Positive photosensitive resin composition and organic EL element partition wall

Abstract

To provide a photosensitive resin composition which has high sensitivity and small surface roughness of an obtained film, has good process window and storage stability, and contains a metal complex dye.SOLUTION: A positive type photosensitive resin composition contains a binder resin (A), an optical acid generator (B), and a metal complex dye (C), wherein the metal complex dye (C) contains a metal complex ion, and a counter cation having a nitrogen-containing heterocyclic structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a positive-type photosensitive resin composition, an organic EL device partition wall, an organic EL device insulating film, and an organic EL device each using the same. More specifically, the present invention relates to a positive-type photosensitive resin composition containing a metal complex dye, and an organic EL device partition wall, an organic EL device insulating film, and an organic EL device each using the same. [Background technology]

[0002] In display devices such as organic light-emitting diode (OLED) displays, partition walls are used in the gaps between colored patterns in the display area or around the edges of the display area to improve display characteristics. In the manufacture of organic EL display devices, partition walls are first formed to prevent organic material pixels from contacting each other, and then organic material pixels are formed between the partition walls.

[0003] These partition walls are generally formed by photolithography using a photosensitive resin composition and have insulating properties. Specifically, a photosensitive resin composition is applied to a substrate using a coating device, and volatile components are removed by heating or other means. The resulting pattern is then developed by removing the unexposed portions (in the case of a negative-tone pattern) or the exposed portions (in the case of a positive-tone pattern) with a developer such as an alkaline aqueous solution. The resulting pattern is then heat-treated to form partition walls (insulating films). Next, organic materials that emit light in three colors (red, green, and blue) are deposited between the partition walls by inkjet printing or other methods to form the pixels of the organic EL display device.

[0004] In recent years, in this field, due to the miniaturization of display devices and the diversification of displayed content, there has been a demand for higher pixel performance and higher resolution. Attempts have been made to impart light-blocking properties to partition wall materials using colorants in order to increase the contrast and improve visibility in display devices. However, when partition wall materials are imparted with light-blocking properties, the photosensitive resin composition tends to have low sensitivity, which may result in longer exposure times and reduced productivity. Therefore, photosensitive resin compositions used to form partition wall materials containing colorants are required to have higher sensitivity.

[0005] Patent Document 1 (JP 2001-281440 A) describes a radiation-sensitive resin composition that exhibits high light-blocking properties through heat treatment after exposure, in which titanium black is added to a positive-tone radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound.

[0006] Patent Document 2 (JP 2002-116536 A) describes a method for blackening a partition wall material by 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.

[0007] Patent Document 3 (JP 2010-237310 A) describes a radiation-sensitive resin composition that exhibits light-blocking properties by heat treatment after exposure, in which a heat-sensitive dye is added to a positive-tone radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound.

[0008] Patent Document 4 (WO 2017 / 069172) describes a positive photosensitive resin composition containing (A) a binder resin, (B) a quinone diazide compound, and (C) at least one black dye selected from black dyes defined by the color index of Solvent Black 27 to 47. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-281440 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-116536 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-237310 [Patent Document 4] International Publication No. 2017 / 069172 Summary of the Invention [Problem to be solved by the invention]

[0010] In the photosensitive resin composition used to form a colored partition wall material, a considerable amount of colorant must be used to sufficiently enhance the light-shielding properties of the cured film. When such a large amount of colorant is used, the radiation irradiated onto the coating of the photosensitive resin composition is absorbed by the colorant, reducing the effective intensity of the radiation in the coating and resulting in insufficient exposure of the photosensitive resin composition, resulting in poor pattern formability.

[0011] In particular, when attempting to form a thick coating, e.g., a coating having a thickness of 2 to 3 μm, using a photosensitive resin composition containing a black agent, the amount of radiation reaching the bottom of the coating in the exposed area is significantly reduced due to the absorption of radiation by the radiation-sensitive compound in addition to the black agent. Therefore, in a positive-tone film, the bottom of the coating in the exposed area may not be sufficiently alkaline-soluble, resulting in the generation of resin residue during development, or a large amount of photosensitive resin composition may be consumed to obtain a coating of the desired thickness, i.e., the film retention rate may be reduced. On the other hand, in a negative-tone film, the bottom of the coating in the exposed area may not be sufficiently insolubilized, resulting in film peeling during development. Therefore, there is a strong demand for a photosensitive resin composition containing a black agent that can impart a high optical density (OD value) to the cured coating while increasing the thickness of the cured coating.

[0012] In the development process, if microscopically uneven resin dissolution occurs, the surface area of ​​the resin in that area, i.e., the contact area with the developer, increases, and the resin dissolution rate increases locally. As a result, the coating dissolves unevenly in the development process, which can cause rough coating surfaces after development and deterioration of pattern shape. This is particularly noticeable in thick-film development processes, which generally require long development times or the use of highly concentrated developers.

[0013] The present inventors have found that photosensitive resin compositions using commercially available metal complex dyes as colorants may have reduced sensitivity, resulting in the generation of resin residues during development, roughness on the surface of the coating film after development, and an increased change in solubility (hereinafter referred to as the process window) when the pre-bake temperature is changed. Furthermore, photosensitive resin compositions using commercially available metal complex dyes as colorants have poor storage stability, and the diameter of pattern holes in the coating film may increase after storage at room temperature.

[0014] An object of the present invention is to provide a photosensitive resin composition containing a metal complex dye, which has high sensitivity, produces a coating film with little surface roughness, and has a good process window and storage stability. [Means for solving the problem]

[0015] The present inventors have found that, in a positive photosensitive resin composition containing a metal complex dye, by changing the counter cation constituting the metal complex dye to a cation having a nitrogen-containing heterocyclic structure, it is possible to increase the sensitivity of the positive photosensitive resin composition, prevent roughness of the surface of the resulting coating film, and improve the process window and storage stability.

[0016] That is, the present invention includes the following aspects. [1] a binder resin (A); a photoacid generator (B); a metal complex dye (C); wherein the metal complex dye (C) contains a metal complex ion and a counter cation having a nitrogen-containing heterocyclic structure. [2] The positive photosensitive resin composition according to [1], wherein the binder resin (A) has an alkali-soluble functional group. [3] The positive photosensitive resin composition according to [1] or [2], wherein the counter cation is at least one selected from the group consisting of an N-alkylmorpholinium cation and an N-alkylpiperidinium cation. [4] The positive photosensitive resin composition according to any one of [1] to [3], wherein the metal element that forms the gold metal complex ion is at least one selected from the group consisting of chromium, copper, cobalt, nickel, and iron. [5] The positive photosensitive resin composition according to [4], wherein the metal element is chromium. [6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the metal complex dye (C) is a black dye. [7] The positive photosensitive resin composition according to [6], wherein the metal complex ion is a metal complex ion contained in a compound defined by a color index of Solvent Black 22 to 47. [8] The positive photosensitive resin composition according to any one of [1] to [7], wherein the binder resin (A) has a plurality of phenolic hydroxyl groups. [9] The positive photosensitive resin composition according to [8], wherein the binder resin (A) contains a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer.

[10] The binder resin (A) is a compound represented by the formula (10): [ka] (In Equation (10), R 15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5. The positive photosensitive resin composition according to [8] or [9], having a structural unit represented by the following formula:

[11] The binder resin (A) is a compound represented by the formula (11): [ka] (In Equation (11), R 16 and R 17are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 18 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The positive photosensitive resin composition according to

[10] , having a structural unit represented by the following formula:

[12] The positive photosensitive resin composition according to any one of [8] to

[11] , wherein the binder resin (A) further contains a resin having an epoxy group and a phenolic hydroxyl group.

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

[12] , which contains 5% by mass to 50% by mass of the metal complex dye (C) based on 100% by mass of the solid content of the positive photosensitive resin composition.

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

[13] , wherein the photoacid generator (B) is contained in an amount of 1% by mass to 50% by mass, based on 100% by mass of the solid content of the positive photosensitive resin composition.

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

[14] , wherein the optical density (OD value) of a cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness.

[16] A partition wall for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to any one of [1] to

[15] .

[17] An insulating film for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to any one of [1] to

[15] .

[18] An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to

[15] . [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a photosensitive resin composition containing a metal complex dye, which has high sensitivity, produces a coating film with little surface roughness, and has an improved process window and storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in detail below.

[0019] In this disclosure, "alkali-soluble" and "alkali aqueous solution soluble" mean that the positive photosensitive resin composition or its components, or a coating or cured coating of the positive photosensitive resin composition, is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. The term "alkali-soluble functional group" refers to a group that imparts such alkali-solubility to the positive photosensitive resin composition or its components, or a coating or cured coating of the positive photosensitive resin composition. Examples of alkali-soluble functional groups include a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group.

[0020] In the present disclosure, the term "acid-decomposable group" refers to a group that is decomposed (deprotected) in the presence of an acid, optionally with heating, to generate an alkali-soluble functional group.

[0021] In the present disclosure, the term "radically polymerizable functional group" refers to an ethylenically unsaturated group, and the term "radically polymerizable compound" refers to a compound having one or more ethylenically unsaturated groups.

[0022] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0023] In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin, polymer, or copolymer refer to values ​​calculated as standard polystyrene, measured by gel permeation chromatography (GPC).

[0024] In the present disclosure, the term "resin component" refers to the binder resin (A).

[0025] In the present disclosure, the term "solid content" refers to the total mass of components in a positive photosensitive resin composition, including the binder resin (A), the photoacid generator (B), the metal complex dye (C), the dissolution promoter (D), and the optional component (E), but excluding the solvent (F).

[0026] [Positive-type photosensitive resin composition] A positive photosensitive resin composition according to one embodiment contains a binder resin (A), a photoacid generator (B), and a metal complex dye (C).

[0027] <Binder resin (A)> The binder resin (A) is not particularly limited and may or may not have an alkali-soluble functional group. Among these, it is preferable that the binder resin (A) has an alkali-soluble functional group and that the binder resin (A) itself is alkali-soluble, since this eliminates the need for an alkali-soluble low-molecular-weight dissolution promoter as an optional component. Examples of alkali-soluble functional groups include, but are not limited to, a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group. The binder resin (A) may have two or more types of alkali-soluble functional groups.

[0028] 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, and derivatives of these resins, as well as resins to which an alkali-soluble functional group is bonded. The binder resin (A) may also be a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group. These resins may be used alone or in combination of two or more types. The binder resin (A) may have a radically polymerizable functional group. In one embodiment, the binder resin (A) has a (meth)acrylic group, an allyl group, or a methallyl group as the radically polymerizable functional group.

[0029] In one embodiment, the binder resin (A) contains at least one selected from the following resin components (a) to (l): (a) Polyalkenylphenol resin (b) Hydroxypolystyrene resin derivatives (c) Alkaline aqueous solution soluble resin having epoxy groups and phenolic hydroxyl groups (d) Alkali aqueous solution soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer (e) Polyimide resin (f) Polyamic acid resin (g) Polybenzoxazole resin (h) Polybenzoxazole resin precursor (i) Silicone resin (j) Cyclic olefin polymer (k) Cardo resin (l) Epoxy resins that do not have phenolic hydroxyl groups

[0030] (a) Polyalkenylphenol resin The polyalkenyl phenol resin can be obtained by converting the hydroxyl groups of a known phenol resin into alkenyl ether groups, and then subjecting the alkenyl ether groups to Claisen rearrangement. [ka] It is preferable that the resin has the structural unit represented by the formula: By including such a resin, the development characteristics of the resulting photosensitive resin composition can be improved and outgassing can be reduced.

