Photosensitive resin composition and organic EL element partition wall

Abstract

The present invention reduces inhibition of light sensitization of a photosensitive resin composition containing a black dye and increases sensitivity by improving pattern forming ability. The photosensitive resin composition according to one embodiment of the present invention contains a binder resin (A), a radiation-sensitive compound (B), and a dye (C), wherein the dye (C) contains a black dye (C1) and a dye (C2) other than (C1), the dye (C2) has an absorption maximum at a wavelength of 480-550 nm in an wavelength range of 300-800 nm, and, when the absorbance of the dye (C2) at the absorption maximum wavelength is defined as Abs1 and the average absorbance of the dye (C2) at wavelengths 560-600 nm is defined as Abs2, Abs2 / Abs1 equals 0.1-1.0.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, an organic EL element partition wall, an organic EL element insulating film, and an organic EL element using the same. More specifically, the present invention relates to a photosensitive resin composition containing a black dye, an organic EL element partition wall, an organic EL element insulating film, and an organic EL element using the same.

Background Art

[0002] In display devices such as organic EL displays (OLEDs), in order to improve display characteristics, a partition wall material is used in an interval portion of a coloring pattern in a display area or an edge of a peripheral portion of the display area. In the manufacture of an organic EL display device, in order to prevent pixels of organic substances from contacting each other, first, a partition wall is formed, and pixels of organic substances are formed between the partition walls. This partition wall is generally formed by photolithography using a photosensitive resin composition and has insulating properties. Specifically, the photosensitive resin composition is applied onto a substrate using a coating device, volatile components are removed by means such as heating, then exposed through a mask, and then developed by removing unexposed portions in the case of a negative type or exposed portions in the case of a positive type with a developer such as an alkaline aqueous solution. The obtained pattern is heat-treated to form a partition wall (insulating film). Next, organic substances that emit red, green, and blue light are formed into a film between the partition walls by an inkjet method or the like to form pixels of the organic EL display device.

[0003] In this field, in recent years, due to the miniaturization of display devices and the diversification of displayed content, higher performance and higher definition of pixels have been required. For the purpose of enhancing contrast and improving visibility in a display device, attempts have been made to impart light-shielding properties to a partition wall material using a colorant. However, when the partition wall material has light-shielding properties, the photosensitive resin composition tends to have low sensitivity, and as a result, the exposure time may become longer and the productivity may decrease. Therefore, the photosensitive resin composition used for forming a partition wall material containing a colorant is required to be more sensitive.

[0004] Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-281440) describes a composition obtained by adding titanium black to a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting high light-shielding properties by heat treatment after exposure.

[0005] Patent Document 2 (Japanese Patent Application Laid-Open No. 2002-116536) describes a method for blackening a partition member using carbon black in a radiation-sensitive resin composition containing [A] an alkali-soluble resin, [B] a 1,2-quinonediazide compound, and [C] a colorant.

[0006] Patent Document 3 (Japanese Patent Application Laid-Open No. 2010-237310) describes a composition obtained by adding a thermosensitive dye to a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting light-shielding properties by heat treatment after exposure.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] In a photosensitive resin composition used for forming a colored partition member, in order to sufficiently enhance the light-shielding property of the cured film, it is necessary to use a considerable amount of a colorant. When such a large amount of colorant is used, since the radiation irradiated on the film of the photosensitive resin composition is absorbed by the colorant, the effective intensity of the radiation in the film particularly decreases at the lower part of the film (the side closer to the substrate), and the photosensitive resin composition is not sufficiently exposed (radiation inhibition), resulting in a decrease in pattern formability.

[0009] In the formation of partition walls in an organic EL element, from the viewpoint of productivity and the like, it is important that the material for forming the partition walls is highly sensitive. However, when using a black photosensitive resin composition containing a colorant, exposure failure occurs under the usually used exposure conditions. For example, it is necessary to increase the exposure time, which has been a factor in reducing productivity.

[0010] In the use of a partition wall material for an organic EL element, it is common to use ghi rays for exposure using an ultra-high pressure mercury lamp including g rays (wavelength 436 nm), h rays (wavelength 405 nm), and i rays (wavelength 365 nm). However, due to restrictions on the equipment and apparatuses of manufacturers, there is a demand for exposure using only i rays. When using only i rays for exposure, the total irradiation energy becomes small, so the reaction rate of a radiation-sensitive compound, for example, a photoacid generator, decreases, and there is a possibility of occurrence of undissolved residues of the binder resin and deterioration of pattern formability in the developing process. Therefore, it is desired to further increase the sensitivity of the photosensitive resin composition containing a colorant to increase the degree of freedom of the radiation used for exposure.

[0011] An object of the present invention is to reduce the photosensitivity inhibition of a photosensitive resin composition containing a black dye, improve the pattern formability, and increase the sensitivity.

Means for Solving the Problems

[0012] The present inventors have found that, in a photosensitive resin composition containing a black dye as a colorant, by adding a dye other than black, while ensuring the light-shielding property of the photosensitive resin composition, the content of the black dye can be reduced, and the pattern formability of the photosensitive resin composition can be improved and the sensitivity can be increased.

[0013] That is, the present invention includes the following aspects. [1] A photosensitive resin composition containing a binder resin (A), a radiation-sensitive compound (B), and a dye (C), wherein the dye (C) includes a black dye (C1) and a dye (C2) other than (C1), the dye (C2) has an absorption maximum at a wavelength of 480 to 550 nm in the wavelength range of 300 to 800 nm, and when the absorbance at the wavelength of the absorption maximum of the dye (C2) is Abs1 and the average absorbance at a wavelength of 560 to 600 nm is Abs2, Abs2 / Abs1 is 0.1 to 1.0. [2] In the absorbance curve of the photosensitive resin composition, when the average absorbance at a wavelength of 450 to 545 nm is Abs3 and the average absorbance at a wavelength of 550 to 650 nm is Abs4, Abs4 / Abs3 is 0.8 to 1.6. The photosensitive resin composition according to [1]. [3] When the absorbance at the wavelength of the absorption maximum of the dye (C2) in the wavelength range of 300 to 800 nm is 100, the absorbance of the dye (C2) at a wavelength of 365 nm is 0 to 80. The photosensitive resin composition according to any one of [1] or [2]. [4] The photosensitive resin composition contains 50 to 95% by mass of the black dye (C1) based on the total mass of the dye (C). The photosensitive resin composition according to any one of [1] to [3]. [5] The dye (C2) is a red dye. The photosensitive resin composition according to any one of [1] to [4]. [6] The photosensitive resin composition contains 5 to 35% by mass of the dye (C2) based on the total mass of the dye (C). The photosensitive resin composition according to any one of [1] to [5]. [7] The color index of the black dye (C1) is Solvent Black 7 to 47. The photosensitive resin composition according to any one of [1] to [6]. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the radiation-sensitive compound (B) is at least one photoacid generator selected from the group consisting of quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. [9] The photosensitive resin composition according to [8], containing 5 to 50 parts by mass of the photoacid generator based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C).

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the binder resin (A) has an alkali-soluble functional group.

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

[10] , containing 15 to 50 parts by mass of the dye (C) based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C).

[12] The binder resin (A) is (a) Formula (1)

Chemical formula

Chemical formula

Chemical formula

[11] , which is at least one selected from the group consisting of

[13] The binder resin (A) is (c) An alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and (d) An alkali aqueous solution-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers The photosensitive resin composition according to any one of [1] to

[11] , which is at least one selected from the group consisting of

[14] An organic EL element partition wall containing a cured product of the photosensitive resin composition according to any one of [1] to

[13] .

[15] An organic EL element insulating film containing a cured product of the photosensitive resin composition according to any one of [1] to

[13] .

[16] An organic EL element containing a cured product of the photosensitive resin composition according to any one of [1] to

[13] . [Effect of the Invention]

[0014] According to the present invention, it is possible to reduce the photosensitivity inhibition of the photosensitive resin composition containing a black dye, improve the pattern formability, and enhance the sensitivity. [Brief Description of the Drawings]

[0015]

Figure 1

Figure 2

[0016] The present invention will be described in detail below.

[0017] In the present disclosure, "alkali-soluble" and "alkali aqueous solution-soluble" mean that the photosensitive resin composition or its components, or the film or cured film of the photosensitive resin composition can be dissolved in an aqueous alkali solution, for example, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. "Alkali-soluble functional group" means a group that imparts such alkali solubility to the photosensitive resin composition or its components, or the film or cured film of the photosensitive resin composition.

[0018] In the present disclosure, the "radical polymerizable functional group" refers to one or more ethylenically unsaturated groups, and the "radical polymerizable compound" refers to a compound having one or more ethylenically unsaturated groups.

[0019] In the present disclosure, "(meth)acryl" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0020] The photosensitive resin composition of one embodiment contains a binder resin (A), a radiation-sensitive compound (B), and a dye (C). The dye (C) contains a black dye (C1) and a dye (C2) other than (C1). The dye (C2) has an absorption maximum at a wavelength of 480 to 550 nm in the wavelength range of 300 to 800 nm, and when the absorbance at the wavelength of the absorption maximum of the dye (C2) is Abs1 and the average absorbance at a wavelength of 560 to 600 nm is Abs2, Abs2 / Abs1 is 0.1 to 1.0.

[0021] [Binder resin (A)] The binder resin (A) is not particularly limited, but preferably has an alkali-soluble functional group and is alkali-soluble. The alkali-soluble functional group is not particularly limited, and examples thereof include a carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphate group, and a mercapto group. A binder resin having two or more alkali-soluble functional groups may be used.

[0022] Examples of the binder resin (A) include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenolic resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, cardo resins, derivatives of these resins, and those obtained by bonding an alkali-soluble functional group to these resins. As the binder resin (A), a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group can also be used. These resins can be used alone or in combination of two or more resins. The binder resin (A) may have a radical-polymerizable functional group. In one embodiment, the binder resin (A) has a (meth)acryloyloxy group, an allyl group, or a methallyl group as a radical-polymerizable functional group.

