TWI836710B - Positive photosensitive resin composition - Google Patents

Abstract

The present invention provides a positive photosensitive resin composition capable of forming thick film patterns with high precision. A positive photosensitive resin composition according to an embodiment includes a hydrophobic resin (A), an alkali-soluble resin (B), a quinonediazide compound (C), and a fluorine-based surfactant (D), The positive photosensitive resin composition is applied so that the prebaked film thickness becomes 3±0.3μm, and prebaked at 125°C for 120 seconds. After forming a film, it is exposed at a temperature of 30mJ/ ^cm2 . When developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23°C, the dissolution rate of the surface layer of the film is lower than the dissolution rate of the entire film. Here, the dissolution rate of the film surface layer refers to the average dissolution rate at the time until the film thickness of the film is dissolved to 80%, and the so-called dissolution rate of the entire film is the time until the film thickness of the film is dissolved to 30%. The average dissolution rate of a point.

Description

Positive photosensitive resin composition

The present invention relates to a positive photosensitive resin composition. More specifically, the present invention relates to a positive photosensitive resin composition containing a quinonediazide compound as a radiation-sensitive compound.

Positive photosensitive resin compositions are widely used as interlayer insulating films, planarizing films, or protective films for semiconductor devices, or as insulating films, planarizing films, or partition materials for display devices such as organic EL displays (OLED) and liquid crystal displays. use.

For example, in display devices such as organic EL displays, in order to improve display characteristics, partition materials are used at intervals between colored patterns in the display area or at edges around the display area. In the manufacture of organic EL display devices, since pixels of organic substances are not in contact with each other, partition walls are first formed, and pixels of organic substances are formed between the partition walls. Generally speaking, this partition wall is formed by photolithography using a photosensitive resin composition and has insulation properties. Specifically, a coating device is used to coat the photosensitive resin composition on the substrate, and the volatile components are removed by heating or other means, and then exposed through a mask. The unexposed part is removed with a developer such as an alkali aqueous solution. When it is a positive type, the exposed part is removed with a developer such as an alkali aqueous solution, developed, and the resulting pattern is heat-treated to form a partition (insulating film). Next, an organic substance that emits three colors of red, green, and blue light is deposited between the partition walls by an inkjet method or the like to form a pixel of the organic EL display device.

In this field, in recent years, the miniaturization of display devices and the diversification of displayed contents have required higher performance and higher definition of pixels. In order to improve the contrast and visibility of display devices, attempts have been made to use colorants to make partition materials shading.

Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-281440) describes a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits high light-shielding properties by heat treatment after exposure. Radioactive resin composition is a composition in which titanium black is added.

Patent Document 2 (Japanese Patent Application Publication No. 2002-116536) describes a radiation-sensitive resin composition containing [A] alkali-soluble resin, [B] 1,2-quinonediazide compound and [C] colorant, Use carbon black to blacken partition wall materials.

Patent document 3 (Japanese Patent Application Laid-Open No. 2010-237310) describes a composition in which a thermosensitive dye is added to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits light-shielding properties by heat treatment after exposure.

Patent document 4 (International Publication No. 2017/069172) describes a positive photosensitive resin composition containing (A) a binder resin, (B) a quinone diazide compound, and (C) at least one black dye selected from black dyes specified by the colorimetric index of Solvent Black 27 to 47.

On the other hand, as a method for improving the sensitivity of positive photosensitive resin compositions, it is widely known to use photosensitive resin compositions as chemically amplified systems. Generally speaking, chemically amplified photosensitive resin compositions include a resin in which an alkali-soluble functional group is protected by an acid-degradable group, and a photoacid generator. The acid generated from the photoacid generator during exposure promotes the decomposition (deprotection) of the acid-degradable group and regenerates the alkali-soluble functional group. In this way, the alkaline dissolution of the resin in the exposed part is promoted during development. The acid derived from the photoacid generator decomposes a certain acid-degradable group and then regenerates it, which is associated with the decomposition of other acid-degradable groups. According to the quantum efficiency of the above reaction mechanism applied only to the chemical amplification system, since it is expressed as the product of the quantum efficiency of the acid product and the reaction chain, high sensitivity can be achieved by setting the photosensitive resin composition as a chemical amplification system.

Patent Document 5 (International Publication No. 2015/087830) describes a polybenzoxazole precursor containing a specific repeating unit, a photoacid generator, a solvent, a cross-linking agent, and an acid group in the molecule to achieve acid decomposition. Photosensitive resin composition of a group-protected compound.

Patent Document 6 (International Publication No. 2020/246517) describes a positive photosensitive resin composition containing a plurality of phenolic hydroxyl groups, and at least part of the plurality of phenolic hydroxyl groups is protected with an acid-decomposable group. the first resin (A), the second resin (B) having an epoxy group and a phenolic hydroxyl group, and at least one colorant (C) selected from the group consisting of a black dye and a black pigment, and Photoacid generator (D). [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2001-281440 [Patent Document 2] Japanese Patent Application Publication No. 2002-116536 [Patent Document 3] Japanese Patent Application Publication No. 2010-237310 [Patent Document 4] International Publication No. 2017/069172 [Patent Document 5] International Publication No. 2015/087830 [Patent Document 6] International Publication No. 2020/246517

[Problem to be solved by the invention]

However, when the partition material has light-shielding properties, the photosensitive resin composition tends to have low sensitivity, resulting in a longer exposure time and a decrease in productivity. Therefore, the photosensitive resin composition used in the formation of the partition material containing a colorant is required to have a higher sensitivity.

In order to fully improve the light-shielding property of the cured film, it is necessary to use a considerable amount of colorant in the photosensitive resin composition used in the formation of the colored partition material. In this way, when a large amount of colorant is used, the radiation irradiated on the film of the photosensitive resin composition is absorbed by the colorant, which reduces the effective intensity of the radiation in the film, and the photosensitive resin composition cannot be fully exposed, resulting in reduced pattern formation. This point is significant when a black colorant is mixed into the photosensitive resin composition to form a thicker film, such as a film with a thickness of 2~3μm, in order to improve the image quality of the display device, make it flexible or save power.

A positive-type photosensitive resin composition of a chemical amplification system has a higher sensitivity than a positive-type photosensitive resin composition containing a quinonediazide compound as a radiation-sensitive compound, for example. However, the photoacid generator used in the chemical amplification system is expensive, and the positive photosensitive resin composition of the chemical amplification system is prone to uneven coating of the film. Post-exposure baking is used to promote the decomposition of the acid-decomposable group ( PEB, Post Exposure Bake) become necessary. In addition, in the chemical amplification system, the acid generated by the photoacid generator during exposure diffuses into the film during the PEB step, so the shape, size, sensitivity, etc. of the pattern may change due to the conditions of PEB. Therefore, it is difficult to form a step pattern with high precision on a thick film using a chemically amplified positive photosensitive resin composition.

An object of the present invention is to provide a positive photosensitive resin composition capable of forming thick film patterns with high precision. [Means used to solve problems]

The inventors found that by combining a hydrophobic resin, an alkali-soluble resin, and a fluorine-based surfactant as a resin component in a positive-type photosensitive resin composition containing a quinonediazide compound as a radiation-sensitive compound, the relative reduction in Due to the alkali solubility of the film surface, thick film patterns can be formed with high precision.

That is, the present invention includes the following aspects. [1] A positive photosensitive resin composition, which is a positive photosensitive resin composition comprising a hydrophobic resin (A), an alkali-soluble resin (B), a quinone diazide compound (C), and a fluorine-based surfactant (D), wherein the positive photosensitive resin composition is applied in a manner such that the film thickness after pre-baking becomes 3±0.3μm, and the positive photosensitive resin composition is pre-baked at 125°C for 120 seconds to form a film, and then the film is exposed to a 30mJ/cm ² , and when developed at 23°C with a 2.38 mass % tetramethylammonium hydroxide aqueous solution, the dissolution rate of the surface layer of the film is lower than the dissolution rate of the entire film, the so-called dissolution rate of the surface layer of the film is the average dissolution rate at the time when the film thickness of the film is dissolved to 80%, and the so-called dissolution rate of the entire film is the average dissolution rate at the time when the film thickness of the film is dissolved to 30%. [2] A positive photosensitive resin composition as described in [1], wherein the difference between the dissolution rate of the surface layer of the film and the dissolution rate of the entire film is 3 nm/sec or more. [3] A positive photosensitive resin composition as described in [1] or [2], wherein the hydrophobic resin (A) is a resin having at least one selected from the group consisting of a silicon-containing group and a fluorine-containing group. [4] A positive photosensitive resin composition as described in [3], wherein the hydrophobic resin (A) has a structural unit represented by formula (1), and has at least one structural unit represented by formula (1) wherein s is an integer greater than 1, (In formula (1), ^R1 is a hydrogen atom or ^an alkyl group having 1 to ⁵ carbon atoms, ^R2 is represented by ^SiR3R4R5 , ^R3 , ^R4 and ^R5 are independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, but r+s is an integer of 1 to 5). [5] A positive photosensitive resin composition as described in [4], wherein the hydrophobic resin (A) further comprises a structural unit represented by formula (2), (In formula (2), ^R6 and ^R7 are independently hydrogen or an alkyl group having 1 to 3 carbon atoms, and ^R8 is a phenyl group substituted by at least one selected from the group consisting of hydrogen, 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 hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms). [6] A positive photosensitive resin composition as described in any one of [1] to [5], wherein the fluorinated surfactant (D) comprises an acrylic copolymer having at least one fluorinated alkyl group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group. [7] The positive photosensitive resin composition as described in any one of [1] to [6], wherein the alkali-soluble resin (B) comprises a copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers, a resin having an epoxy group and a phenolic hydroxyl group, or a combination thereof. [8] The positive photosensitive resin composition as described in any one of [1] to [7], further comprising at least one colorant (E) selected from the group consisting of a black dye and a black pigment. [9] The positive photosensitive resin composition as described in [8], wherein the colorant (E) is contained in an amount of 10 to 150 parts by weight based on 100 parts by weight of the total resin components. [10] A positive photosensitive resin composition as described in [8] or [9], wherein the optical density (OD value) of the cured film of the positive photosensitive resin composition is greater than 0.5 per 1 μm of film thickness. [11] An organic EL element partition, which comprises a cured product of the positive photosensitive resin composition as described in any one of [1] to [10]. [12] An organic EL element insulating film, which comprises a cured product of the positive photosensitive resin composition as described in any one of [1] to [10]. [13] An organic EL element, which comprises a cured product of the positive photosensitive resin composition as described in any one of [1] to [10]. [Effect of the invention]

According to the present invention, a positive photosensitive resin composition can be provided which can form a thick film pattern with high precision.

The present invention is described in detail below.

In this disclosure, "alkali solubility" means that the positive photosensitive resin composition or its components or the film or cured film of the positive photosensitive resin composition can be dissolved in a 2.38 mass % tetramethylammonium hydroxide aqueous solution. The term "alkali-soluble resin" refers to a resin that is soluble in a 2.38 mass% tetramethylammonium hydroxide aqueous solution as a single substance or in a state containing a positive photosensitive resin composition before or after exposure. Although the positive-type photosensitive resin composition is not alkali-soluble at the time of non-exposure, resins whose alkali-solubility changes by exposure are also included in alkali-soluble resins. The "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 film or cured film of the positive photosensitive resin composition. Examples of the alkali-soluble functional group include phenolic hydroxyl group, carboxyl group, sulfonic acid group, phosphate group, acid anhydride group and mercapto group.

The term "acid-decomposable group" as used herein refers to a group that is decomposed (deprotected) in the presence of an acid and, if necessary, heated to generate an alkali-soluble functional group.

In this disclosure, the "radically polymerizable functional group" means an ethylenically unsaturated group, and the "radically polymerizable compound" means a compound having one or a plurality of ethylenically unsaturated groups.

The term "structural unit" as used herein refers to an atomic group that constitutes a part of the basic structure of a polymer, and this atomic group may have pendant atoms or pendant atomic groups. For example, in the case of a free radical (co)polymer, it refers to a unit derived from a free radical polymerizable compound used as a monomer, and in the case of a phenol novolac resin, it refers to the following unit formed by the condensation reaction of one molecule of phenol (C ₆ H ₅ OH) and one molecule of formaldehyde (HCHO). For structural units having pendant groups (side groups), pendant groups formed at the crosslinking site or structural units having a group derived therefrom, and structural units having free pendant groups not related to the formation of the crosslinking site are considered to be different from each other. In a branched polymer having a molecular chain (branched chain), the structural unit containing the branch point (branching unit) and the structural unit contained in the linear molecular chain are considered to be different from each other.

In the present disclosure, "(meth)acryl" means acryl or methacryl, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryl or methacryloyl.

In this disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin, polymer or copolymer refer to the standard polystyrene measured by gel permeation chromatography (GPC, gel permeation chromatography). Conversion value.

In the present disclosure, the phenolic hydroxyl equivalent is a theoretical value calculated from the molecular weight and composition ratio of the structural units constituting the resin. Specifically, the phenolic hydroxyl equivalent refers to the 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 monomer i (i=1~n) is 1.