[0031] 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, or a group represented by the formula (2) [ka] (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 a bond to a carbon atom constituting an aromatic ring. ) is an alkenyl group represented by, 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 the groups is an alkenyl group represented by formula (2), and Q is a group represented by 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 formed by combining these, and R 4 and R 5are 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 respective structural units of formula (1) may be the same or different.

[0032] R in Equation (1) 1 , R 2 , and R 3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by 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 R in formula (1) is an alkenyl group represented by formula (2). 1 , R 2 , and R 3 In the formula (I), 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 t-butyl group, and an n-pentyl group.Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an ethoxy group.

[0033] In the alkenyl group represented by formula (2), R 6 , R 7 , R 8 , R 9 , and R 10are 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 alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, and n-pentyl. Specific examples of cycloalkyl groups having 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl. Specific examples of aryl groups having 6 to 12 carbon atoms include phenyl, methylphenyl, ethylphenyl, biphenyl, and naphthyl. R 6 , R 7 , R 8 , R 9 , and R 10 are each preferably independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferred alkenyl groups represented by formula (2) include an allyl group and a methallyl group in terms of reactivity, and an allyl group is more preferred.

[0034] R 1 , R 2 , and R 3 It is most preferable that one of these groups is an allyl group or a methallyl group, and the other two groups are hydrogen atoms.

[0035] Q in equation (1) is 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 formed by combining these. 4 and R 5are 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 alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, and n-pentyl. Specific examples of alkenyl groups having 2 to 6 carbon atoms include vinyl, allyl, butenyl, pentenyl, and hexenyl. Specific examples of cycloalkyl groups having 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl. Specific examples of aryl groups having 6 to 12 carbon atoms include phenyl, methylphenyl, ethylphenyl, biphenyl, and naphthyl. R 4 and R 5 and are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably both are hydrogen atoms.

[0036] Specific examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, and a cycloheptylene group. 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, or a group represented by the formula (6): [ka] A specific example of the divalent organic group having a fused alicyclic ring is a dicyclopentadienylene group.

[0037] When a polyalkenylphenol resin is used as the binder resin (A), a particularly preferred polyalkenylphenol resin from the viewpoints of alkali developability, reduction of outgassing, etc. is one in which Q in formula (1) is —CH—, that is, a polyalkenylphenol resin represented by formula (4): [ka] In 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:

[0038] The structural unit represented by formula (1) or formula (4) preferably accounts for 50 to 100 mol %, more preferably 70 to 100 mol %, and even more preferably 80 to 100 mol % of the polyalkenyl phenol resin. It is preferable that the structural unit represented by formula (1) or formula (4) accounts for 50 mol % or more of the polyalkenyl phenol resin, since this improves heat resistance. The phenolic hydroxyl groups in the polyalkenyl phenol resin ionize in the presence of a basic compound, making it soluble in water. Therefore, from the viewpoint of alkaline developability, it is preferable that the phenolic hydroxyl groups are present in a certain amount or more. Therefore, the polyalkenyl phenol resin containing the structural unit of formula (4) contains the structural unit represented by formula (4) and the structural unit represented by formula (7) [ka] In formula (7), it is particularly preferable that the polyalkenylphenol resin has a structural unit represented by the formula: 1a , R 2a , and R 3a are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 1a , R 2a , and R 3a Specific examples of the alkyl group having 1 to 5 carbon atoms include R 1 , R 2 , and R 3 The alkyl group has 1 to 5 carbon atoms.

[0039] In the polyalkenylphenol resin having the structural unit represented by the formula (4) and the structural unit represented by the formula (7), when the number of the structural units represented by the formula (4) is x and the number of the structural units represented by the formula (7) is y, 0.5≦x / (x + y)<1, 0<y / (x + y)≦0.5, x + y is preferably 2 to 50, more preferably 3 to 40, and still more preferably 5 to 25.

[0040] When using a polyalkenylphenol resin as the binder resin (A), the preferred number average molecular weight (Mn) of the polyalkenylphenol resin is 500 to 5000, more preferably 800 to 3000, and still more preferably 900 to 2000. If the number average molecular weight is 500 or more, the alkaline 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 it is 5000 or less, the alkaline developability is good.

[0041] (b) Hydroxypolystyrene resin derivative As the binder resin (A), the formula (3)

Chemical formula

[0042] In the 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 within 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.

[0043] When using a hydroxypolystyrene resin derivative as the binder resin (A), from the viewpoints of alkaline developability and outgas reduction, the structural unit represented by the formula (3) and the formula (5) [ka] It is preferable that the copolymer has a structural unit represented by the following formula:

[0044] In equation (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.

[0045] The hydroxypolystyrene resin derivative having a structural unit represented by formula (3) and the hydroxypolystyrene resin derivative having a structural unit represented by formula (3) and a structural unit represented by formula (5) can be obtained by reacting a part of a polymer or copolymer obtained by polymerizing, by a known method, one or more aromatic vinyl compounds having a phenolic hydroxyl group, such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol, with formaldehyde by a known method, or by further reacting with an alcohol.

[0046] As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene or m-hydroxystyrene is preferably used.

[0047] When a hydroxypolystyrene resin derivative is used as the binder resin (A), the number average molecular weight (Mn) of the hydroxypolystyrene resin derivative is preferably 1000 to 20000, more preferably 3000 to 10000, and even more preferably 4000 to 9000. If the number average molecular weight is 1000 or more, the resin has appropriate alkali solubility and is therefore suitable as a resin for photosensitive materials, and if it is 20000 or less, the coating property and developability are good.

[0048] (c) Alkaline aqueous solution soluble resin having epoxy groups and phenolic hydroxyl groups An aqueous alkali solution-soluble resin having an epoxy group and a phenolic hydroxyl group can also be used as the binder resin (A). Such an aqueous alkali solution-soluble resin can be obtained, for example, by reacting the epoxy group of a compound having at least two epoxy groups per molecule (hereinafter sometimes referred to as an "epoxy compound") with the carboxyl group of a hydroxybenzoic acid compound. The epoxy group in the aqueous alkali solution-soluble resin forms a crosslink upon heating by reaction with the phenolic hydroxyl group, improving the chemical resistance, heat resistance, and other properties of the coating. The phenolic hydroxyl group contributes to solubility in an aqueous alkali solution during development.

[0049] An example of a reaction in which one of the epoxy groups of an epoxy compound reacts with the carboxy group of a hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group is shown in the following reaction formula 1. [ka]

[0050] Examples of compounds having at least two epoxy groups per molecule include phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol epoxy resins, biphenol epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These epoxy compounds may contain two or more epoxy groups per molecule, and may be used alone or in combination of two or more. Because these compounds are thermosetting, it is common knowledge among those skilled in the art that their structures cannot be unambiguously described due to differences in the presence or absence of epoxy groups, the type of functional group, the degree of polymerization, and the like.

[0051] An example of the structure of a novolac 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 or 2 carbon atoms, or a hydroxyl group; and m is an integer of 1 to 50. [ka]

[0052] Examples of phenol novolac epoxy resins include EPICLON (registered trademark) N-770 (DIC Corporation) and jER (registered trademark)-152 (Mitsubishi Chemical Corporation). Examples of cresol novolac epoxy resins include EPICLON (registered trademark) N-695 (DIC Corporation) and EOCN (registered trademark)-102S (Nippon Kayaku Co., Ltd.). Examples of bisphenol epoxy resins include bisphenol A epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (Mitsubishi Chemical Corporation), and YD-128 (trade name, Nippon Steel Chemical & Material Co., Ltd.), and bisphenol F epoxy resins such as jER (registered trademark) 806 (Mitsubishi Chemical Corporation) and YDF-170 (trade name, Nippon Steel Chemical & Material Co., Ltd.). Examples of biphenol-type epoxy resins include jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (Mitsubishi Chemical Corporation). Examples of naphthalene skeleton-containing epoxy resins include NC-7000 (trade name, Nippon Kayaku Co., Ltd.) and EXA-4750 (trade name, DIC Corporation). Examples of alicyclic epoxy resins include EHPE (registered trademark)-3150 (Daicel Chemical Industries, Ltd.). Examples of heterocyclic epoxy resins include TEPIC (registered trademark), TEPIC-L, TEPIC-H, and TEPIC-S (Nissan Chemical Industries, Ltd.).

[0053] The compound having at least two epoxy groups per molecule is preferably a novolac epoxy resin, more preferably at least one selected from the group consisting of phenol novolac epoxy resins and cresol novolac epoxy resins. A photosensitive resin composition containing an aqueous alkali-soluble resin having an epoxy group derived from a novolac epoxy resin and a phenolic hydroxyl group has excellent pattern formability, easy adjustment of alkali solubility, and little outgassing.

[0054] 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, and 4-hydroxy-3-nitrobenzoic acid. Dihydroxybenzoic acid compounds are preferred in terms of enhancing alkaline developability. One type of hydroxybenzoic acid compound may be used alone, or two or more types may be used in combination.

[0055] In one embodiment, the alkali aqueous solution-soluble resin 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 with a hydroxybenzoic acid compound, and is represented by the formula (8): [ka] In formula (8), d is an integer of 1 to 5, and * represents a bond to a residue other than the epoxy group of a compound having at least two epoxy groups in one molecule.

[0056] In a method for obtaining an aqueous alkali-soluble resin having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound, 0.2 to 1.0 equivalents of the hydroxybenzoic acid compound can be used relative to 1 equivalent of the epoxy group of the epoxy compound, preferably 0.3 to 0.9 equivalents, and more preferably 0.4 to 0.8 equivalents. If the amount of the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and if the amount is 1.0 equivalents or less, an increase in molecular weight due to side reactions can be suppressed.

[0057] A catalyst may be used to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of catalyst used may be 0.1 to 10 mass% based on the mass of the reaction raw material mixture consisting of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature may be 60 to 150°C, and the reaction time may be 3 to 30 hours.

[0058] Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octoate, and zirconium octoate.

[0059] When an alkali aqueous solution soluble resin having an epoxy group and a phenolic hydroxyl group is used as the binder resin (A), the number average molecular weight (Mn) of the alkali aqueous solution soluble resin 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 the resin is suitable as a resin for photosensitive materials, and if it is 8000 or less, the coating property and developability are good.

[0060] (d) Alkali aqueous solution soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer The binder resin (A) can be an alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. Examples of alkali-soluble functional groups include carboxyl groups, alcoholic hydroxyl groups, phenolic hydroxyl groups, sulfo groups, phosphate groups, acid anhydride groups, and mercapto groups. Examples of polymerizable functional groups contained in the polymerizable monomer include radically polymerizable functional groups, such as CH═CH—, CH═C(CH═)—, CH═CHCO—, CH═C(CH═)CO—, and —OC—CH═CH—CO—.

