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

Abstract

The present invention provides a positive photosensitive resin composition, an organic EL element partition wall, an organic EL element insulating film, and an organic EL element, which have excellent residue removal properties without using an organic fluorine compound, a small amount of film reduction, and are capable of forming fine pores. The present invention also provides a positive photosensitive resin composition, an organic EL element partition wall, an organic EL element insulating film, and an organic EL element. The present invention provides a hydrophobic resin composition containing (A) a hydrophobic resin, (C) a quinonediazide compound, and (D) a polysiloxane-based surfactant having a silicon atom in a side chain.

Description

Technical Field

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

[0002] Positive photosensitive resin compositions are widely used as barrier rib materials, insulating films and planarizing films of display devices such as organic EL displays (OLEDs) and liquid crystal displays, and as interlayer insulating films, planarizing films and protective films of semiconductor devices.

[0003] For example, in display devices such as organic EL displays, in order to improve display characteristics, a partition material is used at the edge of the spacer of the colored pattern in the display area or the peripheral part of the display area. In the manufacture of an organic EL display device, in order to prevent the pixels of the organic substance from contacting each other, a partition is first formed, and the pixels of the organic substance are formed between the partitions. The partition is usually formed by photolithography using a photosensitive resin composition and has insulating properties. In detail, a photosensitive resin composition is applied to a substrate using a coating device, and after removing the volatile components by heating and other means, it is exposed across a mask, and then, in the case of a negative type, the unexposed part is removed with a developer such as an alkaline aqueous solution, and in the case of a positive type, the exposed part is removed with a developer such as an alkaline aqueous solution and developed, and the pattern obtained by heat treatment is formed to form a partition (insulating film). Then, by an inkjet method, an organic substance emitting red, green, and blue light is formed between the partitions to form pixels of an organic EL display device.

[0004] In recent years, in the above-mentioned field, with the miniaturization of display devices and the diversification of displayed contents, the performance and high definition of pixels are required. In order to improve the contrast and visibility of display devices, attempts have been made to use colorants to keep the light-shielding properties of the partition wall materials.

[0005] Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-281440) describes a composition obtained by adding titanium black to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits high light-shielding properties by heat treatment after exposure.

[0006] Patent Document 2 (Japanese Patent Application Laid-Open No. 2002-116536) describes a method of blackening a barrier rib material 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 (Japanese Patent Application Laid-Open No. 2010-237310) describes a radiation-sensitive resin composition having light-shielding properties by heat treatment after exposure, wherein a composition is prepared by adding a thermosensitive dye to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound.

[0008] Patent Document 4 (International Publication No. 2017 / 069172) describes a positive photosensitive resin composition containing (A) a binder resin, (B) a quinonediazide compound, and (C) at least one black dye selected from black dyes specified in the color index of Solvent Black 27 to 47.

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

[0010] On the other hand, as one of the methods for improving the sensitivity of the positive photosensitive resin composition, it is possible to make the photosensitive resin composition into a chemically amplified type. As for the chemically amplified photosensitive resin composition, it usually contains a resin in which the alkali-soluble functional group is protected by the acid-degradable group and a photoacid generator. The acid generated by the photoacid generator during exposure promotes the decomposition (deprotection) of the acid-degradable group and regenerates the alkali-soluble functional group. This promotes the alkaline dissolution of the resin in the exposed part during development. The acid derived from the photoacid generator is regenerated after decomposing a certain acid-degradable group and participates in the decomposition of another acid-degradable group. Since the apparent quantum efficiency of the chemically amplified type based on the reaction mechanism is expressed as the product of the quantum efficiency generated by the acid and the reaction chain, it is expected that high sensitivity can be achieved by making the photosensitive resin composition into a chemically amplified type.

[0011] Prior art literature

[0012] Patent Literature

[0013] [Patent Document 1] Japanese Patent Application Publication No. 2001-281440

[0014] [Patent Document 2] Japanese Patent Application Publication No. 2002-116536

[0015] [Patent Document 3] Japanese Patent Application Publication No. 2010-237310

[0016] [Patent Document 4] International Publication No. 2017 / 069172

[0017] [Patent Document 5] International Publication No. 2023 / 080254 Summary of the invention

[0018] Technical problem solved by the invention

[0019] However, when the partition material maintains light-shielding properties, the photosensitive resin composition tends to have low sensitivity, resulting in a prolonged exposure time and reduced productivity. Therefore, a photosensitive resin composition used in forming a partition material containing a colorant is required to have higher sensitivity.

[0020] For example, in the photosensitive resin composition used in the formation of the colored partition material, a colorant is used in order to fully improve the light-shielding property of the cured film. However, when a colorant is used, the radiation irradiating the film of the photosensitive resin composition is absorbed by the colorant, so the effective intensity of the radiation in the film is reduced, and the photosensitive resin composition is not fully exposed, resulting in reduced hole formation, etc. This is significant in the case of mixing a black colorant in the photosensitive resin composition for the purpose of improving the image quality, flexibility or power saving of the display device, for example, in the case of forming a black partition material.

[0021] Furthermore, in recent years, there has been a need to control the use of organic fluorine compounds such as PFAS, and there has been a demand for so-called Non-PFAS.

[0022] In addition, positive photosensitive resin compositions that do not use an organic fluorine compound are required to have excellent residue removability, less film reduction, and high-level pore-forming properties as described above. However, a positive photosensitive resin composition that fully meets these requirements has not yet been developed.

[0023] The present invention has been made in view of the above circumstances, and its object is to provide a positive photosensitive resin composition, an organic EL element partition wall, an organic EL element insulating film and an organic EL element which have excellent residue removability, reduce film reduction and can form fine pores even without using an organic fluorine compound.

[0024] Technical means of solving problems

[0025] As a result of intensive studies to achieve the above-mentioned object, the present inventors have obtained a positive photosensitive resin composition containing a hydrophobic resin (A), a quinonediazide compound (C), and a polysiloxane surfactant having a silicon atom on a side chain (D), thereby completing the present invention.

[0026] That is, the present invention includes the following aspects.

[0027] <1>

[0028] A positive photosensitive resin composition comprises: a hydrophobic resin (A), a quinonediazide compound (C), and a polysiloxane surfactant (D) having a silicon atom on the side chain.

[0029] <2>

[0030] according to <1> The positive photosensitive resin composition, wherein

[0031] The content of the component (D) in the total amount of the surfactant is 50% by mass or more.

[0032] <3>

[0033] according to <1> or <2> The positive photosensitive resin composition further contains a colorant (E) comprising a black dye.

[0034] <4>

[0035] according to <1> ~ <3> The positive photosensitive resin composition described in any one of the preceding claims, wherein

[0036] The component (A) contains a structural unit represented by the following formula (1).

[0037] [Chemical formula 1]

[0038]

[0039] (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 SiR 3 R 4 R 5 , R 3 , R 4 and R 5 Each of them is 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 4, s is an integer of 1 to 5, wherein r+s is an integer of 1 to 5.)

[0040] <5>

[0041] according to <1> ~ <4> The positive photosensitive resin composition described in any one of the preceding claims, wherein

[0042] The component (A) is a resin having a silicon atom-containing group.

[0043] <6>

[0044] according to <1> ~ <5> The positive photosensitive resin composition described in any one of the preceding claims, wherein

[0045] The component (A) contains the following structural unit (1a) and / or structural unit (1b).

[0046] [Chemical formula 2]

[0047]

[0048] (In formula (1a), R 1a is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2a , R 3a and R 4a are independently an alkyl group having 1 to 7 carbon atoms. 1b is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 1a and R 1b Can be the same or different.)

[0049] <7>

[0050] according to <1> ~ <6> The positive photosensitive resin composition described in any one of the preceding claims, wherein

[0051] The content of the component (A) in the positive photosensitive resin composition is 5 to 60% by mass based on the total mass of the resin components.

[0052] <8>

[0053] according to <1> ~ <7> The positive photosensitive resin composition described in any one of the preceding claims, wherein

[0054] The component (D) is a polysiloxane-based surfactant comprising an acrylic copolymer having at least one silicon-containing hydrocarbon group selected from a silicon-containing alkyl group and a silicon-containing alkylene group.

[0055] <9>

[0056] according to <3> The positive photosensitive resin composition, wherein

[0057] The (E) component is contained in an amount of 10 to 150 parts by mass based on 100 parts by mass of the total resin components.

[0058] <10>

[0059] according to <1> ~ <9> The positive photosensitive resin composition described in any one of the preceding claims, wherein

[0060] 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.

[0061] <11>

[0062] An organic EL element partition wall comprising <1> ~ <10> A cured product of any one of the positive photosensitive resin compositions.

[0063] <12>

[0064] An organic EL element insulating film comprising <1> ~ <10> A cured product of any one of the positive photosensitive resin compositions.

[0065] <13>

[0066] An organic EL element comprising <1> ~ <10> A cured product of any one of the positive photosensitive resin compositions.

[0067] Effects of the Invention

[0068] According to the present invention, there can be provided a positive photosensitive resin composition, an organic EL element partition wall, an organic EL element insulating film, and an organic EL element which are excellent in residue removability, have a small film reduction, and can form fine pores even without using an organic fluorine compound. DETAILED DESCRIPTION

[0069] Hereinafter, a specific embodiment of the present invention (hereinafter referred to as "this embodiment") is described in detail. The following this embodiment is an example for illustrating the present invention, and the content below does not limit the present invention. The present invention can be appropriately deformed and implemented within the scope of its purpose.

[0070] In this specification, "alkali-soluble" means that the positive photosensitive resin composition or its components, or the film or cured film of the positive photosensitive resin composition can be dissolved in a 2.38% by mass tetramethylammonium hydroxide aqueous solution. "Alkali-soluble resin" refers to a resin that can be dissolved in a 2.38% by mass tetramethylammonium hydroxide aqueous solution in the form of a monomer or contained in an unexposed or exposed positive photosensitive resin composition. Alkali-soluble resins also include resins that are not alkali-soluble in the positive photosensitive resin composition at the unexposed time point but become alkali-soluble by exposure. "Alkali-soluble functional group" refers to a group that has the ability to impart such alkali solubility to the positive photosensitive resin composition or its components, or the film or cured film of the positive photosensitive resin composition. Examples of alkali-soluble functional groups include phenolic hydroxyl groups, carboxyl groups, sulfonic groups, phosphoric acid groups, acid anhydride groups, and mercapto groups.

[0071] In the present specification, the "acid-decomposable group" means a group which is decomposed (deprotected) by heating as necessary in the presence of an acid to generate an alkali-soluble functional group.

[0072] In the present specification, the "radical polymerizable functional group" refers to an ethylenically unsaturated group, and the "radical polymerizable compound" refers to a compound having one or more ethylenically unsaturated groups.

[0073] In this specification, "structural unit" and "unit" (hereinafter collectively referred to as "structural unit") refer to an atomic group that constitutes a part of the basic structure of a polymer, and the atomic group may have a side atom or a side atomic group. For example, in the case of a free radical (co)polymer, it refers to a unit derived from a free radical 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). For structural units having pendant groups, structural units having pendant groups used in the formation of crosslinking sites or groups derived therefrom and structural units having free pendant groups that do not participate in the formation of crosslinking sites are considered to be different from each other. For polymers having branched molecular chains (branches), structural units containing branching points (branch units) and structural units contained in linear molecular chains are considered to be different from each other.

[0074] [Chemical formula 3]

[0075]

[0076] In this specification, unless otherwise specified, "(meth)acrylic" means acrylic, methacrylic, or both, "(meth)acrylate" means acrylate, methacrylate, or both, and "(meth)acryloyl" means acryloyl, methacryloyl, or both.

[0077] In this specification, unless otherwise specified, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin, a polymer or a copolymer refer to the standard polystyrene conversion values ​​measured by gel permeation chromatography (GPC).

[0078] In this specification, unless otherwise specified, the phenolic hydroxyl equivalent is a theoretical value calculated from the molecular weight and composition ratio of the structural units constituting the resin. Specifically, the phenolic hydroxyl equivalent is a value calculated by the following formula when the resin is a (co)polymer of n monomers i (i = 1 to n natural numbers). In the formula, the total copolymerization ratio (molar basis) of the monomers i (i = 1 to n) is 1.

[0079] [Mathematical formula 1]

[0080]

[0081] In the case of the resin (B2) having an epoxy group and a phenolic hydroxyl group hereinafter, unless otherwise specified, the phenolic hydroxyl group equivalent means a value calculated by the following formula.

[0082] Phenolic hydroxyl equivalent = (epoxy equivalent of raw material + molecular weight of added carboxylic acid) / (number of phenolic hydroxyl groups of carboxylic acid)

[0083] Unless otherwise specified, the "resin component" in this specification refers to the hydrophobic resin (A) and the alkali-soluble resin (B). Components corresponding to the polysiloxane surfactant (D) are not included in the hydrophobic resin (A) and the alkali-soluble resin (B).

[0084] Unless otherwise specified in the present specification, "solid content" refers to the total mass of components including the resin component, the quinonediazide compound (C), the polysiloxane surfactant (D), and any other components such as the colorant (E) and the dissolution accelerator (F), excluding the liquid solvent (G).

[0085] [Positive photosensitive resin composition]

[0086] The positive photosensitive resin composition of the present embodiment is a positive photosensitive resin composition containing a hydrophobic resin (A), a quinonediazide compound (C), and a polysiloxane surfactant (D) having a silicon atom on the side chain. The positive photosensitive resin composition of the present embodiment has excellent residue removal properties, less film reduction, and can form fine pores even without using an organic fluorine compound. The reason is not clear, but it is speculated to be due to the following reasons (wherein the action / effect of the present embodiment is not limited to the following).