When it is a resin having an epoxy group and a phenolic hydroxyl group described later, the phenolic hydroxyl group equivalent means a value calculated by the following formula. Phenolic hydroxyl equivalent = (Epoxy equivalent of raw material + molecular weight of added carboxylic acid)/(Number of phenolic hydroxyl groups of carboxylic acid)

The "resin component" in this disclosure refers to the hydrophobic resin (A) and the alkali-soluble resin (B). The component equivalent to the fluorine-based surfactant (D) is defined as that not included in the hydrophobic resin (A) and the alkali-soluble resin (B).

The term "solid component" as used herein refers to the total mass of the components including the resin component, the quinone diazide compound (C), the fluorine-based surfactant (D), and any other components such as the colorant (E), the dissolution promoter (F), etc., excluding the liquid solvent (G).

[Positive photosensitive resin composition] A positive photosensitive resin composition according to one embodiment includes a hydrophobic resin (A), an alkali-soluble resin (B), a quinonediazide compound (C), and a fluorine It is surfactant (D). The positive photosensitive resin composition is applied so that the prebaked film thickness becomes 3±0.3μm, and prebaked at 125°C for 120 seconds to form a film, and then exposed to 30mJ/ ^cm2 at a temperature of 23 When developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at ℃, the dissolution rate of the surface layer of the film is lower than the dissolution rate of the entire film. The dissolution rate of the surface layer of the film is the average dissolution rate at the time point when the film thickness is dissolved to 80%, and the dissolution rate of the entire film is the time point at which the film thickness is dissolved to 30%. the average dissolution rate.

＜Hydrophobic resin (A)＞ The hydrophobic resin (A) is a resin that promotes the localization to the film surface by the fluorine-based surfactant (D) and makes the film surface of the positive photosensitive resin composition insoluble in the alkali aqueous solution. Although not bound by any theory, during the film formation process of the positive photosensitive resin composition, the hydrophobic resin (A) easily moves toward the film surface along with the fluorine-based surfactant (D) that moves to the film surface. Therefore, after the film is formed, the hydrophobic resin (A) exists at a higher concentration through the film surface than inside the film, thereby reducing the alkali solubility of the film surface. During development, the hydrophobic resin (A), as a resin component with low alkali solubility, suppresses dissolution of the film surface in the unexposed portion, and is accompanied by the carboxylic acid compound derived from the quinonediazide compound (C) in the exposed portion. Other resin components with high alkali solubility and optional dissolution accelerators are dissolved and released from the film into the developer. In the exposed part, once the coating surface is dissolved, since the concentration of the hydrophobic resin (A) is relatively low, dissolution proceeds rapidly in the interior of the coating where alkali solubility is high compared to the coating surface. Thereby, the contrast between the exposed part and the unexposed part can be increased, and as a result, the pattern formability of the thick film of the positive photosensitive resin composition can be improved.

On the other hand, in the chemically amplified positive photosensitive resin composition, when a hydrophobic resin and a fluorine-based surfactant are used in combination to make the film surface insoluble in an alkaline aqueous solution, the acid generated from the photoacid generator during exposure diffuses into the film during the PEB step, so the acid concentration near the film surface and inside the film is more uniform compared to the case where a quinone diazide compound (C) is used as a radiation-sensitive compound. Therefore, it is believed that the film surface of the exposed part is difficult to dissolve during development, reducing sensitivity. In addition, the photoacid generator may have low thermal stability. When such a photoacid generator is used, the dissolution of the unexposed part may be promoted, thereby reducing the pattern formation.

Although the hydrophobic resin (A) is not particularly limited, examples thereof include acrylic resin, polystyrene resin, epoxy resin, polyamide resin, phenol resin, polyimide resin, polyamide resin, and polyphenylene resin. Oxazole resin, polybenzoxazole resin precursor, polysiloxane resin, cyclic olefin polymer, Cardo resin and derivatives of these resins. The derivatives of these resins preferably have hydrophobic groups. Examples of the hydrophobic group include a silicon-containing group and a fluorine-containing group. As the hydrophobic resin (A), a single polymer or a copolymer of a polymerizable monomer having an alkali-soluble functional group may be used as the base resin, or a part or all of the alkali-soluble functional group may be converted into the above-mentioned group having the hydrophobic group. of resin. The hydrophobic resin (A) can be used alone or in combination of two or more types.

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

Examples of the silicon-containing group include a silanyl group substituted with an aliphatic hydrocarbon group or an aryl group, a group having a cyclic siloxane structure, and a group having a sesquisiloxane structure.

The silyl group substituted by an aliphatic alkyl group or an aryl group is a 1-substituted group, a 2-substituted group or a 3-substituted group. The substituents of the silyl group substituted by an aliphatic alkyl group or an aryl group may be the same or different from each other. The silyl group substituted by an aliphatic alkyl group or an aryl group is preferably a 3-substituted group. The silyl group substituted by an aliphatic alkyl group or an aryl group may further have a substituent other than an alkyl group or an aryl group, for example, a siloxy group substituted by an aliphatic alkyl group or an aryl group.

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

Part or all of the hydrogen atoms on the silicon atoms of the group having a sesquisiloxane structure may be independently substituted with an aliphatic hydrocarbon group or an aryl group.

Aliphatic hydrocarbon group of a silyl group substituted by an aliphatic hydrocarbon group or an aryl group, aliphatic hydrocarbon group as a substituent of a group having a cyclic siloxane structure, aliphatic hydrocarbon group as a substituent of a group having a sesquioxane structure The hydrocarbon group, and the aliphatic hydrocarbon group as a substituent of the silyloxy group substituted by an aliphatic hydrocarbon group or an aryl group, is preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms, more preferably an aliphatic group with 1 to 8 carbon atoms. hydrocarbyl. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Saturated hydrocarbon groups; unsaturated hydrocarbon groups such as vinyl, propenyl, butenyl, ethynyl, propynyl, etc.; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl saturated monocyclic hydrocarbon groups such as cyclopropenyl, cyclododecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclodecenyl, etc.; Saturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, adamantyl, etc.; and bicyclo[2.2.1]heptenyl, bicyclo[2.2.2] ] Octenyl and other unsaturated polycyclic hydrocarbon groups.

The aryl group of the silyl group substituted with an aliphatic alkyl group or an aryl group, the aryl group as a substituent of the group having a cyclosiloxane structure, the aryl group as a substituent of the group having a silsesquioxane structure, and the aryl group as a substituent of the siloxy group substituted with an aliphatic alkyl group or an aryl group are preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 14 carbon atoms. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, fluorenyl, anthracenyl, and phenanthrenyl.

As the silyl group substituted with an aliphatic alkyl group or an aryl group, for example, there can be mentioned a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group and a trimethylsiloxydimethylsilyl group.

Examples of the group having a cyclic siloxane structure include pentamethylcyclotrisiloxy, heptamethylcyclotetrasiloxy, and nonamethylcyclopentasiloxy.

Examples of the group having a sesquisiloxane structure include sesquisiloxane group, heptamethylsesesquisiloxane group, heptaethylsesquisiloxane group, and hepta(n-propyl)sesesquioxane group. Siloxane group and hepta(n-butyl)sesquioxane group.

As the fluorine-containing group, for example, a fluorine-substituted alkyl group, a fluorine-substituted aryl group and a fluoroacryl group can be mentioned.

The fluorine-substituted alkyl group may be a perfluoroalkyl group or a partially fluorinated alkyl group. The substituents of the fluorine-substituted alkyl group may be the same or different from each other. The fluorine-substituted alkyl group may further have substituents other than fluorine atoms, such as hydroxyl groups.

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

Examples of the fluorine-substituted alkyl group having a hydroxyl group as a substituent include -CH(CF ₃ )OH, -C(CF ₃ ) ₂ OH, -C(CF ₃ )(CH ₃ )OH and -C(C ₂ F ₅ ) ₂ OH, and -C(CF ₃ ) ₂ OH is preferred.

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

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

The hydrophobic resin (A) can be produced by, for example, radical polymerization of a polymerizable monomer having a hydrophobic group, or radical copolymerization of a polymerizable monomer having a hydrophobic group and other polymerizable monomers. Examples of the polymerizable functional group possessed by the polymerizable monomer having a hydrophobic group and other polymerizable monomers include CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CHCO-, CH ₂ =C(CH ₃ )CO-, -OC-CH=CH-CO-, etc. are radically polymerizable functional groups. The hydrophobic resin (A) can also be converted into a group containing a hydrophobic group by reacting a resin having functional groups such as hydroxyl group, carboxyl group, amine group, epoxy group, etc. with a compound having a hydrophobic group. to manufacture.

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

Examples of the polymerizable monomer having a silyl group include trimethylvinylsilane, trimethylallylsilane, trimethyl(3-butenyl)silane, tert-butyldimethylvinylsilane, (trimethylsiloxy)dimethylvinylsilane, (trimethylsiloxy)dimethylallylsilane, triethylvinylsilane, triethylallylsilane, triethyl(3-butenyl)silane, (trimethylsilyl)methyl(meth)acrylate, 2-(trimethylsilyl)ethyl(meth)acrylate, 3-(trimethylsilyl)propyl(meth)acrylate, t-butyldimethylsilyl(meth)acrylate, triisopropylsilylmethyl(meth)acrylate, and the like. ester, bis(trimethylsilylmethyl)methyl(meth)acrylate, 4-(trimethylsilyl)cyclohexyl(meth)acrylate, 3-[(trimethylsilyloxy)dimethylsilyl]propyl(meth)acrylate, 3-[tris(trimethylsilyloxy)silyl]propyl(meth)acrylate, 4-trimethylsiloxyphenyl(meth)acrylate, 4-triethylsiloxyphenyl(meth)acrylate, 4-triisopropylsiloxyphenyl(meth)acrylate, 4-tert-butyldimethylsiloxyphenyl(meth)acrylate, vinylheptamethylcyclotetrasiloxane, and 3-(heptamethylsilsesquioxy)propyl(meth)acrylate.

Examples of the polymerizable monomer having a fluorine-containing group include 2-perfluorohexylethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoropropyl) (meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate, 3,3,4,4,5,5,6,6,6-nonafluorohexyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoro-2-methylpropyl) (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoro-2-phenylpropyl) (meth)acrylate, pentafluorophenyl (meth)acrylate, 3,5-bis(trifluoromethyl)phenyl(meth)acrylate, perfluorocyclohexyl(meth)acrylate, 2,2,2-trifluoroethyl vinyl ether, 2-(1,1,1,3,3,3-hexafluoropropyl)vinyl ether, 2,3,4,5,6-pentafluorostyrene, isopropyl 2-fluoroacrylate, tert-butyl 2-fluoroacrylate, cyclohexyl 2-fluoroacrylate, 4-tert-butylcyclohexyl 2-fluoroacrylate, isopropyl 2-(trifluoromethyl)acrylate, tert-butyl 2-(trifluoromethyl)acrylate, cyclohexyl 2-(trifluoromethyl)acrylate, and 4-tert-butylcyclohexyl 2-(trifluoromethyl)acrylate.

Examples of other polymerizable monomers include styrene; styrene derivatives such as α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, (Meth)acrylates such as butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc.; N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide.

Other polymerizable monomers may also be polymerizable monomers having alkali-soluble functional groups. Examples of the polymerizable monomer having an alkali-soluble functional group include maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; (meth)acrylic acid, (Meth)acrylic acid derivatives such as α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, β-styryl(meth)acrylic acid, etc.; Malay Acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propynoic acid, 3-maleimide propionic acid, 4-maleimide butyric acid, 6-maleimide Unsaturated carboxylic acid compounds such as leximide hexanoic acid; 4-hydroxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, Polymerizable monomers with phenolic hydroxyl groups such as 4-hydroxyphenylacrylamide and 4-hydroxyphenylmaleimide; (meth)allylsulfonic acid and 2-(meth)acrylamide -Polymerizable monomers with sulfonic acid groups such as 2-methylpropanesulfonic acid and styrenesulfonic acid; polymerizable monomers with phosphate groups such as phosphate mono(2-(meth)acryloxyethyl) monomers; and polymerizable monomers with acid anhydride groups such as itaconic anhydride, citraconic anhydride, and maleic anhydride.

The polymerizable monomer having a hydrophobic group is preferably one that forms a structural unit in which s is an integer of 1 or more among the structural units represented by the formula (1) after polymerization. (In formula (1), R ¹ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. R ² is represented by SiR ³ R ⁴ R ^5. R ³ , R ⁴ and R ⁵ are each independently a carbon atom of 1. ~8 alkyl group or aryl group with 6 to 20 carbon atoms, r is an integer from 0 to 5, s is an integer from 0 to 5, but r+s is an integer from 1 to 5). R ¹ is preferably a hydrogen atom or a methyl group. R ³ , R ⁴ and R ⁵ are preferably each independently methyl, ethyl, isopropyl, tert-butyl or phenyl. r is preferably an integer from 0 to 3, more preferably 0. s is preferably an integer from 1 to 3, more preferably 1. As such a polymerizable monomer having a hydrophobic group, 4-triethylsilyloxyphenyl methacrylate and 4-tert-butyldimethylsilyloxyphenyl methacrylate are particularly preferred. ester.

