Positive-type photosensitive resin composition, organic EL element partition, organic EL element insulating film, and organic EL element

Abstract

To provide a positive photosensitive resin composition that achieves excellent removability of residual material and suppressed film thinning, and that allows micro-hole formation, without relying on organofluorine compounds, as well as an organic EL element partition wall, an organic EL element insulating film, and an organic EL element.SOLUTION: Provided is a positive photosensitive resin composition which contains a hydrophobic resin (A), a quinonediazide compound (C), and a silicone-based surfactant (D) having a silicon atom in the side chain.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a positive-type photosensitive resin composition, an organic EL element partition, an organic EL element insulating film, and an organic EL element. [Background technology]

[0002] Positive-type photosensitive resin compositions are widely used as partition materials, insulating films, and planarization films in display devices such as organic light-emitting diodes (OLEDs) and liquid crystal displays, as well as as interlayer insulating films, planarization films, and protective films in semiconductor devices.

[0003] For example, in display devices such as organic EL displays, partition materials are used in the gaps between color patterns within the display area or at the edges of the peripheral areas of the display area to improve display characteristics. In the manufacture of organic EL display devices, partitions are first formed to prevent organic material pixels from coming into contact with each other, and then organic material pixels are formed between these partitions. These partitions are generally formed by photolithography using a photosensitive resin composition and are insulating. Specifically, a photosensitive resin composition is applied to a substrate using a coating apparatus, volatile components are removed by means of heating or other means, then the image is exposed through a mask, and then developed by removing the unexposed areas in the case of a negative type or the exposed areas in the case of a positive type with a developing solution such as an alkaline aqueous solution. The resulting pattern is then heat-treated to form partitions (insulating films). Next, organic materials that emit red, green, and blue light are deposited between the partitions using an inkjet method or the like to form the pixels of the organic EL display device.

[0004] In recent years, the miniaturization of display devices and the diversification of displayed content have led to a demand for higher performance and resolution of pixels in this field. Attempts have been made to improve the contrast and visibility of display devices by using colorants to give partition materials light-shielding properties.

[0005] Patent Document 1 (Japanese Patent Publication No. 2001-281440) describes a radiation-sensitive resin composition that exhibits high light-shielding properties after heat treatment following exposure, which is a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound, to which titanium black is added.

[0006] Patent Document 2 (Japanese Patent Publication No. 2002-116536) describes a method for blackening a partition material using carbon black in a radiation-sensitive resin composition containing [A] an alkali-soluble resin, [B] a 1,2-quinone diazide compound, and [C] a coloring agent.

[0007] Patent Document 3 (Japanese Patent Publication No. 2010-237310) describes a radiation-sensitive resin composition that exhibits light-shielding properties upon heat treatment after exposure, which is a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound to which a heat-sensitive dye has been added.

[0008] Patent Document 4 (International Publication No. 2017 / 069172) describes a positive-type 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.

[0009] Patent document 5 (International Publication No. 2023 / 080254) describes a positive-type photosensitive resin composition comprising a hydrophobic resin (A), an alkali-soluble resin (B), a quinone diazide compound (C), and a fluorine-based surfactant (D).

[0010] On the other hand, one method for increasing the sensitivity of positive-type photosensitive resin compositions is to use a chemical amplification system for the photosensitive resin composition. A chemical amplification system photosensitive resin composition generally contains a resin in which alkali-soluble functional groups are protected by acid-degradable groups, and a photoacid generator. The acid generated from the photoacid generator during exposure promotes the decomposition (deprotection) of acid-degradable groups and regenerates alkali-soluble functional groups. This promotes the alkali dissolution of the resin in the exposed area during development. The acid derived from the photoacid generator decomposes one acid-degradable group, then regenerates it, and participates in the decomposition of another acid-degradable group. Since the apparent quantum efficiency of a chemical amplification system based on the above reaction mechanism is expressed as the product of the quantum efficiency of acid generation and the reaction chain, it is expected that high sensitivity can be achieved by using a chemical amplification system for the photosensitive resin composition. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Japanese Patent Publication No. 2001-281440 [Patent Document 2] Japanese Patent Publication No. 2002-116536 [Patent Document 3] Japanese Patent Publication No. 2010-237310 [Patent Document 4] International Publication No. 2017 / 069172 [Patent Document 5] International Publication No. 2023 / 080254 [Overview of the project] [Problems that the invention aims to solve]

[0012] However, when the partition material is given light-shielding properties, the photosensitive resin composition tends to become less sensitive, which can result in longer exposure times and reduced productivity. Therefore, photosensitive resin compositions used to form partition materials, especially those containing colorants, are required to be more sensitive.

[0013] For example, in photosensitive resin compositions used to form colored partition materials, a coloring agent is used to sufficiently enhance the light-shielding properties of the cured film. However, when a coloring agent is used, the radiation irradiated onto the film of the photosensitive resin composition is absorbed by the coloring agent, reducing the effective intensity of the radiation in the film. As a result, the photosensitive resin composition is not sufficiently exposed, and consequently, the ability to form holes and other properties decreases. This is particularly noticeable when a black coloring agent is incorporated into a photosensitive resin composition for the purpose of improving the image quality, making it more flexible, or saving power in a display device, for example, when forming a black partition material.

[0014] Furthermore, in recent years, there has been a demand to reduce the use of perfluorinated compounds such as PFAS, resulting in a request for so-called Non-PFAS products.

[0015] Furthermore, in positive-type photosensitive resin compositions that do not use organofluorine compounds, there is a requirement that they exhibit excellent residue removal properties, low film loss, and the aforementioned hole-forming properties simultaneously at a high level. However, currently, no positive-type photosensitive resin composition has been developed that can adequately meet these requirements.

[0016] The present invention has been made in view of these circumstances, and aims to provide a positive-type photosensitive resin composition, an organic EL element partition, an organic EL element insulating film, and an organic EL element that exhibit excellent residue removal properties, low film loss, and enable the formation of fine holes, without the use of organofluorine compounds. [Means for solving the problem]

[0017] As a result of diligent research to achieve the above-mentioned objectives, the present inventors have found that a positive-type photosensitive resin composition containing a hydrophobic resin (A), a quinone diazide compound (C), and a silicone-based surfactant (D) having silicon atoms in its side chain is desirable, and have completed the present invention.

[0018] In other words, the present invention includes the following embodiments. <1> This is a positive-type photosensitive resin composition containing a hydrophobic resin (A), a quinone diazide compound (C), and a silicone-based surfactant (D) having silicon atoms in its side chain. <2> The content of component (D) in the total amount of surfactant is 50% by mass or more. <1> This is a positive-type photosensitive resin composition as described above. <3> It further contains a coloring agent (E) containing a black dye, <1> or <2> This is a positive-type photosensitive resin composition as described above. <4> The aforementioned component (A) includes a structural unit represented by the following formula (1): <1> ~ <3> The positive-type photosensitive resin composition is described in any of the above.

[0019] [ka]

[0020] (In equation (1), R 1 R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 2 is SiR 3 R 4 R 5 And R 3 , R 4 and R 5 Each of these is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, where r is an integer from 0 to 4, and s is an integer from 1 to 5, except where r+s is an integer from 1 to 5. <5> The aforementioned component (A) is a resin having a silicon atom-containing group. <1> ~ <4> The positive-type photosensitive resin composition is described in any of the above. <6> The above component (A) includes the following structural units (1a) and / or (1b): <1> ~ <5> The positive-type photosensitive resin composition is described in any of the above.

[0021] [ka]

[0022] (In formula (1a), R 1a is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2a , R 3a , and R 4a are each independently an alkyl group having 1 to 7 carbon atoms. In formula (1b), R 1b is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Note that R 1a and R 1b may be the same or different.) <7> The positive photosensitive resin composition according to any one of <1> to <6>, wherein the content of the component (A) in the positive photosensitive resin composition is 5 to 60% by mass based on the total mass of the resin components. <8> The positive photosensitive resin composition according to any one of <1> to <7>, wherein the component (D) is a silicone surfactant containing an acrylic copolymer having at least one silicon atom-containing hydrocarbon group selected from the group consisting of a silicon atom-containing alkyl group and a silicon atom-containing alkylene group. <9> The positive photosensitive resin composition according to <3>, wherein the component (E) is contained in an amount of 10 to 150 parts by mass with respect to 100 parts by mass of the total resin components. <10> The positive photosensitive resin composition according to any one of <1> to <9>, wherein the optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness. <11> An organic EL device partition wall including a cured product of the positive photosensitive resin composition according to any one of <​​​​​​​​​​​​

[0023] According to the present invention, it is possible to provide a positive-type photosensitive resin composition, an organic EL element partition, an organic EL element insulating film, and an organic EL element that exhibit excellent residue removal properties, low film loss, and enable the formation of fine holes, without the use of organofluorine compounds. [Modes for carrying out the invention]

[0024] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). This embodiment is illustrative for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0025] In this specification, "alkali-soluble" means that a positive-type photosensitive resin composition or its components, or a coating or cured coating of a positive-type photosensitive resin composition, is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. "Alkali-soluble resin" means a resin that is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, either on its own or contained in an unexposed or exposed positive-type photosensitive resin composition. Resins that are not alkali-soluble when the positive-type photosensitive resin composition is unexposed but become alkali-soluble upon exposure are also included in alkali-soluble resins. "Alkali-soluble functional group" means a group that has the ability to impart such alkali solubility to a positive-type photosensitive resin composition or its components, or a coating or cured coating of a positive-type photosensitive resin composition. Examples of alkali-soluble functional groups include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphate groups, acid anhydride groups, and mercapto groups.

[0026] In this specification, "acid-degradable group" means a group that decomposes (deprotects) in the presence of an acid, and optionally by heating, to generate an alkali-soluble functional group.

[0027] In this specification, "radical polymerizable functional group" means an ethylenically unsaturated group, and "radical polymerizable compound" means a compound having one or more ethylenically unsaturated groups.

[0028] In this specification, "structural unit" and "unit" (hereinafter sometimes collectively referred to as "structural unit") mean an atomic group that constitutes a part of the basic structure of a polymer, and this atomic group may have pendant atoms or pendant atomic groups. For example, in the case of a radical (co)polymer, it means a unit derived from a radical polymerizable compound used as a monomer, and in the case of a phenol novolac resin, it means the following unit formed by the condensation reaction of one molecule of phenol (C6H5OH) and one molecule of formaldehyde (HCHO). With respect to structural units having pendant groups (side groups), structural units having pendant groups or groups derived therefrom that are used in the formation of crosslinking sites are considered to be different from structural units having free pendant groups that are not involved in the formation of crosslinking sites. With respect to a polymer having branched molecular chains, structural units containing branching points (branched units) and structural units included in linear molecular chains are considered to be different from each other.

[0029] [ka]

[0030] In this specification, unless otherwise specified, "(meth)acrylic" means acrylic, methacrylic, or both; "(meth)acrylate" means acrylate, methacrylate, or both; and "(meth)acryloyl" means acryloyl, methacryloyl, or both.

[0031] In this specification, unless otherwise specified, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of resins, polymers, or copolymers refer to values ​​on a standard polystyrene basis, measured by gel permeation chromatography (GPC).

[0032] In this specification, unless otherwise specified, the phenolic hydroxyl group equivalent is a theoretical value calculated from the molecular weight and composition ratio of the structural units constituting the resin. Specifically, the phenolic hydroxyl group equivalent refers to the value calculated by the following formula when the resin is a (co)polymer of n types of monomers i (i = natural numbers from 1 to n). In the formula, the sum of the copolymerization ratios (on a molar basis) of monomers i (i = 1 to n) is 1.

[0033]

number

[0034] In the case of resins (B2) having epoxy groups and phenolic hydroxyl groups, as described later, unless otherwise specified, the phenolic hydroxyl group equivalent refers to the value calculated by the following formula. Phenolic hydroxyl group equivalent = (Epoxy equivalent of raw material + Molecular weight of carboxylic acid to be added) / (Number of phenolic hydroxyl groups of carboxylic acid)

[0035] Unless otherwise specified in this specification, "resin component" means hydrophobic resin (A) and alkali-soluble resin (B). Component corresponding to silicone-based surfactant (D) is not included in hydrophobic resin (A) and alkali-soluble resin (B).

[0036] Unless otherwise specified herein, "solids" means the total mass of components excluding the liquid solvent (G), including resin components, quinone diazide compounds (C), silicone-based surfactants (D), and optional components such as colorants (E) and dissolution accelerators (F).

[0037] [Positive-type photosensitive resin composition]

[0038] The positive-type photosensitive resin composition according to this embodiment is a positive-type photosensitive resin composition containing a hydrophobic resin (A), a quinone diazide compound (C), and a silicone-based surfactant (D) having silicon atoms in its side chain. The positive-type photosensitive resin composition according to this embodiment exhibits excellent residue removal properties, low film loss, and the ability to form fine holes, even without the use of organofluorine compounds. The reason for this is not entirely clear, but it is presumed to be due to the following reasons (however, the effects and benefits of this embodiment are not limited to the following).