[0087] By mixing a polysiloxane surfactant (D) having a silicon atom on the side chain with a hydrophobic resin (A), its partialization on the film surface is promoted, and the film surface of the positive photosensitive resin composition is difficult to dissolve in an alkaline aqueous solution. The hydrophobic resin (A) is easily moved to the film surface along with the polysiloxane surfactant (D) moving to the film surface during the formation of the film of the positive photosensitive resin composition. Therefore, after the film is formed, the hydrophobic resin (A) is present at a higher concentration on the film surface than inside the film, reducing the alkali solubility of the film surface. In addition, the hydrophobic resin (A) tends to have low compatibility with the alkali-soluble resin (B), so there is a tendency to easily generate a concentration gradient during curing. Therefore, during development, the hydrophobic resin (A) suppresses the dissolution of the film surface of the unexposed portion as a resin component with low alkali solubility, and is released from the film into the developer in the exposure portion accompanied by the dissolution of the carboxylic acid compound from the quinonediazide compound (C), other resin components with high alkali solubility, and any dissolution promoter. If the film surface of the exposure portion is dissolved once, since the concentration of the hydrophobic resin (A) is relatively low, the dissolution of the film inside with high alkali solubility compared to the film surface is carried out rapidly. It is inferred from this that the contrast between the exposure portion and the unexposed portion can be increased, and as a result, the film reduction amount when the positive photosensitive resin composition is used as a cured product can be reduced, and the hole formation can be improved (wherein, the effect / effect of the present embodiment is not limited thereto).

[0088] On the other hand, when a hydrophobic resin and a fluorine-based surfactant are used in combination to make the film surface insoluble to an alkaline aqueous solution, the acid generated during exposure diffuses into the film, so compared with the case of using a hydrophobic resin (A) and a polysiloxane surfactant (D) having a silicon atom on the side chain, the acid concentration near the film surface and inside the film is more uniform. Therefore, it may be difficult to dissolve the film surface of the exposed portion during development, the sensitivity is reduced, and the film reduction amount when it is a cured film becomes larger. In addition, the photoacid generator has a low thermal stability, and it may be used to promote the dissolution of the unexposed portion and reduce the hole formation when using such a photoacid generator. However, according to the positive photosensitive resin composition of the present embodiment, the generation of such problems can be effectively suppressed (wherein, the effect / effect of the present embodiment is not limited thereto).

[0089] Hereinafter, each component which can be used for the positive photosensitive resin composition of this embodiment is demonstrated.

[0090] <Hydrophobic resin (A)>

[0091] The type of hydrophobic resin (A) is not particularly limited, for example, acrylic resin, polystyrene resin, epoxy resin, polyamide resin, phenolic resin, polyimide resin, polyamic acid resin, polybenzoxazole resin, polybenzoxazole resin precursor, polysiloxane resin, cyclic olefin polymer, Cardo resin and derivatives of these resins can be cited. The derivatives of these resins preferably have a hydrophobic group. As a suitable example of a hydrophobic group, for example, a silicon-containing atom group can be cited. As a hydrophobic resin (A), a homopolymer or copolymer of a polymerizable monomer with an alkali-soluble functional group can also be used as a base resin, and a part or all of the alkali-soluble functional group is converted into a resin obtained by a group with the hydrophobic group. Hydrophobic resin (A) can be used alone or in combination with more than two kinds.

[0092] The hydrophobic resin (A) is preferably a resin having a silicon atom-containing group. The hydrophobic resin (A) may have the silicon atom-containing group on the main chain or on the side chain (which may be a pendant), and preferably has the silicon atom-containing group on the side chain.

[0093] Examples of the silicon atom-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.

[0094] The silyl group substituted with an aliphatic hydrocarbon group or an aryl group is a 1-substituted body, a 2-substituted body or a 3-substituted body. 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 a 3-substituted body. 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 siloxy group substituted with an aliphatic hydrocarbon group or an aryl group.

[0095] The number of ring members of 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 be independently substituted with an aliphatic hydrocarbon group or an aryl group.

[0096] A part 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.

[0097] The aliphatic hydrocarbon group of the silyl group substituted with an aliphatic hydrocarbon group or an aryl group, the aliphatic hydrocarbon group as a substituent of the group having a cyclic siloxane structure, the aliphatic hydrocarbon group as a substituent of the group having a silsesquioxane structure, and the aliphatic hydrocarbon group as a substituent of the siloxy group substituted with an aliphatic hydrocarbon group or an aryl group are preferably aliphatic hydrocarbon groups having 1 to 20 carbon atoms, more preferably aliphatic hydrocarbon groups having 1 to 8 carbon atoms. Examples of the aliphatic hydrocarbon group 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 vinyl, propenyl, butenyl, ethynyl and propynyl; saturated monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl; unsaturated monocyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl and cyclodecenyl; saturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl and adamantyl; and unsaturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptenyl and bicyclo[2.2.2]octenyl.

[0098] The aryl group of the silyl group substituted with an aliphatic hydrocarbon group or an aryl group, the aryl group as a substituent of the group having a cyclic siloxane structure, the aryl group as a substituent of the group having a silsesquioxane structure, and the aryl group as a substituent of the siloxy 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 the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, fluorenyl, anthracenyl, and phenanthryl.

[0099] Examples of the silyl group 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 trimethylsiloxydimethylsilyl group.

[0100] Examples of the group having a cyclic siloxane structure include a pentamethylcyclotrimethylsiloxy group, a heptamethylcyclotetramethylsiloxy group, and a nonamethylcyclopentamethylsiloxy group.

[0101] Examples of the group having a silsesquioxane structure include a silsesquioxane group, a heptamethylsilsesquioxane group, a heptaethylsilsesquioxane group, a hepta(n-propyl)silsesquioxane group, and a hepta(n-butyl)silsesquioxane group.

[0102] The hydrophobic resin (A) can be manufactured, for example, by subjecting a polymerizable monomer having a hydrophobic group to free radical polymerization or by subjecting a polymerizable monomer having a hydrophobic group to free radical copolymerization with other polymerizable monomers. As polymerizable functional groups possessed by the polymerizable monomer having a hydrophobic group and other polymerizable monomers, for example, free radical polymerizable functional groups such as CH2=CH-, CH2=C(CH3)-, CH2=CHCO-, CH2=C(CH3)CO-, -OC-CH=CH-CO- can be cited. The hydrophobic resin (A) can also be manufactured by reacting a resin having functional groups such as hydroxyl, carboxyl, amino, and epoxy groups with a compound having a hydrophobic group to convert the functional group into a group containing a hydrophobic group.

[0103] In this embodiment, the hydrophobic resin (A) is a copolymer of a polymerizable monomer having a hydrophobic group and other polymerizable monomers. Examples of the polymerizable monomer having a hydrophobic group include a polymerizable monomer having a silicon atom-containing group.

[0104] Examples of the polymerizable monomer having a silicon atom-containing group include trimethylvinylsilane, trimethylallylsilane, trimethyl(3-butenyl)silane, tert-butyldimethylvinylsilane, (trimethylsiloxy)dimethylvinylsilane, (trimethylsiloxy)dimethylallylsilane, triethylvinylsilane, triethylallylsilane, triethyl(3-butenyl)silane, (trimethylsilyl)methyl(meth)acrylate, 2-(trimethylsilyl)ethyl(meth)acrylate, 3-(trimethylsilyl)propyl(meth)acrylate, tert-butyldimethylsilyl(meth)acrylate, triisopropylsilylmethyl(meth)acrylate, and the like. Ester, bis(trimethylsilylmethyl)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-(heptamethylsilsesquioxyl)propyl(meth)acrylate.

[0105] Examples of other polymerizable monomers include styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; and (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0106] Other polymerizable monomers may be polymerizable monomers having alkali-soluble functional groups. Examples of polymerizable monomers having alkali-soluble functional groups include maleic acid derivatives such as maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, and maleic anhydride; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; unsaturated carboxylic acid compounds such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid; polymerizable monomers having phenolic hydroxyl groups such as 4-hydroxystyrene and 4-hydroxyphenyl(meth)acrylate; polymerizable monomers having sulfonic groups such as (meth)allyl sulfonic acid and styrene sulfonic acid; polymerizable monomers having phosphate groups such as mono(2-(meth)acryloyloxyethyl) phosphate; and polymerizable monomers having anhydride groups such as itaconic anhydride and citraconic anhydride.

[0107] It should be noted that, as the polymerizable monomer having a hydrophobic group, 4-tert-butyldimethylsilyloxyphenyl (meth)acrylate and / or 4-hydroxyphenyl (meth)acrylate are preferably used, and both are more preferably used. By using a resin obtained by free radical polymerization of these polymerizable monomers, the sensitivity and pore forming properties of the positive photosensitive resin composition can be further improved, and outgassing can be further reduced.

[0108] The hydrophobic resin (A) preferably contains a structural unit represented by the following formula (1). For example, the polymerizable monomer having the hydrophobic group preferably forms a structural unit represented by the formula (1) after polymerization.

[0109] [Chemical formula 4]

[0110]

[0111] (In formula (1), R 1is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 SiR 3 R 4 R 5 , R 3 , R 4 and R 5 Each of them is 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 4, s is an integer of 1 to 5, wherein r+s is an integer of 1 to 5.)

[0112] In formula (1), R 1 It is preferably a hydrogen atom or a methyl group. 3 , R 4 and R 5 Each of them is independently preferably 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 such a polymerizable monomer having a hydrophobic group, 4-triethylsilyloxyphenyl methacrylate and 4-tert-butyldimethylsilyloxyphenyl (meth)acrylate are preferred.

[0113] As a preferred example of the formula (1), the following structural unit (1a) can be mentioned.

[0114] [Chemical formula 5]

[0115]

[0116] (In formula (1a), R 1a is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2a , R 3a and R 4a Each independently represents an alkyl group having 1 to 7 carbon atoms.)

[0117] In formula (1a), R 1a It is preferably a hydrogen atom or a methyl group. 2a , R 3a and R 4a Each independently is preferably methyl, ethyl, isopropyl, tert-butyl or phenyl.

[0118] The hydrophobic resin (A) may have a structural unit represented by the following formula (2) if necessary, but even if it does not have such a structural unit, sufficient effects can be obtained. For example, as other polymerizable monomers, monomers that form a structural unit represented by formula (2) after polymerization can be used.

[0119] [Chemical formula 6]

[0120]

[0121] (In formula (2), R6 and R 7 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 8 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 a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0122] R 6 and R 7 Each of R is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples thereof include cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, or phenyl groups substituted with at least one selected from hydroxyl groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. Examples of such other polymerizable monomers include phenylmaleimide and N-cyclohexylmaleimide.

[0123] However, in the positive photosensitive resin composition of the present embodiment, even if the hydrophobic resin (A) does not have the structural unit represented by the formula (2), sufficient effects can be obtained. In addition, even if the hydrophobic resin (A) does not have a maleimide structure in the structural unit, sufficient effects can be obtained. In addition, from the viewpoint that sufficient effects can be obtained, the hydrophobic resin (A) preferably does not have an imide skeleton in the structural unit. In addition, the hydrophobic resin (A) more preferably does not have a nitrogen atom.

[0124] The hydrophobic resin (A) preferably further has a structural unit represented by the following formula (3) if necessary. For example, the other polymerizable monomer having an alkali-soluble functional group preferably forms a structural unit represented by the formula (3) after polymerization.

[0125] [Chemical formula 7]

[0126]

[0127] (In formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.

[0128] In formula (3), R 9 It 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 (meth)acrylate is preferred.

[0129] An example of a preferred structural unit of the formula (3) includes the following structural unit (1b).

[0130] [Chemical formula 8]

[0131]

[0132] (In formula (1b), R 1b A hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0133] In formula (1b), R 1b A hydrogen atom or a methyl group is preferred. Specific examples of the compound of formula (1b) include, for example, 4-hydroxyphenyl (meth)acrylate.

[0134] The hydrophobic resin (A) is preferably a resin comprising a structural unit represented by the formula (1) and a structural unit represented by the formula (3), and more preferably a resin comprising a structural unit represented by the formula (1a) and a structural unit represented by the formula (1b). 1a R 1b It can be the same or different.

[0135] In the hydrophobic resin (A), the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (3) is preferably formula (1):formula (3)=5-70:10-95, and more preferably formula (1):formula (3)=10-50:30-90.

[0136] It should be noted that, as the polymerization initiator when the hydrophobic resin (A) is produced by free radical polymerization, there is no limitation in the following, and azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN) can be used; diisopropylphenyl peroxide Peroxide polymerization initiators having a 10-hour half-life temperature of 100 to 170°C such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylisopropyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, or benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, tert-butyl peroxypivalate, etc. The amount of the polymerization initiator used is generally preferably 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, and the upper limit is preferably 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerizable monomers.

[0137] In the polymerization of the hydrophobic resin (A), a RAFT (Reversible Addition Fragmentation Transfer) agent can be used in combination with a polymerization initiator. As a RAFT agent, it is not limited to the following substances, and thiocarbonyl thiocompounds such as dithioesters, dithiocarbamates, trithiocarbonates, and xanthates can be used. The RAFT agent can be used in the range of 0.005 to 20 parts by mass, preferably in the range of 0.01 to 10 parts by mass, relative to a total of 100 parts by mass of the polymerizable monomer.

[0138] In the case of a hydrophobic resin (A) having a silicon-containing group, the content of silicon atoms is based on the mass of the hydrophobic resin (A), preferably 1 to 10% by mass, more preferably 3 to 8% by mass. Its lower limit is more preferably 3% by mass or more, and more preferably 3.5% by mass or more. Its upper limit is more preferably 8% by mass or less, more preferably 7% by mass or less, more preferably 6% by mass or less, and more preferably 5% by mass or less. The hydrophobic resin (A) having a silicon-containing group is based on the whole structural unit of the hydrophobic resin (A), preferably 5 to 70 mol%, more preferably 10 to 50 mol% of the amount of the structural unit containing the silicon-containing group. Its lower limit is more preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 25 mol% or more. Its upper limit is more preferably 50 mol% or less, more preferably 40 mol% or less, and more preferably 35 mol% or less.

[0139] The hydrophobic resin (A) may or may not have an alkali-soluble functional group. The hydrophobic resin (A) preferably contains a structural unit having an alkali-soluble functional group in an amount of 20 to 90 mol%, more preferably 30 to 85 mol%, and further preferably 40 to 80 mol%, based on the whole structural unit of the hydrophobic resin (A). In the present embodiment, the hydrophobic resin (A) preferably does not have an alkali-soluble functional group.