As other polymerizable monomers, preferably, those which form the structural unit represented by formula (2) after polymerization, (In formula (2), ^R6 and ^R7 are independently hydrogen atom or alkyl group having 1 to 3 carbon atoms, and ^R8 is phenyl group substituted by at least one selected from the group consisting of hydrogen atom, linear alkyl group having 1 to 6 carbon atoms, cyclic alkyl group having 3 to 12 carbon atoms, phenyl or hydroxyl group, alkyl group having 1 to 6 carbon atoms, and alkoxy group having 1 to 6 carbon atoms). ^R6 and ^R7 are preferably independently hydrogen atom or alkyl group having 1 to 3 carbon atoms, and more preferably hydrogen atom. ^R8 is preferably phenyl group substituted by at least one selected from the group consisting of cyclic alkyl group having 3 to 12 carbon atoms, phenyl or hydroxyl group, alkyl group having 1 to 6 carbon atoms, and alkoxy group having 1 to 6 carbon atoms, and more preferably cyclic alkyl group having 3 to 12 carbon atoms or phenyl group. Particularly preferred examples of such other polymerizable monomers are phenylmaleimide and N-cyclohexylmaleimide.

As other polymerizable monomers having alkali-soluble functional groups, those that form the structural unit represented by formula (3) after polymerization are preferred. (In formula (3), R ⁹ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and a is an integer from 1 to 5). R ⁹ is preferably a hydrogen atom or a methyl group. a is preferably an integer from 1 to 3, more preferably 1. As such other polymerizable monomer having an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is particularly preferred.

In one embodiment, the hydrophobic resin (A) has a structural unit represented by formula (1), and has at least one structural unit represented by formula (1) in which s is an integer greater than 1. (In formula (1), ^R1 is a hydrogen atom or ^an alkyl group having 1 to ⁵ carbon atoms, ^R2 is represented by ^SiR3R4R5 , ^R3 , ^R4 and ^R5 are independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, and r+s is an integer of 1 to 5).

In this embodiment, the hydrophobic resin (A) preferably further has a structural unit represented by formula (2). (In formula (2), R ⁶ and R ⁷ are independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, and R ⁸ is selected from a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, or At least one substituted phenyl group from the group consisting of a cyclic alkyl group with 3 to 12 atoms, phenyl or hydroxyl group, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. ).

In this embodiment, the hydrophobic resin (A) preferably further has a structural unit represented by formula (3). (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).

In the hydrophobic resin (A), the molar ratio between the structural unit represented by the formula (1) and the structural unit represented by the formula (2) and the structural unit represented by the formula (3) in which s is an integer of 1 or more is preferably expressed by the formula ( 1): Formula (2): Formula (3)=5~60: 3~10: 20~90, preferably formula (1): Formula (2): Formula (3)=6~50: 4~9 :30~85.

Particularly preferably, 4-triethylsilyloxyphenyl methacrylate or 4-tert-butyldimethylsiloxyphenyl methacrylate is used as the polymerizable monomer having a hydrophobic group, and benzene is used. N-cyclohexyl maleimide or N-cyclohexyl maleimide, and 4-hydroxyphenyl methacrylate as other polymerizable monomers. By using free radical polymerization of these polymerizable monomer resins, the sensitivity and pattern formation properties of the positive photosensitive resin composition can be improved, and outgassing can also be reduced.

As the polymerization initiator when producing the hydrophobic resin (A) by radical polymerization, it is not limited to the following, but 2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile, Azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2 , 2'-azobis(2,4-dimethylvaleronitrile) (AVN) and other azo polymerization initiators; dicumyl peroxide, 2,5-dimethyl-2,5 -Di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxide Peroxide polymerization initiators with a 10-hour half-life temperature of 100~170°C such as hydrogen and cumene hydroperoxide; or benzoyl peroxide, lauryl peroxide, 1,1'-bis(tert-butyl peroxide) Peroxide polymerization initiator such as cyclohexane, tert-butylperoxypivalate, etc. The usage amount of the polymerization initiator 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, 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass relative to 100 parts by mass in total of the polymerizable monomers. portion or less.

A RAFT (Reversible Addition Fragmentation Transfer) agent may be used together with a polymerization initiator. As the RAFT agent, although not limited to the following, thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, and xanthates may be used. The RAFT agent may be used in an amount of 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the total polymerizable monomer.

When the hydrophobic resin (A) has a silicon-containing group, the content of silicon atoms is based on the mass of the hydrophobic resin (A). It is preferably 1 mass% to 10 mass%, and more preferably 3 mass% to 8 mass%. %. The hydrophobic resin (A) having a silicon-containing group contains the silicon-containing resin in an amount of preferably 3 mol% to 60 mol%, more preferably 5 mol% to 50 mol%, based on the total structural unit of the hydrophobic resin (A). The basic structural unit.

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

The hydrophobic resin (A) may or may not have an alkali-soluble functional group. Based on the total structural unit of the hydrophobic resin (A), the hydrophobic resin (A) is preferably 20 mol% to 90 mol%, more preferably 30 mol% to 85 mol%, and still more preferably 40 mol% to 80 mol%. Amounts include structural units having base-soluble functional groups. In one embodiment, the hydrophobic resin (A) does not have alkali-soluble functional groups.

The weight average molecular weight (Mw) of the hydrophobic resin (A) is preferably 3000-80000, more preferably 4000-70000, and even more preferably 5000-60000. The number average molecular weight (Mn) of the hydrophobic resin (A) is preferably 1000-30000, more preferably 1500-25000, and even more preferably 2000-20000. The polydispersity (Mw/Mn) of the hydrophobic resin (A) is preferably 1.0-3.5, more preferably 1.1-3.0, and even more preferably 1.2-2.8. By setting the weight average molecular weight, number average molecular weight, and polydispersity within the above ranges, a positive photosensitive resin composition having excellent sensitivity and pattern formation properties can be obtained.

In one embodiment, the positive photosensitive resin composition comprises 3% to 50% by weight of the hydrophobic resin (A) based on 100% by weight of the solid component, preferably 4% to 40% by weight, and more preferably 5% to 30% by weight. If the content of the hydrophobic resin (A) is 3% by weight or more based on 100% by weight of the solid component, the hydrophobic resin (A) is localized on the film surface by the fluorine-based surfactant (D), and the hydrophobic resin (A) is concentrated on the film surface, and the film surface is difficult to dissolve in an alkaline aqueous solution, so that high sensitivity can be achieved. The content of the hydrophobic resin (A) is based on 100% by mass of the solid component. If it is 50% by mass or less, the dissolution of the carboxylic acid compound derived from the quinonediazide compound in the exposed area, other resin components with high alkali solubility, and the film surface accompanied by the dissolution of any dissolution accelerator proceeds rapidly, thereby achieving high sensitivity.

The positive photosensitive resin composition preferably contains 5% to 60% by weight of the hydrophobic resin (A) based on the total weight of the resin components, more preferably 10% to 50% by weight, and even more preferably 15% to 40% by weight. If the content of the hydrophobic resin (A) is 5% by weight or more based on the total weight of the resin components, the fluorine-based surfactant (D) promotes the localization of the hydrophobic resin (A) on the film surface, making the hydrophobic resin (A) at a high concentration on the film surface, and the film surface is difficult to dissolve in an alkaline aqueous solution, thereby achieving high sensitivity. When the content of the hydrophobic resin (A) is 60% by mass or less based on the total mass of the resin components, the dissolution of the carboxylic acid compound derived from the quinonediazide compound in the exposed area, other resin components with high alkali solubility, and the film surface accompanied by the dissolution of any dissolution accelerator proceeds rapidly, thereby achieving high sensitivity.

<Alkali-soluble resin (B)> Alkali-soluble resin (B) is not particularly limited, but preferably a resin having an alkali-soluble functional group. Examples of the alkali-soluble functional group include phenolic hydroxyl group, carboxyl group, sulfonic acid group, phosphoric acid group, acid anhydride group and hydroxyl group. Two or more types of alkali-soluble resins (B) having alkali-soluble functional groups can be used. The alkali-soluble resin (B) may have an alkali-soluble functional group protected by an acid-decomposable group.

Examples of the alkali-soluble resin (B) include single polymers or copolymers of polymerizable monomers having an alkali-soluble functional group, and resins having an epoxy group and a phenolic hydroxyl group. Examples of other alkali-soluble resins (B) include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, polyamide resins, polybenzoxazole resins, polybenzoxazole resin precursors, polysilicone resins, cycloolefin polymers, cardo resins, and derivatives of these resins having an alkali-soluble functional group. For example, examples of phenol resin derivatives include polyalkenylphenol resins in which an alkenyl group is bonded to a benzene ring, and examples of polystyrene resin derivatives include hydroxylpolystyrene resin derivatives in which a phenolic hydroxyl group is bonded to a hydroxyalkyl or alkoxy group on a benzene ring. The alkali-soluble resin (B) may be used alone or in combination of two or more.

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

In one embodiment, the positive photosensitive resin composition contains 5% to 80% by mass of alkali-soluble resin (B), preferably 10% to 75% by mass, based on 100% by mass of solid content. More preferably, it contains 15 mass % to 70 mass %. The content of alkali-soluble resin (B) is based on 100% by mass of solid content. If it is 5% by mass or more, the dissolution of the exposed part can be accelerated, high sensitivity can be achieved, and the stability and durability of the film after thermosetting can be ensured. . When the content of the alkali-soluble resin (B) is 80 mass% or less based on 100 mass% of the solid content, the solubility of the unexposed parts can be suppressed to a low level and the residual film rate can be maintained at a high level.

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

In one embodiment, the alkali-soluble resin (B) includes a copolymer of a polymerizable monomer with an alkali-soluble functional group and other polymerizable monomers, a resin with an epoxy group and a phenolic hydroxyl group, or a combination thereof.

"Copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers" As a copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers (hereinafter, also referred to simply as "having Examples of the alkali-soluble functional groups possessed by the "copolymer of alkali-soluble functional groups" include phenolic hydroxyl groups, carboxyl groups, sulfonic acid groups, phosphate groups, acid anhydride groups and mercapto groups. The copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers may have two or more types of alkali-soluble functional groups. Examples of the polymerizable monomer having an alkali-soluble functional group and the polymerizable functional group possessed by other polymerizable monomers include CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CHCO-, CH ₂ =C(CH ₃ )CO-, -OC-CH=CH-CO-, etc. are radically polymerizable functional groups.

From the viewpoint of heat resistance, it is preferable that the copolymer having an alkali-soluble functional group has a group selected from the group consisting of an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure. One or more ring structures in the group.

The copolymer having an alkali-soluble functional group can be prepared, for example, by free radical polymerization of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers. After the copolymer is synthesized by free radical polymerization, the alkali-soluble functional group can be added to the copolymer.

Examples of polymerizable monomers having alkali-soluble functional groups include maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; and unsaturated carboxylic acids such as maleic acid, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid. compounds; polymerizable monomers having a phenolic hydroxyl group such as 4-hydroxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl acrylamide, 4-hydroxyphenylmaleimide, etc.; polymerizable monomers having a sulfonic acid group such as (meth)allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropane sulfonic acid, styrene sulfonic acid, etc.; polymerizable monomers having a phosphate group such as mono(2-(meth)acryloxyethyl) phosphate, etc.; and polymerizable monomers having an anhydride group such as itaconic anhydride, conic anhydride, maleic anhydride, etc.

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.

Examples of other polymerizable monomers include styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, (Meth)acrylates such as ert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc.; N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide.

As the polymerizable monomer having an alkali-soluble functional group, one which forms a structural unit represented by formula (3) after polymerization is preferred. (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). 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 a polymerizable monomer having an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is particularly preferred.

As other polymerizable monomers, those which form the structural unit represented by formula (2) after polymerization are preferable. (In formula (2), R ⁶ and R ⁷ are independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, and R ⁸ is selected from a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, or At least one substituted phenyl group from the group consisting of a cyclic alkyl group with 3 to 12 atoms, phenyl or hydroxyl group, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. ). R ⁶ and R ⁷ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom. R ⁸ is preferably selected from the group consisting of a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group or a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. At least one substituted phenyl group is preferably a cyclic alkyl group or phenyl group having 3 to 12 carbon atoms. As such other polymerizable monomers, phenylmaleimide and N-cyclohexylmaleimide are particularly preferred.

In one embodiment, the copolymer with alkali-soluble functional groups has a structural unit represented by formula (2) and a structural unit represented by formula (3). (In formula (3), R ⁹ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and a is an integer from 1 to 5). (In formula (2), R ⁶ and R ⁷ are independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, and R ⁸ is selected from a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, or At least one substituted phenyl group from the group consisting of a cyclic alkyl group with 3 to 12 atoms, phenyl or hydroxyl group, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. ).

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

Particularly preferably, as the polymerizable monomer having an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is used, and as the other polymerizable monomer, phenylmaleimide or N-cyclohexylmale is used. acyl imine. By using a resin that radically polymerizes these polymerizable monomers, the shape maintenance and developability of the film of the positive photosensitive resin composition can be improved, and outgassing can also be reduced.

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

The weight average molecular weight (Mw) of the copolymer having alkali-soluble functional groups is preferably 3,000 to 80,000, more preferably 4,000 to 70,000, and still more preferably 5,000 to 60,000. The number average molecular weight (Mn) of the copolymer having alkali-soluble functional groups is preferably 1,000 to 30,000, more preferably 1,500 to 25,000, and still more preferably 2,000 to 20,000. The polydispersity (Mw/Mn) of the copolymer having alkali-soluble functional groups is preferably 1.0~3.5, more preferably 1.1~3.0, still more preferably 1.2~2.8. 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 excellent in coatability, pattern formation, and alkali developability can be obtained things.

