Positive type photosensitive resin composition, cured product using the same, organic el element partition wall, organic el element insulator film, organic el element, and method for producing cured product

Abstract

To provide a positive type photosensitive resin composition which enables formation of a thick film pattern with high accuracy.SOLUTION: A positive type photosensitive resin composition contains a hydrophobic resin (A), an alkali-soluble resin (B), a quinonediazide compound (C), and a fluorine-based surfactant (D). When the positive type photosensitive resin composition is applied so that a film thickness after prebaking is 3±0.3 μm, and prebaked at 125°C for 120 seconds to form a film, then exposed under a condition of 30 mJ / cm2, and developed with 2.38 mass% of a tetramethylammonium hydroxide aqueous solution at a temperature of 23°C, a dissolution speed of a coating surface layer is lower than a dissolution speed of the whole film. The dissolution speed of the coating film surface layer is an average dissolution speed when the film surface layer is dissolved until the film thickness of the film become 80%, and the dissolution speed of the whole film is an average dissolution speed when the film is dissolved until the film thickness of the film becomes 30%.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a positive-type photosensitive resin composition, and more particularly to a positive-type photosensitive resin composition containing a quinone diazide compound as a radiation-sensitive compound. [Background technology]

[0002] Positive photosensitive resin compositions are widely used as interlayer insulating films, planarizing films, or protective films in semiconductor devices, or as insulating films, planarizing films, or partition materials in display devices such as organic light-emitting diode (OLED) displays and liquid crystal displays.

[0003] For example, in display devices such as organic electroluminescence (EL) displays, partition walls are used in the gaps between colored patterns within the display area or at the edges of the periphery of the display area to improve display characteristics. In the manufacture of organic EL displays, partition walls are first formed to prevent organic material pixels from contacting each other, and organic material pixels are then formed between the partition walls. These partition walls are generally formed by photolithography using a photosensitive resin composition and have insulating properties. Specifically, a photosensitive resin composition is applied to a substrate using a coating device, volatile components are removed by heating or other means, and the composition is exposed to light through a mask. The resulting pattern is then developed by removing the unexposed portions in the case of a negative-tone pattern and the exposed portions in the case of a positive-tone pattern with a developer such as an alkaline aqueous solution. The resulting pattern is then heat-treated to form partition walls (insulating films). Next, organic materials emitting red, green, and blue light are deposited between the partition walls by inkjet printing or other methods to form the pixels of the organic EL display device.

[0004] In recent years, in this field, due to the miniaturization of display devices and the diversification of displayed contents, there has been a demand for higher performance and higher definition pixels. In order to increase the contrast and improve visibility in display devices, attempts have been made to impart light-blocking properties to partition wall materials by using colorants.

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

[0006] Patent Document 2 (JP 2002-116536 A) describes a method for blackening a partition wall material by using carbon black in a radiation-sensitive resin composition containing [A] an alkali-soluble resin, [B] a 1,2-quinonediazide compound, and [C] a colorant.

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

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

[0009] On the other hand, chemical amplification of a photosensitive resin composition is a widely known method for increasing the sensitivity of a positive-type photosensitive resin composition. Chemically amplified photosensitive resin compositions generally contain a resin in which alkali-soluble functional groups are protected with acid-decomposable groups, and a photoacid generator. The acid generated from the photoacid generator upon exposure promotes the decomposition (deprotection) of the acid-decomposable groups, regenerating the alkali-soluble functional groups. This promotes alkaline dissolution of the resin in the exposed areas during development. The acid derived from the photoacid generator decomposes one acid-decomposable group, then regenerates it, and contributes to the decomposition of another acid-decomposable group. The apparent quantum efficiency of a chemically amplified system based on the above reaction mechanism is expressed as the product of the quantum efficiency of acid generation and the reaction chain. Therefore, high sensitivity can be achieved by using a chemically amplified photosensitive resin composition.

[0010] Patent Document 5 (WO 2015 / 087830) describes a photosensitive resin composition containing a polybenzoxazole precursor containing a specific repeating unit, a photoacid generator, a solvent, a crosslinking agent, and a compound having in its molecule a group in which an acid group is protected with an acid-decomposable group.

[0011] Patent Document 6 (WO 2020 / 246517) describes a positive photosensitive resin composition containing a first resin (A) having multiple phenolic hydroxyl groups, at least a portion of which are protected with acid-decomposable groups, a second resin (B) having epoxy groups and phenolic hydroxyl groups, at least one colorant (C) selected from the group consisting of black dyes and black pigments, and a photoacid generator (D). [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-281440 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-116536 [Patent Document 3] Japanese Patent Application Laid-Open No. 2010-237310 [Patent Document 4] International Publication No. 2017 / 069172 [Patent Document 5] International Publication No. 2015 / 087830 [Patent Document 6] International Publication No. 2020 / 246517 Summary of the Invention [Problem to be solved by the invention]

[0013] However, when a partition wall material is provided with light-shielding properties, the photosensitive resin composition tends to have low sensitivity, which may result in a longer exposure time and a decrease in productivity. Therefore, photosensitive resin compositions used to form partition wall materials, particularly those containing a colorant, are required to have higher sensitivity.

[0014] Photosensitive resin compositions used to form colored partition wall materials require the use of a considerable amount of colorant to sufficiently enhance the light-blocking properties of the cured film. When such a large amount of colorant is used, radiation irradiated onto a coating of the photosensitive resin composition is absorbed by the colorant, reducing the effective intensity of radiation in the coating, resulting in insufficient exposure of the photosensitive resin composition and resulting in poor pattern formability. This is particularly evident when a black colorant is incorporated into a photosensitive resin composition to form a thick coating, for example, a coating with a thickness of 2 to 3 μm, for the purpose of improving the image quality, increasing flexibility, or reducing power consumption of display devices.

[0015] Chemically amplified positive-tone photosensitive resin compositions have higher sensitivity than, for example, positive-tone photosensitive resin compositions containing a quinone diazide compound as a radiation-sensitive compound. However, the photoacid generators used in chemically amplified systems are expensive, and chemically amplified positive-tone photosensitive resin compositions are prone to coating unevenness in the coating and require post-exposure baking (PEB) to promote decomposition of acid-labile groups. Furthermore, in chemically amplified systems, the acid generated from the photoacid generator upon exposure diffuses into the coating during the PEB process, which can change the shape, dimensions, sensitivity, and other aspects of the pattern depending on the PEB conditions. Therefore, it is difficult to form a step pattern with high precision in a thick coating using a chemically amplified positive-tone photosensitive resin composition.

[0016] An object of the present invention is to provide a positive photosensitive resin composition that can form a thick film pattern with high precision. [Means for solving the problem]

[0017] The present inventors have found that in a positive-type photosensitive resin composition containing a quinone diazide compound as a radiation-sensitive compound, by combining a hydrophobic resin and an alkali-soluble resin as resin components with a fluorine-based surfactant, the alkali solubility of the coating surface can be relatively reduced, and as a result, a thick film pattern can be formed with high precision.

[0018] That is, the present invention includes the following aspects. [1] a hydrophobic resin (A); an alkali-soluble resin (B); a quinone diazide compound (C); Fluorosurfactant (D) and The positive photosensitive resin composition is applied so that the film thickness after pre-baking is 3±0.3 μm, and the composition is pre-baked at 125° C. for 120 seconds to form a film, and then the composition is applied with an electric current of 30 mJ / cm 2 and developed at a temperature of 23°C with a 2.38 mass % aqueous solution of tetramethylammonium hydroxide, the dissolution rate of the surface layer of the coating is lower than the dissolution rate of the entire coating, the dissolution rate of the surface layer of the coating being the average dissolution rate at the time when the coating has been dissolved to a thickness of 80%, and the dissolution rate of the entire coating being the average dissolution rate at the time when the coating has been dissolved to a thickness of 30%. [2] The positive photosensitive resin composition according to [1], wherein the difference between the dissolution rate of the surface layer of the coating and the dissolution rate of the entire coating is 3 nm / sec or more. [3] The positive photosensitive resin composition according to [1] or [2], wherein the hydrophobic resin (A) is a resin having at least one group selected from the group consisting of a silicon-containing group and a fluorine-containing group. [4] The hydrophobic resin (A) is represented by the formula (1) [ka] (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is SiR 3 R 4 R 5 and R 3 , R 4 and R 5are 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 of 0 to 5, and s is an integer of 0 to 5, with the proviso that r+s is an integer of 1 to 5. and at least one structural unit represented by formula (1) in which s is an integer of 1 or more. [5] The hydrophobic resin (A) is represented by the formula (2) [ka] (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 8 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The positive photosensitive resin composition according to [4], further comprising a structural unit represented by the following formula: [6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the fluorine-containing surfactant (D) comprises an acrylic copolymer having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group. [7] The positive photosensitive resin composition according to any one of [1] to [6], wherein the alkali-soluble resin (B) comprises a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, a resin having an epoxy group and a phenolic hydroxyl group, or a combination thereof. [8] The positive photosensitive resin composition according to any one of [1] to [7], further comprising at least one colorant (E) selected from the group consisting of black dyes and black pigments. [9] The positive photosensitive resin composition according to [8], which contains the colorant (E) in an amount of 10 to 150 parts by mass based on 100 parts by mass of the total of the resin components.

[10] The positive photosensitive resin composition according to [8] or [9], wherein the optical density (OD value) of a cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness.

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

[10] .

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

[10] .

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

[10] . [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a positive photosensitive resin composition that can form a thick film pattern with high precision. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a chart showing the sputtering time (horizontal axis) and silicon element concentration (vertical axis) of the coatings of Examples 4, 6, and 7 obtained by XPS analysis. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention will be described in detail below.

[0022] In this disclosure, "alkali-soluble" means that a positive photosensitive resin composition or its components, or a coating or cured coating of the positive photosensitive resin composition, is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. An "alkali-soluble resin" refers to a resin that is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide either alone or when contained in an unexposed or exposed positive photosensitive resin composition. Resins that are not alkali-soluble in an unexposed positive photosensitive resin composition but become alkali-soluble upon exposure are also included in the alkali-soluble resin category. An "alkali-soluble functional group" refers to a group capable of imparting such alkali-solubility to a positive photosensitive resin composition or its components, or a coating or cured coating of the positive photosensitive resin composition. Examples of alkali-soluble functional groups include phenolic hydroxyl groups, carboxy groups, sulfo groups, phosphate groups, acid anhydride groups, and mercapto groups.

[0023] In the present disclosure, the term "acid-decomposable group" refers to a group that is decomposed (deprotected) in the presence of an acid, optionally with heating, to generate an alkali-soluble functional group.

[0024] In the present disclosure, the term "radically polymerizable functional group" refers to an ethylenically unsaturated group, and the term "radically polymerizable compound" refers to a compound having one or more ethylenically unsaturated groups.

[0025] In this disclosure, the term "structural unit" refers to an atomic group that constitutes part of the basic structure of a polymer, and this atomic group may have a pendant atom or pendant atomic group. For example, in the case of a radical (co)polymer, it refers to a unit derived from a radically polymerizable compound used as a monomer, and in the case of a phenol novolac resin, it refers to the following unit formed by the condensation reaction of one molecule of phenol (C6H5OH) and one molecule of formaldehyde (HCHO). Regarding structural units having pendant groups (side groups), structural units having pendant groups or groups derived therefrom that are used to form crosslinked sites are considered to be different from structural units having free pendant groups that are not involved in the formation of crosslinked sites. Regarding polymers having branched molecular chains (branched chains), structural units containing branch points (branch units) are considered to be different from structural units contained in linear molecular chains. [ka]

[0026] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0027] In the present disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin, polymer, or copolymer refer to values ​​calculated as standard polystyrene, measured by gel permeation chromatography (GPC).

[0028] In the present disclosure, 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, when the resin is a (co)polymer of n types of monomers i (i = a natural number from 1 to n), the phenolic hydroxyl group equivalent is calculated by the following formula:

number

[0029] In the case of a resin having an epoxy group and a phenolic hydroxyl group, which will be described later, the phenolic hydroxyl group equivalent is 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) The value calculated by

[0030] In this disclosure, the term "resin component" refers to the hydrophobic resin (A) and the alkali-soluble resin (B). Components that fall under the category of fluorosurfactant (D) are not included in the hydrophobic resin (A) and the alkali-soluble resin (B).

[0031] In the present disclosure, the term "solid content" refers to the total mass of components including the resin component, the quinone diazide compound (C), the fluorine-based surfactant (D), and optional components such as the colorant (E) and the dissolution promoter (F), excluding the liquid solvent (G).

