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

Abstract

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

Description

[Technical field]

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

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

[0003] For example, in display devices such as organic EL displays, a partition material is used in the gaps between colored patterns in the display area or in the edges of the peripheral parts of the display area in order to improve display characteristics. In the manufacture of an organic EL display device, partitions are first formed to prevent organic pixels from contacting each other, and organic pixels are formed between the partitions. This partition is generally formed by photolithography using a photosensitive resin composition and has insulating properties. In detail, a photosensitive resin composition is applied onto a substrate using a coating device, and volatile components are removed by heating or other means, and then the substrate is exposed to light through a mask, and then developed by removing the unexposed parts in the case of a negative type and the exposed parts in the case of a positive type with a developer such as an alkaline aqueous solution, and the resulting pattern is heat-treated to form partitions (insulating films). Next, organic materials that emit light of three colors, red, green, and blue, are formed into films between the partitions by an inkjet method or the like to form pixels of the organic EL display device.

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

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

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

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

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

[0009] Patent Document 5 (WO 2023 / 080254) describes a positive-type photosensitive resin composition containing a hydrophobic resin (A), an alkali-soluble resin (B), a quinone diazide compound (C), and a fluorine-based surfactant (D).

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

[0011] [Patent Document 1] JP 2001-281440 A [Patent Document 2] JP 2002-116536 A [Patent Document 3] JP 2010-237310 A [Patent Document 4] International Publication No. 2017 / 069172 [Patent Document 5] International Publication No. 2023 / 080254 Summary of the Invention [Problem to be solved by the invention]

[0012] However, when a partition wall material is provided with a light-shielding property, the photosensitive resin composition tends to have a low sensitivity, which may result in a long exposure time and a decrease in productivity. Therefore, a photosensitive resin composition used to form a partition wall material containing a colorant is required to have a higher sensitivity.

[0013] For example, in the case of a photosensitive resin composition used to form a colored partition wall material, a colorant is used to sufficiently increase the light-shielding property of the cured film. However, when a colorant is used, the radiation irradiated to the coating of the photosensitive resin composition is absorbed by the colorant, so that the effective intensity of the radiation in the coating is reduced, and the photosensitive resin composition is not sufficiently exposed, resulting in a decrease in the formability of holes, etc. This is particularly noticeable when a black colorant is blended into the photosensitive resin composition for the purpose of improving the image quality of the display device, making it more flexible, or saving power, for example, when a black partition wall material is formed.

[0014] Moreover, in recent years, there has been a demand to refrain from using organic fluorine compounds such as PFAS, and there is a demand for so-called non-PFAS.

[0015] Furthermore, there is a demand for a positive-type photosensitive resin composition that does not use an organic fluorine compound to have excellent residue removability, a small amount of film loss, and a high level of hole formability as described above, all at the same time. However, a positive-type photosensitive resin composition that can fully meet these demands has not yet been developed.

[0016] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a positive-type 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 amount of film loss, and are capable of forming fine holes even without using an organic fluorine compound. [Means for solving the problem]

[0017] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above-mentioned object, and have discovered the necessity of a positive-type photosensitive resin composition containing a hydrophobic resin (A), a quinone diazide compound (C), and a silicone-based surfactant (D) having a silicon atom in a side chain, thereby completing the present invention.

[0018] That is, the present invention includes the following aspects. <1> The positive photosensitive resin composition contains a hydrophobic resin (A), a quinone diazide compound (C), and a silicone surfactant (D) having a silicon atom in the side chain. <2> The content of the component (D) in the total amount of surfactants is 50 mass% or more. <1> 2. The positive photosensitive resin composition according to claim 1, <3> Further containing a colorant (E) containing a black dye, <1> or <2> 2. The positive photosensitive resin composition according to claim 1, <4> The component (A) contains a structural unit represented by the following formula (1): <1> ~ <3> 10. The positive photosensitive resin composition according to claim 9,

[0019] [ka]

[0020] (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is SiR 3 R 4 R 5 and R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 4, and s is an integer of 1 to 5, with the proviso that r+s is an integer of 1 to 5. <5> The component (A) is a resin having a silicon atom-containing group. <1> ~ <4> 10. The positive photosensitive resin composition according to claim 9, <6> The component (A) contains the following structural unit (1a) and / or structural unit (1b): <1> ~ <5> 10. The positive photosensitive resin composition according to claim 9,

[0021] [ka]

[0022] (In formula (1a), R 1a is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2a , R 3a , and R 4a are each independently an alkyl group having 1 to 7 carbon atoms. 1b is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 1a and R 1b may be the same or different.) <7> The content of the component (A) in the positive photosensitive resin composition is 5 to 60 mass% based on the total mass of the resin components. <1> ~ <6> 10. The positive photosensitive resin composition according to claim 9, <8> The component (D) is a silicone surfactant containing an acrylic copolymer having at least one silicon-containing hydrocarbon group selected from the group consisting of silicon-containing alkyl groups and silicon-containing alkylene groups. <1> ~ <7> 10. The positive photosensitive resin composition according to claim 9, <9> The (E) component is contained in an amount of 10 to 150 parts by mass relative to 100 parts by mass of the total of the resin components. <3> 2. The positive photosensitive resin composition according to claim 1, <10> The optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness. <1> ~ <9> 10. The positive photosensitive resin composition according to claim 9, <11> <1> ~ <10> 2. A partition wall for an organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of 1 to 11. <12> <1> ~ <10> 2. An insulating film for an organic electroluminescence device, comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 11. <13> <1> ~ <10> 2. An organic EL device comprising a cured product of the positive photosensitive resin composition according to claim 1. Effect of the Invention

[0023] According to the present invention, it is possible to provide a positive-type 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 amount of film loss, and are capable of forming fine holes without using an organic fluorine compound. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] Hereinafter, an embodiment for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0025] In this specification, "alkali soluble" means that the positive photosensitive resin composition or its components, or the coating or cured coating of the positive photosensitive resin composition, is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. "Alkali soluble resin" means a resin that is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide alone or in a state in which it is contained in a positive photosensitive resin composition that has not been exposed to light or has been exposed to light. Resins that are not alkali soluble when the positive photosensitive resin composition is not exposed to light but become alkali soluble upon exposure are also included in the alkali soluble resin. "Alkali soluble functional group" means a group that has the ability to impart such alkali solubility to the positive photosensitive resin composition or its components, or the coating or cured coating of the positive photosensitive resin composition. Examples of alkali soluble functional groups include phenolic hydroxyl groups, carboxy groups, sulfo groups, phosphoric acid groups, acid anhydride groups, and mercapto groups.

[0026] In this specification, the term "acid-decomposable group" refers to a group that is decomposed (deprotected) in the presence of an acid, optionally with heating, to generate an alkali-soluble functional group.

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

[0028] In this specification, the terms "structural unit" and "unit" (hereinafter sometimes collectively referred to as "structural unit") refer to an atomic group constituting a part of the basic structure of a polymer, and this atomic group may have a pendant atom or a pendant atomic group. For example, in the case of a radical (co)polymer, it refers to a unit derived from a radically polymerizable compound used as a monomer, and in the case of a phenol novolac resin, it refers to the following unit formed by a condensation reaction of one molecule of phenol (C6H5OH) and one molecule of formaldehyde (HCHO). Regarding a structural unit having a pendant group (side group), a structural unit having a pendant group or a group derived therefrom used in forming a crosslinking site and a structural unit having a free pendant group not involved in forming a crosslinking site are considered to be different from each other. Regarding a polymer having a branched molecular chain (branched chain), a structural unit (branch unit) containing a branch point and a structural unit contained in a linear molecular chain are considered to be different from each other.

[0029] [ka]

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

[0031] In this specification, unless otherwise specified, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin, polymer, or copolymer refer to values ​​calculated as standard polystyrene, measured by gel permeation chromatography (GPC).

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

[0033]

number

[0034] In the case of the resin (B2) having an epoxy group and a phenolic hydroxyl group described below, unless otherwise specified, the phenolic hydroxyl group equivalent means a value calculated by the following formula. Phenolic hydroxyl group equivalent = (epoxy equivalent of raw material + molecular weight of carboxylic acid to be added) / (number of phenolic hydroxyl groups of carboxylic acid)

[0035] Unless otherwise specified, the term "resin component" in this specification means the hydrophobic resin (A) and the alkali-soluble resin (B). Components that correspond to the silicone surfactant (D) are not included in the hydrophobic resin (A) and the alkali-soluble resin (B).

[0036] Unless otherwise specified in this specification, the "solid content" means the total mass of components including the resin component, the quinone diazide compound (C), and the silicone surfactant (D), as well as optional components such as the colorant (E) and the dissolution promoter (F), excluding the liquid solvent (G).

[0037] [Positive-type photosensitive resin composition]

[0038] The positive photosensitive resin composition according to this embodiment is a positive photosensitive resin composition containing a hydrophobic resin (A), a quinone diazide compound (C), and a silicone surfactant (D) having a silicon atom in the side chain. The positive photosensitive resin composition according to this embodiment is excellent in residue removability, has a small amount of film loss, and can form fine holes even without using an organic fluorine compound. The reason for this is unclear, but is presumed to be due to the following reasons (however, the action and effect of this embodiment are not limited to the following).

[0039] By blending the hydrophobic resin (A) with a silicone-based surfactant (D) having a silicon atom in the side chain, its uneven distribution on the coating surface is promoted, and the coating surface of the positive photosensitive resin composition is made less soluble in an alkaline aqueous solution. The hydrophobic resin (A) is likely to migrate toward the coating surface in association with the silicone-based surfactant (D) that migrates to the coating surface during the formation of the coating of the positive photosensitive resin composition. Therefore, after the coating is formed, the hydrophobic resin (A) is present at a higher concentration on the coating surface than inside the coating, reducing the alkali solubility of the coating surface. In addition, since the hydrophobic resin (A) and the alkali-soluble resin (B) tend to have low compatibility, a concentration gradient tends to be easily formed during curing. Therefore, during development, the hydrophobic resin (A) suppresses dissolution of the coating surface of the unexposed area as a resin component with low alkali solubility, while in the exposed area, the hydrophobic resin (A) is released from the coating into the developer along with dissolution of the carboxylic acid compound derived from the quinone diazide compound (C), other resin components with high alkali solubility, and any dissolution promoter. Once the coating surface in the exposed area dissolves, dissolution of the inside of the coating, which has high alkali solubility compared to the coating surface, proceeds quickly because the concentration of the hydrophobic resin (A) is relatively low. This can increase the contrast between the exposed area and the unexposed area, and as a result, it is presumed that the amount of film loss when the positive photosensitive resin composition is cured can be reduced and hole formability can be improved (however, the action and effect of this embodiment are not limited to these).

