TWI658328B - Positive photosensitive resin composition and titanium black dispersion - Google Patents

Abstract

Provided is a positive-type photosensitive resin composition that can be used for forming a black partition material for forming an organic EL display element with high sensitivity and characteristics satisfying developability, resolution, and heat resistance. A positive photosensitive resin composition comprising (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, (C) a solvent having a solubility parameter of 10.5 or more, (D) a binder resin, and (E) a quinonediazide compound.

Description

Positive photosensitive resin composition and titanium black dispersion

[0001] The present invention relates to a positive-type photosensitive resin composition, the production method, a titanium black dispersion used for the production, and a partition wall and an insulating film of an organic EL display element.

[0002] In a display device such as an organic EL display, in order to improve display characteristics, a partition wall material is used in a colored pattern-shaped partition portion in a display area, an edge of a peripheral portion of a display area, or the like. In the manufacture of an organic EL display device, in order to prevent pixels of an organic substance from contacting each other, a partition wall is formed first, and then a pixel of an organic substance is formed between the partition walls. Generally, this partition wall is formed by photolithography using a photosensitive resin composition and has insulation properties. More specifically, the photosensitive resin composition is coated on a substrate using a coating device, and the volatile components are removed by means such as heating, and then exposed through a mask. If it is a negative type, then Use a developing solution such as an alkaline aqueous solution to remove and develop the unexposed portion. If it is a positive type, use a developing solution such as an aqueous alkaline solution to remove and develop the exposed portion, and heat the obtained pattern. A partition wall (insulating film) is formed. Next, an organic substance that emits three colors of red, green, and blue light is formed between the partition walls by an inkjet method to form pixels of an organic EL display device. [0003] In recent years, due to the miniaturization of display devices and the diversification of display contents, high performance and high definition of pixels are required. In order to improve the contrast and visibility in display devices, it has been attempted to blacken the partition material by using a colorant to make it light-shielding. However, even if it has a light-shielding property, if the sensitivity to the light used to make it react is low, the exposure time will be longer and productivity will be lowered, so high sensitivity becomes important. In order to respond to the requirements of high definition, it is required to have an excellent pattern shape and a smooth pattern surface to cope with the narrow pitch of the pattern. In order to improve the visibility, the blackened partition wall material is required to be closer to black. Since the partition wall material is subjected to various steps after being formed, it is required to have excellent heat resistance without affecting the surrounding members. [0004] For example, Patent Document 1 proposes a method for blackening a partition wall material using carbon black. However, in these radiation-sensitive resin compositions, the light-shielding property of the cured film is insufficient, and an improvement in contrast cannot be expected. [0005] On the other hand, as a radiation-sensitive resin composition having high resolution and exhibiting high light-shielding properties by heat treatment after exposure, a composition like Patent Document 2 has been proposed, which is alkali-soluble A positive-type radiation-sensitive resin composition of a resin and a quinonediazide compound is formed by adding titanium black. Although these compositions have sufficient sensitivity and light-shielding properties, in order to improve the light-shielding properties, they are heated at high temperature in the air and use the coloring accompanying the oxidative degradation of the resin. This is because the out gas increases due to the deterioration of the resin, so the heat resistance is poor, which is not suitable for the manufacture and stable driving of organic EL display devices. Without touching the properties of titanium black, it cannot be said to have sufficient surface smoothness. [0006] In general, as the partition wall material, a polyimide resin having excellent insulation properties is used, but in order to make it have light-shielding properties, blackening must be performed. However, when the blackened polyfluorene imine resin is formed by a lithography method, it is difficult in terms of storage stability and cost of the photosensitive polyfluorene imide, and it is difficult to obtain a good resolution. Therefore, a technique for blackening the partition wall material and satisfying the sensitivity, developability, resolution, and heat resistance has not yet been obtained. [Prior Art Document] [Patent Document] [0007] [Patent Document 1] Japanese Patent Laid-Open No. 2002-116536 [Patent Document 2] Japanese Patent Laid-Open No. 2001-281440