When the alkali-soluble functional group of the copolymer having an alkali-soluble functional group is a phenolic hydroxyl group, the phenolic hydroxyl 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 equivalent of the copolymer having an alkali-soluble functional group is 60 or more, the film thickness of the unexposed portion can be sufficiently maintained during alkali development. When the phenolic hydroxyl equivalent of the copolymer having an alkali-soluble functional group is 400 or less, the desired alkali solubility can be obtained.

In the present disclosure, when the copolymer having an alkali-soluble functional group is also equivalent to the resin having an epoxy group and a phenolic hydroxyl group described later, it is defined as being operated as a copolymer having an alkali-soluble functional group. That is, the resin having an epoxy group and a phenolic hydroxyl group does not include a copolymer equivalent to the copolymer having an alkali-soluble functional group.

《Resins having epoxy groups and phenolic hydroxyl groups》 Resins having epoxy groups and phenolic hydroxyl groups are soluble in alkaline aqueous solutions. Resins having epoxy groups and phenolic hydroxyl groups may have alkali-soluble functional groups other than phenolic hydroxyl groups. Resins having epoxy groups and phenolic hydroxyl groups can be obtained by reacting a part of the epoxy groups of a compound having at least two epoxy groups in one molecule (hereinafter referred to as "epoxy compound") with the carboxyl group of a hydroxybenzoic acid compound. The epoxy group of the resin having epoxy and phenolic hydroxyl groups forms crosslinks by reacting with phenolic hydroxyl groups during the heat treatment (post-baking) after development, thereby improving the chemical resistance and heat resistance of the film. Since phenolic hydroxyl groups contribute to the solubility in alkaline aqueous solutions during development, resins having epoxy and phenolic hydroxyl groups are also used as dissolution promoters for other resins when exposed at low exposure, thereby making the photosensitive resin composition highly sensitive.

An example of the reaction in which one of the epoxy groups of the epoxy compound reacts with the carboxyl group of the hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group is shown in the following reaction formula 1.

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, epoxy resins containing a naphthalene skeleton, alicyclic epoxy resins, and heterocyclic epoxy resins. Such epoxy compounds may have two or more epoxy groups in one molecule, and may be used alone or in combination of two or more types. Since such compounds are thermosetting, it is common knowledge for those skilled in the art to which the present invention belongs that the structure cannot be described without differences based on the presence or absence of epoxy groups, the type of functional group, the degree of polymerization, etc.

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

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

The compound having at least two epoxy groups in one molecule is preferably a novolac epoxy resin, more preferably at least one selected from the group consisting of a phenol novolac epoxy resin and a cresol novolac epoxy resin, and even more preferably a cresol novolac epoxy resin. The novolac epoxy resin, especially the positive photosensitive resin composition containing a resin having an epoxy group and a phenolic hydroxyl group derived from a cresol novolac epoxy resin, has excellent pattern forming properties, is easy to adjust the alkali solubility, and has little outgassing.

Hydroxybenzoic acid compounds are compounds in which at least one of the 2 to 6 positions of benzoic acid is substituted by a hydroxyl group. Examples include salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, and 2,4-dihydroxybenzoic acid. Formic 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 are preferably dihydroxybenzoic acid compounds from the viewpoint of improving alkali developability. The hydroxybenzoic acid compound can be used alone or in combination of two or more types.

In one embodiment, the resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and has a structure of formula (5). (In formula (5), b is an integer of 1 to 5, and * represents a bond with a compound having at least two epoxy groups in one molecule excluding the residual epoxy group applied to the reaction).

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 It is better to use 0.3~0.9 equivalents, more preferably 0.4~0.8 equivalents. If the amount of the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and if the amount is 0.95 equivalent or less, the increase in molecular weight due to side reactions can be suppressed.

In order to promote the reaction between the epoxy compound and the hydroxybenzoic acid compound, a catalyst can be used. The usage amount of the catalyst is based on 100 parts by mass of the reaction raw material mixture composed of the epoxy compound and the hydroxybenzoic acid compound, and can be set at 0.1 to 10 parts by mass. The reaction temperature can be set at 60~150°C, and the reaction time can be set at 3~30 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triethylammonium iodide. Phenylphosphine, chromium octoate and zirconium octoate.

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 weight average molecular weight (Mw) of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 30000, more preferably 2000 to 25000, and even more preferably 3000 to 20000. When the number average molecular weight is 500 or more or the weight average molecular weight is 500 or more, the resolution of the pattern is good because the alkali development speed is appropriate and the difference in dissolution speed between the exposed part and the unexposed part is sufficient. When the number average molecular weight is 8000 or less or the weight average molecular weight is 30000 or less, the coating property and alkali development property are good.

In one embodiment, the epoxy equivalent of the resin having epoxy and phenolic hydroxyl groups is 300 to 7000, preferably 400 to 6000, and more preferably 500 to 5000. If the epoxy equivalent of the resin having epoxy and phenolic hydroxyl groups is 300 or more, sufficient alkaline solubility can be imparted to the resin having epoxy and phenolic hydroxyl groups. If the epoxy equivalent of the resin having epoxy and phenolic hydroxyl groups is 7000 or less, the strength and heat resistance of the cured film can be improved. The epoxy equivalent is determined by JIS K 7236:2009.

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

"Protective Resin" The alkali-soluble resin (B) may include a resin having an alkali-soluble functional group protected by an acid-decomposable group (hereinafter, also simply referred to as "protected resin"). The protective resin is not particularly limited as long as it has a plurality of alkali-soluble functional groups and at least part of the plurality of alkali-soluble functional groups is protected with an acid-decomposable group. As the protective resin, for example, the above-mentioned alkali-soluble resin having a plurality of alkali-soluble functional groups is used as the base resin, and at least part of the alkali-soluble functional groups is protected by an acid-decomposable group. Examples of the alkali-soluble functional group include phenolic hydroxyl group, carboxyl group, sulfonic acid group, phosphate group, acid anhydride group and mercapto group. The alkali-soluble functional group is preferably a phenolic hydroxyl group or a carboxyl group, more preferably a phenolic hydroxyl group. By protecting part of the alkali-soluble functional group with an acid-decomposable group, the alkali solubility of the protective resin before exposure is suppressed. The protective resin may have an alkali-soluble functional group other than the alkali-soluble functional group protected with an acid-decomposable group. By performing post-exposure bake (PEB, post exposure bake) if necessary in the presence of acid generated during exposure, the decomposition (deprotection) of the acid-decomposable group is promoted and the alkali-soluble functional group is regenerated. This promotes alkali dissolution of the protective resin in the exposed portion during development. The protective resin can be used alone or in combination of two or more types. For example, the protective resin may be a combination of two or more types of resins with different protection ratios of structural units of polymers or copolymers, acid-decomposable groups, alkali-soluble functional groups, or combinations thereof.

(Protection of Alkali-Soluble Functional Groups by Acid-Decomposable Groups) A protective resin can be obtained by protecting a portion of the alkali-soluble functional groups of a base resin having a plurality of alkali-soluble functional groups with acid-decomposable groups. For example, when the alkali-soluble functional group is a phenolic hydroxyl group, the protective resin having a phenolic hydroxyl group protected by an acid-decomposable group has a partial structure of Ar-OR ¹¹ , wherein Ar represents an aromatic ring derived from phenol, and R ¹¹ represents an acid-decomposable group.

The acid-decomposable group is a group that is decomposed (deprotected) in the presence of an acid and heated as necessary to generate an alkali-soluble functional group. Specifically, for example, groups having a tertiary alkyl group such as tert-butyl, 1,1-dimethyl-propyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methyladamantyl, 1-ethyladamantyl, tert-butoxycarbonyl, 1,1-dimethyl-propyloxycarbonyl, and the like; and the group represented by formula (6) are listed. (In formula (6), ^R12 and ^R13 are independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and ^R14 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. One of ^R12 or ^R13 may be bonded to ^R14 to form a ring structure having 3 to 10 ring members, and ^R12 , ^R13 and ^R14 may be substituted by a halogen atom selected from the group consisting of chlorine, bromine and iodine). When the alkali-soluble functional group represented by formula (6) is a phenolic hydroxyl group, it forms an acetal structure or a 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.

Since a photosensitive resin composition with high sensitivity can be obtained even at a low exposure, the acid-decomposable group is preferably a group represented by formula (6). More preferably, ^R12 and ^R13 are independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and ^R14 is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine. Examples of such an acid-decomposable group include 1-alkoxyalkyl groups. Examples of the 1-alkoxyalkyl group include methoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-cyclohexyloxyethyl and 1-(2-cyclohexylethoxy)ethyl, with 1-ethoxyethyl and 1-n-propoxyethyl being preferred. As the acid-decomposable group, a group represented by formula (6) can be suitably used, wherein one of R ¹² or R ¹³ is bonded to R ¹⁴ to form a ring structure having 3 to 10 ring members. In this case, R ¹² or R ¹³ not involved in the formation of the ring structure is preferably a hydrogen atom. Examples of such an acid-decomposable group include 2-tetrahydrofuranyl and 2-tetrahydropyranyl, and 2-tetrahydrofuranyl is preferred.

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

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

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 salt of p-toluenesulfonic acid can also be used as the acid supply source. Examples of the base include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate, metal hydrides such as sodium hydride, and pyridine and N. Amine compounds such as N-dimethyl-4-aminopyridine, imidazole, triethylamine, diisopropylethylamine, etc.

In other embodiments, the alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group is protected by an acid-decomposable group, and then the polymerization or copolymerization of the alkali-soluble functional group protected by the acid-decomposable group is performed. Protective resin can also be obtained by using other polymerizable monomers and, if necessary, other polymerizable monomers. The alkali-soluble functional group of the polymerizable monomer having an alkali-soluble functional group can be protected by the same method as the alkali-soluble functional group of the base resin.

The protective resin preferably has a structural unit represented by formula (7), and has at least one structural unit represented by formula (7) in which q is an integer greater than 1. (In formula (7), ^R15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ^R16 is an acid-decomposable group, p is an integer of 0 to 5, q is an integer of 0 to 5, and p+q is an integer of 1 to 5.) The acid-decomposable group of ^R16 is preferably a group represented by formula (6). (In formula (6), R ¹² , R ¹³ and R ¹⁴ are as described above.) In formula (6), it is more preferred that R ¹² and R ¹³ are independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R ¹⁴ is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms substituted with a halogen atom selected from the group consisting of chlorine, bromine and iodine. Examples of such an acid-decomposable group include 1-alkoxyalkyl groups. Examples of the 1-alkoxyalkyl group include methoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-cyclohexyloxyethyl and 1-(2-cyclohexylethoxy)ethyl, preferably 1-ethoxyethyl and 1-n-propoxyethyl. Examples of the acid-decomposable group that bonds one of R ¹² or R ¹³ to R ¹⁴ to form a ring structure having 3 to 10 ring members include 2-tetrahydrofuranyl and 2-tetrahydropyranyl, preferably 2-tetrahydrofuranyl.

The protective resin preferably has a structural unit represented by formula (2). (In formula (2), ^R6 and ^R7 are independently hydrogen atom or alkyl group having 1 to 3 carbon atoms, and ^R8 is phenyl group substituted by at least one selected from the group consisting of hydrogen atom, linear alkyl group having 1 to 6 carbon atoms, cyclic alkyl group having 3 to 12 carbon atoms, phenyl or hydroxyl group, alkyl group having 1 to 6 carbon atoms, and alkoxy group having 1 to 6 carbon atoms). ^R6 and ^R7 are preferably independently hydrogen atom or alkyl group having 1 to 3 carbon atoms, and more preferably hydrogen atom. ^R8 is preferably phenyl group substituted by at least one selected from the group consisting of cyclic alkyl group having 3 to 12 carbon atoms, phenyl or hydroxyl group, alkyl group having 1 to 6 carbon atoms, and alkoxy group having 1 to 6 carbon atoms, and more preferably cyclic alkyl group having 3 to 12 carbon atoms or phenyl group.

In one embodiment, the structural unit represented by formula (7), and q is an integer above 1, that is, 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 The number of total structural units of the protective resin is 5% to 95%, preferably 15% to 90%, and more preferably 25% to 85%. By setting the proportion of the above-mentioned structural units to 5% or more, the dissolution of the exposed part is promoted, and the solubility of the unexposed part and the exposed part can be differentiated. Therefore, high sensitivity can be achieved and the stability of the film after thermal hardening can be ensured. Stability and durability. By setting the proportion of the above-mentioned structural units to 95% or less, the remaining amount of unreacted acid-decomposable groups can be reduced, the solubility of the exposed part can be improved, and high sensitivity can be achieved.

In one embodiment, the positive photosensitive resin composition contains 0.5% to 50% by mass of the protective resin based on 100% by mass of solid content, preferably 1% to 40% by mass, and more preferably 1% by mass to 40% by mass. 2% by mass to 30% by mass. The content of the protective resin is based on 100% by mass of the solid content. If it is 0.5% by mass or more, dissolution of the exposed part is promoted and a difference in solubility between the unexposed part and the exposed part can be achieved. Therefore, high sensitivity can be achieved, and It can ensure the stability and durability of the film after heat hardening. The content of the protective resin is based on 100% by mass of the solid content. If it is 50% by mass or less, the remaining amount of unreacted acid-decomposable groups can be reduced, the solubility of the exposed part can be improved, and high sensitivity can be achieved.

