon-carbon double bonds in the (meth) acryloyl group of a polyfunctional (meth) acrylate. .. Specifically, it is obtained by reacting the (meth) acryloyl group of the polyfunctional (meth) acrylate represented by the general formula (5) with the thiol group of the polyvalent mercapto compound represented by the general formula (6). Includes dendritic polymers.

（式（５）中、Ｒ_６は水素原子またはメチル基であり、Ｒ_７はＲ_９（ＯＨ）_ｋのｋ個のヒドロキシル基の内ｌ個のヒドロキシル基を式中のエステル結合に供与した残り部分である。好ましいＲ_９（ＯＨ）_ｋとしては、炭素数が２〜８の非芳香族の直鎖または分枝鎖の炭化水素骨格に基づく多価アルコールであるか、当該多価アルコールの複数分子がアルコールの脱水縮合によりエーテル結合を介して連結してなる多価アルコールエーテルであるか、またはこれらの多価アルコールまたは多価アルコールエーテルとヒドロキシ酸とのエステルである。ｋおよびｌは独立に２〜２０の整数であり、ｋ≧ｌである。）

(In formula (5), R ₆ is a hydrogen atom or a methyl group, and R ₇ is the remainder of donating l hydroxyl groups out of k hydroxyl groups of _{R 9} (OH) _{k to the ester bond in the formula.} A preferred R ₉ (OH) _k is a polyhydric alcohol based on a non-aromatic linear or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a plurality of the polyhydric alcohols. A polyhydric alcohol ether in which the molecules are linked via an ether bond by dehydration condensation of alcohol, or an ester of these polyhydric alcohols or polyhydric alcohol ethers with a hydroxy acid. K and l are independent. It is an integer of 2 to 20, and k ≧ l.)

（式（６）中、Ｒ_８は単結合または２〜６価のＣ１〜Ｃ６の炭化水素基であり、ｐはＲ_８が単結合であるときは２であり、Ｒ_８が２〜６価の基であるときは２〜６の整数である。）

(In formula (6), R ₈ is a single bond or a 2 to 6 valent C1 to C6 hydrocarbon group, p _{is 2 when R 8} is a single bond, and R ₈ is 2 to 6 valent. When it is the basis of, it is an integer of 2 to 6.)

Examples of the polyfunctional (meth) acrylate represented by the general formula (5) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and tetraethylene glycol di (meth). ) Acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolethanetri ( Meta) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (Meta) acrylate, tripentaerythritol hepta (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, epichlorohydrin-modified hexahydrophthal Acid di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) Acrylate, trimethylolpropane benzoate (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, alkoxy-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri ( Includes (meth) acrylic acid esters such as meta) acrylates and ditrimethylolpropane tetra (meth) acrylates. Only one of these compounds may be used alone, or two or more of these compounds may be used in combination.

Examples of the polyvalent mercapto compound represented by the general formula (6) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, and trimethylol. Propanetri (mercaptoacetate), trimethylpropantri (mercaptopropionate), pentaerythritoltetra (mercaptoacetate), pentaerythritoltri (mercaptoacetate), pentaerythritoltetra (mercaptopropionate), dipentaerythritol hexa (mercapto) Acetate), dipentaerythritol hexa (mercaptopropionate), etc. are included. Only one of these compounds may be used alone, or two or more of these compounds may be used in combination.

In addition, when synthesizing the dendritic polymer, a polymerization inhibitor may be added if necessary. Examples of the polymerization inhibitor include hydroquinone compounds and phenol compounds. Specific examples thereof include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, 2,4,6-tri-tert-butylphenol (BHT) and the like.

The component (B) can play a role of cross-linking the molecules of the unsaturated group-containing alkali-soluble resin, and in order to exert this function, it is necessary to use a component having three or more unsaturated bonds. preferable. Further, the acrylic equivalent obtained by dividing the molecular weight of the monomer by the number of (meth) acryloyl groups in one molecule is preferably 50 g / eq or more and 300 g / eq or less, and the acrylic equivalent is 80 g / eq or more and 200 g / eq or less. Is more preferable. The component (B) does not have a free carboxy group.

The content of the component (B) is preferably 10% by mass or more and 40% by mass or less with respect to the total mass of the solid content.

Here, when the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150 ° C. or lower, the content of the component (B) is 10% by mass or more and 40% by mass or more with respect to the total mass of the solid content. It is preferably mass% or less. Here, when a cardo resin is used as the component (A), the content of the component (B) is preferably 10% by mass or more and 30% by mass or less. When other acrylic copolymer type resins or the like are used as the component (A), the content of the component (B) is preferably 10% by mass or more and 35% by mass or less.

Further, when the content of the component (B) is a composition in which the photosensitive resin composition of the present invention is fired at a high temperature of more than 150 ° C., the content of the component (B) is the total mass of the solid content. It is preferably 10% by mass or more and 40% by mass or less. Here, when a cardo resin is used as the component (A), the content of the component (B) is preferably 10% by mass or more and 30% by mass or less. When other acrylic copolymer type resins or the like are used as the component (A), the content of the component (B) is preferably 10% by mass or more and 35% by mass or less.

When the content of the component (B) is 10% by mass or more with respect to the total mass of the solid content, the cured product is less likely to become brittle, and when it is 40% by mass or less, the decrease in the acid value of the composition is suppressed. As a result, the solubility of the unexposed portion in the alkaline developer can be increased, and the pattern adhesion, pattern linearity, and pattern definition of the cured product can be improved.

[(C) component]
The component (C) is a metal oxide particle or a resin particle having an average particle diameter of 40 nm or more and 600 nm or less and a refractive index of 1.2 or more and 1.5 or less. By including the component (C), a light scattering function can be imparted to the cured film (coating film). In addition, in this specification, a "metal oxide" means an oxide of a metal and a metalloid, and a composite oxide containing a metal and a metalloid.

The particle size and shape of the metal oxide particles or resin particles having a refractive index of 1.2 or more and 1.5 or less are particularly limited as long as the formed cured film (coating film) can exert a light scattering function. Not limited.

The average particle size of the metal oxide particles or resin particles is preferably 40 nm or more and 600 nm or less. When the average particle size of the metal oxide particles or the resin particles is 40 nm or more, the light scattering property of the cured product can be exhibited and the desired light scattering intensity can be adjusted. When the average particle size is 600 nm or less, the light transmittance and the light scattering intensity can be appropriately adjusted, and the pattern adhesion, pattern linearity, and pattern fineness of the cured product can be sufficiently improved.

Examples of the metal oxide particles include silica particles. As long as the particle size of the silica particles is within the above range, the production method such as vapor phase reaction or liquid phase reaction and the shape (spherical, non-spherical, hollow, solid, etc.) are not particularly limited. Further, as long as the particle size is within the above range, silica particles surface-treated by a silane coupling agent treatment or the like can also be used without particular limitation.