[Problems to be Solved by the Invention] [0008] In order to improve the contrast of organic EL display elements, efforts have been made to blacken the partition materials, but so far there has been no high-sensitivity and satisfactory development, resolution, and heat resistance. A positive-type photosensitive resin composition having all the properties and the manufacturing method thereof. [0009] The present invention has been completed based on the above-mentioned circumstances, and an object of the present invention is to provide a positive-type photosensitive resin composition capable of providing high sensitivity and satisfying developability in a blackened partition material. , Characteristics of resolution, heat resistance, and a method for producing the positive photosensitive resin composition. [Means to Solve the Problem] [0010] As a result of intensive research, the inventor found that a dispersant containing titanium black, an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, and a solubility parameter (SP value) A positive-type photosensitive resin composition made of a solvent, an adhesive resin, and a quinonediazide compound of 10.5 or more, which can provide high sensitivity and satisfy development, resolution, and heat resistance in a blackened partition material. characteristic. [0011] That is, the present invention includes the following aspects. [1]. A positive photosensitive resin composition comprising (A) titanium black, 、 (B) dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, and (C) solubility parameters It is a solvent of 10.5 or more, a fluorene (D) binder resin, and (E) a quinonediazide compound. [0012] [2]. The composition according to the above [1], wherein the solvent (C) is γ-butyrolactone or n-methyl-2-pyrrolidone. [3] The composition according to the above [1] or [2], wherein the dispersant (B) is 1 to 40 parts by mass based on 100 parts by mass of titanium black (A), and the solvent (C ) Is 250 to 600 parts by mass. [4]. The composition according to any one of the above [1] to [3], wherein the titanium resin (D) is 3 to 30 masses based on 100 parts by mass of the binder resin (D) The quinonediazide compound (E) is 3 to 20 parts by mass. [5]. The composition according to any one of the above [1] to [4], wherein the binder resin (D) comprises an alkali-soluble copolymer selected from (d1) having an alkali-soluble group, (d2) At least one of a group consisting of an alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and (d3) a polyalkenyl phenol resin. [6] A titanium black dispersion containing (A) titanium black, a dispersant having a amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, and (C) solubility The solvent is 10.5 or more. [7]. A method for producing a positive photosensitive resin composition, which comprises (1) (A) titanium black, (B) an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mg KOH / g of dispersant, (C) a step of preparing a titanium black dispersion by mixing a solvent having a solubility parameter of 10.5 or more, and (2) the aforementioned titanium black dispersion, (D) a binder resin and (E) quinone Step of mixing diazide compounds. [0018] [8]. A hardened material, which is a hardened material of the composition according to any one of the above [1] to [5]. [9]. A method for producing a radiation lithographic structure, comprising (I) applying a positive photosensitive resin composition according to any one of the above [1] to [5] to a substrate A coating step, (II) a drying step of removing a solvent from the coated positive-type photosensitive resin composition, (III) an exposure step of irradiating radiation through a photomask, (IV) pattern formation by alkali development The developing step and (V) a heat treatment step of heating at a temperature of 100 to 350 ° C. [0020] [10]. A partition wall of an organic EL element, which is formed of a cured product of the positive-type photosensitive resin composition according to any one of [1] to [5]. [0021] [11]. An insulating film of an organic EL element, which is formed of a cured product of the positive-type photosensitive resin composition according to any one of [1] to [5]. [0022] [12]. An organic EL element comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [5]. [Effects of the Invention] [0023] According to the present invention, it is possible to provide a positive-type photosensitive resin composition capable of satisfying the characteristics of developability, resolution, and heat resistance with high sensitivity in a blackened partition material.

[Best Mode for Carrying Out the Invention] The present invention will be described in detail below. [0025] The titanium black dispersion of the present invention comprises (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, and (C) a solubility parameter of 10.5 or more solvents. [0026] The positive photosensitive resin composition of the present invention comprises (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mg KOH / g, and (C) A solvent having a solubility parameter of 10.5 or more, (D) a binder resin, and (E) a quinonediazide compound. [0027] (A) Titanium black As the titanium black used in the present invention, those produced by the following methods can be used, but are not limited to these: a mixture of titanium dioxide and metallic titanium is reduced under heating in a reducing environment; Method (Japanese Patent Application Laid-Open No. 49-5432); a method of hydrolyzing titanium tetrachloride at a high temperature and reducing the obtained ultrafine titanium dioxide in a reducing environment containing hydrogen (Japanese Patent Application Laid-Open No. 57-205322) ; A method for reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Application Laid-Open No. 60-65069, Japanese Patent Application Laid-Open No. 61-201610); attaching a vanadium compound to titanium dioxide or titanium hydroxide and A method for performing high-temperature reduction in the presence of ammonia (Japanese Patent Application Laid-Open No. 61-201610) and the like. Examples of commercially available titanium blacks include titanium blacks 10S, 12S, 13R, 13M, 13M-C, 13-MT, 