[0032] [Positive-type photosensitive resin composition] A positive photosensitive resin composition according to one embodiment contains a hydrophobic resin (A), an alkali-soluble resin (B), a quinone diazide compound (C), and a fluorine-containing surfactant (D). The positive photosensitive resin composition is applied to a substrate so that the film thickness after pre-baking is 3±0.3 μm, and the substrate is pre-baked at 125° C. for 120 seconds to form a film. After that, the substrate is subjected to a 30 mJ / cm 2 2 and developed with a 2.38 mass % aqueous tetramethylammonium hydroxide solution at a temperature of 23° C., the dissolution rate of the surface layer of the coating is lower than the dissolution rate of the entire coating. The dissolution rate of the surface layer of the coating is the average dissolution rate at the time when the coating has dissolved to a thickness of 80%, and the dissolution rate of the entire coating is the average dissolution rate at the time when the coating has dissolved to a thickness of 30%.

[0033] <Hydrophobic resin (A)> The hydrophobic resin (A) is a resin whose uneven distribution on the coating surface is promoted by the fluorosurfactant (D), making the coating surface of the positive-tone photosensitive resin composition less soluble in alkaline aqueous solutions. Without being bound by any theory, the hydrophobic resin (A) tends to migrate toward the coating surface, accompanying the fluorosurfactant (D) that migrates to the coating surface during the formation of the coating of the positive-tone photosensitive resin composition. Therefore, after coating formation, the hydrophobic resin (A) is present in a higher concentration on the coating surface than in the interior of the coating, reducing the alkali solubility of the coating surface. During development, the hydrophobic resin (A) suppresses dissolution of the coating surface in unexposed areas as a resin component with low alkali solubility, while in exposed areas it is released from the coating into the developer along with the dissolution of the carboxylic acid compound derived from the quinone diazide compound (C), other highly alkali-soluble resin components, and any dissolution promoter. Once the exposed area of ​​the coating surface dissolves, dissolution of the interior of the coating, which has a higher alkali solubility than the surface of the coating due to a relatively low concentration of the hydrophobic resin (A), proceeds rapidly, thereby increasing the contrast between the exposed and unexposed areas and, as a result, improving the pattern formability of the positive photosensitive resin composition in a thick film.

[0034] On the other hand, when a chemically amplified positive-tone photosensitive resin composition is similarly made less soluble in an alkaline aqueous solution by using a hydrophobic resin and a fluorochemical surfactant in combination, the acid generated from the photoacid generator upon exposure diffuses throughout the film during the PEB process, resulting in a more uniform acid concentration near the film surface and within the film compared to when a quinone diazide compound (C) is used as the radiation-sensitive compound. This is thought to result in less dissolution of the exposed film surface during development, resulting in reduced sensitivity. Furthermore, photoacid generators may have poor thermal stability, and the use of such photoacid generators may also promote dissolution of unexposed areas, potentially resulting in reduced pattern formability.

[0035] The hydrophobic resin (A) is not particularly limited, and examples thereof 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 contain hydrophobic groups. Examples of hydrophobic groups include silicon-containing groups and fluorine-containing groups. The hydrophobic resin (A) may be a resin in which a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group is used as the base resin, and some or all of the alkali-soluble functional groups have been converted to groups having the hydrophobic group. The hydrophobic resin (A) may be used alone or in combination of two or more types.

[0036] In one embodiment, the hydrophobic resin (A) is a resin having at least one group selected from the group consisting of a silicon-containing group and a fluorine-containing group. The silicon-containing group and the fluorine-containing group may constitute the main chain of the hydrophobic resin (A) or may be a pendant group.

[0037] Examples of silicon-containing groups include silyl groups substituted with an aliphatic hydrocarbon group or an aryl group, groups having a cyclic siloxane structure, and groups having a silsesquioxane structure.

[0038] The silyl group substituted with an aliphatic hydrocarbon group or an aryl group may be mono-, di-, or tri-substituted. The substituents of the silyl group substituted with an aliphatic hydrocarbon group or an aryl group may be the same or different from each other. The silyl group substituted with an aliphatic hydrocarbon group or an aryl group is preferably tri-substituted. The silyl group substituted with an aliphatic hydrocarbon group or an aryl group may further have a substituent other than an alkyl group or an aryl group, for example, a silyloxy group substituted with an aliphatic hydrocarbon group or an aryl group.

[0039] 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 atoms of the group having a cyclic siloxane structure may each independently be substituted with an aliphatic hydrocarbon group or an aryl group.

[0040] 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.

[0041] The aliphatic hydrocarbon groups of silyl groups substituted with an aliphatic hydrocarbon group or an aryl group, the aliphatic hydrocarbon groups as substituents of groups having a cyclic siloxane structure, the aliphatic hydrocarbon groups as substituents of groups having a silsesquioxane structure, and the aliphatic hydrocarbon groups as substituents of silyloxy groups substituted with an aliphatic hydrocarbon group or an aryl group 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 the 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; unsaturated hydrocarbon groups such as ethenyl, propenyl, butenyl, ethynyl, and propynyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclohexyl groups. saturated monocyclic hydrocarbon groups such as chlorododecyl group; unsaturated monocyclic hydrocarbon groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, and cyclodecenyl group; saturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptanyl group, bicyclo[2.2.2]octanyl group, and adamantyl group; and unsaturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptenyl group and bicyclo[2.2.2]octenyl group.

[0042] The aryl group of a silyl group substituted with an aliphatic hydrocarbon group or an aryl group, the aryl group as a substituent of a group having a cyclic siloxane structure, the aryl group as a substituent of a group having a silsesquioxane structure, and the aryl group as a substituent of 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 a phenyl group, a naphthyl group, a fluorenyl group, an anthryl group, and a phenanthrenyl group.

[0043] Examples of silyl groups substituted with an aliphatic hydrocarbon group or an aryl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, and a trimethylsilyloxydimethylsilyl group.

[0044] Examples of groups having a cyclic siloxane structure include a pentamethylcyclotrisilyloxy group, a heptamethylcyclotetrasilyloxy group, and a nonamethylcyclopentasilyloxy group.

[0045] Examples of groups having a silsesquioxane structure include a silsesquioxanyl group, a heptamethylsilsesquioxanyl group, a heptaethylsilsesquioxanyl group, a hepta(n-propyl)silsesquioxanyl group, and a hepta(n-butyl)silsesquioxanyl group.

[0046] Examples of the fluorine-containing group include a fluorine-substituted alkyl group, a fluorine-substituted aryl group, and a fluoroacryloyl group.

[0047] The fluorine-substituted alkyl group may be a perfluoroalkyl group or a partially fluorinated alkyl group. The substituents of the fluorine-substituted alkyl group may be the same or different from each other. The fluorine-substituted alkyl group may further have a substituent other than a fluorine atom, such as a hydroxy group.

[0048] The fluorine-substituted alkyl group is preferably a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a perfluoroalkyl group having 1 to 8 carbon atoms or a partially fluorinated alkyl group having 1 to 8 carbon atoms. Examples of the perfluoroalkyl group having 1 to 20 carbon atoms and the partially fluorinated alkyl group having 1 to 20 carbon atoms include linear or branched fluorine-substituted alkyl groups such as trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, pentafluoropropyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro(2-methyl)isopropyl group, heptafluorobutyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluoro-tert-butyl group, perfluoroisopentyl group, nonafluorohexyl group, perfluoro(trimethyl)hexyl group, perfluorooctyl group, and 2-perfluorohexylethyl group; and cyclic fluorine-substituted alkyl groups such as 2,2,3,3-tetrafluorocyclobutyl group, and perfluorocyclohexyl group. The fluorine-substituted alkyl group is preferably a 2,2,2-trifluoroethyl group or a 2-perfluorohexylethyl group.

[0049] Examples of fluorine-substituted alkyl groups having a hydroxy group as a substituent include -CH(CF3)OH, -C(CF3)2OH, -C(CF3)(CH3)OH, and -C(C2F5)2OH, with -C(CF3)2OH being preferred.

[0050] The fluorine-substituted aryl group may be a perfluoroaryl group or a partially fluorinated aryl group. The substituents of the fluorine-substituted aryl group may be the same or different from each other. The fluorine-substituted aryl group may further have a substituent other than a fluorine atom, such as a hydroxyl group.

[0051] The fluorine-substituted aryl group is preferably a perfluoroaryl group having 6 to 20 carbon atoms or a partially fluorinated aryl group having 6 to 20 carbon atoms. Examples of the perfluoroaryl group having 6 to 20 carbon atoms and the partially fluorinated aryl group having 6 to 20 carbon atoms include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di(trifluoromethyl)phenyl group. The fluorine-substituted aryl group is preferably a pentafluorophenyl group.

[0052] The 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 another polymerizable monomer. Examples of polymerizable functional groups possessed by the polymerizable monomer having a hydrophobic group and the other polymerizable monomer include radically polymerizable functional groups such as CH═CH—, CH═C(CH)—, CH═CHCO—, CH═C(CH)CO—, and —OC—CH═CH—CO—. The hydrophobic resin (A) can also be produced by reacting a resin having a functional group such as a hydroxy group, a carboxy group, an amino group, or an epoxy group with a compound having a hydrophobic group to convert the functional group into a group containing a hydrophobic group.

[0053] In one embodiment, the hydrophobic resin (A) is a copolymer of a polymerizable monomer having a hydrophobic group and another polymerizable monomer. Examples of the polymerizable monomer having a hydrophobic group include a polymerizable monomer having a silicon-containing group and a polymerizable monomer having a fluorine-containing group.

[0054] Examples of polymerizable monomers having a silicon-containing group 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, t-butyldimethylsilyl(meth)acrylate, triisopropylsilylmethyl(meth)acrylate, bis(trimethylsilyl)

[0033] Examples of suitable silyloxyphenyl (meth)acrylates include 4-(trimethylsilyl)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.

[0055] Examples of the polymerizable monomer having a fluorine-containing group include 2-perfluorohexylethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoropropyl) (meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate, 3,3,4,4,5,5,6,6,6-nonafluorohexyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoro-2-methylpropyl) (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoro-2-phenylpropyl) (meth)acrylate, pentafluorophenyl (meth)acrylate, 3,5-bis(trifluoromethyl)methyl (meth)acrylate, 2 ...

[0043] Examples of suitable fluoroacrylates include 2-(1,1,1,3,3,3-hexafluoropropyl)phenyl (meth)acrylate, perfluorocyclohexyl (meth)acrylate, 2,2,2-trifluoroethyl vinyl ether, 2-(1,1,1,3,3,3-hexafluoropropyl)vinyl ether, 2,3,4,5,6-pentafluorostyrene, isopropyl 2-fluoroacrylate, tert-butyl 2-fluoroacrylate, cyclohexyl 2-fluoroacrylate, 4-tert-butylcyclohexyl 2-fluoroacrylate, isopropyl 2-(trifluoromethyl)acrylate, tert-butyl 2-(trifluoromethyl)acrylate, cyclohexyl 2-(trifluoromethyl)acrylate, and 4-tert-butylcyclohexyl 2-(trifluoromethyl)acrylate.

[0056] Examples of other polymerizable monomers include styrene; styrene derivatives such as α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. (meth)acrylic acid esters such as tetrahydrofurfuryl (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; and N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide.

[0057] The other polymerizable monomer may be a polymerizable monomer having an alkali-soluble functional group. Examples of the polymerizable monomer having an alkali-soluble functional group include maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; (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 maleic acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid; 4-hydroxystyrene, Examples of the polymerizable monomer include polymerizable monomers having a phenolic hydroxyl group, such as 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, and 4-hydroxyphenyl maleimide; polymerizable monomers having a sulfo group, such as (meth)allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid; polymerizable monomers having a phosphate group, such as mono(2-(meth)acryloyloxyethyl)phosphate; and polymerizable monomers having an acid anhydride group, such as itaconic anhydride, citraconic anhydride, and maleic anhydride.

[0058] As a polymerizable monomer having a hydrophobic group, after polymerization, [ka] (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is SiR 3 R 4 R 5 and R 3 , R 4 and R 5are 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 of 0 to 5, and s is an integer of 0 to 5, provided that r+s is an integer of 1 to 5. Of the structural units represented by the above formula (I), those which form a structural unit in which s is an integer of 1 or more are preferred. 1 is preferably a hydrogen atom or a methyl group. 3 , R 4 , and R 5 are preferably each independently a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group. r is preferably an integer of 0 to 3, and more preferably 0. s is preferably an integer of 1 to 3, and more preferably 1. As polymerizable monomers having such a hydrophobic group, 4-triethylsilyloxyphenyl methacrylate and 4-tert-butyldimethylsilyloxyphenyl methacrylate are particularly preferred.

[0059] Other polymerizable monomers include those represented by the formula (2) after polymerization. [ka] (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 8 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one group selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. 6 and R 7 are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. 8is preferably a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and more preferably a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group. As such other polymerizable monomers, phenylmaleimide and N-cyclohexylmaleimide are particularly preferred.

[0060] Other polymerizable monomers having an alkali-soluble functional group include those represented by the formula (3) after polymerization. [ka] (In formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. 9 is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 3, and more preferably 1. As such another polymerizable monomer having an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is particularly preferred.