[0061] An aqueous alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer can be produced, for example, by radical polymerization of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer. After synthesizing the copolymer by radical polymerization, the alkali-soluble functional group may be added to the copolymer.

[0062] Examples of polymerizable monomers 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, and 6-maleimidohexanoic acid.

[0063] Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene; ether compounds of vinyl alcohol such as acrylamide, acrylonitrile, and vinyl-n-butyl ether; (meth)acrylic acid esters such as (meth)acrylic acid alkyl esters, (meth)acrylic acid tetrahydrofurfuryl esters, (meth)acrylic acid dimethylaminoethyl esters, (meth)acrylic acid diethylaminoethyl esters, and (meth)acrylic acid glycidyl esters; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, isobornyl (meth)acrylate, maleic anhydride, maleic acid monoesters; and N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide.

[0064] From the viewpoint of heat resistance, etc., the aqueous alkali solution-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer preferably has one or more cyclic structures selected from the group consisting of an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure. From the viewpoint of sensitivity, the polymerizable monomer having an alkali-soluble functional group is preferably an acrylic acid derivative or a polymerizable monomer having a phenolic hydroxyl group, more preferably a polymerizable monomer having a phenolic hydroxyl group.

[0065] As a polymerizable monomer having a phenolic hydroxyl group, after polymerization, [ka] In formula (10), it is preferable to form a structural unit represented by the formula: 15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5.

[0066] In equation (10), R 15 is preferably a hydrogen atom or a methyl group. e is preferably an integer of 1 to 3, more preferably 1. As such a polymerizable monomer having a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is particularly preferred.

[0067] Other polymerizable monomers include those represented by the formula (11) after polymerization. [ka] In formula (11), it is preferable to form a structural unit represented by the formula: 16 and R 17 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R 18is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. As such other polymerizable monomers, phenylmaleimide and cyclohexylmaleimide are particularly preferred.

[0068] In one embodiment, the aqueous alkali solution-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer has a structural unit represented by the above formula (10).

[0069] In one embodiment, the aqueous alkali solution-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer has a structural unit represented by the above formula (10) and a structural unit represented by the above formula (11).

[0070] It is particularly preferred to use 4-hydroxyphenyl methacrylate, a polymerizable monomer having a phenolic hydroxyl group, 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 radical polymerization of these polymerizable monomers, it is possible to improve shape retention and developability and reduce outgassing.

[0071] Examples of polymerization initiators for producing an alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer by radical polymerization include, but are not limited to, azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN), and dicumyl peroxide. Examples of peroxide polymerization initiators that can be used include peroxide polymerization initiators having a 10-hour half-life temperature of 100 to 170°C, such as 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, and peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(t-butylperoxy)cyclohexane, and t-butyl peroxypivalate.

[0072] The amount of the polymerization initiator used is preferably 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, and is preferably 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, relative to 100 parts by mass of the total of the polymerizable monomers.

[0073] A RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator. Examples of the RAFT agent include, but are not limited to, thiocarbonylthiolated dithioesters, dithiocarbamates, trithiocarbonates, xanthates, and the like.

[0074] The RAFT agent can be used in the range of 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of the total of the polymerizable monomers.

[0075] When an alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is used as the binder resin (A), the weight-average molecular weight (Mw) of the alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer can be 3,000 to 80,000, preferably 4,000 to 70,000, and more preferably 5,000 to 60,000. The number-average molecular weight (Mn) can be 1,000 to 30,000, preferably 1,500 to 25,000, and more preferably 2,000 to 20,000. The polydispersity (Mw / Mn) can be 1.0 to 3.5, preferably 1.1 to 3.0, and more preferably 1.2 to 2.8. By setting the weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (Mw / Mn) within the above ranges, a photosensitive resin composition with excellent alkali solubility and developability can be obtained.

[0076] In this disclosure, when an alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer also falls under the category of hydroxypolystyrene resin derivative (b), it is treated as an alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. When an alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer also falls under the category of alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group, it is treated as an alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. In other words, hydroxypolystyrene resin derivative (b) and alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group are excluded from those that fall under the category of alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer.

[0077] In one embodiment, the aqueous alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer that constitutes the binder resin (A) includes a phenolic resin, such as a phenol novolac resin, a cresol novolac resin, a triphenylmethane-type phenolic resin, a phenol aralkyl resin, a biphenyl aralkyl phenolic resin, a phenol-dicyclopentadiene copolymer resin, or a derivative thereof, in which a polymerizable monomer having a phenolic hydroxyl group as the alkali-soluble functional group is used. When a phenolic resin is used as the binder resin (A), the preferred number-average molecular weight (Mn) varies depending on the resin structure, but is generally 100 to 50,000, more preferably 500 to 30,000, and even more preferably 800 to 10,000. A number-average molecular weight of 100 or more provides an appropriate alkali development rate and a sufficient difference in dissolution rate between exposed and unexposed areas, resulting in good pattern resolution. A number-average molecular weight of 50,000 or less provides good alkali developability.

[0078] (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 the group consisting of (e) polyimide resin, (f) polyamic acid resin, (g) polybenzoxazole resin, and (h) polybenzoxazole resin precursor. The polyamic acid resin becomes a resin having a polyimide structure by dehydration and ring closure. The polybenzoxazole resin precursor becomes a polybenzoxazole resin by dehydration and ring closure.

[0079] (e) The polyimide resin has a structural unit represented by formula (12). (f) The polyamic acid resin and (h) the polybenzoxazole resin precursor have a structural unit represented by formula (13). (g) The polybenzoxazole resin has a structural unit represented by formula (14). The polyimide resin may have both the structural unit represented by formula (12) and the structural unit represented by formula (13), and the polybenzoxazole resin may have both the structural unit represented by formula (14) and the structural unit represented by formula (13).

[0080] [ka]

[0081] In equation (12), R 19 is a tetravalent to decavalent organic group, and R 20 is a divalent to octavalent organic group, and R 21 and R 22 are each independently a hydroxyl group, a carboxyl group, a sulfo group, or a mercapto group, and f and g are each independently an integer of 0 to 6.

[0082] [ka]

[0083] In equation (13), R 23 is a divalent to octavalent organic group, and R 24 is a divalent to octavalent organic group, and R 25 and R 26 each independently represents a hydroxyl group, a sulfo group, a mercapto group, or -COOR 27 and 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 a polyamic acid resin, h is an integer of 1 or more, and R 25 At least one of -COOR 27 In the case of a polybenzoxazole resin precursor, i is an integer of 1 or more, and R 26 At least one of the groups is a phenolic hydroxyl group.

[0084] [ka]

[0085] In equation (14), R 28 is a divalent to octavalent organic group, and R 29 is a divalent to octavalent organic group, and R 30and R 31 are each independently a hydroxyl group, a carboxyl group, a sulfo group, or a mercapto group, and j and k are each independently an integer of 0 to 6.

[0086] R in equation (12) 19 -(R 21 ) f represents the residue of an acid dianhydride. 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.

[0087] Examples of acid dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic 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, Examples of suitable tetracarboxylic acid dianhydrides include aromatic tetracarboxylic acid dianhydrides such as bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; and aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, as well as combinations of two or more thereof.

[0088] R in equation (13) 23 -(R 25 ) h , and R in Eq. (14) 28 -(R 30 ) j R represents the residue of an acid. 23 and R 28 are each independently a divalent to octavalent organic group, and are preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.

[0089] 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; pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane. Examples of the tetracarboxylic acids include aromatic tetracarboxylic acids such as fluoropropane, 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, and 3,4,9,10-perylenetetracarboxylic acid; and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid, as well as combinations of two or more thereof. In the above tricarboxylic acids and tetracarboxylic acids, one or two carboxy groups may be selected from the R 25or R in formula (14) 30 These acids may be in the form of esters or acid anhydrides.

[0090] R in equation (12) 20 -(R 22 ) g , R in Eq. (13) 24 -(R 26 ) i , and R in Eq. (14) 29 -(R 31 ) k R represents a diamine residue. 20 , R 24 , and R 29 are each independently a divalent to octavalent organic group, and are preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.

[0091] R in equation (12) 20 and R of formula (13) relating to polyamic acid resin 24Examples of diamines corresponding to the above include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 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, and 2,2'-diethyl-4,4'-diaminobiphenyl. aromatic diamines such as 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, and 9,9-bis(4-aminophenyl)fluorene, or compounds in which at least one hydrogen atom on the aromatic ring of these aromatic diamines has been substituted with an alkyl group or a halogen atom; aliphatic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine, and combinations of two or more of these.

[0092] R of formula (13) relating to the polybenzoxazole resin precursor 24 , and R in Eq. (14) 29 Examples of diamines corresponding to the above include bisaminophenol compounds having a phenolic hydroxyl group at the ortho position relative to the amino group on the aromatic ring of the aromatic diamine, and combinations of two or more of these compounds.

[0093] The polyimide resin, polyamic acid resin, polybenzoxazole resin, and polybenzoxazole resin precursor may have an acidic group at the end of the main chain by being terminated at their ends with a monoamine, acid anhydride, acid chloride, monocarboxylic acid, or the like having an acidic group.

[0094] The polyamic acid resin can be synthesized, for example, by a method of reacting a tetracarboxylic dianhydride with a diamine; a method of generating a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent; or a method of generating a diester from a tetracarboxylic dianhydride with an alcohol, converting the remaining dicarboxylic acid into an acid chloride, and then reacting the resulting intermediate with a diamine.

[0095] The polybenzoxazole resin precursor can be synthesized, for example, by a condensation reaction between a bisaminophenol compound and a polycarboxylic acid such as a dicarboxylic acid, a tricarboxylic acid, or a tetracarboxylic acid. Specific examples include a method of reacting a bisaminophenol compound with an intermediate obtained by reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with a polycarboxylic acid, and a method of adding a dicarboxylic acid dichloride solution dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0096] The polyimide resin can be synthesized, for example, by dehydrating and ring-closing the polyamic acid resin obtained by the above-mentioned method by heating or chemical treatment with an acid or a base.

[0097] The polybenzoxazole resin can be synthesized, for example, by dehydrating and cyclizing the polybenzoxazole resin precursor obtained by the above-mentioned method by heating or chemical treatment with an acid or a base.

[0098] When a polyimide resin, a polyamic acid resin, a polybenzoxazole resin, or a polybenzoxazole resin precursor is used as the binder resin (A), the number average molecular weight (Mn) of the polyimide resin, the polyamic acid resin, the polybenzoxazole resin, or the polybenzoxazole resin precursor 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 resin has appropriate alkali solubility and is therefore suitable as a resin for photosensitive materials, and if it is 8000 or less, the resin has good coatability and developability.

[0099] (i) Silicone resin In one embodiment, the binder resin (A) includes (i) a silicone resin. The silicone resin can be synthesized by hydrolysis and condensation of at least one compound selected from organosilanes represented by formula (15) and organosilanes represented by formula (16). By using organosilanes represented by formula (15) and formula (16), a photosensitive resin composition excellent in sensitivity and resolution can be obtained.