[0040] On the other hand, when a hydrophobic resin and a fluorine-based surfactant are used in combination to make the coating surface less soluble in an alkaline aqueous solution, the acid generated during exposure diffuses in the coating, and the acid concentration in the vicinity of the coating surface and inside the coating is more uniform than when a hydrophobic resin (A) and a silicone-based surfactant (D) having a silicon atom in the side chain are used in combination. Therefore, the coating surface of the exposed part is less likely to dissolve during development, the sensitivity is reduced, and the amount of film loss when the film is cured may be large. In addition, the photoacid generator may have low thermal stability, and the use of such a photoacid generator may also promote the dissolution of the unexposed part, resulting in a problem of reduced hole formation. However, according to the positive photosensitive resin composition of this embodiment, the occurrence of such problems can be effectively suppressed (however, the action and effect of this embodiment are not limited to these).

[0041] Hereinafter, each component that can be used in the positive photosensitive resin composition according to this embodiment will be described.

[0042] <Hydrophobic resin (A)>

[0043] The type of hydrophobic resin (A) is not particularly limited, and examples thereof include acrylic resin, polystyrene resin, epoxy resin, polyamide resin, phenol resin, polyimide resin, polyamic acid resin, polybenzoxazole resin, polybenzoxazole resin precursor, silicone resin, cyclic olefin polymer, cardo resin, and derivatives of these resins. The derivatives of these resins preferably have a hydrophobic group. Suitable examples of the hydrophobic group include, for example, a silicon atom-containing group. As the hydrophobic resin (A), a resin in which a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group is used as the base resin and a part or all of the alkali-soluble functional group is converted to a group having the hydrophobic group can also be used. The hydrophobic resin (A) may be used alone or in combination of two or more types.

[0044] The hydrophobic resin (A) is preferably a resin having a silicon atom-containing group. The silicon atom-containing group may be present in the main chain of the hydrophobic resin (A) or in a side chain (pendant group), but is preferably present in the side chain.

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

[0046] The silyl group substituted with an aliphatic hydrocarbon group or an aryl group is mono-substituted, di-substituted or tri-substituted. The substituents of the silyl group substituted with an aliphatic hydrocarbon group or an aryl group may be the same or different from each other. The silyl group substituted with an aliphatic hydrocarbon group or an aryl group is preferably tri-substituted. The silyl group substituted with an aliphatic hydrocarbon group or an aryl group may further have a substituent other than an alkyl group or an aryl group, for example, a silyloxy group substituted with an aliphatic hydrocarbon group or an aryl group.

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

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

[0049] The aliphatic hydrocarbon group of a silyl group substituted with an aliphatic hydrocarbon group or an aryl group, the aliphatic hydrocarbon group as a substituent of a group having a cyclic siloxane structure, the aliphatic hydrocarbon group as a substituent of a group having a silsesquioxane structure, and the aliphatic hydrocarbon group as a substituent of a silyloxy group substituted with an aliphatic hydrocarbon group or an aryl group are preferably aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and more preferably aliphatic hydrocarbon groups having 1 to 8 carbon atoms. Examples of the aliphatic hydrocarbon 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 groups; unsaturated hydrocarbon groups such as ethenyl, propenyl, butenyl, ethynyl, and propynyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclohex ... Examples of such groups include saturated monocyclic hydrocarbon groups such as a cyclododecyl group; unsaturated monocyclic hydrocarbon groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, and a cyclodecenyl group; saturated polycyclic hydrocarbon groups such as a bicyclo[2.2.1]heptanyl group, a bicyclo[2.2.2]octanyl group, and an adamantyl group; and unsaturated polycyclic hydrocarbon groups such as a bicyclo[2.2.1]heptenyl group and a bicyclo[2.2.2]octenyl group.

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

[0051] 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 trimethylsilyloxydimethylsilyl group.

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

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

[0054] The hydrophobic resin (A) can be produced, for example, by radically polymerizing a polymerizable monomer having a hydrophobic group, or by radically copolymerizing a polymerizable monomer having a hydrophobic group with another polymerizable monomer. Examples of the polymerizable functional groups possessed by the polymerizable monomer having a hydrophobic group and the other polymerizable monomer include radically polymerizable functional groups such as CH2=CH-, CH2=C(CH3)-, CH2=CHCO-, CH2=C(CH3)CO-, -OC-CH=CH-CO-, etc. The hydrophobic resin (A) can also be produced by reacting a resin having a functional group such as a hydroxy group, a carboxy group, an amino group, or an epoxy group with a compound having a hydrophobic group to convert the functional group into a group containing a hydrophobic group.

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

[0056] Examples of polymerizable monomers having a silicon atom-containing group include trimethylvinylsilane, trimethylallylsilane, trimethyl(3-butenyl)silane, tert-butyldimethylvinylsilane, (trimethylsilyloxy)dimethylvinylsilane, (trimethylsilyloxy)dimethylallylsilane, triethylvinylsilane, triethylallylsilane, triethyl(3-butenyl)silane, (trimethylsilyl)methyl(meth)acrylate, 2-(trimethylsilyl)ethyl(meth)acrylate, 3-(trimethylsilyl)propyl(meth)acrylate, tert-butyldimethylsilyl(meth)acrylate, triisopropylsilylmethyl(meth)acrylate, bis(trimethylsilyl)methyl ...

[0113] Examples of suitable silyloxyphenyl (meth)acrylates include 4-(trimethylsilyl)cyclohexyl (meth)acrylate, 3-[(trimethylsilyloxy)dimethylsilyl]propyl (meth)acrylate, 3-[tris(trimethylsilyloxy)silyl]propyl (meth)acrylate, 4-trimethylsilyloxyphenyl (meth)acrylate, 4-triethylsilyloxyphenyl (meth)acrylate, 4-triisopropylsilyloxyphenyl (meth)acrylate, 4-tert-butyldimethylsilyloxyphenyl (meth)acrylate, vinylheptamethylcyclotetrasiloxane, and 3-(heptamethylsilsesquioxanyl)propyl (meth)acrylate.

[0057] 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)acrylic acid esters such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, sec-butyl(meth)acrylate, tert-butyl(meth)acrylate, phenyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, glycidyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentenyl(meth)acrylate, and dicyclopentanyl(meth)acrylate.

[0058] The other polymerizable monomer may be a polymerizable monomer having an alkali-soluble functional group. Examples of polymerizable monomers having an alkali-soluble functional group include maleic acid, 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-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; unsaturated carboxylic acid compounds such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid; polymerizable monomers having a phenolic hydroxyl group such as 4-hydroxystyrene and 4-hydroxyphenyl(meth)acrylate; polymerizable monomers having a sulfo group such as (meth)allylsulfonic acid and styrenesulfonic acid; polymerizable monomers having a phosphoric acid group such as mono(2-(meth)acryloyloxyethyl)phosphate; and polymerizable monomers having an acid anhydride group such as itaconic anhydride and citraconic anhydride.

[0059] As the polymerizable monomer having a hydrophobic group, it is preferable to use 4-tert-butyldimethylsilyloxyphenyl(meth)acrylate and / or 4-hydroxyphenyl(meth)acrylate, and it is more preferable to use both of them. By using a resin obtained by radical polymerization of these polymerizable monomers, it is possible to further improve the sensitivity and hole-forming property of the positive photosensitive resin composition and further reduce outgassing.

[0060] The hydrophobic resin (A) preferably contains a structural unit represented by the following formula (1): For example, the above-mentioned polymerizable monomer having a hydrophobic group is preferably one that forms a structural unit represented by formula (1) after polymerization.

[0061] [ka]

[0062] (In formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 2 is SiR 3 R 4 R 5 and R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 4, and s is an integer of 1 to 5, with the proviso that r+s is an integer of 1 to 5.

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

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

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

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

[0067] The hydrophobic resin (A) may have a structural unit represented by the following formula (2) if necessary, but sufficient effects can be obtained even if it does not have the structural unit. For example, other polymerizable monomers that form the structural unit represented by formula (2) after polymerization can be used.

[0068] [ka]

[0069] (In formula (2), R6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 8 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0070] R 6 and R 7 are each independently exemplified by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples of such other polymerizable monomers 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 hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Examples of such other polymerizable monomers include phenylmaleimide and N-cyclohexylmaleimide.

[0071] However, the positive photosensitive resin composition according to this embodiment can obtain a sufficient effect even if the hydrophobic resin (A) does not have the structural unit represented by the above formula (2). Furthermore, the hydrophobic resin (A) can obtain a sufficient effect even if the structural unit does not have a maleimide structure. From the viewpoint of obtaining a sufficient effect, it is preferable that the hydrophobic resin (A) does not have an imide skeleton in the structural unit. Furthermore, it is more preferable that the hydrophobic resin (A) does not have a nitrogen atom.

[0072] If necessary, the hydrophobic resin (A) preferably further has a structural unit represented by the following formula (3). For example, the other polymerizable monomer having an alkali-soluble functional group is preferably one that forms a structural unit represented by formula (3) after polymerization.

[0073] [ka]

[0074] (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.

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

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

[0077] [ka]

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

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

[0080] As the hydrophobic resin (A), a resin containing the structural unit represented by the above formula (1) and the structural unit represented by the formula (3) is preferable, and a resin containing the structural unit represented by the above formula (1a) and the structural unit represented by the formula (1b) is more preferable. 1a and R in Eq. (1b) 1b may be the same or different.

[0081] 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.

[0082] The polymerization initiator used in producing the hydrophobic resin (A) by radical polymerization may be, but is not limited to, azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN); dicumyl peroxide, 2,5-dimethyl-2,5-di(tert Peroxide polymerization initiators having a 10-hour half-life temperature of 100 to 170°C, such as di-tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide, or peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, and tert-butylperoxypivalate, can be used. 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 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, based on 100 parts by mass of the total of the polymerizable monomers.

[0083] In the polymerization of the hydrophobic resin (A), a RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with a polymerization initiator. The RAFT agent is not limited to the following, but may be a thiocarbonylthio compound such as a dithioester, dithiocarbamate, trithiocarbonate, or xanthate. The RAFT agent may be used in the range of 0.005 to 20 parts by mass, and preferably in the range of 0.01 to 10 parts by mass, relative to 100 parts by mass of the total of the polymerizable monomers.

