Positive photosensitive resin composition

Abstract

A positive-acting photosensitive resin composition containing: a hydrophobic resin (A), which is an addition (co)polymer; an alkali-soluble resin (B) having a structural unit represented by formula (1); a quinone diazide compound (C); a fluorine-based surfactant (D); and a cresol novolak resin (In formula (1), x represents an integer of 0 to 3, each R1 independently represents a C1 to C5 alkyl group, and R2 represents an organic group having an alkali-soluble functional group).

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] To form a stepped pattern with high precision, it is important to suppress the occurrence of surface roughness and pores in the stepped portions (intermediately exposed portions) in addition to ensuring a large difference in solubility between the exposed and unexposed portions. The present inventors discovered that in a positive-type photosensitive resin composition containing a quinone diazide compound as a radiation-sensitive compound, the alkali solubility of the coating surface can be relatively reduced by combining a hydrophobic resin that is an addition (co)polymer, an alkali-soluble resin having a novolac skeleton, and a fluorine-based surfactant as resin components, thereby increasing the contrast between the exposed and unexposed portions. However, there is still room for improvement in the surface smoothness of the stepped portions.

[0017] 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]

[0018] The present inventors have found that by adding a cresol novolac resin to a positive-type photosensitive resin composition containing a quinone diazide compound as a radiation-sensitive compound, a hydrophobic resin that is an addition (co)polymer and an alkali-soluble resin having a novolac skeleton as resin components, and a fluorine-containing surfactant, it is possible to suppress surface roughness and the generation of pores in stepped portions, and as a result, it is possible to form a thick film pattern with high precision.

[0019] That is, the present invention includes the following aspects. [1] a hydrophobic resin (A) which is an addition (co)polymer; an alkali-soluble resin (B) having a structural unit represented by formula (1); a quinone diazide compound (C); a fluorosurfactant (D); Cresol novolac resin A positive photosensitive resin composition comprising: [ka] (In formula (1), x is an integer of 0 to 3, and R 1 are each independently an alkyl group having 1 to 5 carbon atoms, and R 2 is an organic group having an alkali-soluble functional group. [2] The positive photosensitive resin composition according to [1], wherein the alkali-soluble functional group in the formula (1) is a phenolic hydroxyl group. [3] The positive photosensitive resin composition according to [1] or [2], wherein the alkali-soluble resin (B) further has a structural unit represented by formula (2). [ka] (In formula (2), y is an integer of 0 to 3, and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, and R 4 is an organic group that does not have an alkali-soluble functional group. [4] In the formula (2), R 4 is an organic group having an epoxy group. [5] The positive photosensitive resin composition according to [3] or [4], wherein the alkali-soluble resin (B) contains the structural units represented by the formula (1) and the structural units represented by the formula (2) in a total amount of 30 mol % to 100 mol % based on all structural units of the alkali-soluble resin (B). [6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the cresol novolac resin has a weight average molecular weight (Mw) of 500 to 17,500. [7] The positive photosensitive resin composition according to any one of [1] to [6], wherein the cresol novolac resin is contained in an amount of 0.5% by mass to 35% by mass based on the total mass of the resin components. [8] The positive photosensitive resin composition according to any one of [1] to [7], wherein the 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. [9] The hydrophobic resin (A) is represented by the formula (3) [ka] (In formula (3), R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 6 is SiR 7 R 8 R 9 and R 7 , R 8 and R 9are 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 (3) in which s is an integer of 1 or more.

[10] The hydrophobic resin (A) is represented by the formula (4) [ka] (In formula (4), R 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 12 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 [9], further comprising a structural unit represented by the following formula:

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

[10] , 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.

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

[11] , further comprising an alkali-soluble resin which is a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer and does not have a structural unit represented by formula (1).

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

[12] , further comprising at least one colorant (E) selected from the group consisting of black dyes and black pigments.

[14] The positive photosensitive resin composition according to

[13] , comprising 10 to 150 parts by mass of the colorant (E) based on 100 parts by mass of the total of the resin components.

[15] The positive photosensitive resin composition according to

[13] or

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

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

[15] .

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

[15] .

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

[15] . [Effects of the Invention]

[0020] 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]

[0021] [Figure 1] 1A is an FE-SEM image of the surface of a sample of Comparative Example 1, and FIG. 1B is an FE-SEM image of the surface of a sample of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention will be described in detail below.

[0023] In this specification, when "to" is used to describe a range of values, the values ​​at both ends are the upper and lower limits, respectively, and are included in the range.

[0024] In this disclosure, "alkali-soluble" means that a positive photosensitive resin composition or a component thereof, 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. An "alkali-soluble functional group" refers to a group capable of imparting such alkali-solubility to a positive photosensitive resin composition or a component thereof, 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.

[0025] 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.

[0026] 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]

[0027] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)allyl" means allyl or methallyl.

[0028] In the present disclosure, "(co)polymer" means a homopolymer or a copolymer.

[0029] 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).

[0030] 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

[0031] 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

[0032] In this disclosure, the term "resin component" refers to the hydrophobic resin (A), the alkali-soluble resin (B), the cresol novolac resin, and the copolymer having an alkali-soluble functional group that is optionally contained. The component corresponding to the fluorosurfactant (D) is not included in the hydrophobic resin (A), the alkali-soluble resin (B), and the copolymer having an alkali-soluble functional group that is optionally contained.

[0033] In the present disclosure, the term "solid content" refers to the total mass of components including the hydrophobic resin (A), the alkali-soluble resin (B), the quinone diazide compound (C), the fluorine-based surfactant (D), and the cresol novolac resin, as well as optional components such as the copolymer having an alkali-soluble functional group, the colorant (E), and the dissolution promoter (F), excluding the liquid solvent (G).