<Quinone diazide compound (C)> When the quinone diazide compound (C) is irradiated with radiation such as visible light, ultraviolet light, gamma rays, electron beams, etc., an alkali-soluble carboxylic acid compound is generated through the reaction shown in the following reaction formula 2. Before exposure to light, the quinone diazide compound (C) interacts with the alkali-soluble functional group of the alkali-soluble resin (B), such as phenolic hydroxyl group (e.g., hydrogen bond formation), so that the alkali-soluble resin (B) is insoluble relative to the alkaline aqueous solution. On the other hand, since the alkali-soluble carboxylic acid compound exists in the part irradiated with radiation, the resin in this part becomes easily soluble in the alkaline aqueous solution together with the carboxylic acid compound. In addition, the generated carboxylic acid compound promotes the decomposition of the acid-degradable group of the protective resin arbitrarily contained in the positive photosensitive resin composition, regenerates the alkali-soluble functional group, and increases the alkali solubility of the protective resin. Furthermore, the carboxylic acid compound has a relatively larger molecular structure than the acid generated by the photoacid generator generally used in chemically amplified anti-etching agents, such as p-toluenesulfonic acid, 1-propanesulfonic acid, etc., and is difficult to diffuse in the film. As a result of the synergistic effect, the difference in alkali solubility between the unexposed part and the exposed part can be increased, and thereby, a high-resolution pattern can be formed with high sensitivity even with a low exposure amount. The quinonediazide compound (C) can be used alone or in combination of two or more types. The positive photosensitive resin composition preferably does not substantially contain a photoacid generator commonly used in chemically amplified resists, and more preferably does not contain the photoacid generator and contains only a quinone diazide compound (C) as a photosensitive agent. The so-called "does not substantially contain a photoacid generator commonly used in chemically amplified resists" means that the amount of the photoacid generator contained in the positive photosensitive resin composition is 0.2 parts by mass or less, 0.1 parts by mass or less, or 0.05 parts by mass or less based on 100 parts by mass of the total resin components. Positive photosensitive resin compositions are preferred when chemically amplified resists do not contain the photoacid generator commonly used because of their good process stability and ability to achieve high sensitivity.

In one embodiment, high-resolution patterns can be formed without performing the post-exposure heat treatment (PEB) required for general chemical amplification resists. The quinonediazide compound (C) has a relatively high quantum yield and efficiently generates a carboxylic acid compound in the exposed part. By omitting PEB, the acid generated by the photoacid generator can avoid deterioration in pattern formability caused by excessive diffusion into unexposed areas in the high-temperature environment of the PEB step. Furthermore, when the alkali-soluble resin (B) contains a resin having an epoxy group and a phenolic hydroxyl group, and PEB is omitted, since the ring-opening polymerization of the epoxy group of the resin having an epoxy group and a phenolic hydroxyl group is not performed, it can be Maintain the alkali solubility of resins with epoxy and phenolic hydroxyl groups during development.

Examples of the quinonediazide compound (C) include polyhydroxy compounds in which quinonediazide's sulfonic acid is bonded with an ester, polyamino compounds in which sulfonamide-bonded quinonediazide's sulfonic acid is bonded, and polyhydroxy compounds in which quinonediazide's sulfonic acid is bonded with an ester. Polyamine-based compounds, ester bond or sulfonamide bond, quinone diazide, sulfonic acid, etc. From the viewpoint of comparison between the exposed part and the unexposed part, it is preferable that 20 mol% or more of all the functional groups of the polyhydroxy compound or polyamine compound be substituted with quinonediazide.

Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP- IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP , DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are 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 (the above are trade names, Asahi has Machine Materials Co., Ltd.), tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.), etc. , but is not limited to this.

Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl sulfide, but the polyamino compound is not limited thereto.

Examples of the polyhydroxypolyamino compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but the polyhydroxypolyamino compound is not limited thereto.

The quinonediazide compound (C) is preferably 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate of a polyhydroxy compound.

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

＜Fluorine-based surfactant (D)＞ The fluorine-based surfactant (D) is not particularly limited, but a surfactant having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group and a hydrophilic group can be used. . Examples of such fluorine-based surfactant (D) include perfluoroalkyl sulfonic acid, partially fluorinated alkyl sulfonic acid, perfluoroalkyl carboxylic acid, partially fluorinated alkyl carboxylic acid, and perfluoroalkyl carboxylic acid. Phosphate ester, partially fluorinated alkyl phosphate, perfluoroalkyl trimethyl ammonium salt, partially fluorinated alkyl trimethyl ammonium salt, perfluoroalkyl betaine, partially fluorinated alkyl betaine, perfluoroalkyl Based EO adducts and fluoro-telomeric alcohols. As the fluorine-based surfactant (D), it is also possible to use those having a perfluoroalkyl group, a partially fluorinated alkyl group, a perfluoroalkylene group or a partially fluorinated alkylene group, and a sulfonic acid group, a carboxyl group, or a phosphate group in the molecule. Individual polymers or copolymers of hydrophilic groups such as ammonium group, oxyalkylene group, polyoxyalkylene group, etc. The fluorine-based surfactant (D) can be used alone or in combination of two or more types.

The fluorinated surfactant (D) is preferably an acrylic copolymer having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group. The above-mentioned acrylic copolymer promotes the movement of the hydrophobic resin (A) to the film surface of the positive photosensitive resin composition, and can make the film surface more alkali-insoluble.

In one embodiment, the acrylic copolymer is a copolymer (D1) of a fluorine-containing polymerizable monomer represented by formula (8) and a polymerizable monomer having a group represented by formula (9). (In formula (8), R ¹⁷ is a hydrogen atom or a methyl group, L ¹ is a divalent group with a carbon number of 1 to 30, and Rf ¹ is a carbon number 4 that may contain one or more ether bonds in the chain. ~6 perfluoroalkyl or partially fluorinated alkyl). (In formula (9), R ¹⁸ is a hydrogen atom or a methyl group, and R ¹⁹ is independently a linear or branched alkylene group with 2 to 4 carbon atoms, or a linear perfluorinated alkylene group with 1 to 4 carbon atoms. Alkyl group or linear partially fluorinated alkylene group, or branched perfluoroalkylene group with 2 to 4 carbon atoms or branched partially fluorinated alkylene group, R ²⁰ is independently a hydrogen atom, carbon number from 1 to 4 6 alkyl group, or a perfluoroalkyl group or a partially fluorinated alkyl group with 1 to 6 carbon atoms, c is an integer from 2 to 50).

In formula (8), the divalent group having 1 to 30 carbon atoms represented by ^L1 may contain at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, and may also contain a perfluoroalkyl group or a partially fluorinated alkyl group having 4 to 6 carbon atoms. ^L1 is preferably _{-OCH2CH2- , -OCH2CH2NH (} C ₌ O)OCH _{( CH2OCH2CH2C4F9 ) CH2OCH2CH2- , -OCH2CH2NH ( C} =O)OCH _{( CH2OCH2CH2C6F13 ) CH2OCH2CH2- , -OCH2CH2N} ( _{C3H7 ) SO2- , -OCH2CH2NH ( C} =O _{) OCH2CH2- , -OCH2CH} (OH _{) CH2O- or} -N( _{C4H9 ) CH2CH2- .}

In formula (8), Rf ¹ is preferably -C ₄ F ₉ or -C ₆ F ₁₃ .

The fluorine-containing polymerizable monomer represented by the formula (8) may be used alone or in combination of two or more kinds.

In formula (9), examples of the linear or branched alkylene group having 2 to 4 carbon atoms represented by R ¹⁹ include ethylene, propylene, tetramethylene, and 1-methylethylene. base, 2-methylethylidene, 1-ethylethylidene, 2-ethylethylidene and isobutyl. Examples of the linear perfluoroalkylene group or linear partially fluorinated alkylene group having 1 to 4 carbon atoms represented by R ¹⁹ include -CF ₂ -, -CF ₂ CF ₂ -, and -CF ₂ CF ₂ CF. ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, -CHF-, CF ₂ CH ₂ - and -CF ₂ CHF-. Examples of the branched perfluoroalkylene group or branched partially fluorinated alkylene group having 2 to 4 carbon atoms represented by R ¹⁹ include -CF(CF ₃ )-, -CF(CF ₃ )CF ₂ -, - CF ₂ CF(CF ₃ )-, -CF(CF ₂ CF ₃ )CF ₂ -, -CF ₂ CF(CF ₂ CF ₃ )-, -CF(CHF ₂ )CF ₂ -, -CF ₂ CF(CHF ₂ )-, -CF(CF ₂ CHF ₂ )CF ₂ -, and -CF ₂ CF(CF ₂ CHF ₂ )-. R ¹⁹ can be the same or different from each other. From the viewpoint of leveling properties, R ¹⁹ is preferably propylene, tetramethylene, 1-methylethylidene, 2-methylethylidene, 1-ethylethylene, or 2-ethylidene. Ethyl or isobutylene, preferably adjacent oxygen atoms of the same group, are connected in plural to form a polyoxypropylene chain, a polyoxytetramethylene chain, a polyoxymethylethylene chain, or a polyoxyethylethylene chain. or polyoxyisobutylene chains.

In formula (9), examples of the alkyl group having 1 to 6 carbon atoms represented by ^R20 include methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl. Examples of the perfluoroalkyl group or partially fluorinated alkyl group having 1 to ₆ carbon atoms represented by ^R20 include _{-CF3 , -C2F5 , -C3F7 , -C4F9 , -C5F11 , -C6F13 , -CH2F , -CHF2 , -C2HF4} , _-C3H2F5 , _{-C3HF6 , -C4HF8 , -C5HF10 and -C6HF12 .}

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

The copolymer (D1) may be a copolymer with other polymerizable monomers besides the fluorine-containing polymerizable monomer represented by the formula (8) and the polymerizable monomer having a polyoxyalkylene group represented by the formula (9).

As other polymerizable monomers, for example, there can be mentioned polymerizable monomers represented by formula (10). (In formula (10), R ²¹ is a hydrogen atom or a methyl group, and R ²² is independently a linear, branched or cyclic alkyl or silyl group containing 1 to 18 carbon atoms).

In formula (10), examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms represented by ^R22 include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, stearyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, isoborneol, adamantyl and dicyclopentanyl. Examples of the group containing a silyl group include trimethoxysilylpropyl, (trimethylsilyloxy)dimethylsilylpropyl and tris(trimethylsilyloxy)silylpropyl.

As other polymerizable monomers, there can be mentioned aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene; and maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, n-propylmaleimide, isopropylmaleimide, n-butylmaleimide, n-hexylmaleimide, n-octylmaleimide, n-dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide.

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

From the viewpoint of leveling properties, the mass ratio of the fluorine-containing polymerizable monomer represented by the formula (8) and the polymerizable monomer having the polyoxyalkylene group represented by the formula (9) in the copolymer (D1) (formula ( 8) The mass of the fluorine-containing polymerizable monomer expressed/the mass of the polymerizable monomer having the polyoxyalkylene group represented by formula (9)), preferably 10/90~70/30, more preferably 15/85 ~60/40, and even better is 25/75~50/50. When using other polymerizable monomers, it is preferable to use the other polymerizable monomers in an amount of 50 mass % or less based on the mass of the copolymer (D1).

The copolymer (D1) can be obtained by free radical polymerization of a fluorine-containing polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), and other polymerizable monomers as necessary 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, chain transfer agents such as lauryl mercaptan, 2-butylethanol, thioglycerol, ethyl butyl acetic acid (thioglycolic acid), and octyl butyl acetic acid can be used.

Since it has good compatibility or miscibility with the resin component and obtains excellent leveling properties, the number average molecular weight (Mn) of the copolymer (D1) is preferably 2,000 to 100,000, more preferably 2,500 to 50,000.

From the viewpoint of compatibility or miscibility with the resin component and leveling properties, the fluorine atom content of the copolymer (D1) is preferably 2 to 40 mass %, more preferably 5 to 30 mass %, and still more preferably It is 10~25% by mass. The fluorine atom content rate of the copolymer (D1) is a value calculated from the mass ratio of fluorine atoms, based on the total mass of the polymerizable monomers used.

In another embodiment, the acrylic copolymer is a copolymer (D2) of a fluorine-containing polymerizable monomer represented by formula (11) and a polymerizable monomer having an oxyalkylene group represented by formula (12). (In formula (11), R ²³ is a radically polymerizable functional group, L ² is a divalent group having 1 to 8 carbon atoms, L ³ is a divalent group having 1 to 8 carbon atoms, and Rf ² is independently Fluorinated alkylene group with 1 to 3 carbon atoms, d is an integer from 1 to 100). (In formula (12), R ²⁴ is a hydrogen atom or a methyl group, R ²⁵ is independently a straight-chain or branched alkylene group with 2 to 4 carbon atoms, and R ²⁶ is a hydrogen atom or a carbon number of 1 to 6 alkyl group, e is an integer from 1 to 80).