[0061] In one embodiment, the hydrophobic resin (A) is represented by the formula (1): [ka] (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is SiR 3 R 4 R 5 and R 3 , R 4 and R 5 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 of 0 to 5, and s is an integer of 0 to 5, provided that r+s is an integer of 1 to 5.) and has at least one structural unit represented by formula (1) in which s is an integer of 1 or more.

[0062] In this embodiment, the hydrophobic resin (A) is represented by the formula (2): [ka] (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 8 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0063] In this embodiment, the hydrophobic resin (A) is represented by the formula (3): [ka] (In formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. It is preferable that the compound further has a structural unit represented by the following formula:

[0064] In the hydrophobic resin (A), the molar ratio of the structural units represented by formula (1), where s is an integer of 1 or more, to the structural units represented by formula (2), and to the structural units represented by formula (3) is preferably formula (1):formula (2):formula (3)=5-60:3-10:20-90, and more preferably formula (1):formula (2):formula (3)=6-50:4-9:30-85.

[0065] It is particularly preferred to use 4-triethylsilyloxyphenyl methacrylate or 4-tert-butyldimethylsilyloxyphenyl methacrylate as the polymerizable monomer having a hydrophobic group, and phenylmaleimide or N-cyclohexylmaleimide and 4-hydroxyphenyl methacrylate as other polymerizable monomers. By using a resin obtained by radical polymerization of these polymerizable monomers, the sensitivity and pattern formability of the positive photosensitive resin composition can be improved, and outgassing can also be reduced.

[0066] Examples of polymerization initiators used in producing the hydrophobic resin (A) by radical polymerization include, but are not limited to, azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN); dicumyl peroxide, 2,5-dimethyl-2,5-di(tert- Examples of peroxide polymerization initiators that can be used include peroxide polymerization initiators having a 10-hour half-life temperature of 100 to 170°C, such as di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide; and peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, and tert-butyl peroxypivalate. The amount of polymerization initiator used is generally at least 0.01 parts by mass, at least 0.05 parts by mass, or at least 0.5 parts by mass, and preferably at most 40 parts by mass, at most 20 parts by mass, or at most 15 parts by mass, per 100 parts by mass of the total polymerizable monomers.

[0067] A RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator. The RAFT agent may be, but is not limited to, a thiocarbonylthio compound such as a dithioester, dithiocarbamate, trithiocarbonate, or xanthate. The RAFT agent may be used in an amount of 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of the total of the polymerizable monomers.

[0068] When the hydrophobic resin (A) has a silicon-containing group, the content of silicon atoms is preferably 1 to 10% by mass, more preferably 3 to 8% by mass, based on the mass of the hydrophobic resin (A). The hydrophobic resin (A) having a silicon-containing group contains structural units having a silicon-containing group in an amount of preferably 3 to 60% by mol, more preferably 5 to 50% by mol, based on all structural units of the hydrophobic resin (A).

[0069] When the hydrophobic resin (A) has a fluorine-containing group, the content of fluorine atoms is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, based on the mass of the hydrophobic resin (A). The hydrophobic resin (A) having a fluorine-containing group contains structural units having a fluorine-containing group in an amount of preferably 5 to 55% by mol, more preferably 6 to 50% by mol, based on all structural units of the hydrophobic resin (A).

[0070] The hydrophobic resin (A) may or may not have an alkali-soluble functional group. The hydrophobic resin (A) contains structural units having an alkali-soluble functional group in an amount of preferably 20 mol % to 90 mol %, more preferably 30 mol % to 85 mol %, and even more preferably 40 mol % to 80 mol %, based on the total structural units of the hydrophobic resin (A). In one embodiment, the hydrophobic resin (A) does not have an alkali-soluble functional group.

[0071] The weight-average molecular weight (Mw) of the hydrophobic resin (A) 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 hydrophobic resin (A) 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 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. By setting the weight-average molecular weight, number-average molecular weight, and polydispersity within the above ranges, a positive-type photosensitive resin composition with excellent sensitivity and pattern formability can be obtained.

[0072] In one embodiment, the positive-type photosensitive resin composition contains 3% to 50% by mass, preferably 4% to 40% by mass, and more preferably 5% to 30% by mass of hydrophobic resin (A) based on 100% by mass of solids. When the content of hydrophobic resin (A) is 3% by mass or more based on 100% by mass of solids, the fluorine-containing surfactant (D) promotes uneven distribution of the hydrophobic resin (A) on the coating surface, resulting in a high concentration of the hydrophobic resin (A) on the coating surface, making the coating surface less soluble in alkaline aqueous solutions, thereby achieving high sensitivity. When the content of hydrophobic resin (A) is 50% by mass or less based on 100% by mass of solids, dissolution of the coating surface in the exposed area proceeds rapidly, accompanied by dissolution of the carboxylic acid compound derived from the quinone diazide compound, other highly alkali-soluble resin components, and any dissolution promoter, thereby achieving high sensitivity.

[0073] The positive-type photosensitive resin composition preferably contains 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) based on the total mass of the resin components. When the content of hydrophobic resin (A) is 5% by mass or more based on the total mass of the resin components, the fluorine-containing surfactant (D) promotes uneven distribution of the hydrophobic resin (A) on the coating surface, resulting in a high concentration of the hydrophobic resin (A) on the coating surface, making the coating surface less soluble in alkaline aqueous solutions, thereby achieving high sensitivity. When the content of hydrophobic resin (A) is 60% by mass or less based on the total mass of the resin components, dissolution of the coating surface in exposed areas proceeds rapidly, accompanied by dissolution of the carboxylic acid compound derived from the quinone diazide compound, other highly alkali-soluble resin components, and any dissolution promoter, thereby achieving high sensitivity.

[0074] <Alkali-soluble resin (B)> The alkali-soluble resin (B) is not particularly limited, but is preferably a resin having an alkali-soluble functional group. Examples of the alkali-soluble functional group include, but are not limited to, a phenolic hydroxyl group, a carboxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group. 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 an alkali-soluble functional group protected by an acid-decomposable group.

[0075] Examples of alkali-soluble resins (B) include homopolymers or copolymers of polymerizable monomers having alkali-soluble functional groups, and resins having epoxy groups and phenolic hydroxyl groups. Other alkali-soluble resins (B) 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. Examples of phenolic resin derivatives include polyalkenylphenolic resins in which an alkenyl group is bonded to a benzene ring, and examples of polystyrene resin derivatives include hydroxypolystyrene resin derivatives in which a phenolic hydroxyl group and a hydroxyalkyl group or alkoxy group are bonded to a benzene ring. The alkali-soluble resins (B) can be used alone or in combination of two or more.

[0076] The alkali-soluble resin (B) may have a radically polymerizable functional group. In one embodiment, the alkali-soluble resin (B) has a (meth)acryloyloxy group, an allyl group, or a methallyl group as the radically polymerizable functional group.

[0077] In one embodiment, the positive photosensitive resin composition contains 5% to 80% by mass, preferably 10% to 75% by mass, and more preferably 15% to 70% by mass of the alkali-soluble resin (B) based on 100% by mass of the solids content. If the content of the alkali-soluble resin (B) is 5% by mass or more based on 100% by mass of the solids content, dissolution of the exposed area can be promoted, achieving high sensitivity and ensuring the stability and durability of the coating film after thermal curing. If the content of the alkali-soluble resin (B) is 80% by mass or less based on 100% by mass of the solids content, the solubility of the unexposed area can be kept low, maintaining a high film residual rate.

[0078] The positive photosensitive resin composition contains the alkali-soluble resin (B) in an amount of preferably 40% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and even more preferably 60% by mass to 85% by mass, based on the total mass of the resin components. When the content of the alkali-soluble resin (B) is 40% by mass or more, based on the total mass of the resin components, a desired alkali solubility can be obtained. When the content of the alkali-soluble resin (B) is 95% by mass or less, based on the total mass of the resin components, a highly sensitive positive photosensitive resin composition can be obtained.

[0079] In one embodiment, the alkali-soluble resin (B) includes a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, a resin having an epoxy group and a phenolic hydroxyl group, or a combination thereof.

[0080] <Copolymer of polymerizable monomer having alkali-soluble functional group and other polymerizable monomer> Examples of the alkali-soluble functional group possessed by a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer (hereinafter simply referred to as a "copolymer having an alkali-soluble functional group") include a phenolic hydroxyl group, a carboxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group. The copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer may have two or more types of alkali-soluble functional groups. Examples of the polymerizable functional group possessed by the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer include radically polymerizable functional groups such as CH═CH—, CH═C(CH)—, CH═CHCO—, CH═C(CH)CO—, and —OC—CH═CH—CO—.

[0081] From the viewpoint of heat resistance, the copolymer having an alkali-soluble functional group preferably has one or more cyclic structures selected from the group consisting of an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure.

[0082] The copolymer having an alkali-soluble functional group can be produced, for example, by radical polymerization of a polymerizable monomer having an alkali-soluble functional group with another polymerizable monomer. After synthesizing the copolymer by radical polymerization, the alkali-soluble functional group may be added to the copolymer.

[0083] Examples of polymerizable monomers having an alkali-soluble functional group include maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; (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 maleic acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid; 4-hydroxystyrene, Examples of the polymerizable monomer include polymerizable monomers having a phenolic hydroxyl group, such as 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, and 4-hydroxyphenyl maleimide; polymerizable monomers having a sulfo group, such as (meth)allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid; polymerizable monomers having a phosphate group, such as mono(2-(meth)acryloyloxyethyl)phosphate; and polymerizable monomers having an acid anhydride group, such as itaconic anhydride, citraconic anhydride, and maleic anhydride.

[0084] 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.

[0085] 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; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. Examples of the methacrylic acid esters include methyl (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; and N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide.

[0086] As a polymerizable monomer having an alkali-soluble functional group, after polymerization, [ka] (In formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. 9 is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 3, and more preferably 1. 4-hydroxyphenyl methacrylate is particularly preferred as a polymerizable monomer having such an alkali-soluble functional group.

[0087] Other polymerizable monomers include those represented by the formula (2) after polymerization. [ka] (In formula (2), R 6and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 8 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one group selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. 6 and R 7 are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. 8 is preferably a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and more preferably a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group. As such other polymerizable monomers, phenylmaleimide and N-cyclohexylmaleimide are particularly preferred.

[0088] In one embodiment, the copolymer having an alkali-soluble functional group is represented by formula (3): [ka] (In formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. [ka] (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 8is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0089] In the copolymer having an alkali-soluble functional group, the molar ratio of the structural unit represented by formula (3) to the structural unit represented by formula (2) is preferably formula (3): formula (2)=70-95:30-5, and more preferably formula (3): formula (2)=75-90:25-10.

[0090] It is particularly preferred to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having an alkali-soluble functional group and phenylmaleimide or N-cyclohexylmaleimide as the other polymerizable monomer. By using a resin obtained by radical polymerization of these polymerizable monomers, the shape retention and developability of the film of the positive photosensitive resin composition can be improved, and outgassing can also be reduced.

[0091] The type and amount of the polymerization initiator used when producing a copolymer having an alkali-soluble functional group by radical polymerization are the same as those described for the polymerization initiator used when producing the hydrophobic resin (A) by radical polymerization. The type and amount of the RAFT agent that can be used in combination with the polymerization initiator are the same as those described for the RAFT agent used when producing the hydrophobic resin (A) by radical polymerization.

[0092] The weight-average molecular weight (Mw) of the copolymer having an alkali-soluble functional group 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 an alkali-soluble functional group 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 an alkali-soluble functional group 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 an alkali-soluble functional group within the above ranges, a positive-type photosensitive resin composition with excellent coatability, pattern formability, and alkali developability can be obtained.

[0093] When the alkali-soluble functional group of the copolymer having an alkali-soluble functional group is a phenolic hydroxyl group, the phenolic hydroxyl group equivalent of the copolymer having an alkali-soluble functional group is preferably 60 to 400, more preferably 80 to 350, and even more preferably 100 to 300. When the phenolic hydroxyl group equivalent of the copolymer having an alkali-soluble functional group is 60 or more, the film thickness of the unexposed area can be sufficiently maintained during alkaline development. When the phenolic hydroxyl group equivalent of the copolymer having an alkali-soluble functional group is 400 or less, the desired alkali solubility can be obtained.

[0094] In the present disclosure, when a copolymer having an alkali-soluble functional group also falls under the category of a resin having an epoxy group and a phenolic hydroxyl group, which will be described later, it will be treated as a copolymer having an alkali-soluble functional group. In other words, resins having an epoxy group and a phenolic hydroxyl group do not include those that fall under the category of a copolymer having an alkali-soluble functional group.