[0034] [Positive-type photosensitive resin composition] A positive-type photosensitive resin composition according to one embodiment comprises a hydrophobic resin (A) that is an addition (co)polymer, an alkali-soluble resin (B) having a structural unit represented by formula (1), a quinone diazide compound (C), a fluorine-containing surfactant (D), and a cresol novolac resin. [ka] (In formula (1), x is an integer of 0 to 3, and R 1 are each independently an alkyl group having 1 to 5 carbon atoms, and R 2 is an organic group having an alkali-soluble functional group.

[0035] <Hydrophobic resin (A)> The hydrophobic resin (A) (also simply referred to as hydrophobic resin (A)), which is an addition (co)polymer, is a resin whose uneven distribution on the coating surface is promoted by the fluorosurfactant (D), making the coating surface of a positive-tone photosensitive resin composition less soluble in an alkaline aqueous solution. 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 coating formation process 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 alkaline 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.

[0036] The hydrophobic resin (A) is not particularly limited as long as it is an addition (co)polymer, and may be a radical (co)polymer, a cationic (co)polymer, or anionic (co)polymer. Examples of the hydrophobic resin (A) include olefin (co)polymers, (meth)acrylic (co)polymers, styrene (co)polymers, acrylamide (co)polymers, acrylonitrile (co)polymers, N-substituted maleimide (co)polymers, 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 obtained by converting some or all of the alkali-soluble functional groups into groups having the hydrophobic groups, using a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group as the base resin. The hydrophobic resin (A) may be used alone or in combination of two or more types.

[0037] 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.

[0038] Examples of the silicon-containing group include a silyl group substituted with an aliphatic hydrocarbon group or an aryl group, a group having a cyclic siloxane structure, and a group having a silsesquioxane structure.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] Examples of groups having a cyclic siloxane structure include a pentamethylcyclotrisilyloxy group, a heptamethylcyclotetrasilyloxy group, and a nonamethylcyclopentasilyloxy group.

[0046] 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.

[0047] Examples of the fluorine-containing group include a fluorine-substituted alkyl group, a fluorine-substituted aryl group, and a fluoroacryloyl group.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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. When producing the hydrophobic resin (A) by radical polymerization, a polymerization initiator and a RAFT (Reversible Addition Fragmentation Transfer) agent can be used as needed. Examples of polymerizable functional groups possessed by the polymerizable monomer having a hydrophobic group and other polymerizable monomers 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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 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.

[0058] 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.

[0059] As a polymerizable monomer having a hydrophobic group, after polymerization, [ka] (In formula (3), R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 6 is SiR 7 R 8 R 9 and R 7 , R 8 and R 9 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. 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.5 is preferably a hydrogen atom or a methyl group. 7 , R 8 , and R 9 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.

[0060] Other polymerizable monomers include those represented by the formula (4) after polymerization. [ka] (In formula (4), R 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 12 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. 10 and R 11 is preferably a hydrogen atom. 12 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.

[0061] Other polymerizable monomers having an alkali-soluble functional group include those represented by the formula (5) after polymerization. [ka] (In equation (5), R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. 13 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.

[0062] In one embodiment, the hydrophobic resin (A) is represented by the formula (3): [ka] (In formula (3), R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 6 is SiR 7 R 8 R 9 and R 7 , R 8 and R 9 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 (3) in which s is an integer of 1 or greater.

[0063] In this embodiment, the hydrophobic resin (A) is represented by the formula (4): [ka] (In formula (4), R 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 12is 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.

[0064] In this embodiment, the hydrophobic resin (A) is represented by the formula (5): [ka] (In equation (5), R 13 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:

[0065] In the hydrophobic resin (A), the molar ratio of the structural units represented by formula (3), where s is an integer of 1 or more, to the structural units represented by formula (4), and to the structural units represented by formula (5) is preferably formula (3):formula (4):formula (5)=5-60:3-10:20-90, and more preferably formula (3):formula (4):formula (5)=6-50:4-9:30-85.

[0066] 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.

[0067] When the hydrophobic resin (A) has a silicon-containing group, the silicon atom content is preferably 1.0 to 10% by mass, more preferably 3.0 to 8.0% by mass, based on the mass of the hydrophobic resin (A). The hydrophobic resin (A) having a silicon-containing group contains structural units having the silicon-containing group in an amount of preferably 3 to 60% by mol, more preferably 5 to 50% by mol, based on the total structural units of the hydrophobic resin (A).

[0068] 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).

[0069] 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.

[0070] 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.

[0071] In one embodiment, the positive-type photosensitive resin composition contains 1% by mass to 50% by mass, preferably 2% by mass to 40% by mass, and more preferably 3% by mass to 30% by mass of hydrophobic resin (A) based on 100% by mass of solids. When the content of hydrophobic resin (A) is 1% 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.

[0072] The positive-type photosensitive resin composition preferably contains 1% by mass to 50% by mass, more preferably 3% by mass to 45% by mass, and even more preferably 5% by mass to 40% by mass of the hydrophobic resin (A) based on the total mass of the resin components. When the content of the hydrophobic resin (A) is 1% 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 the hydrophobic resin (A) is 50% by mass or less based on the total mass of the resin components, 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] <Alkali-soluble resin (B)> The alkali-soluble resin (B) has a structural unit represented by formula (1). [ka] In formula (1), x is an integer of 0 to 3, and R 1 are each independently an alkyl group having 1 to 5 carbon atoms, and R2 is an organic group having an alkali-soluble functional group. x is preferably 0 or 1. R 1 is preferably a methyl group. 2 is not particularly limited, but is preferably an organic group having an alkali-soluble functional group and including an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylene group, an alkenylene group, an alkynylene group, an ester group, an ether group, a carbonyl group, an arylene group, an amino group, an imino group, an imido group, an amide group, a heterocyclic group, a sulfonyl group, or a combination of two or more of these groups. 2 R is an organic group consisting of an alkali-soluble functional group and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylene group, an alkenylene group, an alkynylene group, an ester group, an ether group, a carbonyl group, an arylene group, an amino group, an imino group, an imide group, an amide group, a heterocyclic group, a sulfonyl group, or a combination of two or more of these groups. 2 The number of carbon atoms in R is, for example, 1 to 30, and preferably 2 to 25. The alkali-soluble functional group is not particularly limited, but examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfo group, a phosphate group, an acid anhydride group, and a mercapto group, and a phenolic hydroxyl group is preferred. 2 is preferably an organic group having one or more phenolic hydroxyl groups, and more preferably an organic group represented by -CHCH(OH)CH-O-(C=O)-X (X represents a phenyl group substituted with one or more hydroxyl groups).