[0023] In one embodiment, the binder resin (A) contains at least one selected from the following resin components (a) to (k). (a) Polyalkenylphenol resin having a specific structure (b) Hydroxystyrene resin derivative having a specific structure (c) Alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group (d) Alkali aqueous solution-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers (e) Polyimide resin (f) Polyamic acid resin (g) Polybenzoxazole resin (h) Polybenzoxazole resin precursor (i) Silicone resin (j) Cyclic olefin polymer (k) Cardo resin

[0024] (a) Polyalkenylphenol resin The polyalkenylphenol resin (a) can be obtained by alkenyl etherifying the hydroxyl group of a known phenol resin and further subjecting the alkenyl ether group to a Claisen rearrangement. Among them, formula (1) [Chemical formula] A polyalkenylphenol resin having the structural unit is preferable. By containing such a resin, the developing properties of the resulting photosensitive resin composition can be improved and outgas can be reduced.

[0025] In formula (1), R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, formula (2) [Chemical formula] (In formula (2), R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and * in formula (2) represents the bonding part with the carbon atom constituting the aromatic ring.), an alkenyl group represented by, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R 1 , R 2 and R 3 is an alkenyl group represented by formula (2), Q is an alkylene group represented by -CR 4 R 5 -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring or a divalent group combining these, and R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. When two or more structural units of formula (1) are present in one molecule, the structural units of each formula (1) may be the same or different.

[0026] R 1 , R 2 and R3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by the formula (2), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and R 1 , R 2 and R 3 at least one of which is an alkenyl group represented by the formula (2). In R 1 , R 2 and R 3 of the formula (1), specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and the like. Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an ethoxy group.

[0027] In the alkenyl group represented by the formula (2), R 6 , R 7 , R 8 , R 9 , and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and the like. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group and the like. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, a naphthyl group and the like. R 6 , R 7 , R 8 , R 9 , and R 10 are each independently preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferred alkenyl groups represented by the formula (2) include an allyl group and a methallyl group from the viewpoint of reactivity, and more preferably an allyl group.

[0028] R 1 、R 2 and R 3 Among them, it is most preferable that any one of them is an allyl group or a methallyl group, and the other two are hydrogen atoms.

[0029] Q in formula (1) is an alkylene group represented by -CR 4 R 5 -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group combining these. R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, etc. Specific examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, etc. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, etc. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, a naphthyl group, etc. R 4 and R 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably both are hydrogen atoms.

[0030] Specific examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group, etc. Specific examples of the divalent organic group having an aromatic ring include a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, a 4,4-methylenediphenyl group, formula (6) [ka] A specific example of the divalent organic group having a fused alicyclic ring is a dicyclopentadienylene group.

[0031] When a polyalkenylphenol resin (a) is used as the binder resin (A), the polyalkenylphenol resin (a) is particularly preferably a polyalkenylphenol resin (a) in terms of alkali developability, outgassing, etc., where Q in formula (1) is -CH 2 -, i.e., formula (4) [ka] In the formula (4), R 1 , R 2 and R 3 is the same as in formula (1). 1 , R 2 and R 3 is a preferred R in formula (1) 1 , R 2 and R 3 is the same as:

[0032] The structural unit represented by formula (1) or formula (4) is preferably 50 to 100 mol % in the polyalkenylphenol resin (a), more preferably 70 to 100 mol %, and even more preferably 80 to 100 mol %. The structural unit represented by formula (1) or formula (4) is preferably 50 mol % or more in the polyalkenylphenol resin (a) in order to improve heat resistance. Since the phenolic hydroxyl group in the polyalkenylphenol resin (a) is ionized in the presence of a basic compound and becomes soluble in water, it is necessary that the phenolic hydroxyl group is present in a certain amount or more from the viewpoint of alkaline developability. Therefore, the polyalkenylphenol resin (a) containing the structural unit of formula (4) contains the structural unit represented by formula (4) and the structural unit represented by formula (7) [ka] It is particularly preferable that the polyalkenylphenol resin has a structural unit represented by the formula. In formula (7), R 1a , R 2a and R 3a are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferred R 1a , R 2a and R 3a are the same as the preferred R 1 , R 2 and R 3 in formula (1).

[0033] In the polyalkenylphenol resin (a) having a structural unit represented by formula (4) and a structural unit represented by formula (7), when the number of structural units represented by formula (4) is x and the number of structural units represented by formula (7) is y, 0.5 ≦ x / (x + y) < 1 and 0 < y / (x + y) ≦ 0.5, and x + y is preferably 2 to 50, more preferably 3 to 40, and even more preferably 5 to 25.

[0034] When using the polyalkenylphenol resin (a) as the binder resin (A), the preferred number average molecular weight of the polyalkenylphenol resin (a) is 500 to 5000, more preferably 800 to 3000, and even more preferably 900 to 2000. The preferred weight average molecular weight of the polyalkenylphenol resin (a) is 500 to 30000, more preferably 3000 to 25000, and even more preferably 5000 to 20000. If the number average molecular weight is 500 or more, or the weight average molecular weight is 500 or more, the alkali developing rate is appropriate and the dissolution rate difference between the exposed part and the unexposed part is sufficient, so the pattern resolution is good. If the number average molecular weight is 5000 or less, or the weight average molecular weight is 30000 or less, the alkali developability is good. In the present disclosure, the number average molecular weight and the weight average molecular weight of the binder resin (A) mean the standard polystyrene conversion values measured by gel permeation chromatography (GPC).

[0035] (b) Hydroxystyrene resin derivative As the binder resin (A), the hydroxystyrene resin derivative (b) having the structural unit of formula (3)

Chemical formula

[0036] In formula (3), R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is an integer of 1 to 4, b is an integer of 1 to 4, a + b is in the range of 2 to 5, and R 12 is at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and a propyl group.

[0037] When using the hydroxystyrene resin derivative (b) as the binder resin (A), from the viewpoints of alkali developability and outgas, a copolymer having the structural unit represented by formula (3) and the structural unit represented by formula (5)

Chemical formula

[0038] In formula (5), R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c is an integer of 1 to 5.

[0039] The hydroxy polystyrene resin derivative (b) having a structural unit represented by the formula (3), and the hydroxy polystyrene resin derivative (b) having a structural unit represented by the formula (3) and a structural unit represented by the formula (5) can be obtained, for example, by reacting formaldehyde with a part of a polymer or copolymer obtained by polymerizing alone or two or more of aromatic vinyl compounds having a phenolic hydroxyl group such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol, etc. by a known method, or further reacting with an alcohol by a known method, for example, the method described in JP-A-2013-151705.

[0040] As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene or m-hydroxystyrene is preferably used.

[0041] When using the hydroxy polystyrene resin derivative (b) as the binder resin (A), the preferred number average molecular weight of the hydroxy polystyrene resin derivative (b) is from 1000 to 20000, more preferably from 3000 to 10000, and even more preferably from 4000 to 9000. The preferred weight average molecular weight of the hydroxy polystyrene resin derivative (b) is from 1000 to 100000, more preferably from 5000 to 75000, and even more preferably from 10000 to 50000. If the number average molecular weight is 1000 or more, or the weight average molecular weight is 1000 or more, it is suitable as a resin of a photosensitive material because of appropriate alkali solubility, and if the number average molecular weight is 20000 or less, or the weight average molecular weight is 100000 or less, the coating property and developability are good.

[0042] (c) An alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group As the binder resin (A), an alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group can also be used. Such an alkali aqueous solution-soluble resin (c) can be obtained, for example, by reacting an epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as an "epoxy compound") with a carboxy group of a hydroxybenzoic acid compound. Since the alkali aqueous solution-soluble resin (c) has an epoxy group, crosslinking can be formed by reaction with a phenolic hydroxyl group during heating, and the chemical resistance, heat resistance, etc. of the film can be improved. The phenolic hydroxyl group contributes to the solubility in the alkali aqueous solution during development.

[0043] An example of a reaction in which one of the epoxy groups of the epoxy compound reacts with the carboxy group of the hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group is shown in the following Reaction Formula 1.

Chemical formula

[0044] Examples of the compound having at least two epoxy groups in one molecule include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, etc. These epoxy compounds only need to have two or more epoxy groups in one molecule, and may be used alone or in combination of two or more. Since these compounds are thermosetting, as common knowledge of those skilled in the art, their structures cannot be uniquely described due to differences such as the presence or absence of epoxy groups, the types of functional groups, and the degree of polymerization. An example of the structure of a novolak type epoxy resin is shown in Formula (9). In Formula (9), for example, R 14 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a hydroxyl group, and m is an integer of 1 to 50.

Chemical formula

[0045] Examples of the phenol novolak type epoxy resin include EPLICLON (registered trademark) N-770 (manufactured by DIC Corporation), jER (registered trademark)-152 (manufactured by Mitsubishi Chemical Corporation), and the like. Examples of the cresol novolak type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation), EOCN (registered trademark)-102S (manufactured by Nippon Kayaku Co., Ltd.), and the like. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), YD-128 (trade name, manufactured by Nippon Steel Chemical & Material Co., Ltd.), bisphenol F type epoxy resins such as jER (registered trademark) 806 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (trade name, manufactured by Nippon Steel Chemical & Material Co., Ltd.), and the like. Examples of the biphenol type epoxy resin include jER (registered trademark) YX-4000, jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation), and the like. Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (trade name, manufactured by DIC Corporation), and the like. Examples of the alicyclic epoxy resin include EHPE (registered trademark)-3150 (manufactured by Daicel Chemical Industries, Ltd.), and the like. Examples of the heterocyclic epoxy resin include TEPIC (registered trademark), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), and the like.

[0046] It is preferable that the compound having at least two epoxy groups in one molecule is a cresol novolak type epoxy resin. The photosensitive resin composition containing the alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group derived from the cresol novolak type epoxy resin is excellent in pattern formability, easy to adjust the alkali solubility, and has little outgas.

[0047] The hydroxybenzoic acid compound is a compound in which at least one of the 2- to 6-positions of benzoic acid is substituted with a hydroxyl group, and examples thereof include salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, etc. Among them, the dihydroxybenzoic acid compound is preferable in terms of enhancing alkali developability. These hydroxybenzoic acid compounds may be used alone or in combination of two or more.

[0048] In one embodiment, the alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and has the formula (8)

Chemical formula

[0049] In the method for obtaining the alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound, 0.2 to 1.0 equivalent of the hydroxybenzoic acid compound can be used with respect to 1 equivalent of the epoxy group of the epoxy compound, preferably 0.3 to 0.9 equivalent, and more preferably 0.4 to 0.8 equivalent. If the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and if it is 1.0 equivalent or less, an increase in molecular weight due to side reactions can be suppressed.

[0050] A catalyst may be used to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of the catalyst used can be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture composed of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature can be 60 to 150 °C, and the reaction time can be 3 to 30 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, zirconium octanoate, and the like.