16M, UF-8, and red spike chemical (manufactured by Mitsubishi Materials) Tilack D, etc. These titanium blacks may be used singly or in combination of two or more kinds. [0028] Based on 100 parts by mass of the binder resin (D), the titanium black (A) is preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 8 to 15 parts by mass. When 100 parts by mass of the binder resin (D) is used as a reference, as long as the content of titanium black (A) is 3 to 30 parts by mass, the desired OD value (optical concentration) can be obtained. [0029] The average particle diameter D50 (volume basis) of titanium black (A) in the dispersion is preferably 5 to 100 nm. As long as the average particle diameter D50 is 5 to 100 nm, high light-shielding properties can be obtained. The average particle diameter D50 can be measured using a laser diffraction / scattering type particle size distribution measuring device Microtrac wave (Nikkiso Co., Ltd.). (B) Dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g The amine value used in dispersing the titanium black of the present invention is 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH A well-known dispersant can be used. Examples include phosphate esters such as trade names DISPERBYK110, DISPERBYK111 (manufactured by BYK Japan), trade names DISPARLON PW-36, DISPARLON DA-375 (manufactured by Kusumoto Kasei Co., Ltd.), polyphosphates, and polyphosphates. Phosphate-based dispersants such as esters and polyether phosphates, carboxyl-containing polymer-based dispersions such as FLOWLEN G-700, FLOWLEN G-900, and FLOWLEN GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.) Agent, trade name AJISPER PN411, AJISPER PA111 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and other higher fatty acid ester-based dispersants. Among them, a dispersant which does not have a graft chain in the skeleton, for example, trade names DISPERBYK110 and DISPERBYK111 (by BYK Japan) may be preferably used. [0031] The acid value of the dispersant is 20 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, and more preferably 40 to 150 mgKOH / g. The amine value of the dispersant is 5 mgKOH / g or less, preferably 4 mgKOH / g or less, still more preferably 3 mgKOH / g or less, and most preferably 0 mgKOH / g. As long as it has an acid value of 20 to 200 mgKOH / g and an amine value of 5 mgKOH / g or less, it has a moderate bond with titanium black and a good dispersion liquid can be easily obtained. These dispersants may be used singly or in combination of two or more kinds. [0032] As long as the effect of the present invention is not impaired, a dispersant having a salt structure, a dispersant having an ester or ether structure, a dispersant having a pigment affinity group, and the like can be used in combination. In order to improve the compatibility with the binder resin, storage stability, various physical properties or characteristics, the resin component having a functional group such as a hydroxyl group, a carboxyl group, an amine group, and a sulfo group can be used in combination. [0033] With respect to 100 parts by mass of titanium black (A), it is preferably 1 to 40 parts by mass of the dispersant (B), more preferably 2 to 30 parts by mass, and even more preferably 3 to 20 parts by mass. As long as the dispersant is 1 to 40 parts by mass based on 100 parts by mass of titanium black (A), the particles can be dispersed well. [0034] The amine value refers to the mg of potassium hydroxide equivalent to the amount of perchloric acid required to neutralize the all-basic nitrogen contained in the sample 1 g. The measurement method is as follows. The sample was dissolved in a mixed solvent of o-nitrotoluene and acetic acid, and a glass electrode and a comparative electrode were used to perform titration with a 0.1 mol / L perchloric acid solution. A graph of the relationship between the reading of a potentiometer or pH meter and the titer of a 0.1 mol / L perchloroacetic acid solution corresponding to this was prepared, and the inflection point obtained in the titration curve was set as the end point. The total amine value was calculated from the amount of the 0.1 mol / L perchloric acid acetic acid solution consumed. [0035] The so-called acid value refers to the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, and the like contained in 1 g of the sample. The measurement methods include a neutralization titration method and a potential difference titration method. In the case of the neutralization titration method, the sample is dissolved in a solvent, phenolphthalein is added as an indicator, and the acid value is determined by titration with a potassium hydroxide ethanol solution. (C) A solvent having a solubility parameter (SP value) of 10.5 or more is used as the dispersion solvent of the titanium black of the present invention, and the SP value is 10.5 to 15.0, preferably 10.5 to 13.0. It is also preferable not to contain a hydroxyl group. Specific examples of the solvent having an SP value of 10.5 or more include γ-butyrolactone (12.6), N-methyl-2-pyrrolidone (11.3), N, N-dimethylformamide (12.1), and N, N -Dimethylacetamide (10.8), etc. Among them, N-methyl-2-pyrrolidone or γ-butyrolactone is more preferable, and γ-butyrolactone is more preferable. By using a solvent having an SP value of 10.5 or more, titanium black (A) can be uniformly dispersed. These solvents may be used singly or in combination of two or more kinds. [0037] With respect to 100 parts by mass of titanium black (A), it is preferably 250 to 600 parts by mass of the solvent (C), more preferably 300 to 500 parts by mass, and more preferably 350 to 450 parts by mass. As long as the solvent is 250 to 600 parts by mass based on 100 parts by mass of titanium black (A), moderate