[0095] <Resin having an epoxy group and a phenolic hydroxyl group> Resins containing epoxy groups and phenolic hydroxyl groups are alkaline aqueous solution-soluble resins. Resins containing epoxy groups and phenolic hydroxyl groups may also contain alkaline-soluble functional groups other than phenolic hydroxyl groups. Resins containing epoxy groups and phenolic hydroxyl groups can be obtained, for example, by reacting a portion of the epoxy groups of a compound having at least two epoxy groups per molecule (hereinafter sometimes referred to as an "epoxy compound") with the carboxyl group of a hydroxybenzoic acid compound. The epoxy groups of resins containing epoxy groups and phenolic hydroxyl groups react with the phenolic hydroxyl groups to form crosslinks during post-development heat treatment (post-baking), thereby improving the chemical resistance, heat resistance, and other properties of the coating. Because the phenolic hydroxyl groups contribute to solubility in alkaline aqueous solutions during development, resins containing epoxy groups and phenolic hydroxyl groups also function as a dissolution promoter for other resins when exposed to low light exposure, thereby improving the sensitivity of photosensitive resin compositions.

[0096] The following reaction formula 1 shows an example of a reaction in which one of the epoxy groups of an epoxy compound reacts with a carboxy group of a hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group. [ka]

[0097] Examples of compounds having at least two epoxy groups per molecule include novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins, bisphenol epoxy resins, biphenol epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These epoxy compounds may contain two or more epoxy groups per molecule, and may be used alone or in combination of two or more. Because these compounds are thermosetting, it is common knowledge among those skilled in the art that their structures cannot be unambiguously described due to differences in the presence or absence of epoxy groups, the type of functional group, the degree of polymerization, and other factors.

[0098] An example of the structure of a novolac epoxy resin is shown in formula (4). In formula (4), R 10 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a hydroxyl group; and m is an integer of 1 to 50. [ka]

[0099] Examples of phenol novolac epoxy resins include EPICLON® N-770 (DIC Corporation) and jER®-152 (Mitsubishi Chemical Corporation). Examples of cresol novolac epoxy resins include EPICLON® N-695 (DIC Corporation) and EOCN®-102S (Nippon Kayaku Co., Ltd.). Examples of bisphenol epoxy resins include bisphenol A epoxy resins such as jER® 828, jER® 1001 (Mitsubishi Chemical Corporation), and YD-128 (trade name, Nippon Steel Chemical & Material Co., Ltd.), and bisphenol F epoxy resins such as jER® 806 (Mitsubishi Chemical Corporation) and YDF-170 (trade name, Nippon Steel Chemical & Material Co., Ltd.). Examples of biphenol-type epoxy resins include jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (Mitsubishi Chemical Corporation). Examples of naphthalene skeleton-containing epoxy resins include NC-7000 (trade name, Nippon Kayaku Co., Ltd.) and EXA-4750 (trade name, DIC Corporation). Examples of alicyclic epoxy resins include EHPE (registered trademark)-3150 (Daicel Chemical Industries, Ltd.). Examples of heterocyclic epoxy resins include TEPIC (registered trademark), TEPIC-L, TEPIC-H, and TEPIC-S (Nissan Chemical Industries, Ltd.).

[0100] The compound having at least two epoxy groups per molecule is preferably a novolac epoxy resin, more preferably at least one selected from the group consisting of phenol novolac epoxy resins and cresol novolac epoxy resins, and even more preferably a cresol novolac epoxy resin. A positive-type photosensitive resin composition containing a resin having epoxy groups and phenolic hydroxyl groups derived from a novolac epoxy resin, particularly a cresol novolac epoxy resin, has excellent pattern formability, easy adjustment of alkali solubility, and little outgassing.

[0101] The hydroxybenzoic acid compound is a compound in which at least one of the 2- to 6-positions of benzoic acid is substituted with a hydroxyl group, and examples thereof include salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, and 4-hydroxy-3-nitrobenzoic acid. Dihydroxybenzoic acid compounds are preferred in terms of enhancing alkaline developability. The hydroxybenzoic acid compounds can be used alone or in combination of two or more.

[0102] In one embodiment, the resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid compound, and is represented by the formula (5): [ka] (In formula (5), b is an integer of 1 to 5, and * represents a bond to a residue other than the epoxy group involved in the reaction of a compound having at least two epoxy groups in one molecule.)

[0103] In a method for obtaining a resin having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound, 0.2 to 0.95 equivalents of the hydroxybenzoic acid compound can be used relative to 1 equivalent of the epoxy group of the epoxy compound, preferably 0.3 to 0.9 equivalents, and more preferably 0.4 to 0.8 equivalents. If the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and if it is 0.95 equivalents or less, an increase in molecular weight due to side reactions can be suppressed.

[0104] A catalyst may be used to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of catalyst used may be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture consisting of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature may be 60 to 150°C, and the reaction time may be 3 to 30 hours. Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate.

[0105] The number-average molecular weight (Mn) of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8,000, more preferably 800 to 6,000, and even more preferably 1,000 to 5,000. The weight-average molecular weight (Mw) of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 30,000, more preferably 2,000 to 25,000, and even more preferably 3,000 to 20,000. If the number-average molecular weight is 500 or more, or if the weight-average molecular weight is 500 or more, the alkali development rate is appropriate and the difference in dissolution rate between the exposed and unexposed areas is sufficient, resulting in good pattern resolution. If the number-average molecular weight is 8,000 or less, or if the weight-average molecular weight is 30,000 or less, the coatability and alkali developability are good.

[0106] In one embodiment, the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 to 7000, preferably 400 to 6000, and more preferably 500 to 5000. When the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 or more, sufficient alkali solubility can be imparted to the resin having an epoxy group and a phenolic hydroxyl group. When the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 7000 or less, the strength and heat resistance of the cured coating can be improved. The epoxy equivalent is determined according to JIS K 7236:2009.

[0107] In one embodiment, the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 160 to 500, preferably 170 to 400, and more preferably 180 to 300. If the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 160 or more, the strength and heat resistance of the coating film after curing can be increased. If the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 500 or less, sufficient alkali solubility can be imparted to the resin having an epoxy group and a phenolic hydroxyl group. The hydroxyl equivalent is determined according to JIS K 0070:1992.

[0108] Protective resin The alkali-soluble resin (B) may contain a resin having alkali-soluble functional groups protected by acid-decomposable groups (hereinafter, simply referred to as "protected resin"). The protective resin is not particularly limited as long as it has multiple alkali-soluble functional groups, at least some of which are protected with acid-decomposable groups. Examples of the protective resin include resins in which the alkali-soluble resin having multiple alkali-soluble functional groups described above is used as a base resin, and at least some of the alkali-soluble functional groups are protected with acid-decomposable groups. Examples of alkali-soluble functional groups include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphate groups, acid anhydride groups, and mercapto groups. The alkali-soluble functional group is preferably a phenolic hydroxyl group or a carboxyl group, and more preferably a phenolic hydroxyl group. By protecting some of the alkali-soluble functional groups with acid-decomposable groups, the alkali solubility of the protective resin before exposure is suppressed. The protective resin may have an alkali-soluble functional group other than the alkali-soluble functional group protected by the acid-decomposable group. By optionally performing post-exposure baking (PEB) in the presence of acid generated during exposure, decomposition (deprotection) of the acid-decomposable group is promoted, and the alkali-soluble functional group is regenerated. This promotes alkaline dissolution of the protective resin in the exposed area during development. The protective resin may be used alone or in combination of two or more types. For example, the protective resin may be a combination of two or more types of resins that differ in the structural unit of the polymer or copolymer, the acid-decomposable group, the protection rate of the alkali-soluble functional group, or a combination thereof.

[0109] (Protection of alkali-soluble functional groups by acid-decomposable groups) The protected resin can be obtained by protecting some of the alkali-soluble functional groups of a base resin having a plurality of alkali-soluble functional groups with an acid-decomposable group. For example, when the alkali-soluble functional groups are phenolic hydroxyl groups, the protected resin having phenolic hydroxyl groups protected with an acid-decomposable group can be obtained by the following reaction: Ar-OR 11 Ar represents an aromatic ring derived from phenol, and R 11 represents an acid-decomposable group.

[0110] The acid-decomposable group is a group that is decomposed (deprotected) in the presence of an acid, if necessary by heating, to generate an alkali-soluble functional group. Specific examples thereof include groups having a tertiary alkyl group, such as a tert-butyl group, a 1,1-dimethyl-propyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 1-methyladamantyl group, a 1-ethyladamantyl group, a tert-butoxycarbonyl group, and a 1,1-dimethyl-propoxycarbonyl group; and -CR 12 R 13 -OR 14 (6) (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 14 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, and R 12 or R 13 One of the two and R 14 may be bonded to form a ring structure having 3 to 10 ring members, and R 12 , R 13 and R 14 may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine. 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 when the alkali-soluble functional group is a phenolic hydroxyl group. These acid-decomposable groups may be used alone or in combination of two or more.

[0111] The acid-decomposable group is preferably a group represented by formula (6), since this allows a photosensitive resin composition with high sensitivity to be obtained even at a low exposure dose. 12 and R 13are 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 14 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, each of 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, 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-cyclohexyloxyethyl, and 1-(2-cyclohexylethoxy)ethyl groups, with 1-ethoxyethyl and 1-n-propoxyethyl groups being preferred. Examples of acid-decomposable groups include a group represented by formula (6), in which R 12 or R 13 One of the two and R 14 and R bonded to form a ring structure having 3 to 10 ring members can also be suitably used. In this case, R not involved in the formation of the ring structure can be used. 12 or R 13 is preferably a hydrogen atom. Examples of such an acid-decomposable group include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, with a 2-tetrahydrofuranyl group being preferred.

[0112] The protection reaction of the alkali-soluble functional group can be carried out using a general protecting agent under known conditions. For example, the protected resin can be obtained by reacting the base resin of the protected resin with the protecting agent in the presence of an acid or a base at a reaction temperature of −20 to 50° C. without a solvent or in a solvent such as toluene or hexane.

[0113] As the protecting agent, a known protecting agent capable of protecting an alkali-soluble functional group can be used. For example, isobutene can be used when the acid-decomposable group is a tert-butyl group, and di-tert-butyl dicarbonate can be used when the acid-decomposable group is a tert-butoxycarbonyl group. For example, chloromethyl methyl ether can be used when the acid-decomposable group is a methoxymethyl group; ethyl vinyl ether can be used when the acid-decomposable group is a 1-ethoxyethyl group; n-propyl vinyl ether can be used when the acid-decomposable group is a 1-n-propoxyethyl group; 2,3-dihydrofuran can be used when the acid-decomposable group is a 2-tetrahydrofuranyl group; and 3,4-dihydro-2H-pyran can be used when the acid-decomposable group is a 2-tetrahydropyranyl group.

[0114] 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 pyridinium salts 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.

[0115] In another embodiment, a protected resin can be obtained by protecting the alkali-soluble functional group of a polymerizable monomer having an alkali-soluble functional group with an acid-decomposable group, and then polymerizing or copolymerizing the polymerizable monomer having the alkali-soluble functional group protected with the acid-decomposable 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.

[0116] The protective resin is represented by the formula (7) [ka] (In equation (7), R 15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 16 is an acid-decomposable group, p is an integer of 0 to 5, and q is an integer of 0 to 5, with the proviso that p+q is an integer of 1 to 5. It is preferable that the compound has a structural unit represented by formula (7), and has at least one structural unit represented by formula (7) in which q is an integer of 1 or more. 16 The acid-decomposable group is represented by the formula (6): -CR 12 R 13 -OR 14 (6) (In formula (6), R 12 , R 13 and R 14 is as defined above. 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 14 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, each of 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, 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-cyclohexyloxyethyl, and 1-(2-cyclohexylethoxy)ethyl groups, with 1-ethoxyethyl and 1-n-propoxyethyl groups being preferred. 12 or R 13 One of the two and R 14 Examples of the acid-decomposable group in which the above are bonded to form a ring structure having 3 to 10 ring members include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, with a 2-tetrahydrofuranyl group being preferred.

[0117] The protective resin is represented by the formula (2) [ka] (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 8 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one group selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. 6 and R 7 are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. 8 is preferably a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and more preferably a cyclic alkyl group having 3 to 12 carbon atoms or a phenyl group.

[0118] In one embodiment, the number of structural units represented by formula (7) where q is an integer of 1 or greater, i.e., structural units represented by formula (7) in which at least one alkali-soluble functional group is protected with an acid-decomposable group, accounts for 5% to 95%, preferably 15% to 90%, and more preferably 25% to 85% of the total number of structural units in the protective resin. By setting the proportion of these structural units to 5% or greater, it is possible to promote dissolution of the exposed area and differentiate the solubility of the unexposed area from the exposed area, thereby achieving high sensitivity and ensuring the stability and durability of the coating after thermal curing. By setting the proportion of these structural units to 95% or less, it is possible to reduce the amount of unreacted acid-decomposable groups remaining, increase the solubility of the exposed area, and achieve high sensitivity.