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

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

[0086] 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, even more preferably 5000 or more, still more preferably 6000 or more, and even more preferably 7000 or more. The upper limit is more preferably 70000 or less, even more preferably 60000 or less, still more preferably 30000 or less, still more preferably 15000 or less, still more preferably 13000 or less, and even more preferably 10000 or less.

[0087] 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, even more preferably 2000 or more, still more preferably 2500 or more, and even more preferably 3000 or more. The upper limit is more preferably 25000 or less, even more preferably 20000 or less, still more preferably 10000 or less, and even more preferably 5000 or less.

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

[0089] By setting the weight average molecular weight, number average molecular weight and polydispersity in the above ranges, it is possible to obtain a positive photosensitive resin composition having even more excellent sensitivity and hole-forming properties.

[0090] The positive photosensitive resin composition according to the present embodiment contains the hydrophobic resin (A) in an amount of preferably 3 to 50% by mass, more preferably 4 to 40% by mass, and even more preferably 5 to 30% by mass, based on 100% by mass of the solid content. The lower limit is more preferably 4% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, even more preferably 10% by mass or more, and even more preferably 12% by mass or more. The upper limit is more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 18% by mass or less, and even more preferably 16% by mass or less. If the content of the hydrophobic resin (A) is equal to or more than the above lower limit, the silicone surfactant (D) promotes uneven distribution of the hydrophobic resin (A) on the coating surface, the hydrophobic resin (A) becomes highly concentrated on the coating surface, and the coating surface becomes poorly soluble in an alkaline aqueous solution, so that even higher sensitivity can be achieved. When the content of the hydrophobic resin (A) is equal to or less than the above upper limit, dissolution of the coating surface proceeds rapidly along with dissolution of the carboxylic acid compound derived from the quinone diazide compound in the exposed area, other resin components that are highly alkali-soluble, and any dissolution promoter, thereby achieving even higher sensitivity.

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

[0092] The positive photosensitive resin composition according to the present embodiment contains the hydrophobic resin (A) in an amount of preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 40% by mass, based on the total mass of the resin components. The lower limit is more preferably 10% by mass or more, even more preferably 15% by mass or more, still more preferably 20% by mass or more, and even more preferably 25% by mass or more. The upper limit is more preferably 50% by mass or less, even more preferably 40% by mass or less, still more preferably 35% by mass or less, and even more preferably 30% by mass or less. If the content of the hydrophobic resin (A) is equal to or more than the above lower limit, the silicone surfactant (D) promotes uneven distribution of the hydrophobic resin (A) on the coating surface, the hydrophobic resin (A) becomes highly concentrated on the coating surface, and the coating surface becomes poorly soluble in an alkaline aqueous solution, thereby achieving even higher sensitivity. When the content of the hydrophobic resin (A) is equal to or less than the above upper limit, dissolution of the coating surface proceeds rapidly along with dissolution of the carboxylic acid compound derived from the quinone diazide compound in the exposed area, other resin components that are highly alkali-soluble, and any dissolution promoter, thereby achieving even higher sensitivity.

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

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

[0095] 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 an epoxy group and a phenolic hydroxyl group, etc. The alkali-soluble resin (B) may be used alone or in combination of two or more kinds.

[0096] The alkali-soluble resin (B) may have a radically polymerizable functional group, specific examples of which include a (meth)acryloyloxy group, an allyl group, and a methallyl group.

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

[0098] In addition, when the positive photosensitive resin composition according to 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 solid content. The lower limit is more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more. The upper limit is more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. By making the content of the alkali-soluble resin (B) to this extent, it is possible to effectively ensure the stability and durability of the coating film after heat curing while further suppressing the decrease in dissolution and the decrease in sensitivity of the exposed part.

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

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

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

[0102] Specific examples of the component (B1) include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins, all of which have an alkali-soluble functional group. For example, a derivative of a phenol resin may be a polyalkenylphenol resin in which an alkenyl group is bonded to a benzene ring, and a derivative of a polystyrene resin may be a hydroxypolystyrene resin in which a phenolic hydroxyl group and a hydroxyalkyl group or an alkoxy group are bonded to a benzene ring.

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

[0104] 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.

[0105] The copolymer having an alkali-soluble functional group can be produced, for example, by radical polymerization of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. After synthesizing the copolymer by radical polymerization, the alkali-soluble functional group may be added to the copolymer.

[0106] Examples of polymerizable monomers having an alkali-soluble functional group include maleic acid, maleic acid derivatives such as 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-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; unsaturated carboxylic acid compounds such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid; Examples of polymerizable monomers include polymerizable monomers having a phenolic hydroxyl group, such as hydroxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, and 4-hydroxyphenyl maleimide; polymerizable monomers having a sulfo group, such as (meth)allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, and styrenesulfonic acid; polymerizable monomers having a phosphate group, such as mono(2-(meth)acryloyloxyethyl)phosphate; and polymerizable monomers having an acid anhydride group, such as itaconic anhydride and citraconic anhydride.

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

[0108] 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)acrylic acid esters such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, sec-butyl(meth)acrylate, tert-butyl(meth)acrylate, phenyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, glycidyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentenyl(meth)acrylate, and dicyclopentanyl(meth)acrylate.

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

[0110] [ka]

[0111] (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.

[0112] Examples of other polymerizable monomers include those that form a structural unit represented by formula (2) after polymerization, but they do not necessarily have to be included. 6 and R 7are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples of the other polymerizable monomer include a phenyl group substituted with at least one selected from the group consisting of a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Phenylmaleimide and N-cyclohexylmaleimide are examples of such other polymerizable monomers, but the positive-type photosensitive resin composition according to this embodiment can obtain a sufficient effect even if the alkali-soluble resin (B) does not contain such a maleimide skeleton. From the viewpoint of obtaining a sufficient effect, it is preferable that the alkali-soluble resin (B) does not have an imide skeleton in the structural unit. Furthermore, it is more preferable that the alkali-soluble resin (B) does not have a nitrogen atom.

[0113] [ka]

[0114] (In formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 8 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0115] 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, even if the copolymer does not have the structural unit represented by formula (2), sufficient effects can be obtained.

[0116] [ka]

[0117] (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.

[0118] [ka]

[0119] (In formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 8 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

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

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

[0122] The weight average molecular weight (Mw) of the copolymer having an alkali-soluble functional group is preferably 3000 to 80000, more preferably 4000 to 70000, and even more preferably 5000 to 60000. The number average molecular weight (Mn) of the copolymer having an alkali-soluble functional group is preferably 1000 to 30000, more preferably 1500 to 25000, and even more preferably 2000 to 20000. The polydispersity (Mw / Mn) of the copolymer having an alkali-soluble functional group is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2.8. By setting the weight average molecular weight, number average molecular weight, and polydispersity of the copolymer having an alkali-soluble functional group within the above ranges, a positive photosensitive resin composition having even better coatability, hole-forming property, and alkali developability can be obtained.

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

[0124] In this specification, when a copolymer having an alkali-soluble functional group also corresponds to a resin having an epoxy group and a phenolic hydroxyl group described below, it is treated as a copolymer having an alkali-soluble functional group. In other words, the resin having an epoxy group and a phenolic hydroxyl group does not include those that correspond to a copolymer having an alkali-soluble functional group.

[0125] <Resin having an epoxy group and a phenolic hydroxyl group (B2)>

[0126] 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. The resin having an epoxy group and a phenolic hydroxyl group can be obtained, for example, by reacting a part of the epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter, sometimes referred to as "epoxy compound") with a carboxy 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 heat treatment (post-baking) after development, thereby improving the chemical resistance, heat resistance, etc. of the coating. Since the phenolic hydroxyl group contributes to solubility in an alkaline aqueous solution during development, the resin having an epoxy group and a phenolic hydroxyl group also functions as a dissolution promoter for other resins when exposed to light at a low exposure dose, thereby making the photosensitive resin composition even more sensitive.

[0127] The following reaction formula 1 shows an example of a reaction in which one of the epoxy groups of an epoxy compound reacts with a carboxy group of a hydroxybenzoic acid compound to produce a compound having a phenolic hydroxyl group.

[0128] [ka]

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

[0130] An example of the structure of a novolac type epoxy resin is shown in formula (4). In formula (4), R 10 represents 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.

[0131] [ka]

[0132] Examples of phenol novolac type epoxy resins include "EPICLON (registered trademark) N-770", "EPICLON (registered trademark) N-730A" (trade names, DIC Corporation), and "jER (registered trademark)-152" (trade name, Mitsubishi Chemical Corporation). Examples of cresol novolac type epoxy resins include "EPICLON (registered trademark) N-695 (trade name, DIC Corporation)" and "EOCN (registered trademark)-102S" (trade name, Nippon Kayaku Co., Ltd.). Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins such as "jER (registered trademark) 828", "jER (registered trademark) 1001" (trade names, Mitsubishi Chemical Corporation), and "YD-128" (trade name, Nippon Steel Chemical & Material Co., Ltd.), and bisphenol F type epoxy resins such as "jER (registered trademark) 806" (trade name, Mitsubishi Chemical Corporation) and "YDF-170" (trade name, Nippon Steel Chemical & Material Co., Ltd.). Examples of biphenol-type epoxy resins include "jER (registered trademark) YX-4000" and "jER (registered trademark) YL-6121H" (all trade names, Mitsubishi Chemical Corporation). Examples of naphthalene skeleton-containing epoxy resins include "NC-7000" (trade name, Nippon Kayaku Co., Ltd.) and "EXA-4750" (trade name, DIC Corporation). Examples of alicyclic epoxy resins include "EHPE (registered trademark)-3150" (Daicel Corporation). Examples of heterocyclic epoxy resins include "TEPIC (registered trademark)", "TEPIC (registered trademark)-L", "TEPIC (registered trademark)-H", and "TEPIC (registered trademark)-S" (all trade names, Nissan Chemical Industries, Ltd.).

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

[0134] 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. In terms of enhancing alkaline developability, dihydroxybenzoic acid compounds are preferred. The hydroxybenzoic acid compounds may be used alone or in combination of two or more.

[0135] In this embodiment, a specific example of a resin having an epoxy group and a phenolic hydroxyl group is, for example, a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid compound, and has a structure represented by formula (5).

[0136] [ka]

[0137] (In formula (5), b is an integer of 1 to 5, and * represents a bond to a residue other than the epoxy group involved in the reaction of a compound having at least two epoxy groups in one molecule.)