[0140] The weight average molecular weight (Mw) of the hydrophobic resin (A) is preferably 3000 to 80000. The lower limit is more preferably 4000 or more, further preferably 5000 or more, further preferably 6000 or more, and further preferably 7000 or more. In addition, the upper limit is more preferably 70000 or less, further preferably 60000 or less, further preferably 30000 or less, further preferably 15000 or less, further preferably 13000 or less, and further preferably 10000 or less.

[0141] The number average molecular weight (Mn) of the hydrophobic resin (A) is preferably 1000 to 30000. The lower limit is more preferably 1500 or more, further preferably 2000 or more, further preferably 2500 or more, and further preferably 3000 or more. In addition, the upper limit is more preferably 25000 or less, further preferably 20000 or less, further preferably 10000 or less, and further preferably 5000 or less.

[0142] The polydispersity coefficient (Mw / Mn) of the hydrophobic resin (A) is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2.8. The lower limit is more preferably 1.1 or more, more preferably 1.2 or more, even more preferably 1.5 or more, and even more preferably 1.8 or more. The upper limit is more preferably 3.0 or less, even more preferably 2.8 or less, even more preferably 2.6 or less, and even more preferably 2.4 or less.

[0143] By setting the weight average molecular weight, number average molecular weight, and polydispersity coefficient within the above ranges, a positive photosensitive resin composition having more excellent sensitivity and pore-forming properties can be obtained.

[0144] The positive photosensitive resin composition of the present embodiment preferably contains a hydrophobic resin (A) at 3 to 50% by mass, more preferably at 4 to 40% by mass, and further preferably at 5 to 30% by mass, based on 100% by mass of solid content. In addition, the lower limit is more preferably 4% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, more preferably 10% by mass or more, and more preferably 12% by mass or more. The upper limit is more preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 18% by mass or less, and more preferably 16% by mass or less. When the content of the hydrophobic resin (A) is above the lower limit, the polysiloxane surfactant (D) promotes the partialization of the hydrophobic resin (A) to the surface of the film, and the hydrophobic resin (A) on the surface of the film becomes a high concentration, and the surface of the film is difficult to dissolve in an alkaline aqueous solution, so that further high sensitivity can be achieved. When the content of the hydrophobic resin (A) is below the upper limit, dissolution of the film surface proceeds rapidly along with the dissolution of the carboxylic acid compound derived from the quinonediazide compound, other resin components with high alkali solubility, and any dissolution accelerator in the exposed area, thereby achieving further high sensitivity.

[0145] In addition, the positive photosensitive resin composition of the present embodiment preferably contains 3 to 50 parts by mass, more preferably 4 to 40 parts by mass, and further preferably 5 to 30 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the solid content. In addition, the lower limit is more preferably 4 parts by mass or more, more preferably 5 parts by mass or more, more preferably 7 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 12 parts by mass or more. The upper limit is more preferably 40 parts by mass or less, more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and further preferably 16 parts by mass or less.

[0146] The positive photosensitive resin composition of the present embodiment contains a hydrophobic resin (A) based on the total mass of the resin components, preferably 5 to 60 mass%, more preferably 10 to 50 mass%, and further preferably 15 to 40 mass%. The lower limit is more preferably 10 mass% or more, more preferably 15 mass% or more, more preferably 20 mass% or more, and more preferably 25 mass% or more. The upper limit is more preferably 50 mass% or less, more preferably 40 mass% or less, more preferably 35 mass% or less, and more preferably 30 mass% or less. When the content of the hydrophobic resin (A) is above the lower limit, the polysiloxane surfactant (D) promotes the partialization of the hydrophobic resin (A) to the surface of the film, and the hydrophobic resin (A) on the surface of the film becomes a high concentration, and the surface of the film is difficult to dissolve in an alkaline aqueous solution, so that further high sensitivity can be achieved. When the content of the hydrophobic resin (A) is below the upper limit, dissolution of the film surface proceeds rapidly along with the dissolution of the carboxylic acid compound derived from the quinonediazide compound, other resin components with high alkali solubility, and any dissolution accelerator in the exposed area, thereby achieving further high sensitivity.

[0147] <Alkali-soluble resin (B)>

[0148] As for the positive photosensitive resin composition of this embodiment, as a resin other than the hydrophobic resin (A), it is preferred to further contain an alkali-soluble resin (B). The type of the alkali-soluble resin (B) is not particularly limited, and preferably a resin having an alkali-soluble functional group. The alkali-soluble functional group is not particularly limited, and phenolic hydroxyl group, carboxyl group, sulfonic group, phosphoric acid group, acid anhydride group and mercapto group can be cited. An alkali-soluble resin (B) having two or more alkali-soluble functional groups can be used. The alkali-soluble resin (B) can have an alkali-soluble functional group protected by an acid-decomposable group.

[0149] Specific examples of the alkali-soluble resin (B) include homopolymers or copolymers (B1) containing polymerizable monomers having an alkali-soluble functional group, resins (B2) having epoxy groups and phenolic hydroxyl groups, etc. The alkali-soluble resin (B) can be used alone or in combination of two or more.

[0150] The alkali-soluble resin (B) may have a radical polymerizable functional group. Specific examples of the radical polymerizable functional group include a (meth)acryloyloxy group, an allyl group, or a methallyl group.

[0151] In the case where the positive photosensitive resin composition of the present embodiment includes an alkali-soluble resin (B), based on 100% by mass of the solid content, the alkali-soluble resin (B) is preferably 5 to 80% by mass. The lower limit is more preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, more preferably 25% by mass or more, and more preferably 30% by mass or more. The upper limit is more preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 40% by mass or less. When the content of the alkali-soluble resin (B) is the amount of the above degree based on 100% by mass of the solid content, the reduction in dissolution and sensitivity of the exposed portion can be further suppressed, and the stability and durability of the film after thermal curing can be effectively ensured.

[0152] In addition, when the positive photosensitive resin composition of the present embodiment contains an alkali-soluble resin (B), the alkali-soluble resin (B) is preferably 5 to 80 parts by mass based on 100 parts by mass of the solid content. The lower limit is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, further preferably 20 parts by mass or more, further preferably 25 parts by mass or more, and further preferably 30 parts by mass or more. The upper limit is more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, further preferably 50 parts by mass or less, further preferably 45 parts by mass or less, and further preferably 40 parts by mass or less. By making the content of the alkali-soluble resin (B) the amount of the above-mentioned degree of formulation, the reduction in dissolution of the exposed part and the reduction in sensitivity can be further suppressed, and the stability and durability of the film after thermal curing can be effectively ensured.

[0153] In the case where the positive photosensitive resin composition of the present embodiment includes an alkali-soluble resin (B), the content thereof is not particularly limited, and the alkali-soluble resin (B) can be generally included in an amount of 0 to 90% by mass based on the total mass of the resin components. The upper limit may be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less. When the content of the alkali-soluble resin (B) is the above-described amount based on the total mass of the resin components, a certain alkali solubility can be effectively ensured, and a certain effect can be maintained.

[0154] <<Homopolymer or copolymer containing a polymerizable monomer having an alkali-soluble functional group (B1)>>

[0155] Examples of the alkali-soluble functional group possessed by the homopolymer or copolymer (B1) containing a polymerizable monomer having an alkali-soluble functional group include a phenolic hydroxyl group, a carboxyl group, a sulfone group, a phosphoric acid group, an acid anhydride group, and a mercapto group.

[0156] In addition, specific examples of the component (B1) include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenolic resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, polysiloxane resins, cyclic olefin polymers, cardo resins, and derivatives of these resins, which have alkali-soluble functional groups. For example, as derivatives of phenolic resins, polyalkenylphenolic resins having alkenyl groups bonded to benzene rings can be cited, and as derivatives of polystyrene resins, hydroxypolystyrene resin derivatives having phenolic hydroxyl groups and hydroxyalkyl or alkoxy groups bonded to benzene rings can be cited.

[0157] The copolymer of component (B1) may have two or more alkali-soluble functional groups. Examples of the polymerizable monomer having an alkali-soluble functional group and the polymerizable functional groups possessed by other polymerizable monomers include free radical polymerizable functional groups such as CH2=CH-, CH2=C(CH3)-, CH2=CHCO-, CH2=C(CH3)CO-, and -OC-CH=CH-CO-.

[0158] 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.

[0159] The copolymer having an alkali-soluble functional group can be produced by, for example, radically polymerizing a polymerizable monomer having an alkali-soluble functional group with other polymerizable monomers. After the copolymer is synthesized by radical polymerization, the alkali-soluble functional group may be added to the copolymer.

[0160] Examples of polymerizable monomers having an alkali-soluble functional group include maleic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester, maleic anhydride and other maleic acid derivatives; (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, β-styryl(meth)acrylic acid and other (meth)acrylic acid derivatives; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 6-maleimidocaproic acid and the like. unsaturated carboxylic acid compounds; polymerizable monomers having phenolic hydroxyl groups, such as 4-hydroxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, and 4-hydroxyphenylmaleimide; polymerizable monomers having sulfonic groups, such as (meth)allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, and styrene sulfonic acid; polymerizable monomers having phosphate groups, such as mono(2-(meth)acryloyloxyethyl) phosphate; and polymerizable monomers having anhydride groups, such as itaconic anhydride and citraconic anhydride.

[0161] From the viewpoint of sensitivity, the polymerizable monomer having an alkali-soluble functional group is preferably a (meth)acrylic acid derivative or a polymerizable monomer having a phenolic hydroxyl group, and more preferably a polymerizable monomer having a phenolic hydroxyl group.

[0162] Examples of other polymerizable monomers include styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; ether compounds of vinyl alcohol such as vinyl-n-butyl ether; and (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0163] The polymerizable monomer having an alkali-soluble functional group is preferably one that forms a structural unit represented by formula (3) after polymerization. 9 It is preferably a hydrogen atom or a methyl group. a is preferably an integer of 1 to 3, and more preferably 1. As such a polymerizable monomer having an alkali-soluble functional group, 4-hydroxyphenyl (meth)acrylate is particularly preferred.

[0164] [Chemical formula 9]

[0165]

[0166] (In formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.

[0167] As other polymerizable monomers, there may be mentioned those which form the structural unit represented by formula (2) after polymerization, but they may not be included. 6 and R 7 Each R is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples include cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, phenyl groups substituted with at least one selected from hydroxyl groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. As such other polymerizable monomers, phenylmaleimide and N-cyclohexylmaleimide can be mentioned. For the positive photosensitive resin composition of this embodiment, even if the alkali-soluble resin (B) does not contain such a maleimide skeleton, sufficient effects can be obtained. In addition, from the viewpoint of being able to obtain sufficient effects, the alkali-soluble resin (B) preferably does not have an imide skeleton in the structural unit. In addition, the alkali-soluble resin (B) more preferably does not have a nitrogen atom.

[0168] [Chemical formula 10]

[0169]

[0170] (In formula (2), R 6 and R 7 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 8 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 a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0171] In this embodiment, the copolymer having an alkali-soluble functional group may have a structural unit represented by formula (3) and a structural unit represented by formula (2). However, as described above, a sufficient effect can be obtained even without having a structural unit represented by formula (2).

[0172] [Chemical formula 11]

[0173]

[0174] (In formula (3), R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 5.

[0175] [Chemical formula 12]

[0176]

[0177] (In formula (2), R 6 and R 7 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 8 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 a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0178] As the polymerizable monomer having an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is used, and as other polymerizable monomers, phenylmaleimide or N-cyclohexylmaleimide may be used or may not be used.

[0179] The type and amount of the polymerization initiator used in producing the copolymer having an alkali-soluble functional group by free radical polymerization are the same as those described for the polymerization initiator used in producing the hydrophobic resin (A) by free radical polymerization. The type and amount of the RAFT agent that can be used in combination with the polymerization initiator are the same as those described for the RAFT agent used in producing the hydrophobic resin (A) by free radical polymerization.

[0180] 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 further 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 further preferably 2,000 to 20,000. The polydispersity index (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 further preferably 1.2 to 2.8. By making the weight average molecular weight, number average molecular weight and polydispersity index of the copolymer having an alkali-soluble functional group within the above range, a positive photosensitive resin composition having better coating properties, pore forming properties and alkali developability can be obtained.

[0181] 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 further 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 portion during alkali development can be sufficiently maintained. 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.

[0182] In this specification, the copolymer having an alkali-soluble functional group is regarded as a copolymer having an alkali-soluble functional group when it also meets the following resin having an epoxy group and a phenolic hydroxyl group. That is, the resin having an epoxy group and a phenolic hydroxyl group does not include a substance that meets the copolymer having an alkali-soluble functional group.

[0183] <<Resin having epoxy group and phenolic hydroxyl group (B2)>>

[0184] The resin having an epoxy group and a phenolic hydroxyl group is an alkaline aqueous solution soluble resin. The resin having an epoxy group and a phenolic hydroxyl group may have an alkali soluble functional group other than the phenolic hydroxyl group. As for the resin having an epoxy group and a phenolic hydroxyl group, for example, it can be obtained by reacting a part of the epoxy group of a compound having at least 2 epoxy groups in one molecule (hereinafter, there is a case where it is expressed as "epoxy compound") with the carboxyl group of a hydroxybenzoic acid compound. The epoxy group of the resin having an epoxy group and a phenolic hydroxyl group forms a crosslink by reacting with the phenolic hydroxyl group during the heat treatment (post-baking) after development, thereby improving the chemical resistance, heat resistance, etc. of the film. The phenolic hydroxyl group contributes to the solubility in alkaline aqueous solution during development, so the resin having an epoxy group and a phenolic hydroxyl group functions as a dissolution promoter of other resins when exposed by a low exposure amount, thereby further making the photosensitive resin composition highly sensitive.

[0185] An example of a reaction in which one epoxy group contained in an epoxy compound reacts with a carboxyl group of a hydroxybenzoic acid compound to generate a compound having a phenolic hydroxyl group is shown in the following reaction formula 1.

[0186] [Chemical formula 13]

[0187]

[0188] As a compound having at least 2 epoxy groups in 1 molecule, for example, novolac epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol epoxy resins, biphenol epoxy resins, epoxy resins containing naphthalene skeletons, alicyclic epoxy resins and heterocyclic epoxy resins can be cited. For these epoxy compounds, it is sufficient to have more than 2 epoxy groups in 1 molecule, and more than 2 kinds can be used alone or in combination. These compounds are thermosetting, and therefore, as common sense of those skilled in the art, their structures cannot be uniquely recorded due to differences such as the presence or absence of epoxy groups, the type of functional groups, and the degree of polymerization.