[0119] In one embodiment, the positive photosensitive resin composition contains 0.5% by mass to 50% by mass, preferably 1% by mass to 40% by mass, and more preferably 2% by mass to 30% by mass of a protective resin, based on 100% by mass of solids. When the protective resin content is 0.5% by mass or more, based on 100% by mass of solids, it is possible to promote dissolution of the exposed area and create a difference in solubility between the unexposed area and the exposed area, thereby achieving high sensitivity and ensuring the stability and durability of the coating after thermal curing. When the protective resin content is 50% by mass or less, based on 100% by mass of solids, it is possible to reduce the amount of unreacted acid-decomposable groups remaining, increase the solubility of the exposed area, and achieve high sensitivity.

[0120] <Quinone diazide compounds (C)> When irradiated with radiation such as visible light, ultraviolet light, gamma rays, or electron beams, the quinone diazide compound (C) generates an alkali-soluble carboxylic acid compound via the reaction shown in Reaction Scheme 2 below. Before exposure, the quinone diazide compound (C) interacts (e.g., forms hydrogen bonds) with alkali-soluble functional groups, such as phenolic hydroxyl groups, of the alkali-soluble resin (B), rendering the alkali-soluble resin (B) insoluble in an alkaline aqueous solution. Meanwhile, the presence of the alkali-soluble carboxylic acid compound in the irradiated area facilitates the dissolution of the resin in that area together with the carboxylic acid compound in an alkaline aqueous solution. Furthermore, the generated carboxylic acid compound promotes the decomposition of acid-labile groups in the protective resin optionally contained in the positive photosensitive resin composition, regenerating the alkali-soluble functional groups and increasing the alkaline solubility of the protective resin. Furthermore, the carboxylic acid compound has a relatively larger molecular structure than acids generated from photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is therefore less likely to diffuse in the coating. These synergistic effects result in a greater difference in alkali solubility between unexposed and exposed areas, enabling the formation of high-sensitivity, high-resolution patterns even at low exposure doses. The quinone diazide compound (C) can be used alone or in combination of two or more. The positive-type photosensitive resin composition preferably contains substantially no photoacid generators commonly used in chemically amplified resists, and more preferably contains only the quinone diazide compound (C) as a photosensitizer without the photoacid generator. "Substantially free of photoacid generators commonly used in chemically amplified resists" means that the amount of the photoacid generator contained in the positive-type photosensitive resin composition is 0.2 parts by mass or less, 0.1 parts by mass or less, or 0.05 parts by mass or less, based on 100 parts by mass of the total resin components. It is preferable for the positive-type photosensitive resin composition to be substantially free of photoacid generators commonly used in chemically amplified resists, since this composition provides good process stability and high sensitivity.

[0121] [ka]

[0122] In one embodiment, high-resolution patterns can be formed without the post-exposure bake (PEB) required for typical chemically amplified resists. The quinone diazide compound (C) has a relatively high quantum yield, efficiently generating a carboxylic acid compound in the exposed area. By omitting PEB, it is possible to avoid a decrease in pattern formability due to excessive diffusion of the acid generated from the photoacid generator to the unexposed area in the high-temperature environment of the PEB process. Furthermore, when the alkali-soluble resin (B) contains a resin having an epoxy group and a phenolic hydroxyl group, omitting PEB prevents ring-opening polymerization of the epoxy group in the resin having an epoxy group and a phenolic hydroxyl group, thereby maintaining the alkali solubility of the resin having an epoxy group and a phenolic hydroxyl group during development.

[0123] Examples of the quinone diazide compound (C) include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond or a sulfonamide bond. From the viewpoint of contrast between exposed and unexposed areas, it is preferred that 20 mol % or more of the total functional groups of the polyhydroxy compound or polyamino compound be substituted with quinone diazide.

[0124] Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP. -OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML- P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (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.), tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.), and the like.

[0125] 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.

[0126] Polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like.

[0127] The quinone diazide compound (C) is preferably a 1,2-naphthoquinone diazide-4-sulfonic acid ester or a 1,2-naphthoquinone diazide-5-sulfonic acid ester of a polyhydroxy compound.

[0128] In one embodiment, the positive photosensitive resin composition contains 5 to 60 parts by mass, preferably 10 to 50 parts by mass, and more preferably 15 to 42 parts by mass of the quinone diazide compound (C) based on 100 parts by mass of the total resin components. When the content of the quinone diazide compound (C) is 5 parts by mass or more based on the total 100 parts by mass, high sensitivity can be achieved. When the content of the quinone diazide compound (C) is 60 parts by mass or less based on the total 100 parts by mass, alkaline developability is good.

[0129] <Fluorosurfactant (D)> The fluorosurfactant (D) is not particularly limited, but can be a surfactant having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group, and a hydrophilic group. Examples of such fluorosurfactants (D) include perfluoroalkyl sulfonic acids, partially fluorinated alkyl sulfonic acids, perfluoroalkyl carboxylic acids, partially fluorinated alkyl carboxylic acids, perfluoroalkyl phosphate esters, partially fluorinated alkyl phosphate esters, perfluoroalkyl trimethylammonium salts, partially fluorinated alkyl trimethylammonium salts, perfluoroalkyl betaines, partially fluorinated alkyl betaines, perfluoroalkyl EO adducts, and fluorotelomer alcohols. The fluorosurfactant (D) can also be a homopolymer or copolymer having a perfluoroalkyl group, partially fluorinated alkyl group, perfluoroalkylene group, or partially fluorinated alkylene group, and a hydrophilic group such as a sulfo group, a carboxy group, a phosphate group, an ammonium group, an oxyalkylene group, or a polyoxyalkylene group, within the molecule. The fluorosurfactant (D) can be used alone or in combination of two or more types.

[0130] The fluorosurfactant (D) preferably contains an acrylic copolymer having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group. The acrylic copolymer can promote migration of the hydrophobic resin (A) to the coating surface of the positive photosensitive resin composition, thereby making the coating surface more alkali-insoluble.

[0131] In one embodiment, the acrylic copolymer is represented by formula (8): [ka] (In equation (8), R 17 is a hydrogen atom or a methyl group, and L 1 is a divalent group having 1 to 30 carbon atoms, and Rf 1 is a perfluoroalkyl group or partially fluorinated alkyl group having 4 to 6 carbon atoms which may contain one or more ether bonds in the chain. and a fluorine-containing polymerizable monomer represented by formula (9): [ka] (In equation (9), R 18 is a hydrogen atom or a methyl group, and R 19 are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, a linear perfluoroalkylene group or a linear partially fluorinated alkylene group having 1 to 4 carbon atoms, or a branched perfluoroalkylene group or a branched partially fluorinated alkylene group having 2 to 4 carbon atoms, and R 20 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a perfluoroalkyl or partially fluorinated alkyl group having 1 to 6 carbon atoms, and c is an integer of 2 to 50. The copolymer (D1) is a copolymer of the copolymer (D1) and a polymerizable monomer having a group represented by the following formula:

[0132] In equation (8), L 1The divalent group having 1 to 30 carbon atoms represented by the formula (I) may contain at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, and may contain a perfluoroalkyl group or a partially fluorinated alkyl group having 4 to 6 carbon atoms. 1 is -OCH2CH2-, -OCH2CH2NH(C=O)OCH(CH2OCH2CH2C4F9)CH2OCH2CH2-, -OCH2CH2NH(C=O)OCH(CH2OCH2CH2C6F 13 )CH2OCH2CH2-, -OCH2CH2N(C3H7)SO2-, -OCH2CH2NH(C=O)OCH2CH2-, -OCH2CH(OH)CH2O-, or -N(C4H9)CH2CH2-.

[0133] In formula (8), Rf 1 is -C4F9 or -C6F 13 It is preferable that:

[0134] The fluorine-containing polymerizable monomers represented by formula (8) can be used alone or in combination of two or more kinds.

[0135] In equation (9), R 19 Examples of the linear or branched alkylene group having 2 to 4 carbon atoms and represented by the formula (R) include an ethylene group, a propylene group, a tetramethylene group, a 1-methylethylene group, a 2-methylethylene group, a 1-ethylethylene group, a 2-ethylethylene group, and an isobutylene group. 19 Examples of the linear perfluoroalkylene group or linear partially fluorinated alkylene group having 1 to 4 carbon atoms represented by the formula (I) include -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF2CF2CF2-, -CHF-, CF2CH2-, and -CF2CHF-. 19Examples of the branched perfluoroalkylene group or branched partially fluorinated alkylene group having 2 to 4 carbon atoms represented by the formula (I) include -CF(CF3)-, -CF(CF3)CF2-, -CF2CF(CF3)-, -CF(CF2CF3)CF2-, -CF2CF(CF2CF3)-, -CF(CHF2)CF2-, -CF2CF(CHF2)-, -CF(CF2CHF2)CF2-, and -CF2CF(CF2CHF2)-. 19 may be the same or different from each other. From the viewpoint of leveling property, R 19 is preferably a propylene group, a tetramethylene group, a 1-methylethylene group, a 2-methylethylene group, a 1-ethylethylene group, a 2-ethylethylene group, or an isobutylene group, and more preferably a plurality of the same groups are linked via adjacent oxygen atoms to form a polyoxypropylene chain, a polyoxytetramethylene chain, a polyoxymethylethylene chain, a polyoxyethylethylene chain, or a polyoxyisobutylene chain.

[0136] In equation (9), R 20 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (R) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an n-hexyl group. 20 Examples of the perfluoroalkyl group or partially fluorinated alkyl group having 1 to 6 carbon atoms represented by the formula (I) include -CF3, -C2F5, -C3F7, -C4F9, -C5F 11 , -CF 13 , -CH2F, -CHF2, -C2HF4, -C3H2F5, -C3HF6, -C4HF8, -C5HF 10 , and -CHF 12 Examples include:

[0137] The polymerizable monomer having a polyoxyalkylene group represented by formula (9) can be used alone or in combination of two or more kinds.

[0138] The copolymer (D1) may be a copolymer containing the fluorine-containing polymerizable monomer represented by formula (8) and the polymerizable monomer having a polyoxyalkylene group represented by formula (9) as well as other polymerizable monomers.

[0139] Other polymerizable monomers include, for example, those represented by the formula (10): [ka] (In equation (10), R 21 is a hydrogen atom or a methyl group, and R 22 are each independently a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, or a group containing a silyl group. Examples of the polymerizable monomer include those represented by the following formula:

[0140] In equation (10), R 22 Examples of the linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms and represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, a stearyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclohexyl group, an isobornyl group, an adamantyl group, and a dicyclopentanyl group. Examples of groups containing a silyl group include a trimethoxysilylpropyl group, a (trimethylsilyloxy)dimethylsilylpropyl group, and a tris(trimethylsilyloxy)silylpropyl group.

[0141] Other polymerizable monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene; and maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, n-propylmaleimide, isopropylmaleimide, n-butylmaleimide, n-hexylmaleimide, n-octylmaleimide, n-dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide.

[0142] The other polymerizable monomers may be used alone or in combination of two or more kinds.

[0143] From the viewpoint of leveling property, the mass ratio of the fluorine-containing polymerizable monomer represented by formula (8) to the polymerizable monomer having a polyoxyalkylene group represented by formula (9) in copolymer (D1) (mass of fluorine-containing 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, they are preferably used in an amount such that the amount of the other polymerizable monomers is 50 mass% or less, based on the mass of copolymer (D1).

[0144] Copolymer (D1) can be obtained, for example, by radical polymerization of a fluorine-containing polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), and, if necessary, other polymerizable monomers, 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, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl thioglycolic acid, or octyl thioglycolic acid may be used.

[0145] The number average molecular weight (Mn) of the copolymer (D1) is preferably 2,000 to 100,000, more preferably 2,500 to 50,000, since this provides good compatibility or miscibility with the resin component and excellent leveling properties.

[0146] From the viewpoints of compatibility or miscibility with the resin component and leveling property, the fluorine atom content of the copolymer (D1) is preferably 2 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 10 to 25 mass%. The fluorine atom content of the copolymer (D1) is a value calculated from the mass ratio of fluorine atoms based on the total mass of the polymerizable monomers used.

[0147] In another embodiment, the acrylic copolymer is represented by formula (11): [ka] (In formula (11), R 23 is a radical polymerizable functional group, and L 2 is a divalent group having 1 to 8 carbon atoms, and L 3 is a divalent group having 1 to 8 carbon atoms, and Rf 2 are each independently a fluorinated alkylene group having 1 to 3 carbon atoms, and d is an integer of 1 to 100. and a fluorine-containing polymerizable monomer represented by formula (12): [ka] (In equation (12), R 24 is a hydrogen atom or a methyl group, and R 25 are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, and R 26 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and e is an integer of 1 to 80. The copolymer (D2) is a copolymer of the copolymer (D2) and a polymerizable monomer having an oxyalkylene group represented by the following formula:

[0148] In equation (11), R 23Examples of the radical polymerizable functional group represented by the formula include CH2=CHCO-, CH2=C(CH3)CO-, and CH2=CH-C6H4-. 23 may be the same or different from each other. 23 is preferably CH2=CHCO- or CH2=C(CH3)CO- from the viewpoints of availability and radical polymerizability, and more preferably CH2=CHCO- because of its excellent leveling properties.