Further, examples of the resin particles include hollow acrylic resin particles. The hollow acrylic resin particles are, for example, a resin obtained by radically copolymerizing several types of monomers having a (meth) acryloyl group in the shell portion of the hollow particles, having an average particle diameter of 40 nm or more and 150 nm or less, and a hollow ratio of 10. Particles of% or more and 90% or less are preferable. As a method for producing such hollow acrylic resin particles, for example, the production method described in JP-A-2017-66351 can be used.

The average particle size of the metal oxide particles and the resin particles can be measured by the cumulant method using, for example, a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) of a dynamic light scattering method. can. The refractive index of the metal oxide particles (silica particles) and the resin particles (hollow acrylic resin particles) is the same as that of the silica particles or the hollow acrylic resin particles processed into a powder, and a standard refraction solution having a known refractive index. It can be obtained from the transparent mixed solution obtained by mixing. In this case, the refractive index of the standard refractive index of the mixture is defined as the refractive index of the silica particles or the hollow acrylic resin particles.

Further, the shapes of the metal oxide particles and the resin particles and the hollow ratio of the hollow particles can be observed and measured using a transmission electron microscope (TEM).

The refractive index of the metal oxide particles and the resin particles can be measured using an Abbe refractive index meter.

Further, the metal oxide particles or resin particles as the component (C) can be mixed with other compounding components as a particle dispersion dispersed in a solvent together with a dispersant. As the dispersant, for example, known compounds used for pigment dispersion (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) and the like can be used without particular limitation.

The content of the metal oxide particles or resin particles as the component (C) is preferably 10% by mass or more and 70% by mass or less with respect to the total mass of the solid content. When the content of the component (C) is 10% by mass or more, the light scattering property can be imparted while maintaining the light transmittance of the cured product. When the content of the component (C) is 70% by mass or less, the development characteristics (pattern adhesion, pattern linearity, pattern definition), light transmission and solvent resistance are excellent.

[(D) component]
The component (D) is a photopolymerization initiator. By including the component (D), the reaction of the portion irradiated with light proceeds sufficiently, the solubility of the cured portion during development is lowered, and a desired fine pattern can be formed. The term "photopolymerization initiator" as used in the present invention is used to include a sensitizer.

Examples of the component (D) include acetophenones, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone and other acetophenones; benzophenone. , 2-Chlorobenzophenone, p, p'-bisdimethylaminobenzophenone and other benzophenones; benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 2- (o-chlorophenyl) -4 , 5-Phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 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-oxadiazol, Halos such as 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole and 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Methyldiazole 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) Halomethyl-s-triazine compounds such as -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine; 1,2- Octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), etanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1 O-acyloxime compounds such as-(4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butane-1-oneoxime-O-acetate, etc. Classes; sulfur compounds such as benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, Anthraquinones such as 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and oxime peroxide; tertiary amines such as triethanolamine and triethylamine are included. As these photopolymerization initiators, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

In particular, when the amount of metal oxide added is large, the amount of photopolymerization initiator added is small, or when the heat curing process at a high temperature of 150 ° C. cannot be performed and photocuring is desired to be performed more effectively. When a highly sensitive photopolymerization initiator is required, it is preferable to use O-acyloxime compounds (including ketooxime). Among them, the compound group represented by the general formula (7) and the general formula (8) can be applied as a more sensitive photopolymerization initiator. Among them, when it is desired to carry out photocuring more effectively in response to low temperature curing, it is preferable to use an O-acyloxime-based photopolymerization initiator having a molar extinction coefficient at 365 nm of 10000 L / mol · cm or more.

（式（７）中、Ｒ_１０、Ｒ_１１は、それぞれ独立に、炭素数が１〜１５のアルキル基、炭素数が６〜１８のアリール基、炭素数が７〜２０のアリールアルキル基または炭素数が４〜１２の複素環基を表し、Ｒ_１２は炭素数が１〜１５のアルキル基、炭素数が６〜１８のアリール基、炭素数が７〜２０のアリールアルキル基を表す。ここで、アルキル基およびアリール基は、炭素数が１〜１０のアルキル基、炭素数が１〜１０のアルコキシ基、炭素数が１〜１０のアルカノイル基、ハロゲンからなる群から選択される基で置換されていてもよく、アルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合を含んでいてもよい。また、上記アルキル基は直鎖、分岐、または環状のいずれのアルキル基であってもよい。）

(In formula (7), R ₁₀ and R ₁₁ are independently alkyl groups having 1 to 15 carbon atoms, aryl groups having 6 to 18 carbon atoms, and arylalkyl groups or carbon atoms having 7 to 20 carbon atoms, respectively. It represents a heterocyclic group having a number of 4 to 12, and R ₁₂ represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. , Alkyl groups and aryl groups are substituted with groups selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkanoyl groups having 1 to 10 carbon atoms, and halogens. The alkylene moiety may contain an unsaturated bond, an ether bond, a thioether bond, and an ester bond, and the alkyl group may be a linear, branched, or cyclic alkyl group. good.)

（式（８）中、Ｒ_１３およびＲ_１４はそれぞれ独立に、炭素数が１〜１０の直鎖または分岐鎖のアルキル基であるか、炭素数が４〜１０のシクロアルキル基、シクロアルキルアルキル基もしくはアルキルシクロアルキル基であるか、または炭素数が１〜６のアルキル基で置換されていてもよいフェニル基である。Ｒ_１５は独立に炭素数が２〜１０の直鎖状または分岐鎖のアルキル基またはアルケニル基であり、当該アルキル基またはアルケニル基中の−ＣＨ_２−基の一部が−Ｏ−基で置換されていてもよい。さらに、これらＲ_１３〜Ｒ_１５の基中の水素原子の一部がハロゲン原子で置換されていてもよい。）

In formula (8), R ₁₃ and R ₁₄ are independently linear or branched alkyl groups having 1 to 10 carbon atoms, or cycloalkyl groups having 4 to 10 carbon atoms, cycloalkylalkyls. A phenyl group that is a group or an alkylcycloalkyl group or may be substituted with an alkyl group having 1 to 6 carbon atoms. R ₁₅ is an independently linear or branched chain having 2 to 10 carbon atoms. Alkyl group or alkenyl group of the above, and _{a part of -CH 2-} group in the alkyl group or alkenyl group may be substituted with -O- group. Further, in these groups of _{R 13 to} R _15. A part of the hydrogen atom may be replaced with a halogen atom.)

Here, the content of the component (D) is preferably 0.1% by mass or more and 30% by mass or less, and preferably 1% by mass or more and 25% by mass or less, based on the total mass of the components (A) and (B). .. When the content of the component (D) is 0.1% by mass or more, it has an appropriate photopolymerization rate, so that a decrease in sensitivity can be suppressed, and when it is 30% by mass or less, the sensitivity to exposure of the composition Is not too high, so the line width faithful to the mask can be reproduced and the pattern edge can be sharpened.