[0074] The alkali-soluble resin (B) may have two or more types of alkali-soluble functional groups, and may be used alone or in combination of two or more types.

[0075] The alkali-soluble resin (B) preferably contains the structural unit represented by formula (1) in an amount of 20 mol% to 95 mol%, more preferably 25 mol% to 90 mol%, and even more preferably 30 mol% to 85 mol%, based on the total structural units of the alkali-soluble resin (B). If the amount is 20 mol% or more, alkali solubility is sufficiently exhibited and no residue problems occur at the bottom of the pattern. If the amount is 95 mol% or less, the solubility of the unexposed area is not affected.

[0076] The alkali-soluble resin (B) may contain structural units other than the structural unit represented by formula (1). Examples of the structural units include structural units represented by the following formula (2). [ka] (In formula (2), y is an integer of 0 to 3, and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, and R 4 is an organic group that does not have an alkali-soluble functional group. In formula (2), y is preferably 0 or 1. 3 is preferably a methyl group. 4 R is preferably an organic group containing an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylene group, an alkenylene group, an alkynylene group, an ester group, an ether group, a carbonyl group, an arylene group, an amino group, an imino group, an imido group, an amide group, a heterocyclic group, a sulfonyl group, or a combination of two or more of these groups. 4 The organic group R may be a monovalent group or a polyvalent group, and in the case of a polyvalent group, it means that it is bonded to other parts of the alkali-soluble resin (B) to form a crosslinked structure. 4 The number of carbon atoms in R is, for example, 1 to 30, preferably 1 to 20, and more preferably 2 to 10. 4 is preferably an organic group having a heterocyclic group, and more preferably an organic group having an epoxy group. 4 is preferably an organic group (glycidyl group) represented by -CH2-Y (Y represents an epoxy group).

[0077] The alkali-soluble resin (B) preferably contains the structural units represented by formula (1) and the structural units represented by formula (2) in a total amount of 30 mol % to 100 mol %, more preferably 40 mol % to 100 mol %, and even more preferably 50 mol % to 100 mol %, based on the total structural units of the alkali-soluble resin (B). When the amount is 30 mol % or more, the effect of improving the compatibility between the hydrophobic resin (A) and the alkali-soluble resin (B) by adding the cresol novolac resin to the resin component can be sufficiently obtained.

[0078] The alkali-soluble resin (B) is a compound represented by the formula (1) R 2 is an organic group having a phenolic hydroxyl group. Examples of such alkali-soluble resin (B) include resins in which an organic group having a phenolic hydroxyl group has been introduced into a novolac epoxy resin such as a phenol novolac epoxy resin or a cresol novolac epoxy resin. Novolac epoxy resins are resins in which a glycidyl group has been introduced into the hydroxyl group moiety of a phenol novolac or cresol novolac. A novolac epoxy resin in which an organic group having a phenolic hydroxyl group has been introduced may have an alkali-soluble functional group other than a phenolic hydroxyl group.

[0079] When the alkali-soluble resin (B) contains a structural unit represented by formula (1) and a structural unit represented by formula (2), the alkali-soluble resin (B) is 2 is a structural unit in which R in formula (2) is an organic group having a phenolic hydroxyl group 4 It is more preferable that the alkali-soluble resin (B) contains a structural unit in which R in formula (1) is an organic group having an epoxy group. 2 is an organic group represented by -CHCH(OH)CH-O-(C=O)-X (X represents a phenyl group substituted with one or more hydroxyl groups), and R in formula (2) 4 is an organic group represented by -CH2-Y (Y represents an epoxy group).

[0080] Such an alkali-soluble resin (B) can be obtained by reacting a portion of the epoxy groups of a novolac epoxy resin with the carboxyl groups of a hydroxybenzoic acid compound (hereinafter, this resin may be referred to as a "resin having epoxy groups and phenolic hydroxyl groups"). This resin has unreacted epoxy groups derived from the novolac epoxy resin and phenolic hydroxyl groups derived from the hydroxybenzoic acid compound. Because this resin is thermosetting, it is common knowledge among those skilled in the art that its structure cannot be unambiguously described due to differences in the presence or absence of epoxy groups, the type of functional group, the degree of polymerization, etc. The epoxy groups of the resin having 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 and heat resistance of the coating. Because the phenolic hydroxyl groups contribute to solubility in an aqueous alkaline solution during development, the resin having epoxy groups and phenolic hydroxyl groups also functions as a dissolution promoter for other resins when exposed to low light exposure, thereby improving the sensitivity of the photosensitive resin composition.

[0081] The following reaction formula 1 shows an example of a reaction in which one of the epoxy groups of a novolac epoxy resin reacts with a carboxy group of a hydroxybenzoic acid compound to produce a resin having an epoxy group and a phenolic hydroxyl group. [ka]

[0082] An example of the structure of a novolac type epoxy resin is shown in formula (6). In formula (6), R 14 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m is an integer of 1 to 50. [ka]

[0083] 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.).

[0084] The novolac epoxy resin is preferably at least one selected from the group consisting of phenol novolac epoxy resins and cresol novolac epoxy resins, and more preferably cresol novolac epoxy resins. A positive photosensitive resin composition containing a resin having an epoxy group and a phenolic hydroxyl group derived from a novolac epoxy resin, particularly a cresol novolac epoxy resin, has excellent pattern formability, easy adjustment of alkali solubility, and little outgassing.

[0085] 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.