In formula (11), examples of the radical polymerizable functional group represented by R ²³ include CH ₂ =CHCO-, CH ₂ =C(CH ₃ )CO-, and CH ₂ =CH-C ₆ H ₄ -. R ²³ may be the same or different from each other. From the viewpoint of availability and radical polymerizability, R ²³ is preferably CH ₂ =CHCO- or CH ₂ =C(CH ₃ )CO-, and more preferably CH ₂ =CHCO- due to its excellent leveling property.

In formula (11), the divalent group having 1 to 8 carbon atoms represented by L ² may also include at least one heteroatom selected from the group consisting of oxygen atoms and nitrogen atoms. L ² is preferably -OCH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ NH(C=O)OCH ₂ -, -OCH ₂ CH ₂ NH(C=O)OCH ₂ CH ₂ -, - OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH(OH)CH ₂ O(C=O)-, -OCH ₂ CH(OH)CH ₂ O(C=O)-, -OCH ₂ CH(OH)CH ₂ OCH ₂ - or -CH ₂ OCH ₂ -, more preferably -OCH ₂ - or -OCH ₂ CH ₂ NH(C=O)OCH ₂ -, still more preferably -OCH ₂ -.

In formula (11), the divalent group having 1 to 8 carbon atoms represented by ^L3 may also contain at least one impurity atom selected from the group consisting of oxygen atoms and nitrogen atoms. ^L3 is preferably _{-CH2O- ,} -CH2CH2O- _{, -CH2O} (C=O _{) NHCH2CH2O- , -CH2CH2O} (C=O _{) NHCH2CH2O- ,} -(C= _O )OCH2CH ₍ OH ₎ CH2OCH2CH2CH2CH2O- _, -(C=O) _{OCH2CH (} OH ₎ CH2O- _, -CH2OCH2CH(OH _{) CH2O- ,} or _-CH2OCH2- , more preferably _-CH2O- or _-CH2O (C=O _{) NHCH2CH2O-} , and even more preferably _-CH2O- .

In formula (11), the fluorinated alkylene group having 1 to 3 carbon atoms represented by Rf ² is specifically selected from -CF ₂ -(perfluoromethylene), -CF ₂ CF ₂ -(perfluoromethylene). Fluoroethylidene), -CF ₂ CF ₂ CF ₂ -, -CF ₂ CF(CF ₃ )- and -CF(CF ₃ )CF ₂ -.

From the viewpoint of leveling properties, in formula (11), it is preferable that the site represented by -(Rf ² O) _d Rf ² - contains a combination of a perfluoromethylene group and a perfluoroethylene group. In this embodiment, the molar ratio of perfluoromethylene to perfluoroethylidene (the molar number of perfluoromethylene/the molar number of perfluoroethylidene) is preferably 1/10 to 10 /1.

In formula (11), d is preferably 3 to 100, more preferably 6 to 70.

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

The fluorine-containing polymerizable monomer represented by formula (11) can be used alone or in combination of two or more types.

In formula (12), examples of the linear or branched alkylene group having 2 to 4 carbon atoms represented by R ²⁵ include ethylene group, propylene group, tetramethylene group and isobutylene group. R ²⁵ may be the same or different from each other. From the perspective of leveling properties, it is preferable that R ²⁵ is an ethylidene group or a propylene group, and it is more preferable that R 25 is connected in plural through adjacent oxygen atoms of the same group to form a bonded polyoxyethylene chain or polyoxypropylene. chain or a chain of polyoxyethylene chain and polyoxypropylene chain.

In formula (12), examples of the alkyl group having 1 to 6 carbon atoms represented by R ²⁶ include methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl.

In formula (12), e is preferably 3~50.

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

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

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

Since the copolymer (D2) has good compatibility or miscibility with the resin component and obtains excellent leveling property, the number average molecular weight (Mn) is preferably 500-20,000, more preferably 1,500-10,000, and the weight average molecular weight (Mw) of the copolymer (D2) is preferably 2,000-100,000, more preferably 3,000-50,000.

From the viewpoint of compatibility or miscibility with the resin component and leveling properties, the fluorine atom content of the copolymer (D2) is preferably 2 to 40 mass %, more preferably 5 to 30 mass %, and still more preferably It is 10~25% by mass. The fluorine atom content rate of the copolymer (D2) is a value calculated from the mass ratio of fluorine atoms, based on the total mass of the polymerizable monomers used.

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

The content of the fluorine-based surfactant (D) in the positive photosensitive resin composition is based on 100 parts by mass of the total resin components, preferably 0.01 parts by mass to 5 parts by mass, more preferably 0.03 parts by mass to 3 parts by mass, and even more preferably 0.05 parts by mass to 2 parts by mass. The content of the fluorine-based surfactant (D) is based on 100 parts by mass of the total resin components. If it is 0.01 parts by mass or more, the positive photosensitive resin composition can be uniformly coated on the substrate because the leveling property of the positive photosensitive resin composition is improved, thereby promoting the localization of the hydrophobic resin (A). The content of the fluorine-based surfactant (D) is based on the above total of 100 parts by mass. If it is 5 parts by mass or less, it will not have an adverse effect on the cured film after post-baking, improve the leveling of the positive photosensitive resin composition, and promote the localization of the hydrophobic resin (A).

＜Color(E)＞ The positive photosensitive resin composition may further contain at least one colorant (E) selected from the group consisting of a black dye and a black pigment. By using a photosensitive resin composition containing a colorant (E) to form a black partition wall on an organic EL element, the visibility of a display device such as an organic EL display can be improved. In this embodiment, due to the presence of the colorant (E), the amount of radiation transmitted from the surface of the film to the inside during exposure is drastically reduced. Therefore, although the carboxylic acid compound derived from the quinonediazide compound (C) occurs relatively frequently near the surface of the film, it is unlikely to occur inside the film. Since the carboxylic acid compound derived from the quinonediazide compound (C) has low diffusivity in the film, it remains near the film surface and contributes to the dissolution of the film surface in the exposed portion. Since the concentration of the hydrophobic resin (A) inside the film is relatively low, the alkali solubility is relatively high. Therefore, even if radiation cannot sufficiently penetrate into the film, by using the positive photosensitive resin composition of this embodiment, a high-precision thick film pattern can be formed with high sensitivity.

As black dyes, for example, dyes specified by colorimetric index (C.I.) of Solvent Black 27 to 47 can be cited. Black dyes are preferably specified by C.I. of Solvent Black 27, 29 or 34. When at least one type of dye specified by C.I. of Solvent Black 27 to 47 is used as a black dye, the light shielding property of the film of the positive photosensitive resin composition after curing can be maintained. Compared with a positive photosensitive resin composition containing a black pigment, a positive photosensitive resin composition containing a black dye has less coloring agent residue during development and can form a high-precision pattern.

Examples of the black pigment include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene-based pigments, and lactam-based pigments. These black pigments can also be used for surface treatment. Examples of commercially available perylene pigments include BASF's K0084, K0086, and Pigment Black 21, 30, 31, 32, 33, and 34. An example of a commercially available lactam-based pigment is BASF's Irgaphor (registered trademark) Black S0100CF. Since it has high light-shielding properties, the black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene-based pigments, and lactam-based pigments.

The content of the colorant (E) in the positive photosensitive resin composition is based on a total of 100 parts by mass of the resin components, and is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass, and still more preferably 10 to 150 parts by mass. 20~80 parts by mass. The content of the colorant (E) is based on the above total of 100 parts by mass. If it is 10 parts by mass or more, sufficient light-shielding properties can be obtained. Especially when the colorant (E) contains a black dye, the film after curing can be maintained. Light blocking properties. The content of the colorant (E) is based on the above total of 100 parts by mass. If it is 150 parts by mass or less, the residual film rate and sensitivity will be appropriate. Especially when the colorant (E) contains a black dye, high heat resistance can be imparted to the film. .

＜Optional ingredients＞ The positive photosensitive resin composition may contain, as optional components, a dissolution accelerator (F), a thermosetting agent, a second surfactant other than the fluorine-based surfactant (D), and a second coloring other than the coloring agent (E). Agents, etc. In this disclosure, any component can be defined as one that does not meet any of (A) to (E).

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

The "low molecular weight compound" in this disclosure refers to a compound with a molecular weight of less than 1000. The above-mentioned organic low molecular weight compound has a carboxyl group or a plurality of phenolic hydroxyl groups and is alkali soluble.

Examples of such organic low molecular compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and octanoic acid; oxalic acid , malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethyl Aliphatic dicarboxylic acids such as malonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc.; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, norcamphoric acid, etc.; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid , aromatic polycarboxylic acids such as mellitic acid, pyromellitic acid, and hemimellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, gallic acid, etc.; phenyl Acetic acid, hydrogenated atropine acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropine acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, phenylene (Cinnamylidene) acetic acid, coumaric acid, umbrella Other carboxylic acids such as acids; aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, bisphenol, etc. wait.

The content of the dissolution accelerator (F) in the positive photosensitive resin composition is based on a total of 100 parts by mass of the resin components and can be set at 0.1 to 50 parts by mass, preferably 1 to 35 parts by mass. , more preferably 2 parts by mass to 20 parts by mass. The content of the dissolution accelerator (F) is based on the above total of 100 parts by mass. If it is 0.1 parts by mass or more, the dissolution of the resin component can be effectively promoted, and if it is 50 parts by mass or less, excessive dissolution of the resin component can be suppressed. , which can improve the pattern formation and surface quality of the film.

＜Thermal hardener＞ As the thermal hardener, a thermal radical generator can be used. Preferable thermal radical generators include organic peroxides, and specifically, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl) Peroxy) hexane, tert-butyl cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene peroxide Hydrogen and other organic peroxides have a half-life temperature of 100~170℃ in 10 hours.

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

<Second surfactant> The positive photosensitive resin composition may contain a second surfactant other than the fluorine-based surfactant (D) for the purpose of improving coating properties, improving the smoothness of the film, or improving the developing properties of the film. Examples of the second surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and organosiloxane polymers KP323, KP326, and KP341 (trade names, Shin-Etsu Chemical Co., Ltd.). The second surfactant can be used alone or in combination of two or more types.

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

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

Examples of dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, Croconium dyes, and Cyanine-based dyes, diphenylethylene-based dyes, diphenylmethane-based dyes, triphenylmethane-based dyes, fluoran-based dyes, spiropyran-based dyes, phthalocyanine-based dyes, indigo-based dyes, fulgide-based dyes Dyes, nickel complex dyes and azulene dyes.

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

[Coating composition] ＜Solvent (G)＞ The positive photosensitive resin composition is dissolved or dispersed in the solvent (G) and can be used as a coating composition in a solution state or a dispersion state. For example, in a solution obtained by dissolving the hydrophobic resin (A) and the alkali-soluble resin (B) in the solvent (G), a quinonediazide compound (C) and a fluorine-based surfactant (D) are added, as well as A coating composition including a positive photosensitive resin composition can be prepared by mixing optional components such as a necessary colorant (E), a dissolution accelerator (F), a thermosetting agent, and other surfactants in a specified ratio. The coating composition can be adjusted to a viscosity suitable for the coating method being used by changing the amount of solvent (G).

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; methyl solvents Ethylene glycol alkyl ether acetate such as cellulose acetate, ethyl cellosolve acetate, etc.; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, etc. Diethylene glycol compounds such as diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc.; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, etc. Propylene glycol monoalkyl ether acetate compounds such as ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl Ketones such as 2-pentanone, cyclohexanone, etc.; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxy Ethyl acetate, ethyl glycolate, methyl 2-hydroxy-2-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Esters such as methyl ester, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, etc.; and N-methyl-2-pyrrolidone, N, Amide compounds such as N-dimethylformamide and N,N-dimethylacetamide. The solvent (G) can be used alone or in combination of two or more types.

The solid content concentration of the coating composition can be appropriately determined according to the purpose of use. For example, the solid content concentration of the coating composition can be set to 1 to 60 mass %, 3 to 50 mass %, or 5 to 40 mass %.

As for the dispersion and mixing method when using pigments, a known method can be used. For example, ball mills, sand mills, bead mills, paint mixers, shaker mills, etc., kneaders, paddle mixers, planetary mixers, Henschel mixers, etc. blade type, 3-roller mixers, etc. can be used. As for the roll type, crushing machines, colloid grinders, ultrasonics, homogenizers, rotational and revolution mixers, etc. can be used as others. From the viewpoint of dispersion efficiency and micro-dispersion, it is preferable to use a bead mill.

The prepared coating composition is usually filtered before use. As a filtering means, for example, a microporous filter with a pore size of 0.05-1.0 μm can be cited.

The coating composition prepared in this way also has excellent storage stability over a long period of time.

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

After the coating composition is applied to the substrate surface, the solvent is usually removed by heating to form a film (prebaking). Although the heating conditions vary depending on the type and blending ratio of each component, they can generally be 70 to 130°C. For example, heating on a hot plate will take 30 seconds to 20 minutes, and heating in an oven will take 1 to 60 minutes. Process to obtain a film. In one embodiment, the thickness of the film formed is 2~3 μm.

Next, the pre-baked film is irradiated with radiation (e.g., visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, gamma ray, or synchrotron radiation) through a mask having a specified pattern (exposure step). Preferably, the radiation is ultraviolet light to visible light with a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-ray. In other embodiments, the radiation is ghi-ray.