[(E) component]
The photosensitive resin composition according to the embodiment of the present invention preferably contains (E) an epoxy compound. When the photosensitive resin composition is fired at a low temperature of 150 ° C. or lower, the solvent resistance of the cured product can be sufficiently enhanced by containing the (E) epoxy compound if necessary.

Examples of the component (E) include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, bisnaphthol fluorene type epoxy compound, diphenylfluorene type epoxy compound, phenol novolac type epoxy compound, and cresol novolac type epoxy compound. Compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (for example, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds (for example, EPPN-501H: Japan) (Made by Kayaku Co., Ltd.), Epoxy compounds with aromatic structure such as tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyvalent carboxylic acids, representatives of copolymers of methacrylic acid and glycidyl methacrylate A copolymer of a monomer having a (meth) acryloyl group containing glycidyl (meth) acrylate as a unit, glycidyl such as bisphenol hydride A diglycidyl ether (for example, lycaresin HBE-100: manufactured by Shin Nihon Rika Co., Ltd.) Epoxy compounds with groups, 1,4-cyclohexanedimethanol-bis 3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,1-spiro (3,4-epoxy) cyclohexyl-m -Dioxane (eg, Araldite CY175: manufactured by Huntsman), Bis (3,4-epoxycyclohexylmethyl) adipate (eg, CYRACURE UVR-6128: manufactured by Dow Chemical), 3', 4'-epoxycyclohexylmethyl 3, An alicyclic epoxy compound typified by 4-epoxycyclohexanecarboxylate (eg, celloxide 2021P: manufactured by Daicel Co., Ltd.), modified ε-caprolactone (3,4-epoxycyclohexylmethyl) of butanetetracarboxylate (eg, epipolyd GT401). : Dycel Co., Ltd.), Epoxy compound having an epoxycyclohexyl group (for example, HiREM-1: Shikoku Kasei Kogyo Co., Ltd.), Polyfunctional epoxy compound having a dicyclopentadiene skeleton (for example, HP7200 series: DIC Co., Ltd.) , 2,2-Bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct (For example, EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (for example, NISSOPB JP-100: manufactured by Nippon Soda Co., Ltd.), an epoxy compound having a silicone skeleton, and the like are included. As these compounds, only one kind of compound may be used, or two or more kinds thereof may be used in combination.

The epoxy equivalent of the component (E) is preferably 100 g / eq or more and 500 g / eq or less, and more preferably 130 g / eq or more and 480 g / eq or less. The number average molecular weight (Mn) of the component (E) is preferably 100 or more and 5000 or less. When the epoxy equivalent is 100 g / eq or more and the number average molecular weight (Mn) of the epoxy compound is 100 or more, a cured film having good solvent resistance can be obtained, and the epoxy equivalent is 300 g / eq or less. When the number average molecular weight (Mn) is 5000 or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in a subsequent step.

The epoxy equivalent is, for example, 1 / 10N-perchloric acid using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) after dissolving a resin solution in dioxane and adding an acetic acid solution of tetraethylammonium bromide. It can be determined by titrating with a solution. The number average molecular weight (Mn) can be determined in terms of polystyrene using, for example, the above-mentioned gel permeation chromatography (GPC) measurement (HLC-8220 GPC, manufactured by Tosoh Corporation).

The content of the component (E) is preferably 5% by mass or more and 35% by mass or less, and more preferably 10% by mass or more and 25% by mass or less with respect to the total mass of the solid content. When the content of the component (E) is 5% by mass or more, the curing reaction can be sufficiently advanced even when firing at a low temperature of 150 ° C. or lower. When it is 35% by mass or less, the developing characteristics and solvent resistance of the cured product can be sufficiently enhanced.

On the other hand, when the photosensitive resin composition is fired at a high temperature of more than 150 ° C., the component (E) is easily cured, so that the content of the component (E) is 30% by mass with respect to the total mass of the solid content. % Or less is preferable.

[(F) component]
The photosensitive resin composition according to the embodiment of the present invention preferably contains a curing agent or a curing accelerator of the (F) epoxy compound. By containing the component (F), the photosensitive resin composition can be sufficiently cured even when firing at a low temperature of 150 ° C. or lower.

Examples of the curing agent for the epoxy compound as the component (F) include amine compounds, polyvalent carboxylic acid compounds, phenol resins, amino resins, dicyandiamides, Lewis acid complex compounds and the like. Among these, a polyvalent carboxylic acid compound is preferable.

Examples of polyvalent carboxylic acid compounds include polyvalent carboxylic acids, anhydrides of polyvalent carboxylic acids, and thermodegradable esters of polyvalent carboxylic acids.

A polyvalent carboxylic acid is a compound having two or more carboxy groups in one molecule, for example, succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-. 4,5-dicarboxylic acid, norbornan-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2, 4-Tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, butane-1,2, Includes 3,4-tetracarboxylic acid and the like.

Examples of polyvalent carboxylic acid anhydrides include acid anhydrides of the above compounds. This may be an intermolecular acid anhydride, but generally an intramolecularly ring-closed acid anhydride is used.

Examples of thermally decomposable esters of polyvalent carboxylic acids include t-butyl ester, 1- (alkyloxy) ethyl ester, and 1- (alkylsulfanyl) ethyl ester of the above compounds (where alkyl has 1 to 20 carbon atoms). It is a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may have a branched structure or a ring structure, or may be substituted with an arbitrary substituent) and the like.

Further, as the polyvalent carboxylic acid compound, a polymer or copolymer having two or more carboxy groups can also be used, and the carboxy group may be an anhydride or a pyrolytic ester.

Examples of the polymer or copolymer having two or more carboxy groups include a polymer or copolymer containing (meth) acrylic acid as a constituent, a copolymer containing maleic anhydride as a constituent, and tetra. A compound obtained by reacting a carboxylic acid dianhydride with a diamine or a diol to open a ring of the acid anhydride is included. Of these, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and benzene-1,2,4-tricarboxylic acid anhydrides can be used. preferable. When the polyvalent carboxylic acid compound is used as a curing agent for the epoxy compound, the compounding ratio is 0.5 to 1.5 mol of the carboxyl group of the polyvalent carboxylic acid compound with respect to 1 mol of the epoxy group of the epoxy compound. Preferably, 0.6 to 1.2 mol is more preferable.

As the curing accelerator of the epoxy compound as the component (F), a known compound known as a curing accelerator of the epoxy compound, a curing catalyst, a latent curing agent, or the like can be used. Examples of curing accelerators for epoxy compounds include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organic metal compounds, imidazoles and the like. Among the above curing accelerators, 1,8-diazabicyclo [5.4.0] undec-7-ene or 1,5-diazabicyclo [4.3.0] nona-5-ene or a salt thereof. Is preferable.

The content of the curing accelerator is preferably 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the epoxy compound. The content of the curing accelerator can be adjusted according to the state of development of chemical resistance (solvent resistance) of the resin film pattern after heat curing.