[0039] By blending a hydrophobic resin (A) with a silicone-based surfactant (D) having silicon atoms in its side chain, its uneven distribution on the film surface is promoted, making the film surface of the positive-type photosensitive resin composition less soluble in alkaline aqueous solutions. During the film formation process of the positive-type photosensitive resin composition, the hydrophobic resin (A) tends to move toward the film surface, accompanying the silicone-based surfactant (D) that moves toward the film surface. Therefore, after film formation, the hydrophobic resin (A) is present at a higher concentration on the film surface compared to the interior of the film, reducing the alkali solubility of the film surface. Furthermore, because the hydrophobic resin (A) and the alkali-soluble resin (B) tend to have low compatibility, it tends to be easy to create a concentration gradient during curing. Therefore, during development, the hydrophobic resin (A), acting as a resin component with low alkali solubility, suppresses the dissolution of the film surface in the unexposed areas, while in the exposed areas, it is released from the film into the developer solution along with the dissolution of carboxylic acid compounds derived from the quinone diazide compound (C), other highly alkali-soluble resin components, and any dissolution accelerator. Once the film surface dissolves in the exposed areas, the dissolution of the interior of the film, which has higher alkali solubility than the film surface due to the relatively low concentration of hydrophobic resin (A), proceeds rapidly. This increases the contrast between the exposed and unexposed areas, and as a result, it is presumed that the amount of film loss when the positive-type photosensitive resin composition is cured can be reduced, and the hole-forming ability can be improved (however, the effects and benefits of this embodiment are not limited to these).

[0040] On the other hand, when attempting to make the film surface less soluble in an alkaline aqueous solution by using a hydrophobic resin and a fluorine-based surfactant in combination, the acid generated during exposure diffuses within the film. As a result, the acid concentration near the film surface and inside the film becomes more uniform compared to the case where a hydrophobic resin (A) and a silicone-based surfactant (D) having silicon atoms in its side chain are used in combination. Therefore, problems may occur such as difficulty in dissolving the exposed film surface during development, reduced sensitivity, and increased film loss when cured. In addition, photoacid generators may have low thermal stability, and using such photoacid generators may promote the dissolution of unexposed areas, leading to problems such as reduced hole formation. However, the positive-type photosensitive resin composition according to this embodiment can effectively suppress the occurrence of such problems (however, the effects and benefits of this embodiment are not limited to these).

[0041] The following describes each component that can be used in the positive-type photosensitive resin composition according to this embodiment.

[0042] <Hydrophobic resin (A)>

[0043] The type of hydrophobic resin (A) is not particularly limited, but examples 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. Derivatives of these resins preferably have hydrophobic groups. A suitable example of a hydrophobic group is a silicon atom-containing group. As the hydrophobic resin (A), a homopolymer or copolymer of a polymerizable monomer having alkali-soluble functional groups can be used as the base resin, and some or all of the alkali-soluble functional groups can be converted into groups having the above-mentioned hydrophobic groups. The hydrophobic resin (A) may be used alone or in combination of two or more types.

[0044] The hydrophobic resin (A) is preferably a resin having silicon atom-containing groups. The silicon atom-containing groups may be present in the main chain of the hydrophobic resin (A) or in the side chains (they may also be pendant groups), but it is preferable that they be present in the side chains.

[0045] Examples of silicon atom-containing groups include silyl groups substituted with aliphatic hydrocarbon groups or aryl groups, groups having a cyclic siloxane structure, and groups having a silsesquioxane structure.

[0046] Silyl groups substituted with aliphatic hydrocarbon groups or aryl groups are monosubstituted, disubstituted, or trisubstituted. The substituents on a silyl group substituted with aliphatic hydrocarbon groups or aryl groups may be the same or different from each other. It is preferable that the silyl group substituted with aliphatic hydrocarbon groups or aryl groups is trisubstituted. The silyl group substituted with aliphatic hydrocarbon groups or aryl groups may further have substituents other than alkyl or aryl groups, such as a silyloxy group substituted with an aliphatic hydrocarbon group or aryl group.

[0047] The number of ring members in the cyclic siloxane moiety of the group having a cyclic siloxane structure is preferably 6 to 14. Some or all of the hydrogen atoms on the silicon atom of the group having a cyclic siloxane structure may be independently substituted with an aliphatic hydrocarbon group or an aryl group.

[0048] Some or all of the hydrogen atoms on the silicon atom of the group having a silsesquioxane structure may be independently substituted with an aliphatic hydrocarbon group or an aryl group.

[0049] Aliphatic hydrocarbon groups of silyl groups substituted with aliphatic hydrocarbon groups or aryl groups, aliphatic hydrocarbon groups as substituents on groups having a cyclic siloxane structure, aliphatic hydrocarbon groups as substituents on groups having a silsesquioxane structure, and aliphatic hydrocarbon groups as substituents on silyloxy groups substituted with aliphatic hydrocarbon groups or aryl groups are preferably aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and more preferably aliphatic hydrocarbon groups having 1 to 8 carbon atoms. Examples of aliphatic hydrocarbon groups having 1 to 20 carbon atoms include saturated hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups; unsaturated hydrocarbon groups such as ethenyl, propenyl, butenyl, ethinyl, and propynyl groups; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclohexyl groups. Examples include saturated monocyclic hydrocarbon groups such as chlordodecyl groups; unsaturated monocyclic hydrocarbon groups such as cyclopropenyl groups, cyclobutenyl groups, cyclopentenyl groups, cyclohexenyl groups, cyclooctenyl groups, and cyclodecenyl groups; saturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptanyl groups, bicyclo[2.2.2]octanyl groups, and adamantyl groups; and unsaturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptenyl groups and bicyclo[2.2.2]octenyl groups.

[0050] The aryl group of a silyl group substituted with an aliphatic hydrocarbon group or an aryl group, the aryl group as a substituent on a group having a cyclic siloxane structure, the aryl group as a substituent on a group having a silsesquioxane structure, and the aryl group as a substituent on a silyloxy group substituted with an aliphatic hydrocarbon group or an aryl group are preferably aryl groups having 6 to 20 carbon atoms, and more preferably aryl groups having 6 to 14 carbon atoms. Examples of aryl groups having 6 to 20 carbon atoms include the phenyl group, naphthyl group, fluorenyl group, anthryl group, and phenantrenyl group.

[0051] Examples of silyl groups substituted with aliphatic hydrocarbon groups or aryl groups include trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, diphenylmethylsilyl, triphenylsilyl, and trimethylsilyloxydimethylsilyl.

[0052] Examples of groups having a cyclic siloxane structure include the pentamethylcyclotrisilyloxy group, the heptamethylcyclotetrasilyloxy group, and the nonamethylcyclopentasilyloxy group.

[0053] Examples of groups having a silsesquioxane structure include silsesquioxanyl group, heptamethylsilsesquioxanyl group, heptaethylsilsesquioxanyl group, hepta(n-propyl)silsesquioxanyl group, and hepta(n-butyl)silsesquioxanyl group.

[0054] Hydrophobic resin (A) can be produced, for example, by radical polymerization of a polymerizable monomer having a hydrophobic group, or by radical copolymerization of a polymerizable monomer having a hydrophobic group with other polymerizable monomers. Examples of polymerizable functional groups that polymerizable monomers having a hydrophobic group and other polymerizable monomers include radical polymerizable functional groups such as CH2=CH-, CH2=C(CH3)-, CH2=CHCO-, CH2=C(CH3)CO-, and -OC-CH=CH-CO-. Hydrophobic resin (A) can also be produced by reacting a resin having a functional group such as a hydroxyl group, carboxyl group, amino group, or epoxy group with a compound having a hydrophobic group to convert the functional group into a group containing a hydrophobic group.

[0055] In this embodiment, the hydrophobic resin (A) is a copolymer of a polymerizable monomer having a hydrophobic group and another polymerizable monomer. Examples of polymerizable monomers having a hydrophobic group include polymerizable monomers having a silicon atom-containing group.

[0056] Examples of polymerizable monomers having silicon atom-containing groups include trimethylvinylsilane, trimethylallylsilane, trimethyl(3-butenyl)silane, tert-butyldimethylvinylsilane, (trimethylsilyloxy)dimethylvinylsilane, (trimethylsilyloxy)dimethylallylsilane, triethylvinylsilane, triethylallylsilane, triethyl(3-butenyl)silane, (trimethylsilyl)methyl(meth)acrylate, 2-(trimethylsilyl)ethyl(meth)acrylate, 3-(trimethylsilyl)propyl(meth)acrylate, tert-butyldimethylsilyl(meth)acrylate, triisopropylsilylmethyl(meth)acrylate, and bis(trimethylsilyl) Examples include methyl(meth)acrylate, 4-(trimethylsilyl)cyclohexyl(meth)acrylate, 3-[(trimethylsilyloxy)dimethylsilyl]propyl(meth)acrylate, 3-[tris(trimethylsilyloxy)silyl]propyl(meth)acrylate, 4-trimethylsilyloxyphenyl(meth)acrylate, 4-triethylsilyloxyphenyl(meth)acrylate, 4-triisopropylsilyloxyphenyl(meth)acrylate, 4-tert-butyldimethylsilyloxyphenyl(meth)acrylate, vinylheptamethylcyclotetrasiloxane, and 3-(heptamethylsilsesquioxanyl)propyl(meth)acrylate.

[0057] Other polymerizable monomers include, for example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; and (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0058] Other polymerizable monomers may be polymerizable monomers having alkali-soluble functional groups. Examples of polymerizable monomers having alkali-soluble functional groups include maleic acid derivatives such as maleic acid, monomethyl maleic acid, monoethyl maleic acid, monoisopropyl maleic acid, and maleic anhydride; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; unsaturated carboxylic acid compounds such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid; polymerizable monomers having phenolic hydroxyl groups such as 4-hydroxystyrene and 4-hydroxyphenyl(meth)acrylate; polymerizable monomers having sulfo groups such as (meth)allylsulfonic acid and styrenesulfonic acid; polymerizable monomers having phosphate groups such as mono(2-(meth)acryloyloxyethyl) phosphate; and polymerizable monomers having acid anhydride groups such as itaconic acid and citraconic acid anhydride.

[0059] Furthermore, it is preferable to use 4-tert-butyldimethylsilyloxyphenyl (meth)acrylate and / or 4-hydroxyphenyl (meth)acrylate as polymerizable monomers having hydrophobic groups, and it is more preferable to use both. By using resins obtained by radical polymerization of these polymerizable monomers, the sensitivity and hole-forming properties of the positive-type photosensitive resin composition can be further improved, and outgassing can be further reduced.

[0060] The hydrophobic resin (A) preferably contains structural units represented by the following formula (1). For example, it is preferable that the polymerizable monomer having the hydrophobic group described above forms structural units represented by formula (1) after polymerization.

[0061] [ka]

[0062] (In formula (1), R 1 R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 2 is SiR 3 R 4 R 5 And R 3 , R 4 and R 5 Each of these is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, where r is an integer from 0 to 4, and s is an integer from 1 to 5, except where r+s is an integer from 1 to 5.

[0063] In formula (1), R 1 R is preferably a hydrogen atom or a methyl group. 3 , R 4 , and R 5Each of these groups is preferably independently a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group. r is preferably an integer from 0 to 3, and more preferably 0. s is preferably an integer from 1 to 3, and more preferably 1. As polymerizable monomers having such hydrophobic groups, 4-triethylsilyloxyphenyl methacrylate and 4-tert-butyldimethylsilyloxyphenyl (meth)acrylate are preferred.

[0064] A preferred example of formula (1) is the following structural unit (1a). [ka]

[0065] (In formula (1a), R 1a R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 2a , R 3a , and R 4a Each of these is an alkyl group having 1 to 7 carbon atoms.

[0066] In equation (1a), R 1a R is preferably a hydrogen atom or a methyl group. 2a , R 3a , and R 4a Each of these is preferably independently a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group.

[0067] The hydrophobic resin (A) may have structural units represented by formula (2) below if necessary, but sufficient effects can be obtained even without them. For example, other polymerizable monomers that form structural units represented by formula (2) after polymerization can be used.

[0068] [ka]

[0069] (In formula (2), R6 and R 7 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 This refers to a phenyl group substituted with 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 at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0070] R 6 and R 7 Each of these independently exemplifies a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples of polymerizable monomers include cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, or hydroxyl groups, and phenyl groups substituted with at least one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms. Examples of other polymerizable monomers include phenylmaleimide and N-cyclohexylmaleimide.

[0071] However, the positive-type photosensitive resin composition according to this embodiment can achieve sufficient effects even if the hydrophobic resin (A) does not have the structural unit represented by formula (2) described above. Furthermore, sufficient effects can be achieved even if the hydrophobic resin (A) does not have a maleimide structure in its structural unit. Moreover, from the viewpoint of achieving sufficient effects, it is preferable that the hydrophobic resin (A) does not have an imide skeleton in its structural unit. Furthermore, it is even more preferable that the hydrophobic resin (A) does not have a nitrogen atom.

[0072] The hydrophobic resin (A) preferably further has structural units represented by the following formula (3), if necessary. For example, other polymerizable monomers having alkali-soluble functional groups that form structural units represented by formula (3) after polymerization are preferred.

[0073] [ka]

[0074] (In formula (3), R 9 (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0075] In formula (3), R 9 is preferably a hydrogen atom or a methyl group. a is preferably an integer from 1 to 3, and more preferably 1. As another polymerizable monomer having such alkali-soluble functional groups, 4-hydroxyphenyl(meth)acrylate is preferred.

[0076] An example of a preferred structural unit of formula (3) is the following structural unit (1b).

[0077] [ka]

[0078] (In formula (1b), R 1b (This is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

[0079] In equation (1b), R 1b The atom is preferably a hydrogen atom or a methyl group. A specific example of the compound of formula (1b) is, for example, 4-hydroxyphenyl (meth)acrylate.

[0080] As the hydrophobic resin (A), a resin containing the structural unit represented by formula (1) and the structural unit represented by formula (3) is preferred, and a resin containing the structural unit represented by formula (1a) and the structural unit represented by formula (1b) is more preferred. Note that R in formula (1a) 1a And, R in equation (1b) 1b They may be the same or they may be different.

[0081] In the hydrophobic resin (A), the molar ratio of structural units represented by formula (1) to structural units represented by formula (3) is preferably formula (1):formula (3) = 5 to 70:10 to 95, and more preferably formula (1):formula (3) = 10 to 50:30 to 90.