fluidity can be obtained and the dispersed state can be easily made good. [0038] The solubility parameter is defined by the square root of the cohesive energy density of the substance, and can be used as a scale to predict the thermodynamic properties of the sample when it is mixed. The numerical values described in the Chemical Stool Application (Revised 3rd Edition, Maruzen, 1980) or the 4th edition of the Experimental Chemistry Lecture (Maruzen, 1990, p. 186) can be used. [0039] (D) Binder resin The binder resin (D) used in the positive photosensitive resin composition of the present invention is not particularly limited, but is preferably alkali-soluble having an alkali-soluble group. [0040] The alkali-soluble group contained in the binder resin is not particularly limited, and examples thereof include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphate group, and an acid anhydride group, and two or more types of alkali-soluble groups may be used. Based resin. In the present invention, the term “base-soluble” means that it is soluble in an alkali solution, for example, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. [0041] Examples of the binder resin include those obtained by adding an alkali-soluble group to, for example, an acrylic resin, a styrene resin, an epoxy resin, a polyamide resin, a phenol resin, a polyamic acid resin, or the like. . These can be used alone or in combination of two or more types of resins. [0042] Examples of the binder resin having a phenolic hydroxyl group include phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenolaralkyl resin, biphenylaralkylphenol resin, and phenol. -A well-known phenol resin such as a dicyclopentadiene copolymer resin. [0043] The binder resin (D) in the present invention preferably contains at least one component selected from the following (d1) to (d3) components. (D1) An alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble group and other polymerizable monomers as the alkali-soluble group, and examples thereof include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphate group, Acid anhydride groups, etc. An alkali-soluble resin formed from a copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer can be obtained, for example, by combining a polymerizable monomer having an alkali-soluble group with another polymerizable monomer. A polymerization initiator, a RAFT agent (Reversible Addition Fragmentation Transfer; reversible addition cracking type chain transfer agent), and the like can be produced by performing radical polymerization. Alkali-soluble copolymers of a polymerizable monomer having an alkali-soluble group and other polymerizable monomers can be added to an alkali-soluble group after the copolymer is synthesized by radical polymerization. [0045] Examples of the polymerizable functional group included in the polymerizable monomer include a radical polymerizable functional group. Specifically can be exemplified CH ₂ = CH-, CH ₂ = C (CH ₃ )-, CH ₂ = CHCO-, CH ₂ = C (CH ₃ ) CO-, -OC-CH = CH-CO-, etc. Examples of the polymerizable monomer having an alkali-soluble group include 4-hydroxystyrene, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, and β-furyl (methyl Base) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, cinnamon Acid, alpha-cyanocinnamic acid, itaconic acid, crotonic acid, propynic acid, 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzylpropenamide, 4-hydroxy Phenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimidepropionic acid, 4-maleimide butyric acid, 6-maleimide hexanoic acid, and the like. [0046] Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene. Ethers of vinyl alcohol such as acrylamide, acrylonitrile, vinyl-n-butyl ether, alkyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, dimethyl (meth) acrylate (Meth) acrylates such as aminoethyl esters, diethylaminoethyl (meth) acrylates, glycidyl (meth) acrylates, 2,2,2-trifluoroethyl (methyl ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, isofluorenyl (meth) acrylate, maleic anhydride, phenylmaleimide, cyclohexylmaleimide N-substituted maleimidines such as imines. Here, "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". [0047] As the polymerizable monomer having an alkali-soluble group, 4-hydroxyphenylmethacrylate is used, and as the other polymerizable monomer, a polymer selected from phenylmaleimide and cyclohexylmaleimide is used. At least one of the groups formed by imines is particularly preferred. By using a resin obtained by radically polymerizing these polymerizable monomers, shape retention and developability can be improved, and at the same time, it can contribute to reduction of outgassing. [0048] When an alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer is produced by radical polymerization, the polymerization initiator is not limited to the following, Can use 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl2,2'-azobis (2-methylpropionate) ), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile) (AVN), etc. Dicumyl diperoxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, tert-butyl dicumyl peroxide, di-tert-butyl Peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc., a peroxide polymerization initiator having a 10-hour half-life temperature of 100 to 170 ° C, or Peroxide of benzamidine peroxide, lauryl peroxide, 1,1'-di (t-butylperoxy) cyclohexane, t-butyl peroxypivalate, etc. Polymerization initiator. The amount of the polymerization initiator used is generally 0.01 parts by mass or more, 0.05 parts by mass or more, 0.5 parts by mass or more, 40 parts by mass or less, 20 parts by mass or less, based on 100 parts by mass of the polymerizable monomer mixture. The content is preferably not more than mass parts. [0049] The RAFT