[0100] The organosilane represented by formula (15) is shown below. [ka]

[0101] In equation (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, multiple R 32 may be the same or different. When p is 2 or less, multiple R 33 may be the same or different.

[0102] Examples of organosilanes represented by formula (15) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane, 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-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2- Examples of suitable silanes include trifunctional silanes such as indenyltrimethoxysilane and 5-acenaphthenyltrimethoxysilane; bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, and di(1-naphthyl)diethoxysilane; monofunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane, and combinations of two or more of these.

[0103] The organosilane represented by formula (16) is shown below. [ka]

[0104] In equation (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, multiple R 35 and R 36 may be the same or different.

[0105] Specific examples of organosilanes represented by formula (16) include methyl silicate 51 (R 34 ~R 37 is a methyl group, n is an average of 4), Tama Chemical Industry Co., Ltd.: M Silicate 51 (R 34 ~R 37 is a methyl group, n is an average of 3 to 5), silicate 40 (R 34 ~R 37 is an ethyl group, n is an average of 4-6), silicate 45 (R 34 ~R 37 is an ethyl group, n is an average of 6 to 8), Colcoat Co., Ltd.: Methyl silicate 51 (R 34 ~R 37 is a methyl group, n is an average of 4), methyl silicate 53A (R 34 ~R 37 is a methyl group, n is an average of 7), ethyl silicate 40 (R 34 ~R 37 is an ethyl group, and n is an average of 5. Two or more of these may be used in combination.

[0106] Silicone resins can be synthesized by hydrolysis and partial condensation of organosilanes represented by formula (15) and formula (16). Due to the partial condensation, residual silanol groups remain in the silicone resin. For example, hydrolysis and partial condensation can be performed by adding a solvent, water, a catalyst, etc. to an organosilane mixture as needed, and then heating and stirring the mixture at 50°C to 150°C for approximately 0.5 to 100 hours. If necessary, hydrolysis by-products (alcohols such as methanol) or condensation by-products (water) may be removed by distillation.

[0107] As the catalyst, an acid catalyst or a base catalyst is preferably used. Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, and ion exchange resins. Examples of base catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having amino groups, and ion exchange resins. After hydrolysis and partial condensation, the catalyst may be removed, if necessary, by washing with water, treatment with an ion exchange resin, or a combination thereof. Removal of the catalyst can improve the storage stability of the photosensitive resin composition.

[0108] When a silicone resin is used as the binder resin (A), the weight-average molecular weight (Mw) of the silicone resin is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000. If the weight-average molecular weight is 1,000 or more, film-forming properties can be improved, and if it is 100,000 or less, alkaline developability is good.

[0109] (j) Cyclic olefin polymer In one embodiment, the binder resin (A) includes (j) a cyclic olefin polymer. The cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic or aromatic ring) and a carbon-carbon double bond. The cyclic olefin polymer may have structural units derived from a monomer other than the cyclic olefin monomer.

[0110] Examples of monomers constituting cyclic olefin polymers include cyclic olefin monomers having a protic polar group, cyclic olefin monomers having a non-protic polar group, cyclic olefin monomers having no polar group, and monomers other than cyclic olefins. The monomers other than cyclic olefins may have a protic polar group or a polar group other than this, or may not have a polar group.

[0111] Examples of cyclic olefin monomers 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[4.4.0.12,5.17,10]dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8- Examples include carboxyl group-containing cyclic olefins such as exo-9-endo-dihydroxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene; hydroxyl group-containing cyclic olefins such as 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[4.4.0.12,5.17,10]dodec-3-ene, and 8-methyl-8-(4-hydroxyphenyl)tetracyclo[4.4.0.12,5.17,10]dodec-3-ene; and combinations of two or more of these.

[0112] Examples of cyclic olefin monomers having a polar group other than a protic group 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[4.4.0.12,5.17,10]dodec-3-ene, 8-methoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, and 8-ethoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene. Dec-3-ene, 8-n-propoxycarbonyltetracyclo[4.4.0.112,5.17,10]dodec-3-ene, 8-isopropoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-n-butoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-Methyl-8-n-propoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyl-8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.12,5.17,10]dodec-3-ene Cyclic olefins having an ester group such as tetracyclo[4.4.0.12,5.17,10]dodec-3-ene; cyclic olefins having an N-substituted imide group such as N-phenyl-(5-norbornene-2,3-dicarboximide); cyclic olefins having a cyano group such as 8-cyanotetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyl-8-cyanotetracyclo[4.4.0.12,5.17,10]dodec-3-ene, and 5-cyanobicyclo[2.2.1]hept-2-ene; 8-chlorotetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyl-8-chlorotetracyclo[4.4.0.12,5.17,10]dodec-3-ene, and other cyclic olefins having halogen atoms, as well as combinations of two or more of these.

[0113] Examples of cyclic olefin monomers 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[4.3.0.12,5]deca-3,7-diene, and cyclohexane. ene, tetracyclo[8.4.0.111,14.03,7]pentadeca-3,5,7,12,11-pentaene, tetracyclo[4.4.0.12,5.17,10]dec-3-ene, 8-methyl-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethyl-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methylidene-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethyl 1,4-Methano-1,4,4a,5,10,10a-hexacyclo[6.5.1.13,6.02,7.09,13]pentadeca-3,10-diene, ... Examples include hydroanthracene, 8-phenyl-tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, tetracyclo[9.2.1.02,10.03,8]tetradeca-3,5,7,12-tetraene, pentacyclo[7.4.0.13,6.110,13.02,7]pentadeca-4,11-diene, pentacyclo[9.2.1.14,7.02,10.03,8]pentadeca-5,12-diene, and combinations of two or more thereof.

[0114] Specific examples of the monomer other than the cyclic olefin 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, and 1-eicosene; chain olefins such as non-conjugated dienes, such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene; and combinations of two or more of these.

[0115] The cyclic olefin polymer can be synthesized by polymerizing the above-mentioned monomers by ring-opening polymerization or addition polymerization. As the polymerization catalyst, for example, a metal complex of molybdenum, ruthenium, osmium, or the like, or a combination of two or more of these, is preferably used. The cyclic olefin polymer may be subjected to a hydrogenation treatment. As the hydrogenation catalyst, those generally used for hydrogenating olefin compounds can be used, such as Ziegler-type homogeneous catalysts, noble metal complex catalysts, and supported noble metal catalysts.

[0116] When a cyclic olefin polymer is used as the binder resin (A), the weight average molecular weight (Mw) of the cyclic olefin polymer is preferably 1000 to 100000, and more preferably 1000 to 50000. If the weight average molecular weight is 1000 or more, film formability can be improved, and if it is 100000 or less, alkaline developability is good.

[0117] (k) Cardo resin In one embodiment, the binder resin (A) includes (k) a cardo resin. A cardo resin has a cardo structure, i.e., a skeletal structure in which two other cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure. Examples of skeletal structures in which two other cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure include a fluorene skeleton, a bisphenolfluorene skeleton, a bisaminophenylfluorene skeleton, a fluorene skeleton having an epoxy group, and a fluorene skeleton having an acrylic group. An example of a cardo structure is one in which a benzene ring is bonded to a fluorene ring.

[0118] Cardo resins can be synthesized by polymerizing monomers having a cardo structure through a reaction between functional groups of the monomers. Examples of polymerization methods for the cardo structure monomers include ring-opening polymerization and addition polymerization.

[0119] Examples of monomers having a cardo structure include bis(glycidyloxyphenyl)fluorene epoxy resins, cardo structure-containing bisphenol compounds such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(cyanoalkyl)fluorene compounds such as 9,9-bis(cyanomethyl)fluorene, and 9,9-bis(aminoalkyl)fluorene compounds such as 9,9-bis(3-aminopropyl)fluorene, as well as combinations of two or more of these. Cardo resins may also be copolymers of a monomer having a cardo structure with other copolymerizable monomers.

[0120] When a cardo resin is used as the binder resin (A), the weight average molecular weight (Mw) of the cardo resin is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000. If the weight average molecular weight is 1,000 or more, film formability can be improved, and if it is 100,000 or less, alkaline developability is good.

[0121] (l) Epoxy resins that do not have phenolic hydroxyl groups In one embodiment, the binder resin (A) includes (1) an epoxy resin having no phenolic hydroxyl groups. Examples of epoxy resins having no phenolic hydroxyl groups include phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol epoxy resins, biphenol epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These epoxy resins may be used alone or in combination of two or more.

[0122] An example of the structure of the novolac type epoxy resin is the structure represented by the above formula (9), which was explained in the alkali aqueous solution soluble resin (c) having an epoxy group and a phenolic hydroxyl group.

[0123] Specific examples of the phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol epoxy resin, biphenol epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin, and heterocyclic epoxy resin include the epoxy resins described in the alkali aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group.

[0124] The epoxy resin having no phenolic hydroxyl group is preferably a novolac epoxy resin, more preferably at least one selected from the group consisting of a phenol novolac epoxy resin and a cresol novolac epoxy resin. Photosensitive resin compositions containing a novolac epoxy resin have excellent pattern formability.

[0125] When an epoxy resin having no phenolic hydroxyl group is used as the binder resin (A), it is preferable to use it in combination with a dissolution promoter (D), which is an optional component described later, and / or to use it in combination with a resin having an alkali-soluble functional group as the binder resin (A).

[0126] When an epoxy resin having no phenolic hydroxyl groups is used as the binder resin (A), the weight-average molecular weight (Mw) of the epoxy resin having no phenolic hydroxyl groups is preferably 300 to 8000, more preferably 400 to 7000. If the weight-average molecular weight is 300 or more, the unexposed portion does not dissolve more than necessary during alkaline development, and if it is 8000 or less, excellent pattern formability is achieved.

[0127] The binder resin (A) may be a single resin or a combination of two or more resins.

[0128] The content of the binder resin (A) in the positive photosensitive resin composition can be 5 to 80% by mass, preferably 10 to 75% by mass, and more preferably 20 to 70% by mass, based on 100% by mass of the solid content. When the content of the binder resin (A) is 5 parts by mass or more based on 100% by mass of the solid content, the residual film rate, heat resistance, sensitivity, etc. are appropriate. When the content of the binder resin (A) is 80% by mass or less based on 100% by mass of the solid content, the optical density (OD value) of the cured coating can be 0.5 or more per 1 μm of film thickness, and light-blocking properties can be maintained even after curing.

[0129] The binder resin (A) preferably contains at least one selected from the resin components (a) to (l), and when it contains a plurality of the resin components (a) to (l), any combination is possible. The binder resin (A) more preferably contains at least one selected from the resin components (a) to (d), and further preferably contains the resin components (c) and (d).

[0130] The content of at least one resin component selected from (a) to (d) relative to 100% by mass of the binder resin (A) is preferably 0.5% by mass or more, more preferably 50% by mass or more, and even more preferably 80% by mass or more. If the content of at least one resin component selected from (a) to (d) relative to 100% by mass of the binder resin (A) is 0.5% by mass or more, the resin composition has good heat resistance.