[0082] Furthermore, the polymerization initiator used when producing hydrophobic resin (A) by radical polymerization is not limited to the following, but includes 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); dicumyl peroxide, 2,5-dimethyl-2,5-di(tert Peroxide polymerization initiators with a 10-hour half-life temperature of 100 to 170°C, such as 1,1'-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide, can be used. Alternatively, peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, and tert-butylperoxypivalate can be used. The amount of polymerization initiator used is generally preferably at a lower limit of 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, and at an upper limit of 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, per 100 parts by mass of the total polymerizable monomers.

[0083] In the polymerization of hydrophobic resin (A), a RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator. The RAFT agent is not limited to the following, but thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, and xanthanthates can be used. The RAFT agent can be used in the range of 0.005 to 20 parts by mass, and preferably in the range of 0.01 to 10 parts by mass, per 100 parts by mass of the total polymerizable monomers.

[0084] When the hydrophobic resin (A) has silicon atom-containing groups, the silicon atom content is preferably 1 to 10% by mass, more preferably 3 to 8% by mass, based on the mass of the hydrophobic resin (A). The lower limit is more preferably 3% by mass or more, even more preferably 3.5% by mass or more. The upper limit is more preferably 8% by mass or less, even more preferably 7% by mass or less, even more preferably 6% by mass or less, and even more preferably 5% by mass or less. The hydrophobic resin (A) having silicon atom-containing groups contains structural units having silicon atom-containing groups in an amount of preferably 5 to 70 mol%, more preferably 10 to 50 mol%, based on the total structural units of the hydrophobic resin (A). The lower limit is more preferably 10 mol% or more, even more preferably 20 mol% or more, and even more preferably 25 mol% or more. The upper limit is more preferably 50 mol% or less, even more preferably 40 mol% or less, and even more preferably 35 mol% or less.

[0085] The hydrophobic resin (A) may or may not have alkali-soluble functional groups. The hydrophobic resin (A) contains alkali-soluble functional groups in an amount of preferably 20 to 90 mol%, more preferably 30 to 85 mol%, and even more preferably 40 to 80 mol%, of the total structural units of the hydrophobic resin (A). In this embodiment, it is preferable that the hydrophobic resin (A) does not have alkali-soluble functional groups.

[0086] The weight-average molecular weight (Mw) of the hydrophobic resin (A) is preferably 3,000 to 80,000. The lower limit is more preferably 4,000 or more, even more preferably 5,000 or more, even more preferably 6,000 or more, and still more preferably 7,000 or more. The upper limit is more preferably 70,000 or less, even more preferably 60,000 or less, even more preferably 30,000 or less, even more preferably 15,000 or less, even more preferably 13,000 or less, and still still more preferably 10,000 or less.

[0087] The number-average molecular weight (Mn) of the hydrophobic resin (A) is preferably 1,000 to 30,000. The lower limit is more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 2,500 or more, and still more preferably 3,000 or more. The upper limit is more preferably 25,000 or less, even more preferably 20,000 or less, even more preferably 10,000 or less, and still still more preferably 5,000 or less.

[0088] The polydispersity (Mw / Mn) of the hydrophobic resin (A) is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2.8. The lower limit is more preferably 1.1 or higher, even more preferably 1.2 or higher, even more preferably 1.5 or higher, and even more preferably 1.8 or higher. The upper limit is more preferably 3.0 or lower, even more preferably 2.8 or lower, even more preferably 2.6 or lower, and even more preferably 2.4 or lower.

[0089] By setting the weight-average molecular weight, number-average molecular weight, and polydispersity within the above ranges, a positive-type photosensitive resin composition with even better sensitivity and hole-forming properties can be obtained.

[0090] The positive-type photosensitive resin composition according to this embodiment preferably contains 3 to 50% by mass, more preferably 4 to 40% by mass, and even more preferably 5 to 30% by mass of hydrophobic resin (A) based on 100% by mass of solids. The lower limit is more preferably 4% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, even more preferably 10% by mass or more, and even more preferably 12% by mass or more. The upper limit is more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 18% by mass or less, and even more preferably 16% by mass or less. If the content of hydrophobic resin (A) is above the above lower limit, the silicone-based surfactant (D) promotes the uneven distribution of hydrophobic resin (A) on the film surface, resulting in a high concentration of hydrophobic resin (A) on the film surface, and the film surface becomes poorly soluble in alkaline aqueous solution, thus achieving even higher sensitivity. If the content of hydrophobic resin (A) is below the above upper limit, the dissolution of the film surface due to the dissolution of carboxylic acid compounds derived from quinone diazide compounds, other highly alkali-soluble resin components, and any dissolution accelerator in the exposed area proceeds rapidly, thus enabling even higher sensitivity.

[0091] Furthermore, the positive-type photosensitive resin composition according to this embodiment preferably contains 3 to 50 parts by mass, more preferably 4 to 40 parts by mass, and even more preferably 5 to 30 parts by mass of hydrophobic resin (A) based on 100 parts by mass of solids. The lower limit is more preferably 4 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 12 parts by mass or more. The upper limit is more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 18 parts by mass or less, and even more preferably 16 parts by mass or less.

[0092] The positive-type photosensitive resin composition according to this embodiment contains, based on the total mass of the resin components, preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 40% by mass of hydrophobic resin (A). The lower limit is more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more. The upper limit is more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less. If the content of hydrophobic resin (A) is above the above lower limit, the silicone-based surfactant (D) promotes the uneven distribution of hydrophobic resin (A) on the film surface, resulting in a high concentration of hydrophobic resin (A) on the film surface, and the film surface becomes poorly soluble in alkaline aqueous solution, thus achieving even higher sensitivity. If the content of hydrophobic resin (A) is below the above upper limit, the dissolution of the film surface due to the dissolution of carboxylic acid compounds derived from quinone diazide compounds, other highly alkali-soluble resin components, and any dissolution accelerator in the exposed area proceeds rapidly, thus enabling even higher sensitivity.

[0093] <Alkali-soluble resin (B)>

[0094] The positive-type photosensitive resin composition according to this embodiment preferably further contains an alkali-soluble resin (B) as a resin other than the hydrophobic resin (A). The type of alkali-soluble resin (B) is not particularly limited, but it is preferably a resin having alkali-soluble functional groups. Examples of alkali-soluble functional groups are not particularly limited, but include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphate groups, acid anhydride groups, and mercapto groups. An alkali-soluble resin (B) having two or more types of alkali-soluble functional groups may be used. The alkali-soluble resin (B) may have alkali-soluble functional groups protected by acid-degradable groups.

[0095] Specific examples of alkali-soluble resin (B) include, for example, homopolymers or copolymers (B1) containing polymerizable monomers having alkali-soluble functional groups, and resins (B2) having epoxy groups and phenolic hydroxyl groups. Alkali-soluble resin (B) may be used alone or in combination of two or more types.

[0096] The alkali-soluble resin (B) may have radical polymerizable functional groups. Specific examples of radical polymerizable functional groups include (meth)acryloyloxy groups, allyl groups, or methallyl groups.

[0097] When the positive-type photosensitive resin composition according to this embodiment contains an alkali-soluble resin (B), it is generally preferable that the alkali-soluble resin (B) is 5 to 80% by mass, based on 100% by mass of solids. The lower limit is more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and even more preferably 30% by mass or more. The upper limit is more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and even more preferably 40% by mass or less. If the alkali-soluble resin (B) content is in this amount based on 100% by mass of solids, it is possible to effectively ensure the stability and durability of the film after heat curing while further suppressing the decrease in dissolution of the exposed area and the decrease in sensitivity.

[0098] Furthermore, if the positive-type photosensitive resin composition according to this embodiment contains an alkali-soluble resin (B), it is generally preferable that the amount of alkali-soluble resin (B) is 5 to 80 parts by mass, based on 100 parts by mass of solids. The lower limit is more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more. The upper limit is more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. By blending the alkali-soluble resin (B) in this amount, it is possible to further suppress the decrease in dissolution of the exposed area and the decrease in sensitivity while effectively ensuring the stability and durability of the film after heat curing.

[0099] When the positive-type photosensitive resin composition according to this embodiment contains an alkali-soluble resin (B), its content is not particularly limited, but typically, it can contain 0 to 90% by mass of the alkali-soluble resin (B) based on the total mass of the resin components. This upper limit may be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less. If the content of the alkali-soluble resin (B) is within this range based on the total mass of the resin components, it is possible to maintain a certain effect while effectively ensuring a certain level of alkali solubility.

[0100] (B1) Homopolymer or copolymer containing a polymerizable monomer having an alkali-soluble functional group.

[0101] Examples of alkali-soluble functional groups in a homopolymer or copolymer (B1) containing a polymerizable monomer having an alkali-soluble functional group include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, acid anhydride groups, and mercapto groups.

[0102] Specific examples of component (B1) 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, all of which have alkali-soluble functional groups. For example, a derivative of phenolic resin is polyalkenylphenol resin, in which an alkenyl group is bonded to a benzene ring, and a derivative of polystyrene resin is a hydroxypolystyrene resin derivative, in which a phenolic hydroxyl group and a hydroxyalkyl group or alkoxy group are bonded to a benzene ring.

[0103] The copolymer of component (B1) may have two or more alkali-soluble functional groups. Examples of polymerizable functional groups that polymerizable monomers and other polymerizable monomers have include radical polymerizable functional groups such as CH2=CH-, CH2=C(CH3)-, CH2=CHCO-, CH2=C(CH3)CO-, and -OC-CH=CH-CO-.

[0104] From the viewpoint of heat resistance, copolymers having alkali-soluble functional groups preferably have one or more cyclic structures selected from the group consisting of alicyclic structures, aromatic structures, polycyclic structures, inorganic cyclic structures, and heterocyclic structures.

[0105] Copolymers having alkali-soluble functional groups can be produced, for example, by radical polymerization of a polymerizable monomer having alkali-soluble functional groups with other polymerizable monomers. After synthesizing the copolymer by radical polymerization, alkali-soluble functional groups may be added to the copolymer as described above.

[0106] Polymerizable monomers having alkali-soluble functional groups include, for example, maleic acid derivatives such as maleic acid, monomethyl maleic acid, monoethyl maleic acid, monoisopropyl maleic acid, and maleic anhydride; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; unsaturated carboxylic acid compounds such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid; and 4-H Examples include polymerizable monomers having phenolic hydroxyl groups such as droxystyrene, 4-hydroxyphenyl(meth)acrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, and 4-hydroxyphenylmaleimide; polymerizable monomers having sulfo groups such as (meth)allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, and styrenesulfonic acid; polymerizable monomers having phosphate groups such as mono(2-(meth)acryloyloxyethyl) phosphate; and polymerizable monomers having acid anhydride groups such as itaconic acid anhydride and citraconic acid anhydride.

[0107] From the viewpoint of sensitivity, the polymerizable monomer having an alkali-soluble functional group is preferably a (meth)acrylic acid derivative or a polymerizable monomer having a phenolic hydroxyl group, and more preferably a polymerizable monomer having a phenolic hydroxyl group.

[0108] Other polymerizable monomers include, for example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; and (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0109] As a polymerizable monomer having an alkali-soluble functional group, it is preferable that it forms a structural unit represented by formula (3) after polymerization. 9 is preferably a hydrogen atom or a methyl group. a is preferably an integer from 1 to 3, and more preferably 1. 4-hydroxyphenyl(meth)acrylate is particularly preferred as a polymerizable monomer having such an alkali-soluble functional group.

[0110] [ka]

[0111] (In equation (3), R 9 (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0112] Other polymerizable monomers include those that form structural units represented by formula (2) after polymerization, but they do not need to be included. 6 and R 7Each of these is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples of such polymerizable monomers include phenyl groups substituted with at least one selected from the group consisting of cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, hydroxyl groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. Other examples of such polymerizable monomers include phenylmaleimide and N-cyclohexylmaleimide, but the positive-type photosensitive resin composition according to this embodiment can achieve sufficient effects even if the alkali-soluble resin (B) does not contain such a maleimide skeleton. Furthermore, from the viewpoint of achieving sufficient effects, it is preferable that the alkali-soluble resin (B) does not have an imide skeleton in its structural units. Moreover, it is even more preferable that the alkali-soluble resin (B) does not have a nitrogen atom.

[0113] [ka]

[0114] (In equation (2), R 6 and R 7 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 This refers to a phenyl group substituted with 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 at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0115] In this embodiment, the copolymer having alkali-soluble functional groups may have structural units represented by formula (3) and structural units represented by formula (2). However, as described above, sufficient effects can be obtained even without having structural units represented by formula (2).

[0116] [ka]

[0117] (In equation (3), R 9 (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0118] [ka]

[0119] (In equation (2), R 6 and R 7 Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 This refers to a phenyl group substituted with 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 at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0120] 4-hydroxyphenyl methacrylate may be used as the polymerizable monomer having an alkali-soluble functional group, and phenylmaleimide or N-cyclohexylmaleimide may be used as other polymerizable monomers, but they are not required.

[0121] The type and amount of polymerization initiator used when producing copolymers having alkali-soluble functional groups by radical polymerization are as described for the polymerization initiator used when producing hydrophobic resin (A) by radical polymerization. The type and amount of RAFT agent that can be used in combination with the polymerization initiator are as described for the RAFT agent used when producing hydrophobic resin (A) by radical polymerization.