agent is not limited to the following, and a thiocarbonylthio compound such as a dithioester, a dithiocarbamate, a trithiocarbonate, or a xanthate can be used. The RAFT agent may be used in a range of 0.005 to 20 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer, and it is preferable to use it in a range of 0.01 to 10 parts by mass. [0050] As the binder resin (D) of the positive photosensitive resin composition of the present invention, if 4-hydroxyphenylmethacrylate, phenylmaleimide and cyclohexylmaleimide are used, In the case of a free-radical copolymer or a free-radical copolymer of 4-hydroxyphenylmethacrylate and cyclohexylmaleimide, the number average molecular weight is preferably in the range of 1,000 to 30,000, and more preferably 3,000. The range is ~ 20,000, more preferably 10000 ~ 15000. When the molecular weight is 1,000 or more, since alkali solubility is moderate, it is suitable as a resin for a photosensitive material. When the molecular weight is 30,000 or less, developability is good. (D2) The alkali-soluble resin of the alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group, for example, a compound having at least two epoxy groups in one molecule (hereinafter referred to as "epoxy It is obtained by reacting an epoxy group of the compound ") with a carboxyl group of a hydroxybenzoic acid. However, the reaction rate is adjusted so that an epoxy group remains. [0052] In the positive photosensitive resin composition of the present invention, the alkali-soluble resin has an epoxy group, and reacts with a phenolic hydroxyl group and crosslinks when heated, thereby improving chemical resistance and heat resistance. The merits of such properties as phenolic hydroxyl group have the advantage of being so-called soluble in alkaline aqueous solution. [0053] A reaction example in which one epoxy group of the epoxy compound is reacted with a carboxyl group of a hydroxybenzoic acid to form a compound having a phenolic hydroxyl group is shown by the following reaction formula 1. [0054] [0055] Examples of the compound having at least two epoxy groups in one molecule include phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol epoxy resin, and biphenyl epoxy resin. Resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, and the like. These epoxy compounds may be those having two or more epoxy groups in one molecule, and only one kind may be used, or two or more kinds may be used in combination. However, since these compounds are thermosetting, as the general knowledge of those with ordinary knowledge in the technical field, they should understand that there is no difference due to differences in the presence or absence of epoxy groups, the type of functional groups, and the degree of polymerization. Recorded. An example of the structure of a novolak-type epoxy resin is shown in Formula (1). R in the formula (1) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 50. [0056] [0057] Examples of the phenol novolac-type epoxy resin include EPICLON (registered trademark) N-770 (manufactured by DIC (stock)), jER (registered trademark) -152 (manufactured by Mitsubishi Chemical (stock)), and the like. [0058] Examples of the cresol novolac epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC) and EOCN (registered trademark) -102S (manufactured by Nippon Kayaku Co., Ltd.). [0059] Examples of the bisphenol-type epoxy resin include jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), and YD-128 (trade name, Nippon Steel & Sumikin Chemical Co., Ltd.) ) And other bisphenol A-type epoxy resins, jER (registered trademark) 806 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (trade name, Nippon Steel & Sumikin Chemical Co., Ltd.), and other bisphenol F Type epoxy resin and so on. [0060] Examples of the biphenyl type epoxy resin include jER (registered trademark) YX-4000, jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation), and the like. [0061] Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (trade name, manufactured by DIC (Korea) Co., Ltd.), and the like. [0062] Examples of the alicyclic epoxy resin include EHPE (registered trademark) -3150 (manufactured by DAICEL Chemical Industry Co., Ltd.). [0063] As the heterocyclic epoxy resin, for example, TEPIC (registered trademark), TEPIC (registered trademark) -L, TEPIC (registered trademark) -H, TEPIC (registered trademark) -S (Nissan Chemical Industry Co., Ltd.)制) and so on. [0064] The so-called "hydroxybenzoic acid" refers to a compound in which at least one of positions 2 to 6 of benzoic acid is substituted with a hydroxyl group, and examples thereof include salicylic acid, 4-hydroxybenzoic acid, 2, 3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzene Formic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, and the like are preferred from the viewpoint of improving alkali developability. Hydroxybenzoic acids. These hydroxybenzoic acids may be used alone or in combination of two or more. [0065] The aforementioned method for obtaining a compound having an alkali-soluble phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid, uses 0.2 to 0.9 equivalent of the hydroxybenzoic acid to 1 equivalent of the epoxy group of the epoxy compound, and It is preferably 0.4 to 0.8 equivalents, and more preferably 0.5 to 0.7 equivalents. As long as the hydroxybenzoic acid is 0.2 equivalent or more, sufficient alkali solubility can be exhibited, and as long as it is 0.9 equivalent or less, an increase in molecular weight due to side reactions can be suppressed. [0066] To promote the reaction, a catalyst may be used. The amount of the catalyst used is 0.1 to 10 parts by mass relative to 100 parts by mass of a reaction raw material mixture made of an epoxy compound and hydroxybenzoic acid. The reaction