When the positive photosensitive resin composition contains a protective resin as the alkali-soluble resin (B), after the exposure step, heat treatment (PEB) for promoting the decomposition of the acid-decomposable group may be performed. PEB can promote the deprotection of the protected alkali-soluble functional groups of the exposed part in the protective resin, and further improve the alkali solubility of the exposed part. Although the heating conditions vary depending on the type and blending ratio of each component, it can usually be heated at 70 to 140°C, for example, 30 seconds to 20 minutes on a hot plate, or 1 to 60 minutes in an oven. processing, to perform PEB.

In one embodiment, the PEB step is not included after the exposure step. This prevents the film from flowing and deforming due to heating, and allows high-precision thick film pattern formation. It also reduces the steps involved in forming a partition or insulating film.

After the exposure step or PEB step, the film is brought into contact with a developer and developed to remove unnecessary parts, thereby forming a pattern on the film (development step). As the developer, for example, inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc.; first-level amines such as ethylamine, n-propylamine, etc. can be used; Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; tetrahydramines Fourth-level ammonium salts of methylammonium hydroxide, tetraethylammonium hydroxide, choline, etc.; pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1 , Aqueous solution of alkali compounds such as 5-diazabicyclo[4.3.0]-5-nonane and other cyclic amines. An aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added to an alkali aqueous solution as a developer. The development time is usually 30~180 seconds. The development method may be any of liquid filling method, shower method, dipping method, etc. After development, the film can be washed with running water for 30 to 90 seconds to remove unnecessary parts, and air-dried with compressed air or compressed nitrogen to form a pattern on the film.

Then, the patterned film can be heated for 20 to 200 minutes at 100 to 350°C on a heating device such as a hot plate or oven to obtain a hardened film (post-baking, heating treatment step). During the heating treatment, the temperature can be maintained at a constant, or it can be continuously or stepwise increased. The heating treatment is preferably performed in a nitrogen gas environment.

<Dissolution rate difference> The positive photosensitive resin composition can form a film whose alkaline solubility on the film surface is lower than that of the entire film. Specifically, the positive photosensitive resin composition is applied in a manner such that the film thickness after pre-baking becomes 3±0.3μm, and pre-baked at 125℃ for 120 seconds. After the film is formed, it is exposed under the condition of 30mJ/ ^cm2 , and when it is developed at a temperature of 23℃ with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, the dissolution rate of the film surface layer is lower than the dissolution rate of the entire film. The so-called dissolution rate of the film surface layer is the average dissolution rate at the time point when the film thickness of the above-mentioned film is dissolved to 80%, and the so-called dissolution rate of the entire film is the average dissolution rate at the time point when the film thickness of the above-mentioned film is dissolved to 30%. The average dissolution rate of the surface and the whole film is determined by the order described in the examples. The difference between the dissolution rate of the film surface layer and the dissolution rate of the whole film is preferably 3 nm/sec or more, more preferably 5 nm/sec or more, and even more preferably 8 nm/sec or more.

＜Residual film rate＞ In one embodiment, the positive photosensitive resin composition is applied so that the film thickness after prebaking becomes 3±0.3 μm, and is prebaked at 125°C for 120 seconds. When using mass% tetramethylammonium hydroxide aqueous solution for alkali development for 60 seconds, the residual film rate defined by the following formula is more than 90%, Residual film rate (%) = film thickness after development (μm) / film thickness before development (μm) More preferably, it is 95% or more, and more preferably, it is 99% or more. The residual film rate is an indicator of the solubility of the unexposed part. The higher the residual film rate, the greater the difference in solubility between the exposed part and the unexposed part. Thick film patterns with large height differences can be formed with high precision.

＜Optical density＞ In an embodiment in which the positive photosensitive resin composition contains the colorant (E), the optical density (OD value) of the cured film of the positive photosensitive resin composition is preferably 0.5 or more per 1 μm of film thickness, more preferably 0.7 or above, preferably 1.0 or above. If the OD value of the cured film is 0.5 or more per 1 μm of film thickness, sufficient light-shielding properties can be obtained.

A method for manufacturing an organic EL element partition wall or an organic EL element insulating film according to an embodiment includes: dissolving or dispersing a positive photosensitive resin composition in a solvent, preparing a coating composition, coating the coating composition on a substrate to form a film, removing the solvent contained in the film, drying the film, irradiating the dried film with radiation through a mask, exposing the film, developing the exposed film by contacting it with a developer, forming a pattern on the film, and heating the film with the pattern formed at a temperature of 100° C. to 350° C. to form an organic EL element partition wall or an organic EL element insulating film. The above-mentioned PEB can also be performed after exposure and before development. The positive photosensitive resin composition disclosed herein can form a high-precision thick film pattern with high sensitivity even in the embodiment in which the positive photosensitive resin composition contains a colorant (E).

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

[Organic EL element insulating film] One embodiment is an organic EL element insulating film comprising a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a coloring agent (E).

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

Although the present invention is specifically described below based on embodiments and comparative examples, the present invention is not limited to these embodiments.

(1) Raw materials The raw materials used in the embodiments and comparative examples were manufactured or obtained as follows.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were calculated using the following measurement conditions, polystyrene standard substances, and the prepared calibration curve. Apparatus name: Shodex (registered trademark) GPC-101 Column: Shodex (registered trademark) LF-804 Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL/min Detector: Shodex (registered trademark) RI-71 Temperature: 40°C

[Production Example 1] Alkali-soluble resin (B): Production of a copolymer (PCX-01) of a polymerizable monomer having an alkali-soluble functional group (phenolic hydroxyl group) and other polymerizable monomers Completely dissolve 28.0g of 4-hydroxyphenyl methacrylate (Showa Denko Co., Ltd. "PQMA") and 7.89g of N-cyclohexylmaleimide (Nihon Shokubai Co., Ltd.) in 1- of the solvent. 77.1g of methoxy-2-propyl acetate (Daicel Co., Ltd.), and 3.66g of V-601 (Fuji Film Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were completely dissolved in 1-methoxy -2-propyl acetate (Daicel Co., Ltd.) 14.6 g. The two obtained solutions were placed in a 300 mL 3-neck flask, and 1-methoxy-2-propyl acetate (Daicel Co., Ltd.) heated to 85°C was dropped simultaneously for 2 hours under a nitrogen atmosphere. )61.2g, and then reacted at 85°C for 3 hours. The reaction solution cooled to room temperature was dropped into 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, vacuum dried at 90°C for 4 hours, and 33.4 g of white powder was recovered. The number average molecular weight of the obtained PCX-01 was 6600, and the weight average molecular weight was 11600.

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

[Production Example 3] Hydrophobic resin (A): Production of a resin containing a silicon group (PCX-02e-TBDMS34) 15.9 g of 4-hydroxyphenyl methacrylate (Showa Denko Co., Ltd. "PQMA"), 16.6 g of 4-tert-butyldimethylsiloxyphenyl 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 Chemicals Co., Ltd.) as a solvent. 2.86 g of V-601 (Fuji Film Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.). The two solutions were added to 90.5 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) heated to 89°C in a 300 mL three-necked flask with a reflux tube under a nitrogen atmosphere over a period of 2 hours, and then reacted at 89°C for 4 hours. 50 g of the reaction solution cooled to room temperature was added to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 80°C for 5 hours to recover 9.73 g of white powder (PCX-02e-TBDMS34). The number average molecular weight of the obtained PCX-02e-TBDMS34 was 3753, and the weight average molecular weight was 7581. In PCX-02e-TBDMS34, the molar ratio of the structural unit represented by formula (1) where s is an integer greater than 1, the structural unit represented by formula (2), and the structural unit represented by formula (3) is formula (1): formula (2): formula (3) = 32:7:61. Based on the total structural units, the structural unit having an alkali-soluble functional group is 61 mol%. The content of silicon atoms is 4.0 mass % based on the mass of PCX-02e-TBDMS34.

[Manufacture Example 4] Hydrophobic resin (A): Production of resin having a silicone group (PCX-02e-TES34) Mix 15.9 g of 4-hydroxyphenyl methacrylate (Showa Denko Co., Ltd. "PQMA"), 16.6 g of 4-triethylsilyloxyphenyl methacrylate (PQMA-TES) and N-cyclohexylma 4.62g of leximine (Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 55.8g of isopropyl acetate (Kamiko Organic Chemical Industry Co., Ltd.) in the solvent. As a polymerization initiator, 2.86 g of V-601 (Fuji Film Wako Pure Chemical Industries, Ltd.) was completely dissolved in 4.29 g of isopropyl acetate (Kamiko Organic Chemical Industries, Ltd.). The two obtained solutions were placed in a 300 mL 3-neck flask with a reflux tube, and simultaneously, under a nitrogen atmosphere, it took 2 hours to drop isopropyl acetate (Kamiko Organic Chemical Industry Co., Ltd.) heated to 89°C. Co., Ltd.) 90.4g, 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 recovered by filtration, vacuum dried at 80°C for 5 hours, and 9.49g of white powder (PCX-02e-TES34) was recovered. The number average molecular weight of the obtained PCX-02e-TES34 was 3847, and the weight average molecular weight was 7534. In PCX-02e-TES34, the molar ratio between the structural unit represented by formula (1) and the structural unit represented by formula (2) and the structural unit represented by formula (3) when s is an integer above 1 is formula (1): Formula (2): Formula (3) = 32:7:61. Taking all structural units as the basis, the structural units with alkali-soluble functional groups are 61 mol%. The content of silicon atoms is 4.0% by mass based on the mass of PCX-02e-TES34.

[Production Example 5] Hydrophobic resin (A): Production of a resin having a fluorine group (PCX-02e-C6SFMA36) 12.1 g of 4-hydroxyphenyl methacrylate (Showa Denko Co., Ltd. "PQMA"), 20.5 g of 2-perfluorohexylethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), and 3.62 g of N-cyclohexylmaleimide (Tokyo Chemical Industry Co., Ltd.) were completely dissolved in 84.5 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) as a solvent. 3.74 g of V-601 (Fuji Film Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.9 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.). The two solutions were added to 51.0 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) heated to 89°C in a 300 mL three-necked flask with a reflux tube under a nitrogen atmosphere over a period of 2 hours, and then reacted at 89°C for 4 hours. 50 g of the reaction solution cooled to room temperature was added to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 80°C for 5 hours to recover 5.58 g of white powder (PCX-02e-C6SFMA36). The number average molecular weight of the obtained PCX-02e-C6SFMA36 was 2869, and the weight average molecular weight was 5743. In PCX-02e-C6SFMA36, the molar ratio of the structural unit derived from 2-perfluorohexylethyl methacrylate to the structural unit represented by formula (2) and the structural unit represented by formula (3) is 36:6:58. Taking all structural units as a reference, the structural unit having an alkali-soluble functional group is 58 mol%. The content of fluorine atoms is 24 mass % based on the mass of PCX-02e-C6SFMA36.

[Production Example 6] Alkali-soluble resin (B): Production of a resin (PCX-02e-THF28) in which the alkali-soluble functional group (phenolic hydroxyl group) is protected with a 2-tetrahydrofuryl group In a 100 mL 3-neck flask, 10.0 g of PCX-02e of Production Example 2 and 0.60 g of pyridinium salt of p-toluenesulfonic acid (Tokyo Chemical Industry Co., Ltd.) as an acid catalyst were dissolved in tetrahydrofuran (Fuji Soft tablets (Wako Pure Chemical Industries, Ltd.) 50.0g. Then, it was ice-cooled in a nitrogen gas environment, and 2.34 g of 2,3-dihydrofuran (Tokyo Chemical Industry Co., Ltd.) was dropped over 1 hour. Then, stir at room temperature for 4 hours. After neutralizing the acid catalyst with a saturated sodium bicarbonate aqueous solution, remove the water layer. Furthermore, the organic layer was washed twice with water. Then, tetrahydrofuran was distilled off. The obtained solid was dissolved in 50.0 g of ethyl acetate and dropped into 200 g of toluene to precipitate the product. The precipitate was recovered by filtration, dried under vacuum at 80°C for 4 hours, and 10.0 g of white powder was recovered. The obtained powder was dissolved in propylene glycol monomethyl ether acetate to obtain a 20 mass % solid content solution of a resin (PCX-02e-THF28) in which an alkali-soluble functional group (phenolic hydroxyl group) is protected with a 2-tetrahydrofuryl group. The number average molecular weight of the obtained PCX-02e-THF28 was 3700, the weight average molecular weight was 6800, the proportion of phenolic hydroxyl groups protected by acid-decomposable groups was 28 mol%, and at least one phenolic hydroxyl group was protected by acid-decomposable groups. The number of structural units represented by formula (7) is 25% of the total number of structural units of PCX-02e-THF28. The proportion of phenolic hydroxyl groups protected by acid-decomposable groups was determined using a thermogravimetric differential thermal analysis device (TG/DTA6200, Hitachi High-Tech Science Co., Ltd.) in a nitrogen gas flow at a temperature rise rate of 10°C/min. The temperature is raised from room temperature to 250°C and maintained for 10 minutes. Further, the weight reduction rate (%) of the resin at 260°C when the temperature is raised to 400°C is calculated at a temperature rise rate of 10°C/minute.