[0051] The number average molecular weight of the alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and even more preferably 1000 to 5000. If the number average molecular weight is 500 or more, the alkali solubility is appropriate and it is good as a resin of the photosensitive material. If it is 8000 or less, the coating property and developability are good.

[0052] (d) An alkali aqueous solution-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers As the binder resin (A), an alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers can be used. Examples of the alkali-soluble functional group include a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group, and the like. Examples of the polymerizable functional group of the polymerizable monomer include a radical polymerizable functional group, such as CH 2 =CH-, CH 2 =C(CH 3 )-, CH 2 =CHCO-, CH 2 =C(CH 3 )CO-, -OC-CH=CH-CO-, and the like.

[0053] The alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers can be produced, for example, by radical polymerization of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers. After synthesizing the copolymer by radical polymerization, a derivative having an alkali-soluble functional group may be used. Examples of the polymerizable monomer having an alkali-soluble functional group include 4-hydroxystyrene, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, β-styryl(meth)acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, 4-hydroxyphenyl maleimide, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 6-maleimidohexanoic acid, and the like. Examples of other polymerizable monomers include styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene; acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; (meth)acrylic acid esters such as alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, isobornyl (meth)acrylate; maleic acid derivatives such as maleic anhydride, maleic acid monoester; N-substituted maleimides such as phenyl maleimide, cyclohexyl maleimide. From the viewpoint of heat resistance and the like, the alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers preferably has one or more cyclic structures such as an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure.

[0054] As the polymerizable monomer having an alkali-soluble functional group, the structural unit represented by formula (10)

Chemical formula

[0055] As other polymerizable monomers, for example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene; acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, isobornyl (meth)acrylate and other (meth)acrylic acid esters; maleic anhydride, maleic acid monoester and other maleic acid derivatives; N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide and the like. Among them, the polymerizable monomer that forms the structural unit represented by formula (11)

Chemical formula

[0056] In one embodiment, an alkali-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers has the formula (10)

Chemical formula

Chemical formula

[0057] It is particularly preferred to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having an alkali-soluble functional group and phenylmaleimide or cyclohexylmaleimide as the other polymerizable monomer. By using a resin obtained by radically polymerizing these polymerizable monomers, the shape retention and developability can be improved, and outgassing can also be reduced.

[0058] When producing an alkali-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers by radical polymerization, the polymerization initiator is not limited to the following, but 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN) and other azo polymerization initiators, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and other peroxide polymerization initiators with a 10-hour half-life temperature of 100 to 170 °C, or peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, tert-butylperoxypivalate can be used. The amount of the polymerization initiator used is generally preferably 0.01 parts by mass or more, 0.05 parts by mass or more or 0.5 parts by mass or more, and 40 parts by mass or less, 20 parts by mass or less or 15 parts by mass or less with respect to 100 parts by mass of the mixture of the polymerizable monomers.

[0059] A RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator. As the RAFT agent, thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, and xanthates can be used, although not limited to the following. The RAFT agent can be used in the range of 0.005 to 20 parts by mass, and preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomers.

[0060] The weight average molecular weight (Mw) of the alkali-soluble copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers can be from 3,000 to 80,000, preferably from 4,000 to 70,000, and more preferably from 5,000 to 60,000. The number average molecular weight (Mn) can be from 1,000 to 30,000, preferably from 1,500 to 25,000, and more preferably from 2,000 to 20,000. The polydispersity (Mw / Mn) can be from 1.0 to 3.5, preferably from 1.1 to 3.0, and more preferably from 1.2 to 2.8. By setting the weight average molecular weight, number average molecular weight, and polydispersity within the above ranges, a photosensitive resin composition excellent in alkali solubility and developability can be obtained.

[0061] In the present disclosure, when the alkali aqueous solution-soluble copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers also corresponds to the hydroxystyrene resin derivative (b), it shall be treated as the alkali aqueous solution-soluble copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers. When the alkali aqueous solution-soluble copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers also corresponds to the alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group, it shall be treated as the alkali aqueous solution-soluble copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers. That is, the hydroxystyrene resin derivative (b) and the alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group shall exclude those corresponding to the alkali aqueous solution-soluble copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers.

[0062] (e) Polyimide resin, (f) Polyamic acid resin, (g) Polybenzoxazole resin, (h) Polybenzoxazole resin precursor In one embodiment, the binder resin (A) is at least one selected from a polyimide resin (e), a polyamic acid resin (f), a polybenzoxazole resin (g), and a polybenzoxazole resin precursor (h). The polyamic acid resin (f) becomes a resin having a polyimide structure by dehydration ring closure. The polybenzoxazole resin precursor (h) becomes a polybenzoxazole resin (g) by dehydration ring closure.

[0063] The polyimide resin (e) has a structural unit represented by formula (12). The polyamic acid resin (f) and the polybenzoxazole resin precursor (h) have a structural unit represented by formula (13). The polybenzoxazole resin (g) has a structural unit represented by formula (14). The polyimide resin (e) may have both the structural unit represented by formula (12) and the structural unit represented by formula (13), and the polybenzoxazole resin (g) may have both the structural unit represented by formula (14) and the structural unit represented by formula (13).

[0064]

Chemical formula

[0065] In formula (12), R 19 is a 4- to 10-valent organic group, R 20 is a 2- to 8-valent organic group, R 21 and R 22 are each independently a hydroxyl group, a carboxy group, a sulfo group, or a mercapto group, and f and g are each independently an integer of 0 to 6.

[0066]

Chemical formula

[0067] In formula (13), R 23 is a 2- to 8-valent organic group, R 24 is a 2- to 8-valent organic group, R 25 and R 26is independently a hydroxyl group, a sulfo group, a mercapto group, or -COOR 27 wherein R 27 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and h and i are each independently an integer of 0 to 6, provided that h + i > 0. In the case of the polyamic acid resin (f), h is an integer of 1 or more, and at least one of R 25 is -COOR 27 In the case of the polybenzoxazole resin precursor (h), i is an integer of 1 or more, and at least one of R 26 is a phenolic hydroxyl group.

[0068]

Chemical formula

[0069] In formula (14), R 28 is a divalent to octavalent organic group, R 29 is a divalent to octavalent organic group, and R 30 and R 31 are each independently a hydroxyl group, a carboxy group, a sulfo group or a mercapto group, and j and k are each independently an integer of 0 to 6.

[0070] R 19 - (R 21 ) f in formula (12) represents the residue of an acid dianhydride. R 19 is a tetravalent to decavalent organic group, and is preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.

[0071] Examples of the dianhydride include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and combinations of two or more thereof.

[0072] R of formula (13) 23 -(R 25 ) h and R of formula (14) 28 -(R 30 ) j each represent a residue of an acid. R 23 and R 28 are each independently an organic group having a valence of 2 to 8, preferably an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cycloaliphatic group.

[0073] Examples of the acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid; aromatic tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid; aromatic tetracarboxylic acids such as pyromellitic acid, 3,3’,4,4’-biphenyltetracarboxylic acid, 2,3,3’,4’-biphenyltetracarboxylic acid, 2,2’,3,3’-biphenyltetracarboxylic acid, 3,3’,4,4’-benzophenone tetracarboxylic acid, 2,2’,3,3’-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid; aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid, and combinations of two or more of these. In the above tricarboxylic acids and tetracarboxylic acids, one or two carboxy groups correspond to R in formula (13) 25 or R in formula (14) 30 . These acids may be in the form of esters or acid anhydrides.

[0074] R in formula (12) 20 -(R 22 ) g , R in formula (13) 24 -(R 26 ) i , and R in formula (14) 29 -(R 31 ) k each represent the residue of a diamine. R20 , R 24 and R 29 are each independently an organic group having a valence of 2 to 8, and are preferably an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cycloaliphatic group.

[0075] R in formula (12) 20 , and as the diamine corresponding to R in formula (13) for the polyamic acid resin (f) 24 , for example, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene and other aromatic diamines, or compounds in which at least one hydrogen atom of the aromatic ring of these aromatic diamines is substituted with an alkyl group or a halogen atom; cyclohexyldiamine, methylenebiscyclohexylamine and other aliphatic diamines, and combinations of two or more of these are exemplified.

[0076] R in formula (13) for the polybenzoxazole resin precursor (h) 24 , and as the diamine corresponding to R in formula (14) 29 , for example, bisaminophenol compounds having a phenolic hydroxyl group in the ortho position with respect to the amino group on the aromatic ring of the above aromatic diamines, and combinations of two or more of these are exemplified.

[0077] The polyimide resin (e), polyamic acid resin (f), polybenzoxazole resin (g), and polybenzoxazole resin precursor (h) may have an acidic group at the main chain terminal by being capped at their terminals with a monoamine, acid anhydride, acid chloride, monocarboxylic acid, etc. having an acidic group.

[0078] The polyamic acid resin (f) can be synthesized, for example, by a method of reacting a tetracarboxylic dianhydride with a diamine, a method of producing a diester from a tetracarboxylic dianhydride and an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, a method of producing a diester from a tetracarboxylic dianhydride and an alcohol, acid chlorinating the remaining dicarboxylic acid, and then reacting the obtained intermediate with a diamine.

[0079] The polybenzoxazole resin precursor (h) can be synthesized, for example, by subjecting a bisaminophenol compound and a polyvalent carboxylic acid such as a dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid to a condensation reaction. Specifically, a method of reacting an intermediate obtained by reacting a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) with a polyvalent carboxylic acid with a bisaminophenol compound, a method of dropping a dicarboxylic acid dichloride solution into a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added, etc. can be mentioned.

[0080] The polyimide resin (e) can be synthesized, for example, by subjecting the polyamic acid resin (f) obtained by the above method to heat or dehydration ring closure by chemical treatment with an acid or a base.

[0081] The polybenzoxazole resin (g) can be synthesized, for example, by subjecting the polybenzoxazole resin precursor (h) obtained by the above method to heat or dehydration ring closure by chemical treatment with an acid or a base.

[0082] The number average molecular weight of the polyimide resin (e), polyamic acid resin (f), polybenzoxazole resin (g), and polybenzoxazole resin precursor (h) is preferably from 500 to 8000, more preferably from 800 to 6000, and even more preferably from 1000 to 5000. When the number average molecular weight is 500 or more, the alkali solubility is appropriate and it is good as a resin for a photosensitive material. When it is 8000 or less, the coating property and developability are good.