[0149] In equation (11), L 2 The divalent group having 1 to 8 carbon atoms represented by the formula (I) may contain at least one heteroatom selected from the group consisting of an oxygen atom and a nitrogen atom. 2 is preferably -OCH2-, -OCH2CH2-, -OCH2CH2NH(C=O)OCH2-, -OCH2CH2NH(C=O)OCH2CH2-, -OCH2CH2CH2CH2OCH2CH(OH)CHO(C=O)-, -OCH2CH(OH)CHO(C=O)-, -OCH2CH(OH)CHOCH2-, or -CH2OCH2-, more preferably -OCH2- or -OCH2CH2NH(C=O)OCH2-, and even more preferably -OCH2-.

[0150] In equation (11), L 3 The divalent group having 1 to 8 carbon atoms represented by the formula (I) may contain at least one heteroatom selected from the group consisting of an oxygen atom and a nitrogen atom. 3 is preferably —CHO—, —CHCHO—, —CHO(C═O)NHCHCHO—, —CHCHO(C═O)NHCHCHO—, —(C═O)OCHCH(OH)CHOCHCHCHCHO—, —(C═O)OCHCH(OH)CHO—, —CHOCHCH(OH)CHO—, or —CHOCH—, more preferably —CHO— or —CHO(C═O)NHCHCHO—, and even more preferably —CHO—.

[0151] In formula (11), Rf2 The fluorinated alkylene group having 1 to 3 carbon atoms represented by the formula (I) is specifically selected from the group consisting of -CF2- (perfluoromethylene group), -CF2CF2- (perfluoroethylene group), -CF2CF2CF2-, -CF2CF(CF3)-, and -CF(CF3)CF2-.

[0152] From the viewpoint of leveling property, in formula (11), -(Rf 2 O) d Rf 2 The moiety represented by - preferably contains a combination of a perfluoromethylene group and a perfluoroethylene group. In this embodiment, the molar ratio of the perfluoromethylene group to the perfluoroethylene group (moles of perfluoromethylene groups / moles of perfluoroethylene groups) is preferably 1 / 10 to 10 / 1.

[0153] In the formula (11), d is preferably 3 to 100, and more preferably 6 to 70.

[0154] From the viewpoints of compatibility or miscibility with the resin component and leveling properties, the fluorine-containing polymerizable monomer represented by formula (11) preferably contains 18 to 200, and more preferably 25 to 150, fluorine atoms.

[0155] The fluorine-containing polymerizable monomers represented by formula (11) can be used alone or in combination of two or more kinds.

[0156] In equation (12), R 25 Examples of the linear or branched alkylene group having 2 to 4 carbon atoms represented by the formula (R) include an ethylene group, a propylene group, a tetramethylene group, and an isobutylene group. 25 may be the same or different from each other. From the viewpoint of leveling property, R 25 is preferably an ethylene group or a propylene group, and more preferably a plurality of the same groups are linked via adjacent oxygen atoms to form a polyoxyethylene chain, a polyoxypropylene chain, or a chain in which a polyoxyethylene chain and a polyoxypropylene chain are linked.

[0157] In equation (12), R 26 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an n-hexyl group.

[0158] In the formula (12), e is preferably 3 to 50.

[0159] The polymerizable monomer having an oxyalkylene group represented by formula (12) can be used alone or in combination of two or more kinds.

[0160] The copolymer (D2) may be a copolymer containing other polymerizable monomers in addition to the fluorine-containing polymerizable monomer represented by formula (11) and the polymerizable monomer having an oxyalkylene group represented by formula (12). Examples of the other polymerizable monomers include those described above for the copolymer (D1).

[0161] The copolymer (D2) can be obtained by the radical polymerization described for the copolymer (D1).

[0162] The number average molecular weight (Mn) of the copolymer (D2) is preferably 500 to 20,000, more preferably 1,500 to 10,000, and the weight average molecular weight (Mw) of the copolymer (D2) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, in order to obtain good compatibility or miscibility with the resin component and excellent leveling properties.

[0163] From the viewpoints of compatibility or miscibility with the resin component and leveling property, the fluorine atom content of the copolymer (D2) is preferably 2 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 10 to 25 mass%. The fluorine atom content of the copolymer (D2) is a value calculated from the mass ratio of fluorine atoms based on the total mass of the polymerizable monomers used.

[0164] Specific examples of the fluorine-based surfactant (D) include Megafac (registered trademark) F-251, F-281, F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-562, and F-563 (trade names, DIC Corporation), and Surflon (registered trademark) S-242, S-243, S-386, S-420, and S-611 (trade names, AGC Seimi Chemical Co., Ltd.). The fluorine-based surfactant (D) is preferably Megafac (registered trademark) F-563, F-559, F-554, R-40, or F-562, and more preferably Megafac (registered trademark) F-563, F-554, or R-40.

[0165] The content of the fluorosurfactant (D) in the positive 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. When the content of the fluorosurfactant (D) is 0.01 part by mass or more based on the total 100 parts by mass, the leveling properties of the positive photosensitive resin composition are improved, allowing the positive photosensitive resin composition to be uniformly applied to a substrate, thereby promoting uneven distribution of the hydrophobic resin (A). When the content of the fluorosurfactant (D) is 5 parts by mass or less based on the total 100 parts by mass, the leveling properties of the positive photosensitive resin composition are improved and uneven distribution of the hydrophobic resin (A) is promoted without adversely affecting the cured film after post-baking.

[0166] <Colorant (E)> The positive-type photosensitive resin composition may further contain at least one colorant (E) selected from the group consisting of black dyes and black pigments. Forming black partition walls in an organic electroluminescent (EL) element using a photosensitive resin composition containing the colorant (E) can improve the visibility of display devices such as organic electroluminescent (EL) displays. In this embodiment, the presence of the colorant (E) causes the amount of radiation transmitted during exposure to rapidly decrease from the surface to the interior of the coating. Therefore, the carboxylic acid compound derived from the quinone diazide compound (C) is generated in relatively large amounts near the coating surface but is unlikely to be generated inside the coating. Because the carboxylic acid compound derived from the quinone diazide compound (C) has low diffusibility in the coating, it remains near the coating surface and contributes to promoting dissolution of the exposed coating surface. The interior of the coating has a relatively low concentration of the hydrophobic resin (A), resulting in relatively high alkali solubility. Therefore, even when radiation does not sufficiently penetrate into the interior of the coating, the positive-type photosensitive resin composition of this embodiment can be used to form a thick film pattern with high sensitivity and high precision.

[0167] Examples of black dyes include dyes defined by the color index (CI) of Solvent Black 27 to 47. The black dye is preferably defined by the CI of Solvent Black 27, 29, or 34. When at least one of the dyes defined by the CI of Solvent Black 27 to 47 is used as the black dye, the light-blocking properties of the coating of the cured positive photosensitive resin composition can be maintained. Compared to positive photosensitive resin compositions containing a black dye, positive photosensitive resin compositions leave less colorant residue during development and can form high-definition patterns.

[0168] Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigments, and lactam pigments. Surface-treated versions of these black pigments can also be used. Examples of commercially available perylene pigments include BASF's K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34. Examples of commercially available lactam pigments include BASF's Irgaphor® Black S0100CF. Because of their high light-blocking properties, the black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene pigments, and lactam pigments.

[0169] The content of 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. When the content of colorant (E) is 10 parts by mass or more based on the total 100 parts by mass, sufficient light-blocking properties can be obtained, and particularly when colorant (E) contains a black dye, the light-blocking properties of the cured coating can be maintained. When the content of colorant (E) is 150 parts by mass or less based on the total 100 parts by mass, the film retention rate and sensitivity are appropriate, and particularly when colorant (E) contains a black dye, high heat resistance can be imparted to the coating.

[0170] <Optional ingredients> The positive photosensitive resin composition may contain, as optional components, a dissolution promoter (F), a heat curing agent, a second surfactant other than the fluorine-based surfactant (D), a second colorant other than the colorant (E), etc. In the present disclosure, optional components are defined as those that do not fall into any of (A) to (E).

[0171] <Dissolution promoter (F)> The positive photosensitive resin composition may further contain a dissolution promoter (F) for improving the solubility of the alkali-soluble portion in the developer during development. Examples of the dissolution promoter (F) include organic low-molecular-weight compounds selected from the group consisting of compounds having a carboxy group and compounds having a phenolic hydroxyl group. The dissolution promoter (F) may be used alone or in combination of two or more types.

[0172] In the present disclosure, the term "low molecular weight compound" refers to a compound having a molecular weight of not more than 1000. The organic low molecular weight compound has a carboxy group or multiple phenolic hydroxyl groups and is alkali-soluble.

[0173] Examples of such organic low molecular weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, and mesitylene acid; phthalic acid, isoflurane, and the like. aromatic polycarboxylic acids such as taric acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid, and hemimellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umbellic acid; and aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol.

[0174] The content of the dissolution promoter (F) in the positive photosensitive resin composition can be 0.1 to 50 parts by mass, preferably 1 to 35 parts by mass, and more preferably 2 to 20 parts by mass, based on 100 parts by mass of the total resin components. If the content of the dissolution promoter (F) is 0.1 part by mass or more based on the total 100 parts by mass, the dissolution of the resin components can be effectively promoted, and if it is 50 parts by mass or less, excessive dissolution of the resin components can be suppressed, and the pattern formability and surface quality of the coating can be improved.

[0175] <Thermal hardener> A thermal radical generator can be used as the thermal curing agent. Preferred examples of the thermal radical generator include organic peroxides, specifically organic peroxides having a 10-hour half-life temperature of 100 to 170°C, such as dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

[0176] The content of the heat curing agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the heat curing agent.

[0177] <Second surfactant> The positive-type photosensitive resin composition may contain a second surfactant other than the fluorine-containing surfactant (D) to improve, for example, the coatability, the smoothness of the coating, or the developability of the coating. 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 organosiloxane polymers KP323, KP326, and KP341 (trade names, Shin-Etsu Chemical Co., Ltd.). The second surfactant may be used alone or in combination of two or more.

[0178] The content of the second surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, based on 100 parts by mass of the total solid content excluding the second surfactant. In one embodiment, the positive photosensitive resin composition does not contain a second surfactant.

[0179] <Second colorant> The positive photosensitive resin composition may contain a second colorant other than the colorant (E). Examples of the second colorant include dyes, organic pigments, and inorganic pigments. The second colorant can be used in an amount that does not impair the effects of the present invention, depending on the purpose.

[0180] Examples of dyes 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.

[0181] Examples of pigments include 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.

[0182] [Coating composition] <Solvent (G)> The positive-type photosensitive resin composition can be dissolved or dispersed in a solvent (G) to prepare a coating composition in solution or dispersion. For example, a coating composition containing the positive-type photosensitive resin composition can be prepared by mixing a quinone diazide compound (C), a fluorine-based surfactant (D), and, if necessary, optional components such as a colorant (E), a dissolution promoter (F), a thermosetting agent, and other surfactants in a predetermined ratio with the resulting solution obtained by dissolving a hydrophobic resin (A) and an alkali-soluble resin (B) in a solvent (G). The viscosity of the coating composition can be adjusted to suit the application method used by varying the amount of solvent (G).

[0183] Examples of the solvent (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 of suitable solvents include acetates, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and cyclohexanone, esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone, and amides such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. The solvent (G) can be used alone or in combination of two or more.

[0184] The solid content of the coating composition can be appropriately determined depending on the purpose of use. For example, the solid content of the coating composition may be 1 to 60 mass %, 3 to 50 mass %, or 5 to 40 mass %.

[0185] When a pigment is used, known methods can be used for dispersion and mixing. For example, ball-type mills such as a ball mill, sand mill, bead mill, paint shaker, and rocking mill, blade-type mills such as a kneader, paddle mixer, planetary mixer, and Henschel mixer, and roll-type mills such as a three-roll mixer, as well as Raikai mixers, colloid mills, ultrasonic mixers, homogenizers, and rotation-revolution mixers may be used. From the viewpoints of dispersion efficiency and fine dispersion, it is preferable to use a bead mill.

[0186] The prepared coating composition is usually filtered before use, for example, using a Millipore filter with a pore size of 0.05 to 1.0 μm.

[0187] The coating composition thus prepared also has excellent long-term storage stability.

[0188] [Method of using the positive photosensitive resin composition] When a positive-type photosensitive resin composition is used in radiation lithography, the positive-type photosensitive resin composition is first dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition is applied to a substrate surface, and the solvent is removed by heating or other means to form a coating film. The method for applying the coating composition to the substrate surface is not particularly limited, and for example, spraying, roll coating, slit coating, or spin coating can be used.

[0189] After applying the coating composition to the substrate surface, the solvent is typically removed by heating to form a coating (pre-baking). Heating conditions vary depending on the type and blending ratio of each component, but a coating can typically be obtained by heating at 70 to 130°C for 30 seconds to 20 minutes on a hot plate or 1 to 60 minutes in an oven. In one embodiment, the thickness of the formed coating is 2 to 3 μm.