temperature is 60 to 150 ° C, and the reaction time is 3 to 30 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, Triphenylphosphine, chromium octoate, zirconium octoate, etc. [0067] The number average molecular weight of the aforementioned alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group is preferably in the range of 500 to 8000, more preferably in the range of 1500 to 5000, and more preferably in the range of 2000 to 3500. range. As long as the molecular weight is 500 or more, since the solubility in an alkaline aqueous solution is appropriate, the resin as a photosensitive material is good, and as long as the molecular weight is 8000 or less, coatability and developability are good. (D3) Polyalkenyl phenol resin The polyalkenyl phenol resin can be alkenyl etherified by hydroxyl groups of a well-known phenol resin, and the Claisen rearrangement of the alkenyl ether group can be further performed. And available. The polyalkenyl phenol resin preferably has a structure of formula (2). By containing such a resin, the developing characteristics of the obtained photosensitive resin composition can be improved, and at the same time, it can contribute to the reduction of outgassing. [0069] In formula (2), R ¹ , R ² And R ³ Are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by formula (3), an alkoxy group or a hydroxyl group having 1 to 2 carbon atoms, [0071] (In formula (3), R ⁶ , R ⁷ , R ⁸ , R ⁹ And R ¹⁰ It independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, respectively. Carbon atom bond. ) And R ¹ , R ² And R ³ At least one of them is an alkenyl group represented by formula (3); Q is formula -CR ⁴ R ⁵ -An alkylene group, a cycloalkyl group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensation ring, or a divalent group combining these, R ⁴ And R ⁵ Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms; 1 molecule If there are two or more structures of the formula (2), the structures of the respective formulas (2) may be the same or different. R of Formula (2) ¹ , R ² And R ³ Represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by formula (3), an alkoxy group or a hydroxyl group having 1 to 2 carbon atoms, and R ¹ , R ² And R ³ At least one of them is an alkenyl group represented by formula (3). R of Formula (2) ¹ , R ² And R ³ In the specific examples of the alkyl group having 1 to 5 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n- Amyl and others. Specific examples of the alkoxy group having 1 to 2 carbon atoms include a methoxy group and an ethoxy group. In the alkenyl group represented by formula (3), R ⁶ , R ⁷ , R ⁸ , R ⁹ , And R ¹⁰ It is a specific example of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, respectively, as specific examples of an alkyl group having 1 to 5 carbon atoms Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, etc., as a cycloalkane having 5 to 10 carbon atoms Examples include cyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl. Specific examples of aryl groups having 6 to 12 carbon atoms include phenyl, methylphenyl, ethylphenyl, Biphenyl, naphthyl, etc. As R ⁶ , R ⁷ , R ⁸ , R ⁹ , And R ¹⁰ Preferably, they are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As the alkenyl group represented by the preferred formula (3), in terms of reactivity, allyl, metallyl, and allyl are preferred. Then, take R ¹ , R ² And R ³ Any one of them is allyl or methallyl, and the other two are preferably hydrogen atoms. Q of formula (2) is formula -CR ⁴ R ⁵ -An alkylene group, a cycloalkyl group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group combining these, R ⁴ And R ⁵ Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, and n-pentyl. Wait. Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl, allyl, butenyl, pentenyl, and hexenyl. Examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl. Specific examples of the aryl group having 6 to 12 carbon atoms include phenyl, methylphenyl, ethylphenyl, biphenyl, and naphthyl. R ⁴ And R ⁵ It is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the hydrogen atom is the most preferable. [0077] Here, specific examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, and the like. Specific examples of the divalent organic group having an aromatic ring include phenylene, methylphenyl, naphthyl, biphenyl, fluorenyl, anthracenyl, phenylene, 4,4'- Methylene diphenyl, a group represented by formula (4), and the like. [0078] [0079] Specific examples of the divalent organic group having an alicyclic condensed ring include dicyclopentadienyl and the like. [0080] As the binder resin (D) used in the photosensitive resin composition of the present invention, when a polyalkenyl phenol resin is used, it is particularly preferable in terms of alkali developability and outgassing. Polyalkenyl phenol resin, for example, Q of formula (2) is -CH ₂ -The person having the structure represented by the formula (5). [0081] In formula (5), R ¹ , R ² And R ³ Is the same as in formula (2). [0083] Preferred R ¹ , R ² And R ³ Is the better R in formula (2) ¹ , R ² And R ³ For the same. [0084] It is preferable that 50 to 100 mole% in the polyalkenyl phenol resin is a structural unit represented by formula (2) or formula (5), and further preferably 70 to 100 mole%, more preferably 85 ~ 100 mole%. As long as 50 mol% or more in the polyalkenyl phenol resin is a structural unit represented by formula (2) or formula (5), heat resistance can be improved, so it is preferable. The phenolic hydroxyl group in the polyalkenyl phenol resin must have a certain amount or more of phenolic hydroxyl groups from the viewpoint of alkali developability in order to be ionizable in the presence of a basic compound and soluble in water. Therefore, the polyalkenyl phenol resin containing a