[0189] An example of the structure of a novolac epoxy resin is shown in formula (4). In formula (4), R 10 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a hydroxyl group; and m is an integer of 1 to 50.

[0190] [Chemical formula 14]

[0191]

[0192] Examples of the phenol novolac epoxy resin include "EPICLON (registered trademark) N-770", "EPICLON (registered trademark) N-730A" (as described above, trade names, DIC Corporation) and "jER (registered trademark) -152" (trade name, MITSUBISHI CHEMICAL Co., Ltd.). Examples of the cresol novolac epoxy resin include "EPICLON (registered trademark) N-695 (trade name, DIC Corporation)" and "EOCN (registered trademark) -102S" (trade name, Nippon Kayaku Co., Ltd.). Examples of bisphenol epoxy resins include bisphenol A epoxy resins such as "jER (registered trademark) 828", "jER (registered trademark) 1001" (as described above, trade names, MITSUBISHI CHEMICAL Co., Ltd.), and "YD-128" (trade name, NIPPON STEEL CHEMICAL CO., LTD.), and bisphenol F epoxy resins such as "jER (registered trademark) 806" (trade name, MITSUBISHI CHEMICAL Co., Ltd.), and "YDF-170" (trade name, NIPPON STEEL CHEMICAL CO., LTD.). Examples of biphenol epoxy resins include "jER (registered trademark) YX-4000" and "jER (registered trademark) YL-6121H" (as described above, trade names, MITSUBISHI CHEMICAL CO., LTD.). Examples of epoxy resins containing a naphthalene skeleton include "NC-7000" (trade name, Nippon Kayaku Co., Ltd.) and "EXA-4750" (trade name, DIC Corporation). Examples of alicyclic epoxy resins include "EHPE (registered trademark)-3150" (Daicel Corporation). Examples of heterocyclic epoxy resins include "TEPIC (registered trademark)", "TEPIC (registered trademark)-L", "TEPIC (registered trademark)-H" and "TEPIC (registered trademark)-S" (as mentioned above, trade names, Nissan Chemical Co., Ltd.).

[0193] As component (B2), the compound having at least two epoxy groups in one molecule is preferably a novolac epoxy resin, more preferably at least one selected from a phenol novolac epoxy resin and a cresol novolac epoxy resin, and further preferably a cresol novolac epoxy resin. A positive photosensitive resin composition containing a resin having epoxy groups and phenolic hydroxyl groups derived from a novolac epoxy resin, especially a cresol novolac epoxy resin, has better pore forming properties, easier adjustment of alkali solubility, and less outgassing.

[0194] The hydroxybenzoic acid compound is a compound in which at least one of the 2-6 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. From the perspective of improving alkali developability, dihydroxybenzoic acid compounds are preferred. The hydroxybenzoic acid compound may be used alone or in combination of two or more.

[0195] In the present embodiment, specific examples of the resin having an epoxy group and a phenolic hydroxyl group include a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, which has a structure of formula (5).

[0196] [Chemical formula 15]

[0197]

[0198] (In formula (5), b is an integer of 1 to 5, and * represents a bonding site of a compound having at least two epoxy groups in one molecule to a residue other than the epoxy group involved in the reaction.)

[0199] In the method of obtaining a resin having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound, 0.2 to 0.95 equivalents of the hydroxybenzoic acid compound can be used relative to 1 equivalent of the epoxy group of the epoxy compound, preferably 0.3 to 0.9 equivalents, and more preferably 0.4 to 0.8 equivalents. When the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and when it is 0.95 equivalents or less, the increase in molecular weight caused by side reactions can be suppressed.

[0200] In order to promote the reaction of the epoxy compound and the hydroxybenzoic acid compound, a catalyst can be used. The amount of the catalyst used is based on 100 parts by mass of the reaction raw material mixture containing the epoxy compound and the hydroxybenzoic acid compound, and can be 0.1 to 10 parts by mass. The reaction temperature can be 60 to 150° C. and the reaction time can be 3 to 30 hours. As the catalyst used in the reaction, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate and zirconium octanoate can be cited.

[0201] The number average molecular weight (Mn) of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and even more preferably 1000 to 5000. The lower limit is more preferably 800 or more, more preferably 1000 or more, and even more preferably 2000 or more. The upper limit is more preferably 6000 or less, more preferably 5000 or less, and even more preferably 4000 or less.

[0202] The weight average molecular weight (Mw) of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 30,000, more preferably 2,000 to 25,000, and even more preferably 3,000 to 20,000. The lower limit is more preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more. The upper limit is more preferably 25,000 or less, more preferably 20,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and even more preferably 7,000 or less.

[0203] For example, when the number average molecular weight is 500 or more or the weight average molecular weight is 500 or more, the alkali development speed is appropriate and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is better. When the number average molecular weight is 8000 or less or the weight average molecular weight is 30000 or less, the coating property and alkali developability are better.

[0204] The polydispersity coefficient (Mw / Mn) of the resin having an epoxy group and a phenolic hydroxyl group is preferably 1.0 to 3.5. The lower limit is more preferably 1.2 or more, and further preferably 1.5 or more. The upper limit is more preferably 3.0 or less, and further preferably 2.0 or less.

[0205] In the present embodiment, the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is preferably 300 to 7000, more preferably 400 to 6000, and further preferably 500 to 5000. The lower limit is more preferably 400 or more, more preferably 500 or more, more preferably 1000 or more, and further preferably 1500 or more. The upper limit is more preferably 6000 or less, more preferably 5000 or less, more preferably 4000 or less, and further preferably 3000 or less. 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 by the resin having an epoxy group and a phenolic hydroxyl group. When the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 7000 or less, the strength and heat resistance of the cured film can be further improved. The epoxy equivalent is determined by JIS K 7236:2009.

[0206] In the present embodiment, the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is preferably 140 to 550, more preferably 160 to 500, further preferably 170 to 400, and further preferably 180 to 300. When the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is above the upper limit, the strength and heat resistance of the cured film can be further improved. For example, when the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is above 160, the strength and heat resistance of the cured film can be further improved. When the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is below the lower limit, sufficient alkali solubility can be imparted by the resin having an epoxy group and a phenolic hydroxyl group. For example, when the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is below 500, more sufficient alkali solubility can be imparted to the resin having an epoxy group and a phenolic hydroxyl group. The hydroxyl equivalent is determined by JIS K0070:1992.

[0207] <<Protective resin (B3)>>

[0208] The alkali-soluble resin (B) may include a resin having an alkali-soluble functional group protected by an acid-decomposable group (hereinafter also referred to as a "protective resin"). The protective resin (B3) is not particularly limited as long as it has multiple alkali-soluble functional groups and at least a portion of the multiple alkali-soluble functional groups is protected by an acid-decomposable group. As the protective resin (B3), for example, a resin having the alkali-soluble resin (B) having multiple alkali-soluble functional groups as a base resin and at least a portion of its alkali-soluble functional groups being protected by an acid-decomposable group can be cited. As the alkali-soluble functional group, for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic group, a phosphoric acid group, an anhydride group and a mercapto group can be cited. The alkali-soluble functional group is preferably a phenolic hydroxyl group or a carboxyl group, more preferably a phenolic hydroxyl group. By protecting a portion of the alkali-soluble functional groups with acid-decomposable groups, the alkali solubility of the protective resin (B3) before exposure is suppressed. The protective resin (B3) may have alkali-soluble functional groups other than alkali-soluble functional groups protected with acid-decomposable groups. By performing post-exposure baking (PEB, post exposure bake) as needed in the presence of an acid generated during exposure, the decomposition (deprotection) of the acid-decomposable groups is promoted to regenerate the alkali-soluble functional groups. This promotes the alkali dissolution of the protective resin (B3) in the exposed part during development. The protective resin (B3) may be used alone or in combination of two or more. For example, the protective resin (B3) may be a combination of two or more resins having different structural units, acid-decomposable groups, and alkali-soluble functional group protection rates or a combination of these in a polymer or copolymer.

[0209] (Protection of Alkali-Soluble Functional Groups by Acid-Decomposable Groups)

[0210] The protective resin (B3) can be obtained by protecting a part of the alkali-soluble functional groups of the base resin having a plurality of alkali-soluble functional groups with an acid-decomposable group. For example, when the alkali-soluble functional group is a phenolic hydroxyl group, the protective resin (B3) having the phenolic hydroxyl group protected with an acid-decomposable group has Ar-OR 11 Partial structure, Ar represents the aromatic ring derived from phenol, R 11 It represents an acid-decomposable group.

[0211] The acid-decomposable group is a group that is decomposed (deprotected) by heating as needed in the presence of an acid to generate an alkali-soluble functional group. Specifically, for example, groups having tertiary alkyl groups such as tert-butyl, 1,1-dimethyl-propyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methyladamantyl, 1-ethyladamantyl, tert-butoxycarbonyl, 1,1-dimethyl-propoxycarbonyl, and the like; and groups represented by formula (6). When the alkali-soluble functional group is a phenolic hydroxyl group, the group represented by formula (6) forms an acetal structure or a ketal structure together with an oxygen atom derived from the alkali-soluble functional group. These acid-decomposable groups can be used alone or in combination of two or more.

[0212] -CR 12 R 13 -OR 14 …(6)

[0213] (In formula (6), R 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 14 is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, R 12 or R 13 One of them can be combined with R 14 The ring structure is formed by bonding to form a ring structure having 3 to 10 ring members, R 12 , R 13 and R 14 Optionally substituted with a halogen atom selected from chlorine, bromine and iodine.)

[0214] From the viewpoint of efficiently obtaining a photosensitive resin composition with high sensitivity even at a low exposure amount, the acid-decomposable group is preferably a group represented by formula (6). 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 14More preferably, it is a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which is optionally substituted with a halogen atom selected from chlorine, bromine and iodine. Examples of such an acid-decomposable group include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-cyclohexyloxyethyl and 1-(2-cyclohexylethoxy)ethyl, preferably 1-ethoxyethyl and 1-n-propoxyethyl. As the acid-decomposable group, a group represented by formula (6) can be suitably used, wherein R 12 or R 13 One of them and R 14 The ring structure is formed by bonding to form a ring structure having 3 to 10 ring members. 12 or R 13 A hydrogen atom is preferred. Examples of such an acid-decomposable group include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, and a 2-tetrahydrofuranyl group is preferred.

[0215] The protection reaction of the alkali-soluble functional group can be carried out using a common protective agent under known conditions. For example, the protective resin (B3) can be obtained by reacting the base resin of the protective resin (B3) with the protective agent in the presence of an acid or a base at a reaction temperature of -20 to 50°C in the absence of a solvent or in a solvent such as toluene or hexane.

[0216] As a protective agent, a known protective agent capable of protecting an alkali-soluble functional group can be used. As a protective agent, for example, isobutylene can be used when the acid-decomposable group is a tert-butyl group, and di-tert-butyl dicarbonate can be used when it is a tert-butoxycarbonyl group. When the acid-decomposable group is a methoxymethyl group, chloromethyl methyl ether can be used, when it is a 1-ethoxyethyl group, ethyl vinyl ether can be used, when it is a 1-n-propoxyethyl group, n-propyl vinyl ether can be used, when it is a 2-tetrahydrofuranyl group, 2,3-dihydrofuran can be used, and when it is a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran can be used.

[0217] As the acid, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid can be cited. Salts of organic acids, such as pyridinium salts of p-toluenesulfonic acid, can also be used as an acid supply source. As the base, for example, inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate, metal hydrides such as sodium hydride, and amine compounds such as pyridine, N,N-dimethyl-4-aminopyridine, imidazole, triethylamine, and diisopropylethylamine can be cited.

[0218] In another embodiment, after the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group is protected with an acid-decomposable group, the polymerizable monomer having an alkali-soluble functional group protected with an acid-decomposable group and other polymerizable monomers as required are polymerized or copolymerized to obtain a protected resin (B3). The protection of the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group can be carried out by the same method as the protection of the alkali-soluble functional group of the base resin.

[0219] The protective resin (B3) has a structural unit represented by the formula (7), and preferably has at least one structural unit represented by the formula (7) wherein q is an integer of 1 or more.

[0220] [Chemical formula 16]

[0221]

[0222] (In formula (7), R 15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 16 is an acid-decomposable group, p is an integer of 0 to 5, q is an integer of 0 to 5, wherein p+q is an integer of 1 to 5. )

[0223] It should be noted that, in the formula, R 16 The acid-decomposable group is preferably a group represented by formula (6).

[0224] -CR 12 R 13 -OR 14 …(6)

[0225] (In formula (6), R 12 , R 13 and R 14 As described above.)

[0226] In formula (6), R 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R 14More preferably, it is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which is optionally substituted with a halogen atom selected from chlorine, bromine and iodine. Examples of such an acid-decomposable group include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-cyclohexyloxyethyl and 1-(2-cyclohexylethoxy)ethyl, preferably 1-ethoxyethyl and 1-n-propoxyethyl. As R 12 or R 13 One of them and R 14 Examples of the acid-decomposable group that is bonded to form a ring structure having 3 to 10 ring members include 2-tetrahydrofuranyl and 2-tetrahydropyranyl, and 2-tetrahydrofuranyl is preferred.

[0227] The protective resin (B3) may or may not have the structural unit represented by formula (2). Even if the protective resin (B3) does not have the structural unit represented by formula (2), sufficient effects can be obtained. From the viewpoint of being able to obtain sufficient effects, the protective resin (B3) preferably does not have an imide skeleton in the structural unit. In addition, the protective resin (B3) more preferably does not have a nitrogen atom.