[0190] Next, the prebaked coating is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation) through a photomask having a predetermined pattern (exposure step). Preferred radiation is ultraviolet light or visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-ray. In another embodiment, the radiation is ghi-ray.

[0191] When the positive-type photosensitive resin composition contains a protective resin as the alkali-soluble resin (B), a post-exposure bake (PEB) can be performed after the exposure step to promote decomposition of the acid-decomposable groups. PEB promotes deprotection of the alkali-soluble functional groups protected in the protective resin in the exposed areas, thereby further increasing the alkali solubility of the exposed areas. The heating conditions vary depending on the types and blending ratios of each component, but PEB can usually be performed by heating at 70 to 140°C, for example, on a hot plate for 30 seconds to 20 minutes, or in an oven for 1 to 60 minutes.

[0192] In one embodiment, the PEB step is not included after the exposure step, which prevents the film from flowing or deforming due to heating, allowing a thick film pattern to be formed with high precision and reducing the number of steps related to the formation of barrier ribs or insulating films.

[0193] After the exposure step or PEB step, the coating is developed by contacting it with a developer to remove unnecessary portions and form a pattern in the coating (development step). Examples of the developer include aqueous solutions of alkaline compounds such as inorganic alkaline compounds (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-propylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline); and cyclic amines (e.g., pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonane). An aqueous solution containing an appropriate amount of a water-soluble organic solvent (e.g., methanol or ethanol), a surfactant, etc., can also be used as the developer. The development time is typically 30 to 180 seconds. The developing method may be any of a puddle method, a shower method, a dipping method, etc. After development, the film is washed with running water for 30 to 90 seconds to remove unnecessary portions, and then air-dried with compressed air or compressed nitrogen, thereby forming a pattern in the film.

[0194] Thereafter, the coating film on which the pattern has been formed can be heat-treated, for example, at 100 to 350°C for 20 to 200 minutes using a heating device such as a hot plate or oven, to obtain a cured coating film (post-baking, heat treatment step). In the heat treatment, the temperature may be maintained constant, or may be increased continuously or stepwise. The heat treatment is preferably carried out in a nitrogen gas atmosphere.

[0195] <Difference in dissolution rate> The positive photosensitive resin composition can form a coating in which the alkali solubility of the coating surface is lower than that of the entire coating. Specifically, the positive photosensitive resin composition is applied so that the film thickness after pre-baking is 3±0.3 μm, and the coating is formed by pre-baking at 125° C. for 120 seconds. Then, the coating is subjected to 30 mJ / cm 2 irradiation. 2 and developed at 23°C with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, the dissolution rate of the surface layer of the coating is lower than the dissolution rate of the entire coating. The dissolution rate of the surface layer of the coating is the average dissolution rate at the time when the coating is dissolved to a thickness of 80%, and the dissolution rate of the entire coating is the average dissolution rate at the time when the coating is dissolved to a thickness of 30%. The average dissolution rates of the surface and entire coating are determined by the procedure described in the Examples. The difference between the dissolution rate of the surface layer of the coating and the dissolution rate of the entire coating is preferably 3 nm / sec or more, more preferably 5 nm / sec or more, and even more preferably 8 nm / sec or more.

[0196] <Remaining film rate> In one embodiment, a positive photosensitive resin composition is applied so that the film thickness after pre-baking is 3±0.3 μm, and the coating is formed by pre-baking at 125° C. for 120 seconds. When the coating is then subjected to alkaline development at a temperature of 23° C. for 60 seconds in a 2.38 mass % aqueous tetramethylammonium hydroxide solution, a photosensitive resin having a viscosity of 1000 ppm or more is obtained. Residual film rate (%) = Film thickness after development (μm) / Film thickness before development (μm) The residual film ratio, defined as: is 90% or more, preferably 95% or more, and more preferably 99% or more. The residual film ratio is an index of the solubility of the unexposed area, and the higher the residual film ratio, the greater the difference in solubility between the exposed area and the unexposed area, making it possible to form a thick film pattern with a large difference in height with high precision.

[0197] <Optical density> In an embodiment in which the positive photosensitive resin composition contains a colorant (E), the optical density (OD value) of the cured film of the positive 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 0.5 or more per 1 μm of film thickness, sufficient light-blocking properties can be obtained.

[0198] In one embodiment, a method for producing an organic EL device partition wall or an organic EL device insulating film includes dissolving or dispersing a positive photosensitive resin composition in a solvent to prepare a coating composition, applying the coating composition to a substrate to form a coating film, removing the solvent contained in the coating and drying the coating, exposing the dried coating to radiation through a photomask, developing the exposed coating by contacting it with a developer to form a pattern in the coating, and heat-treating the patterned coating at a temperature of 100°C to 350°C to form an organic EL device partition wall or an organic EL device insulating film. The above-mentioned PEB can also be performed after exposure and before development. The positive photosensitive resin composition of the present disclosure can form a thick film pattern with high sensitivity and high precision, even in an embodiment in which the positive photosensitive resin composition contains a colorant (E).

[0199] [Organic EL element partition] One embodiment is a partition wall for an organic EL device comprising a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E).

[0200] [Insulating film for organic EL elements] One embodiment is an insulating film for an organic EL device, which contains a cured product of the positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E).

[0201] [Organic EL element] One embodiment is an organic EL device containing a cured product of the positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E). [Example]

[0202] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

[0203] (1) Raw materials The raw materials used in the examples and comparative examples were produced or obtained as follows.

[0204] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were calculated using a calibration curve prepared using a polystyrene standard substance 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℃

[0205] [Production Example 1] Production of alkali-soluble resin (B): copolymer (PCX-01) of polymerizable monomer having alkali-soluble functional group (phenolic hydroxyl group) and other polymerizable monomer 28.0 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA") and 7.89 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Corporation) as a solvent, and 3.66 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (Daicel Corporation). The two resulting solutions were simultaneously added dropwise over 2 hours to 61.2 g of 1-methoxy-2-propyl acetate (Daicel Corporation) heated to 85 °C under a nitrogen gas atmosphere in a 300 mL three-neck flask, and then reacted at 85 °C for 3 hours. The reaction solution was cooled to room temperature and added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 90°C for 4 hours, and 33.4g of white powder was collected. The number average molecular weight of the obtained PCX-01 was 6,600 and the weight average molecular weight was 11,600.

[0206] [Production Example 2] Production of alkali-soluble resin (B): copolymer (PCX-02e) of polymerizable monomer having alkali-soluble functional group (phenolic hydroxyl group) and other polymerizable monomer 25.5 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA") and 4.50 g of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Corporation) as a solvent, and 3.66 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (Daicel Corporation). The two resulting solutions were simultaneously added dropwise over 2 hours to 61.2 g of 1-methoxy-2-propyl acetate (Daicel Corporation) heated to 85 °C under a nitrogen gas atmosphere in a 300 mL three-neck flask, and then reacted at 85 °C for 3 hours. The reaction solution was cooled to room temperature and added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 90°C for 4 hours, yielding 32.4g of white powder. The resulting PCX-02e had a number-average molecular weight of 3100, a weight-average molecular weight of 6700, and a phenolic hydroxyl group equivalent of 210.

[0207] [Production Example 3] Production of Hydrophobic Resin (A): Resin Having Silicon-Containing Groups (PCX-02e-TBDMS34) 15.9 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA"), 16.6 g of 4-tert-butyldimethylsilyloxyphenyl methacrylate (PQMA-TBDMS), and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Corporation) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two resulting solutions were simultaneously added dropwise over 2 hours to 90.5 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89 °C under a nitrogen gas atmosphere in a 300 mL three-neck flask equipped with a reflux condenser. The mixture was then allowed to react 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 collected by filtration and vacuum-dried at 80°C for 5 hours, yielding 9.73 g of a white powder (PCX-02e-TBDMS34). The resulting PCX-02e-TBDMS34 had a number-average molecular weight of 3753 and a weight-average molecular weight of 7581. In PCX-02e-TBDMS34, the molar ratio of the structural units represented by formula (1), (2), and (3), where s is an integer of 1 or greater, was formula (1):formula (2):formula (3) = 32:7:61. Based on the total structural units, the structural units having alkali-soluble functional groups accounted for 61 mol%. The silicon atom content was 4.0 mass% based on the mass of PCX-02e-TBDMS34.

[0208] [Production Example 4] Production of Hydrophobic Resin (A): Resin Having Silicon-Containing Groups (PCX-02e-TES34) 15.9 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA"), 16.6 g of 4-triethylsilyloxyphenyl methacrylate (PQMA-TES), and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Corporation) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two resulting solutions were simultaneously added dropwise over 2 hours to 90.4 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89 °C under a nitrogen gas atmosphere in a 300 mL three-neck flask equipped with a reflux condenser. The mixture was then allowed to react 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 collected by filtration and vacuum-dried at 80 °C for 5 hours, yielding 9.49 g of a white powder (PCX-02e-TES34). The resulting PCX-02e-TES34 had a number-average molecular weight of 3,847 and a weight-average molecular weight of 7,534. In PCX-02e-TES34, the molar ratio of the structural units represented by formula (1), (2), and (3), where s is an integer of 1 or greater, was formula (1):formula (2):formula (3) = 32:7:61. Based on the total structural units, the structural units having alkali-soluble functional groups accounted for 61 mol%. The silicon atom content was 4.0 mass% based on the mass of PCX-02e-TES34.

[0209] [Production Example 5] Production of hydrophobic resin (A): resin having fluorine-containing groups (PCX-02e-C6SFMA36) 12.1 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA"), 20.5 g of 2-perfluorohexylethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), and 3.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 84.5 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 3.74 g of V-601 (Fujifilm Wako Pure Chemical Industries Co., Ltd.) as a polymerization initiator was completely dissolved in 14.9 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two resulting solutions were simultaneously added dropwise over 2 hours to 51.0 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89 °C under a nitrogen gas atmosphere in a 300 mL three-neck flask equipped with a reflux condenser. The mixture was then allowed to react 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 collected by filtration and vacuum-dried at 80°C for 5 hours, yielding 5.58 g of a white powder (PCX-02e-C6SFMA36). The resulting PCX-02e-C6SFMA36 had a number-average molecular weight of 2,869 and a weight-average molecular weight of 5,743. In PCX-02e-C6SFMA36, the molar ratio of structural units derived from 2-perfluorohexylethyl methacrylate, structural units represented by formula (2), and structural units represented by formula (3) was 36:6:58, and the structural units having alkali-soluble functional groups accounted for 58 mol% of the total structural units. The fluorine atom content was 24 mass% based on the mass of PCX-02e-C6SFMA36.

[0210] [Production Example 6] Production of alkali-soluble resin (B): resin (PCX-02e-THF28) in which alkali-soluble functional groups (phenolic hydroxyl groups) are protected with 2-tetrahydrofuranyl groups In a 100 mL three-neck flask, 10.0 g of PCX-02e from Preparation Example 2 and 0.60 g of pyridinium salt of p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.) as an acid catalyst were dissolved in 50.0 g of tetrahydrofuran (Fujifilm Wako Pure Chemical Industries Co., Ltd.). The mixture was then ice-cooled under a nitrogen gas atmosphere, and 2.34 g of 2,3-dihydrofuran (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. The mixture was then stirred at room temperature for 4 hours. The acid catalyst was neutralized with a saturated aqueous solution of sodium bicarbonate, and the aqueous layer was removed. The organic layer was further washed twice with water. The tetrahydrofuran was then distilled off. The resulting solid was dissolved in 50.0 g of ethyl acetate and added dropwise to 200 g of toluene to precipitate the product. The precipitate was collected by filtration and dried under vacuum at 80°C for 4 hours, yielding 10.0 g of a white powder. The resulting powder was dissolved in propylene glycol monomethyl ether acetate to obtain a 20% solids solution of a resin (PCX-02e-THF28) in which alkali-soluble functional groups (phenolic hydroxyl groups) were protected with 2-tetrahydrofuranyl groups. The resulting PCX-02e-THF28 had a number-average molecular weight of 3700, a weight-average molecular weight of 6800, 28 mol% of phenolic hydroxyl groups protected with acid-labile groups, and 25% of the total number of structural units of PCX-02e-THF28. The proportion of phenolic hydroxyl groups protected by acid-decomposable groups was calculated using a thermogravimetric differential thermal analyzer (TG / DTA6200, Hitachi High-Tech Science Corporation) by heating the resin from room temperature to 250°C at a heating rate of 10°C / min in a nitrogen gas flow, holding the temperature for 10 minutes, and then heating it further to 400°C at a heating rate of 10°C / min. The weight loss (%) of the resin at 260°C was then calculated.