structure represented by Formula (5) is particularly preferably a polyalkenyl phenol resin having a structural unit represented by Formula (5) and a structural unit represented by Formula (6). [0085] In formula (6), R ^1a , R ^2a And R ^3a Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. [0087] In the polyalkenyl phenol resin having the structural unit represented by Formula (5) and the structural unit represented by Formula (6), the number of structural units represented by Formula (5) is set to x, and the formula ( 6) When the number of structural units represented is set to y, it is 0.5 ≦ x / (x + y) <1, 0 <y / (x + y) ≦ 0.5, (x + y) is preferably 2 to 3000, and more preferably 2 ~ 2000, more preferably 2 ~ 1000. [0088] When a polyalkenyl phenol resin is used as the binder resin (D), the preferred number average molecular weight is 500 to 5000, more preferably 800 to 3000, and more preferably 1000 to 1500. As long as the number average molecular weight is 500 or more, the alkali development speed is appropriate, and the difference in the dissolution speed between the exposed and unexposed areas is sufficient, so the resolution is good, and if it is 5,000 or less, the alkali developability is good. [0089] As the binder resin, one kind of resin may be used alone, or two or more kinds of resins may be used in combination. Among them, it is preferable to include at least one selected from the resin components (d1) to (d3), and it is more preferable to include at least (d1) and (d2). With respect to 100 parts by mass of the binder resin (D), the total amount of one or more components selected from (d1) to (d3) is preferably 1 to 100 parts by mass, and more preferably 10 to 100 parts by mass , More preferably 30 to 100 parts by mass. With respect to 100 parts by mass of the binder resin (D), if the total component selected from one or more of (d1) to (d3) is 1 to 100 parts by mass, the heat resistance of the resin composition is good. [0090] For example, the binder resin (D) may be used in combination with the resin components (d1) and (d2), etc., and may be used in any combination, or a plurality of components (d1) to (d3) may be used in combination. [0091] For example, three types of an alkali-soluble copolymer (d1) having an alkali-soluble group, an alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group, and a polyalkenylphenol resin (d3) can be used in combination. When 3 types are used in combination, the proportion of the alkali-soluble copolymer (d1) having an alkali-soluble group in the binder resin (D) is preferably 5 to 60% by mass, and the alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group ) Is preferably 35 to 90% by mass, and the ratio of the polyalkenyl phenol resin (d3) is preferably 5 to 60% by mass. [0092] If the alkali-soluble copolymer (d1) having an alkali-soluble group is also equivalent to the alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group, it is set as an alkali-soluble copolymer having an alkali-soluble group. (d1). When the alkali-soluble copolymer (d1) having an alkali-soluble group also corresponds to the polyalkenyl phenol resin (d3), it is set to operate as an alkali-soluble copolymer (d1) having an alkali-soluble group. That is, the alkali-soluble resin (d2) and the polyalkenylphenol resin (d3) having an epoxy group and a phenolic hydroxyl group are set to exclude those equivalent to the alkali-soluble copolymer (d1) having an alkali-soluble group. (E) Quinonediazide Compound The positive photosensitive resin composition of the present invention contains a quinonediazide compound as a radiation-sensitive compound. Examples of the quinonediazide compound include: a quinonediazide sulfonic acid is bonded to a polyhydroxy compound with an ester; a quinonediazide sulfonic acid is bonded to a polyamine compound through a sulfonamide The quinonediazide sulfonic acid is formed by ester bonding, sulfonamide bonding, or ester bonding and sulfonamide bonding to a polyhydroxypolyamine compound. From the viewpoint of comparison between the exposed portion and the unexposed portion, it is preferable that 20 to 100 mole% of the functional groups of the polyhydroxy compound or the polyamine compound is substituted with quinonediazide. By using such a quinonediazide compound, a positive-type photosensitive resin composition that is sensitive to the i-ray (365 nm), h-ray (405 nm), and g-line (436 nm) of a general ultraviolet mercury lamp can be obtained. [0094] As the polyhydroxy compound, 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, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are the trade names, manufactured by 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 Organic Materials Industry ( )), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl -P-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP -AP (trade name, Honshu Chemical Industry Co., Ltd. ) 制), etc., but not limited to Wait. [0095] As specific examples of the quinonediazide compound, 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonic acid of the polyhydroxy compound may be exemplified. ester. [0096] When a quinonediazide compound is exposed to ultraviolet light or the like, a carboxyl group is formed through a reaction represented by the following reaction formula 2. By generating a carboxyl group, the exposed portion (film) becomes soluble in an alkaline solution and exhibits alkali developability. [0097] [0098] In the photosensitive resin composition of the present invention, the content of the quinonediazide compound varies depending on the quinonediazide compound used, but based on 100 parts by mass of the binder resin (D), It is preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 7 to 10 parts by mass. Based on 100 parts