[0131] When the binder resin (A) contains a resin component (c), the content of the resin component (c) relative to 100% by mass of the binder resin (A) is preferably 20 to 70% by mass, and more preferably 25 to 60% by mass. When the content of the resin component (c) relative to 100% by mass of the binder resin (A) is 20% by mass or more, the number of crosslinking points when the resin is heat-cured increases, improving heat resistance. When the content of the resin component (c) relative to 100% by mass of the binder resin (A) is 70% by mass or less, the hole shape is improved.

[0132] When the binder resin (A) contains the resin component (d), the content of the resin component (d) relative to 100% by mass of the binder resin (A) is preferably 15 to 70% by mass, more preferably 20 to 60% by mass. When the content of the resin component (d) relative to 100% by mass of the binder resin (A) is 15% by mass or more, the hole shape becomes good. When the content of the resin component (d) relative to 100% by mass of the binder resin (A) is 70% by mass or less, residues are less likely to appear in exposed areas.

[0133] When the binder resin (A) contains resin components (c) and (d), the total content of resin components (c) and (d) relative to 100% by mass of the binder resin (A) is preferably 60% by mass or more, more preferably 70% by mass or more. When the total content of resin components (c) and (d) relative to 100% by mass of the binder resin (A) is 60% by mass or more, residues in exposed areas and surface roughness in unexposed areas are less likely to occur.

[0134] When the binder resin (A) contains resin components (c) and (d), it preferably further contains resin component (l). The content of resin component (l) relative to 100% by mass of binder resin (A) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass. When the content of resin component (l) relative to 100% by mass of binder resin (A) is 1% by mass or more, unexposed areas do not dissolve more than necessary during alkaline development. When the content of resin component (l) relative to 100% by mass of binder resin (A) is 30% by mass or less, good pattern formability is achieved.

[0135] The binder resin (A) may contain a resin in which some of the alkali-soluble functional groups are protected with acid-decomposable groups.

[0136] A resin in which some of the alkali-soluble functional groups are protected with acid-decomposable groups has reduced alkali solubility before exposure. By performing post-exposure bake (PEB) as needed in the presence of acid generated during exposure, decomposition (deprotection) of the acid-decomposable groups is promoted, and the alkali-soluble functional groups are regenerated. This promotes alkali dissolution of the binder resin (A) in the exposed areas during development. The binder resin (A) may contain one type or a combination of two or more types. For example, the binder resin (A) may contain two or more resins that differ in the polymer structural unit, acid-decomposable group, protection rate of alkali-soluble functional groups, or combinations thereof.

[0137] <Photoacid generator (B)> The positive-type photosensitive resin composition contains a photoacid generator (B). The photoacid generator (B) is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, gamma rays, or electron beams. The presence of the acid generated by the photoacid generator (B) in the irradiated area facilitates the dissolution of the resin in that area in an alkaline aqueous solution together with the acid. When the binder resin (A) contains an alkali-soluble functional group, some of which is protected with an acid-decomposable group, the photoacid generator (B) promotes the decomposition of the acid-decomposable group to regenerate the alkali-soluble functional group, thereby increasing the alkali solubility of the binder resin (A). Therefore, by including the photoacid generator (B) in the positive-type photosensitive resin composition, it is possible to form a high-resolution pattern with high sensitivity even at a low exposure dose. The photoacid generator (B) can be used alone or in combination of two or more types.

[0138] In one embodiment, the positive photosensitive resin composition contains 1% by mass to 50% by mass, preferably 5% by mass to 40% by mass, and more preferably 8% by mass to 30% by mass of the photoacid generator (B) based on 100% by mass of the solid content. When the content of the photoacid generator (B) is 1% by mass or more based on 100% by mass of the solid content, high sensitivity can be achieved. When the content of the photoacid generator (B) is 50% by mass or less based on 100% by mass of the solid content, alkaline developability is good and residue generation can be suppressed.

[0139] In one embodiment, the positive-type photosensitive resin composition contains a quinone diazide compound as the photoacid generator (B). When irradiated with radiation such as visible light, ultraviolet light, gamma rays, or electron beams, the quinone diazide compound generates an alkali-soluble carboxylic acid compound via the reaction shown in Reaction Scheme 2 below. Before exposure, the quinone diazide compound interacts (e.g., forms hydrogen bonds) with functional groups of the binder resin (A) such as a novolac resin, rendering the binder resin (A) insoluble in an alkaline aqueous solution. Meanwhile, the presence of the alkali-soluble carboxylic acid compound in the irradiated area facilitates the dissolution of the resin in that area together with the carboxylic acid compound in an alkaline aqueous solution. Furthermore, the carboxylic acid compound has a relatively larger molecular structure than acids generated by photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is therefore less likely to diffuse in the coating. These synergistic effects increase the difference in alkali solubility between the unexposed and exposed areas, thereby enabling the formation of high-sensitivity, high-resolution patterns even at low exposure doses. The quinone diazide compounds can be used alone or in combination of two or more.

[0140] [ka]

[0141] Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond or a sulfonamide bond. From the viewpoint of contrast between exposed and unexposed areas, it is preferred that 20 mol % or more of the total functional groups of the polyhydroxy compound or polyamino compound be substituted with quinone diazide.

[0142] Polyhydroxy compounds include 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, Tyrol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TM Examples of suitable phenols include, but are not limited to, L-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all trade names, 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 (all trade names, Asahi Organic Chemicals 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, methylene bisphenol, and BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.).

[0143] Examples of polyamino compounds include, but are not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0144] Polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

[0145] The quinone diazide compound is preferably a 1,2-naphthoquinone diazide-4-sulfonic acid ester or a 1,2-naphthoquinone diazide-5-sulfonic acid ester of a polyhydroxy compound.

[0146] In one embodiment, the positive photosensitive resin composition contains a quinone diazide compound in an amount of 1% by mass to 50% by mass, preferably 5% by mass to 40% by mass, and more preferably 8% by mass to 35% by mass, based on 100% by mass of the solid content. When the content of the quinone diazide compound is 1% by mass or more, based on 100% by mass of the solid content, high sensitivity can be achieved. When the content of the quinone diazide compound is 50% by mass or less, based on 100% by mass of the solid content, good alkaline developability can be achieved.

[0147] Examples of the photoacid generator (B) other than quinone diazide compounds include trichloromethyl-s-triazine compounds, onium salts such as sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, oxime sulfonate compounds are preferred because of their high sensitivity and insulating properties.

[0148] An example of the oxime sulfonate compound is a compound represented by formula (17). [ka]

[0149] In equation (17), R 9 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom; R 10 and R 11 R are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, an acyloxy group, a carboxy group, an alkoxycarbonyl group, or a fluoroalkyl group. 10 and R 11 may be bonded to form a ring structure. The ring structure preferably has 3 to 10 ring members.

[0150] R 9 Examples of the substituted or unsubstituted alkyl group include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms, and a methyl group, an ethyl group, or an n-propyl group is preferred.

[0151] R 9 The substituted or unsubstituted alkoxy group includes, for example, a linear alkoxy group having 1 to 5 carbon atoms or a branched alkoxy group having 3 to 5 carbon atoms, and is preferably a methoxy group or an ethoxy group.

[0152] R 9 Examples of the substituents on the alkyl and alkoxy groups include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), cyano groups, nitro groups, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cycloalkyl groups having 3 to 10 carbon atoms.

[0153] R 9 The alkyl group of the substituent is preferably a fluoroalkyl group, more preferably a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group, and even more preferably a trifluoromethyl group.

[0154] R 9 The substituted or unsubstituted aryl group includes, for example, an aryl group having 6 to 20 carbon atoms, and is preferably a phenyl group, a 4-methylphenyl group, or a naphthyl group.

[0155] R 9 Examples of the substituent on the aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom).

[0156] R 9 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0157] R 10 and R 11 The substituted or unsubstituted aryl group of R is, for example, an aryl group having 6 to 20 carbon atoms, and is preferably a phenyl group or a naphthyl group. 10 and R 11 Examples of the substituted or unsubstituted heterocyclic group include a 2-benzofuranyl group, a 3-benzofuranyl group, a 2-benzimidazolyl group, a 2-benzoxazolyl group, a 2-benzothiazolyl group, a 2-indolyl group, a 3-coumarinyl group, a 4-coumarinyl group, a 3-isocoumarinyl group, and a 4-isocoumarinyl group.

[0158] R 10 and R 11 Examples of the substituents on the aryl group and heterocyclic group include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, acyloxy groups having 2 to 4 carbon atoms, and halogen atoms (fluorine atom, chlorine atom, bromine atom, and iodine atom).

[0159] R 10 and R 11 Examples of the acyloxy group of R include an acetoxy group and a benzoyl group. 10 and R 11The alkoxycarbonyl group includes, for example, an ethoxycarbonyl group.

[0160] R 10 and R 11 Examples of the fluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.

[0161] R 10 is preferably a cyano group, a carboxy group, an alkoxycarbonyl group, or a fluoroalkyl group, and more preferably a cyano group or a trifluoromethyl group.

[0162] R 11 is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and is preferably a 4-methoxyphenyl group, or a substituted or unsubstituted 2-benzofuranyl group, 3-benzofuranyl group, 3-coumarinyl group, 4-coumarinyl group, 3-isocoumarinyl group, or 4-isocoumarinyl group.

[0163] R 10 and R 11 Examples of the oxime sulfonate compound having a ring structure formed by bonding include the oxime sulfonate compound represented by formula (17a). [ka]

[0164] In formula (17a), R 9 is as explained for equation (17), and R 12 are each independently an alkyl group, an alkoxy group, or a halogen atom, and m represents an integer of 0 to 5.

[0165] R 12 Examples of the alkyl group include a linear alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms, and a methyl group, an ethyl group, or an n-propyl group is preferred.

[0166] R 12 Examples of the alkoxy group include a linear alkoxy group having 1 to 5 carbon atoms and a branched alkoxy group having 3 to 5 carbon atoms, and a methoxy group or an ethoxy group is preferred.

[0167] R 12 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a fluorine atom is preferred. m is preferably 0 or 1.

[0168] Examples of oxime sulfonate compounds include (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 2-[2-(propylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, and 2-[2-(4-methylphenylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile.

[0169] <Metal complex dyes (C)> The positive-type photosensitive resin composition contains a metal complex dye (C). A typical metal complex dye (C) consists of a monoazo dye having a coordinating functional group such as a hydroxyl group, carboxyl group, or amino group, which is coordinated to a metal ion (anion) of chromium, copper, cobalt, iron, nickel, or other metal ion, and a countercation. Metal complex dyes (C) are generally classified into two classes: 1:1 type metal complex dyes (one monoazo dye molecule coordinated to one metal atom) and 1:2 type metal complex dyes (two monoazo dye molecules coordinated to one metal atom). Monoazo dyes generally have one of the following structures: o,o'-dihydroxyazo, o-hydroxy-o'-aminoazo, or o-hydroxy-o'-carboxyazo. Metal complex dyes (C) leave less residue during development than pigments and can form high-resolution patterns in coatings. In addition, the metal complex dye (C) is easily soluble in organic solvents and does not precipitate in solution even when incorporated at high concentrations. Furthermore, it is resistant to fading during heat treatment after exposure, which allows for efficient enhancement of the optical density (OD value) of the cured coating. The metal complex dye (C) can be used alone or in combination of two or more types.