[0122] The weight-average molecular weight (Mw) of the copolymer having alkali-soluble functional groups is preferably 3,000 to 80,000, more preferably 4,000 to 70,000, and even more preferably 5,000 to 60,000. The number-average molecular weight (Mn) of the copolymer having alkali-soluble functional groups is preferably 1,000 to 30,000, more preferably 1,500 to 25,000, and even more preferably 2,000 to 20,000. The polydispersity (Mw / Mn) of the copolymer having alkali-soluble functional groups is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2.8. By setting the weight-average molecular weight, number-average molecular weight, and polydispersity of the copolymer having alkali-soluble functional groups within the above ranges, a positive-type photosensitive resin composition with even better coating properties, hole-forming properties, and alkali-developable properties can be obtained.

[0123] When the alkali-soluble functional group of a copolymer having an alkali-soluble functional group is a phenolic hydroxyl group, the equivalent amount of phenolic hydroxyl groups in the copolymer having the alkali-soluble functional group is preferably 60 to 400, more preferably 80 to 350, and even more preferably 100 to 300. If the equivalent amount of phenolic hydroxyl groups in the copolymer having the alkali-soluble functional group is 60 or more, the film thickness of the unexposed areas can be sufficiently maintained during alkali development. If the equivalent amount of phenolic hydroxyl groups in the copolymer having the alkali-soluble functional group is 400 or less, the desired alkali solubility can be obtained.

[0124] In this specification, if a copolymer having an alkali-soluble functional group also falls under the category of a resin having epoxy groups and phenolic hydroxyl groups, as described later, it shall be treated as a copolymer having an alkali-soluble functional group. That is, resins having epoxy groups and phenolic hydroxyl groups do not include those that fall under the category of copolymer having an alkali-soluble functional group.

[0125] 《Resin having epoxy groups and phenolic hydroxyl groups (B2)》

[0126] Resins having epoxy groups and phenolic hydroxyl groups are alkaline aqueous solution soluble resins. Resins having epoxy groups and phenolic hydroxyl groups may also have alkali-soluble functional groups other than phenolic hydroxyl groups. Resins having epoxy groups and phenolic hydroxyl groups can be obtained, for example, by reacting some of the epoxy groups of a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as "epoxy compound") with the carboxyl group of a hydroxybenzoic acid compound. The epoxy groups of resins having epoxy groups and phenolic hydroxyl groups form crosslinks by reaction with phenolic hydroxyl groups during post-development heat treatment (post-bake), thereby improving the chemical resistance, heat resistance, etc. of the coating. Since phenolic hydroxyl groups contribute to solubility in alkaline aqueous solutions during development, resins having epoxy groups and phenolic hydroxyl groups also function as dissolution accelerators for other resins when exposed at low exposure levels, thereby making the photosensitive resin composition even more sensitive.

[0127] Reaction Equation 1 below shows an example of a reaction in which one of the epoxy groups of an epoxy compound reacts with the carboxyl group of a hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group.

[0128] [ka]

[0129] Examples of compounds having at least two epoxy groups in one molecule include novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins, bisphenol-type epoxy resins, biphenol-type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These epoxy compounds only need to have two or more epoxy groups in one molecule and can be used individually or in combination of two or more types. Since these compounds are thermosetting, it is common knowledge to those skilled in the art that their structure cannot be uniquely described based on differences such as the presence or absence of epoxy groups, the type of functional group, and the degree of polymerization.

[0130] An example of the structure of a novolac-type epoxy resin is shown in formula (4). In formula (4), R 10 m is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a hydroxyl group, and m is an integer from 1 to 50.

[0131] [ka]

[0132] Examples of phenol novolac type epoxy resins include "EPICLON(registered trademark) N-770", "EPICLON(registered trademark) N-730A" (both product names, DIC Corporation), and "jER(registered trademark)-152" (product name, Mitsubishi Chemical Corporation). Examples of cresol novolac type epoxy resins include "EPICLON(registered trademark) N-695" (product name, DIC Corporation) and "EOCN(registered trademark)-102S" (product name, Nippon Kayaku Co., Ltd.). Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins such as "jER(registered trademark) 828", "jER(registered trademark) 1001" (both product names, Mitsubishi Chemical Corporation) and "YD-128" (product name, Nippon Steel Chemical & Material Co., Ltd.), and bisphenol F type epoxy resins such as "jER(registered trademark) 806" (product name, Mitsubishi Chemical Corporation) and "YDF-170" (product 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" (both product names, Mitsubishi Chemical Corporation). Examples of naphthalene skeleton-containing epoxy resins include "NC-7000" (product name, Nippon Kayaku Co., Ltd.) and "EXA-4750" (product name, DIC Corporation). Examples of alicyclic epoxy resins include "EHPE(registered trademark)-3150" (Daicel Corporation). Examples of heterocyclic epoxy resins include "TEPIC(registered trademark)", "TEPIC(registered trademark)-L", "TEPIC(registered trademark)-H", and "TEPIC(registered trademark)-S" (all product names, Nissan Chemical Corporation).

[0133] (B2) The compound having at least two epoxy groups in one molecule is preferably a novolac-type epoxy resin, more preferably at least one selected from the group consisting of phenol novolac-type epoxy resins and cresol novolac-type epoxy resins, and even more preferably a cresol novolac-type epoxy resin. A positive-type photosensitive resin composition containing a resin having epoxy groups and phenolic hydroxyl groups derived from a novolac-type epoxy resin, particularly a cresol novolac-type epoxy resin, exhibits superior hole-forming properties, easier adjustment of alkali solubility, and less outgassing.

[0134] Hydroxybenzoic acid compounds are compounds in which at least one of the 2-6 positions of benzoic acid is substituted with a hydroxyl group. Examples 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 that they enhance alkali developability. Hydroxybenzoic acid compounds may be used alone or in combination of two or more.

[0135] In this embodiment, specific examples of resins having epoxy groups and phenolic hydroxyl groups include, for example, a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, having the structure of formula (5).

[0136] [ka]

[0137] (In formula (5), b is an integer between 1 and 5, and * represents the binding site with the residue excluding the epoxy group involved in the reaction, in a compound having at least two epoxy groups in one molecule.)

[0138] In a method for obtaining a resin having epoxy groups and phenolic hydroxyl groups from an epoxy compound and a hydroxybenzoic acid compound, 0.2 to 0.95 equivalents of the hydroxybenzoic acid compound can be used per 1 equivalent of epoxy groups in the epoxy compound, preferably 0.3 to 0.9 equivalents, and more preferably 0.4 to 0.8 equivalents. If the amount of hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkaline solubility can be obtained, and if it is 0.95 equivalents or less, the increase in molecular weight due to side reactions can be suppressed.

[0139] A catalyst may be used to accelerate the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of catalyst used can be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction material mixture consisting of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature can be 60 to 150°C, and the reaction time can be 3 to 30 hours. Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate.

[0140] The number-average molecular weight (Mn) of the resin having epoxy groups and phenolic hydroxyl groups is preferably 500 to 8000, more preferably 800 to 6000, and even more preferably 1000 to 5000. The lower limit is more preferably 800 or more, even more preferably 1000 or more, and even more preferably 2000 or more. The upper limit is more preferably 6000 or less, even more preferably 5000 or less, and even more preferably 4000 or less.

[0141] The weight-average molecular weight (Mw) of the resin having epoxy groups and phenolic hydroxyl groups is preferably 500 to 30000, more preferably 2000 to 25000, and even more preferably 3000 to 20000. The lower limit is more preferably 2000 or more, even more preferably 3000 or more, and even more preferably 4000 or more. The upper limit is more preferably 25000 or less, even more preferably 20000 or less, even more preferably 10000 or less, even more preferably 8000 or less, and even more preferably 7000 or less.

[0142] For example, if the number-average molecular weight is 500 or higher, or the weight-average molecular weight is 500 or higher, the alkaline development rate is appropriate and the difference in dissolution rates between the exposed and unexposed areas is sufficient, resulting in even better pattern resolution. If the number-average molecular weight is 8000 or lower, or the weight-average molecular weight is 30000 or lower, the coating properties and alkaline developability are even better.

[0143] The polydispersity (Mw / Mn) of the resin having epoxy groups and phenolic hydroxyl groups is preferably 1.0 to 3.5. The lower limit is more preferably 1.2 or higher, and even more preferably 1.5 or higher. The upper limit is more preferably 3.0 or lower, and even more preferably 2.0 or lower.

[0144] In this embodiment, the epoxy equivalent of the resin having epoxy groups and phenolic hydroxyl groups is preferably 300 to 7000, more preferably 400 to 6000, and even more preferably 500 to 5000. The lower limit is more preferably 400 or more, even more preferably 500 or more, even more preferably 1000 or more, and even more preferably 1500 or more. The upper limit is more preferably 6000 or less, even more preferably 5000 or less, even more preferably 4000 or less, and even more preferably 3000 or less. If the epoxy equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 300 or more, sufficient alkali solubility can be imparted to the resin having epoxy groups and phenolic hydroxyl groups. If the epoxy equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 7000 or less, the strength and heat resistance of the cured film can be further increased. The epoxy equivalent is determined according to JIS K 7236:2009.

[0145] In this embodiment, the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is preferably 140 to 550, more preferably 160 to 500, even more preferably 170 to 400, and even more preferably 180 to 300. If the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is above the above upper limit, the strength and heat resistance of the cured film can be further increased. For example, if the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 160 or more, the strength and heat resistance of the cured film can be further increased. If the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is below the above lower limit, sufficient alkali solubility can be imparted by the resin having epoxy groups and phenolic hydroxyl groups. For example, if the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 500 or less, even more sufficient alkali solubility can be imparted by the resin having epoxy groups and phenolic hydroxyl groups. The hydroxyl equivalent is determined according to JIS K 0070:1992.

[0146] 《Protective resin (B3)》

[0147] The alkali-soluble resin (B) may include a resin having alkali-soluble functional groups protected by acid-degradable groups (hereinafter also simply referred to as the "protective resin"). The protective resin (B3) is not particularly limited as long as it has multiple alkali-soluble functional groups, and at least a portion of the multiple alkali-soluble functional groups are protected by acid-degradable groups. Examples of protective resin (B3) include a resin in which the above-mentioned alkali-soluble resin (B) having multiple alkali-soluble functional groups is used as a base resin, and at least a portion of the alkali-soluble functional groups are protected by acid-degradable groups. Examples of alkali-soluble functional groups include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, acid anhydride groups, and mercapto groups. The alkali-soluble functional groups are preferably phenolic hydroxyl groups or carboxyl groups, and more preferably phenolic hydroxyl groups. Because a portion of the alkali-soluble functional groups are protected by acid-degradable groups, the alkali solubility of the protective resin (B3) before exposure is suppressed. The protective resin (B3) may have alkali-soluble functional groups other than alkali-soluble functional groups protected by acid-degradable groups. In the presence of acid generated during exposure, post-exposure baking (PEB) is performed as needed to promote the decomposition (deprotection) of acid-degradable groups and regenerate alkali-soluble functional groups. This promotes the alkali dissolution of the protective resin (B3) in the exposed area during development. The protective resin (B3) may be used alone or in combination of two or more types. For example, the protective resin (B3) may be a combination of two or more resins with different polymer or copolymer structural units, acid-degradable groups, protection rates of alkali-soluble functional groups, or combinations thereof.

[0148] (Protection of alkali-soluble functional groups by acid-degradable groups)

[0149] The protective resin (B3) can be obtained by protecting some of the alkali-soluble functional groups of a base resin having multiple alkali-soluble functional groups with acid-degradable groups. For example, if the alkali-soluble functional group is a phenolic hydroxyl group, the protective resin (B3) having phenolic hydroxyl groups protected by acid-degradable groups is Ar-OR 11 It has a substructure where Ar represents an aromatic ring derived from phenol, and R 11 This represents an acid-degradable group.

[0150] Acid-degradable groups are groups that decompose (deprotect) in the presence of an acid, and optionally by heating, to generate alkali-soluble functional groups. Specifically, examples include groups having tertiary alkyl groups such as tert-butyl group, 1,1-dimethyl-propyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-methyladamantyl group, 1-ethyladamantyl group, tert-butoxycarbonyl group, and 1,1-dimethyl-propoxycarbonyl group; and groups represented by formula (6). When the alkali-soluble functional group is a phenolic hydroxyl group, the group represented by formula (6) forms an acetal structure or a ketal structure together with the oxygen atom derived from the alkali-soluble functional group. These acid-degradable groups can be used individually or in combination of two or more types. -CR 12 R 13 -OR 14 ...(6) (In formula (6), R 12 and R 13 Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 14 R is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. 12 or R 13 One of the two and R 14 They may combine to form a ring structure with 3 to 10 members, R 12, R 13 and R 14 (This may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine.)

[0151] Since a highly sensitive photosensitive resin composition can be effectively obtained even with low exposure, the acid-degradable group is preferably a group represented by formula (6). 12 and R 13 Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 14 It is more preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine. Examples of such acid-degradable groups include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group, with 1-ethoxyethyl group and 1-n-propoxyethyl group being preferred. As an acid-degradable group, there is a group represented by formula (6), where R 12 or R 13 One of the two and R 14 A ring structure with 3 to 10 members formed by the bonding of these elements can also be suitably used. In this case, R, which is not involved in the formation of the ring structure, can also be used. 12 or R 13 It is preferable that the group is a hydrogen atom. Examples of such acid-degradable groups include the 2-tetrahydrofuranyl group and the 2-tetrahydropyranyl group, with the 2-tetrahydrofuranyl group being preferred.

[0152] The protection reaction of alkali-soluble functional groups can be carried out under known conditions using common protective agents. For example, protective resin (B3) can be obtained by reacting the base resin of protective resin (B3) with a protective agent in the presence of an acid or base in a solvent-free environment or in a solvent such as toluene or hexane at a reaction temperature of -20 to 50°C.