[0086] In one embodiment, the alkali-soluble resin (B) is a reaction product of a novolac epoxy resin and a hydroxybenzoic acid compound, and is represented by the formula (7): [ka] (In formula (7), b is an integer of 1 to 5, and * represents a bond to a residue of the novolac epoxy resin excluding the epoxy group involved in the reaction.)

[0087] In the method for obtaining the alkali-soluble resin (B) from a novolac epoxy resin 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 novolac epoxy resin, preferably 0.3 to 0.9 equivalents, and more preferably 0.4 to 0.8 equivalents. If the amount of the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and if it is 0.95 equivalents or less, an increase in molecular weight due to side reactions can be suppressed.

[0088] A catalyst may be used to promote the reaction between the epoxy groups of the novolac epoxy resin and the carboxyl groups of 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 novolac epoxy resin 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.

[0089] The number-average molecular weight (Mn) of the alkali-soluble resin (B) 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 alkali-soluble resin (B) is preferably 500 to 30,000, more preferably 2,000 to 25,000, and even more preferably 3,000 to 20,000. When the number-average molecular weight is 500 or more, or when 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. When the number-average molecular weight is 8,000 or less, or when the weight-average molecular weight is 30,000 or less, the coatability and alkali developability are good.

[0090] When the alkali-soluble resin (B) is a resin having an epoxy group and a phenolic hydroxyl group, its epoxy equivalent is preferably 300 to 7,000, more preferably 400 to 6,000, and even more preferably 500 to 5,000. 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 7,000 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.

[0091] In one embodiment, the positive photosensitive resin composition contains 5% to 60% by mass, preferably 10% to 50% by mass, and more preferably 15% to 40% by mass of the alkali-soluble resin (B) based on 100% by mass of the solid content. When the content of the alkali-soluble resin (B) is 5% by mass or more based on 100% by mass of the solid content, phase separation from the hydrophobic resin (A) is maintained and uneven distribution of the hydrophobic resin (A) on the surface is not hindered. When the content of the alkali-soluble resin (B) is 60% by mass or less based on 100% by mass of the solid content, phase separation from the hydrophobic resin (A) is maintained and uneven distribution of the hydrophobic resin (A) on the surface is not hindered and the solubility of the unexposed area is not affected.

[0092] The positive-type photosensitive resin composition preferably contains 15% by mass to 80% by mass, more preferably 20% by mass to 75% by mass, and even more preferably 25% by mass to 70% by mass of the alkali-soluble resin (B) based on the total mass of the resin components. When the content of the alkali-soluble resin (B) is 15% by mass or more based on the total mass of the resin components, phase separation from the hydrophobic resin (A) is maintained and the hydrophobic resin (A) is not hindered from being unevenly distributed on the surface. When the content of the alkali-soluble resin (B) is 80% by mass or less based on the total mass of the resin components, phase separation from the hydrophobic resin (A) is maintained and the hydrophobic resin (A) is not hindered from being unevenly distributed on the surface and the solubility of the unexposed area is not affected.

[0093] <Alkali-soluble resin which is a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer and does not have a structural unit represented by formula (1)> In one embodiment, the positive photosensitive resin composition may further contain an alkali-soluble resin (also simply referred to as a "copolymer having an alkali-soluble functional group") which is a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer and does not have a structural unit represented by formula (1).

[0094] Examples of the alkali-soluble functional group contained in the 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. A 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 contained in the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer include radical polymerizable functional groups such as CH═CH—, CH═C(CH)—, CH═CHCO—, CH═C(CH)CO—, and —OC—CH═CH—CO—.

[0095] 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.

[0096] A 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 and another polymerizable monomer. When producing a copolymer having an alkali-soluble functional group by radical polymerization, a polymerization initiator and a RAFT (Reversible Addition Fragmentation Transfer) agent can be used as needed. After synthesizing the copolymer by radical polymerization, the alkali-soluble functional group may be added to the copolymer.

[0097] As the polymerizable monomer having an alkali-soluble functional group, for example, the polymerizable monomer having an alkali-soluble functional group described for the hydrophobic resin (A) can be used.

[0098] From the viewpoint of sensitivity, the polymerizable monomer having an alkali-soluble functional group is preferably a polymerizable monomer having a carboxy group or a phenolic hydroxyl group, and more preferably a polymerizable monomer having a phenolic hydroxyl group.

[0099] As the other polymerizable monomer, for example, the other polymerizable monomers described for the hydrophobic resin (A) can be used.

[0100] As a polymerizable monomer having an alkali-soluble functional group, after polymerization, [ka] (In equation (5), R 13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5. 13 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.

[0101] Other polymerizable monomers include those represented by the formula (4) after polymerization. [ka] (In formula (4), R 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 12 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. 10 and R 11 is preferably a hydrogen atom. 12 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.

[0102] In one embodiment, the copolymer having an alkali-soluble functional group is represented by formula (5): [ka] (In equation (5), R 13 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 (4), R 10 and R 11 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 12is 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.

[0103] In the copolymer having an alkali-soluble functional group, the molar ratio of the structural unit represented by formula (5) to the structural unit represented by formula (4) is preferably formula (5): formula (4)=70-95:30-5, and more preferably formula (5): formula (4)=75-90:25-10.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] In one embodiment, the positive photosensitive resin composition contains 1% by mass to 70% by mass, preferably 3% by mass to 60% by mass, and more preferably 5% by mass to 50% by mass of a copolymer having an alkali-soluble functional group, based on 100% by mass of the solid content. When the content of the copolymer having an alkali-soluble functional group is 1% by mass or more, based on 100% by mass of the solid content, dissolution of the exposed area can be promoted, achieving high sensitivity and ensuring the stability and durability of the coating after thermal curing. When the content of the copolymer having an alkali-soluble functional group is 70% by mass or less, based on 100% by mass of the solid content, the problem of residue at the bottom of the exposed area pattern does not occur, and a clean pattern can be formed.