[0170] The metal element forming the metal complex ion contained in the metal complex dye (C) is preferably at least one selected from the group consisting of chromium, copper, cobalt, nickel, and iron, and more preferably chromium.

[0171] The metal complex dye (C) contains a counter cation having a nitrogen-containing heterocyclic structure. The counter cation having a nitrogen-containing heterocyclic structure is constituted by a proton or the like being coordinated to the nitrogen atom of the nitrogen-containing heterocyclic ring. The nitrogen-containing heterocyclic ring may contain heteroatoms such as oxygen atoms and sulfur atoms as constituent atoms in addition to the nitrogen atom.

[0172] Examples of counter cations having a nitrogen-containing heterocyclic structure include proton adducts of nitrogen-containing heterocyclic compounds having a 4-, 5-, 6-, 7-, or 8-membered ring or two or more ring structures containing a nitrogen atom. Specific examples include proton adducts of azetidine, azeto, diazetidine, diazeto, pyrrolidine, pyrrole, imidazolidine, pyrazolidine, imidazole, pyrazole, oxazolidine, oxazole, isoxazole, thiazolidine, thiazole, isothiazole, triazole, furazan, oxadiazole, thiadiazole, dioxazole, dithiazole, piperidine, pyridine, piperazine, diazine, morpholine, oxazine, thiomorpholine, thiazine, triazine, azepane, azepine, diazepane, diazepine, azocane, azocine, diazabicycloundecene, diazabicyclononene, and derivatives thereof. Derivatives of these nitrogen-containing heterocyclic compounds include compounds in which any hydrogen atom bonded to a carbon atom forming a heterocyclic structure is substituted with another atom or atomic group, and compounds in which a hydrogen atom bonded to a nitrogen atom is substituted with another atom or atomic group.

[0173] The nitrogen-containing heterocycle is preferably a 5- or 6-membered nitrogen-containing heterocycle because the nitrogen-containing heterocycle has appropriate hydrophilicity and the photosensitive resin composition using the metal complex dye containing the nitrogen-containing heterocycle has high sensitivity. The nitrogen-containing heterocycle is preferably an alicyclic nitrogen-containing heterocycle because the nitrogen-containing heterocycle has a low crystallinity and the metal complex dye containing the nitrogen-containing heterocycle has high solubility in a solvent.

[0174] The nitrogen atom of the nitrogen-containing heterocycle has a structure that makes it less likely to react even when it comes into contact with a compound that is reactive with amines, and therefore the nitrogen-containing heterocycle preferably has a tertiary amine structure.

[0175] The nitrogen-containing heterocyclic compound forming the counter cation having a nitrogen-containing heterocyclic structure is preferably at least one selected from the group consisting of morpholine, piperidine, pyrrolidine, and derivatives thereof, and more preferably at least one selected from the group consisting of N-substituted morpholine, N-substituted piperidine, and N-substituted pyrrolidine. The substituent on the nitrogen atom in the N-substituted morpholine, N-substituted piperidine, and N-substituted pyrrolidine may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The substituent on the nitrogen atom is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 1 to 4 carbon atoms.

[0176] Among the above, it is more preferable that the nitrogen-containing heterocyclic compound forming the counter cation having a nitrogen-containing heterocyclic structure is at least one selected from the group consisting of N-alkylmorpholine and N-alkylpiperidine. That is, it is more preferable that the counter cation having a nitrogen-containing heterocyclic structure is at least one selected from the group consisting of N-alkylmorpholinium cation and N-alkylpiperidinium cation. This is because if the nitrogen-containing heterocyclic compound is any of these, it has low hydrophobicity and is less likely to affect pattern formability.

[0177] In the N-alkylmorpholine and N-alkylpiperidine, the alkyl group bonded to the nitrogen atom may have a functional group such as a hydroxyl group or an alkoxy group. Examples of N-alkylmorpholine include N-methylmorpholine, N-ethylmorpholine, N-isobutylmorpholine, Nn-butylmorpholine, and 2-morpholinoethanol. Examples of N-alkylpiperidine include N-methylpiperidine and N-ethylpiperidine.

[0178] The metal complex dye (C) contains a counter cation having a nitrogen-containing heterocyclic structure. Without being bound by any theory, in the case of a metal complex dye containing a cation resulting from the protonation of a nitrogen-containing compound having no heterocyclic structure as a counter cation, the nitrogen-containing compound having no heterocyclic structure tightly caps alkali-soluble functional groups in other components either immediately or over time, resulting in difficulty in achieving sensitivity and deterioration of storage stability. However, in the case of a metal complex dye containing a cation having a heterocyclic structure as a counter cation, it has appropriate basicity and hydrogen-bonding ability, and therefore can provide a positive-type photosensitive resin composition having good sensitivity, process window, and storage stability.

[0179] The metal complex dye (C) can be produced by a general production method. Generally, metal complex dyes are produced through the following steps 1 to 4. Step 1: Preparation of diazo compounds by diazotization of aminophenol derivatives Step 2: Preparation of a monoazo compound by coupling reaction of the diazo compound obtained in Step 1 with a hydroxynaphthalene derivative Step 3: Formation of a metal complex by mixing the monoazo compound obtained in step 2 with a metal salt Step 4: Ion exchange by adding an amine or an amine salt to the metal complex obtained in Step 3

[0180] The metal complex dye (C) contained in the positive photosensitive resin composition of the present invention can be produced in the above step 4 by using a nitrogen-containing heterocyclic compound or a salt thereof.

[0181] The metal complex dye (C) may be produced by cation exchange using a commercially available metal complex dye as a raw material. Specifically, it can be produced by mixing and stirring the raw material metal complex dye and a nitrogen-containing heterocyclic compound in a solvent.

[0182] The cation exchange reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas. The reaction temperature is preferably 0 to 150° C., more preferably 20 to 130° C. The reaction time is preferably 1 to 50 hours, more preferably 5 to 40 hours.

[0183] Examples of metal complex dyes that can be used as raw materials for the metal complex dye (C) include black dyes specified by the color index (CI) of Solvent Black 22 to 47, blue dyes specified by the CI of Solvent Blue 44 and 137, yellow dyes specified by the CI of Solvent Yellow 13, 19, 21, 25, 25:1, 62, 79, 81, 82, 83, 83:1, 88, 89, 90, 151, and 161, orange dyes specified by the CI of Solvent Orange 5, 11, 20, 40:1, 41, 45, 54, 56, 58, 62, 70, 81, and 99, and solvent red 8 and 3 Examples of dyes include red dyes specified by CIs of 5, 83:1, 84:1, 90, 90:1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, and 243; purple dyes specified by CIs of Solvent Violet 2, 21, 21:1, 46, 49, 58, and 6; brown dyes specified by CIs of Solvent Brown 28, 42, 43, 44, 53, 62, and 63; and dyes specified by CIs of Acid Yellow 59, 121, Acid Orange 74, 162, and Acid Red 211.

[0184] The metal complex dye used as a raw material is preferably at least one type selected from black dyes defined by the CIs of Solvent Black 22 to 47, and more preferably at least one type selected from black dyes defined by the CIs of Solvent Black 27, 29, or 34. That is, the metal complex ion contained in the metal complex dye (C) is preferably a metal complex ion contained in a compound defined by the CIs of Solvent Black 22 to 47, and more preferably a metal complex ion contained in a compound defined by the CIs of Solvent Black 27, 29, or 34. In the case of a positive photosensitive resin composition using the metal complex dye (C) produced using the above metal complex dye as a raw material, the light-blocking properties of the cured coating can be maintained.

[0185] In the cation exchange, the amount of the nitrogen-containing heterocyclic compound to be reacted with the raw material metal complex dye is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of the raw material metal complex dye.

[0186] Examples of solvents for carrying out cation exchange include ether compounds such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and triethylene glycol ethyl methyl ether; glycol monoalkyl ether acetate compounds such as methyl cellosolve acetate, ethyl cellosolve acetate, 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 and 4-hydroxy-4-methyl-2-pentanone; esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 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.

[0187] The solvent is preferably γ-butyrolactone, from the viewpoint of facilitating the discharge of the counter amine before cation exchange. The amount of the solvent used is preferably 50 to 400 parts by mass, more preferably 100 to 300 parts by mass, per 100 parts by mass of the metal complex dye as the raw material.

[0188] After the cation exchange, the resulting solution is added dropwise to a poor solvent such as methanol, ethanol, isopropanol, toluene, hexane, or methylcyclohexane, and the mixture is stirred to precipitate a precipitate. The precipitate is collected by filtration to obtain the metal complex dye (C). The collected precipitate is preferably washed with the solvent used to precipitate the precipitate and then vacuum dried.

[0189] In one embodiment, the positive photosensitive resin composition contains 5% by mass to 50% by mass, preferably 10% by mass to 45% by mass, and more preferably 15% by mass to 40% by mass of the metal complex dye (C) based on 100% by mass of the solid content. When the content of the metal complex dye (C) is 5% by mass or more based on the total 100 parts by mass, the light-blocking properties of the cured coating can be maintained. When the content of the metal complex dye (C) is 50% by mass or less based on 100% by mass of the solid content, the coating can be colored without impairing alkaline developability.

[0190] <Solubility enhancer (D)> The positive photosensitive resin composition may further contain a dissolution promoter (D) for improving the solubility of the alkali-soluble portion in the developer during development.

[0191] The dissolution promoter (D) may be an organic low molecular weight compound selected from the group consisting of compounds having a carboxy group and compounds having a phenolic hydroxyl group. The dissolution promoter (D) may be used alone or in combination of two or more kinds.

[0192] In the present disclosure, the term "low molecular weight compound" refers to a compound having a molecular weight of not more than 1000. The above organic low molecular weight compound has a carboxy group or multiple phenolic hydroxyl groups and is alkali-soluble.

[0193] Examples of such organic low molecular weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and 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, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; and aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimellitic acid, and mesitylene acid. aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, and pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umbellic acid; and aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol.

[0194] The content of the dissolution promoter (D) in the positive-type photosensitive resin composition can be 0.1 to 50 parts by mass, preferably 1 to 35 parts by mass, and more preferably 2 to 20 parts by mass, based on 100 parts by mass of the total of the resin components (binder resin (A)). If the content of the dissolution promoter (D) is 0.1 part by mass or more based on the total of 100 parts by mass, the dissolution of the resin components can be effectively promoted, and if it is 50 parts by mass or less, excessive dissolution of the resin components can be suppressed, and the pattern formability and surface quality of the coating can be improved.

[0195] <Optional component (E)> The positive photosensitive resin composition may contain, as optional component (E), a heat curing agent, a surfactant, a colorant other than the metal complex dye (C), etc. In the present disclosure, optional component (E) is defined as not falling under any of (A) to (D).

[0196] A thermal radical generator can be used as the thermal curing agent. Preferred examples of the thermal radical generator 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.