[0153] As a protective agent, known protective agents capable of protecting alkali-soluble functional groups can be used. For example, if the acid-degradable group is a tert-butyl group, isobutene can be used; if it is a tert-butoxycarbonyl group, di-tert-butyl dicarbonate can be used. If the acid-degradable group is a methoxymethyl group, chloromethyl methyl ether can be used; if it is a 1-ethoxyethyl group, ethyl vinyl ether can be used; if it is a 1-n-propoxyethyl group, n-propyl vinyl ether can be used; if it is a 2-tetrahydrofuranyl group, 2,3-dihydrofuran can be used; and if it is a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran can be used.

[0154] Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid. Salts of organic acids, such as the pyridinium salt of p-toluenesulfonic acid, can also be used as acid sources. Examples of bases include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate, metal hydrides such as sodium hydride, and amine compounds such as pyridine, N,N-dimethyl-4-aminopyridine, imidazole, triethylamine, and diisopropylethylamine.

[0155] In another embodiment, after protecting the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group with an acid-degradable group, a protective resin (B3) can also be obtained by polymerizing or copolymerizing the polymerizable monomer having an alkali-soluble functional group protected with an acid-degradable group and, if necessary, other polymerizable monomers. The protection of the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group can be carried out in the same manner as the protection of the alkali-soluble functional group of the base resin.

[0156] The protective resin (B3) preferably has a structural unit represented by the formula (7) and at least one structural unit represented by the formula (7) in which q is an integer of 1 or more.

[0157] [Chemical formula]

[0158] (In formula (7), R 15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 16 is an acid-degradable group, p is an integer of 0 to 5, q is an integer of 0 to 5, provided that p + q is an integer of 1 to 5.)

[0159] In the formula, the acid-degradable group of R 16 is preferably a group represented by the formula (6). -CR 12 R 13 -O-R 14 ···(6) (In formula (6), R 12 , R 13 and R 14 are as described above.)

[0160] In formula (6), R 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 14is more preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine. Examples of such acid-decomposable groups include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group, and 1-ethoxyethyl group and 1-n-propoxyethyl group are preferred. R 12 or R 13 One of and R 14 Examples of the acid-decomposable group in which and R

[0161] combine to form a ring structure having 3 to 10 ring members include, for example, 2-tetrahydrofuranyl group and 2-tetrahydropyranyl group, and 2-tetrahydrofuranyl group is preferred.

[0161] The protective resin (B3) may or may not have a structural unit represented by the formula (2). Even if the protective resin (B3) does not have a structural unit represented by the formula (2), sufficient effects can be obtained. From the viewpoint of obtaining sufficient effects, it is preferable that the protective resin (B3) does not have an imide skeleton in the structural unit. Furthermore, it is more preferable that the protective resin (B3) does not have a nitrogen atom.

[0162] [Chemical formula]

[0163] (In formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8This refers to a phenyl group substituted with 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 at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0164] In formula (2), R 6 and R 7 Each of these can be independently exemplified by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples include cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, or hydroxyl groups, and phenyl groups substituted with at least one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms.

[0165] In this embodiment, the number of structural units represented by formula (7) where q is an integer of 1 or more, i.e., structural units represented by formula (7) in which at least one alkali-soluble functional group is protected by an acid-degradable group, is preferably 5 to 95%, more preferably 15 to 90%, and even more preferably 25 to 85% of the total number of structural units in the protective resin (B3). By setting the proportion of the above structural units to 5% or more, the dissolution of the exposed area can be further promoted, creating a greater difference in solubility between the unexposed and exposed areas, thereby achieving even higher sensitivity and effectively ensuring the stability and durability of the film after heat curing. By setting the proportion of the above structural units to 95% or less, the amount of unreacted acid-degradable groups remaining can be further reduced, increasing the solubility of the exposed area and achieving even higher sensitivity.

[0166] In this embodiment, the positive-type photosensitive resin composition contains, based on 100% by mass of solids, a protective resin (B3) preferably in an amount of 0.5 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably 2 to 30% by mass. If the content of the protective resin (B3) is above the lower limit based on 100% by mass of solids, the dissolution of the exposed area can be further promoted, creating a greater difference in solubility between the unexposed and exposed areas, thereby achieving even higher sensitivity and effectively ensuring the stability and durability of the film after heat curing. If the content of the protective resin (B3) is below the upper limit based on 100% by mass of solids, the amount of unreacted acid-degradable groups remaining can be further reduced, increasing the solubility of the exposed area and achieving even higher sensitivity.

[0167] <Quinone diazide compound (C)>

[0168] When quinone diazide compounds (C) are irradiated with visible light, ultraviolet light, or radiation (gamma rays, electron beams, etc.), they undergo the reaction shown in reaction equation 2 below to produce alkali-soluble carboxylic acid compounds.

[0169] [ka]

[0170] The quinone diazide compound (C) interacts with the alkali-soluble functional groups of the alkali-soluble resin (B), such as phenolic hydroxyl groups, before photosensitivity (e.g., by hydrogen bonding), rendering the alkali-soluble resin (B) insoluble in an alkaline aqueous solution. On the other hand, the presence of an alkali-soluble carboxylic acid compound in the irradiated area makes the resin in that area more easily soluble in the alkaline aqueous solution along with the carboxylic acid compound. Furthermore, the generated carboxylic acid compound promotes the decomposition of the acid-degradable groups of the protective resin (B3), which is optionally included in the positive-type photosensitive resin composition, regenerating its alkali-soluble functional groups and increasing the alkali solubility of the protective resin (B3). Moreover, the carboxylic acid compound has a relatively larger molecular structure than acids produced from photoacid generators commonly used in chemical amplification resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is less likely to diffuse in the film. As a result of the synergistic action of these factors, the difference in alkali solubility between the unexposed and exposed areas can be increased, thereby enabling the formation of highly sensitive and high-resolution patterns even with low exposure levels. The quinone diazide compound (C) may be used alone or in combination of two or more types.

[0171] The positive-type photosensitive resin composition preferably contains substantially no photoacid generators commonly used in chemically amplified resists, and more preferably contains only a quinone diazide compound (C) as a photosensitive agent without the photoacid generator. "Substantially free of photoacid generators" means that the component is not actively added or mixed, and does not exclude its unavoidable inclusion or mixing. A preferred example of "substantially free of photoacid generators" is that the amount of the photoacid generator contained in the positive-type photosensitive resin composition is preferably 0.2 parts by mass or less, more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0 parts by mass, based on 100 parts by mass of the total resin components.

[0172] In this embodiment, high-resolution patterns can be formed without the post-exposure heating (PEB) required for typical chemically amplified resists. The quinone diazide compound (C) has a relatively high quantum yield, and carboxylic acid compounds are efficiently generated in the exposed areas. By omitting PEB, it is possible to avoid a decrease in hole formation performance caused by excessive diffusion of acid generated from the photoacid generator into the unexposed areas under the high-temperature environment of the PEB process. Furthermore, if the alkali-soluble resin (B) contains a resin having epoxy groups and phenolic hydroxyl groups, omitting PEB prevents ring-opening polymerization of the epoxy groups in the resin having epoxy groups and phenolic hydroxyl groups, thus effectively maintaining the alkali solubility of the resin having epoxy groups and phenolic hydroxyl groups during development.

[0173] Examples of quinone diazide compounds (C) include those in which the sulfonic acid of quinone diazide is esterified to a polyhydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, and those in which the sulfonic acid of quinone diazide is esterified or sulfonamide bonded to a polyhydroxypolyamino compound. From the viewpoint of further enhancing the contrast between the exposed and unexposed areas, it is preferable that 20 mol% or more of the total functional groups of the polyhydroxy compound or polyamino compound are substituted with quinone diazide.

[0174] Polyhydroxy compounds include "Bis-Z", "BisP-EZ", "TekP-4HBPA", "TrisP-HAP", "TrisP-PA", "TrisP-SA", "TrisOCR-PA", "BisOCH" P-Z”, “BisP-MZ”, “BisP-PZ”, “BisP-IPZ”, “BisOCP-IPZ”, “BisP-CP”, “BisRS-2P”, “BisRS-3P”, “BisP-OCHP”, “Methylene tris -FR-CR", "BisRS-26X", "DML-MBPC", "DML-MBOC", "DML-OCHP", "DML-PCHP", "DML-PC", "DML-PTBP", "DML-34X", "DML-E P”, “DML-POP”, “Dimethylol-BisOC-P”, “DML-PFP”, “DML-PSBP”, “DML-MTrisPC”, “TriML-P”, “TriML-35XL”, “TML-BP”, “TML Examples include, but are not limited to, "-HQ", "TML-pp-BPF", "TML-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, methylenebisphenol, "BisP-AP" (trade name, Honshu Chemical Industry Co., Ltd.), etc.

[0175] 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.

[0176] Examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0177] The quinone diazide compound (C) is preferably 1,2-naphthoquinone diazide-5-sulfonic acid ester of a polyhydroxy compound or 1,2-naphthoquinone diazide-4-sulfonic acid ester of a polyhydroxy compound. Commercially available products such as "TS-150A," "TS-200A," and "TPPA-150DF" (all trade names, manufactured by Toyo Gosei Kogyo Co., Ltd.) can be used.

[0178] In this embodiment, the positive-type photosensitive resin composition contains, based on 100 parts by mass of the total resin components, preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 15 to 42 parts by mass of quinone diazide compound (C). The lower limit is more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more. The upper limit is more preferably 50 parts by mass or less, even more preferably 42 parts by mass or less, even more preferably 37 parts by mass or less, and even more preferably 35 parts by mass or less. If the content of quinone diazide compound (C) is above the lower limit based on the total 100 parts by mass, high sensitivity can be achieved. If the content of quinone diazide compound (C) is below the upper limit based on the total 100 parts by mass, good alkaline developability is achieved.

[0179] Furthermore, the positive-type photosensitive resin composition according to this embodiment preferably contains 2.5 to 30 parts by mass of quinone diazide compound (C) based on 100 parts by mass of solids. The lower limit is more preferably 5 parts by mass or more, even more preferably 7.5 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 12.5 parts by mass or more. The upper limit is more preferably 25 parts by mass or less, even more preferably 21 parts by mass or less, even more preferably 18.5 parts by mass or less, and even more preferably 17.5 parts by mass or less. If the content of quinone diazide compound (C) is above the lower limit, high sensitivity can be achieved. If the content of quinone diazide compound (C) is below the upper limit, alkaline developability is good.

[0180] <Silicone-based surfactants (D) having silicon atoms in their side chains>

[0181] The silicone-based surfactant (D) is not particularly limited, but any silicone-based surfactant having silicon atoms in its side chain is acceptable. For example, a preferred silicone-based surfactant (D) is one comprising a (meth)acrylic copolymer having at least one silicon-containing hydrocarbon group selected from the group consisting of silicon-containing alkyl groups and silicon-containing alkylene groups. The acrylic copolymer promotes the migration of the hydrophobic resin (A) to the film surface of the positive-type photosensitive resin composition, thereby making the film surface more alkali-insoluble. Furthermore, from the viewpoint of further enhancing this effect, it is preferable that the silicone-based surfactant (D) is a silicone-based surfactant that does not have silicon atoms in its main chain but has silicon atoms in its side chain. The silicone-based surfactant (D) may be used alone or in combination of two or more types.

[0182] Examples of the (meth)acrylic copolymers mentioned above include (D1), a copolymer of a polymerizable monomer represented by formula (8) and a polymerizable monomer having a polyoxyalkylene group represented by formula (9).

[0183] [ka]

[0184] (In formula (8), R 17 L is a hydrogen atom or a methyl group. 1 Rf is a divalent group with 1 to 30 carbon atoms. 1 This is a silicon-containing alkyl group or partially silicate alkyl group having 4 to 6 carbon atoms, which may contain one or more ether bonds in the chain.

[0185] [ka]

[0186] (In formula (9), R 18 R is a hydrogen atom or a methyl group, 19 Each of these is independently a linear or branched alkylene group having 2 to 4 carbon atoms, and R 20 (where c is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and c is an integer from 2 to 50.)

[0187] In formula (8), L 1 The divalent group having 1 to 30 carbon atoms represented by may contain at least one heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur atoms, and may also contain a silicon atom-containing alkyl group or a partially silicate alkyl group having 4 to 6 carbon atoms. 1 Preferably, the compound is -OCH2CH2-, -OCH2CH2N(C3H7)SO2-, -OCH2CH2NH(C=O)OCH2CH2-, -OCH2CH(OH)CH2O-, or -N(C4H9)CH2CH2-.

[0188] The polymerizable monomer represented by formula (8) may be used alone or in combination of two or more types.

[0189] In formula (9), R 19 Examples of linear or branched alkylene groups having 2 to 4 carbon atoms, represented by R, include ethylene, propylene, tetramethylene, and isobutylene groups. 19They may be the same or they may be different from each other. From the standpoint of leveling, R 19 The group is preferably a propylene group, a tetramethylene group, or an isobutylene group, and it is more preferable that multiple identical groups are linked together via adjacent oxygen atoms to form a polyoxypropylene chain, a polytetramethylene chain, or a polyisobutylene chain.

[0190] In formula (9), R 20 Examples of alkyl groups having 1 to 6 carbon atoms, represented by , include methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-hexyl groups.

[0191] The polymerizable monomer having a polyoxyalkylene group represented by formula (9) may be used alone or in combination of two or more types.

[0192] The copolymer (D1) may be a copolymer of a polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), or other polymerizable monomers.

[0193] Other polymerizable monomers include, for example, the polymerizable monomer represented by formula (10).

[0194] [ka]

[0195] (In equation (10), R 21 R is a hydrogen atom or a methyl group, 22 (A C-C is a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms.)