[0138] 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, more preferably 0.4 to 0.8 equivalents. If the amount of the hydroxybenzoic acid compound is 0.2 equivalents or more, sufficient alkali solubility can be obtained, and if it is 0.95 equivalents or less, an increase in molecular weight due to a side reaction can be suppressed.

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

[0140] The number average molecular weight (Mn) of the resin having 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, even more preferably 1000 or more, and still more preferably 2000 or more. The upper limit is more preferably 6000 or less, even more preferably 5000 or less, and still more preferably 4000 or less.

[0141] 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, even more preferably 3,000 or more, and still more preferably 4,000 or more. The upper limit is more preferably 25,000 or less, even more preferably 20,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and even more preferably 7,000 or less.

[0142] For example, if the number average molecular weight is 500 or more, or if the weight average molecular weight is 500 or more, the alkali development rate is appropriate and the difference in dissolution rate between the exposed and unexposed areas is sufficient, resulting in better pattern resolution. If the number average molecular weight is 8000 or less, or if the weight average molecular weight is 30000 or less, the coatability and alkali developability are better.

[0143] The polydispersity (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 even more preferably 1.5 or more. The upper limit is more preferably 3.0 or less, and even more preferably 2.0 or less.

[0144] In this 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 even more preferably 500 to 5000. The lower limit is more preferably 400 or more, even more preferably 500 or more, even more preferably 1000 or more, and even more preferably 1500 or more. The upper limit is more preferably 6000 or less, even more preferably 5000 or less, even more preferably 4000 or less, and even more preferably 3000 or less. If the epoxy equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 or more, the resin having an epoxy group and a phenolic hydroxyl group can impart sufficient alkali solubility. If 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 coating after curing can be further increased. The epoxy equivalent is determined according to JIS K 7236:2009.

[0145] In this embodiment, the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is preferably 140 to 550, more preferably 160 to 500, even more preferably 170 to 400, and even more preferably 180 to 300. If the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is equal to or greater than the upper limit, the strength and heat resistance of the cured coating can be further improved. For example, if the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is equal to or greater than 160, the strength and heat resistance of the cured coating can be further improved. If the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is equal to or less than the lower limit, the resin having an epoxy group and a phenolic hydroxyl group can provide sufficient alkali solubility. For example, if the hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is equal to or less than 500, the resin having an epoxy group and a phenolic hydroxyl group can provide even more sufficient alkali solubility. The hydroxyl equivalent is determined according to JIS K 0070:1992.

[0146] Protective resin (B3)

[0147] The alkali-soluble resin (B) may contain a resin having an alkali-soluble functional group protected by an acid-decomposable group (hereinafter, simply referred to as a "protected resin"). The protective resin (B3) is not particularly limited as long as it has a plurality of alkali-soluble functional groups, and at least a part of the alkali-soluble functional groups is protected by an acid-decomposable group. For example, the protective resin (B3) may be a resin in which the above-mentioned alkali-soluble resin (B) having a plurality of alkali-soluble functional groups is used as a base resin, and at least a part of the alkali-soluble functional groups are protected by an acid-decomposable group. For example, the alkali-soluble functional group may be a phenolic hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group, or a mercapto group. The alkali-soluble functional group is preferably a phenolic hydroxyl group or a carboxyl group, and more preferably a phenolic hydroxyl group. Since a part of the alkali-soluble functional group is protected by an acid-decomposable group, the alkali solubility of the protective resin (B3) before exposure is suppressed. The protective resin (B3) may have an alkali-soluble functional group other than the alkali-soluble functional group protected by the acid-decomposable group. In the presence of acid generated during exposure, post-exposure bake (PEB, post exposure bake) is performed as necessary to promote decomposition (deprotection) of the acid-decomposable group, and the alkali-soluble functional group is regenerated. This promotes alkali dissolution of the protective resin (B3) in the exposed area during development. The protective resin (B3) may be used alone or in combination of two or more types. For example, the protective resin (B3) may be a combination of two or more types of resins that are different in the structural unit of the polymer or copolymer, the acid-decomposable group, the protection rate of the alkali-soluble functional group, or a combination thereof.

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

[0149] The protected resin (B3) can be obtained by protecting some of the alkali-soluble functional groups of a base resin having a plurality of alkali-soluble functional groups with an acid-decomposable group. For example, when the alkali-soluble functional group is a phenolic hydroxyl group, the protected resin (B3) having a phenolic hydroxyl group protected with an acid-decomposable group can be obtained by the reaction of Ar-OR 11 Ar represents an aromatic ring derived from phenol, and R 11 represents an acid-decomposable group.

[0150] The acid decomposable group is a group that decomposes (deprotects) in the presence of an acid, if necessary, by heating, to generate an alkali-soluble functional group. Specific examples include groups having a tertiary alkyl group such as tert-butyl group, 1,1-dimethyl-propyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-methyladamantyl group, 1-ethyladamantyl group, tert-butoxycarbonyl group, and 1,1-dimethyl-propoxycarbonyl group; and a group 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 ketal structure together with the oxygen atom derived from the alkali-soluble functional group. These acid decomposable groups can be used alone or in combination of two or more kinds. -CR 12 R 13 -OR 14 (6) (In formula (6), R 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms; 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 the two and R 14 may be bonded to form a ring structure having 3 to 10 ring members, R 12, R 13 and R 14 may be substituted with a halogen atom selected from the group consisting of chlorine, bromine and iodine.

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

[0152] The protection reaction of the alkali-soluble functional group can be carried out under known conditions using a general protecting agent. For example, the base resin of the protected resin (B3) is reacted with the protecting agent in the presence of an acid or base at a reaction temperature of -20 to 50°C without a solvent or in a solvent such as toluene or hexane to obtain the protected resin (B3).

[0153] As the protecting agent, a known protecting agent capable of protecting an alkali-soluble functional group can be used. As the protecting agent, for example, isobutene can be used when the acid decomposable group is a tert-butyl group, and di-tert-butyl dicarbonate can be used when the acid decomposable group is a tert-butoxycarbonyl group. Chloromethyl methyl ether can be used when the acid decomposable group is a methoxymethyl group, ethyl vinyl ether can be used when the acid decomposable group is a 1-ethoxyethyl group, n-propyl vinyl ether can be used when the acid decomposable group is a 1-n-propoxyethyl group, 2,3-dihydrofuran can be used when the acid decomposable group is a 2-tetrahydrofuranyl group, and 3,4-dihydro-2H-pyran can be used when the acid decomposable group is a 2-tetrahydropyranyl group.

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

[0155] In another embodiment, the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group is protected with an acid-decomposable group, and then the polymerizable monomer having the alkali-soluble functional group protected with the acid-decomposable group and other polymerizable monomers as necessary are polymerized or copolymerized to obtain the 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 in the same manner as the protection of the alkali-soluble functional group of the base resin.

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

[0157] [ka]

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

[0159] In the formula, R 16 The acid-decomposable group is preferably a group represented by formula (6). -CR 12 R 13 -OR 14 (6) (In formula (6), R 12 , R 13 and R 14 is as above.)

[0160] In formula (6), R 12 and R 13 are each independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms; R 14is more preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine. Examples of such acid-decomposable groups include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl groups, 1-methoxyethyl groups, 1-ethoxyethyl groups, 1-n-propoxyethyl groups, 1-n-butoxyethyl groups, 1-isobutoxyethyl groups, 1-(2-chloroethoxy)ethyl groups, 1-(2-ethylhexyloxy)ethyl groups, 1-cyclohexyloxyethyl groups, and 1-(2-cyclohexylethoxy)ethyl groups, with 1-ethoxyethyl and 1-n-propoxyethyl groups being preferred. 12 or R 13 One of the two and R 14 Examples of the acid-decomposable group in which the above are bonded to form a ring structure having 3 to 10 ring members include a 2-tetrahydrofuranyl group and a 2-tetrahydropyranyl group, with the 2-tetrahydrofuranyl group being preferred.

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

[0162] [ka]

[0163] (In formula (2), R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 8is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0164] In formula (2), R 6 and R 7 are each independently exemplified by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 Examples of the aryl group 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 hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0165] In this embodiment, the number of structural units represented by formula (7) where q is an integer of 1 or more, i.e., the number of 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%, more preferably 15 to 90%, and even more preferably 25 to 85% of the total number of structural units in the protective resin (B3). By making the ratio of the above structural units 5% or more, the dissolution of the exposed area can be further promoted and the solubility of the unexposed area and the exposed area can be further differentiated, so that further high sensitivity can be realized and the stability and durability of the coating after thermal curing can be effectively ensured. By making the ratio of the above structural units 95% or less, the amount of remaining unreacted acid-decomposable groups can be further reduced, and the solubility of the exposed area can be further increased, thereby achieving further high sensitivity.

[0166] In this embodiment, the positive photosensitive resin composition contains the protective resin (B3) in an amount of preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably 2 to 30% by mass, based on 100% by mass of the solid content. If the content of the protective resin (B3) is equal to or more than the lower limit based on 100% by mass of the solid content, the dissolution of the exposed part can be further promoted to further differentiate the solubility of the unexposed part and the exposed part, so that even higher sensitivity can be realized and the stability and durability of the coating film after thermal curing can be effectively ensured. If the content of the protective resin (B3) is equal to or less than the upper limit based on 100% by mass of the solid content, the amount of remaining unreacted acid-decomposable groups can be further reduced, and the solubility of the exposed part can be further increased to realize even higher sensitivity.

[0167] <Quinone diazide compounds (C)>

[0168] When quinone diazide compound (C) is irradiated with visible light, ultraviolet light, or radiation (gamma rays, electron beams, etc.), it undergoes the reaction shown in the following reaction formula 2 to produce an alkali-soluble carboxylic acid compound.

[0169] [ka]

[0170] Before exposure, the quinone diazide compound (C) interacts (e.g., forms hydrogen bonds) with the alkali-soluble functional groups, such as phenolic hydroxyl groups, of the alkali-soluble resin (B), making the alkali-soluble resin (B) insoluble in an alkaline aqueous solution. On the other hand, the presence of an alkali-soluble carboxylic acid compound in the portion irradiated with radiation makes the resin in that portion more soluble in an alkaline aqueous solution together with the carboxylic acid compound. In addition, the generated carboxylic acid compound promotes the decomposition of the acid-decomposable groups of the protective resin (B3) optionally contained in the positive photosensitive resin composition, regenerating the alkali-soluble functional groups, and increasing the alkali solubility of the protective resin (B3). Furthermore, the carboxylic acid compound has a relatively larger molecular structure than acids generated from photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is less likely to diffuse in the coating. As a result of these synergistic effects, the difference in alkali solubility between the unexposed and exposed portions can be increased, thereby making it possible to form a high-resolution pattern with high sensitivity even at low exposure doses. The quinone diazide compound (C) may be used alone or in combination of two or more kinds.