[0083] (i) silicone resin In one embodiment, the binder resin (A) contains a silicone resin (i). The silicone resin (i) can be synthesized by hydrolytic condensation of at least one compound selected from the organosilane represented by the formula (15) and the organosilane represented by the formula (16). By using the organosilanes represented by the formula (15) and the formula (16), a photosensitive resin composition excellent in sensitivity and resolution can be obtained.

[0084] The organosilane represented by the formula (15) is shown below. [Chemical formula]

[0085] In the formula (15), R 32 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and R 33 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and p is an integer of 0 to 3. When p is 2 or more, the plurality of R 32 may be the same or different from each other. When p is 2 or less, the plurality of R 33 may be the same or different from each other.

[0086] Examples of the organosilane represented by the formula (15) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,(4-Epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropionic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acephenanthrylyltrimethoxysilane and other trifunctional silanes; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, di(1-naphthyl)diethoxysilane and other bifunctional silanes; trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane and other monofunctional silanes, and combinations of two or more of these.,

[0087] The organosilane represented by formula (16) is shown below., [Chemical formula]

[0088] In formula (16), R 34 ~R 37 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and n is in the range of 2 to 8. When n is 2 or more, a plurality of R 35 and R 36 may be the same or different from each other.,

[0089] Specific examples of the organosilane represented by formula (16) include Methyl Silicate 51 manufactured by Fuso Chemical Industry Co., Ltd. (R 34 ~R 37 are methyl groups, n is on average 4), M Silicate 51 manufactured by Tama Chemical Industry Co., Ltd. (R 34 ~R 37 are methyl groups, n is on average 3 - 5), Silicate 40 (R 34 ~R 37 are ethyl groups, n is on average 4 - 6), Silicate 45 (R 34 ~R 37 are ethyl groups, n is on average 6 - 8), Methyl Silicate 51 manufactured by Colcoat Co., Ltd. (R 34 ~R 37 are methyl groups, n is on average 4), Methyl Silicate 53A (R 34 ~R 37 are methyl groups, n is on average 7), Ethyl Silicate 40 (R 34 ~R 37 are ethyl groups, n is on average 5), etc. Two or more of these can also be used in combination.

[0090] The silicone resin (i) can be synthesized by hydrolyzing and partially condensing the organosilanes represented by formula (15) and formula (16). Due to partial condensation, residual silanol groups exist in the silicone resin (i). Hydrolysis and partial condensation include, for example, methods of adding a solvent, water, a catalyst, etc. to the organosilane mixture as necessary and heating and stirring at 50°C to 150°C for about 0.5 to 100 hours. As necessary, hydrolysis by-products (alcohols such as methanol) or condensation by-products (water) may be distilled off.

[0091] As the catalyst, an acid catalyst or a base catalyst is preferably used. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or its anhydride, ion exchange resin, and the like. Examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilane having an amino group, ion exchange resin, and the like. The catalyst may be removed by washing with water, treatment with an ion exchange resin, or a combination thereof, as necessary, after hydrolysis and partial condensation. By removing the catalyst, the storage stability of the photosensitive resin composition can be enhanced.

[0092] The weight average molecular weight (Mw) of the silicone resin (i) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000. If the weight average molecular weight is 1,000 or more, the film-forming property can be improved, and if it is 100,000 or less, the alkali developability is good.

[0093] (j) Cyclic olefin polymer In one embodiment, the binder resin (A) contains a cyclic olefin polymer (j). The cyclic olefin polymer (j) is a homopolymer or copolymer of a cyclic olefin monomer having an alicyclic structure and an ethylenically unsaturated double bond. The cyclic olefin polymer (j) may have a structural unit derived from a monomer other than the cyclic olefin monomer.

[0094] Examples of the monomer constituting the cyclic olefin polymer (j) include cyclic olefin monomers having a protic polar group, cyclic olefin monomers having a polar group other than a protic polar group, cyclic olefin monomers having no polar group, and monomers other than cyclic olefins. Monomers other than cyclic olefins may or may not have a protic polar group or other polar groups, and may or may not have a polar group.

[0095] Examples of the cyclic olefin monomer having a protic polar group include 5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo[2.2.1]hept-2-ene, 8-hydroxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene and other carboxy group-containing cyclic olefins; 5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 5-methyl-5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 8-(4-hydroxyphenyl)tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-methyl-8-(4-hydroxyphenyl)tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene and other hydroxy group-containing cyclic olefins, and combinations of two or more of these may be mentioned.

[0096] Examples of the cyclic olefin monomer having a polar group other than protic include 5-acetoxybicyclo[2.2.1]hept-2-ene, 5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 8-acetoxytetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-methoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, 8-ethoxycarbonyltetracyclo[4.4.0.1 2,5 .17,10 Dodeca-3-ene, 8-n-propoxycarbonyltetracyclo[4.4.0.11 2,5 .1 7,10 Dodeca-3-ene, 8-isopropoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-n-butoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-methyl-8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1 2,5 .1 7,10 Cyclic olefins having an ester group such as dodeca-3-ene; cyclic olefins having an N-substituted imide group such as N-phenyl-(5-norbornene-2,3-dicarboxyimide); 8-cyanotetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-methyl-8-cyanotetracyclo[4.4.0.1 2,5 .1 7,10 Cyclic olefins having a cyano group such as dodeca-3-ene, 5-cyanobicyclo[2.2.1]hept-2-ene; 8-chlorotetracyclo[4.4.0.1 2,5.1 7,10 Dodeca-3-ene, 8-methyl-8-chlorotetracyclo[4.4.0.1 2,5 .1 7,10 Cyclic olefins having halogen atoms such as dodeca-3-ene, and combinations of two or more of these may be mentioned.

[0097] Examples of the cyclic olefin monomer having no polar group include bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 2,5 Deca-3,7-diene, tetracyclo[8.4.0.1 11,14 .0 3,7 Pentadeca-3,5,7,12,11-pentaene, tetracyclo[4.4.0.1 2,5 .1 7,10 Deca-3-ene, 8-methyl-tetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-ethyl-tetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-methylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-vinyl-tetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 Dodeca-3-ene, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13Pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 dodeca-3-ene, tetracyclo[9.2.1.0 2,10 .0 3,8 tetradeca-3,5,7,12-tetraene, pentacyclo[7.4.0.1 3,6 .1 10,13 .0 2,7 pentadeca-4,11-diene, pentacyclo[9.2.1.14,7.0 2,10 .0 3,8 pentadeca-5,12-diene and the like, and combinations of two or more of these may be mentioned.

[0098] Specific examples of monomers other than cyclic olefins include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; chain olefins such as non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and combinations of two or more of these may be mentioned.

[0099] The cyclic olefin polymer (j) can be synthesized by polymerizing the above monomers by ring-opening polymerization or addition polymerization. As the polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium, osmium, or a combination of two or more of these are preferably used. The cyclic olefin polymer may be subjected to a hydrogenation treatment. As the hydrogenation catalyst, those generally used for the hydrogenation of olefin compounds can be used, and examples include Ziegler-type homogeneous catalysts, noble metal complex catalysts, and supported noble metal catalysts.

[0100] The weight average molecular weight (Mw) of the cyclic olefin polymer (j) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000. If the weight average molecular weight is 1,000 or more, the film-forming property can be improved, and if it is 100,000 or less, the alkali developability is good.

[0101] (k) Cardo resin In one embodiment, the binder resin (A) contains a cardo resin (k). The cardo resin (k) has a cardo structure, that is, a skeletal structure in which two other cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure. Examples of the skeletal structure in which two other cyclic structures are bonded to the quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and a fluorene skeleton having an acrylic group. An example of the cardo structure is one in which a benzene ring is bonded to a fluorene ring.

[0102] The cald resin (k) can be synthesized by polymerizing monomers through the reaction of functional groups of monomers having a cald structure. Examples of the polymerization method of monomers having a cald structure include ring-opening polymerization method, addition polymerization method, etc. Examples of monomers having a cald structure include cald structure-containing bisphenol compounds such as bis(glycidyloxyphenyl)fluorene type epoxy resin, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene; 9,9-bis(cyanoalkyl)fluorene compounds such as 9,9-bis(cyanomethyl)fluorene; 9,9-bis(aminoalkyl)fluorene compounds such as 9,9-bis(3-aminopropyl)fluorene, etc., and combinations of two or more of these. The cald resin (k) may be a copolymer of a monomer having a cald structure and other copolymerizable monomers.

[0103] The weight average molecular weight (Mw) of the cald resin (k) is preferably from 1000 to 100000, more preferably from 1000 to 50000. If the weight average molecular weight is 1000 or more, the film-forming property can be improved, and if it is 100000 or less, the alkali developability is good.

[0104] In one embodiment, the binder resin (A) includes phenolic resins such as phenol novolak resin, cresol novolak resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, phenol-dicyclopentadiene copolymer resin, or derivatives thereof. The preferred number average molecular weight when using a phenolic resin as the binder resin (A) varies depending on the resin structure, but generally it is from 100 to 50000, more preferably from 500 to 30000, and still more preferably from 800 to 10000. If the number average molecular weight is 100 or more, the alkali development rate is appropriate and the dissolution rate difference between the exposed part and the unexposed part is sufficient, so the pattern resolution is good, and if it is 50000 or less, the alkali developability is good.

[0105] The binder resin (A) may be used alone as one type of resin, or two or more types of resins may be used in combination.

[0106] The content of the binder resin (A) in the photosensitive resin composition can be 5 to 60 parts by mass, preferably 10 to 55 parts by mass, more preferably 10 to 50 parts by mass, based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C). If the content of the binder resin (A) is 5 parts by mass or more based on 100 parts by mass in total, the residual film ratio, heat resistance, sensitivity, etc. are appropriate. If the content of the binder resin (A) is 60 parts by mass or less based on 100 parts by mass in total, the optical density (OD value) of the film after curing can be 1 or more, for example, 1 or more per 1 μm of film thickness, and the light-shielding property can be maintained even after curing.

[0107] The binder resin (A) is preferably at least one selected from the resin components (a) to (k), more preferably at least one selected from the resin components (a) to (d), and still more preferably at least one selected from the resin components (c) and (d). In another preferred embodiment, the binder resin (A) is at least one selected from (a), (b), and (c).