[Production Example 7] Alkali-soluble resin (B): Production of resin (N695OH70) having epoxy groups and phenolic hydroxyl groups 75.2 g of γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as a solvent and 37.8 g of EPICLON (registered trademark) N-695 (DIC Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent 214) as a compound having at least two epoxy groups in one molecule were placed in a 300 mL three-necked flask and dissolved at 60°C in a nitrogen atmosphere. 20.1 g (0.65 equivalents to 1 equivalent of epoxide) of 3,5-dihydroxybenzoic acid (Fuji Film Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound and 0.166 g (0.660 mmol) of triphenylphosphine (Tokyo Chemical Industry Co., Ltd.) as a reaction catalyst were added thereto, and the mixture was reacted at 110°C for 21 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain 274.2 g of a resin (N695OH70) solution having an epoxide group and a phenolic hydroxyl group. The obtained reactant had a number average molecular weight of 3000, a weight average molecular weight of 5100, an epoxide equivalent of 2200, and a phenolic hydroxyl equivalent of 161.

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

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

[Quinone diazide compound (C)] As the quinone diazide compound (C), TS-150A and TS-200A (ester of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) and 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinone diazide-5-sulfonic acid), Toyo Gosei Kogyo Co., Ltd.) were used; TPPA(4)-150DF ( 4,4’-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylene]bisphenol (TrisP-PA) 1,2-naphthoquinone diazide-4-sulfonate, Toyo Gosei Kogyo Co., Ltd.); and THDPP-280 (2-(4-hydroxyphenyl)-2-(2’,4’-dihydroxyphenyl)propane 1,2-naphthoquinone diazide-5-sulfonate, Toyo Gosei Kogyo Co., Ltd.).

The structures of TS-150A and TS-200A are shown below. In TS-150A, an average of 1.5 out of the three Rs per molecule have a quinone diazide structure. In TS-200A, an average of 2.0 out of the three Rs per molecule have a quinone diazide structure.

[Fluorine-based surfactant (D)] As fluorine-based surfactant (D), MEGAFACE (registered trademark) F-562, MEGAFACE (registered trademark) F-554, MEGAFACE (registered trademark) R-40, MEGAFACE (registered trademark) F-563 and MEGAFACE (registered trademark) F-559 (all DIC Corporation) were used.

As another surfactant, KF2201 (polysilicone-based surfactant, Shin-Etsu Chemical Co., Ltd.) was used.

[Color(E)] As the colorant, black dye VALIFAST (registered trademark) BLACK 3820 (black dye specified by the C.I. of Solvent Black 27, Dongfang Chemical Industry Co., Ltd., "VB3820" in Table 1), and VALIFAST (registered trademark) are used BLACK 3804 (a black dye specified by the C.I. of Solvent Black 34, Dongfang Chemical Industry Co., Ltd., "VB3804" in Table 1).

[Dissolution accelerator (F)] Pyrogallol was used as a dissolution accelerator (F).

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

(2) Evaluation method The evaluation method used in the embodiments and comparative examples is as follows.

[Alkali dissolution rate] A positive photosensitive resin composition was bar-coated on a glass substrate (size 100mm×100mm×1mm) to a dry film thickness of 3±0.3μm. After vacuum drying at room temperature for 60 seconds, the solvent was dried by heating at 125°C for 120 seconds on a hot plate with a lid (pre-baking). The dry film thickness was measured using an optical film thickness measuring device (F20-NIR, FILMETRICS Co., Ltd.), and then exposed at 30mJ/ ^cm2 using an exposure device equipped with an ultrahigh pressure mercury lamp (trade name Multilight ML-251A/B, Ushio Electric Co., Ltd.). The exposure amount was measured using an ultraviolet integrated light meter (trade name UIT-150 light receiving unit UVD-S365, Ushio Electric Co., Ltd.). Then, a rotary developing device (AD-1200, Takizawa Industrial Co., Ltd.) was used to develop at a temperature of 23°C with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, and the film thickness of the developed film was measured using an optical film thickness measuring device. By changing the development time, alkali development was performed to obtain the development time when the film thickness of the exposed part becomes 80% or 30%, respectively. The reduction amount (nm) of the film after development was divided by the development time (seconds) to obtain the alkali dissolution rate (nm/second). The above-mentioned alkali dissolution rate at the time point when the film thickness of the exposed part is dissolved to 80% is defined as the average dissolution rate of the surface layer of the film, and the above-mentioned alkali dissolution rate at the time point when the film thickness of the exposed part is dissolved to 30% is defined as the average dissolution rate of the entire film.

[Sensitivity] A positive photosensitive resin composition was bar-coated on a glass substrate (size 100mm×100mm×1mm) to a dry film thickness of 3.0μm. After vacuum drying at room temperature for 60 seconds, it was pre-baked by heating at 125℃ for 120 seconds on a hot plate with a lid. The film was exposed through a quartz mask (with a φ10μm opening pattern) using an exposure device equipped with an ultrahigh pressure mercury lamp (trade name Multilight ML-251A/B, Ushio Electric Co., Ltd.). The exposure amount was measured using an ultraviolet integrated light meter (trade name UIT-150 light receiving unit UVD-S365, Ushio Electric Co., Ltd.). After exposure, alkaline development was performed for 60 seconds using a rotary developer (AD-1200, Takizawa Industrial Co., Ltd.) with a 2.38 mass % tetramethylammonium hydroxide aqueous solution. The above sequence was repeated while changing the exposure amount, and the minimum exposure amount (mJ/cm ² ) that could form a pattern with a pore diameter of 10 μm that completely reached the glass substrate after development was taken as the sensitivity.

[Solubility of unexposed part] On a glass substrate (size 100mm×100mm×1mm), a positive photosensitive resin composition was bar-coated to a dry film thickness of 3.0μm, and after vacuum drying at room temperature for 60 seconds, it 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 Co., Ltd.), and then alkali developed for 60 seconds using a rotary developer (AD-1200, Takisawa Industrial Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. The film thickness after alkali development was measured again using an optical film thickness measuring device (F20-NIR, FILMETRICS Co., Ltd.), and the film thickness (μm) dissolved before and after development was used as an indicator of the solubility of the unexposed part. The solubility of the unexposed part is 0μm, which is equivalent to the residual film rate defined by the following formula being 100%. Residual film rate (%) = film thickness after development (μm) / film thickness before development (μm)

[OD value of cured film] On a glass substrate (size 100mm×100mm×1mm), a positive photosensitive resin composition was spin-coated in a manner such that the dry film thickness became about 1.5μm, and pre-baked by heating on a hot plate at 125℃ for 120 seconds. Then, the film was obtained by curing at 250℃ for 60 minutes in a nitrogen atmosphere. The OD value of the cured film was measured using a concentration meter (BMT-1, Sakata Inx Engineering Co., Ltd.), and the OD value of the glass was corrected and converted into the OD value per 1μm of the film thickness. The film thickness was measured using an optical film thickness measuring device (F20-NIR, FILMETRICS Co., Ltd.).

(3) Preparation and evaluation of positive photosensitive resin composition [Examples 1-14, Comparative Examples 1-2] The resin components of the composition listed in Table 1 were mixed and dissolved in a solvent (G), and the quinone diazide compound (C), fluorine-based surfactant (D) or other surfactants, coloring agent (E) and dissolution promoter (F) listed in Table 1 were added to the solution and further mixed. After visual confirmation of the dissolution of the components, the mixture was filtered with a microporous filter with a pore size of 0.22 μm to prepare a positive photosensitive resin composition with a solid component concentration of 12% by mass. The mass fractions of the compositions in Table 1 are converted to solid components. The evaluation results of the positive photosensitive resin compositions of Examples 1-14 and Comparative Examples 1-2 are shown in Table 1. The positive photosensitive resin composition of Comparative Example 2 was not evaluated because it could not form a pattern due to repulsion during coating.

From the evaluation results in Table 1, the positive photosensitive resin compositions of Examples 1 to 14 have a solubility of 0 μm in the unexposed part, which can increase the contrast between the exposed part and the unexposed part, and it is judged that thick film patterns can be formed with high accuracy. . Furthermore, after development, the exposure dose that can form a pattern with apertures of 10 μm is 300 mJ/cm ² or less, and it is also confirmed that the sensitivity is high.

In order to confirm the concentration distribution of the hydrophobic resin (A) in the thickness direction, sputtering was performed from the film surface of Example 4, Example 6 and Example 7, and XPS analysis was performed. Figure 1 shows a graph of the sputtering time (horizontal axis) and the silicon element concentration (vertical axis) of the films of Examples 4, 6 and 7, which were analyzed by XPS. The equipment and measurement conditions used in XPS analysis are as follows. [device] Device: Quantera II (ULVAC-PHI Co., Ltd.) X-ray: Al monochro 100μm, 25W, 15kV Analysis area: 100μm (Spot) Electron and ion neutralization gun: ON Photoelectron extraction angle: 45 degrees [Measurement conditions] Depth profile Ar2500+ (Argon gas cluster beam: GCIB) acceleration voltage and cluster area: 5kV, 17nA, 2×2mm Pass Energy: 224eV Step:0.1eV Dwell: 20ms Sweep time: C,O(2); F(4); Si,Cr,N,S(10) Sputtering interval: 0.25 minutes × 4 cycles/1 minute × 5 cycles/3 minutes × 8 cycles Sample fixation: copper clamp For binding energy correction, the C-C and C-H peaks of the C1s spectrum are set at 284.6eV.

In Examples 4, 6, and 7, it was found that the silicon element concentration near the surface of the film is high, and the silicon element concentration decreases toward the inside of the film. This point is revealed in that when the film is formed, PCX-02e-TBDMS34 of the hydrophobic resin (A) is localized on the surface of the film. [Industrial utilization possibility]

The positive photosensitive resin composition disclosed in the present disclosure can be suitably used for radiation lithography in forming partition walls or insulating films of organic EL elements. In particular, an organic EL element having a partition or an insulating film formed of the positive photosensitive resin composition of the embodiment containing the colorant (E) is suitable for use as an electronic component of a display device showing good contrast.

FIG. 1 is a graph showing the sputtering time (horizontal axis) and the silicon element concentration (vertical axis) of the films of Example 4, Example 6 and Example 7 obtained by XPS analysis.

Claims (11)

A positive photosensitive resin composition, which is a positive photosensitive resin composition containing a hydrophobic resin (A), an alkali-soluble resin (B), a quinonediazide compound (C), and a fluorine-based surfactant (D) A sexual resin composition, wherein the hydrophobic resin (A) is a resin having at least one selected from the group consisting of a silicon-containing group and a fluorine-containing group, and the content of the hydrophobic resin (A) is the solid content of 100 The mass % is 3 mass % to 50 mass %, and the fluorine-based surfactant (D) contains acrylic acid having at least one fluorinated hydrocarbon group selected from the group consisting of a fluorinated alkyl group and a fluorinated alkylene group. copolymer, the content of the aforementioned fluorine-based surfactant (D) is 0.01 to 5 parts by mass based on 100 parts by mass of the total resin components, and the aforementioned positive photosensitive resin composition is used as a prebaked film Coat to a thickness of 3±0.3μm, pre-bake at 125°C for 120 seconds, form a film, expose at 30mJ/ ^cm2 , and develop with 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23°C , the dissolution rate of the film surface layer is lower than the dissolution rate of the entire film. The so-called dissolution rate of the aforementioned film surface layer is the average dissolution rate at the time point until the film thickness of the aforementioned film is dissolved to 80%. The so-called dissolution rate of the aforementioned film as a whole is The dissolution rate is the average dissolution rate at the time point when the film thickness of the film is dissolved to 30%. As in claim 1, the positive photosensitive resin composition, wherein the difference between the dissolution rate of the surface layer of the film and the dissolution rate of the entire film is 3 nm/sec or more. A positive photosensitive resin composition as claimed in claim 1 or 2, wherein the hydrophobic resin (A) has a structural unit represented by formula (1), and has at least one structural unit represented by formula (1) wherein s is an integer greater than 1,

(In formula (1), ^R1 is a hydrogen atom or ^an alkyl group having 1 to ⁵ carbon atoms, ^R2 is represented by ^SiR3R4R5 , ^R3 , ^R4 and ^R5 are independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, and r+s is an integer of 1 to 5). The positive photosensitive resin composition of claim 3, wherein the hydrophobic resin (A) further has a structural unit represented by formula (2),

(In formula (2), R ⁶ and R ⁷ are independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, and R ⁸ is selected from a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, or At least one substituted phenyl group from the group consisting of a cyclic alkyl group with 3 to 12 atoms, phenyl or hydroxyl group, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. ). The positive photosensitive resin composition of claim 1 or 2, wherein the alkali-soluble resin (B) includes a copolymer of a polymerizable monomer with an alkali-soluble functional group and other polymerizable monomers, an epoxy group, and a Phenolic hydroxyl resin or combination thereof. The positive photosensitive resin composition of claim 1 or 2 further comprises at least one coloring agent (E) selected from the group consisting of black dyes and black pigments. The positive photosensitive resin composition of claim 6, wherein the colorant (E) is contained in an amount of 10 to 150 parts by weight based on 100 parts by weight of the total resin components. The positive photosensitive resin composition of claim 6, wherein the optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness. An organic EL element partition wall comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 8. An organic EL element insulating film, comprising a cured product of a positive photosensitive resin composition as described in any one of claims 1 to 8. An organic EL element comprising a cured product of the positive photosensitive resin composition according to any one of claims 1 to 8.

Images