When the photosensitive resin composition of the present invention is a composition that is fired at a low temperature of 150 ° C. or lower, the total content of the components (E) and (F) is 5% by mass with respect to the total mass of the solid content. % Or more and 35% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. When the total content of the component (E) and the component (F) is 5% by mass or more, the curability when cured at a low temperature of 150 ° C. or less is sufficiently ensured, and when it is 35% by mass or less, it is alkaline. Curability can be improved without adversely affecting patterning property, linearity and solvent resistance during development.

When the photosensitive resin composition of the present invention is a composition that is fired at a high temperature of more than 150 ° C., the total content of the components (E) and (F) is 0 mass with respect to the total mass of the solid content. % Or more and 25% by mass or less are preferable.

[(G) component]
The photosensitive resin composition according to the embodiment of the present invention preferably contains (G) a solvent. By containing the solvent (G), a liquid photosensitive resin composition containing the above-mentioned components (A) to (F) can be obtained.

Examples of the component (G) include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, diacetone alcohol and the like. Alcohols; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; 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, tri Glycol ethers such as ethylene glycol monomethyl ether and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate. , Carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other esters and the like are included. In order to obtain the required properties such as coatability, these solvents may be used alone or in combination of two or more.

The content of the component (G) varies depending on the target viscosity, but is preferably 60% by mass or more and 90% by mass or less in the photosensitive resin composition solution.

[(H) component]
The photosensitive resin composition according to the embodiment of the present invention preferably contains a coupling agent as the component (H). By including the coupling agent, the adhesion to the substrate can be improved.

Examples of the component (H) include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, and 3-isocyanatopropyltri. Ethoxysilane, 3-aminopropyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-ureidopropyltriethoxysilane and the like are included.

[(I) component]
The photosensitive resin composition according to the embodiment of the present invention preferably contains a surfactant as the component (I). By including a surfactant, a uniform coating film can be obtained.

Examples of the component (I) include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, anionic surfactants, betaine-based surfactants, and the like. .. Among these, a fluorine-based surfactant is preferable.

Examples of fluorine-based surfactants have a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Includes polyoxyalkylene ether polymer compounds and the like. As the surfactant, only one kind thereof may be used alone, or two or more kinds thereof may be used in combination.

[Other ingredients]
The photosensitive resin composition of the present invention may contain additives such as a thermal polymerization inhibitor, an antioxidant, a plasticizer, a leveling agent, an antifoaming agent, and a chain transfer agent, if necessary.

Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic antioxidants, phosphorus-based heat stabilizers.

Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like.

Examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds.

Examples of chain transfer agents include thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole.

The photosensitive resin composition of the present invention can be obtained by mixing the above-mentioned components (A) to (I) and any other components.

The photosensitive resin composition of the present invention can satisfy the required optical properties and other cured film properties even when a metal oxide or resin particles having a refractive index of 1.2 or more and 1.5 or less are used. Further, in the development of a new display device, the photosensitive resin composition of the present invention is applied to a light scattering layer in which diffuse transmitted light is strengthened in order to improve the light extraction efficiency of a light emitting element such as an organic EL. In a display device that utilizes light wavelength conversion of a light emitting element, it can be applied to a light scattering layer in which diffusely reflected light becomes strong.

2. Method for producing a cured film A method for producing a cured film obtained by curing the photosensitive resin composition of the present invention will be described. The cured film (coating film) of the present invention can be formed by a photolithography method using the photosensitive resin composition of the present invention.

[Manufacturing method 1]
In the method for producing a cured film of the present invention, the above-mentioned photosensitive resin composition is applied onto a substrate having a heat resistant temperature of 150 ° C. or lower, exposed through a photomask, and an unexposed portion is removed by development. This is a manufacturing method in which a predetermined cured film pattern is formed by heating at a temperature of ° C. or lower.

Examples of the substrate used in the method for producing a cured film of the present invention include resin films (plastic substrates) such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) having a heat resistant temperature of 150 ° C. or less, and resin films. The substrate and the like are also included in which electrodes such as ITO and gold are vapor-deposited or patterned. Here, the "heat-resistant temperature" refers to a temperature at which problems such as deformation do not occur even if the substrate is exposed in a processing process such as pattern formation of a cured film on the substrate. Although the resin film changes depending on the degree of stretching treatment, it is necessary that the resin film does not exceed at least the glass transition temperature (Tg).

Further, as an example of another substrate used in the method for producing a cured film of the present invention, a thin film having high heat resistance of the substrate itself but having low heat resistance such as a glass substrate, a silicon wafer and a polyimide film can be used on the substrate. The formed one is included. Specific examples of other substrates include a substrate with an organic device in which an organic EL (OLED) or an organic thin film transistor (TFT) is formed on a glass, a silicon wafer, or a polyimide film. The heat-resistant temperature of the substrate having low heat resistance, which is the subject of the present invention, varies depending on the type of resin and the device, but is preferably 80 to 140 ° C. The substrate with an organic device includes a substrate on which a protective film, a protective film, etc. are formed after the formation of the organic device. Even if the heat resistance of these protective films and the protective film itself is 150 ° C. or higher, if the heat resistance is substantially 140 ° C. or lower in order to ensure the function of the organic device, a substrate with an organic device can be used. This is because it is applicable.

As a method for applying the photosensitive resin composition, a coating method can be used. Examples of the above coating method include a method using a roller coater machine, a land coater machine, a slit coater machine, and a spinner machine, in addition to the known solution dipping method and spray method. By these methods, the photosensitive resin composition can be applied to a desired thickness.

By these methods, a coating film is formed by applying to a desired thickness and then removing the solvent (prebaking). Pre-baking can be performed by heating with an oven, a hot plate, a hot air blower, an infrared heater or the like, vacuum drying, or a combination thereof. The heating temperature and heating time in the prebake are appropriately selected according to the solvent used, and are carried out, for example, at a temperature of 60 to 110 ° C. (set so as not to exceed the heat resistant temperature of the substrate) for 1 to 3 minutes.

The exposure performed after the prebaking is performed by an exposure apparatus, and by irradiating radiation through a photomask, only the resist of the portion corresponding to the pattern is exposed. The exposure apparatus and its exposure irradiation conditions can be appropriately selected. Examples of irradiated radiation include visible light, ultraviolet light, far ultraviolet light, electron beams and X-rays. Among the above radiations, ultraviolet rays are preferable. Further, as a device for irradiating radiation, a known exposure device (a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, or a far ultraviolet lamp) can be used. Further, the wavelength of the radiation to be irradiated is preferably 250 nm or more and 400 nm or less. Exposure of radiation is preferably 25 mJ / cm ² or more 3000 mJ / cm ² or less, and more preferably 50 mJ / cm ² or more 2000 mJ / cm ² or less.

A known photomask can be used. Examples of photomasks include multi-tone masks such as halftone masks and gray tone masks.

Further, the development performed after the exposure is performed for the purpose of alkaline-developing the coating film after the exposure to remove the coating film in the unexposed portion, and this development forms a desired pattern. Examples of the coating film developing method include a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method, and the like. The above-mentioned developing method can be performed using a commercially available developing machine, an ultrasonic cleaner, or the like.