[0108] When including a plurality of the resin components (a) to (k), any combination is possible. Preferably, it includes at least two selected from the resin components (a) to (d), more preferably at least two selected from the resin components (a), (c), and (d), and still more preferably includes the resin components (c) and (d).

[0109] The total amount of at least one resin component selected from (a) to (d) in the binder resin (A) is preferably 0.5% by mass or more, more preferably 50% by mass or more, and still more preferably 88% by mass or more. If the total amount of at least one resin component selected from (a) to (d) in the binder resin (A) is 0.5% by mass or more, the heat resistance of the resin composition is good.

[0110] Four types of resin components (a) to (d) may be used in combination. When the four types are used in combination, the proportion of the polyalkenylphenol resin (a) in the binder resin (A) is 5 to 50% by mass, the proportion of the hydroxystyrene resin derivative (b) is 5 to 30% by mass, the proportion of the alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group is 10 to 80% by mass, and the proportion of the alkali aqueous solution-soluble copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers is preferably 10 to 80% by mass.

[0111] [Radiation-sensitive compound (B)] As the radiation-sensitive compound (B), a photoacid generator, a photobase generator, or a photoinitiator can be used. A photoacid generator is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, γ-rays, or electron beams. Since a photoacid generator increases the solubility of the irradiated portion in an alkali aqueous solution, it can be used in a positive-type photosensitive resin composition in which that portion dissolves. A photobase generator is a compound that generates a base when irradiated with radiation. Since a photobase generator decreases the solubility of the irradiated portion in an alkali aqueous solution, it can be used in a negative-type photosensitive resin composition in which that portion becomes insoluble. A photoinitiator is a compound that generates radicals when irradiated with radiation. When the photosensitive resin composition contains a binder resin having a radical-polymerizable functional group or a radical-polymerizable compound, a photoinitiator can be used in a negative-type photosensitive resin composition in which the radical polymerization of the radical-polymerizable functional group of the binder resin or the radical-polymerizable compound in the irradiated portion proceeds, and a polymer insoluble in an alkali aqueous solution is formed in that portion.

[0112] In terms of being able to obtain a high-sensitivity and high-resolution pattern, it is preferable that the radiation-sensitive compound (B) is a photoacid generator. As the photoacid generator, at least one selected from the group consisting of quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts can be used. In one embodiment, the photoacid generator is a compound or salt having high sensitivity to i-line (365 nm).

[0113] It is preferable to use a quinonediazide compound as the photoacid generator. Examples of the quinonediazide compound include those in which the sulfonic acid of quinonediazide is ester-bonded to a polyhydroxy compound, those in which the sulfonic acid of quinonediazide is sulfonamide-bonded to a polyamino compound, and those in which the sulfonic acid of quinonediazide is ester-bonded or sulfonamide-bonded to a polyhydroxy polyamino compound. From the viewpoint of the contrast between the exposed portion and the unexposed portion, it is preferable that 20 mol% or more of the entire functional group of the polyhydroxy compound or polyamino compound is substituted with quinonediazide.

[0114] Examples of the polyhydroxy compound include, but are not limited to, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above are trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

[0115] Examples of the polyamino compound include, but are not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, etc.

[0116] Examples of the polyhydroxy polyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

[0117] The quinonediazide compound is preferably a 1,2-naphthoquinonediazide-4-sulfonic acid ester or a 1,2-naphthoquinonediazide-5-sulfonic acid ester of a polyhydroxy compound, and more preferably a 1,2-naphthoquinonediazide-4-sulfonic acid ester.

[0118] When the quinonediazide compound is irradiated with ultraviolet light or the like, a carboxy group is generated through the reaction shown in the following Reaction Formula 2. The generation of the carboxy group makes the exposed portion (film) soluble in an alkaline aqueous solution, and alkali developability occurs in that portion.

[0119] [Chemical formula]

[0120] When the radiation-sensitive compound (B) is a photoacid generator, the content of the photoacid generator in the photosensitive resin composition can be 5 to 50 parts by mass, preferably 10 to 45 parts by mass, and more preferably 15 to 40 parts by mass based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C). When the content of the photoacid generator is 5 parts by mass or more based on 100 parts by mass in total, the alkali developability is good, and when it is 50 parts by mass or less, a decrease in the film due to heating at 300°C or higher can be suppressed.

[0121] A photobase generator may be used as the radiation-sensitive compound (B). As the photobase generator, at least one selected from the group consisting of amide compounds and ammonium salts can be used. In one embodiment, the photobase generator is a compound or salt highly sensitive to i-line (365 nm).

[0122] Examples of the amide compound include 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 9-anthrylmethyl N,N-dimethylcarbamate, 1-(anthraquinon-2-yl)ethyl imidazole carboxylate, (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, and the like. Examples of the ammonium salt include 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidinium 2-(3-benzoylphenyl)propionate, (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexylamino)methanaminium tetrakis(3-fluorophenyl)borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate, and the like.

[0123] When the radiation-sensitive compound (B) is a photo-base generator, the content of the photo-base generator in the photosensitive resin composition can be 0.1 to 25 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C). When the content of the photo-base generator is 0.1 part by mass or more based on 100 parts by mass in total, the alkali developability is good, and when it is 20 parts by mass or less, the reduction of the film due to heating at 300°C or higher can be suppressed.

[0124] As the radiation-sensitive compound (B), a photopolymerization initiator may be used. As the photopolymerization initiator, at least one selected from the group consisting of benzyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine oxide compounds, oxime ester compounds, acridine compounds, benzophenone compounds, acetophenone compounds, aromatic ketoester compounds, and benzoic acid ester compounds can be used. In one embodiment, the photopolymerization initiator is a compound highly sensitive to i-line (365 nm). Since the sensitivity during exposure is high, the photopolymerization initiator is preferably an α-hydroxy ketone compound, an α-amino ketone compound, an acylphosphine oxide compound, an oxime ester compound, an acridine compound, or a benzophenone compound, and more preferably an α-amino ketone compound, an acylphosphine oxide compound, or an oxime ester compound.

[0125] Examples of the benzyl ketal compound include 2,2-dimethoxy-1,2-diphenylethane-1-one. Examples of the α-hydroxy ketone compound include 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, or 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one. Examples of the α-amino ketone compound include 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propan-1-one, 2-dimethylamino-1-(4-ethylphenyl)-2-methylpropan-1-one, 2-dimethylamino-1-(4-isopropylphenyl)-2-methylpropan-1-one, 1-(4-butylphenyl)-2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1-(4-methoxyphenyl)-2-methylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylthiophenyl)propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butan-1-one, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholyl)phenyl]-1-butanone. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.Examples of the oxime ester compounds include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, and 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime. Examples of the acridine compounds include 1,7-bis(acridin-9-yl)-n-heptane. Examples of the benzophenone compounds include benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone, alkylated benzophenone, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 4-methylbenzophenone, dibenzyl ketone, or fluorenone. Examples of the acetophenone compounds include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-tert-butyldichloroacetophenone, benzalacetophenone, or 4-azidobenzalacetophenone. Examples of the aromatic ketoester compounds include methyl 2-phenyl-2-oxyacetate. Examples of the benzoic acid ester compounds include ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, or methyl 2-benzoylbenzoate.

[0126] When the binder resin (A) has a cationic polymerizable group such as an epoxy group, a cationic photopolymerization initiator that generates a cationic species or a Lewis acid by light can be used as the photopolymerization initiator. Examples of the cationic photopolymerization initiator include those in which the cationic part is a sulfonium such as triphenylsulfonium, diphenyl-4-(phenylthio)phenylsulfonium, an iodonium such as diphenyliodonium, bis(dodecylphenyl)iodonium, a diazonium such as phenyldiazonium, a pyridinium such as 1-benzyl-2-cyanopyridinium, 1-(naphthylmethyl)-2-cyanopyridinium, an Fe cation such as (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe, and the anionic part is BF 4 - 、PF 6 - 、SbF 6 - 、[BX 4 - (X is a phenyl group substituted with at least two or more fluorine atoms or a trifluoromethyl group), and the like. Examples of the onium salt include those composed of the above.

[0127] When the radiation-sensitive compound (B) is a photopolymerization initiator, the content of the photopolymerization initiator in the photosensitive resin composition can be 0.1 to 25 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C). When the content of the photopolymerization initiator is 0.1 part by mass or more based on the above total 100 parts by mass, the alkali developability is good, and when it is 20 parts by mass or less, the reduction of the film due to heating at 300°C or higher can be suppressed.

[0128] When the radiation-sensitive compound (B) is a photopolymerization initiator, the photosensitive resin composition may further contain a radically polymerizable compound. Resins and compounds having a plurality of ethylenically unsaturated groups as the radically polymerizable compound can crosslink the film to increase its hardness.

[0129] ​From the viewpoints of reactivity during exposure, hardness of the film, heat resistance, etc., as the radical polymerizable compound, it is preferable to use a compound having a plurality of (meth)acrylic groups. Such compounds include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9 - bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9 - bis[4-(3-(meth)acryloxypropoxy)phenyl]fluorene, 9,9 - bis(4-(meth)acryloxyphenyl)fluorene, or their acid - modified products, ethylene oxide - modified products, or propylene oxide - modified products may be mentioned.,

[0130] The content of the radical - polymerizable compound in the photosensitive resin composition can be 15 parts by mass to 65 parts by mass, preferably 20 parts by mass to 60 parts by mass, and more preferably 25 parts by mass to 50 parts by mass with respect to 100 parts by mass of the binder resin (A). When the content of the radical - polymerizable compound is within the above range, the alkali developability is good, and the heat resistance of the cured film can be improved.,

[0131] [Dye (C)] The dye (C) contains a black dye (C1) and a dye (C2) other than (C1). The dye (C2) has an absorption maximum at a wavelength of 480 to 550 nm in the wavelength range of 300 to 800 nm, and when the absorbance at the absorption maximum wavelength of the dye (C2) is Abs1 and the average absorbance at a wavelength of 560 to 600 nm is Abs2, Abs2 / Abs1 is 0.1 to 1.0. By combining the black dye (C1) and the dye (C2) as the dye, while ensuring the light - shielding property of the photosensitive resin composition, the content of the black dye (C1) can be reduced, the pattern - forming property of the photosensitive resin composition can be improved, and the sensitivity can be increased. The photosensitive resin composition containing the dye can form a high - definition pattern on the film with less residue of the colorant during development compared with the photosensitive resin composition containing a pigment. By forming a black partition wall or insulating film on the organic EL element using the photosensitive resin composition containing the combination of the black dye (C1) and the dye (C2) as the dye, the visibility of a display device such as an organic EL display can be improved.,

[0132] The types and contents of the black dye (C1) and the dye (C2) can be selected and determined such that the optical density (OD value) of the cured film of the photosensitive resin composition is not less than a desired value, for example, 1 or more per 1 μm of film thickness. The black dye (C1) and the dye (C2) can each be used alone or in combination of two or more.