[0108] The positive-type photosensitive resin composition preferably contains 1% by mass to 80% by mass, more preferably 3% by mass to 70% by mass, and even more preferably 5% by mass to 60% by mass of a copolymer having an alkali-soluble functional group, based on the total mass of the resin components. When the content of the copolymer having an alkali-soluble functional group is 1% by mass or more based on the total mass of the resin components, dissolution of the exposed area can be promoted, achieving high sensitivity, and ensuring the stability and durability of the coating film after thermal curing. When the content of the copolymer having an alkali-soluble functional group is 80% by mass or less based on the total mass of the resin components, the problem of residue at the bottom of the exposed area pattern does not occur, and a clean pattern can be formed.

[0109] <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 the alkali-soluble functional groups, such as phenolic hydroxyl groups, of the alkali-soluble resin (B), the cresol novolac resin, and any optional copolymers containing alkali-soluble functional groups, rendering these resins insoluble in alkaline aqueous solutions. Meanwhile, the presence of the alkali-soluble carboxylic acid compound in the irradiated area facilitates the dissolution of the resin in that area in alkaline aqueous solutions, along with the carboxylic acid compound. Furthermore, the carboxylic acid compound has a relatively larger molecular structure than acids generated by photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is therefore less likely to diffuse within the film. These synergistic effects result in a greater difference in alkali solubility between the 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 types. The positive photosensitive resin composition preferably does not substantially contain a photoacid generator commonly used in chemically amplified resists, and more preferably contains only the quinone diazide compound (C) as a photosensitizer without containing any such photoacid generator. "Substantially does not contain a photoacid generator" means that the amount of the photoacid generator contained in the positive 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.

[0110] [ka]

[0111] 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 quinone diazide compound (C) into the unexposed area under 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.

[0112] Examples of the quinone diazide compound (C) include a compound in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, a compound in which the sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, a compound in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy polyamino compound via an ester bond or a sulfonamide bond, etc. 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, polyamino compound, or polyhydroxy polyamino compound be substituted with quinone diazide.

[0113] 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.

[0114] 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.

[0115] In one embodiment, the positive photosensitive resin composition contains 5 to 70 parts by mass, preferably 7 to 65 parts by mass, and more preferably 10 to 60 parts by mass of the quinone diazide compound (C) based on a total of 100 parts by mass of the resin components. When the content of the quinone diazide compound (C) is 5 parts by mass or more based on the total of 100 parts by mass, high sensitivity can be achieved. When the content of the quinone diazide compound (C) is 70 parts by mass or less based on the total of 100 parts by mass, alkaline developability is good.

[0116] <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.

[0117] 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.

[0118] In one embodiment, the acrylic copolymer is represented by formula (8): [ka] (In equation (8), R 15 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 16 is a hydrogen atom or a methyl group, and R 17 are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, and R 18 is a hydrogen atom or an 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 above with a polymerizable monomer having a polyoxyalkylene group represented by the following formula:

[0119] In equation (8), L 1 The 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. 1is -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-.

[0120] In formula (8), Rf 1 is -C4F9 or -C6F 13 It is preferable that:

[0121] The fluorine-containing polymerizable monomers represented by formula (8) can be used alone or in combination of two or more kinds.

[0122] In equation (9), R 17 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. 17 may be the same or different from each other. From the viewpoint of leveling property, R 17 is preferably a propylene group, a tetramethylene 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, or a polyoxyisobutylene chain.

[0123] In equation (9), R 18 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.

[0124] The polymerizable monomer having a polyoxyalkylene group represented by formula (9) can be used alone or in combination of two or more kinds.

[0125] 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.

[0126] Other polymerizable monomers include, for example, those represented by the formula (10): [ka] (In equation (10), R 19 is a hydrogen atom or a methyl group, and R 20 is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of the polymerizable monomer include those represented by the following formula:

[0127] In equation (10), R 20 Examples of the linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms 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.

[0128] 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.

[0129] The other polymerizable monomers may be used alone or in combination of two or more kinds.

[0130] 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).

[0131] 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.

[0132] 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.

[0133] 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.

[0134] In another embodiment, the acrylic copolymer is represented by formula (11): [ka] (In formula (11), R 21 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 22 is a hydrogen atom or a methyl group, and R 23 are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, and R 24 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:

[0135] In equation (11), R 21 Examples of the radical polymerizable functional group represented by the formula include CH2=CHCO-, CH2=C(CH3)CO-, and CH2=CH-C6H4-. 21 may be the same or different from each other. 21is 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.

[0136] 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-.

[0137] 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—.

[0138] In formula (11), Rf 2Specifically, the fluorinated alkylene group having 1 to 3 carbon atoms represented by the formula (I) is preferably selected from the group consisting of -CF2- (perfluoromethylene group), -CF2CF2- (perfluoroethylene group), -CF2CF2CF2-, -CF2CF(CF3)-, and -CF(CF3)CF2-.

[0139] 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.

[0140] In the formula (11), d is preferably 3 to 100, and more preferably 6 to 70.

[0141] 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.

[0142] The fluorine-containing polymerizable monomers represented by formula (11) can be used alone or in combination of two or more kinds.

[0143] In equation (12), R 23 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. 23 may be the same or different from each other. From the viewpoint of leveling property, R 23 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.

[0144] In equation (12), R 24 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.

[0145] In the formula (12), e is preferably 3 to 50.

[0146] The polymerizable monomer having an oxyalkylene group represented by formula (12) can be used alone or in combination of two or more kinds.

[0147] 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).

[0148] The copolymer (D2) can be obtained by the radical polymerization described for the copolymer (D1).

[0149] 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.

[0150] 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.

[0151] Specific examples of the fluorosurfactant (D) include Megafac (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 (trademark) S-242, S-243, S-386, S-420, and S-611 (trade names, AGC Seimi Chemical Co., Ltd.). The fluorosurfactant (D) is preferably Megafac (trademark) F-563, F-559, F-554, R-40, or F-562, and more preferably Megafac (trademark) F-563, F-554, or R-40.

[0152] 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.