Examples of the developing solution suitable for development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of an alkali metal hydroxide, and an aqueous solution of diethanolamine, tetramethylammonium hydroxide or the like. Among these, a weak alkaline aqueous solution containing 0.05 to 3% by mass of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate can be used at a temperature of 23 to 28 ° C. After alkaline development, it is usually washed with water. The developer can be appropriately selected according to the characteristics of the resin layer, but a surfactant may be added if necessary.

The developed coating film is preferably heat-treated (post-baked) under the conditions of 80 to 140 ° C. (set so as not to exceed the heat resistant temperature of the substrate) and 20 to 90 minutes, and the temperature is 90 to 120 ° C. It is more preferable that the heating time is 30 to 60 minutes. The post-baking is performed for the purpose of enhancing the adhesion between the patterned cured film and the substrate. Like pre-baking, post-baking is performed by heating in an oven, a hot plate, or the like. In this way, the patterned substrate with a cured film of the present invention can be obtained.

[Manufacturing method 2]
In the method for producing a cured film of the present invention, the above-mentioned photosensitive resin composition is applied onto a substrate having a heat resistant temperature of more than 150 ° C., exposed through a photomask, and an unexposed portion is removed by development. This is a manufacturing method in which a predetermined cured film pattern is formed by heating at a temperature of ° C. or higher.

The manufacturing method for forming a predetermined cured film pattern on a substrate having a heat resistant temperature of more than 150 ° C. is the same as in manufacturing method 1, in which coating, exposure, and development are performed, and after development, a temperature of 80 to 250 ° C. and 20 The heat treatment (post-baking) is preferably performed under the conditions of ~ 90 minutes, and more preferably performed under the conditions of a temperature of 180 to 230 ° C. and a heating time of 30 to 60 minutes. The post-baking is performed for the purpose of enhancing the adhesion between the patterned cured film and the substrate. This is done by heating in an oven, hot plate, etc., similar to prebaking. In this way, the patterned substrate with a cured film of the present invention can be obtained.

3. 3. Cured Film The cured film of the present invention can be obtained by curing the above-mentioned photosensitive resin composition by the production method 1 or the production method 2.

When the cured film of the present invention was formed on a transparent substrate, the transparency of the visible light region was 80% or more, and the transparent substrate on which the cured film was formed was irradiated with white light perpendicularly. When the angle of the straight-ahead directly transmitted light is 0 °, the intensity of the scattered light at 60 ° is 10 with respect to the intensity of the scattered light at 5 ° when the angle of the straight-ahead directly transmitted light is 0 °. It is preferably% or more and less than 80%.

The cured film of the present invention satisfies the above-mentioned optical characteristics (transparency and light scattering property in the visible light region), and when the film is formed on a transparent substrate, the cured film is formed on the transparent substrate. When the white light is irradiated vertically, the intensity of the scattered light at 120 ° when the angle of the directly transmitted light traveling straight is 0 ° is 60 ° when the angle of the directly transmitted light traveling straight is 0 °. It is preferably less than 80%, more preferably less than 50% with respect to the intensity of the scattered light in.

The substrate for measuring the transmittance and scattered light intensity of the substrate with the cured film is a transparent substrate, and for example, a transparent glass substrate "EagleXG" (manufactured by Corning Inc.) can be used.

By setting the intensity of the scattered light within the above range, a light scattering layer can be formed in which the diffused transmitted light becomes stronger in order to improve the light extraction efficiency of a light emitting element such as an organic EL.

The cured film of the present invention is a light wavelength conversion layer in which the light emitted from the light emitting element is highly diffused by adding quantum dots or a fluorescent substance for light wavelength conversion to improve the light confinement effect. You can also. Further, for a display device that utilizes the light wavelength conversion of the light emitting element, in order to make the cured film a light scattering layer in which the diffused reflected light becomes strong, when the angle of the directly transmitted light traveling straight is set to 0 °. The intensity of the scattered light at 120 ° is preferably more than 80% of the intensity of the scattered light at 60 ° when the angle of the straight-ahead directly transmitted light is 0 °. For such applications, it is preferable to apply magnesium fluoride or hollow silica having a smaller refractive index.

4. Display device The display device of the present invention has the above-mentioned cured film. Since the display device of the present invention has the above-mentioned cured film, it can have a light scattering layer capable of improving the light extraction efficiency of a light emitting element such as an organic EL.

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

First, the examples of synthesizing the alkali-soluble resin of the component (A) will be described. Unless otherwise specified, the evaluation of the resin in these synthetic examples was carried out as follows. When the same model is used for various measuring devices, the device manufacturer name is omitted from the second place. Further, in [Experiment 1] and [Experiment 2], the glass substrates used for producing the substrate with the cured film for measurement are all glass substrates subjected to the same treatment.

[Solid content concentration]
The solid content concentration was determined by the weight [W _{1 (g)] obtained by impregnating a glass filter [weight: W 0} (g)] with 1 g of the resin solution obtained in the synthetic example, and after heating at 160 ° C. for 2 hours. It was calculated from the weight [W ₂ (g)] of
Solid content concentration (% by weight) = 100 × (W _2- W ₀ ) / (W _1- W ₀ )

[Epoxy equivalent]
For the epoxy equivalent, add an acetic acid solution of tetraethylammonium bromide after dissolving the resin solution in dioxane, and use a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to prepare a 1/10 N-perchloric acid solution. It was determined by titration.

[Acid value]
The acid value was determined by dissolving the resin solution in dioxane and titrating with a 1/10 N-KOH aqueous solution using a potentiometric titrator "COM-1600".

[Molecular weight]
The molecular weight is gel permeation chromatography (GPC) "HLC-8220 GPC" (manufactured by Tosoh Corporation, solvent: polystyrene, column: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1). 1) + TSKgelSuper H-5000 (1) (manufactured by Tosoh Corporation), temperature: 40 ° C., speed: 0.6 ml / min), converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligoene kit) The weight average molecular weight (Mw) was determined as a value.

[Refractive index]
The refractive index of the silica particles and the hollow acrylic resin particles was measured using an Abbe refractive index meter.

[Average particle size]
The average particle size of the silica particles and the hollow acrylic resin particles was determined by the cumulant method using a particle size distribution meter "particle size analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.) by a dynamic light scattering method.

The abbreviations used in the synthesis example are as follows.
DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: Styrene AA: Acrylic acid SA: Succinic anhydride BPFE: Bisphenol fluorene type epoxy compound (9,9-bis (4-hydroxyphenyl) Reaction of fluorene with chloromethyloxylan Stuff)
BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride THPA: tetrahydrophthalic anhydride TEAB: tetraethylammonium bromide AIBN: azobisisobutyronitrile TDMAMP: trisdimethylaminomethylphenol HQ: hydroquinone TEA : Triethylamine PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example 1]
BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g) and TEAB (0.48 g) were charged in a 500 ml four-necked flask equipped with a return condenser. The reaction was carried out by stirring at 100 to 105 ° C. for 20 hours. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged in a flask and stirred at 120 to 125 ° C. for 6 hours to obtain a resin solution (A) -1. rice field. The solid content concentration of the resin solution was 56.1% by mass, the acid value (in terms of solid content) was 103 mgKOH / g, and the Mw by GPC analysis was 3600.