[0133] The black dye (C1) is not particularly limited, and examples thereof include dyes defined by the Color Index (C.I.) of Solvent Black 7 to 47. The black dye is preferably one defined by the C.I. of Solvent Black 27 to 47, and more preferably one defined by the C.I. of Solvent Black 27, 29 or 34. By using at least one of the dyes defined by the C.I. of Solvent Black 7 to 47 as the black dye, the light-shielding property of the film of the photosensitive resin composition after curing can be maintained more effectively.

[0134] Specific examples of the black dye (C1) include VALIFAST (registered trademark) BLACK 3804 (a black dye defined by the C.I. of Solvent Black 34, manufactured by Orient Chemical Industries, Ltd.), VALIFAST (registered trademark) BLACK 3830 (a black dye defined by the C.I. of Solvent Black 27, manufactured by Orient Chemical Industries, Ltd.), VALIFAST (registered trademark) BLACK 3810 (a black dye defined by the C.I. of Solvent Black 29, manufactured by Orient Chemical Industries, Ltd.), VALIFAST (registered trademark) BLACK 3820 (a black dye defined by the C.I. of Solvent Black 27, manufactured by Orient Chemical Industries, Ltd.), NUBIAN (registered trademark) BLACK TN-870 (a black dye defined by the C.I. of Solvent Black 7, manufactured by Orient Chemical Industries, Ltd.), and the like.

[0135] The dye (C2) is a dye other than the black dye (C1), and has an absorption maximum at a wavelength of 480 to 550 nm in the wavelength range of 300 to 800 nm. The absorbance of the black dye (C1) is generally relatively small in the region of wavelengths 450 to 550 nm. By using the dye (C2) having an absorption maximum at a wavelength of 480 to 550 nm, the low absorbance of the black dye (C1) in the above wavelength region can be compensated, and while ensuring the light-shielding property of the photosensitive resin composition, the content of the black dye (C1) can be made less, and the improvement of the pattern forming property and the increase in sensitivity of the photosensitive resin composition can be effectively achieved. In one embodiment, the dye (C2) preferably has an absorption maximum at a wavelength of 500 to 550 nm in the wavelength range of 300 to 800 nm, and more preferably has an absorption maximum at a wavelength of 500 to 540 nm.

[0136] Furthermore, when the absorbance at the absorption maximum wavelength of the dye (C2) is Abs1 and the average absorbance at wavelengths of 560 to 600 nm is Abs2, Abs2 / Abs1 is 0.1 to 1.0. By using the dye (C2), even when the ratio of the black dye (C1) is relatively decreased and the ratio of the dye (C2) is relatively increased, the improvement of the pattern forming property and the increase in sensitivity of the photosensitive resin composition can be effectively achieved while suppressing the decrease in absorbance at wavelengths of 560 to 600 nm due to the decrease in the black dye (C1). In one embodiment, the dye (C2) preferably has Abs2 / Abs1 of 0.2 to 0.8, and more preferably 0.3 to 0.6. The absorbance of the dye (C2) is determined by using a solution diluted to 10 ppm (mass basis) with γ-butyrolactone and measuring the absorption spectrum in the wavelength range of 300 to 800 nm at 23 °C in 1 nm increments with a spectrophotometer (trade name V670, manufactured by JASCO Corporation). The average absorbance is the number average value of the absorbances measured in 1 nm increments in a predetermined wavelength range.

[0137] As the dye (C2), for example, those generally classified as red dyes can be used, but dyes other than red dyes may also be used.

[0138] When the absorbance at the maximum absorption wavelength in the wavelength range of 300 to 800 nm of the dye (C2) is set to 100, the absorbance of the dye (C2) at a wavelength of 365 nm is preferably 0 to 80, more preferably 30 to 75, and even more preferably 50 to 70. When the absorbance of the dye (C2) at a wavelength of 365 nm is within the above range, the sensitivity of the photosensitive resin composition, particularly the sensitivity to i-line, can be enhanced.

[0139] As the dye (C2), a red dye is preferable. Specifically, VALIFAST (registered trademark) RED 3312 (a red dye defined by the C.I. of Solvent Red 122, manufactured by Orient Chemical Industries, Ltd.), VALIFAST (registered trademark) RED 3311 (a red dye defined by the C.I. of Solvent Red 8, manufactured by Orient Chemical Industries, Ltd.), etc. can be mentioned.

[0140] The dye (C) may contain other dyes (C3) other than the black dye (C1) and the dye (C2) as long as the effects of the present invention are not impaired. Specific examples of the other dyes (C3) include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, fluoran dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes. Specifically, VALIFAST (registered trademark) ORANGE 3209 (an orange dye defined by the C.I. of Solvent Orange 62, manufactured by Orient Chemical Industries, Ltd.), VALIFAST (registered trademark) BROWN 3405 (a mixture of a dye defined by the C.I. of Solvent Yellow 82 and other dyes, manufactured by Orient Chemical Industries, Ltd.), VALIFAST (registered trademark) BLUE 2602 (a blue dye defined by the C.I. of Solvent Blue 44, manufactured by Orient Chemical Industries, Ltd.), etc. can be mentioned.

[0141] The content of the dye (C) in the photosensitive resin composition is preferably 15 to 50 parts by mass, more preferably 20 to 45 parts by mass, and still more preferably 25 to 40 parts by mass, based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C). If the content of the dye (C) is 15 parts by mass or more based on 100 parts by mass in total, the light-shielding property of the film after curing can be maintained. If the content of the dye (C) is 50 parts by mass or less based on 100 parts by mass in total, the remaining film ratio, heat resistance, sensitivity, etc. are appropriate.

[0142] The content of the black dye (C1) in the photosensitive resin composition is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and still more preferably 70 to 85% by mass, based on the total mass of the dye (C). By setting the content of the black dye (C1) in the photosensitive resin composition to 50% by mass or more based on the total mass of the dye (C), the chroma and lightness of the cured film can be reduced to such an extent that an observer can visually recognize the cured film as black. By setting it to 95% by mass or less, improvement in pattern formability and high sensitivity of the photosensitive resin composition can be effectively achieved.

[0143] The content of the dye (C2) in the photosensitive resin composition is preferably 5 to 35% by mass, more preferably 11 to 33% by mass, and still more preferably 15 to 25% by mass, based on the total mass of the dye (C). By setting the content of the dye (C2) in the photosensitive resin composition to 5% by mass or more based on the total mass of the dye (C), improvement in pattern formability and high sensitivity of the photosensitive resin composition can be effectively achieved. By setting it to 35% by mass or less, the chroma and lightness of the cured film can be reduced to such an extent that an observer can visually recognize the cured film as black.

[0144] [Optional component (D)] The photosensitive resin composition can contain, as optional components, a dissolution accelerator, a thermosetting agent, a surfactant, a colorant other than the dye (C), etc. The optional component (D) is defined as not belonging to any of (A) to (C).

[0145] The photosensitive resin composition can contain a dissolution accelerator, for example, to improve the solubility of the alkali-soluble portion during development. As the dissolution accelerator, a low-molecular compound having an alkali-soluble functional group is used. Among them, a compound having at least one group selected from a carboxy group and a phenolic hydroxyl group is preferable. The low-molecular compound having an alkali-soluble functional group can be used alone or in combination of two or more.

[0146] For example, as the low-molecular compound having a carboxy group, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassilic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimellitic acid, mesitylenic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, gallic acid; and other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umbellic acid can be mentioned.

[0147] Examples of the low molecular weight compound having a phenolic hydroxyl group include catechol, resorcinol, hydroquinone, propyl gallate, dihydroxynaphthalene, leucoquinizarin, 1,2,4-benzenetriol, anthracenetriol, pyrogallol, phloroglucinol, tetrahydroxybenzophenone, phenolphthalein, phenolphthalin, tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, and the like.

[0148] The content of the dissolution accelerator can be 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, and more preferably 3 to 12 parts by mass based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C). If the content of the dissolution accelerator is 0.1 part by mass or more based on 100 parts by mass in total, the dissolution of the binder resin (A) can be effectively promoted. If it is 20 parts by mass or less, excessive dissolution of the binder resin (A) can be suppressed, and the pattern formability, surface quality, etc. of the film can be improved.

[0149] As the thermosetting agent, a thermal radical generator can be used. Preferred thermal radical generators include organic peroxides. Specifically, organic peroxides having a 10-hour half-life temperature of 100 to 170 °C such as dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide can be mentioned.

[0150] The content of the thermosetting agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), the dye (C), and other solid components (excluding the thermosetting agent).

[0151] The photosensitive resin composition can contain a surfactant, for example, to improve coatability, to improve the smoothness of the film, or to improve the developability of the film. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers like polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers like polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; fluorosurfactants such as Megafac (registered trademark) F-251, F-281, F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559 (above are trade names, manufactured by DIC Corporation), Surflon (registered trademark) S-242, S-243, S-386, S-420, S-611 (above are trade names, manufactured by ACG Seimi Chemical Co., Ltd.); organosiloxane polymers such as KP323, KP326, KP341 (above are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). These can be used alone or in combination of two or more.

[0152] The content of the surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.5 part by mass or less, based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), the dye (C), and other solid components (excluding the surfactant).

[0153] The photosensitive resin composition can contain a second colorant other than the dye (C). Examples of the second colorant include organic pigments and inorganic pigments, and they can be used according to the purpose. The second colorant can be used in a content that does not impair the effects of the disclosure of the present invention.

[0154] Examples of the pigment include black pigments such as carbon black, carbon nanotube, acetylene black, graphite, iron black, aniline black, titanium black, perylene-based pigment, lactam-based pigment; C.I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. Pigment Green 7, C.I. Pigment Brown 23, 25, 26, etc.