[0153] <Cresol novolac resin> The positive-type photosensitive resin composition contains a cresol novolac resin. Addition of the cresol novolac resin can suppress the occurrence of surface roughness and pores in stepped portions. Without being bound by any theory, when a positive-type photosensitive resin composition contains a hydrophobic resin (A) that is an addition (co)polymer and an alkali-soluble resin (B) having a novolac skeleton represented by formula (1) as resin components, phase separation occurs between the hydrophobic resin (A) and the alkali-soluble resin (B) within the coating, resulting in the occurrence of surface roughness and pores in stepped portions. Addition of the cresol novolac resin to this resin component improves the compatibility between the hydrophobic resin (A) and the alkali-soluble resin (B), suppressing phase separation within the coating. As a result, the occurrence of surface roughness and pores in stepped portions is suppressed.

[0154] The weight-average molecular weight (Mw) of the cresol novolac resin is preferably 500 or more, more preferably 1000 or more, and even more preferably 1500 or more. The weight-average molecular weight (Mw) of the cresol novolac resin is preferably 17,500 or less, more preferably 15,000 or less, and even more preferably 12,500 or less. Any combination of these lower and upper limits may be used. The weight-average molecular weight (Mw) of the cresol novolac resin is preferably 500 to 17,500, more preferably 1000 to 15,000, and even more preferably 1500 to 12,500. By keeping the weight-average molecular weight within the above range, it is possible to improve the smoothness of stepped portions without generating residue at the bottom of the pattern.

[0155] Examples of cresol novolac resins include TR4020G, TR4080G, and TR4000B (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0156] In one embodiment, the positive photosensitive resin composition contains 0.1% by mass to 40% by mass, preferably 0.2% by mass to 30% by mass, and more preferably 0.3% by mass to 20% by mass of a cresol novolac resin, based on 100% by mass of solids. When the content of the cresol novolac resin is 0.1% by mass or more, based on 100% by mass of solids, the surface smoothness of the stepped portion can be sufficiently improved. When the content of the cresol novolac resin is 40% by mass or less, based on 100% by mass of solids, there is no decrease in sensitivity and no effect on the solubility of unexposed areas.

[0157] The positive-type photosensitive resin composition contains, based on the total mass of the resin components, preferably 0.5% by mass or more of the cresol novolac resin, more preferably 0.6% by mass or more, and even more preferably 0.7% by mass or more. The positive-type photosensitive resin composition contains, based on the total mass of the resin components, preferably 35% by mass or less of the cresol novolac resin, more preferably 30% by mass or less, and even more preferably 25% by mass or less. Any combination of these lower and upper limits may be used. The positive-type photosensitive resin composition contains, based on the total mass of the resin components, preferably 0.5% by mass to 35% by mass of the cresol novolac resin, more preferably 0.6% by mass to 30% by mass, and even more preferably 0.7% by mass to 25% by mass. When the content of the cresol novolac resin is 0.5% by mass or more based on the total mass of the resin components, the surface smoothness of the stepped portion can be sufficiently improved. When the content of the cresol novolac resin is 35% by mass or less based on the total mass of the resin components, there is no decrease in sensitivity and no effect on the solubility of the unexposed areas.

[0158] <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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] <Optional ingredients> The positive-type 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 components that do not fall under any of (A) to (E), cresol novolac resin, and copolymers having an alkali-soluble functional group.

[0163] <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.

[0164] In the present disclosure, the term "low molecular weight compound" refers to a compound having a molecular weight of not more than 1000. The above organic low molecular weight compound has one or more carboxy groups or multiple phenolic hydroxyl groups and is alkali-soluble.

[0165] 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.

[0166] 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.

[0167] [Coating composition] <Solvent (G)> The positive-type photosensitive resin composition can be dissolved or dispersed in a solvent (G) to form a coating composition in solution or dispersion state. For example, a coating composition containing the positive-type photosensitive resin composition can be prepared by dissolving a hydrophobic resin (A), an alkali-soluble resin (B), a cresol novolac resin, and optionally a copolymer having an alkali-soluble functional group in a solvent (G) to obtain a solution, and then mixing the solution with a quinone diazide compound (C), a fluorine-based surfactant (D), and optionally optional components such as a solubility promoter (E), a heat curing agent, and other surfactants in a predetermined ratio. The viscosity of the coating composition can be adjusted to suit the coating method used by changing the amount of solvent (G).

[0168] 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.

[0169] 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 %.

[0170] 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.

[0171] 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.

[0172] The coating composition thus prepared also has excellent long-term storage stability.

[0173] [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.

[0174] 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.

[0175] 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.

[0176] After the exposure 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, and 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.

[0177] 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.

[0178] <Remaining film rate> In one embodiment, a positive photosensitive resin composition is applied so that the film thickness after pre-baking is 3.0±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 with 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.

[0179] <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.

[0180] In one embodiment, a method for producing an organic EL element partition wall or an organic EL element insulating film includes dissolving or dispersing a positive photosensitive resin composition in a solvent to prepare a coating composition, applying the coating composition to a substrate to form a film, removing the solvent contained in the film and drying the film, exposing the dried film to radiation through a photomask, developing the exposed film by contacting it with a developer to form a pattern in the film, and heat-treating the patterned film at a temperature of 100°C to 350°C to form an organic EL element partition wall or an organic EL element insulating film. 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).

[0181] [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).

[0182] [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).

[0183] [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]

[0184] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

[0185] (1) Raw materials The raw materials used in the examples and comparative examples were produced or obtained as follows.

[0186] 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 (trademark) GPC-101 Column: Shodex (trademark) LF-804 Mobile phase: tetrahydrofuran Flow rate: 1.0mL / min Detector: Shodex (trademark) RI-71 Temperature: 40℃

[0187] [Production Example 1] Copolymer having alkali-soluble functional group (PCX-01): Production of copolymer of polymerizable monomer having 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 dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Corporation) as a solvent, and 3.66 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 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.