[0228] [Chemical formula 17]

[0229]

[0230] (In formula (2), R 6 and R 7 are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 8 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 a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0231] In formula (2), R 6 and R 7 Each of them independently includes a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples thereof include 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 hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0232] In the present embodiment, the number of structural units represented by formula (7) in which q is an integer greater than 1, i.e., structural units represented by formula (7) in which at least one alkali-soluble functional group is protected by an acid-decomposable group, is preferably 5 to 95% of the total number of structural units of the protective resin (B3), more preferably 15 to 90%, and even more preferably 25 to 85%. By making the proportion of the structural units greater than 5%, the dissolution of the exposed portion can be further promoted and the solubility of the unexposed portion and the exposed portion can be further differentiated, thereby further achieving high sensitivity and effectively ensuring the stability and durability of the film after thermal curing. By making the proportion of the structural units less than 95%, the residual amount of unreacted acid-decomposable groups can be further reduced, the solubility of the exposed portion can be improved, and high sensitivity can be further achieved.

[0233] In this embodiment, the positive photosensitive resin composition preferably contains the protective resin (B3) at 0.5 to 50% by mass, more preferably at 1 to 40% by mass, and further preferably at 2 to 30% by mass, based on 100% by mass of the solid content. When the content of the protective resin (B3) is above the lower limit value based on 100% by mass of the solid content, the dissolution of the exposed part is further promoted, and the solubility of the unexposed part and the exposed part is further different, so that high sensitivity can be further achieved, and the stability and durability of the film after thermal curing can be effectively ensured. When the content of the protective resin (B3) is below the upper limit value based on 100% by mass of the solid content, the residual amount of unreacted acid-decomposable groups can be further reduced, the solubility of the exposed part is improved, and high sensitivity can be further achieved.

[0234] <Quinonediazide compound (C)>

[0235] When the quinonediazide compound (C) is irradiated with visible light, ultraviolet light, or radiation (gamma rays, electron beams, etc.), it undergoes a reaction represented by the following reaction formula 2 to generate an alkali-soluble carboxylic acid compound.

[0236] [Chemical formula 18]

[0237]

[0238] As for the quinonediazide compound (C), before exposure, it interacts with the alkali-soluble functional groups of the alkali-soluble resin (B), such as phenolic hydroxyl groups (e.g., forming hydrogen bonds), so that the alkali-soluble resin (B) is insoluble in alkaline aqueous solution. On the other hand, by the presence of an alkali-soluble carboxylic acid compound in the portion irradiated with radiation, the resin located in this portion is easily dissolved in the alkaline aqueous solution together with the carboxylic acid compound. In addition, the generated carboxylic acid compound promotes the decomposition of the acid-decomposable group of the protective resin (B3) arbitrarily contained in the positive photosensitive resin composition, regenerates the alkali-soluble functional group, and increases the alkali solubility of the protective resin (B3). In addition, the carboxylic acid compound has a relatively large molecular structure compared to the acid generated by the photoacid generator commonly used in chemically amplified resists, such as p-toluenesulfonic acid, 1-propanesulfonic acid, etc., and is not easy to diffuse in the film. As a result of these synergistic effects, the difference in alkali solubility between the unexposed portion and the exposed portion can be increased, thereby forming a high-resolution pattern with high sensitivity even at low exposure. The quinonediazide compound (C) can be used alone or in combination of two or more.

[0239] The positive photosensitive resin composition preferably does not substantially contain a photoacid generator commonly used in chemically amplified resists, and more preferably does not contain the photoacid generator and contains only a quinonediazide compound (C) as a photosensitizer. "Substantially containing no photoacid generator" means that the component is not actively added or mixed, but does not exclude the inclusion or mixing that is unavoidable. As a suitable example of the case of "substantially containing no photoacid generator", the amount of the photoacid generator contained in the positive photosensitive resin composition is preferably 0.2 parts by mass or less, more preferably 0.1 parts by mass or less, more preferably 0.05 parts by mass or less, and even more preferably 0 parts by mass, based on 100 parts by mass of the total resin components.

[0240] In this embodiment, a high-resolution pattern can be formed without performing the post-exposure heat treatment (PEB) required for a conventional chemically amplified resist. The quantum yield of the quinonediazide compound (C) is relatively high, and a carboxylic acid compound is efficiently generated in the exposed portion. By omitting PEB, it is possible to avoid a decrease in pore formation caused by excessive diffusion of the acid generated by the photoacid generator to the unexposed portion under the high temperature environment of the PEB process. In addition, when the alkali-soluble resin (B) contains a resin having an epoxy group and a phenolic hydroxyl group, when PEB is omitted, the ring-opening polymerization of the epoxy group of the resin having an epoxy group and a phenolic hydroxyl group is not performed, so that the alkali solubility of the resin having an epoxy group and a phenolic hydroxyl group can be effectively maintained during development.

[0241] Examples of the quinonediazide compound (C) include a compound in which the sulfonic acid of a quinonediazide is ester-bonded to a polyhydroxy compound, a compound in which the sulfonic acid of a quinonediazide is ester-bonded to a polyamino compound, a compound in which the sulfonic acid of a quinonediazide is ester-bonded or sulfonamide-bonded to a polyhydroxypolyamino compound, etc. From the viewpoint of further improving the contrast between the exposed portion and the unexposed portion, it is preferred that 20 mol% or more of the functional groups of the polyhydroxy compound or the polyamino compound are substituted with quinonediazide.

[0242] Examples of the 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", "dihydroxymethyl-BisOC-P", "DML-PFP", "DML-PSBP", "DML-MTrisPC", and "TriML- P", "TriML-35XL", "TML-BP", "TML-HQ", "TML-pp-BPF", "TML-BPA", "TMOM-BP", "HML-TPPHBA", "HML-TPHAP" (as mentioned above, trade names, Honshu Chemical Industry Co., Ltd.), "BIR-OC", "BIP-PC", "BIR-PC", "BIR-PTBP", "BIR-PCHP", "BIP-BIOC-F", "4PC", "BI R-BIPC-F", "TEP-BIP-A", "46DMOC", "46DMOEP", "TM-BIP-A" (as mentioned above, trade name, Asahi Organic Materials Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, "BisP-AP" (trade name, Honshu Chemical Industry Co., Ltd.), etc., but not limited to these.

[0243] Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, and 4,4′-diaminodiphenyl sulfide, but are not limited thereto.

[0244] Examples of the polyhydroxypolyamino compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3′-dihydroxybenzidine, but are not limited thereto.

[0245] The quinonediazide compound (C) is preferably a 1,2-diazide naphthoquinone-5-sulfonate of a polyhydroxy compound or a 1,2-diazide naphthoquinone-4-sulfonate of a polyhydroxy compound. For example, commercial products such as "TS-150A", "TS-200A" and "TPPA-150DF" (as mentioned above, trade names, Toyo Gosei Kogyo Co., Ltd.) can be used.

[0246] In the present embodiment, the positive photosensitive resin composition preferably contains the quinonediazide compound (C) in an amount of 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 15 to 42 parts by mass, based on a total of 100 parts by mass of the resin components. The lower limit is more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 25 parts by mass or more. The upper limit is more preferably 50 parts by mass or less, more preferably 42 parts by mass or less, more preferably 37 parts by mass or less, and further preferably 35 parts by mass or less. When the content of the quinonediazide compound (C) is above the lower limit value based on the total of 100 parts by mass, high sensitivity can be achieved. When the content of the quinonediazide compound (C) is below the upper limit value based on the total of 100 parts by mass, alkali developability is good.

[0247] In addition, the positive photosensitive resin composition of the present embodiment preferably contains quinonediazide compound (C) in an amount of 2.5 to 30 parts by mass based on 100 parts by mass of solid content. The lower limit is more preferably 5 parts by mass or more, further preferably 7.5 parts by mass or more, further preferably 10 parts by mass or more, and further preferably 12.5 parts by mass or more. The upper limit is more preferably 25 parts by mass or less, further preferably 21 parts by mass or less, further preferably 18.5 parts by mass or less, and further preferably 17.5 parts by mass or less. When the content of quinonediazide compound (C) is above the lower limit, high sensitivity can be achieved. When the content of quinonediazide compound (C) is below the upper limit, alkali developability is good.

[0248] <Polysiloxane surfactant having silicon atoms on the side chain (D)>

[0249] The polysiloxane surfactant (D) is not particularly limited, and may be a polysiloxane surfactant having a silicon atom on the side chain. As such a polysiloxane surfactant (D), for example, a polysiloxane surfactant comprising a (meth) acrylic copolymer having at least one silicon-atom-containing hydrocarbon group selected from a silicon-atom-containing alkyl group and a silicon-atom-containing alkylene group is preferred. The acrylic copolymer can promote the movement of the hydrophobic resin (A) to the film surface of the positive photosensitive resin composition, making the film surface further alkali-insoluble. In addition, from the viewpoint of further improving the relevant effect, the polysiloxane surfactant (D) is preferably a polysiloxane surfactant having no silicon atom on the main chain and having a silicon atom on the side chain. The polysiloxane surfactant (D) can be used alone or in combination of two or more.

[0250] Examples of the (meth)acrylic copolymer include a copolymer (D1) of a polymerizable monomer represented by formula (8) and a polymerizable monomer having a polyoxyalkylene group represented by formula (9).

[0251] [Chemical formula 19]

[0252]

[0253] (In formula (8), R 17 is a hydrogen atom or a methyl group, L 1 is a divalent group having 1 to 30 carbon atoms, Rf 1 It is a silicon-containing alkyl group or a partially silicified alkyl group having 4 to 6 carbon atoms and optionally containing one or more ether bonds in the chain.

[0254] [Chemical formula 20]

[0255]

[0256] (In formula (9), R 18 is a hydrogen atom or a methyl group, R 19 are each independently a linear or branched alkylene group having 2 to 4 carbon atoms, R 20 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and c is an integer of 2 to 50.

[0257] In formula (8), L 1 The divalent group having 1 to 30 carbon atoms represented by may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and may also contain a silicon atom-containing alkyl group or a partially silicified alkyl group having 4 to 6 carbon atoms. 1Preferred are -OCH2CH2-, -OCH2CH2N(C3H7)SO2-, -OCH2CH2NH(C=O)OCH2CH2-, -OCH2CH(OH)CH2O- or -N(C4H9)CH2CH2-.

[0258] The polymerizable monomer represented by formula (8) can be used alone or in combination of two or more.

[0259] In formula (9), as R 19 The straight-chain or branched alkylene group having 2 to 4 carbon atoms represented by R includes ethylene, propylene, tetramethylene, isobutylene and the like. 19 They may be the same or different from each other. From the perspective of leveling, R 19 It is preferably a propylene group, a tetramethylene group or an isobutylene group, and more preferably the same group is linked multiple times via adjacent oxygen atoms to form a polyoxypropylene chain, a polytetramethylene chain or a polyisobutylene chain.

[0260] In formula (9), as R 20 Examples of the alkyl group having 1 to 6 carbon atoms represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl.

[0261] The polymerizable monomer having a polyoxyalkylene group represented by formula (9) may be used alone or in combination of two or more.

[0262] The copolymer (D1) may be a copolymer with other polymerizable monomers in addition to the polymerizable monomer represented by the formula (8) and the polymerizable monomer having a polyoxyalkylene group represented by the formula (9).

[0263] As other polymerizable monomers, for example, there can be mentioned polymerizable monomers represented by formula (10).

[0264] [Chemical formula 21]

[0265]

[0266] (In formula (10), R 21 is a hydrogen atom or a methyl group, R 22 It is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.

[0267] In formula (10), as R 22 The straight-chain, branched or cyclic alkyl group having 1 to 18 carbon atoms can be exemplified by methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, stearyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, isobornyl, adamantyl, dicyclopentyl and dicyclopentenyl.

[0268] Examples of other polymerizable monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0269] Other polymerizable monomers may be used alone or in combination of two or more.

[0270] From the viewpoint of leveling properties, the mass ratio of the polymerizable monomer represented by formula (8) to the polymerizable monomer having a polyoxyalkylene group represented by formula (9) in the copolymer (D1) (mass of the polymerizable monomer represented by formula (8) / mass of the 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 still more preferably 25 / 75 to 50 / 50. When other polymerizable monomers are used, they are preferably used in an amount that is 50% by mass or less based on the mass of the copolymer (D1).

[0271] As for the copolymer (D1), for example, it can be obtained by free radical polymerization of a polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), and other polymerizable monomers as needed in an organic solvent using a polymerization initiator. As an organic solvent, for example, 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. As a polymerization initiator, for example, peroxide polymerization initiators such as benzoyl peroxide and azo polymerization initiators such as 2,2'-azobisisobutyronitrile can be mentioned. Chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl thioglycolate, and octyl thioglycolate can be used as needed.

[0272] Preferred specific examples of the polysiloxane-based surfactant (D) include "MEGAFACE EFS-131", "MEGAFACE EFS-321", "MEGAFACE EFS-521" and "MEGAFACE EFS-801" (as described above, these are trade names, all manufactured by DIC Corporation).

[0273] In particular, from the viewpoint of being fluorine-free, having silicon atoms on the side chains and not having silicon atoms on the main chain, and containing both the structure represented by the above formula (8) and the structure represented by the formula (9), "MEGAFACE EFS-131", "MEGAFACE EFS-321" and "MEGAFACE EFS-521" are more preferred. These are (meth)acrylic copolymers having no silicon atoms on the main chain and having at least one silicon-containing hydrocarbon group selected from a silicon-containing alkyl group and a silicon-containing alkylene group.

[0274] The content of the polysiloxane surfactant (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 further preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total resin component. The lower limit is more preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, and further preferably 0.15 parts by mass or more. The upper limit is more preferably 3 parts by mass or less, more preferably 2 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less. When the content of the polysiloxane surfactant (D) is more than the lower limit value based on 100 parts by mass of the total, the leveling property of the positive photosensitive resin composition is further improved, so that the positive photosensitive resin composition can be applied to the substrate more uniformly, thereby further promoting the localization of the hydrophobic resin (A). When the content of the polysiloxane surfactant (D) is not more than the upper limit based on 100 parts by mass of the total, the leveling property of the positive photosensitive resin composition can be improved without adversely affecting the cured film after post-baking, and localization of the hydrophobic resin (A) can be further promoted.