[0155] [Solvent (E)] The photosensitive resin composition can be used in a solution state dissolved in a solvent (however, when including a black pigment, the pigment is in a dispersed state). In the present disclosure, the photosensitive resin composition containing the solvent (E) and having a viscosity suitable for use is also referred to as a coating composition. For example, a solution obtained by dissolving the binder resin (A) in the solvent (E) is mixed with the radiation-sensitive compound (B), the dye (C), and optional components (D) such as a dissolution accelerator, a thermosetting agent, and a surfactant at a predetermined ratio, whereby a photosensitive resin composition in a solution state can be prepared. The photosensitive resin composition can be adjusted to a viscosity suitable for the coating method used by changing the amount of the solvent.

[0156] Examples of the solvent include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol compounds such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol alkyl ether acetate compounds such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and cyclohexanone; esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; and amide compounds such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

[0157] The photosensitive resin composition can be prepared by dissolving or dispersing a binder resin (A), a radiation-sensitive compound (B), a dye (C), and, if necessary, an optional component (D) in a solvent (E) and mixing them. The solid content concentration of the photosensitive resin composition can be appropriately determined according to the intended use. For example, the solid content concentration of the photosensitive resin composition may be 1 to 60% by mass, 3 to 50% by mass, or 5 to 40% by mass.

[0158] When using a pigment as the optional component (D), a known method can be used for the dispersion mixing. For example, ball types such as ball mills, sand mills, bead mills, paint shakers, rocking mills, blade types such as kneaders, paddle mixers, planetary mixers, Henschel mixers, roll types such as three-roll mixers, and others such as Rykaiki machines, colloid mills, ultrasonic waves, homogenizers, rotation-revolution mixers, etc. may be used. It is preferable to use a bead mill in terms of dispersion efficiency and fine dispersion.

[0159] The prepared photosensitive resin composition is usually preferably filtered before use. Examples of the filtering means include a Millipore filter with a pore diameter of 0.05 to 1.0 μm.

[0160] The photosensitive resin composition prepared in this way is also excellent in long-term storage stability.

[0161] In one embodiment, in the absorbance curve of the photosensitive resin composition, when the average absorbance at a wavelength of 450 to 545 nm is Abs3 and the average absorbance at a wavelength of 550 to 650 nm is Abs4, Abs4 / Abs3 is 0.8 to 1.6. Abs4 / Abs3 is preferably 0.9 to 1.5, and more preferably 1.0 to 1.4. When Abs4 / Abs3 is 0.8 or more, the OD value is in a preferable range and the light-shielding property of the cured film is improved. When Abs4 / Abs3 is 1.6 or less, the alkali solubility of the exposed part is improved. The absorbance curve of the photosensitive resin composition is determined by using a solution obtained by diluting the photosensitive resin composition with γ-butyrolactone to 12 ppm (mass basis) and measuring the absorption spectrum in the wavelength range of 300 to 800 nm at 1 nm intervals at 23 °C with a spectrophotometer (trade name V670, manufactured by JASCO Corporation). The average absorbance is the number average value of the absorbances measured at 1 nm intervals in a predetermined wavelength range.

[0162] When a photosensitive resin composition is used in radiation lithography, first, the photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition is applied to the surface of a substrate, and the solvent is removed by means such as heating to form a film. The method of applying the coating composition to the substrate surface is not particularly limited, and for example, a spray method, a roll coating method, a slit method, a spin coating method, etc. can be used.

[0163] After the coating composition is applied to the substrate surface, usually, the solvent is removed by heating or the like to form a film (pre-baking). The heating conditions vary depending on the types and blending ratios of the respective components, etc., but usually, heating treatment is performed at 70 to 130 °C, for example, for 30 seconds to 20 minutes on a hot plate or for 1 to 60 minutes in an oven to obtain a film.

[0164] Next, the pre-baked film is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, synchrotron radiation, etc.) through a photomask having a predetermined pattern (exposure step). When a quinonediazide compound is used as the radiation-sensitive compound, the preferred radiation is ultraviolet light to visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is ghi-ray. In another embodiment, the radiation is i-ray.

[0165] After the exposure process, the film is developed by bringing it into contact with a developer solution to remove the exposed portions and form a pattern on the film (development process). Examples of the developer solution include aqueous solutions of alkali compounds such as inorganic alkalis like sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant to the alkaline aqueous solution can also be used as the developer solution. The development time is usually 30 to 180 seconds. The development method may be any of the puddle method, the shower method, the dipping method, etc. After development, running water washing is performed for 30 to 90 seconds to remove unnecessary portions, and then air drying with compressed air or compressed nitrogen can form a pattern on the film.

[0166] Thereafter, the film with the pattern formed thereon can be heat-treated at, for example, 100 to 350 °C for 20 to 200 minutes using a heating device such as a hot plate or an oven to obtain a cured film (post-bake, heat treatment process). In the heat treatment, the temperature may be maintained constant, continuously increased, or increased stepwise.

[0167] In one embodiment, the optical density (OD value) of the cured film of the photosensitive resin composition is 1 or more per 1 μm of film thickness. The optical density (OD value) of the cured film of the photosensitive resin composition is preferably 1.005 or more, and more preferably 1.01 or more. By the OD value of the cured film being 1 or more per 1 μm of film thickness, high light-shielding properties can be obtained. In the present disclosure, the optical density (OD value) of the cured film of the photosensitive resin composition is the value when the film of the photosensitive resin composition is cured by heating at 120 °C for 80 seconds in an air atmosphere and then at 250 °C for 60 minutes in a nitrogen gas atmosphere.

[0168] One embodiment includes preparing a coating composition by dissolving or dispersing a photosensitive resin composition in a solvent, forming a film by applying the coating composition to a substrate, drying the film by removing the solvent contained in the film, exposing the dried film through a photomask by irradiating it with radiation, developing the exposed film by bringing it into contact with a developer to form a pattern on the film, and heat-treating the film on which the pattern is formed at a temperature of 100 °C to 350 °C to form an organic EL element partition or an organic EL element insulating film, which is a method for manufacturing an organic EL element partition or an organic EL element insulating film.

[0169] One embodiment is an organic EL element partition including a cured product of a photosensitive resin composition.

[0170] One embodiment is an organic EL element insulating film including a cured product of a photosensitive resin composition.

[0171] One embodiment is an organic EL element including a cured product of a photosensitive resin composition.

Examples

[0172] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these examples.

[0173] Regarding the weight average molecular weight and number average molecular weight of the binder resin (A), they were calculated using a calibration curve prepared using a polystyrene standard substance under the following measurement conditions. Apparatus name: Shodex (registered trademark) GPC-101 Column: Shodex (registered trademark) LF-804 Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: Shodex (registered trademark) RI-71 Temperature: 40 °C

[0174] (1) Synthesis of binder resin (A)

[0175] [Production Example 1] Production of an alkali aqueous solution-soluble resin (c) (first resin) having an epoxy group and a phenolic hydroxyl group 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent and 17.8 g of EPICLON (registered trademark) N-695 (cresol novolak type epoxy resin manufactured by DIC Corporation, epoxy equivalent 214) as a compound having at least two epoxy groups in one molecule were charged into a 300 mL three-necked flask and dissolved at 60 °C under a nitrogen gas atmosphere. Then, 20.1 g (0.65 equivalent relative to 1 equivalent of epoxy group) of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Corporation) as a hydroxybenzoic acid compound and 0.166 g (0.660 mmol) of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a reaction catalyst were added, and the reaction was carried out at 110 °C for 21 hours. The reaction solution was returned to room temperature and diluted with γ-butyrolactone to a solid content of 20 mass%, and the solution was filtered to obtain a 274.2 g solution of the first resin having an epoxy group and a phenolic hydroxyl group. The number average molecular weight of the obtained reaction product was 3000, and the weight average molecular weight was 7500.

[0176] [Production Example 2] Production of an alkali aqueous solution-soluble resin (c) (second resin) having an epoxy group and a phenolic hydroxyl group In a 300 mL three-necked flask, 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent and 37.6 g of EPICLON (registered trademark) N-770 (phenol novolak type epoxy resin manufactured by DIC Corporation, epoxy equivalent 188) as a compound having at least two epoxy groups in one molecule were charged and dissolved at 60 °C under a nitrogen gas atmosphere. Then, 20.1 g (0.65 equivalent relative to 1 equivalent of epoxy group) of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Corporation) as a hydroxybenzoic acid compound and 0.173 g (0.660 mmol) of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a reaction catalyst were added, and the reaction was carried out at 110 °C for 21 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain a solution of a second resin having epoxy groups and phenolic hydroxyl groups, which was 197.7 g. The number average molecular weight of the obtained reaction product was 2400, and the weight average molecular weight was 8300.

[0177] [Production Example 3] Production of an alkali aqueous solution-soluble copolymer (d) (third resin) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers 25.5 g of 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko K.K.), and 4.50 g of N-cyclohexyl maleimide (manufactured by Nippon Shokubai Co., Ltd.) were each completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) and 14.6 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) which is a solvent, with 3.66 g of V-601 (manufactured by Fuji Film Wako Pure Chemical Corporation) as a polymerization initiator. The two obtained solutions were simultaneously dropped over 2 hours into 61.2 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) heated to 85° C. in a 300 mL three-necked flask under a nitrogen gas atmosphere, and then reacted at 85° C. for 3 hours. The reaction solution cooled to room temperature was dropped into 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 90° C. for 4 hours to recover 32.4 g of an alkali aqueous solution-soluble copolymer (third resin) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers as a white powder. The number average molecular weight of the obtained reaction product was 3100, and the weight average molecular weight was 6600.

[0178] (2) Raw materials Binder resin (A) As the binder resin (A), the first resin to the third resin produced in Production Examples 1 to 3 were used.

[0179] Radiation-sensitive compound (B) The quinonediazide compound TPPA(4)-150DF (1,2-naphthoquinonediazide-4-sulfonic acid ester of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, manufactured by Toyo Gosei Co., Ltd.), which is a photoacid generator, was used.

[0180] Dye (C) As dyes, the black dye (C1), dye (C2), and other dyes (C3) shown in Table 1 were used. The spectral data was obtained by putting a solution prepared by diluting the dye to 10 ppm (mass basis) with γ-butyrolactone (GBL) into a quartz cell (cell optical path length: 1 cm) and measuring the absorption spectrum in the wavelength range of 300 to 800 nm at 1 nm intervals at 23 °C using a spectrophotometer (trade name: V670, manufactured by JASCO Corporation). The absorbance at the maximum absorption wavelength obtained was defined as Abs1, and the average value of the absorbances at wavelengths of 560 to 600 nm was defined as the average absorbance Abs2. The absorbance curves of VALIFAST® BLACK 3804, which is the black dye (C1), and VALIFAST® RED 3312, which is the dye (C2), are shown in Fig. 1, and the absorbance curves of VALIFAST® ORANGE 3209, VALIFAST® BROWN 3405, and VALIFAST® BLUE 2602, which are the other dyes (C3), are shown in Fig. 2, respectively.