[0196] In formula (10), R 22Examples of linear, branched, or cyclic alkyl groups having 1 to 18 carbon atoms, represented by , include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, stearyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, isobornyl, adamantyl, dicyclopentanyl, and dicyclopentenyl groups.

[0197] Other polymerizable monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0198] Other polymerizable monomers may be used individually or in combination of two or more.

[0199] From the viewpoint of leveling properties, the mass ratio of the polymerizable monomer represented by formula (8) to the polymerizable monomer having a polyoxyalkylene group represented by formula (9) in copolymer (D1) (mass of polymerizable monomer represented by formula (8) / mass of polymerizable monomer having a polyoxyalkylene group represented by formula (9)) is preferably 10 / 90 to 70 / 30, more preferably 15 / 85 to 60 / 40, and even more preferably 25 / 75 to 50 / 50. When other polymerizable monomers are used, it is preferable to use them in an amount such that the other polymerizable monomers constitute 50% by mass or less, based on the mass of copolymer (D1).

[0200] Copolymer (D1) can be obtained, for example, by radical polymerization of a polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), and other polymerizable monomers as needed, in an organic solvent using a polymerization initiator. Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfoxides such as dimethyl sulfoxide; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and aromatic hydrocarbons such as toluene and xylene. Examples of polymerization initiators include peroxide polymerization initiators such as benzoyl peroxide, and azo polymerization initiators such as 2,2'-azobisisobutyronitrile. If necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, and octylthioglycolic acid may be used.

[0201] Preferred examples of silicone-based surfactants (D) include "MEGAFACE EFS-131", "MEGAFACE EFS-321", "MEGAFACE EFS-521", and "MEGAFACE EFS-801" (all product names, all manufactured by DIC Corporation).

[0202] In particular, "MEGAFACE EFS-131," "MEGAFACE EFS-321," and "MEGAFACE EFS-521" are more preferred because they are fluorine-free, have silicon atoms in the side chains but not in the main chain, and include both the structure represented by formula (8) and the structure represented by formula (9) described above. All of these are (meth)acrylic copolymers that do not have silicon atoms in the main chain and have at least one silicon atom-containing hydrocarbon group selected from the group consisting of silicon atom-containing alkyl groups and silicon atom-containing alkylene groups.

[0203] The content of the silicone-based surfactant (D) in the positive-type photosensitive resin composition is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and even more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total resin components. The lower limit is more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, and even more preferably 0.15 parts by mass or more. The upper limit is more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, even more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less. If the content of the silicone-based surfactant (D) is equal to or greater than the lower limit based on the total 100 parts by mass, the leveling properties of the positive-type photosensitive resin composition are further improved, so that the positive-type photosensitive resin composition can be applied more uniformly to the substrate, thereby further promoting the uneven distribution of the hydrophobic resin (A). If the content of the silicone-based surfactant (D) is less than or equal to the upper limit value based on the total of 100 parts by mass mentioned above, the leveling properties of the positive-type photosensitive resin composition can be improved without adversely affecting the cured film after post-baking, and the uneven distribution of the hydrophobic resin (A) can be further promoted.

[0204] Furthermore, the positive-type photosensitive resin composition according to this embodiment preferably contains 0.005 to 2.5 parts by mass of a silicone-based surfactant (D) based on 100 parts by mass of solids. The lower limit is more preferably 0.025 parts by mass or more, even more preferably 0.05 parts by mass or more, and even more preferably 0.075 parts by mass or more. The upper limit is more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less. If the content of the silicone-based surfactant (D) is above the lower limit, the leveling properties of the positive-type photosensitive resin composition are further improved, so that the positive-type photosensitive resin composition can be applied to the substrate more uniformly, thereby further promoting the uneven distribution of the hydrophobic resin (A). If the content of the silicone-based surfactant (D) is below the upper limit, the leveling properties of the positive-type photosensitive resin composition can be improved and the uneven distribution of the hydrophobic resin (A) can be further promoted without adversely affecting the cured film after post-baking.

[0205] Furthermore, the content of component (D) in the total amount of surfactant is preferably 50% by mass or more. The lower limit of this content is more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more. Moreover, component (D) alone (100% by mass) is even more preferable. However, the upper limit of this content may be 95% by mass or less, or 90% by mass or less, and the desired effect can be obtained even with such upper limits. By setting the content of component (D) within the above range, wettability with the substrate can be ensured, and uniform coating can be performed without the occurrence of repelling.

[0206] <Coloring agent (E)>

[0207] The positive-type photosensitive resin composition preferably further contains a colorant (E) containing a black dye. Component (E) may also contain other colorants besides the black dye. By forming a black partition on an organic EL element using a photosensitive resin composition containing a colorant (E) containing a black dye, the visibility of display devices such as organic EL displays can be improved.

[0208] In this embodiment, by blending the colorant (E), the amount of radiation transmitted during exposure tends to rapidly decrease from the surface to the inside of the coating film. Therefore, the carboxylic acid compound derived from the quinonediazide compound (C) is generated relatively abundantly near the surface of the coating film, but is less likely to be generated inside the coating film. Since the carboxylic acid compound derived from the quinonediazide compound (C) has low diffusibility in the coating film, it remains near the surface of the coating film and contributes to promoting the dissolution of the coating film surface in the exposed area. Since the concentration of the hydrophobic resin (A) is relatively low inside the coating film, the alkali solubility is relatively high. Therefore, even when radiation does not sufficiently penetrate to the inside of the coating film, by using the positive photosensitive resin composition of this embodiment, a high-sensitivity and high-precision thick film pattern can be formed (however, the actions and effects of this embodiment are not limited to these).

[0209] Examples of the black dye include dyes defined by the Color Index (C.I.) of Solvent Black 27 to 47. The black dye is preferably one defined by the C.I. of Solvent Black 27, 29 or 34. When at least one of the dyes defined by the C.I. of Solvent Black 27 to 47 is used as the black dye, the light-shielding property of the coating film of the cured positive photosensitive resin composition can be effectively maintained. The positive photosensitive resin composition containing the black dye has fewer residues of the colorant during development and can form a high-definition pattern as compared with the positive photosensitive resin composition containing the black pigment.

[0210] Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigments, and lactam pigments. Those obtained by subjecting these black pigments to surface treatment can also be used. Examples of commercially available perylene pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34 from BASF. An example of a commercially available lactam pigment is Irgaphor® Black S0100CF from BASF. Because of its high light-shielding property, the black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene pigments, and lactam pigments.

[0211] In addition, dyes and pigments other than those described above can also be used in combination. These can be used within a range that does not impair the functions and effects of the present embodiment according to the purpose.

[0212] Examples of dyes other than those described above include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, fluoran dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

[0213] Other pigments include, for example, CI Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI Pigment Orange 36, 43, 51, 55, 59, 61; CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240; CI Pigment Violet 19, 23, 29, 30, 37, 40, 50; CI Pigment Blue 15, 15:1, 15:4, 22, 60, 64; CI Pigment Green 7; and CI Pigment Brown 23, 25, 26.

[0214] However, in this embodiment, it is preferable to increase the content of the black dye and decrease the content of other colorants (e.g., pigments). From this viewpoint, the content of colorants other than the black dye in the total amount of colorant (E) is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and most preferably none (0% by mass).

[0215] The content of the colorant (E) in the positive-type photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass, and even more preferably 20 to 80 parts by mass, based on 100 parts by mass of the total resin components. The lower limit is more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more. The upper limit is more preferably 100 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less. If the content of the colorant (E) is equal to or greater than the lower limit based on the total of 100 parts by mass, sufficient light-shielding properties can be obtained, and in particular, since the colorant (E) contains a black dye, the light-shielding properties of the cured film can be effectively maintained. If the content of the coloring agent (E) is below the upper limit based on the total of 100 parts by mass mentioned above, the residual film rate and sensitivity will be appropriate, and in particular, if the coloring agent (E) contains a black dye, the coating can be given high heat resistance.

[0216] Furthermore, the positive-type photosensitive resin composition according to this embodiment preferably contains 5 to 75 parts by mass of a coloring agent (E) based on 100 parts by mass of solids. The lower limit is more preferably 7.5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more. The upper limit is more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less. If the content of the coloring agent (E) is above the lower limit, sufficient light shielding can be obtained, and in particular, since the coloring agent (E) contains a black dye, the light shielding of the cured film can be effectively maintained. If the content of the coloring agent (E) is below the upper limit, the residual film rate and sensitivity are appropriate, and in particular, when the coloring agent (E) contains a black dye, high heat resistance can be imparted to the film.

[0217] <Optional ingredients>

[0218] Positive-type photosensitive resin compositions may contain optional components such as a dissolution accelerator (F), a thermosetting agent, and a secondary surfactant other than a silicone-based surfactant (D) having a silicon atom in its side chain. In this specification, optional components are defined as those that do not fall under any of (A) to (E).

[0219] Dissolution accelerator (F)

[0220] The positive-type photosensitive resin composition may further contain a dissolution accelerator (F) to further improve the solubility of the alkali-soluble portion in the developer during development. Examples of dissolution accelerators (F) include organic low-molecular-weight compounds selected from the group consisting of compounds having a carboxyl group and compounds having a phenolic hydroxyl group. Dissolution accelerators (F) may be used alone or in combination of two or more.

[0221] In this specification, "low molecular weight compound" refers to a compound with a molecular weight of 1000 or less. The above organic low molecular weight compounds have a carboxyl group or multiple phenolic hydroxyl groups and are alkali soluble.

[0222] Examples of such low-molecular-weight organic 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, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoronic acid; and aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimeric acid, and mesitylene acid. Examples include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamyridene acetate, coumaric acid, and umbellic acid; and aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol.

[0223] The content of the dissolution accelerator (F) in the positive-type photosensitive resin composition can be, for example, 0.1 parts by mass 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 resin components. The lower limit is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more. The upper limit is preferably 35 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. If the content of the dissolution accelerator (F) is above the lower limit based on the total of 100 parts by mass, the dissolution of the resin components can be effectively promoted, and if it is below the upper limit based on the total of 100 parts by mass, excessive dissolution of the resin components can be suppressed, further improving the hole-forming properties and surface quality of the coating.

[0224] Furthermore, the positive-type photosensitive resin composition according to this embodiment contains, for example, 0.05 to 25 parts by mass of a dissolution accelerator (F) based on 100 parts by mass of solids. The lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. The upper limit is preferably 17.5 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7.5 parts by mass or less. If the content of the dissolution accelerator (F) is above the lower limit, the dissolution of the resin components can be effectively promoted, and if it is below the upper limit, excessive dissolution of the resin components can be suppressed, further improving the hole-forming properties and surface quality of the coating.

[0225] <Thermosetting agent>

[0226] A thermal radical generator can be used as a thermosetting agent. Preferred thermal radical generators include organic peroxides, specifically organic peroxides with 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.

[0227] The content of the thermosetting 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 thermosetting agent.

[0228] <Second surfactant> The positive-type photosensitive resin composition may contain a second surfactant other than the silicone-based surfactant (D) for, for example, to further improve the coatability, further improve the smoothness of the film, or further improve the developability of the film. Examples of the second surfactant 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; and acetylene-based surfactants such as "Orphin® E1004", "Orphin® E1010", "Orphin® E1020", and "Orphin® E1030W" (all product names, Nisshin Chemical Industry Co., Ltd.), and "Acetylenel® E40", "Acetylenel® E60", "Acetylenel® E100", and "Acetylenel® E200" (all product names, Kawaken Fine Chemical Co., Ltd.). The second surfactant may be used alone or in combination of two or more types.

[0229] The content of the second surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.5 part by mass or less, based on 100 parts by mass of the total solid content excluding the second surfactant. In this embodiment, the positive photosensitive resin composition preferably does not contain the second surfactant.

[0230] [Coating composition]

[0231] 〈Solvent (G)〉

[0232] The positive photosensitive resin composition can be used as a coating composition in a solution state or a dispersion state by dissolving or dispersing it in the solvent (G). For example, a coating composition containing the positive photosensitive resin composition can be prepared by mixing a quinonediazide compound (C), a silicone surfactant (D), and, if necessary, optional components (colorant (E), dissolution accelerator (F), thermosetting agent, and other surfactants, etc.) in a predetermined ratio in a solution obtained by dissolving the resin components (hydrophobic resin (A) and other resins such as alkali-soluble resin (B) if necessary) in the solvent (G). The coating composition can be adjusted to a viscosity suitable for the coating method used by changing the amount of the solvent (G).

[0233] Examples of solvents (G) 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; and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Examples include tate compounds; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and cyclohexanone; esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyethyl acetate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; and amide compounds such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Solvent (G) may be used alone or in combination of two or more.

[0234] The solid content concentration of the coating composition can be appropriately determined depending on the intended use. For example, the solid content concentration of the coating composition may be 1 to 60% by mass, 3 to 50% by mass, or 5 to 40% by mass.

[0235] When using pigments, known methods can be used for dispersion and mixing. For example, ball-type devices such as ball mills, sand mills, bead mills, paint shakers, and rocking mills; blade-type devices such as kneaders, paddle mixers, planetary mixers, and Henschel mixers; roll-type devices such as three-roll mixers; and other devices such as lithographs, colloid mills, ultrasonic devices, homogenizers, and rotational / revolutionary mixers may be used. From the viewpoint of dispersion efficiency and fine dispersion, it is preferable to use a bead mill.

[0236] The prepared coating composition is usually filtered before use. Examples of filtration methods include Millipore filters with a pore size of 0.05 to 1.0 μm.

[0237] The coating composition prepared in this way also exhibits excellent long-term storage stability.