[Synthesis Example 2]
PGMEA (300 g) was placed in a 1 L four-necked flask equipped with a return condenser, the inside of the flask system was replaced with nitrogen, and then the temperature was raised to 120 ° C. AIBN (10 g) was dissolved in a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol)) in this flask. The mixture was added dropwise from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.

Then, after replacing the inside of the flask system with air, AA (24.0 g (95% of glycidyl group)), TDAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution. , 120 ° C. for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. Further, SA (30.0 g (90% of the number of moles added with AA)) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution, and the mixture was reacted at 120 ° C. for 4 hours to prepare a resin solution. (A) -2 was obtained. The solid content concentration of the resin solution was 41.7% by mass, the acid value (in terms of solid content) was 76 mgKOH / g, and the Mw by GPC analysis was 5300.

The compounding components used in the photosensitive resin compositions of the following examples are as follows.

(Alkali-soluble resin)
(A) -1: Resin solution obtained in Synthesis Example 1 (solid content concentration 56.1% by mass)
(A) -2: Resin solution obtained in Synthesis Example 2 (solid content concentration 41.7% by mass)

(Photopolymerizable monomer)
(B): Dipentaerythritol penta / hexaacrylate mixture (KAYARAD DPHA, acrylic equivalent 96-115 g / eq, manufactured by Nippon Kayaku Co., Ltd., "KAYARAD" is a registered trademark of the company)

(Metal oxide particles or resin particles)
(C) -1: Hollow acrylic particle dispersion of hollow acrylic particles "Techpolymer NH" (average particle diameter 65 nm, void ratio 30% by volume, refractive index 1.33) concentration 10% by mass, PGMEA 90% by mass (C)- 2: Silica particle dispersion of silica particles "Admanano YA050C" (average particle diameter 50 nm, refractive index 1.45) concentration 20% by mass, dispersant (DISPERBYK-355) 5% by mass, PGMEA 75% by mass (C) -3: Silica particle dispersion (average particle diameter 400 nm, refractive index 1.45) concentration 20% by mass, dispersant (DISPERBYK-355) 5% by mass, PGMEA 75% by mass Silica particle dispersion (C) -4: Silica particles (average particle diameter) 600 nm, refractive index 1.45) concentration 20% by mass, dispersant (DISPERBYK-355) 5% by mass, PGMEA 75% by mass silica particle dispersion

Techpolymer NH is manufactured by Sekisui Plastics Co., Ltd., and "Techpolymer" is a registered trademark of the company. Admanano YA050C is manufactured by Admatex Co., Ltd., and "Admanano" is a registered trademark of the company. DISPERBYK-355 is manufactured by Big Chemie, and "DISPERBYK" is a registered trademark of the company.

(Photopolymerization initiator)
(D): 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (IrgacureOXE-01, manufactured by BASF, "Irgacure" is a registered trademark of the company)

(Epoxy compound)
(E): 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (celloxide 2021P (epoxy equivalent 135 g / eq), manufactured by Daicel Corporation, "celloxide" is a registered trademark of the same company)

(Curing agent and curing accelerator)
(F) -1: Benzene 1,2,4-tricarboxylic acid-1,2-anhydride (F) -2: 1,8-diazabicyclo [5.4.0] Undec-7-ene (DBU (R)) , San Appro Co., Ltd.) containing 2% by mass of PGMEA solution

(solvent)
(G) -1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)
(G) -2: Ethyl lactate (EL)
(G) -3: Diethylene glycol ethyl methyl ether (EDM)

(Other additives)
(Coupling agent)
(H): 3-glycidoxypropyltrimethoxysilane (surfactant)
(I): Mega Fvck F-477 (manufactured by DIC Corporation, "Mega Fvck" is a registered trademark of the company)

[Experiment 1]
The above-mentioned compounding components were blended in the proportions shown in Table 1 to prepare photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2. All the values in Table 1 represent mass%.

[evaluation]
The following evaluations were carried out using the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2.

(Preparation of substrate with cured film (coating film) for evaluation of development characteristics)
The surface of the photosensitive resin composition shown in Table 1 was ^{washed by irradiating the surface with ultraviolet rays having a wavelength of 254 nm and an illuminance of 1000 mJ / cm 2} in advance with a low-pressure mercury lamp, and a 125 mm × 125 mm glass substrate “# 1737” (manufactured by Corning Inc.). A hard film is applied onto a glass substrate (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing treatment is 2.0 μm, and prebaked at 90 ° C. for 2 minutes using a hot plate. (Coating film) was prepared. Next, using a negative photomask with line / space = 10 μm / 10 μm to 50 μm / 50 μm on the cured film (coating film), an ultrahigh pressure mercury lamp with ^{an i-line illuminance of 30 mW / cm 2 is used to generate 50 mJ / cm 2} ultraviolet rays. Was irradiated to carry out a photocuring reaction.

Next, the exposed cured film (coating film) was subjected to ^{a shower pressure of 1 kgf / cm 2} with a 0.04% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, ^{a spray water wash of 5 kgf / cm 2} was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 90 using a hot air dryer. This curing (post-baking) was performed at ° C. for 60 minutes to obtain a substrate with a cured film (coating film) for evaluating development characteristics.

[Development characteristic evaluation]
(Pattern adhesion)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: The cured film (coating film) is not peeled off at all Δ: Part of the cured film (coating film) is peeled off ×: Most of the cured film (coating film) is peeled off

(Pattern linearity)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: No knurling on the pattern edge part Δ: Some knurling on the pattern edge part is observed ×: Most knurling on the pattern edge part is recognized

(Pattern definition)
(Evaluation method)
The 10 to 50 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
⊚: A pattern of 10 μm or more and less than 15 μm is formed ◯: A pattern of 15 μm or more and less than 24 μm is formed Δ: A pattern of 24 μm or more and less than 50 μm is formed ×: A pattern is not formed

[Solvent resistance evaluation]
(Preparation of substrate with cured film (coating film) for solvent resistance evaluation)
The photosensitive resin composition shown in Table 1 is applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and is applied to a glass substrate at 90 ° C. for 2 minutes using a hot plate. A cured film (coating film) was prepared by prebaking. Next, a negative photomask having a line / space of 20 μm / 20 μm was placed on the cured film (coating film), and an ultrahigh-pressure mercury lamp having ^{an i-line illuminance of 30 mW / cm 2} was used to irradiate ultraviolet rays ^{of 50 mJ / cm 2.} A photocuring reaction was carried out.