[0188] [Production Example 2] Copolymer having alkali-soluble functional group (PCX-02e): Production of copolymer of polymerizable monomer having 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 dissolved in 77.1 g of 1-methoxy-2-propyl acetate (Daicel Corporation) as a solvent, and 3.66 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were 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.

[0189] [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 (dimethyl 2,2'-azobis(2-methylpropionate), Fujifilm Wako Pure Chemical Industries Co., Ltd.) 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 was cooled to room temperature and added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 9.73 g of a white powder (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 (3), (4), and (5), where s is an integer of 1 or greater, was formula (3): (4): (5) = 32:7:61, and the structural units having alkali-soluble functional groups accounted for 61 mol% of all structural units. The silicon atom content was 4.0 mass% based on the mass of PCX-02e-TBDMS34.

[0190] [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 (dimethyl 2,2'-azobis(2-methylpropionate), Fujifilm Wako Pure Chemical Industries Co., Ltd.) 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 number-average molecular weight of the resulting PCX-02e-TES34 was 3847, and the weight-average molecular weight was 7534. In PCX-02e-TES34, the molar ratio of the structural units represented by formula (3), (4), and (5), where s is an integer of 1 or greater, was formula (3):formula (4):formula (5) = 32:7:61, and the structural units having alkali-soluble functional groups accounted for 61 mol% of the total structural units. The silicon atom content was 4.0 mass% based on the mass of PCX-02e-TES34.

[0191] [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.). 3.74 g of V-601 (dimethyl 2,2'-azobis(2-methylpropionate), 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 (4), and structural units represented by formula (5) 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.

[0192] [Production Example 6] 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 the solvent and 37.8 g of EPICLON™ N-695 (DIC Corporation, cresol novolac epoxy resin, epoxy equivalent weight 214) and dissolved at 60 °C under a nitrogen atmosphere. To this was added 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, and the mixture was reacted 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 weight, and filtered to yield 274.2 g of a resin solution (N695OH70) containing epoxy and phenolic hydroxyl groups. 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.

[0193] [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.

[0194] [Alkali-soluble resin (B)] As the alkali-soluble resin (B), N695OH70 of Production Example 6 was used.

[0195] [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.).

[0196] 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]

[0197] [Fluorosurfactant (D)] As the fluorosurfactant (D), Megafac (trademark) F-554, Megafac (trademark) R-40, and Megafac (trademark) F-563 (all manufactured by DIC Corporation) were used.

[0198] [Cresol novolac resin] As the cresol novolac resins, TR4080G (weight average molecular weight (Mw): 4785), TR4020G (weight average molecular weight (Mw): 9920), and TR4000B (weight average molecular weight (Mw): 3021) (all manufactured by Asahi Organic Chemicals Co., Ltd.) were used.

[0199] [Copolymer of polymerizable monomers having alkali-soluble functional groups and other polymerizable monomers] PCX-01 of Production Example 1 and PCX-02e of Production Example 2 were used as copolymers of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer.

[0200] As the phenol novolac resins, Shonol (trademark) BRG-556 (weight average molecular weight (Mw): 558 or less, manufactured by Showa Denko K.K.), Shonol (trademark) BRG-558 (weight average molecular weight (Mw): 3000, manufactured by Showa Denko K.K.), and BRN-5834Y (weight average molecular weight (Mw): 7400, manufactured by Showa Denko K.K.) were used.

[0201] [Colorant (E)] As colorants, black dyes VALIFAST (trademark) BLACK 3820 (a black dye specified with the CI of Solvent Black 27, manufactured by Orient Chemical Industry Co., Ltd.) and VALIFAST (trademark) BLACK 3804 (a black dye specified with the CI of Solvent Black 34, manufactured by Orient Chemical Industry Co., Ltd.) were used.

[0202] [Solubility enhancer (F)] Phloroglucinol was used as the solubility enhancer (F).

[0203] [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.

[0204] (2) Evaluation method The evaluation methods used in the examples and comparative examples are as follows.

[0205] [sensitivity] A positive photosensitive resin composition was bar-coated onto a glass substrate (100 mm × 100 mm × 1 mm) to a dry film thickness of 3.0 ± 0.3 μm. The substrate was vacuum dried at room temperature for 60 seconds and then prebaked by heating on a lidded hot plate at 125 °C for 120 seconds. The coating was exposed through a quartz photomask (with a φ10 μm opening pattern) using an exposure system equipped with an ultra-high pressure mercury lamp (product name: Multilight ML-251A / B, Ushio Inc.). 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% tetramethylammonium hydroxide aqueous solution at 23 °C using a spin development system (AD-1200, Takizawa Sangyo Co., Ltd.). The above procedure was repeated while changing the exposure dose to determine the minimum exposure dose (mJ / cm) that would allow a pattern with a hole diameter of 10 μm to be formed completely through the glass substrate after development. 2 ) was used as the sensitivity.

[0206] [Evaluation method for intermediate exposure area Ra] A positive photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 ± 0.3 μm. The coating was vacuum dried at room temperature for 60 seconds and then prebaked by heating on a lidded hot plate at 125°C for 120 seconds. The dried coating was exposed to light using an exposure system equipped with an ultra-high pressure mercury lamp (Product Name: Multilight ML-251A / B, Ushio Inc.) through a mercury exposure bandpass filter (Product Name: HB0365, Asahi Spectroscopic Co., Ltd.). The exposure dose was measured using an ultraviolet integrating actinometer (Product Name: UIT-150, Photoreceptor: UVD-S365, Ushio Inc.) and adjusted to 25% of the sensitivity of each formulation. After exposure, the coating was developed for 80 seconds using a spin-developer (AD-1200, Takizawa Sangyo Co., Ltd.) with a 2.38 wt% aqueous tetramethylammonium hydroxide solution at 23°C. The sample was then post-baked in an inert oven under a nitrogen gas atmosphere at 250°C for 60 minutes to obtain a measurement sample. The surface of the obtained sample was measured for arithmetic mean roughness Ra using a laser microscope (VK-X200, Keyence Corporation) at a magnification of 50x and a measurement pitch of 0.02µm, and this was taken as the intermediate exposure area Ra. Regarding the evaluation of the roughness of the intermediate exposure area, an Ra of less than 0.06 was considered a pass, and an Ra of 0.06 or more was considered a fail.