[0275] In addition, the positive photosensitive resin composition of the present embodiment preferably contains a polysiloxane surfactant (D) in an amount of 0.005 to 2.5 parts by mass based on 100 parts by mass of solid content. The lower limit is more preferably 0.025 parts by mass or more, further preferably 0.05 parts by mass or more, and further preferably 0.075 parts by mass or more. The upper limit is more preferably 1.5 parts by mass or less, further preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less. When the content of the polysiloxane surfactant (D) is above the lower limit, the leveling property of the positive photosensitive resin composition is further improved, so that the positive photosensitive resin composition can be more evenly applied to the substrate, thereby further promoting the partialization of the hydrophobic resin (A). When the content of the polysiloxane surfactant (D) is below the upper limit, it will not adversely affect the cured film after post-baking, can improve the leveling property of the positive photosensitive resin composition, and further promote the partialization of the hydrophobic resin (A).

[0276] In addition, the content of (D) component in the total amount of surfactant is preferably 50 mass % or more. The lower limit of this content is more preferably 60 mass % or more, more preferably 70 mass % or more, more preferably 80 mass % or more, more preferably 85 mass % or more, more preferably 90 mass % or more, more preferably 95 mass % or more, more preferably 98 mass % or more. In addition, it is more preferably only (D) component (100 mass %). Wherein, the upper limit of this content can be 95 mass % or less, can be 90 mass % or less, even with such an upper limit, the desired effect can be obtained. By making the content of (D) component within the range, it is possible to ensure wettability with the substrate, and it is possible to apply evenly without repelling.

[0277] <Colorant (E)>

[0278] The positive photosensitive resin composition preferably further contains a colorant (E) containing a black dye. The (E) component may contain other colorants other than the black dye. By using a photosensitive resin composition containing a colorant (E) containing a black dye to form a black partition wall in an organic EL element, the visual recognition of a display device such as an organic EL display can be improved.

[0279] In the present embodiment, there is a tendency that the amount of radiation transmitted during exposure due to the deployment of coloring agent (E) is sharply reduced from the surface of the film to the inside. Therefore, the carboxylic acid compound from the quinonediazide compound (C) source is relatively more produced near the film surface, and is not easy to produce inside the film. The diffusibility of the carboxylic acid compound from the quinonediazide compound (C) source in the film is low, so it stays near the film surface and helps to promote the dissolution of the film surface of the exposure portion. Since the concentration of the hydrophobic resin (A) is relatively low inside the film, the alkali solubility is relatively high. Therefore, even in the case where radiation cannot be fully transmitted to the inside of the film, by using the positive photosensitive resin composition of the embodiment, it is also possible to form a high-precision thick film pattern with high sensitivity (wherein, the effect / effect of the present embodiment is not limited thereto).

[0280] As the black dye, for example, dyes specified in the color index (CI) of solvent black 27 to 47 can be cited. Preferably, it is a black dye specified in the CI of solvent black 27, 29 or 34. When at least one of the dyes specified in the CI of solvent black 27 to 47 is used as the black dye, the light shielding property of the film of the positive photosensitive resin composition after curing can be effectively maintained. Compared with the positive photosensitive resin composition containing a black pigment, the positive photosensitive resin composition containing a black dye has less colorant residue during development, and a high-definition pattern can be formed.

[0281] As black pigment, for example, carbon black, carbon nanotube, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigment and lactam pigment can be cited. The black pigment obtained by surface treatment can be used. As commercially available perylene pigment examples, BASF's K0084, K0086, Pigment Black 21, 30, 31, 32, 33 and 34 can be cited. As commercially available lactam pigment examples, BASF's Irgaphor (registered trademark) BLACK S0100CF can be cited. From the aspect of having higher light-shielding properties, the black pigment is preferably at least one selected from carbon black, titanium black, perylene pigment and lactam pigment.

[0282] On the other hand, dyes and pigments other than those described above may be used in combination. These may be used according to the purpose within a range that does not impair the function and effect of the present embodiment.

[0283] As dyes other than those mentioned above, for example, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, crotonyl cyanine dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes and azulene dyes can be mentioned.

[0284] As pigments other than those mentioned above, for example, CI Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI Pigment Orange 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, CI Pigment Blue 15, 15:1, 15:4, 22, 60, 64, CI Pigment Green 7, and CI Pigment Brown 23, 25, 26 can be mentioned.

[0285] However, in the present embodiment, it is preferred to increase the content of the black dye and reduce the content of other colorants (e.g., pigments, etc.). From such a viewpoint, the content of colorants other than the black dye in the total amount of the colorant (E) is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably not contained (0% by mass).

[0286] The content of the colorant (E) in the positive photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass, and further preferably 20 to 80 parts by mass, based on 100 parts by mass of the total resin component. The lower limit is more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and further preferably 30 parts by mass or more. The upper limit is more preferably 100 parts by mass or less, more preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and further preferably 70 parts by mass or less. When the content of the colorant (E) is more than the lower limit value based on the total 100 parts by mass, sufficient light-shielding properties can be obtained, and in particular, when the colorant (E) contains a black dye, the light-shielding properties of the cured film can be effectively maintained. When the content of the colorant (E) is not more than the upper limit based on 100 parts by mass of the total, the residual film rate and sensitivity are appropriate, and particularly when the colorant (E) contains a black dye, high heat resistance can be imparted to the film.

[0287] In addition, the positive photosensitive resin composition of the present embodiment preferably contains a colorant (E) in an amount of 5 to 75 parts by mass based on 100 parts by mass of solid content. The lower limit is more preferably 7.5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and further preferably 20 parts by mass or more. The upper limit is more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and further preferably 35 parts by mass or less. When the content of the colorant (E) is above the lower limit, sufficient light-shielding properties can be obtained, and in particular, when the colorant (E) contains a black dye, the light-shielding properties of the cured film can be effectively maintained. When the content of the colorant (E) is below the upper limit, the residual film rate and sensitivity are appropriate, and in particular, when the colorant (E) contains a black dye, higher heat resistance can be imparted to the film.

[0288] <Optional Ingredients>

[0289] The positive photosensitive resin composition may contain a dissolution accelerator (F), a thermosetting agent, a second surfactant other than the polysiloxane surfactant (D) having a silicon atom in the side chain, etc. as optional components. In this specification, an optional component is defined as any component not belonging to (A) to (E).

[0290] <<Dissolution accelerator (F)>>

[0291] The positive photosensitive resin composition may further contain a dissolution promoter (F) for further 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 compounds having a carboxyl group and compounds having a phenolic hydroxyl group. The dissolution promoter (F) may be used alone or in combination of two or more.

[0292] In the present specification, the term "low molecular weight compound" refers to a compound having a molecular weight of 1000 or less. The organic low molecular weight compound has a carboxyl group or a plurality of phenolic hydroxyl groups and is alkali-soluble.

[0293] 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, heptanoic acid, and octanoic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphortric acid; benzoic acid, toluic acid, cumic acid, and hemimellitic acid; Aromatic monocarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, benzene tetracarboxylic acid, pyromellitic acid, etc.; aromatic polycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, gallic acid, etc.; other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, 5-phenyl-2,4-pentadienoic acid (Cinnamylidene acetic acid), coumaric acid, umbelliferous acid, etc.; aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, bisphenol, etc.

[0294] The content of the dissolution promoter (F) in the positive photosensitive resin composition is based on a total of 100 parts by mass of the resin component, for example, 0.1 parts by mass to 50 parts by mass, preferably 1 part by mass to 35 parts by mass, and more preferably 2 parts by mass to 20 parts by mass. The lower limit is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, further preferably 4 parts by mass or more, and further preferably 5 parts by mass or more. The upper limit is preferably 35 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less. When the content of the dissolution promoter (F) is above the lower limit value based on the total of 100 parts by mass, the dissolution of the resin component can be effectively promoted. When the content is below the upper limit value based on the total of 100 parts by mass, the excessive dissolution of the resin component can be suppressed, and the pore formation and surface quality of the film can be further improved.

[0295] In addition, the positive photosensitive resin composition of the present embodiment contains a dissolution promoter (F) in an amount of, for example, 0.05 to 25 parts by mass, based on 100 parts by mass of solid content. The lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 1.5 parts by mass or more, further preferably 2 parts by mass or more, and further preferably 3 parts by mass or more. The upper limit is preferably 17.5 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 7.5 parts by mass or less. When the content of the dissolution promoter (F) is above the lower limit, the dissolution of the resin component can be effectively promoted, and when it is below the upper limit, the excessive dissolution of the resin component can be suppressed, thereby further improving the pore formation and surface quality of the film.

[0296] <Thermosetting Agent>

[0297] As a heat curing agent, a thermal free radical initiator can be used. As a preferred thermal free radical initiator, an organic peroxide can be mentioned, and specifically, an organic peroxide having a 10-hour half-life temperature of 100 to 170° C. such as diisopropyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl isopropyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide can be mentioned.

[0298] The content of the thermosetting agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the thermosetting agent.

[0299] <Second Surfactant>

[0300] The positive photosensitive resin composition may contain a second surfactant other than the polysiloxane surfactant (D) in order to further improve coating properties, to further improve film smoothness, or to further improve film developability. Examples of the second surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and acetylene surfactants such as "OLFINE (registered trademark) E1004", "OLFINE (registered trademark) E1010", "OLFINE (registered trademark) E1020", and "OLFINE (registered trademark) E1030W" (as mentioned above, trade names, Nissin Chemical Industry Co., Ltd.), "ACETYLENOL (registered trademark) E40", "ACETYLENOL (registered trademark) E60", "ACETYLENOL (registered trademark) E100", and "ACETYLENOL (registered trademark) E200" (as mentioned above, trade names, Kawaken Fine Chemicals Co., Ltd.). The second surfactant may be used alone or in combination of two or more.

[0301] The content of the second surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less, based on 100 parts by mass of the total solid content excluding the second surfactant. In this embodiment, the positive photosensitive resin composition preferably does not contain the second surfactant.

[0302] [Coating composition]

[0303] <Solvent (G)>

[0304] The positive photosensitive resin composition can be dissolved or dispersed in a solvent (G) and used as a coating composition in a solution state or a dispersed liquid state. For example, a coating composition containing a positive photosensitive resin composition can be prepared by mixing a quinonediazide compound (C) and a polysiloxane surfactant (D) and any components as required (colorant (E), dissolution promoter (F), thermosetting agent and other surfactants, etc.) in a given ratio in a solution in which a resin component (hydrophobic resin (A) and other resins such as an alkali-soluble resin (B) as required) have been dissolved in a solvent (G). The coating composition can be adjusted to a viscosity suitable for the coating method used by changing the amount of the solvent (G).

[0305] 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; propylene glycol monoalkyl ether acetate compounds such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-nitropropene; -hydroxy-4-methyl-2-pentanone, cyclohexanone and other ketones; 2-hydroxy-ethyl propionate, 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-2-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone and other esters; and amide compounds such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide. The solvent (G) can be used alone or in combination of two or more.

[0306] The solid content concentration of the coating composition can be appropriately determined according to the intended use. For example, the solid content concentration of the coating composition may be 1 to 60% by mass, 3 to 50% by mass, or 5 to 40% by mass.

[0307] For the dispersion and mixing method under the use of pigment, known methods can be used. For example, a ball mill, sand mill, bead mill, paint stirrer, rocking mill and other ball-type, kneading machine, paddle mixer, planetary mixer, Henschel mixer and other blade-type, 3-roller mixer and other roller-type, as other crushing machine, colloid mill, ultrasonic wave, homogenizer (homogenizer), rotation / revolution mixer and the like can be used. From the viewpoint of dispersion efficiency and microdispersion, it is preferred to use a bead mill.

[0308] The prepared coating composition is usually filtered before use. Examples of the filtering method include a microporous filter having a pore size of 0.05 to 1.0 μm.

[0309] The coating composition prepared in this way is excellent in long-term storage stability.

[0310] [Method of using the positive photosensitive resin composition]

[0311] When the positive photosensitive resin composition is used for radiation lithography, for example, first, the positive photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition can be applied to the surface of the substrate, and the solvent can be removed by heating or other means to form a film. The coating method of the coating composition on the surface of the substrate is not particularly limited, and for example, a spray coating method, a roll coating method, a slit coating method or a spin coating method can be used.

[0312] After the coating composition is applied to the surface of the substrate, the solvent is usually removed by heating to form a film (pre-baking). The heating conditions vary depending on the type and proportion of each component, and the film can usually be obtained by heating at 70 to 130° C., for example, on a hot plate for 30 seconds to 20 minutes, or in an oven for 1 to 60 minutes. In this embodiment, the thickness of the film formed is preferably 2 to 3 μm.

[0313] Next, the pre-baked film is irradiated with radiation (e.g., visible light, ultraviolet light, extreme ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation) through a photomask having a given pattern (exposure step). Preferably, the radiation is ultraviolet light to visible light with a wavelength of 250 to 450 nm. In this embodiment, the radiation is preferably i-rays. In another embodiment, the radiation is preferably ghi-rays.

[0314] In the case of a positive photosensitive resin composition containing a protective resin (B3) as an alkali-soluble resin (B), a heat treatment (PEB) for promoting the decomposition of an acid-decomposable group may be performed after the exposure step. PEB promotes the deprotection of the protected alkali-soluble functional group in the protective resin (B3) of the exposed portion, thereby further improving the alkali solubility of the exposed portion. The heating conditions vary depending on the type and blending ratio of each component, and PEB can usually be performed by heating at 70 to 140° C., for example, on a hot plate for 30 seconds to 20 minutes or in an oven for 1 to 60 minutes.

[0315] In this embodiment, it is preferred that the PEB step is not included after the exposure step. This can prevent the film from flowing and deforming due to heating, and can form a thick film pattern with higher precision, while reducing the steps for forming partition walls or insulating films.

[0316] After the exposure process or the PEB process, for example, the film is brought into contact with a developer for development (for example, alkali development), and the unnecessary portion is removed to form a pattern on the film (development process). As the developer, for example, an inorganic alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; a primary amine such as ethylamine and n-propylamine; a secondary amine such as diethylamine and di-n-propylamine; a tertiary amine such as triethylamine and methyldiethylamine; an alcohol amine such as dimethylethanolamine and triethanolamine; a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; an aqueous solution of an alkaline compound such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. to an alkaline aqueous solution can also be used as a developer. The development time is usually 30 to 180 seconds. The developing method may be any of a puddle developing method, a spray method, an immersion method, etc. After the developing method, the film is washed with running water for 30 to 90 seconds to remove the unnecessary parts, and then dried with compressed air or compressed nitrogen to form a pattern on the film.