[0197] The content of the heat curing agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the heat curing agent.

[0198] The positive photosensitive resin composition may contain a surfactant, for example, to improve the coatability, the smoothness of the coating, or the developability of the coating.

[0199] Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafac (registered trademark) F-251, Megafac (registered trademark) F-252, Megafac (registered trademark) F-253, Megafac (registered trademark) F-254, Megafac (registered trademark) F-255, Megafac (registered trademark) F-256, Megafac (registered trademark) F-257, Megafac (registered trademark) F-258, Megafac (registered trademark) F-259 ... Fluorine-based surfactants such as Surflon® S-281, F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-562, and F-563 (all trade names, DIC Corporation), Surflon® S-242, S-243, S-386, S-420, and S-611 (all trade names, AGC Seimi Chemical Co., Ltd.), and organosiloxane polymers KP323, KP326, and KP341 (all trade names, Shin-Etsu Chemical Co., Ltd.). The surfactants can be used alone or in combination of two or more.

[0200] The content of the surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, based on 100 parts by mass of the total solid content excluding the surfactant.

[0201] [Coating composition] <Solvent (F)> The positive-type photosensitive resin composition can be dissolved in a solvent (F) and used as a coating composition in solution form. For example, a coating composition containing the positive-type photosensitive resin composition can be prepared by mixing a photoacid generator (B), a metal complex dye (C), and, if necessary, optional components (E) such as a dissolution promoter (D), a heat curing agent, and a surfactant in a predetermined ratio with the resulting solution obtained by dissolving the binder resin (A) in the solvent (F). The viscosity of the coating composition can be adjusted to suit the coating method to be used by changing the amount of the solvent (F).

[0202] Examples of the solvent (F) 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 monoalkyl ether acetate compounds such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; toluene; Examples of suitable solvents include aromatic hydrocarbons such as ethanol 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-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone, and amide compounds such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more.

[0203] The solid content of the coating composition can be appropriately determined depending on the purpose of use. For example, the solid content of the coating composition may be 1 to 60 mass %, 3 to 50 mass %, or 5 to 40 mass %.

[0204] The prepared coating composition is usually filtered before use. Examples of filtering methods include a Millipore filter with a pore size of 0.05 to 1.0 μm.

[0205] The coating composition thus prepared also has excellent long-term storage stability.

[0206] [Method of using the positive photosensitive resin composition] When a positive-type photosensitive resin composition is used in radiation lithography, the positive-type photosensitive resin composition is first dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition is applied to a substrate surface, and the solvent is removed by heating or other means to form a coating film. The method for applying the coating composition to the substrate surface is not particularly limited, and for example, spraying, roll coating, slit coating, or spin coating can be used.

[0207] After applying the coating composition to the surface of a substrate, the solvent is usually removed by heating to form a coating (pre-baking). The heating conditions vary depending on the type and blending ratio of each component, but the coating can usually be obtained by heating at 70 to 130°C for 30 seconds to 20 minutes on a hot plate or 1 to 60 minutes in an oven.

[0208] Next, the prebaked coating is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation) through a photomask having a predetermined pattern (exposure step). Preferred radiation is ultraviolet light or visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-ray. In another embodiment, the radiation is ghi-ray.

[0209] After the exposure step, a heat treatment (PEB) can be performed to promote decomposition of the acid-decomposable group by the acid generated from the photoacid generator (B). When the binder resin (A) of the positive photosensitive resin composition has a protected alkali-soluble functional group, PEB promotes deprotection of the protected alkali-soluble functional group in the exposed area, thereby further increasing the alkali solubility of the binder resin (A). The heating conditions vary depending on the type and blending ratio of each component, but PEB can usually be performed by heating at 70 to 140°C for, for example, 30 seconds to 20 minutes on a hot plate or 1 to 60 minutes in an oven. In one embodiment, PEB after the exposure step can be omitted.

[0210] After the exposure step or PEB step, the coating is developed by contacting it with a developer to remove unnecessary portions and form a pattern in the coating (development step). Examples of the developer include aqueous solutions of alkaline compounds such as inorganic alkaline compounds such as 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. Aqueous solutions prepared by adding appropriate amounts of water-soluble organic solvents such as methanol and ethanol, surfactants, etc. to an alkaline aqueous solution can also be used as the developer.

[0211] The development time is usually 30 to 180 seconds. The development method may be any of the puddle method, shower method, or dipping method. After development, the film is washed with running water for 30 to 90 seconds to remove unnecessary portions, and then air-dried with compressed air or compressed nitrogen, thereby forming a pattern in the film.

[0212] Thereafter, the coating film on which the pattern has been formed is heat-treated, for example, at 100 to 350°C for 20 to 200 minutes using a heating device such as a hot plate or oven, to obtain a cured coating film (post-baking, heat treatment step). In the heat treatment, the temperature may be maintained constant, or may be increased continuously or stepwise. The heat treatment is preferably carried out in a nitrogen atmosphere.

[0213] The optical density (OD value) of the cured film of the positive photosensitive resin composition is preferably 0.4 or more per 1 μm of film thickness, more preferably 0.6 or more, and even more preferably 0.7 or more. If the OD value of the cured film is 0.4 or more per 1 μm of film thickness, sufficient light-blocking properties can be obtained.

[0214] In one embodiment, a method for producing an organic EL device partition wall or insulating film includes dissolving or dispersing a positive photosensitive resin composition in a solvent to prepare a coating composition, applying the coating composition to a substrate to form a film, removing the solvent contained in the film and drying the film, exposing the dried film to radiation through a photomask, developing the exposed film by contacting it with a developer to form a pattern in the film, and heat-treating the patterned film at a temperature of 100° C. to 350° C. to form an organic EL device partition wall or insulating film. The PEB described above can also be performed after exposure and before development.

[0215] One embodiment is a partition wall for an organic EL device, which comprises a cured product of a positive-type photosensitive resin composition.

[0216] One embodiment is an insulating film for an organic EL device, which comprises a cured product of a positive photosensitive resin composition.

[0217] One embodiment is an organic EL device containing a cured product of the positive photosensitive resin composition. [Example]

[0218] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

[0219] (1) Raw materials The raw materials used in the examples and comparative examples were produced or obtained as follows.

[0220] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the binder resin (A) were calculated using a calibration curve prepared using a polystyrene standard substance under the following measurement conditions. Equipment: Shodex® GPC-101 Column: Shodex (registered trademark) LF-804 Mobile phase: tetrahydrofuran Flow rate: 1.0mL / min Detector: Shodex (registered trademark) RI-71 Temperature: 40℃

[0221] [Production Example 1] Production of a copolymer (PCX-02e) of a polymerizable monomer having an alkali-soluble functional group (phenolic hydroxyl group) and another polymerizable monomer 25.5 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA") and 4.50 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Corporation) as a solvent, and 3.66 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (Daicel Corporation). The two resulting solutions were simultaneously added dropwise over 2 hours to 61.2 g of 1-methoxy-2-propyl acetate (Daicel Corporation) heated to 85 °C under a nitrogen gas atmosphere in a 300 mL three-neck flask, and then reacted at 85 °C for 3 hours. The reaction solution was cooled to room temperature and added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 90°C for 4 hours, and 32.4 g of white powder (PCX-02e) was collected. The number-average molecular weight of the obtained PCX-02e was 3,100 and the weight-average molecular weight was 6,600.

[0222] [Production Example 2] Production of a resin (N695OH70) having epoxy groups and phenolic hydroxyl groups A 300 mL three-neck flask was charged with 2000 g of 1-methoxy-2-propyl acetate (MMPGAC, Daicel Corporation) as a solvent and 500 g of EPICLON® N-695 (DIC Corporation, cresol novolac epoxy resin, epoxy equivalent weight 214) as a compound having at least two epoxy groups per molecule, and dissolved under a nitrogen gas atmosphere at 60 °C. 235.12 g (0.65 equivalents per epoxy equivalent) of 3,5-dihydroxybenzoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound and 2.20 g (0.660 mmol) of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) as a reaction catalyst were added, and the mixture was allowed to react at 110 °C for 25 hours. The reaction solution was returned to room temperature, diluted with 1-methoxy-2-propyl acetate to a solids content of 20% by mass, and filtered to obtain 2676 g of a solution of a resin (N695OH70) having epoxy groups and phenolic hydroxyl groups. The resulting resin (N695OH70) had a number average molecular weight of 2419, a weight average molecular weight of 5051, and an epoxy equivalent of 1118.

[0223] [Production Example 3] Dye C-1: Production of a dye in which the counter cation having a nitrogen-containing heterocyclic structure is a protonated N-ethylmorpholine compound A 300 mL separable flask was charged with 30 g of VALIFAST BLACK 3804 (Orient Chemical Industry Co., Ltd., Color Index: Solvent Black 34), 4.0 g of N-ethylmorpholine (Tokyo Chemical Industry Co., Ltd.), and 45 g of γ-butyrolactone (Mitsubishi Chemical Corporation), and the mixture was stirred at 80°C under a nitrogen atmosphere for 28 hours to prepare a solution in which the ammonium cation in the dye had been converted to a protonated form of N-ethylmorpholine. This solution was added dropwise to isopropanol (Kanto Chemical Co., Ltd.) and stirred, and the resulting precipitate was collected by filtration. The residue was washed with isopropanol (Kanto Chemical Co., Ltd.) and vacuum dried at 80°C for 6 hours to obtain Dye C-1.

[0224] [Production Example 4] Dye C-2: Production of a dye in which the counter cation having a nitrogen-containing heterocyclic structure is a protonated N-methylpiperidine compound A 300 mL separable flask was charged with 40 g of VALIFAST BLACK 3820 (Orient Chemical Industry Co., Ltd., Color Index: Solvent Black 27), 8.0 g of N-methylpiperidine (Tokyo Chemical Industry Co., Ltd.), and 60 g of γ-butyrolactone (Mitsubishi Chemical Corporation), and the mixture was stirred at 80°C for 16 hours under a nitrogen atmosphere to prepare a solution in which the ammonium cation in the dye had been converted to a protonated form of N-methylpiperidine. This solution was added dropwise to isopropanol (Kanto Chemical Co., Ltd.) and stirred, and the resulting precipitate was collected by filtration. The residue was washed with isopropanol (Kanto Chemical Co., Ltd.) and vacuum dried at 80°C for 6 hours to obtain Dye C-2.

[0225] [Production Example 5] Dye C-3: Production of a dye in which the counter cation having a nitrogen-containing heterocyclic structure is a protonated compound of N-isobutylmorpholine A 300 mL separable flask was charged with 15 g of VALIFAST BLACK 3804 (Orient Chemical Industry Co., Ltd., Color Index: Solvent Black 34), 3.0 g of N-isobutylmorpholine (Tokyo Chemical Industry Co., Ltd.), and 22.5 g of γ-butyrolactone (Mitsubishi Chemical Corporation), and the mixture was stirred at 80°C for 20 hours under a nitrogen atmosphere to prepare a solution in which the ammonium cation in the dye had been converted to a protonated form of N-isobutylmorpholine. This solution was added dropwise to isopropanol (Kanto Chemical Co., Ltd.) and stirred, and the resulting precipitate was collected by filtration. The residue was washed with isopropanol (Kanto Chemical Co., Ltd.) and vacuum dried at 80°C for 6 hours to obtain Dye C-3.