[0207] [Pores in the intermediate exposure area] A positive photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 ± 0.3 μm. The coating was vacuum dried at room temperature for 60 seconds and then prebaked by heating on a lidded hot plate at 125°C for 120 seconds. The dried coating was exposed to light using an exposure system equipped with an ultra-high pressure mercury lamp (Product Name: Multilight ML-251A / B, Ushio Inc.) through a mercury exposure bandpass filter (Product Name: HB0365, Asahi Spectroscopic Co., Ltd.). The exposure dose was measured using an ultraviolet integrating actinometer (Product Name: UIT-150, Photoreceptor: UVD-S365, Ushio Inc.) and adjusted to 25% of the sensitivity of each formulation. After exposure, the coating was developed for 80 seconds using a spin-developer (AD-1200, Takizawa Sangyo Co., Ltd.) with a 2.38 wt% aqueous tetramethylammonium hydroxide solution at 23°C. Then, in an inert oven, post-baking was performed in a nitrogen gas atmosphere at 250 ° C. for 60 minutes to obtain a measurement sample. The obtained sample was cut into 10 mm squares, and the sample surface was platinum-deposited using a fully automatic ion coater (JFC1500, JEOL Ltd.) under conditions of 25 s × 2 sets. The sample was then introduced into a FE-SEM (JSM-7600F, JEOL Ltd.), and the sample was observed at an acceleration voltage of 2.0 kV, in LEI (Lower Secondary Electron Image) mode, and at a magnification of 15,000 times. Regarding the evaluation of the presence or absence of pores, when fine holes (pores) were observed on the sample surface as in FIG. 1 (A) (Comparative Example 1), it was determined that there were pores, and when fine holes (pores) were not observed on the sample surface as in FIG. 1 (B) (Example 1), it was determined that there were no pores.

[0208] [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±0.3 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 at 23°C using a spin development device (AD-1200, Takizawa Sangyo Co., Ltd.) in 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%.

[0209] [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.).

[0210] (3) Preparation and evaluation of positive photosensitive resin compositions [Examples 1 to 14, Comparative Examples 1 to 4] The resin components and phenol novolac resin 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-based surfactant (D), 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 to 4 are shown in Table 1.

[0211] 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 the exposed and unexposed areas because the solubility of the unexposed areas was 0 μm, and furthermore, the surface roughness of the intermediately exposed areas was small and no pores were observed, making it possible to form a thick film pattern having a stepped structure with high precision. Furthermore, the exposure dose at which a pattern with a hole diameter of 10 μm could be formed after development was 300 mJ / cm. 2 or less, confirming high sensitivity. In contrast, the positive-type photosensitive resin compositions of Comparative Examples 1 to 3, in which a phenol novolac resin was added instead of a cresol novolac resin, and the positive-type photosensitive resin composition of Comparative Example 4, in which no cresol novolac resin was added, failed the Ra of the intermediate exposure area (0.06 or more), and pores were observed on the sample surface. In the case of phenol novolac resin, since there is no alkyl group on the benzene ring, it is compatible with the alkali-soluble resin (B) but not with the hydrophobic resin (A), and as a result, it is presumed that it has no effect in mitigating phase separation between the two. This confirms that the addition of a cresol novolac resin can suppress surface roughness and the generation of pores in stepped portions.

[0212] [Table 1-1]

[0213] [Table 1-2] [Industrial Applicability]

[0214] 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) which is an addition (co)polymer; an alkali-soluble resin (B) having a structural unit represented by formula (1); a quinone diazide compound (C); a fluorosurfactant (D); Cresol novolac resin Including, The positive photosensitive resin composition, 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. 【Chemistry 1】 (In formula (1), x is an integer of 0 to 3, and R １ are each independently an alkyl group having 1 to 5 carbon atoms, and R ２ is an organic group having an alkali-soluble functional group.

2. 2. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble functional group in formula (1) is a phenolic hydroxyl group.

3. 2. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) further has a structural unit represented by formula (2): 【Chemistry 2】 (In formula (2), y is an integer of 0 to 3, and R ３ are each independently an alkyl group having 1 to 5 carbon atoms, and R ４ is an organic group that does not have an alkali-soluble functional group.

4. In the formula (2), R ４ The positive photosensitive resin composition according to claim 3, wherein is an organic group having an epoxy group.

5. 5. The positive photosensitive resin composition according to claim 3, wherein the alkali-soluble resin (B) contains the structural units represented by formula (1) and the structural units represented by formula (2) in a total amount of 30 mol % to 100 mol % based on all structural units of the alkali-soluble resin (B).

6. 5. The positive photosensitive resin composition according to claim 1, wherein the cresol novolac resin has a weight average molecular weight (Mw) of 500 to 17,500.

7. 5. The positive photosensitive resin composition according to claim 1, wherein the cresol novolac resin is contained in an amount of 0.5% by mass to 35% by mass based on the total mass of the resin components.

8. The hydrophobic resin (A) is represented by the formula (3) 【Transformation 3】 (In formula (3), R ５ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ６ is SiR ７ R ８ R ９ and R ７ , R ８ and R ９ 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.

8. The positive photosensitive resin composition according to claim 7, which has a structural unit represented by formula (3):

9. The hydrophobic resin (A) is represented by the formula (4) 【Chemistry 4】 (In formula (4), R １０ and R １１ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １２ 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 8, further comprising a structural unit represented by the following formula:

10. 5. 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.

11. 5. The positive photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin which is a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer and does not have a structural unit represented by formula (1).

12. 5. 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.

13. 13. The positive photosensitive resin composition according to claim 12, 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.

14. 13. The positive photosensitive resin composition according to claim 12, 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.

15. A partition wall for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 4.

16. An insulating film for an organic EL device, comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 4.

17. An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 4.

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