[0181] [Table 1]

[0182] Optional component (D) Phloroglucinol or adipic acid was used as a dissolution promoter. Megafac® F-559 (a fluorine-based surfactant, manufactured by DIC Corporation) was used as a surfactant (leveling agent).

[0183] Solvent (E) As the solvent, a mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA = 40:60 (mass ratio)) was used.

[0184] (3) Evaluation method The evaluation methods used in the examples and comparative examples are as follows.

[0185] [Spectral data] The average absorbance Abs3 at wavelengths of 450 to 545 nm and the average absorbance Abs4 at wavelengths of 550 to 650 nm of the photosensitive resin composition were measured by the following procedure. A solution obtained by diluting the photosensitive resin composition with GBL to a concentration of 12 ppm was placed in a quartz cell (cell optical path length: 1 cm) and used. Using a spectrophotometer (trade name: V670, manufactured by JASCO Corporation), the absorption spectrum in the wavelength range of 300 to 800 nm was measured at 23 °C in 1-nm increments. The average value of the absorbances at wavelengths of 450 to 545 nm and the average value of the absorbances at wavelengths of 550 to 650 nm obtained were defined as the average absorbances Abs3 and Abs4, respectively, and Abs4 / Abs3 was calculated.

[0186] [Pattern peeling, pattern residue, and visual residue] The coating composition was bar-coated on a glass substrate (size: 100 mm × 100 mm × 1 mm) so that the dry film thickness was approximately 1.5 μm, and heated on a hot plate at 120 °C for 80 seconds to dry the solvent. Using an exposure apparatus incorporating an ultra-high pressure mercury lamp (trade name: Multi-Light ML-251A / B, manufactured by USHIO INC.), through a mercury exposure band pass filter (trade name: HB0365, manufactured by Asahi Spectra Co., Ltd.) and a quartz photomask (having line & space (L / S) patterns of 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, and 500 μm), exposure was performed at 100 mJ / cm 2 . The exposure dose was measured using an ultraviolet integrated dosimeter (trade name: UIT-150 light receiving unit UVD-S365, manufactured by USHIO INC.). The exposed film was subjected to alkali development for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide using a spin coater (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). Thereafter, a pattern sample was obtained by curing at 250 °C for 60 minutes in a nitrogen gas atmosphere.

[0187] Regarding pattern peeling, in the observation using an optical microscope (VH-Z250, manufactured by KEYENCE CORPORATION) of the pattern after alkali development, the case where no peeling of the film was observed over the entire substrate was judged as none, and the case where peeling of the film was observed on part or all of the substrate was judged as having.

[0188] Regarding the pattern residue, pattern samples after alkali development with film thicknesses varied between 0.9 and 1.5 μm were observed using an optical microscope (VHX-6000, manufactured by Keyence Corporation). The film thickness of the sample without residue after alkali development, including the edge part of the pattern, was measured using an optical film thickness measurement device (F20-NIR, manufactured by Filmtronics Co., Ltd.). A larger numerical value indicates better exposure sensitivity.

[0189] Regarding the visual residue, pattern samples after alkali development with film thicknesses varied between 0.9 and 1.5 μm were visually observed. The film thickness of the sample without residue and with the glass substrate surface visible was measured using an optical film thickness measurement device (F20-NIR, manufactured by Filmtronics Co., Ltd.). A larger numerical value indicates better exposure sensitivity.

[0190] [Solubility of unexposed part] A glass substrate (size 100 mm × 100 mm × 1 mm) was bar-coated with the coating composition so that the dry film thickness became approximately 1.5 μm, and heated on a hot plate at 120 °C for 80 seconds to dry the solvent. After measuring the dry film thickness using an optical film thickness measurement device (F20-NIR, manufactured by Filmtronics Co., Ltd.), alkali development was performed for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide using a spin developer (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). The film thickness after alkali development was measured again using an optical film thickness measurement device (F20-NIR, manufactured by Filmtronics Co., Ltd.), and the film thickness (μm) dissolved before and after development was calculated as the solubility of the unexposed part.

[0191] [OD value after heating] A coating composition was spin-coated onto a glass substrate (size 100 mm × 100 mm × 1 mm) to a dry film thickness of about 1.5 μm, and then heated on a hot plate at 120 °C for 80 seconds to dry the solvent. Thereafter, a film was obtained by curing at 250 °C for 60 minutes in a nitrogen gas atmosphere. The OD value of the cured film was measured with a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.), corrected with the OD value of only the glass, and converted to the OD value per 1 μm thickness of the film. The film thickness was measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmtronics Co., Ltd.).

[0192] (4) Preparation and evaluation of photosensitive resin composition [Example 1] 22.5 parts by mass (in terms of solid content) of the solution of the first resin and 21.0 parts by mass (in terms of solid content) of the solution of the third resin were mixed and dissolved. To the resulting solution, 24.0 parts by mass of the quinonediazide compound TPPA(4)-150DF, 22.4 parts by mass of VALIFAST® BLACK 3804, 5.6 parts by mass of VALIFAST® RED 3312, 3.0 parts by mass of phloroglucinol, 1.5 parts by mass of adipic acid, 0.14 parts by mass of MEGAFAC® F-559, and a GBL / PGMEA mixed solvent described in Table 2 were added and further mixed. After visually confirming that the components were dissolved, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a photosensitive resin composition (coating composition) with a solid content concentration of 12% by mass.

[0193] [Examples 2 to 7, Comparative Examples 1 to 4] A photosensitive resin composition (coating composition) was prepared in the same manner as in Example 1 with the compositions (parts by mass) shown in Table 2.

[0194] The prepared photosensitive resin composition was evaluated for spectral data, OD value after heating, solubility of unexposed parts, pattern peeling, pattern residue, and visual residue. The results are shown in Table 2. The parts by mass of the compositions in Table 2 are values in terms of solid content. For Comparative Example 4, since VALIFAST® BLUE 2602 did not dissolve sufficiently and precipitated over time, evaluations other than the OD value after heating were not performed.

[0195]

Table 2-1

[0196]

Table 2-2

Industrial Applicability

[0197] The photosensitive resin composition of the present invention can be suitably used for radiation lithography for forming a partition wall or an insulating film of an organic EL element. An organic EL element provided with a partition wall or an insulating film formed from the photosensitive resin composition of the present invention is suitably used as an electronic component of a display device exhibiting good contrast.

Claims

1. A photosensitive resin composition containing a binder resin (A), a radiation-sensitive compound (B), and a dye (C), wherein the binder resin (A) is an alkali aqueous solution-soluble resin having (c) an epoxy group and a phenolic hydroxyl group, the radiation-sensitive compound (B) is at least one photoacid generator selected from the group consisting of a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt, the dye (C) contains a black dye (C1) and a dye (C2) other than (C1), the dye (C2) has an absorption maximum at a wavelength of 480 to 550 nm in the wavelength range of 300 to 800 nm, and when the absorbance at the wavelength of the absorption maximum of the dye (C2) is Abs1 and the average absorbance at a wavelength of 560 to 600 nm is Abs2, Abs2 / Abs1 is 0.1 to 1.0, the photosensitive resin composition contains 50 to 95% by mass of the black dye (C1) based on the total mass of the dye (C), and 5 to 35% by mass of the dye (C2) based on the total mass of the dye (C), a photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein in the absorbance curve of the photosensitive resin composition, when the average absorbance at a wavelength of 450 to 545 nm is Abs3 and the average absorbance at a wavelength of 550 to 650 nm is Abs4, Abs4 / Abs3 is 0.8 to 1.

6.

3. The photosensitive resin composition according to any one of claims 1 or 2, wherein the absorbance of the dye (C2) at a wavelength of 365 nm is 0 to 80 when the absorbance at the wavelength of the absorption maximum in the wavelength range of 300 to 800 nm of the dye (C2) is 100.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the dye (C2) is a red dye.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the color index of the black dye (C1) is Solvent Black 7 to 47.

6. The photosensitive resin composition according to any one of claims 1 to 5, containing 5 to 50 parts by mass of the photoacid generator based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C).

7. The photosensitive resin composition according to any one of claims 1 to 6, comprising 15 to 50 parts by mass of the dye (C) based on 100 parts by mass in total of the binder resin (A), the radiation-sensitive compound (B), and the dye (C).

8. As the binder resin (A), (a) a polyalkenylphenol resin having a structural unit of formula (1) 【Chemical Formula 1】 (In formula (1), R １ , R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, 【Chemical 2】 (In formula (2), R ６ , R ７ , R ８ , R ９ , and R １０ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and * in formula (2) represents the bonding portion with the carbon atom constituting the aromatic ring.), an alkenyl group represented by the formula, an alkoxy group having 1 to 2 carbon atoms, or a hydroxyl group, and at least one of R １ , R ２ , and R ３ is an alkenyl group represented by formula (2), Q is an alkylene group represented by the formula -CR ４ R ５ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group combining these, and R ４ and R ５ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) and (b) a hydroxystyrene resin derivative having a structural unit represented by formula (3), and (d) at least one selected from the group consisting of a polymerizable monomer having an alkali-soluble functional group and an alkali-aqueous solution-soluble copolymer of the polymerizable monomer and other polymerizable monomers. The photosensitive resin composition according to any one of claims 1 to 7. 【Chemical Formula 3】 (In formula (3), R １１ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is an integer of 1 to 4, b is an integer of 1 to 4, a + b is in the range of 2 to 5, and R １２ is at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and a propyl group.)

9. As the binder resin (A), (d) a polymerizable monomer having an alkali-soluble functional group and an alkali-aqueous solution-soluble copolymer of the polymerizable monomer and other polymerizable monomers are further included. The photosensitive resin composition according to any one of claims 1 to 7.

10. An organic EL element partition wall including a cured product of the photosensitive resin composition according to any one of claims 1 to 9.

11. An organic EL element insulating film including a cured product of the photosensitive resin composition according to any one of claims 1 to 9.

12. An organic EL element including a cured product of the photosensitive resin composition according to any one of claims 1 to 9. ​ ​

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