[0211] [Production Example 7] Production of alkali-soluble resin (B): resin having epoxy groups and phenolic hydroxyl groups (N695OH70) A 300 mL three-neck flask was charged with 75.2 g of γ-butyrolactone (Mitsubishi Chemical Corporation) as a solvent and 37.8 g of EPICLON® N-695 (DIC Corporation, cresol novolac epoxy resin, epoxy equivalent weight 214) as a compound containing at least two epoxy groups per molecule, and dissolved under a nitrogen gas atmosphere at 60°C. 20.1 g (0.65 equivalents per epoxy equivalent) of 3,5-dihydroxybenzoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound and 0.166 g (0.660 mmol) of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) as a reaction catalyst were added, and the mixture was allowed to react at 110°C for 21 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solids content of 20% by mass, and filtered to obtain 274.2 g of a resin solution having epoxy groups and phenolic hydroxyl groups (N695OH70). The resulting reaction product had a number-average molecular weight of 3,000, a weight-average molecular weight of 5,100, an epoxy equivalent of 2,200, and a phenolic hydroxyl equivalent of 161.

[0212] [Hydrophobic resin (A)] As the hydrophobic resin (A), PCX-02e-TBDMS34 of Production Example 3, PCX-02e-TES34 of Production Example 4 (resins having silicon-containing groups), and PCX-02e-C6SFMA36 of Production Example 5 (resin having fluorine-containing groups) were used.

[0213] [Alkali-soluble resin (B)] As the alkali-soluble resin (B), PCX-02e-THF28 of Production Example 6, PCX-01 of Production Example 1, PCX-02e of Production Example 2, N695OH70 of Production Example 7, and EPICLON (registered trademark) N-695 (DIC Corporation, cresol novolac epoxy resin, epoxy equivalent weight 214) were used.

[0214] [Quinone diazide compounds (C)] As the quinone diazide compound (C), TS-150A and TS-200A (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), Toyo Gosei Co., Ltd.); TPPA(4)-150DF (4,4'-[ The compounds used were 1,2-naphthoquinone diazide-4-sulfonic acid ester of 1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA), manufactured by Toyo Gosei Co., Ltd.; and THDPP-280 (1,2-naphthoquinone diazide-5-sulfonic acid ester of 2-(4-hydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, manufactured by Toyo Gosei Co., Ltd.).

[0215] The structures of TS-150A and TS-200A are shown below. TS-150A has three R groups per molecule, of which an average of 1.5 have a quinone diazide structure. TS-200A has three R groups per molecule, of which an average of 2.0 have a quinone diazide structure. [ka]

[0216] [Fluorosurfactant (D)] As the fluorosurfactant (D), Megafac (registered trademark) F-562, Megafac (registered trademark) F-554, Megafac (registered trademark) R-40, Megafac (registered trademark) F-563, and Megafac (registered trademark) F-559 (all manufactured by DIC Corporation) were used.

[0217] Another surfactant used was KF2201 (a silicone surfactant, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0218] [Colorant (E)] As colorants, black dyes VALIFAST (registered trademark) BLACK 3820 (a black dye specified by the CI of Solvent Black 27, Orient Chemical Industry Co., Ltd., "VB3820" in Table 1) and VALIFAST (registered trademark) BLACK 3804 (a black dye specified by the CI of Solvent Black 34, Orient Chemical Industry Co., Ltd., "VB3804" in Table 1) were used.

[0219] [Solubility enhancer (F)] Phloroglucinol was used as the solubility enhancer (F).

[0220] [Solvent (G)] As the solvent (G), a mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA=40:60 (mass ratio)) was used.

[0221] (2) Evaluation method The evaluation methods used in the examples and comparative examples are as follows.

[0222] [Alkali dissolution rate] A glass substrate (100 mm × 100 mm × 1 mm) was bar-coated with a positive photosensitive resin composition to a dry film thickness of 3 ± 0.3 μm, and after vacuum drying at room temperature for 60 seconds, the substrate was pre-baked by heating on a hot plate with a lid at 125 °C for 120 seconds to remove the solvent. The dry film thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.), and then exposed to 30 mJ / cm with an exposure device (product name Multilight ML-251A / B, Ushio Inc.) equipped with an ultra-high pressure mercury lamp. 2The exposure was performed under the following conditions. The exposure dose was measured using an ultraviolet integrating actinometer (product name UIT-150, light-receiving part UVD-S365, Ushio Inc.). The film was then developed using a spin developer (AD-1200, Takizawa Sangyo Co., Ltd.) with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C, and the film thickness after development was measured using an optical film thickness measuring device. By varying the development time during alkaline development, the development time required for the film thickness of the exposed area to decrease to 80% or 30% was obtained. The amount of film loss after development (nm) was divided by the development time (seconds) to obtain the alkaline dissolution rate (nm / second). The alkaline dissolution rate at which the film thickness of the exposed area had decreased to 80% was defined as the average dissolution rate of the surface layer of the film, and the alkaline dissolution rate at which the film thickness of the exposed area had decreased to 30% was defined as the average dissolution rate of the entire film.

[0223] [sensitivity] A glass substrate (100 mm × 100 mm × 1 mm) was bar-coated with a positive-type photosensitive resin composition to a dry film thickness of 3.0 μm. After 60 seconds of vacuum drying at room temperature, the composition was prebaked by heating on a lidded hot plate at 125°C for 120 seconds. The coating was exposed to light through a quartz photomask (with a φ10 μm opening pattern) using an exposure system (product name: Multilight ML-251A / B, Ushio Inc.) equipped with an ultra-high pressure mercury lamp. The exposure dose was measured using an ultraviolet integrating actinometer (product name: UIT-150, photoreceptor UVD-S365, Ushio Inc.). After exposure, the coating was subjected to alkaline development for 60 seconds using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide using a spin-on developer (AD-1200, Takizawa Sangyo Co., Ltd.). The above procedure was repeated while varying the exposure dose to determine the minimum exposure dose (mJ / cm) required to form a pattern with a hole diameter of 10 μm that completely penetrated the glass substrate after development. 2 ) was used as the sensitivity.

[0224] [Solubility of unexposed areas] A glass substrate (100 mm x 100 mm x 1 mm) was bar-coated with a positive photosensitive resin composition to a dry film thickness of 3.0 μm. The substrate was vacuum dried at room temperature for 60 seconds, and then pre-baked by heating on a lidded hot plate at 125°C for 120 seconds. The dry film thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.). The substrate was then subjected to alkaline development for 60 seconds using a spin development device (AD-1200, Takizawa Sangyo Co., Ltd.) with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. The film thickness after alkaline development was again measured using the optical film thickness measurement device (F20-NIR, Filmetrics Inc.), and the film thickness (μm) dissolved before and after development was used as an index of unexposed area solubility. A solubility of 0 μm in the unexposed area was determined by the following formula: Residual film rate (%) = Film thickness after development (μm) / Film thickness before development (μm) This is equivalent to a remaining film rate defined as 100%.

[0225] [OD value of cured film] A positive photosensitive resin composition was spin-coated onto a glass substrate (100 mm × 100 mm × 1 mm) to a dry film thickness of approximately 1.5 μm, and pre-baked by heating on a hot plate at 125°C for 120 seconds. A coating was then obtained by curing at 250°C for 60 minutes in a nitrogen gas atmosphere. The OD value of the cured coating was measured using a transmission densitometer (BMT-1, Sakata Inx Engineering Co., Ltd.), corrected for the OD value of the glass alone, and converted to an OD value per 1 μm of coating thickness. The coating thickness was measured using an optical film thickness measurement device (F20-NIR, Filmetrics Inc.).

[0226] (3) Preparation and evaluation of positive photosensitive resin compositions [Examples 1 to 14, Comparative Examples 1 and 2] The resin components were mixed and dissolved in a solvent (G) according to the composition shown in Table 1 to obtain a solution, to which the quinone diazide compound (C), fluorine-containing surfactant (D) or other surfactant, colorant (E), and dissolution promoter (F) shown in Table 1 were added and further mixed. After visually confirming that the components had dissolved, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a positive photosensitive resin composition with a solids concentration of 12 mass %. The parts by mass of the compositions in Table 1 are values ​​calculated as solids. The evaluation results of the positive photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 and 2 are shown in Table 1. The positive photosensitive resin composition of Comparative Example 2 was not evaluated because repellency occurred during application and a pattern could not be formed.

[0227] From the evaluation results in Table 1, it was determined that the positive photosensitive resin compositions of Examples 1 to 14 could increase the contrast between exposed and unexposed areas and form thick film patterns with high precision, since the solubility of the unexposed areas was 0 μm. Furthermore, the exposure dose required to form a pattern with a hole diameter of 10 μm after development was 300 mJ / cm. 2 It was also confirmed that the sensitivity was high.

[0228] [Table 1-1]

[0229] [Table 1-2]

[0230] To confirm the concentration distribution of the hydrophobic resin (A) in the thickness direction, sputtering was performed on the coating surfaces of Examples 4, 6, and 7, followed by XPS analysis. Figure 1 shows a chart showing the sputtering time (horizontal axis) and silicon element concentration (vertical axis) of the coatings of Examples 4, 6, and 7 obtained by XPS analysis. The apparatus and measurement conditions used for the XPS analysis were as follows. [Device] Equipment: Quantera II (ULVAC-PHI, Inc.) X-ray: Aluminum monochromatic 100 μm, 25 W, 15 kV Analysis area: 100μm (Spot) Electron / ion neutralization gun: ON Photoelectron take-off angle: 45 degrees [Measurement conditions] Depth profile Ar2500+ (argon gas cluster beam: GCIB) acceleration voltage and cluster area: 5kV, 17nA, 2×2mm Pass Energy: 224 eV Step: 0.1 eV Dwell: 20ms Sweep time:C,O(2);F(4);Si,Cr,N,S(10) Sputtering interval: 0.25 min x 4 cycles / 1 min x 5 cycles / 3 min x 8 cycles Sample fixing: Copper clip For binding energy correction, the CC and CH peaks of the C1s spectrum were set to 284.6 eV.

[0231] In Examples 4, 6, and 7, the silicon concentration was high near the surface of the coating and decreased toward the interior of the coating, suggesting that the hydrophobic resin (A), PCX-02e-TBDMS34, was unevenly distributed on the surface of the coating during coating formation. [Industrial Applicability]

[0232] The positive photosensitive resin composition according to the present disclosure can be suitably used in radiation lithography to form partition walls or insulating films of organic EL devices. In particular, an organic EL device having a partition wall or insulating film formed from the positive photosensitive resin composition of an embodiment containing colorant (E) is suitably used as an electronic component of a display device exhibiting good contrast.

Claims

1. a hydrophobic resin (A); an alkali-soluble resin (B); a quinone diazide compound (C); Fluorine-based surfactant (D), The positive photosensitive resin composition is applied so that the film thickness after pre-baking is 3±0.3 μm, and the composition is pre-baked at 125° C. for 120 seconds to form a film, and then the composition is applied with an electric current of 30 mJ / cm ２ and developing at a temperature of 23°C with a 2.38 mass% aqueous tetramethylammonium hydroxide solution, the dissolution rate of the surface layer of the coating is lower than the dissolution rate of the entire coating, the dissolution rate of the surface layer of the coating being the average dissolution rate at the time when the coating has been dissolved to a thickness of 80%, and the dissolution rate of the entire coating being the average dissolution rate at the time when the coating has been dissolved to a thickness of 30%.

2. 2. The positive photosensitive resin composition according to claim 1, wherein the difference between the dissolution rate of the surface layer of the coating and the dissolution rate of the entire coating is 3 nm / sec or more.

3. 3. The positive photosensitive resin composition according to claim 1, wherein the hydrophobic resin (A) is a resin having at least one group selected from the group consisting of a silicon-containing group and a fluorine-containing group.

4. The hydrophobic resin (A) is represented by the formula (1) 【Chemistry 1】 (In formula (1), R １ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２ is SiR ３ R ４ R ５ and R ３ , R ４ and R ５ 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 of 0 to 5, and s is an integer of 0 to 5, with the proviso that r+s is an integer of 1 to 5.

4. The positive photosensitive resin composition according to claim 3, which has a structural unit represented by formula (1): wherein s is an integer of 1 or more.

5. The hydrophobic resin (A) is represented by the formula (2) 【Chemistry 2】 (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 ８ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The positive photosensitive resin composition according to claim 4, further comprising a structural unit represented by the following formula:

6. 3. The positive photosensitive resin composition according to claim 1, wherein the fluorosurfactant (D) comprises an acrylic copolymer having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group.

7. 3. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) comprises a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer, a resin having an epoxy group and a phenolic hydroxyl group, or a combination thereof.

8. 3. The positive photosensitive resin composition according to claim 1, further comprising at least one colorant (E) selected from the group consisting of black dyes and black pigments.

9. 9. The positive photosensitive resin composition according to claim 8, wherein the colorant (E) is contained in an amount of 10 parts by mass to 150 parts by mass based on 100 parts by mass of the total of the resin components.

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

11. A partition wall for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2.

12. An insulating film for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2.

13. An organic EL device comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2.

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