[0238] [Method of using positive-type photosensitive resin composition]

[0239] When using a positive-type photosensitive resin composition in radiation lithography, for example, first, the positive-type photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition can be applied to the substrate surface, and the solvent can be removed by means of heating or other means to form a film. The method of applying the coating composition to the substrate surface is not particularly limited, and for example, a spray method, roll coating method, slit method, or spin coating method can be used.

[0240] After applying the coating composition to the substrate surface, the solvent is usually removed by heating to form a film (pre-baking). The heating conditions vary depending on the type and proportion of each component, but typically a temperature of 70-130°C is used. For example, the film can be obtained by heating on a hot plate for 30 seconds to 20 minutes, or in an oven for 1 to 60 minutes. In this embodiment, the thickness of the formed film is preferably 2-3 μm.

[0241] Next, the pre-baked film is irradiated with radiation (e.g., 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 to visible light having a wavelength of 250 to 450 nm. In this embodiment, the radiation is preferably i-rays. In another embodiment, the radiation is preferably ghi-rays.

[0242] When a positive-type photosensitive resin composition contains a protective resin (B3) as an alkali-soluble resin (B), a heat treatment (PEB) can be performed after the exposure process to promote the decomposition of acid-degradable groups. PEB promotes the deprotection of protected alkali-soluble functional groups in the protective resin (B3) of the exposed area, thereby further increasing the alkali solubility of the exposed area. Although the heating conditions vary depending on the type and proportion of each component, PEB can usually be performed at 70 to 140°C, for example, by heating on a hot plate for 30 seconds to 20 minutes or in an oven for 1 to 60 minutes.

[0243] In this embodiment, it is preferable not to include a PEB step after the exposure step. This prevents film flow, deformation, etc. caused by heating, allowing for the formation of thick film patterns with higher precision, and also reduces the steps involved in forming partitions or insulating films.

[0244] After the exposure or PEB process, the film is developed (e.g., by alkaline development) by contacting it with a developer to remove unwanted parts and form a pattern on the film (development process). As the developer, aqueous solutions of alkaline compounds such as inorganic alkali 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 can be used. An aqueous solution obtained by adding an appropriate amount of water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. to an alkaline aqueous solution can also be used as the developer. The development time is usually 30 to 180 seconds. The development method can be any of the following: liquid immersion method, shower method, or dipping method. After development, the film can be rinsed with running water for 30 to 90 seconds to remove unwanted parts, and then air-dried with compressed air or compressed nitrogen to form a pattern.

[0245] Subsequently, the patterned coating can be heated using a heating device such as a hot plate or oven at, for example, 100 to 350°C for 20 to 200 minutes to obtain a cured coating (post-bake, heat treatment step). During the heat treatment, the temperature may be maintained at a constant level, continuously increased, or increased in stages. The heat treatment is preferably carried out under a nitrogen gas atmosphere.

[0246] <Residual film rate>

[0247] In this embodiment, a positive-type photosensitive resin composition is applied so that the film thickness after pre-baking is 3 ± 0.3 μm, and after pre-baking at 125°C for 120 seconds to form a film, the material is alkaline developed at 23°C with a 2.38% by mass aqueous tetramethylammonium hydroxide solution for 60 seconds. The residual film rate, defined by the following formula, is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. The residual film rate is an indicator of the solubility of the unexposed areas. A higher residual film rate indicates a greater difference in solubility between the exposed and unexposed areas, allowing for the formation of a thick film pattern with a large difference in height with high precision. Residual film percentage (%) = Film thickness after development (μm) / Film thickness before development (μm) ... (Formula)

[0248] <Optical density>

[0249] In embodiments in which the positive-type photosensitive resin composition contains a colorant (E), the optical density (OD value) of the cured film of the positive-type photosensitive resin composition is preferably 0.5 or more per 1 μm of film thickness, more preferably 0.7 or more, and even more preferably 1.0 or more. If the OD value of the cured film is equal to or greater than the above lower limit per 1 μm of film thickness, sufficient light shielding can be obtained.

[0250] The method for manufacturing an organic EL element partition or organic EL element insulating film of this embodiment includes, for example, preparing a coating composition by dissolving or dispersing a positive-type photosensitive resin composition in a solvent, applying the coating composition to a substrate to form a film, removing the solvent contained in the film to dry the film, exposing the film by irradiating the dried film with radiation through a photomask, developing the exposed film by contacting it with a developer to form a pattern on the film, and heat-treating the patterned film at a temperature of 100 to 350°C to form an organic EL element partition or organic EL element insulating film. The above PEB can also be performed after exposure and before development. In embodiments in which the positive-type photosensitive resin composition of this specification includes a colorant (E), it is possible to form a highly sensitive and high-precision thick film pattern.

[0251] <Organic EL element partition>

[0252] This embodiment is an organic EL element partition containing a cured product of a positive-type photosensitive resin composition. The positive-type photosensitive resin composition preferably contains a colorant (E). The cured product of the positive-type photosensitive resin composition according to this embodiment, used in the organic EL element partition, can be obtained by the curing method described above. Furthermore, the manufacturing process of the organic EL element partition according to this embodiment is not particularly limited, and known processes and their conditions can be appropriately adopted. For example, it can be obtained by a manufacturing method including the coating process, vacuum drying process, pre-bake process, exposure process, alkaline development process, and post-bake process described above. The organic EL element partition according to this embodiment can be suitably used as a black organic EL element partition. As described above, in display devices such as organic EL displays, partitions (partition materials) are used in the gaps between colored patterns within the display area or at the edges of the peripheral portion of the display area to improve display characteristics. Among the partitions, black partitions have higher light-shielding properties than other colors, which tends to cause problems during UV irradiation in the exposure process, such as (i) difficulty in ultraviolet light reaching deep into the coating film of the positive-type photosensitive resin composition, and (ii) longer exposure times leading to decreased productivity. However, according to this embodiment, such problems can be prevented particularly effectively, making it possible to achieve higher pixel performance and resolution compared to conventional methods.

[0253] <Insulating film for organic EL elements>

[0254] This embodiment is an organic EL element insulating film containing a cured product of a positive-type photosensitive resin composition. The positive-type photosensitive resin composition preferably contains a colorant (E). The cured product of the positive-type photosensitive resin composition according to this embodiment, used in the organic EL element insulating film, can be obtained by the curing method described above. Furthermore, the steps of the manufacturing method for the organic EL element insulating film according to this embodiment are not particularly limited, and known steps and conditions can be appropriately adopted. For example, in the case of organic EL elements used in organic EL displays, the light-emitting layer and other components tend to be susceptible to moisture and impurity gases and are prone to degradation; therefore, providing an insulating film with excellent reliability is significant. The organic EL element insulating film according to this embodiment is expected to meet such requirements.

[0255] <Organic EL element>

[0256] This embodiment is an organic EL element comprising a cured product of a positive-type photosensitive resin composition. The positive-type photosensitive resin composition preferably contains a colorant (E) including a black dye. The cured product of the positive-type photosensitive resin composition according to this embodiment, used in the organic EL element, can be obtained by the curing method described above. By using this cured product in the partition material, insulating film, and other components described above, an excellent organic EL element can be realized. In particular, when applied to black components, it exhibits especially superior effects compared to conventional methods.

[0257] As described above, the positive-type photosensitive resin composition according to this embodiment can be suitably used in radiation lithography for forming partitions and insulating films of organic EL elements. With respect to partitions of organic EL elements, it can be suitably used as a positive-type photosensitive resin composition for forming partition materials. Furthermore, in the case of a positive-type photosensitive resin composition containing the above-mentioned colorant (E), an organic EL element equipped with a partition or insulating film formed using it can be suitably used as an electronic component of a display device that exhibits good contrast. In particular, when used as a black positive-type resist, a black partition material, etc., it is possible to achieve a good balance of high sensitivity, residue removal, low film loss, and fine hole formation at a level that was not possible with conventional methods, while maintaining sufficient light shielding properties. [Examples]

[0258] The present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to these examples.

[0259] (1) Raw materials

[0260] The raw materials used in the examples and comparative examples were manufactured or obtained as follows.

[0261] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin were calculated using a calibration curve created with polystyrene standard materials under the following measurement conditions. Device name: Shodex(registered trademark) GPC-101 Column: Shodex(registered trademark) LF-804 Mobile phase: tetrahydrofuran Flow rate: 1.0mL / min Detector: Shodex(registered trademark) RI-71 Temperature: 40℃

[0262] <Hydrophobic resin (A)>

[0263] (Manufacturing Example 1) Hydrophobic resin (A): Manufacturing of a resin (PSM-TB) containing silicon atom groups 15.9 g of 4-hydroxyphenyl methacrylate (PQMA, manufactured by Resonaq Corporation), 16.6 g of 4-tert-butyldimethylsilyloxyphenyl methacrylate (PQMA-TBDMS), and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industries, Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.), which was used as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) as a polymerization initiator. The two resulting solutions were simultaneously added dropwise over 2 hours to 90.5 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.), which had been heated to 89°C under a nitrogen gas atmosphere, in a 300 mL three-necked flask equipped with a reflux condenser, and then reacted at 89°C for 4 hours. 50 g of the reaction solution, cooled to room temperature, was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 9.73 g of a white powder (PSM-TB). The obtained PSM-TB had a number-average molecular weight of 3753, a weight-average molecular weight of 7581, a polydispersity (Mw / Mn) of 2.0, and a silicon atom-containing monomer unit ratio of 32 mol% of the total monomer units. In PSM-TB, the molar ratio of structural units represented by formula (1), formula (2), and formula (3) where s is an integer of 1 or more was formula (1):(2):(3) = 32:7:61, and based on the total structural units, the structural units with alkali-soluble functional groups accounted for 61 mol%. The silicon atom content was 4.0 mass%, based on the mass of PSM-TB34.

[0264] (Manufacturing Example 2) Hydrophobic resin (A): Manufacturing of a resin (PSM-TE) containing silicon atom groups 15.9 g of 4-hydroxyphenyl methacrylate (PQMA, manufactured by Resonaq Corporation), 16.6 g of 4-triethylsilyloxyphenyl methacrylate (PQMA-TES), and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industries, Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.), which was used as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) as a polymerization initiator. The two resulting solutions were simultaneously added dropwise over 2 hours to 90.4 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.), which had been heated to 89°C under a nitrogen gas atmosphere in a 300 mL three-necked flask equipped with a reflux condenser, and then reacted at 89°C for 4 hours. 50 g of the reaction solution, cooled to room temperature, was added dropwise to a mixed solvent of 200 g of hexane and 50 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 9.49 g of a white powder (PSM-TE). The obtained PSM-TE had a number-average molecular weight of 3847, a weight-average molecular weight of 7534, a polydispersity (Mw / Mn) of 2.0, and a silicon atom-containing monomer unit ratio of 32 mol% of the total monomer units. In PSM-TE, the molar ratio of structural units represented by formula (1), formula (2), and formula (3) where s is an integer of 1 or more was formula (1):(2):(3) = 32:7:61, and based on the total structural units, 61 mol% of the structural units had alkali-soluble functional groups. The silicon atom content was 4.0% by mass, based on the mass of PSM-TE.

[0265] (Manufacturing Example 3) Hydrophobic resin (A): Manufacturing of resin (PS-TB) containing silicon atom groups 15.9 g of 4-hydroxyphenyl methacrylate (PQMA, manufactured by Resonaq Corporation) and 11.2 g of 4-tert-butyldimethylsilyloxyphenyl methacrylate (PQMA-TBDMS) were completely dissolved in 44.14 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) as a polymerization initiator. The two resulting solutions were simultaneously added dropwise over 2 hours to 90.5 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) heated to 89°C under a nitrogen gas atmosphere in a 300 mL three-necked flask equipped with a reflux condenser, and then reacted at 89°C for 4 hours. 50 g of the reaction solution, cooled to room temperature, was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 8.83 g of a white powder (PS-TB). The number-average molecular weight of the obtained PS-TB was 4238, the weight-average molecular weight was 8900, the polydispersity (Mw / Mn) was 2.1, and the proportion of monomer units containing silicon atoms was 27 mol% of the total monomer units. In PS-TB, the molar ratio of structural units represented by formula (1) where s is an integer of 1 or more to structural units represented by formula (3) was formula (1):formula (3) = 27:73, and based on the total structural units, structural units containing alkali-soluble functional groups accounted for 73 mol%. The silicon atom content was 4.2 mass% based on the mass of PS-TB.

[0266] <Alkali-soluble resin (B)>

[0267] (Manufacturing Example 4) Alkali-soluble resin (B): Production of resin (N695OH) having epoxy groups and phenolic hydroxyl groups 75.2 g of γ-butyrolactone (Mitsubishi Chemical Corporation) was placed in a 300 mL three-necked flask as a solvent, and 37.8 g of "EPICLON® N-695" (DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent 214), a compound having at least two epoxy groups in one molecule, was placed in the flask and dissolved at 60°C under a nitrogen gas atmosphere. To this, 20.1 g of 3,5-dihydroxybenzoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound (0.65 equivalents per 1 equivalent of epoxy) and 0.166 g (0.660 mmol) of triphenylphosphine (Tokyo Chemical Industries, Ltd.) as a reaction catalyst were added, and the reaction was carried out at 110°C for 21 hours. The reaction solution was allowed to return to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain a solution of 274.2 g of resin (N695OH) having epoxy groups and phenolic hydroxyl groups. The number average molecular weight of the obtained reactant was 3000, the weight average molecular weight was 5100, the polydispersity (Mw / Mn) was 1.7, the epoxy equivalent was 2200, and the phenolic hydroxyl group equivalent was 161.

[0268] <Quinone diazide compound (C)>

[0269] As the quinone diazide compound (C), "TS-150A" and "TS-200A" (both trade names, Toyo Gosei Kogyo Co., Ltd.; ester of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) and 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinone diazide-5-sulfonic acid)); and "TPPA-150DF" (trade name, Toyo Gosei Kogyo Co., Ltd.; 1,2-naphthoquinone diazide-4-sulfonic acid ester of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA)) were used.