Next, the exposed cured film (coating film) was ^{developed with a 0.05% potassium hydroxide solution at 25 ° C. at a shower pressure of 1 kgf / cm 2} for 60 seconds, and then washed with a spray of ^{5 kgf / cm 2.} The unexposed portion of the cured film (coating film) was removed to form a cured film pattern on the glass substrate, which was main-cured (post-baked) at 90 ° C. for 60 minutes using a hot air dryer to withstand A substrate with a cured film (coating film) for evaluation of solvent properties was obtained.

(Evaluation method)
The surface of the cured film (coating film) prepared on the glass substrate was continuously rubbed 20 times with a waste cloth immersed in PGMEA. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: No dissolution is seen on the surface of the cured film (coating film) and no scratches are made. : The surface of the cured film (coating film) is softened and most of it is scratched.

[Evaluation of optical characteristics]
(Transmittance)
(Evaluation method)
Ultraviolet visible near infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation) using a substrate with a cured film (coating film) similar to the substrate with a cured film (coating film) prepared for solvent resistance evaluation. Was used to measure the transmittance in the visible light region of 380 nm to 780 nm. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: Transmittance is 80% or more Δ: Transmittance is 70% or more and less than 80% ×: Transmittance is less than 70%

(Light scattering)
A substrate with a cured film (coating film) similar to the substrate with a cured film (coating film) prepared for solvent resistance evaluation is vertically irradiated with white light, and the transmitted scattered light is a goniophotometer "GP-1". It was measured using (manufactured by Nikka Densoku Co., Ltd.).

(Evaluation criteria: Light scattering property 1)
◯: The intensity of scattered light at 5 ° and 60 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 60 ° was more than 20% of the light scattering intensity at 5 °. △: The intensity of scattered light at 5 ° and 60 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 60 ° was 10% or more of the light scattering intensity at 5 °. 20% or less ×: When the angle of the directly transmitted light traveling straight is 0 °, the intensity of the scattered light at 5 ° and 60 ° is evaluated, and the light scattering intensity at 60 ° becomes the light scattering intensity at 5 °. Less than 10%

(Evaluation criteria: Light scattering property 2)
A: The intensity of scattered light at 60 ° and 120 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 120 ° was less than 50% of the light scattering intensity at 60 °. B: The intensity of scattered light at 60 ° and 120 ° is evaluated when the angle of the directly transmitted light traveling straight is 0 °, and the light scattering intensity at 120 ° is 50% or more of the light scattering intensity at 60 °. Less than 80% C: The intensity of scattered light at 60 ° and 120 ° when the angle of the directly transmitted light traveling straight is 0 ° is evaluated, and the light scattering intensity at 120 ° becomes the light scattering intensity at 60 °. 80% or more of

The evaluation results of the above evaluation are shown in Table 2.

As is clear from the results of Examples 1 to 6 and Comparative Examples 1 and 2, it has an alkali-soluble resin represented by the general formula (1) of the present invention and specific physical properties (refractive index, average particle size, etc.). It was found that by using a photosensitive resin composition containing hollow acrylic resin particles or silica particles, a cured film having excellent light scattering properties and capable of forming a fine pattern can be produced. Further, in the light scattering property evaluation, when the evaluation of the light scattering property 1 is ◯ and the evaluation of the light scattering property 2 is A, it indicates that the diffused transmitted light is strong and the light emitted from the light emitting element. It was also found that it is the most suitable as a layer for improving the extraction efficiency.

[Experiment 2]
The above-mentioned compounding components were blended in the proportions shown in Table 3 to prepare photosensitive resin compositions of Examples 7 to 12 and Comparative Examples 3 and 4. All the values in Table 3 represent mass%.

[evaluation]
The cured film (coating film) obtained by curing the photosensitive resin compositions of Examples 7 to 12 and Comparative Examples 3 and 4 was evaluated as follows.

(Preparation of substrate with cured film (coating film) for evaluation of development characteristics)
The photosensitive resin composition shown in Table 3 is applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and is applied to a glass substrate at 90 ° C. for 2 minutes using a hot plate. A hard film (coating film) was prepared by prebaking. Next, the exposure gap was adjusted to 100 μm, the cured film (coating film) was covered with a negative photomask of 10 to 50 μm (in 5 μm increments), and an ultra-high pressure mercury lamp ^{with an i-line illuminance of 30 mW / cm 2 was used to cover 50 mJ / cm. The} photocuring reaction was carried out by irradiating with the ultraviolet rays of 2.

Next, the exposed cured film (coating film) was subjected to ^{a shower pressure of 1 kgf / cm 2} with a 0.04% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, ^{a spray water wash of 5 kgf / cm 2} was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 230 using a hot air dryer. This curing (post-baking) was performed at ° C. for 30 minutes to obtain a substrate with a cured film (coating film) for evaluating development characteristics.

[Development characteristic evaluation]
(Pattern adhesion)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: The cured film (coating film) is not peeled off at all Δ: Part of the cured film (coating film) is peeled off ×: Most of the cured film (coating film) is peeled off

(Pattern linearity)
(Evaluation method)
The 20 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
◯: No knurling on the pattern edge part Δ: Some knurling on the pattern edge part is observed ×: Most knurling on the pattern edge part is recognized

(Pattern definition)
(Evaluation method)
The 10 to 50 μm mask pattern after the main curing (post-baking) was observed with an optical microscope. In addition, △ or more was regarded as a pass.

(Evaluation criteria)
⊚: A pattern of 10 μm or more and less than 15 μm is formed ◯: A pattern of 15 μm or more and less than 24 μm is formed Δ: A pattern of 24 μm or more and less than 50 μm is formed ×: A pattern is not formed

[Evaluation of transmittance]
(Evaluation method)
Using a substrate with a cured film (coating film) similar to the substrate with a cured film (coating film) prepared for solvent resistance evaluation, using an ultraviolet-visible near-infrared spectrophotometer "UH4150", visibility of 380 nm to 780 nm The transmittance in the light region was measured. In addition, ○ or more was regarded as a pass.

(Evaluation criteria)
◯: Transmittance is 80% or more Δ: Transmittance is 70% or more and less than 80% ×: Transmittance is less than 70%

[Evaluation of light scattering]
(Preparation of substrate with cured film (coating film) for light scattering evaluation)
The photosensitive resin composition shown in Table 3 is applied onto a glass substrate using a spin coater so that the film thickness after the heat curing treatment is 2.0 μm, and is applied to a glass substrate at 90 ° C. for 2 minutes using a hot plate. A hard film (coating film) was prepared by prebaking. Next, the photocuring reaction was carried out by irradiating ultraviolet rays ^{of 50 mJ / cm 2} with an ultra-high pressure mercury lamp having an i-line illuminance of 30 mW / cm ^{2 without covering with a negative photomask.}

Next, the exposed cured film (coating film) was subjected to ^{a shower pressure of 1 kgf / cm 2} with a 0.05% potassium hydroxide solution at 25 ° C. for 20 seconds from the development time (break time = BT) at which the pattern began to appear. After the development treatment, ^{a spray water wash of 5 kgf / cm 2} was performed to remove the unexposed portion of the cured film (coating film) to form a cured film pattern on the glass substrate, and 230 using a hot air dryer. It was finally cured (post-baked) at ° C. for 30 minutes.