[0317] Then, the patterned film can be passed through a heating device such as a hot plate or an oven, and heat-treated at, for example, 100 to 350° C. for 20 to 200 minutes to obtain a cured film (post-baking, heat treatment step). During the heat treatment, the temperature can be maintained at a constant level, or the temperature can be continuously increased or increased in stages. The heat treatment is preferably performed under a nitrogen atmosphere.

[0318] <Remaining film rate>

[0319] In this embodiment, the positive photosensitive resin composition is coated in such a manner that the film thickness after prebaking is 3±0.3 μm, and after prebaking at 125° C. for 120 seconds to form a film, when alkali development is performed in a 2.38 mass % tetramethylammonium hydroxide aqueous solution at a temperature of 23° C. for 60 seconds, the residual film rate defined by the following formula is preferably 90% or more, more preferably 95% or more, and further preferably 99% or more. The residual film rate is an indicator of the solubility of the unexposed portion. The higher the residual film rate, the greater the difference in solubility between the exposed portion and the unexposed portion, and a thick film pattern with a large height difference can be formed with high precision.

[0320] Residual film rate (%) = film thickness after development (μm) / film thickness before development (μm) (formula)

[0321] <Optical density>

[0322] In an embodiment where 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 film thickness 1 μm, more preferably 0.7 or more, and further preferably 1.0 or more. When the OD value of the cured film is above the lower limit per film thickness 1 μm, sufficient light-shielding properties can be obtained.

[0323] The method for producing an organic EL element partition wall or an organic EL element insulating film of the present embodiment includes, for example, 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; irradiating the dried film with radiation through a photomask to expose the film; developing the exposed film by contacting it with a developer to form a pattern on the film; and heating the film with the pattern formed at a temperature of 100 to 350° C. to form an organic EL element partition wall or an organic EL element insulating film. The PEB described above can be performed after exposure and before development. In the embodiment in which the positive photosensitive resin composition of the present specification contains a colorant (E), a high-precision thick film pattern can also be formed with high sensitivity.

[0324] <Organic EL Element Partition Wall>

[0325] In the present embodiment, the organic EL element partition wall comprises a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably comprises a colorant (E). The cured product of the positive photosensitive resin composition of the present embodiment used in the organic EL element partition wall can be obtained by the curing method. In addition, the process of the manufacturing method of the organic EL element partition wall of the present embodiment is not particularly limited, and known processes and conditions thereof can be appropriately adopted. For example, it can be obtained by a manufacturing method comprising a coating process, a reduced pressure drying process, a pre-baking process, an exposure process, an alkali development process and a post-baking process as described above. The organic EL element partition wall of the present embodiment can be suitably used as a black organic EL element partition wall. As described above, in display devices such as organic EL displays, in order to improve display characteristics, partition walls (partition wall materials) such as the spacers of the colored patterns in the display area or the edges of the peripheral parts of the display area are used. Among the partition walls, the black partition wall has a higher light shielding property than other colors, so during UV irradiation in the exposure process, there is a tendency that (i) ultraviolet rays do not easily reach the deep part of the coating film of the positive photosensitive resin composition, and (ii) the exposure time is easily prolonged, resulting in a decrease in productivity. However, according to the present embodiment, such problems can be particularly effectively prevented, so that the high performance and high precision of the pixel can be achieved at a higher level than before.

[0326] <Organic EL element insulating film>

[0327] In the present embodiment, an organic EL element insulating film is provided which comprises a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably comprises a colorant (E). The cured product of the positive photosensitive resin composition of the present embodiment used in the organic EL element insulating film can be obtained by the curing method. Furthermore, the process of the method for manufacturing the organic EL element insulating film of the present embodiment is not particularly limited, and known processes and conditions thereof can be appropriately adopted. For example, in the case of an organic EL element used in an organic EL display, there is a tendency that the light-emitting layer thereof is easily affected by moisture and impurity gases and is easily degraded, so it is meaningful to provide an insulating film with excellent reliability. The organic EL element insulating film of the present embodiment is expected to meet such requirements.

[0328] <Organic EL element>

[0329] In the present embodiment, an organic EL element is provided that comprises a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E) comprising a black dye. The cured product of the positive photosensitive resin composition of the present embodiment used in the organic EL element can be obtained by the curing method. By using the cured product for the partition material, insulating film and other components, an excellent organic EL element can be achieved. In particular, when it is applied to black components, an effect that is particularly excellent than before can be exerted.

[0330] As described above, the positive photosensitive resin composition of the present embodiment can be suitably used in radiation lithography for forming the partition wall and insulating film of the organic EL element. Regarding the partition wall of the organic EL element, it can be suitably used as a positive photosensitive resin composition for forming the partition wall material. In addition, in the case of a positive photosensitive resin composition containing the colorant (E), an organic EL element having a partition wall or insulating film formed therefrom is suitably used as an electronic component of a display device showing good contrast. In particular, in the case of a black positive resist, a black partition wall material, etc., it is possible to achieve high sensitivity, residue removal, less film reduction, and fine pore formation in a well-balanced manner while maintaining sufficient light-shielding properties at a higher level that could not be achieved in the past.

[0331] [Example]

[0332] Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0333] (1) Raw materials

[0334] The raw materials used in Examples and Comparative Examples were produced or obtained as follows.

[0335] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were calculated from a calibration curve prepared using a polystyrene standard substance under the following measurement conditions.

[0336] Device name: Shodex (registered trademark) GPC-101

[0337] Column: Shodex (registered trademark) LF-804

[0338] Mobile phase: tetrahydrofuran

[0339] Flow rate: 1.0mL / min

[0340] Detector: Shodex (registered trademark) RI-71

[0341] Temperature: 40℃

[0342] <Hydrophobic resin (A)>

[0343] (Manufacturing Example 1) Manufacture of a hydrophobic resin (A): a resin having a silicon atom-containing group (PSM-TB)

[0344] 15.9 g of 4-hydroxyphenyl methacrylate (manufactured by Resonac Co., Ltd., "PQMA"), 16.6 g of 4-tert-butyldimethylsilyloxyphenyl methacrylate (PQMA-TBDMS), and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two solutions obtained were simultaneously added dropwise to 90.5 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated at 89° C. in a 300 mL three-necked flask equipped with a reflux tube over 2 hours, and then reacted at 89° C. for 4 hours. 50g of the reaction solution cooled to room temperature was added dropwise to 250g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 80°C for 5 hours to recover 9.73g of white powder (PSM-TB). The number average molecular weight of the obtained PSM-TB was 3753, the weight average molecular weight was 7581, the polydispersity coefficient (Mw / Mn) was 2.0, and the proportion of monomer units having silicon-containing groups in the whole monomer units was 32 mol%. In PSM-TB, the molar ratio of the structural unit represented by formula (1) in which s is an integer greater than 1, the structural unit represented by formula (2), and the structural unit represented by formula (3) is formula (1): formula (2): formula (3) = 32:7:61, and the structural unit having an alkali-soluble functional group is 61 mol% based on the whole structural unit. The content of silicon atoms is 4.0 mass % based on the mass of PSM-TB34.

[0345] (Manufacturing Example 2) Manufacture of a hydrophobic resin (A): a resin having a silicon atom-containing group (PSM-TE)

[0346] 15.9 g of 4-hydroxyphenyl methacrylate (manufactured by Resonac Co., Ltd., "PQMA"), 16.6 g of 4-triethylsilyloxyphenyl methacrylate (PQMA-TES), and 4.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 55.8 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two solutions obtained were simultaneously added dropwise over 2 hours to 90.4 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated at 89° C. under a nitrogen atmosphere in a 300 mL three-necked flask equipped with a reflux tube, and then reacted at 89° C. for 4 hours. 50g of the reaction solution cooled to room temperature was added dropwise to a mixed solvent of 200g of hexane and 50g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 80°C for 5 hours to recover 9.49g of white powder (PSM-TE). The number average molecular weight of the obtained PSM-TE was 3847, the weight average molecular weight was 7534, the polydispersity coefficient (Mw / Mn) was 2.0, and the proportion of monomer units having silicon-containing groups in the whole monomer units was 32 mol%. In PSM-TE, the molar ratio of the structural unit represented by formula (1) where s is an integer greater than 1, the structural unit represented by formula (2), and the structural unit represented by formula (3) is formula (1): formula (2): formula (3) = 32:7:61, and the structural unit having an alkali-soluble functional group is 61 mol% based on the whole structural unit. The content of silicon atoms is 4.0 mass % based on the mass of PSM-TE.

[0347] (Manufacturing Example 3) Manufacture of a hydrophobic resin (A): a resin having a silicon atom-containing group (PS-TB)

[0348] 15.9 g of 4-hydroxyphenyl methacrylate (manufactured by Resonac Co., Ltd., "PQMA") and 11.2 g of 4-tert-butyldimethylsilyloxyphenyl methacrylate (PQMA-TBDMS) were completely dissolved in 44.14 g of isopropyl acetate (Shinko Organic Chemical Co., Ltd.) as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Co., Ltd.). The two solutions obtained were simultaneously added dropwise to 90.5 g of isopropyl acetate (Shinko Organic Chemical Co., Ltd.) heated at 89°C in a nitrogen atmosphere in a 300 mL three-necked flask equipped with a reflux tube over 2 hours, and then reacted at 89°C for 4 hours. 50 g of the reaction solution that had been cooled to room temperature was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 80°C for 5 hours to recover 8.83g of white powder (PS-TB). The number average molecular weight of the obtained PS-TB was 4238, the weight average molecular weight was 8900, the polydispersity coefficient (Mw / Mn) was 2.1, and the proportion of monomer units having silicon-containing groups in the whole monomer units was 27 mol%. In PS-TB, the molar ratio of the structural unit represented by formula (1) in which s is an integer greater than 1 to the structural unit represented by formula (3) is formula (1): formula (3) = 27:73, and the structural unit having an alkali-soluble functional group is 73 mol% based on the whole structural unit. The content of silicon atoms is 4.2 mass % based on the mass of PS-TB.

[0349] <Alkali-soluble resin (B)>

[0350] (Manufacturing Example 4) Alkali-soluble resin (B): Manufacture of resin (N695OH) having epoxy group and phenolic hydroxyl group

[0351] Into a 300 mL three-necked flask were added 75.2 g of γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as a solvent and 37.8 g of "EPICLON (registered trademark) N-695" (DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent 214) as a compound having at least two epoxy groups in one molecule, and dissolved at 60°C under a nitrogen atmosphere.

[0352] 20.1 g (0.65 equivalents to 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound and 0.166 g (0.660 mmol) of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) as a reaction catalyst were added thereto, 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 solid content of 20% by mass, and the solution was filtered to obtain 274.2 g of a solution of a resin (N695OH) having an epoxy group and a phenolic hydroxyl group. The obtained reactant had a number average molecular weight of 3000, a weight average molecular weight of 5100, a polydispersity coefficient (Mw / Mn) of 1.7, an epoxy equivalent of 2200, and a phenolic hydroxyl equivalent of 161.

[0353] <Quinonediazide compound (C)>

[0354] As quinonediazide compounds (C), "TS-150A" and "TS-200A" (as mentioned above, trade names, Toyo Gosei Kogyo Co., Ltd.; esters 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-diazide naphthoquinone-5-sulfonic acid)) were used; "TPPA-150DF" (trade name, Toyo Gosei Kogyo Co., Ltd.; 1,2-diazide naphthoquinone-4-sulfonic acid ester of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA)).

[0355] The structures of "TS-150A" and "TS-200A" are shown below. For "TS-150A", in the following formula, an average of 1.5 Rs out of 3 Rs per molecule have a quinone diazide structure. For "TS-200A", in the following formula, an average of 2.0 Rs out of 3 Rs per molecule have a quinone diazide structure.

[0356] [Chemical formula 22]

[0357]

[0358] <Polysilicone surfactant (D)>

[0359] As the polysiloxane surfactant (D), “MEGAFACE EFS-131” (trade name, DIC Corporation; a (meth)acrylic copolymer having no silicon atom in the main chain and having at least one silicon atom-containing hydrocarbon group selected from silicon atom-containing alkyl groups and silicon atom-containing alkylene groups), “MEGAFACE EFS-321” (trade name, DIC Corporation; a (meth)acrylic copolymer having no silicon atom in the main chain and having at least one silicon atom-containing hydrocarbon group selected from silicon atom-containing alkyl groups and silicon atom-containing alkylene groups), “MEGAFACE EFS-521” (trade name, DIC Corporation; a (meth)acrylic copolymer having no silicon atom in the main chain and having at least one silicon atom-containing hydrocarbon group selected from silicon atom-containing alkyl groups and silicon atom-containing alkylene groups), and “KF2201” (trade name, Shin-Etsu Chemical Co., Ltd.; a polysiloxane surfactant having a silicon atom in the main chain and no silicon atom-containing group in the side chain) were used.

[0360] <Colorant (E)>

[0361] As the colorant (E), "VALIFAST (registered trademark) BLACK 3804" (abbreviated as "VB3804", ORIENT CHEMICAL INDUSTRY CO., LTD.; a black dye specified in the CI of Solvent Black 34), "VALIFAST (registered trademark) BLACK 3810" (abbreviated as "VB3810", ORIENT CHEMICAL INDUSTRY CO., LTD.; a black dye specified in the CI of Solvent Black 34), and "VALIFAST (registered trademark) BLACK 3804" (abbreviated as "VB3804", ORIENT CHEMICAL INDUSTRY CO., LTD., a black dye specified in the CI of Solvent Black 34) were used as black dyes.

[0362] <Dissolution accelerator (F)>

[0363] As the dissolution accelerator (F), phloroglucinol was used.

[0364] <Solvent (G)>

[0365] 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.

[0366] (2) Evaluation method

[0367] The evaluation methods used in Examples and Comparative Examples are as follows.