[0270] The structures of "TS-150A" and "TS-200A" are shown below. In "TS-150A", on average, 1.5 out of 3 R atoms per molecule have a quinone diazide structure. In "TS-200A", on average, 2.0 out of 3 R atoms per molecule have a quinone diazide structure.

[0271] [ka]

[0272] <Silicone-based surfactant (D)>

[0273] As silicone-based surfactants (D), "MEGAFACE EFS-131" (trade name, DIC Corporation; a (meth)acrylic copolymer having no silicon atoms in the main chain and at least one silicon atom-containing hydrocarbon group selected from the group consisting of silicon atom-containing alkyl groups and silicon atom-containing alkylene groups), "MEGAFACE EFS-321" (trade name, DIC Corporation; a (meth)acrylic copolymer having no silicon atoms in the main chain and at least one silicon atom-containing hydrocarbon group selected from the group consisting of silicon atom-containing alkyl groups and silicon atom-containing alkylene groups), "MEGAFACE EFS-521" (trade name, DIC Corporation; a (meth)acrylic copolymer having no silicon atoms in the main chain and at least one silicon atom-containing hydrocarbon group selected from the group consisting of silicon atom-containing alkyl groups and silicon atom-containing alkylene groups), and "KF2201" (trade name, Shin-Etsu Chemical Co., Ltd.; a silicone-based surfactant having silicon atoms in the main chain and no silicon atom-containing groups in the side chains).

[0274] <Coloring agent (E)>

[0275] As colorants (E), the following black dyes were used: "VALIFAST® BLACK 3804" (abbreviated as "VB3804", Orient Chemical Industry Co., Ltd.; black dye as defined in the CI of Solvent Black 34), "VALIFAST® BLACK 3810" (abbreviated as "VB3810", Orient Chemical Industry Co., Ltd.; black dye as defined in the CI of Solvent Black 34), and "VALIFAST® BLACK 3804" (abbreviated as "VB3804", Orient Chemical Industry Co., Ltd.; black dye as defined in the CI of Solvent Black 34).

[0276] <Dissolution accelerator (F)>

[0277] Phloroglucinol was used as a dissolution accelerator (F).

[0278] <Solvent (G)>

[0279] A mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA = 40:60 (mass ratio)) was used as solvent (G).

[0280] (2) Evaluation method

[0281] The evaluation methods used in the examples and comparative examples are as follows.

[0282] <Sensitivity>

[0283] A positive-type photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 μm. After 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating on a covered hot plate at 125°C for 120 seconds. The film was exposed using an exposure apparatus incorporating a high-pressure mercury lamp (product name "Multi-Light ML-251A / B", Ushio Inc.) via a quartz photomask (with a φ10 μm aperture pattern). The exposure amount was measured using an ultraviolet integrated light meter (product name "UIT-150", light receiving unit "UVD-S365", Ushio Inc.). After exposure, alkaline development was performed for 60 seconds using a spin developing apparatus ("AD-1200", Takizawa Sangyo Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Repeat the above procedure while varying the exposure amount to find the minimum exposure amount (mJ / cm²) at which a pattern with a hole diameter of 10 μm that completely reaches the glass substrate after development can be formed. 2 The sensitivity was defined as ).

[0284] <Dissolvability of unexposed areas>

[0285] A positive-type photosensitive resin composition was bar-coated onto a glass substrate (100 mm × 100 mm × 1 mm) to a dry film thickness of 3.0 μm. After vacuum drying at room temperature for 60 seconds, pre-baking was performed by heating on a covered hot plate at 125°C for 120 seconds. The dry film thickness was measured using an optical film thickness measuring device ("F20-NIR", Filmetrics Inc.), and then alkaline development was performed using a spin developer ("AD-1200", Takizawa Sangyo Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. The film thickness after alkaline development was measured again using an optical film thickness measuring device ("F20-NIR", Filmetrics Inc.), and the film thickness dissolved before and after development (μm) was used as an indicator of the solubility of the unexposed area. An unexposed area solubility of 0 μm is equivalent to a residual film rate of 100%, as defined by the following formula. Residual film percentage (%) = Film thickness after development (μm) / Film thickness before development (μm) ... (Formula)

[0286] <OD value of cured coating>

[0287] A positive-type photosensitive resin composition was spin-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of approximately 1.5 μm. Pre-baking was performed by heating on a hot plate at 125°C for 120 seconds. Subsequently, a film was obtained by curing at 250°C for 60 minutes under a nitrogen gas atmosphere. The OD value of the cured film was measured using a transmission densitometer ("BMT-1", Sakata Inx Corporation), corrected for the OD value of the glass alone, and converted to the OD value per 1 μm of film thickness. The film thickness was measured using an optical film thickness measuring device ("F20-NIR", Filmetrix Co., Ltd.).

[0288] <Hole diameter>

[0289] A positive-type photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 μm. After 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating on a covered hot plate at 125°C for 120 seconds. The film was exposed using an exposure apparatus incorporating a high-pressure mercury lamp (product name "Multi-Light ML-251A / B", Ushio Inc.) via a quartz photomask (with a φ10 μm aperture pattern). The exposure amount was measured using an ultraviolet integrated light meter (product name "UIT-150", light receiving unit "UVD-S365", Ushio Inc.). After exposure, alkaline development was performed for 60 seconds using a spin developer ("AD-1200", Takizawa Sangyo Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Exposure amount: 50 (mJ / cm²) 2 In the experiment, the hole diameters of the opened hole patterns were measured using a microscope (magnification 2,000x).

[0290] <Substrate interface residue>

[0291] A positive-type photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 μm. After 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating on a covered hot plate at 125°C for 120 seconds. The film was exposed using an exposure apparatus incorporating a high-pressure mercury lamp (product name "Multi-Light ML-251A / B", Ushio Inc.) via a quartz photomask (with a φ10 μm aperture pattern). The exposure amount was measured using an ultraviolet integrated light meter (product name "UIT-150", light receiving unit "UVD-S365", Ushio Inc.). After exposure, alkaline development was performed for 60 seconds using a spin developer (product name "AD-1200", Takizawa Sangyo Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Exposure amount: 50 (mJ / cm²) 2 In the experiment, the surface of the substrate with the opened hole pattern was observed with an electron microscope (magnification 20,000x) and judged according to the following criteria. ○: No film-like residue was observed on the surface area (φ10μm), and very few (less than 5) spot residues were also observed. △: No film-like residue was observed on the surface area (φ10μm), but spot residues (= 5 or more) were observed. ×: A film-like residue was observed across the entire surface area (φ10μm).

[0292] (3) Preparation and evaluation of positive-type photosensitive resin compositions

[0293] <Examples 1-9, Comparative Examples 1-3>

[0294] Each component was mixed under the conditions described in Table 1. 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-type photosensitive resin composition with a solid content concentration of 12% by mass. In Table 1, the composition values ​​for components other than the solvent are in "parts by mass," and these values ​​are converted to solid content. The evaluation results of the positive-type photosensitive resin compositions for each example and comparative example are shown in Table 1.

[0295] <Example 1> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), EFS-521 as the silicone-based surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 1 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 1 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 1 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 1 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 1 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 1 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 1 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 1 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 1 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 1 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 1 was 12% by mass.

[0296] <Example 2> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TE) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), EFS-521 as the silicone-based surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 2 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 2 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 2 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 2 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 2 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 2 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 2 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 2 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 2 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 2 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 2 was 12% by mass.

[0297] <Example 3> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PS-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), EFS-521 as the silicone-based surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 3 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 3 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 3 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 3 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 3 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 3 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 3 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 3 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 3 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 3 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 3 was 12% by mass.

[0298] <Example 4> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TS-150A) as the quinone diazide compound (C), EFS-521 as the silicone-based surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 4 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 4 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 4 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 4 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 4 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 4 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 4 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 4 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 4 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 4 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 4 was 12% by mass.

[0299] <Example 5> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TS-200A) as the quinone diazide compound (C), EFS-521 as the silicone-based surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 5 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 5 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 5 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 5 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 5 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 5 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 5 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 5 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 5 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 5 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 5 was 12% by mass.

[0300] <Example 6> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), TS-200A as the quinone diazide compound (C), EFS-131 as the silicone-based surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 6 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 6 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 6 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 6 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 6 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 6 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 6 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 6 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 6 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 6 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 6 was 12% by mass.

[0301] <Example 7> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), TS-200A as the quinone diazide compound (C), EFS-321 as the silicone-based surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 7 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 7 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 7 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 7 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 7 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 7 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 7 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 7 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 7 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 7 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 7 was 12% by mass.

[0302] <Example 8> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), TS-200A as the quinone diazide compound (C), EFS-321 as the silicone-based surfactant (D), a black dye (VB3810) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 8 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 8 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 8 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 8 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 8 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 8 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 8 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 8 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 8 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 8 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 8 was 12% by mass.

[0303] <Example 9> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), TS-200A as the quinone diazide compound (C), EFS-321 as the silicone-based surfactant (D), a black dye (VB3820) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Example 9 contained 14% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 9 contained 29 parts by mass of hydrophobic resin (A) based on 100 parts by mass of the total resin components. Furthermore, the positive-type photosensitive resin composition of Example 9 contained 35% by mass of alkali-soluble resin (B) based on 100% by mass of solids. The positive-type photosensitive resin composition of Example 9 also contained 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of total resin components. Furthermore, the positive-type photosensitive resin composition of Example 9 contained 15% by mass of quinone diazide compound (C) based on 100% by mass of solids. Furthermore, the positive-type photosensitive resin composition of Example 9 contained 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of total resin components. In addition, the positive-type photosensitive resin composition of Example 9 contained 15% by mass of surfactant (D) based on 100% by mass of solids. The surfactant (D) content in the positive-type photosensitive resin composition of Example 9 was 31 parts by mass based on 100 parts by mass of total resin components. The positive-type photosensitive resin composition of Example 9 contained 30% by mass of colorant (E) based on 100% by mass of solids. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 9 was 61 parts by mass based on 100 parts by mass of the total resin components. The solids concentration of the coating composition of Example 9 was 12% by mass.

[0304] <Comparative Example 1> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), KF2201 having silicon atoms in its main chain as a silicone-based surfactant, a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The positive-type photosensitive resin composition of Comparative Example 1 was not evaluated because it failed to form a pattern during coating (indicated as "uncoatable" in the table).

[0305] <Comparative Example 2> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), E-40 as the hydrocarbon surfactant, a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G).

[0306] <Comparative Example 3> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared by blending a silicon atom-containing resin (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), F-554 as the fluorine-based surfactant, a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution accelerator (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G). The surfactant used was the fluorine-based surfactant (trade name "Megafac® F-554", manufactured by DIC Corporation) used in International Publication No. 2023 / 080254.

[0307] [Table 1]

[0308] The positive-type photosensitive resin compositions of each example had a solubility of 0 μm in the unexposed areas, which increased the contrast between the exposed and unexposed areas, and at least confirmed that they enabled the formation of thick film patterns with high precision. Therefore, it was at least confirmed that, according to these examples, even without using organofluorine compounds, excellent residue removal is achieved, film loss is minimal, and fine hole formation is possible.

[0309] This application is based on Japanese Patent Application No. 2023-172518, filed with the Japan Patent Office on October 4, 2023, the contents of which are incorporated herein by reference.

Claims

1. Hydrophobic resin (A), Quinone diazide compound (C) and A silicone-based surfactant (D) having silicon atoms in its side chain and It contains, The aforementioned component (A) includes a structural unit represented by the following formula (1): The content of component (D) in the total amount of surfactant is 50% by mass or more. 【Chemistry 1】 (In formula (1), R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R2 is SiR3R4R5, R3, R4, and R5 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer from 0 to 4, s is an integer from 1 to 5, where r+s is an integer from 1 to 5.) A positive-type photosensitive resin composition.

2. It further contains a coloring agent (E) containing a black dye, The positive-type photosensitive resin composition according to claim 1.

3. The above component (A) is a resin having a silicon atom-containing group. Positive-type photosensitive resin composition according to claim 1

4. The above component (A) includes the following structural unit (1a) and / or structural unit (1b): The positive-type photosensitive resin composition according to claim 1. 【Chemistry 2】 (In formula (1a), R １ａ R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ａ , R ３ａ , and R ４ａ Each of these is an alkyl group having 1 to 7 carbon atoms. In formula (1b), R １ｂ R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １ａ and R １ｂ They may be the same or they may be different.

5. In the positive-type photosensitive resin composition, the content of component (A) is 5 to 60% by mass, based on the total mass of the resin components. The positive-type photosensitive resin composition according to claim 1.

6. The component (D) is a silicone-based surfactant comprising an acrylic copolymer having at least one silicon atom-containing hydrocarbon group selected from the group consisting of silicon atom-containing alkyl groups and silicon atom-containing alkylene groups. The positive-type photosensitive resin composition according to claim 1.

7. The aforementioned component (E) is present in an amount of 10 to 150 parts by mass per 100 parts by mass of the total resin components. The positive-type photosensitive resin composition according to claim 2.

8. The optical density (OD value) of the cured film of the positive-type photosensitive resin composition is 0.5 or more per 1 μm of film thickness. The positive-type photosensitive resin composition according to claim 1.

9. An organic EL element partition comprising a cured product of the positive-type photosensitive resin composition described in claim 1.

10. An insulating film for an organic EL element comprising a cured product of the positive-type photosensitive resin composition described in claim 1.

11. An organic EL element comprising a cured product of the positive-type photosensitive resin composition described in claim 1.

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