[0171] The positive-type photosensitive resin composition is preferably substantially free of a photoacid generator generally used in chemically amplified resists, and more preferably contains only the quinone diazide compound (C) as a photosensitizer without containing the photoacid generator. "Substantially free of a photoacid generator" means that the component is not actively added or mixed, and does not exclude that the component is inevitably contained or mixed. A suitable example of "substantially free of a photoacid generator" means that the amount of the photoacid generator contained in the positive-type photosensitive resin composition is preferably 0.2 parts by mass or less, more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0 parts by mass, based on 100 parts by mass of the total resin components.

[0172] In this embodiment, a high-resolution pattern can be formed without performing post-exposure bake (PEB) required for general chemically amplified resists. The quinone diazide compound (C) has a relatively high quantum yield, and a carboxylic acid compound is efficiently generated in the exposed area. By omitting PEB, it is possible to avoid a decrease in hole formation caused by excessive diffusion of the acid generated from the photoacid generator to the unexposed area in 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, ring-opening polymerization of the epoxy group of the resin having an epoxy group and a phenolic hydroxyl group does not proceed if PEB is omitted, so that the alkali solubility of the resin having an epoxy group and a phenolic hydroxyl group can be effectively maintained during development.

[0173] Examples of the quinone diazide compound (C) include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bound via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bound via a sulfonamide bond, a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bound via an ester bond or a sulfonamide bond, etc. From the viewpoint of further increasing the contrast between the exposed and unexposed areas, it is preferable that 20 mol % or more of the total functional groups of the polyhydroxy compound or polyamino compound are substituted with quinone diazide.

[0174] Examples of polyhydroxy compounds include "Bis-Z", "BisP-EZ", "TekP-4HBPA", "TrisP-HAP", "TrisP-PA", "TrisP-SA", "TrisOCR-PA", and "BisOCH". P-Z”, “BisP-MZ”, “BisP-PZ”, “BisP-IPZ”, “BisOCP-IPZ”, “BisP-CP”, “BisRS-2P”, “BisRS-3P”, “BisP-OCHP”, “Methylene tris -FR-CR", "BisRS-26X", "DML-MBPC", "DML-MBOC", "DML-OCHP", "DML-PCHP", "DML-PC", "DML-PTBP", "DML-34X", "DML-E P”, “DML-POP”, “Dimethylol-BisOC-P”, “DML-PFP”, “DML-PSBP”, “DML-MTrisPC”, “TriML-P”, “TriML-35XL”, “TML-BP”, “TML -HQ", "TML-pp-BPF", "TML-BPA", "TMOM-BP", "HML-TPPHBA", "HML-TPHAP" (all trade names, Honshu Chemical Industry Co., Ltd.), "BIR-OC", "BIP-PC", "BIR-PC", "BIR-PTBP", "BIR-PCHP", "BIP-BIOC-F", "4PC", "BIR-BIPC-F", "TEP-BIP-A", "46DMOC", "46DMOEP", "TM-BIP-A" (all trade names, Asahi Organic Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, "BisP-AP" (trade name, Honshu Chemical Industry Co., Ltd.), and the like are included, but are not limited thereto.

[0175] Polyamino compounds include, but are not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, and the like.

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

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

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

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

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

[0181] The silicone surfactant (D) is not particularly limited, but may be any silicone surfactant having a silicon atom in the side chain. For example, the silicone surfactant (D) is preferably a silicone surfactant containing a (meth)acrylic copolymer having at least one silicon-containing hydrocarbon group selected from the group consisting of a silicon-containing alkyl group and a silicon-containing alkylene group. The acrylic copolymer can promote the migration of the hydrophobic resin (A) to the coating surface of the positive photosensitive resin composition, making the coating surface more poorly soluble in alkali. In addition, from the viewpoint of further enhancing such an effect, the silicone surfactant (D) is preferably a silicone surfactant having no silicon atom in the main chain and having a silicon atom in the side chain. The silicone surfactant (D) may be used alone or in combination of two or more kinds.

[0182] An example of the (meth)acrylic copolymer is a copolymer (D1) of a polymerizable monomer represented by formula (8) and a polymerizable monomer having a polyoxyalkylene group represented by formula (9).

[0183] [ka]

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

[0185] [ka]

[0186] (In formula (9), R 18 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.

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

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

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

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

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

[0192] The copolymer (D1) may be a copolymer containing the polymerizable monomer represented by formula (8) and the polymerizable monomer having a polyoxyalkylene group represented by formula (9) as well as other polymerizable monomers.

[0193] An example of the other polymerizable monomer is a polymerizable monomer represented by the formula (10).

[0194] [ka]

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

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

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

[0198] The other polymerizable monomers may be used alone or in combination of two or more kinds.

[0199] From the viewpoint of leveling property, 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 even more preferably 25 / 75 to 50 / 50. When other polymerizable monomers are used, they are preferably used in an amount such that the amount of the other polymerizable monomers is 50 mass% or less based on the mass of the copolymer (D1).

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

[0201] Preferred specific examples of the silicone surfactant (D) include "MEGAFACE EFS-131", "MEGAFACE EFS-321", "MEGAFACE EFS-521", and "MEGAFACE EFS-801" (all trade names, all from DIC Corporation).

[0202] In particular, "MEGAFACE EFS-131", "MEGAFACE EFS-321" and "MEGAFACE EFS-521" are more preferred because they are fluorine-free, have silicon atoms in the side chains but no silicon atoms in the main chain, and contain both the structure represented by formula (8) and the structure represented by formula (9). All of these are (meth)acrylic copolymers that do not have silicon atoms in the main chain and have at least one silicon-containing hydrocarbon group selected from the group consisting of silicon-containing alkyl groups and silicon-containing alkylene groups.

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

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

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

[0206] <Colorant (E)>

[0207] The positive photosensitive resin composition preferably further contains a colorant (E) containing a black dye. The component (E) may contain a colorant other than the black dye. By forming a black partition wall in an organic EL element using a photosensitive resin composition containing the colorant (E) containing a black dye, the visibility of a display device such as an organic EL display can be improved.

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

[0209] Examples of black dyes include dyes defined by the color index (CI) of Solvent Black 27 to 47. The black dye is preferably defined by the CI of Solvent Black 27, 29, or 34. When at least one of the dyes defined by the CI of Solvent Black 27 to 47 is used as the black dye, the light-shielding properties of the coating of the positive photosensitive resin composition after curing can be effectively maintained. A positive photosensitive resin composition containing a black dye leaves less colorant residue during development and can form a high-definition pattern, compared to a positive photosensitive resin composition containing a black pigment.

[0210] Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigments, and lactam pigments. Surface-treated black pigments can also be used. Examples of commercially available perylene pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34 from BASF. Examples of commercially available lactam pigments include Irgaphor (registered trademark) Black S0100CF from BASF. Since the black pigment has high light-shielding properties, it is preferable that the black pigment is at least one selected from the group consisting of carbon black, titanium black, perylene pigments, and lactam pigments.

[0211] In addition, dyes and pigments other than those mentioned above can also be used in combination. These can be used according to the purpose, as long as the action and effect of the present embodiment are not impaired.

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

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

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

[0215] 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 even more preferably 20 to 80 parts by mass, based on 100 parts by mass of the total of the resin components. The lower limit is more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more. The upper limit is more preferably 100 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less. If the content of the colorant (E) is the lower limit or more based on the total of 100 parts by mass, sufficient light-shielding properties can be obtained, and in particular, since the colorant (E) contains a black dye, the light-shielding properties of the coating after curing can be effectively maintained. When the content of colorant (E) is equal to or less than the upper limit based on the total 100 parts by mass, the film remaining rate and sensitivity are appropriate, and in particular when colorant (E) contains a black dye, high heat resistance can be imparted to the coating.

[0216] Moreover, the positive photosensitive resin composition according to this embodiment preferably contains 5 to 75 parts by mass of the colorant (E) based on 100 parts by mass of the solid content. The lower limit is more preferably 7.5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more. The upper limit is more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less. If the content of the colorant (E) is equal to or more than the lower limit, sufficient light-shielding properties can be obtained, and since the colorant (E) contains a black dye, the light-shielding properties of the film after curing can be effectively maintained. If the content of the colorant (E) is equal to or less than the upper limit, the residual film rate and sensitivity are appropriate, and especially when the colorant (E) contains a black dye, high heat resistance can be imparted to the film.

[0217] <Optional ingredients>

[0218] The positive-type photosensitive resin composition may contain, as optional components, a dissolution promoter (F), a heat curing agent, a second surfactant other than the silicone-based surfactant (D) having a silicon atom in the side chain, etc. In this specification, the optional components are defined as those that do not fall into any of (A) to (E).

[0219] <Solubility enhancer (F)>

[0220] 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 the group consisting of compounds having a carboxy group and compounds having a phenolic hydroxyl group. The dissolution promoter (F) may be used alone or in combination of two or more kinds.

[0221] In this specification, the term "low molecular weight compound" refers to a compound having a molecular weight of less than 1000. The above organic low molecular weight compound has a carboxy group or a plurality of phenolic hydroxyl groups and is alkali-soluble.

[0222] Examples of such organic low molecular weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimellitic acid, and mesitylene acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, and pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; other carboxylic acids such as phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umbellic acid; and aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol.

[0223] The content of the dissolution promoter (F) in the positive photosensitive resin composition can be, 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, based on 100 parts by mass of the total of the resin components. The lower limit is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more. The upper limit is preferably 35 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. If the content of the dissolution promoter (F) is the lower limit or more based on the total of 100 parts by mass, dissolution of the resin components can be effectively promoted, and if the content is the upper limit or less based on the total of 100 parts by mass, excessive dissolution of the resin components can be suppressed, and the hole forming property and surface quality of the coating can be further improved.

[0224] The positive photosensitive resin composition according to this embodiment contains, for example, 0.05 to 25 parts by mass of a dissolution promoter (F) 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, even more preferably 1.5 parts by mass or more, even more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. The upper limit is preferably 17.5 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7.5 parts by mass or less. If the content of the dissolution promoter (F) is equal to or more than the lower limit, the dissolution of the resin component can be effectively promoted, and if it is equal to or less than the upper limit, excessive dissolution of the resin component can be suppressed, and the hole forming property and surface quality of the coating can be further improved.