[0368] <Sensitivity>

[0369] The positive photosensitive resin composition was bar-coated on a glass substrate (size 100 mm×100 mm×1 mm) so that the dry film thickness was 3.0 μm, and after vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125°C for 120 seconds on a covered hot plate. An exposure device (trade name "MULTILIGHT ML-251A / B", USHIO Electric Co., Ltd.) equipped with an ultra-high pressure mercury lamp was used to expose the substrate through a quartz photomask (with The film was exposed to an opening pattern (with an opening pattern). The exposure amount was measured using an ultraviolet integrated light meter (trade name "UIT-150" light receiving unit "UVD-S365", USHIO Electric Co., Ltd.). After exposure, alkali development was performed for 60 seconds in a 2.38% by mass tetramethylammonium hydroxide aqueous solution using a rotary developing device ("AD-1200", TAKIZAWA Industry Co., Ltd.). The above steps were repeated while changing the exposure amount to set the minimum exposure amount (mJ / cm 2 ) as the sensitivity.

[0370] <Solubility of Unexposed Part>

[0371] A positive photosensitive resin composition was bar-coated on a glass substrate (size 100 mm×100 mm×1 mm) in such a way that the dry film thickness was 3.0 μm, and after vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125°C for 120 seconds on a covered hot plate. After measuring the dry film thickness using an optical film thickness measuring device ("F20-NIR", FILMETRICS Co., Ltd.), alkali development was performed for 60 seconds in a 2.38% by mass tetramethylammonium hydroxide aqueous solution using a rotary developing device ("AD-1200", TAKIZAWA Sangyo Co., Ltd.). The film thickness after alkali development was measured again using an optical film thickness measuring device ("F20-NIR", FILMETRICS Co., Ltd.), and the film thickness (μm) dissolved before and after development was used as an indicator of the solubility of the unexposed portion. The solubility of the unexposed portion of 0 μm is equivalent to the residual film rate defined by the following formula of 100%.

[0372] Residual film rate (%) = film thickness after development (μm) / film thickness before development (μm) (formula)

[0373] <OD value of cured film>

[0374] A positive photosensitive resin composition was spin-coated on a glass substrate (size 100 mm × 100 mm × 1 mm) in such a way that the dry film thickness was about 1.5 μm, and pre-baked by heating on a hot plate at 125° C. for 120 seconds. Then, the film was obtained by curing at 250° C. for 60 minutes in a nitrogen atmosphere. The OD value of the cured film was measured by a transmission densitometer ("BMT-1", SAKATA INX Co., Ltd.), and the OD value of the glass was used for correction only, and converted into the OD value of the thickness of the film per 1 μm. The thickness of the film was measured using an optical film thickness measuring device ("F20-NIR", FILMETRICS Co., Ltd.).

[0375] <Aperture>

[0376] The positive photosensitive resin composition was bar-coated on a glass substrate (size 100 mm×100 mm×1 mm) so that the dry film thickness was 3.0 μm, and after vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125°C for 120 seconds on a covered hot plate. An exposure device (trade name "MULTILIGHT ML-251A / B", USHIO Electric Co., Ltd.) equipped with an ultra-high pressure mercury lamp was used to expose the substrate through a quartz photomask (with The film was exposed to an opening pattern (with an opening pattern). The exposure amount was measured using an ultraviolet integrated light meter (trade name "UIT-150" light receiving unit "UVD-S365", USHIO Electric Co., Ltd.). After exposure, alkali development was performed for 60 seconds in a 2.38 mass % tetramethylammonium hydroxide aqueous solution using a rotary developing device ("AD-1200", TAKIZAWA Industrial Co., Ltd.). The exposure amount was 50 (mJ / cm 2 ), the pore diameter of the opened hole pattern was measured using a microscope (magnification 2000 times).

[0377] <Substrate Interface Residue>

[0378] The positive photosensitive resin composition was bar-coated on a glass substrate (size 100 mm×100 mm×1 mm) so that the dry film thickness was 3.0 μm, and after vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125°C for 120 seconds on a covered hot plate. An exposure device (trade name "MULTILIGHT ML-251A / B", USHIO Electric Co., Ltd.) equipped with an ultra-high pressure mercury lamp was used to expose the substrate through a quartz photomask (with The film was exposed to an opening pattern (with an opening pattern). The exposure amount was measured using an ultraviolet integrated light meter (trade name "UIT-150" light receiving unit "UVD-S365", USHIO Electric Co., Ltd.). After exposure, alkali development was performed in a 2.38 mass % tetramethylammonium hydroxide aqueous solution for 60 seconds using a rotary developing device (trade name "AD-1200", TAKIZAWA Industrial Co., Ltd.). The exposure amount was 50 (mJ / cm 2 ) was observed using an electron microscope (magnification 20,000 times) on the substrate surface with the opened hole pattern, and the following criteria were used for judgment.

[0379] ○: Surface area In the experiment, no film-like residue was observed, and almost no dot residue (= less than 5) was observed.

[0380] △: Surface area In the experiment, no film-like residue was observed, but spot residues (= 5 or more) were observed.

[0381] ×: Surface area In the experiment, film-like residues were confirmed throughout.

[0382] (3) Preparation and evaluation of positive photosensitive resin composition

[0383] <Examples 1 to 9, Comparative Examples 1 to 3>

[0384] The components were mixed under the conditions described in Table 1. After visually confirming that the components were dissolved, the components were filtered through a microporous filter with a pore size of 0.22 μm to prepare a positive photosensitive resin composition with a solid content concentration of 12% by mass. In Table 1, the values ​​of the composition of the components other than the solvent are in "parts by mass" units, and the values ​​are converted to solid content. The evaluation results of the positive photosensitive resin compositions of the examples and comparative examples are shown in Table 1.

[0385] <Example 1>

[0386] As shown in Table 1, a resin (PSM-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), (TPPA-150DF) as a quinonediazide compound (C), EFS-521 as a polysiloxane surfactant (D), a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F) and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 1 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 1 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 1 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 1 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 1 contains 15% by mass of quinone diazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 1 contains 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 1 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 1 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 1 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 1 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 1 is 12% by mass.

[0387] <Example 2>

[0388] As shown in Table 1, a resin (PSM-TE) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), (TPPA-150DF) as a quinonediazide compound (C), EFS-521 as a polysiloxane surfactant (D), a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F) and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 2 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 2 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 2 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 2 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 2 contains 15% by mass of quinone diazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 2 contains 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 2 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 2 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 2 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 2 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 2 is 12% by mass.

[0389] <Example 3>

[0390] As shown in Table 1, a resin (PS-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), (TPPA-150DF) as a quinonediazide compound (C), EFS-521 as a polysiloxane surfactant (D), a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F) and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 3 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 3 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 3 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 3 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 3 contains 15% by mass of quinone diazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 3 contains 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 3 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 3 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 3 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 3 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 3 is 12% by mass.

[0391] <Example 4>

[0392] As shown in Table 1, a resin (PSM-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), (TS-150A) as a quinonediazide compound (C), EFS-521 as a polysiloxane surfactant (D), a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F) and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 4 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 4 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 4 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 4 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 4 contains 15% by mass of quinonediazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 4 contains 31 parts by mass of quinonediazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 4 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 4 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 4 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 4 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 4 is 12% by mass.

[0393] <Example 5>

[0394] As shown in Table 1, a resin (PSM-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), (TS-200A) as a quinonediazide compound (C), EFS-521 as a polysiloxane surfactant (D), a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F) and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 5 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 5 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 5 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 5 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 5 contains 15% by mass of quinonediazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 5 contains 31 parts by mass of quinonediazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 5 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 5 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 5 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 5 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 5 is 12% by mass.

[0395] <Example 6>

[0396] As shown in Table 1, a resin having a silicon atom group (PSM-TB) as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), TS-200A as a quinonediazide compound (C), EFS-131 as a polysiloxane surfactant (D), a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F), and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 6 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 6 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 6 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 6 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 6 contains 15% by mass of quinone diazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 6 contains 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 6 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 6 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 6 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 6 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 6 is 12% by mass.

[0397] <Example 7>

[0398] As shown in Table 1, a resin (PSM-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), TS-200A as a quinonediazide compound (C), EFS-321 as a polysiloxane surfactant (D), a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F) and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 7 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 7 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 7 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 7 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 7 contains 15% by mass of quinonediazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 7 contains 31 parts by mass of quinonediazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 7 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 7 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 7 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 7 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 7 is 12% by mass.

[0399] <Example 8>

[0400] As shown in Table 1, a resin (PSM-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), TS-200A as a quinonediazide compound (C), EFS-321 as a polysiloxane surfactant (D), a black dye (VB3810) as a colorant (E), phloroglucinol as a dissolution accelerator (F), and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 8 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 8 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 8 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 8 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 8 contains 15% by mass of quinone diazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 8 contains 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 8 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 8 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 8 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 8 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 8 is 12% by mass.

[0401] <Example 9>

[0402] As shown in Table 1, a resin (PSM-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), TS-200A as a quinonediazide compound (C), EFS-321 as a polysiloxane surfactant (D), a black dye (VB3820) as a colorant (E), phloroglucinol as a dissolution accelerator (F), and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The positive photosensitive resin composition of Example 9 contained 14% by mass of the hydrophobic resin (A) based on 100% by mass of the solid content. In addition, the positive photosensitive resin composition of Example 9 contained 29 parts by mass of the hydrophobic resin (A) based on 100 parts by mass of the total resin components. In addition, the positive photosensitive resin composition of Example 9 contains 35% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 9 contains 71 parts by mass of alkali-soluble resin (B) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 9 contains 15% by mass of quinone diazide compound (C) based on 100% by mass of solid content. In addition, the positive photosensitive resin composition of Example 9 contains 31 parts by mass of quinone diazide compound (C) based on 100 parts by mass of the total resin component. In addition, the positive photosensitive resin composition of Example 9 contains 15% by mass of surfactant (D) based on 100% by mass of solid content. The content of surfactant (D) in the positive photosensitive resin composition of Example 9 is 31 parts by mass based on 100 parts by mass of the total resin component. The positive photosensitive resin composition of Example 9 contains 30% by mass of the colorant (E) based on 100% by mass of the solid content. The content of the colorant (E) in the positive photosensitive resin composition of Example 9 is 61 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 9 is 12% by mass.

[0403] <Comparative Example 1>

[0404] As shown in Table 1, a resin (PSM-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), (TPPA-150DF) as a quinonediazide compound (C), KF2201 having a silicon atom on the main chain as a polysiloxane surfactant, a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F) and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were prepared to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. It should be noted that the positive photosensitive resin composition of Comparative Example 1 was not evaluated because it was repelled during coating and could not form a pattern ("unable to coat" in the table).

[0405] <Comparative Example 2>

[0406] As shown in Table 1, a resin having a silicon atom group (PSM-TB) as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), (TPPA-150DF) as a quinonediazide compound (C), E-40 as a hydrocarbon surfactant, a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution promoter (F) and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass.

[0407] <Comparative Example 3>

[0408] As shown in Table 1, a resin (PSM-TB) having a silicon atom group as a hydrophobic resin (A), an epoxy resin (N695OH) as an alkali-soluble resin (B), (TPPA-150DF) as a quinonediazide compound (C), F-554 as a fluorine-based surfactant, a black dye (VB3804) as a colorant (E), phloroglucinol as a dissolution accelerator (F), and a mixed solvent of GBL / PGMEA = 40 / 60 as a solvent (G) were mixed to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. It should be noted that the surfactant used is a fluorine-based surfactant (trade name "MEGAFAC (registered trademark) F-554", manufactured by DIC Corporation) used in International Publication No. 2023 / 080254.

[0409] [Table 1]

[0410]

[0411] The positive photosensitive resin composition of each embodiment at least confirmed that the contrast between the exposed and unexposed portions can be increased due to the solubility of the unexposed portion being 0 μm, and a thick film pattern can be formed with high precision. From the above, it was at least confirmed that according to this embodiment, even without using an organic fluorine compound, the residue removal property is excellent, the film reduction amount is reduced, and fine holes can be formed.

[0412] This application is based on the Japanese patent application (Japanese Patent Application No. 2023-172518) filed with the Japan Patent Office on October 4, 2023, the contents of which are incorporated into this application as a reference.

Claims

1. A positive photosensitive resin composition comprising: Hydrophobic resin (A), Quinonediazide compounds (C), and A polysiloxane surfactant (D) having a silicon atom in a side chain.

2. The positive photosensitive resin composition according to claim 1, wherein The content of the component (D) in the total amount of the surfactant is 50% by mass or more.

3. The positive photosensitive resin composition according to claim 1 or 2, further comprising: The colorant (E) comprises a black dye.

4. The positive photosensitive resin composition according to claim 1 or 2, wherein The component (A) comprises a structural unit represented by the following formula (1): [Chemical formula 1] In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 SiR 3 R 4 R 5 , R 3 , R 4 and R 5 Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r represents an integer of 0 to 4, s represents an integer of 1 to 5, wherein r+s represents an integer of 1 to 5.

5. The positive photosensitive resin composition according to claim 1 or 2, wherein The component (A) is a resin having a silicon atom-containing group.

6. The positive photosensitive resin composition according to claim 1 or 2, wherein The component (A) comprises the following structural unit (1a) and / or structural unit (1b), [Chemical formula 2] In formula (1a), R 1a is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2a , R 3a and R 4a are independently an alkyl group having 1 to 7 carbon atoms; in formula (1b), R 1b is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It should be noted that R 1a and R 1b It can be the same or different.

7. The positive photosensitive resin composition according to claim 1 or 2, wherein The content of the component (A) in the positive photosensitive resin composition is 5 to 60% by mass based on the total mass of the resin components.

8. The positive photosensitive resin composition according to claim 1 or 2, wherein The component (D) is a polysiloxane-based surfactant comprising an acrylic copolymer having at least one silicon-containing hydrocarbon group selected from a silicon-containing alkyl group and a silicon-containing alkylene group.

9. The positive photosensitive resin composition according to claim 3, wherein The (E) component is contained in an amount of 10 to 150 parts by mass based on 100 parts by mass of the total resin components.

10. The positive photosensitive resin composition according to claim 1 or 2, wherein The optical density (OD value) of a cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness. 11 . An organic EL element partition wall comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2. 12 . An organic EL element insulating film comprising a cured product of the positive photosensitive resin composition according to claim 1 . 13 . An organic EL element comprising a cured product of the positive photosensitive resin composition according to claim 1 or 2.

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