[0226] [Production Example 6] Dye C-4: Production of a dye in which the counter cation having a nitrogen-containing heterocyclic structure is a protonated N-ethylpiperidine compound A 300 mL separable flask was charged with 15 g of VALIFAST BLACK 3804 (Orient Chemical Industry Co., Ltd., Color Index: Solvent Black 34), 3.0 g of N-ethylpiperidine (Tokyo Chemical Industry Co., Ltd.), and 22.5 g of γ-butyrolactone (Mitsubishi Chemical Corporation), and the mixture was stirred at 80°C for 17 hours under a nitrogen atmosphere to prepare a solution in which the ammonium cation in the dye had been converted to a protonated form of N-ethylpiperidine. This solution was added dropwise to isopropanol (Kanto Chemical Co., Ltd.) and stirred, and the resulting precipitate was collected by filtration. The residue was washed with isopropanol (Kanto Chemical Co., Ltd.) and vacuum dried at 80°C for 6 hours to obtain Dye C-4.

[0227] <Binder resin (A)> As the binder resin (A), PCX-02e, N695OH70, and EPICLON (registered trademark) N-695 were used.

[0228] <Photoacid generator (B)> The photoacid generator (B) used was the quinone diazide compound TPPA(4)-150DF (an ester of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) and 3-diazo-3,4-dihydro-4-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinone-2-diazide-4-sulfonic acid), manufactured by Toyo Gosei Co., Ltd.). The structure of TPPA(4)-150DF is shown below. TPPA(4)-150DF has three R groups per molecule, with an average of 1.5 R groups having a quinone diazide structure.

[0229] [ka]

[0230] <Metal complex dyes (C)> As the metal complex dye (C), the following C-1 to C-6 were used. C-1: Dye produced in Production Example 3 C-2: Dye produced in Production Example 4 C-3: Dye produced in Production Example 5 C-4: Dye produced in Production Example 6 C-5: VALIFAST BLACK 3804 (Orient Chemical Industry Co., Ltd., Color Index: Solvent Black 34) C-6: VALIFAST BLACK 3820 (Orient Chemical Industry Co., Ltd., Color Index: Solvent Black 27)

[0231] <Solubility enhancer (D)> Phloroglucinol was used as the solubility enhancer (D).

[0232] <Other ingredients> As optional component (E), a surfactant (leveling agent) Megafac (registered trademark) F-559 (fluorine-based surfactant, DIC Corporation) was used.

[0233] As the solvent (F), a mixed solvent of γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate (PGMEA), and isobutyl acetate (i-BuOAc) (GBL:PGMEA:i-BuOAc = 35:45:20 (mass ratio)), and a mixed solvent of 1,3-dimethyl-2-imidazolidinone (DMI), GBL, PGMEA, and i-BuOAc (DMI:GBL:PGMEA:i-BuOAc = 1.5:33.5:45:20 (mass ratio)) were used.

[0234] (2) Evaluation method The evaluation methods used in the examples and comparative examples are as follows.

[0235] [Exposed area residue, hole formation, surface roughness] A glass substrate (72 mm × 72 mm × 0.7 mm) was bar-coated with a positive photosensitive resin composition to a dry film thickness of 4.3 μm, and after vacuum drying at room temperature for 60 seconds, the composition was pre-baked by heating on a hot plate with a lid at 125°C for 120 seconds. The composition was exposed to 300 mJ / cm through a quartz photomask (having a φ10 μm pattern) using an exposure device (product name: Multilight ML-251A / B, manufactured by Ushio Inc.) equipped with an ultra-high pressure mercury lamp. 2 The exposure dose was measured using an ultraviolet integrating actinometer (product name: UIT-150 light-receiving part UVD-S365, manufactured by Ushio Inc.). Alkaline development was performed for 80 seconds using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.) with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. Visual inspection was performed, and the exposed area residue was evaluated as 'Good' if there was no residue, and 'Poor' if there was residue. Holes formed in the coating film were observed with a microscope (VHX-6000, manufactured by Keyence Corporation) and their diameters were measured. Hole diameters (μm) of 9.0 μm or greater were evaluated as 'Good' for hole formability, and those with a diameter (μm) of less than 9.0 μm were evaluated as 'Poor' for hole formability. A film with no exposed area residue and good hole formability was judged to have high sensitivity. Furthermore, the unexposed areas were visually observed, and those with gloss were judged to have a good surface roughness rating, and those without gloss and with roughness or irregularities were judged to have a bad surface roughness rating.

[0236] [Storage stability] The positive photosensitive resin composition was stored at room temperature of 25°C for 7 days, and then the hole formability was evaluated again. The composition in which the change rate of the hole diameter was less than 10% was judged to have good storage stability, and the composition in which the change rate of the hole diameter was 10% or more was judged to have poor storage stability.

[0237] [Process Window] A positive photosensitive resin composition was bar coated onto an ITO-coated glass substrate (72 mm × 72 mm × 0.7 mm) to a dry film thickness of 4.3 μm, and after vacuum drying at room temperature for 60 seconds, the composition was prebaked by heating on a hot plate with a lid at 125°C for 120 seconds. The prebaking conditions were also changed to 120°C and 130°C, and dried coating films were similarly prepared. The dry film thickness at each prebaking temperature was measured using an optical film thickness measuring device (F20-NIR, Filmetrics Inc.).

[0238] Subsequently, alkaline development was performed for 80 seconds using a spin developing apparatus (AD-1200, Takizawa Sangyo Co., Ltd.) with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. The film thickness after alkaline development was measured again using an optical film thickness measuring apparatus (F20-NIR, Filmetrics Inc.), and the difference in film thickness before and after development (film thickness dissolved by development) was calculated as the solubility of the unexposed area.

[0239] The solubility value of the unexposed area at a pre-bake temperature of 125°C was used as the standard, and if the solubility values ​​of the unexposed area at pre-bake temperatures of 120°C and 130°C were both within ±0.3 μm, the process window was evaluated as good. If at least one of the solubility values ​​of the unexposed area at 120°C and 130°C had a change of more than ±0.3 μm, the process window was evaluated as bad.

[0240] [OD value of cured film] A positive photosensitive resin composition was spin-coated onto a glass substrate (100 mm × 100 mm × 1 mm) to a dry film thickness of approximately 2.0 μm, and the coating was heated on a hot plate at 125°C for 120 seconds to dry off the solvent. The coating was then cured at 250°C for 60 minutes in a nitrogen gas atmosphere to obtain a coating. The OD value of the cured coating was measured using a transmission densitometer (BMT-1, Sakata Inx Engineering Co., Ltd.), corrected for the OD value of the glass alone, and converted to an OD value per 1 μm of coating thickness. The coating thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.).

[0241] (3) Preparation and evaluation of positive photosensitive resin compositions [Examples 1 to 5 and Comparative Examples 1 to 3] The binder resin (A) was dissolved in the composition shown in Table 1, and the photoacid generator (B), metal complex dye (C), dissolution promoter (D), optional component (E) (surfactant), and mixed solvent (F) shown in Table 1 were added to the resulting solution and further mixed. After visually confirming that the components had dissolved, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a positive photosensitive resin composition with a solids concentration of 12 mass %. The parts by mass of the composition in Table 1 are values ​​calculated as solids. The evaluation results of the positive photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1.

[0242] [Table 1]

[0243] The results in Table 1 show that the photosensitive resin compositions of Examples 1 to 5, which used metal complex dyes containing counter cations with nitrogen-containing heterocyclic structures, exhibited high sensitivity, little roughness on the coating surface, and good process window and storage stability. For example, comparing Example 2 and Comparative Example 2, which used the same metal complex ion (color index Solvent Black 27), all evaluation results were good in Example 2, which used dye C-2, whose counter cation-forming amine was N-methylpiperidine, whereas Comparative Example 2, which used dye C-6, whose counter cation-forming amine was a primary amine, showed poor evaluation results in terms of exposed area residue, hole formation ability, surface roughness, and storage stability. [Industrial Applicability]

[0244] The positive-type photosensitive resin composition according to the present disclosure can be suitably used in radiation lithography for forming partition walls or insulating films of organic EL devices. Organic EL devices having partition walls or insulating films formed from the positive-type photosensitive resin composition according to the present disclosure are suitably used as electronic components for display devices that exhibit good contrast.

Claims

1. A binder resin (A), a photoacid generator (B); a metal complex dye (C); wherein the metal complex dye (C) contains a metal complex ion and a counter cation having a nitrogen-containing heterocyclic structure.

2. 2. The positive photosensitive resin composition according to claim 1, wherein the binder resin (A) has an alkali-soluble functional group.

3. 3. The positive photosensitive resin composition according to claim 1, wherein the counter cation is at least one selected from the group consisting of an N-alkylmorpholinium cation and an N-alkylpiperidinium cation.

4. 4. The positive photosensitive resin composition according to claim 1, wherein the metal element forming the metal complex ion is at least one selected from the group consisting of chromium, copper, cobalt, nickel, and iron.

5. 5. The positive photosensitive resin composition according to claim 4, wherein the metal element is chromium.

6. The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the metal complex dye (C) is a black dye.

7. 7. The positive photosensitive resin composition according to claim 6, wherein the metal complex ion is a metal complex ion contained in a compound defined by a color index of Solvent Black 22 to 47.

8. The positive photosensitive resin composition according to any one of claims 1 to 7, wherein the binder resin (A) has a plurality of phenolic hydroxyl groups.

9. 9. The positive photosensitive resin composition according to claim 8, wherein the binder resin (A) comprises a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer.

10. The binder resin (A) is a compound represented by the formula (10): 【Chemistry 1】 (In formula (10), R １５ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5. The positive photosensitive resin composition according to claim 8 or 9, which has a structural unit represented by the following formula:

11. The binder resin (A) is a compound represented by the formula (11): 【Chemistry 2】 (In formula (11), R １６ and R １７ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, or a halogen atom; R １８ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The positive photosensitive resin composition according to claim 10, having a structural unit represented by the following formula:

12. The positive photosensitive resin composition according to any one of claims 8 to 11, wherein the binder resin (A) further contains a resin having an epoxy group and a phenolic hydroxyl group.

13. The positive photosensitive resin composition according to any one of claims 1 to 12, wherein the metal complex dye (C) is contained in an amount of 5% by mass to 50% by mass based on 100% by mass of a solid content of the positive photosensitive resin composition.

14. 14. The positive photosensitive resin composition according to claim 1, wherein the photoacid generator (B) is contained in an amount of 1% by mass to 50% by mass, based on 100% by mass of a solid content of the positive photosensitive resin composition.

15. The positive photosensitive resin composition according to any one of claims 1 to 14, wherein the optical density (OD value) of a cured coating of the positive photosensitive resin composition is 0.5 or more per 1 µm of film thickness.

16. A partition wall for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 15.

17. An insulating film for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 15.

18. An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 15.

Images