[0225] <Thermal hardener>

[0226] A thermal radical generator can be used as the thermal curing agent. A preferred thermal radical generator is an organic peroxide, specifically, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, or other organic peroxides having a 10-hour half-life temperature of 100 to 170°C.

[0227] The content of the heat curing agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the heat curing agent.

[0228] <Second Surfactant> The positive photosensitive resin composition may contain a second surfactant other than the silicone-based surfactant (D) in order to, for example, further improve the coatability, the smoothness of the coating, or the developability of the coating. Examples of the second surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and acetylene surfactants such as "Olfine (registered trademark) E1004", "Olfine (registered trademark) E1010", "Olfine (registered trademark) E1020", and "Olfine (registered trademark) E1030W" (all trade names, Nissin Chemical Industry Co., Ltd.), "Acetylenol (registered trademark) E40", "Acetylenol (registered trademark) E60", "Acetylenol (registered trademark) E100", and "Acetylenol (registered trademark) E200" (all trade names, Kawaken Fine Chemical Co., Ltd.). The second surfactant may be used alone or in combination of two or more types.

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

[0230] [Coating composition]

[0231] <Solvent (G)>

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

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

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

[0235] When a pigment is used, a known method can be used for dispersing and mixing. For example, ball-type mills such as ball mills, sand mills, bead mills, paint shakers, and rocking mills, blade-type mills such as kneaders, paddle mixers, planetary mixers, and Henschel mixers, and roll-type mills such as three-roll mixers, as well as Raikai mixers, colloid mills, ultrasonics, homogenizers, and rotation-revolution mixers may be used. From the viewpoints of dispersion efficiency and fine dispersion, it is preferable to use a bead mill.

[0236] The prepared coating composition is usually filtered before use. Examples of the filtering means include a Millipore filter having a pore size of 0.05 to 1.0 μm.

[0237] The coating composition thus prepared also has excellent long-term storage stability.

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

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

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

[0241] Next, the prebaked coating is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation) through a photomask having a predetermined pattern (exposure step). Preferred radiation is ultraviolet light to visible light having a wavelength of 250 to 450 nm. In this embodiment, the radiation is preferably i-rays. In another embodiment, the radiation is preferably ghi-rays.

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

[0243] In this embodiment, it is preferable not to include a PEB step after the exposure step, which can prevent the film from flowing or deforming due to heating, and can form a thick film pattern with higher accuracy, and can also reduce the number of steps related to the formation of partition walls or insulating films.

[0244] After the exposure step or PEB step, for example, the coating is developed (for example, alkaline development) by contacting the coating with a developer, and unnecessary portions are removed to form a pattern in the coating (development step). As the developer, for example, an aqueous solution of an alkaline compound such as an inorganic alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or ammonia water; a primary amine such as ethylamine or n-propylamine; a secondary amine such as diethylamine or di-n-propylamine; a tertiary amine such as triethylamine or methyldiethylamine; an alcohol amine such as dimethylethanolamine or triethanolamine; a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or choline; or a cyclic amine such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, or 1,5-diazabicyclo[4.3.0]-5-nonane can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant to an alkaline aqueous solution can also be used as the developer. The development time is usually 30 to 180 seconds. The developing method may be any of a puddle method, a shower method, a dipping method, etc. After development, washing with running water is carried out for 30 to 90 seconds to remove unnecessary parts, and the coating is air-dried with compressed air or compressed nitrogen, whereby a pattern can be formed in the coating.

[0245] Thereafter, the coating film on which the pattern has been formed can be heat-treated, for example, at 100 to 350°C for 20 to 200 minutes using a heating device such as a hot plate or oven to obtain a cured coating film (post-baking, heat treatment step). In the heat treatment, the temperature may be kept constant, or may be increased continuously or stepwise. The heat treatment is preferably carried out in a nitrogen gas atmosphere.

[0246] <Film Remaining Rate>

[0247] In this embodiment, the positive photosensitive resin composition is applied so that the film thickness after prebaking is 3±0.3 μm, and the coating is prebaked at 125° C. for 120 seconds to form a coating, and then the coating is alkaline developed for 60 seconds with a 2.38 mass % tetramethylammonium hydroxide aqueous solution at a temperature of 23° C. The residual film ratio defined by the following formula is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. The residual film ratio is an index of the solubility of the unexposed parts, and the higher the residual film ratio, the greater the difference in solubility between the exposed parts and the unexposed parts, and a thick film pattern with a large difference in height can be formed with high precision. Remaining film rate (%) = Film thickness after development (μm) / Film thickness before development (μm) (equation)

[0248] <Optical density>

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

[0250] The method for producing the organic EL element partition or the organic EL element insulating film of this 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 coating film, removing the solvent contained in the coating film to dry the coating film, exposing the coating film by irradiating the dried coating film with radiation through a photomask, developing the exposed coating film by contacting it with a developer to form a pattern in the coating film, and heat-treating the patterned coating film at a temperature of 100 to 350°C to form an organic EL element partition or an organic EL element insulating film. The above-mentioned PEB can also be performed after exposure and before development. The positive photosensitive resin composition of this specification can form a thick film pattern with high sensitivity and high precision even in an embodiment in which the positive photosensitive resin composition contains a colorant (E).

[0251] <Organic EL element partition>

[0252] The present embodiment is an organic EL element partition wall including a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably includes a colorant (E). The cured product of the positive photosensitive resin composition according to the present embodiment used for the organic EL element partition wall can be obtained by the above-mentioned curing method. The steps of the method for producing the organic EL element partition wall according to the present embodiment are not particularly limited, and known steps and their conditions can be appropriately adopted. For example, the organic EL element partition wall according to the present embodiment can be obtained by the above-mentioned production method including the coating step, the reduced pressure drying step, the pre-baking step, the exposure step, the alkali developing step, and the post-baking step. The organic EL element partition wall according to the present embodiment can be suitably used as a black organic EL element partition wall. As described above, in a display device such as an organic EL display, a partition wall (partition wall material) is used in the gaps between colored patterns in the display area or the edges of the peripheral parts of the display area in order to improve display characteristics. Among the partition walls, black partition walls have a higher light-shielding property than other colors, and therefore tend to have problems during UV irradiation in the exposure step, such as (i) the ultraviolet light is unlikely to reach the depths of the coating film of the positive photosensitive resin composition, and (ii) the exposure time is prolonged, resulting in reduced productivity. However, according to the present embodiment, such problems can be particularly effectively prevented, and therefore it is possible to achieve higher pixel performance and higher resolution than ever before.

[0253] <Insulating film for organic electroluminescence devices>

[0254] The present embodiment is an organic EL element insulating film containing a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E). The cured product of the positive photosensitive resin composition according to the present embodiment used for the organic EL element insulating film can be obtained by the above-mentioned curing method. The steps of the method for producing the organic EL element insulating film according to the present embodiment are not particularly limited, and known steps and conditions can be appropriately adopted. For example, in the case of an organic EL element used in an organic EL display, the light-emitting layer and the like are easily affected by moisture and impurity gases and tend to deteriorate, so it is meaningful to be able to provide an insulating film with excellent reliability. It is expected that the organic EL element insulating film according to the present embodiment can also meet such demands.

[0255] <Organic EL element>

[0256] The present embodiment is an organic EL device containing a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E) containing a black dye. The cured product of the positive photosensitive resin composition according to the present embodiment used in an organic EL device can be obtained by the above-mentioned curing method. By using this cured product in the above-mentioned partition material, insulating film and other members, an excellent organic EL device can be realized. In particular, when applied to black members, it can exhibit particularly excellent effects compared to conventional ones.

[0257] As described above, the positive photosensitive resin composition according to this embodiment can be suitably used in radiation lithography for forming the partition wall and insulating film of an organic EL element. Regarding the partition wall of an organic EL element, it can be suitably used as a positive photosensitive resin composition for forming a partition wall material. Furthermore, in the case of a positive photosensitive resin composition containing the above-mentioned colorant (E), an organic EL element having a partition wall or an insulating film formed therewith is suitably used as an electronic component of a display device exhibiting good contrast. In particular, when used in a black positive resist, a black partition wall material, etc., it is possible to achieve a good balance between high sensitivity, residue removability, small film loss, and fine hole formation at a high level that could not be achieved in the past while maintaining sufficient light shielding properties. EXAMPLES

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

[0259] (1) Raw materials

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

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

[0262] <Hydrophobic resin (A)>

[0263] (Production Example 1) Production of Hydrophobic Resin (A): Resin Having Silicon Atom-Containing Group (PSM-TB) 15.9 g of 4-hydroxyphenyl methacrylate (Resonac Corporation, "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 Co., Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two obtained solutions were simultaneously dropped over 2 hours into 90.5 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C under a nitrogen gas atmosphere in a 300 mL three-neck flask equipped with a reflux condenser, and then reacted at 89 ° C for 4 hours. 50 g of the reaction solution cooled to room temperature was dropped into 250 g of hexane to precipitate the copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 80°C for 5 hours, and 9.73 g of a white powder (PSM-TB) was collected. The number average molecular weight of the obtained PSM-TB was 3753, the weight average molecular weight was 7581, the polydispersity (Mw / Mn) was 2.0, and the proportion of monomer units having a silicon atom-containing group in the total monomer units was 32 mol%. In PSM-TB, the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3), in which s is an integer of 1 or more, was formula (1):formula (2):formula (3)=32:7:61, and the structural unit having an alkali-soluble functional group was 61 mol% based on the total structural units. The silicon atom content was 4.0 mass% based on the mass of PSM-TB34.

[0264] (Production Example 2) Production of Hydrophobic Resin (A): Resin Having Silicon Atom-Containing Group (PSM-TE) 15.9 g of 4-hydroxyphenyl methacrylate (Resonac Corporation, "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 Co., Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two obtained solutions were simultaneously dropped over 2 hours into 90.4 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C under a nitrogen gas atmosphere in a 300 mL three-neck flask equipped with a reflux condenser, and then reacted at 89 ° C for 4 hours. 50 g of the reaction solution cooled to room temperature was dropped into a mixed solvent of 200 g of hexane and 50 g of toluene to precipitate the copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 80 ° C for 5 hours, and 9.49 g of white powder (PSM-TE) was collected. The number average molecular weight of the obtained PSM-TE was 3847, the weight average molecular weight was 7534, the polydispersity (Mw / Mn) was 2.0, and the proportion of monomer units having a silicon atom-containing group in the total monomer units was 32 mol%. In PSM-TE, the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3), in which s is an integer of 1 or more, was formula (1): formula (2): formula (3) = 32: 7: 61, and the structural unit having an alkali-soluble functional group was 61 mol% based on the total structural units. The silicon atom content was 4.0 mass % based on the mass of PSM-TE.