(Evaluation method)
A cured film (coating film) similar to the cured film (coating film) prepared for solvent resistance evaluation was vertically irradiated with white light, and the transmitted scattered light was measured using a goniophotometer.

(Evaluation criteria: Light scattering property 1)
◯: The intensity of scattered light at 5 ° and 60 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 60 ° was more than 20% of the light scattering intensity at 5 °. △: The intensity of scattered light at 5 ° and 60 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 60 ° was 10% or more of the light scattering intensity at 5 °. 20% or less ×: When the angle of the directly transmitted light traveling straight is 0 °, the intensity of the scattered light at 5 ° and 60 ° is evaluated, and the light scattering intensity at 60 ° becomes the light scattering intensity at 5 °. Less than 10%

(Evaluation criteria: Light scattering property 2)
A: The intensity of scattered light at 60 ° and 120 ° was evaluated when the angle of the directly transmitted light traveling straight was 0 °, and the light scattering intensity at 120 ° was less than 50% of the light scattering intensity at 60 °. B: The intensity of scattered light at 60 ° and 120 ° is evaluated when the angle of the directly transmitted light traveling straight is 0 °, and the light scattering intensity at 120 ° is 50% or more of the light scattering intensity at 60 °. Less than 80% C: The intensity of scattered light at 60 ° and 120 ° when the angle of the directly transmitted light traveling straight is 0 ° is evaluated, and the light scattering intensity at 120 ° becomes the light scattering intensity at 60 °. 80% or more of

The evaluation results of the above evaluation are shown in Table 4.

As is clear from the results of Examples 7 to 12 and Comparative Examples 3 and 4, it has an alkali-soluble resin represented by the general formula (1) of the present invention and specific physical properties (refractive index, average particle size, etc.). It was found that by using a photosensitive resin composition containing hollow acrylic resin particles and silica particles, a cured film having excellent light scattering properties and capable of forming a fine pattern can be produced. Further, in the light scattering property evaluation, when the evaluation of the light scattering property 1 is ◯ and the evaluation of the light scattering property 2 is A, it indicates that the diffused transmitted light is strong and the light emitted from the light emitting element. It was also found that it is the most suitable as a layer for improving the extraction efficiency.

According to the photosensitive resin composition of the present invention, a substrate with a cured film having excellent light scattering properties can be obtained. Therefore, it is useful for, for example, a display device. That is, since the pattern can be formed by photolithography, there is an advantage that it can be formed by the existing photolithography process. Further, since the film strength can be obtained even at a low temperature, it is suitable for manufacturing a touch panel and a color filter using a substrate having low heat resistance. With regard to light scattering, it is possible to design a cured film according to the required characteristics depending on the application, and it is possible to use it as a layer for improving the light extraction efficiency of light emitted from a light emitting element, which requires an increase in the intensity of diffuse transmitted light. At the same time, it is also possible to provide a layer for improving the high diffusion / confinement efficiency of the light emitted from the light emitting element, which requires an increase in the intensity of the diffuse reflected light.

Claims (14)

(A) Unsaturated group-containing alkali-soluble resin and
(B) A photopolymerizable monomer having at least two ethylenically unsaturated bonds,
(C) Metal oxide particles or resin particles having an average particle size of 40 nm or more and 600 nm or less and a refractive index of 1.2 or more and 1.5 or less.
(D) Photopolymerization initiator and
Including
The content of the component (C) is 10% by mass or more and 70% by mass or less with respect to the total mass of the solid content.
Photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the component (C) is silica particles or hollow acrylic resin particles. The photosensitive resin composition according to claim 1 or 2, wherein the component (A) is an unsaturated group-containing alkali-soluble resin represented by the general formula (1).

(In formula (1), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, linear or branched alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups. Yes, R ₅ is a hydrogen atom or a methyl group, and X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH ₂ -,- C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl group or direct bond, Y is a tetravalent carboxylic acid residue, Z is a hydrogen atom or general, respectively. It is a substituent represented by the formula (2). However, one or more of the Zs are substituents represented by the general formula (2), and n has an average value of 1 to 20.)

(In formula (2), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.) The content of the component (A) is 25% by mass or more and 70% by mass or less with respect to the total mass of the solid content, and the content of the component (B) is 10% by mass with respect to the total mass of the solid content. The photosensitive resin composition according to any one of claims 1 to 3, which is 40% by mass or less. (E) Epoxy compound and
(F) An epoxy compound curing agent or curing accelerator as an optional component, and
Including
The photosensitivity according to any one of claims 1 to 4, wherein the total content of the component (E) and the component (F) is 5% by mass or more and 35% by mass or less with respect to the total mass of the solid content. Sex resin composition. The photosensitive resin composition according to claim 5, wherein the epoxy equivalent of the component (E) is 100 g / eq or more and 500 g / eq or less. The photosensitive resin composition according to claim 5, wherein the component (F) contains an acid anhydride. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 7. When a film is formed on a transparent substrate, the transmittance in the visible light region is 80% or more, and the angle of the direct transmitted light traveling straight when white light is irradiated perpendicularly to the transparent substrate with a cured film is 0 °. The intensity of the scattered light at 60 ° is 10% or more and less than 80% of the intensity of the scattered light at 5 ° when the angle of the straight-ahead directly transmitted light is 0 °. The cured film according to. The intensity of the scattered light at 120 ° when the angle of the directly transmitted light traveling straight when the transparent substrate with the cured film is irradiated with white light is 0 ° is the angle of the directly transmitted light traveling straight. The cured film according to claim 9, which is less than 80% of the intensity of scattered light at 60 ° when 0 °. A substrate with a cured film having the cured film according to any one of claims 8 to 10. A display device having the cured film according to any one of claims 8 to 10 or the substrate with the cured film according to claim 11. The photosensitive resin according to any one of claims 1 to 7, which is a method for producing a substrate with a cured film by forming a cured film pattern having light scattering property on a substrate having a heat resistant temperature of 150 ° C. or lower. A method for producing a substrate with a cured film, which comprises applying the composition onto a substrate, exposing it through a photomask, removing an unexposed portion by development, and heating at 150 ° C. or lower to form a predetermined cured film pattern. .. The photosensitive resin according to any one of claims 1 to 7, which is a method for producing a substrate with a cured film by forming a cured film pattern having light scattering property on a substrate having a heat resistant temperature of more than 150 ° C. A method for producing a substrate with a cured film, wherein the composition is applied onto a substrate, exposed through a photomask, an unexposed portion is removed by development, and heated at over 150 ° C. to form a predetermined cured film pattern. ..