[0265] (Production Example 3) Production of Hydrophobic Resin (A): Resin Having Silicon Atom-Containing Group (PS-TB) 15.9 g of 4-hydroxyphenyl methacrylate (Resonac Corporation, "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 Industry Co., Ltd.) as a solvent. 2.86 g of V-601 (FUJIFILM Wako Pure Chemical Industries Co., Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.). The two obtained solutions were simultaneously dropped over 2 hours into 90.5 g of isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C under a nitrogen gas atmosphere in a 300 mL three-neck flask equipped with a reflux tube, and then reacted at 89 ° C for 4 hours. 50 g of the reaction solution cooled to room temperature was dropped into 250 g of hexane to precipitate a copolymer. The precipitated copolymer was collected by filtration and vacuum dried at 80°C for 5 hours, and 8.83 g of white powder (PS-TB) was collected. The number average molecular weight of the obtained PS-TB was 4238, the weight average molecular weight was 8900, the polydispersity (Mw / Mn) was 2.1, and the proportion of monomer units having a silicon atom-containing group in the total monomer units was 27 mol%. In PS-TB, the molar ratio of the structural unit represented by formula (1) where s is an integer of 1 or more and the structural unit represented by formula (3) was formula (1):formula (3) = 27:73, and the structural unit having an alkali-soluble functional group was 73 mol% based on the total structural units. The silicon atom content was 4.2 mass% based on the mass of PS-TB.

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

[0267] (Production Example 4) Production of alkali-soluble resin (B): resin having epoxy groups and phenolic hydroxyl groups (N695OH) A 300 mL three-neck flask was charged with 75.2 g of γ-butyrolactone (Mitsubishi Chemical Corporation) as a solvent and 37.8 g of “EPICLON (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 gas atmosphere. 20.1g (0.65 equivalents per epoxy equivalent) of 3,5-dihydroxybenzoic acid (FUJIFILM Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound and 0.166g (0.660mmol) 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 274.2g of a solution of a resin (N695OH) having epoxy groups and phenolic hydroxyl groups. The number average molecular weight of the resulting reaction product was 3000, the weight average molecular weight was 5100, the polydispersity (Mw / Mn) was 1.7, the epoxy equivalent was 2200, and the phenolic hydroxyl equivalent was 161.

[0268] <Quinone diazide compounds (C)>

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

[0270] The structures of "TS-150A" and "TS-200A" are shown below. In the formula below, of the three R's per molecule, 1.5 R's on average have a quinone diazide structure. In the formula below, of the three R's per molecule, 2.0 R's on average have a quinone diazide structure.

[0271] [ka]

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

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

[0274] <Colorant (E)>

[0275] As the colorant (E), black dyes "VALIFAST (registered trademark) BLACK 3804" (abbreviation "VB3804", Orient Chemical Industry Co., Ltd.; a black dye defined by the CI of Solvent Black 34), "VALIFAST (registered trademark) BLACK 3810" (abbreviation "VB3810", Orient Chemical Industry Co., Ltd.; a black dye defined by the CI of Solvent Black 34), and "VALIFAST (registered trademark) BLACK 3804" (abbreviation "VB3804", Orient Chemical Industry Co., Ltd.; a black dye defined by the CI of Solvent Black 34) were used.

[0276] <Solubilizer (F)>

[0277] Phloroglucinol was used as the solubility enhancer (F).

[0278] <Solvent (G)>

[0279] 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.

[0280] (2) Evaluation method

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

[0282] <Sensitivity>

[0283] A glass substrate (size 100 mm x 100 mm x 1 mm) was bar-coated with a positive photosensitive resin composition so that the dry film thickness was 3.0 μm, and after 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating at 125°C for 120 seconds on a hot plate with a lid. The coating was exposed to light through a quartz photomask (having an opening pattern of φ10 μm) using an exposure device (product name "Multilight ML-251A / B", Ushio Electric Co., Ltd.) incorporating an ultra-high pressure mercury lamp. The exposure dose was measured using an ultraviolet integrating light meter (product name "UIT-150" light receiving part "UVD-S365", Ushio Electric Co., Ltd.). After exposure, the substrate was subjected to alkaline development for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developing device ("AD-1200", Takizawa Sangyo Co., Ltd.). The above procedure was repeated while changing the exposure dose to determine the minimum exposure dose (mJ / cm) that would allow a pattern with a hole diameter of 10 μm to be formed completely through the glass substrate after development. 2 ) was defined as the sensitivity.

[0284] <Solubility of unexposed areas>

[0285] A glass substrate (size 100 mm x 100 mm x 1 mm) was bar-coated with a positive photosensitive resin composition so that the dry film thickness was 3.0 μm, and after 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating at 125 ° C. for 120 seconds on a hot plate with a lid. The dry film thickness was measured using an optical film thickness measuring device ("F20-NIR", Filmetrics Inc.), and then alkali development was performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developing device ("AD-1200", Takizawa Sangyo Co., Ltd.). The film thickness after alkali development was again measured using an optical film thickness measuring device ("F20-NIR", Filmetrics Inc.), and the film thickness (μm) dissolved before and after development was used as an index of the solubility of the unexposed portion. The solubility of the unexposed portion being 0 μm is equivalent to a remaining film ratio defined by the following formula being 100%. Remaining film rate (%) = Film thickness after development (μm) / Film thickness before development (μm) (equation)

[0286] <OD value of cured film>

[0287] A glass substrate (size 100 mm x 100 mm x 1 mm) was spin-coated with a positive photosensitive resin composition to a dry thickness of about 1.5 μm, and pre-baked by heating on a hot plate at 125°C for 120 seconds. A coating was then obtained by curing at 250°C for 60 minutes in a nitrogen gas atmosphere. The OD value of the cured coating was measured with a transmission densitometer ("BMT-1", Sakata Inx Corporation), corrected with the OD value of the glass alone, and converted to an OD value per 1 μm of coating thickness. The thickness of the coating was measured using an optical film thickness measuring device ("F20-NIR", Filmetrics Inc.).

[0288] <Hole diameter>

[0289] A glass substrate (size 100 mm x 100 mm x 1 mm) was bar-coated with a positive photosensitive resin composition so that the dry film thickness was 3.0 μm, and after 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating at 125°C for 120 seconds on a hot plate with a lid. The coating was exposed through a quartz photomask (having an opening pattern of φ10 μm) using an exposure device (product name "Multilight ML-251A / B", Ushio Electric Co., Ltd.) equipped with an ultra-high pressure mercury lamp. The exposure dose was measured using an ultraviolet integrating light meter (product name "UIT-150" light receiving part "UVD-S365", Ushio Electric Co., Ltd.). After exposure, the substrate was subjected to alkaline development for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developing device ("AD-1200", Takizawa Sangyo Co., Ltd.). Exposure dose 50 (mJ / cm 2 ) The hole diameter of the opened hole pattern was measured using a microscope (magnification: 2,000 times).

[0290] <Substrate interface residue>

[0291] A glass substrate (size 100 mm x 100 mm x 1 mm) was bar-coated with a positive photosensitive resin composition so that the dry film thickness was 3.0 μm, and after 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating at 125°C for 120 seconds on a hot plate with a lid. The coating was exposed to light through a quartz photomask (having an opening pattern of φ10 μm) using an exposure device (product name "Multilight ML-251A / B", Ushio Electric Co., Ltd.) incorporating an ultra-high pressure mercury lamp. The exposure dose was measured using an ultraviolet integrating light meter (product name "UIT-150" light receiving part "UVD-S365", Ushio Electric Co., Ltd.). After exposure, a spin developing device (product name "AD-1200", Takizawa Sangyo Co., Ltd.) was used to perform alkaline development with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Exposure dose 50 (mJ / cm 2 ) The substrate surface with the opened hole pattern was observed under an electron microscope (magnification: 20,000 times) and rated according to the following criteria. ◯: No film-like residue was observed on the surface area (φ10 μm), and few dot residues (= less than 5 pieces) were observed. △: No film-like residue was observed on the surface area (φ10 μm), but dot residues (= 5 or more) were observed. ×: Film-like residue was observed over the entire surface area (φ10 μm).

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

[0293] <Examples 1 to 9 and Comparative Examples 1 to 3>

[0294] The components were mixed under the conditions shown in Table 1. After visually confirming that the components had dissolved, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a positive photosensitive resin composition with a solid content concentration of 12 mass %. In Table 1, the composition values ​​for the components other than the solvent are in "parts by mass" and are solid content equivalent values. The evaluation results of the positive photosensitive resin compositions of each Example and Comparative Example are shown in Table 1.

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

[0296] <Example 2> A resin (PSM-TE) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), EFS-521 as the silicone surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12 mass%. The positive photosensitive resin composition of Example 2 contained 14 mass% of the hydrophobic resin (A) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 2 contained 29 mass parts of the hydrophobic resin (A) based on the total of 100 mass parts of the resin components. The positive photosensitive resin composition of Example 2 contained 35 mass% of the alkali-soluble resin (B) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 2 contained 71 mass parts of the alkali-soluble resin (B) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 2 contained 15 mass% of the quinone diazide compound (C) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 2 contained 31 mass parts of the quinone diazide compound (C) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 2 contained 15 mass% of the surfactant (D) based on 100 mass% of the solid content. The content of the surfactant (D) in the positive photosensitive resin composition of Example 2 was 31 mass parts based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 2 contained 30 mass% of colorant (E) based on 100 mass% of solid content. The content of colorant (E) in the positive photosensitive resin composition of Example 2 was 61 mass parts based on 100 mass parts of the total resin components. The solid content concentration of the coating composition of Example 2 was 12 mass%.

[0297] <Example 3> A resin (PS-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), EFS-521 as the silicone surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12 mass%. The positive photosensitive resin composition of Example 3 contained 14 mass% of the hydrophobic resin (A) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 3 contained 29 mass parts of the hydrophobic resin (A) based on the total of 100 mass parts of the resin components. The positive photosensitive resin composition of Example 3 contained 35 mass% of the alkali-soluble resin (B) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 3 contained 71 mass parts of the alkali-soluble resin (B) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 3 contained 15 mass% of the quinone diazide compound (C) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 3 contained 31 mass parts of the quinone diazide compound (C) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 3 contained 15 mass% of the surfactant (D) based on 100 mass% of the solid content. The content of the surfactant (D) in the positive photosensitive resin composition of Example 3 was 31 mass parts based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 3 contained 30 mass% of colorant (E) based on 100 mass% of solid content. The content of colorant (E) in the positive photosensitive resin composition of Example 3 was 61 mass parts based on 100 mass parts of the total resin components. The solid content concentration of the coating composition of Example 3 was 12 mass%.

[0298] <Example 4> A resin (PSM-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TS-150A) as the quinone diazide compound (C), EFS-521 as the silicone surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12 mass%. The positive photosensitive resin composition of Example 4 contained 14 mass% of the hydrophobic resin (A) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 4 contained 29 mass parts of the hydrophobic resin (A) based on the total of 100 mass parts of the resin components. The positive photosensitive resin composition of Example 4 contained 35 mass% of the alkali-soluble resin (B) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 4 contained 71 mass parts of the alkali-soluble resin (B) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 4 contained 15 mass% of the quinone diazide compound (C) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 4 contained 31 mass parts of the quinone diazide compound (C) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 4 contained 15 mass% of the surfactant (D) based on 100 mass% of the solid content. The content of the surfactant (D) in the positive photosensitive resin composition of Example 4 was 31 mass parts based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 4 contained 30 mass% of colorant (E) based on 100 mass% solid content. The content of colorant (E) in the positive photosensitive resin composition of Example 4 was 61 mass parts based on 100 mass parts of the total resin components. The solid content concentration of the coating composition of Example 4 was 12 mass%.

[0299] <Example 5> A resin (PSM-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TS-200A) as the quinone diazide compound (C), EFS-521 as the silicone surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12 mass%. The positive photosensitive resin composition of Example 5 contained 14 mass% of the hydrophobic resin (A) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 5 contained 29 mass parts of the hydrophobic resin (A) based on the total of 100 mass parts of the resin components. The positive photosensitive resin composition of Example 5 contained 35 mass% of the alkali-soluble resin (B) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 5 contained 71 mass parts of the alkali-soluble resin (B) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 5 contained 15 mass% of the quinone diazide compound (C) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 5 contained 31 mass parts of the quinone diazide compound (C) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 5 contained 15 mass% of the surfactant (D) based on 100 mass% of the solid content. The content of the surfactant (D) in the positive photosensitive resin composition of Example 5 was 31 mass parts based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 5 contained 30 mass% of colorant (E) based on 100 mass% of solid content. The content of colorant (E) in the positive photosensitive resin composition of Example 5 was 61 mass parts based on 100 mass parts of the total resin components. The solid content concentration of the coating composition of Example 5 was 12 mass%.

[0300] <Example 6> A resin (PSM-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), TS-200A as the quinone diazide compound (C), EFS-131 as the silicone surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12 mass%. The positive photosensitive resin composition of Example 6 contained 14 mass% of the hydrophobic resin (A) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 6 contained 29 mass parts of the hydrophobic resin (A) based on the total of 100 mass parts of the resin components. The positive photosensitive resin composition of Example 6 contained 35 mass% of the alkali-soluble resin (B) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 6 contained 71 mass parts of the alkali-soluble resin (B) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 6 contained 15 mass% of the quinone diazide compound (C) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 6 contained 31 mass parts of the quinone diazide compound (C) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 6 contained 15 mass% of the surfactant (D) based on 100 mass% of the solid content. The content of the surfactant (D) in the positive photosensitive resin composition of Example 6 was 31 mass parts based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 6 contained 30 mass% of colorant (E) based on 100 mass% solid content. The content of colorant (E) in the positive photosensitive resin composition of Example 6 was 61 mass parts based on 100 mass parts of the total resin components. The solid content concentration of the coating composition of Example 6 was 12 mass%.

[0301] <Example 7> A resin (PSM-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), TS-200A as the quinone diazide compound (C), EFS-321 as the silicone surfactant (D), a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12 mass%. The positive photosensitive resin composition of Example 7 contained 14 mass% of the hydrophobic resin (A) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 7 contained 29 mass parts of the hydrophobic resin (A) based on the total of 100 mass parts of the resin components. The positive photosensitive resin composition of Example 7 contained 35 mass% of the alkali-soluble resin (B) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 7 contained 71 mass parts of the alkali-soluble resin (B) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 7 contained 15 mass% of the quinone diazide compound (C) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 7 contained 31 mass parts of the quinone diazide compound (C) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 7 contained 15 mass% of the surfactant (D) based on 100 mass% of the solid content. The content of the surfactant (D) in the positive photosensitive resin composition of Example 7 was 31 mass parts based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 7 contained 30 mass% of colorant (E) based on 100 mass% of solid content. The content of colorant (E) in the positive photosensitive resin composition of Example 7 was 61 mass parts based on 100 mass parts of the total resin components. The solid content concentration of the coating composition of Example 7 was 12 mass%.

[0302] <Example 8> A resin (PSM-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), TS-200A as the quinone diazide compound (C), EFS-321 as the silicone surfactant (D), a black dye (VB3810) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12 mass%. The positive photosensitive resin composition of Example 8 contained 14 mass% of the hydrophobic resin (A) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 8 contained 29 mass parts of the hydrophobic resin (A) based on the total of 100 mass parts of the resin components. The positive photosensitive resin composition of Example 8 contained 35 mass% of the alkali-soluble resin (B) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 8 contained 71 mass parts of the alkali-soluble resin (B) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 8 contained 15 mass% of the quinone diazide compound (C) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 8 contained 31 mass parts of the quinone diazide compound (C) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 8 contained 15 mass% of the surfactant (D) based on 100 mass% of the solid content. The content of the surfactant (D) in the positive photosensitive resin composition of Example 8 was 31 mass parts based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 8 contained 30 mass% of colorant (E) based on 100 mass% solid content. The content of colorant (E) in the positive photosensitive resin composition of Example 8 was 61 mass parts based on 100 mass parts of the total resin components. The solid content concentration of the coating composition of Example 8 was 12 mass%.

[0303] <Example 9> A resin (PSM-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), TS-200A as the quinone diazide compound (C), EFS-321 as the silicone surfactant (D), a black dye (VB3820) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12 mass%. The positive photosensitive resin composition of Example 9 contained 14 mass% of the hydrophobic resin (A) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 9 contained 29 mass parts of the hydrophobic resin (A) based on the total of 100 mass parts of the resin components. The positive photosensitive resin composition of Example 9 contained 35 mass% of the alkali-soluble resin (B) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 9 contained 71 mass parts of the alkali-soluble resin (B) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 9 contained 15 mass% of the quinone diazide compound (C) based on 100 mass% of the solid content. The positive photosensitive resin composition of Example 9 contained 31 mass parts of the quinone diazide compound (C) based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 9 contained 15 mass% of the surfactant (D) based on 100 mass% of the solid content. The content of the surfactant (D) in the positive photosensitive resin composition of Example 9 was 31 mass parts based on 100 mass parts of the total resin components. The positive photosensitive resin composition of Example 9 contained 30 mass% of colorant (E) based on 100 mass% of solid content. The content of colorant (E) in the positive photosensitive resin composition of Example 9 was 61 mass parts based on 100 mass parts of the total resin components. The solid content concentration of the coating composition of Example 9 was 12 mass%.

[0304] <Comparative Example 1> A resin (PSM-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), KF2201 having a silicon atom in the main chain as the silicone surfactant, a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were mixed to prepare a positive photosensitive resin composition with a solid content concentration of 12 mass% so as to have the composition shown in Table 1. The positive photosensitive resin composition of Comparative Example 1 was not evaluated because repellency occurred during coating and a pattern could not be formed ("coating not possible" in the table).

[0305] <Comparative Example 2> A resin having a silicon atom-containing group (PSM-TB) as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), E-40 as the hydrocarbon surfactant, a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA=40 / 60 as the solvent (G) were mixed to obtain the composition shown in Table 1, thereby preparing a positive photosensitive resin composition with a solid concentration of 12 mass%.

[0306] <Comparative Example 3> A resin (PSM-TB) having a silicon atom-containing group as the hydrophobic resin (A), an epoxy resin (N695OH) as the alkali-soluble resin (B), (TPPA-150DF) as the quinone diazide compound (C), F-554 as the fluorosurfactant, a black dye (VB3804) as the colorant (E), phloroglucinol as the dissolution promoter (F), and a mixed solvent of GBL / PGMEA = 40 / 60 as the solvent (G) were blended to obtain the composition shown in Table 1, to prepare a positive photosensitive resin composition having a solid content concentration of 12% by mass. The surfactant used was the fluorosurfactant used in International Publication No. 2023 / 080254 (trade name "Megafac (registered trademark) F-554", manufactured by DIC Corporation).

[0307] [Table 1]

[0308] It was confirmed that the positive photosensitive resin composition of each Example had a solubility of 0 μm in the unexposed area, and therefore the contrast between the exposed area and the unexposed area could be increased, and a thick film pattern could be formed with high accuracy. From the above, it was confirmed that the present Example had excellent residue removability, little film loss, and fine hole formation, even without using an organic fluorine compound.

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

Claims

1. A hydrophobic resin (A); A quinone diazide compound (C), A silicone surfactant (D) having a silicon atom in a side chain; A positive-type photosensitive resin composition comprising:

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

3. Further containing a colorant (E) containing a black dye, The positive photosensitive resin composition according to claim 1 or 2.

4. The component (A) contains a structural unit represented by the following formula (1): The positive photosensitive resin composition according to claim 1 or 2. 【Chemistry 1】 (In formula (1), R １ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ２ is SiR ３ R ４ R ５ and R ３ , R ４ and R ５ are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 4, and s is an integer of 1 to 5, with the proviso that r+s is an integer of 1 to 5.

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

6. The component (A) contains the following structural unit (1a) and / or structural unit (1b): The positive photosensitive resin composition according to claim 1 or 2. 【Chemistry 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 each 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 may be the same or different.)

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

8. the component (D) is a silicone surfactant containing an acrylic copolymer having at least one silicon-containing hydrocarbon group selected from the group consisting of silicon-containing alkyl groups and silicon-containing alkylene groups; The positive photosensitive resin composition according to claim 1 or 2.

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

10. 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. The positive photosensitive resin composition according to claim 1 or 2.

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

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

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

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