by mass of the binder resin (D), if it is 3 parts by mass or more, the alkali developability is good. As long as it is 20 parts by mass or less, the heating reduction rate at 300 ° C or higher does not easily increase. (F) Arbitrary component The positive photosensitive resin composition of the present invention may include a thermosetting agent, a surfactant, a coloring agent other than (A), and a solvent other than (C) as optional components. The arbitrary component (F) is defined as not equivalent to (A) to (E). (F1) Thermosetting agent As the thermosetting agent, a thermal radical generator can be used. Examples of the preferred thermal radical generator include organic peroxides, and specifically, dicumyl diperoxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) (Oxy) hexane, tert-butyl dicumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide An organic peroxide or the like having a 10-hour half-life temperature of 100 to 170 ° C. [0101] The content of the thermosetting agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and more preferably 3 parts by mass or less with respect to 100 parts by mass of the binder resin (D). (F2) Surfactant The positive photosensitive resin composition of the present invention may contain a surfactant as a further optional component, for example, in order to improve coatability or to improve developability of a coating film. [0103] Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl Ethers, polyoxyethylene nonylphenyl ethers and other polyoxyethylene aryl ethers; polyoxyethylene dilaurates, polyoxyethylene dialkyl esters, and other nonionic systems Surfactant; MegaFace (registered trademark) F-251, same as F-281, same as F-430, same as F-444, same as R-40, same as F-553, same as F-554, same as F-555, same as F -556, same as F-557, same as F-558 (the above are the trade names, DIC (stock) system), Surflon (registered trademark) S-242, the same as S-243, the same as S-385, the same as S-386, the same S-420, fluorine-based surfactants such as S-611 (the above are trade names, manufactured by ACG Seimi Chemical); organic silicone polymers KP323, KP326, KP341 (the above are trade names, Shin-Etsu Chemical Industry (Share) system) and so on. These can be used alone or in combination of two or more. [0104] Such a surfactant is prepared in an amount of 2 parts by mass or less based on 100 parts by mass of the binder resin (D), and is preferably 1 part by mass or less, and more preferably 0.5 part by mass. the following. (F3) Other Coloring Agent The positive photosensitive resin composition of the present invention may contain a coloring agent other than titanium black (A) as a further optional component. Examples of such coloring agents include dyes, organic pigments, and inorganic pigments, and they can be used according to the purpose. However, the content of the toner other than titanium black (A) is set within a range that does not impair the effects of the present invention. [0106] Specific examples of the dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, ketoacid dyes, merocyanin dyes, and stilbene Dyes, diphenylmethane dyes, triphenylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, capture acid anhydride dyes, nickel complex dyes, and perylene dyes. [0107] Examples of the pigment include black pigments such as carbon black, carbon nanotubes, acetylene black, black lead, iron black, aniline black, and CIpigment yellow 20, 24, 86, 93, 109, 110, 117, 125, and 137. , 138, 147, 148, 153, 154, 166, CIpigment orange36, 43, 51, 55, 59, 61, CIpigment red9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217 , 220, 223, 224, 226, 227, 228, 240, CIpigment violet 19, 23, 29, 30, 37, 40, 50, CIpigment blue15, 15: 1, 15: 4, 22, 60, 64, CIpigment green7, CIpigment brown 23, 25, 26, etc. (F4) Other Solvents The positive-type photosensitive resin composition of the present invention is used in a solution state dissolved in a solvent. The positive photosensitive resin composition of the present invention can be adjusted to a viscosity suitable for various coating methods by the amount of the solvent. A suitable solid content concentration may be adopted according to the purpose of use. For example, the solid content concentration may be 1 to 60% by mass, preferably 3 to 50%, and more preferably 5 to 40%. In addition to the solvent (C) having a solubility parameter (SP value) of 10.5 or more, other solvents may be added in an amount of 5% by mass or less of the entire solvent. [0109] Examples of the other solvents include glycol ethers such as ethylene glycol dimethyl ether and ethylene glycol methyl ethyl ether, and glycol ethane such as methylcellulose acetate and ethelium acetate. Diethylene glycols such as diethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, methyl amyl ketone, and cyclic ring Ketones such as hexanone, 4-hydroxy-4-methyl-2-cyclopentanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and the like. These solvents may be used alone or in combination of two or more. [Production Method of Titanium Black Dispersion Liquid] The titanium black dispersion liquid of the present invention can contain (A) titanium black, (B) an amine value of 5 mgKOH / g or less and an acid value of 20 ~ 200 mg KOH / g dispersant and (C) a solvent having a solubility parameter of 10.5 or more were prepared. [0111] The dispersing machine for disintegrating and dispersing titanium black is not particularly limited, and examples thereof include a ball type, a kneader, and a paddle type such as a ball mill, a sand mill, a bead mill, a paint shaker, and a swing mill. Blade types such as mixers, planetary mixers, Henschel mixers, roller types such as triaxial roller mixers, other Raikai mixers, colloid mills, ultrasonics, homogenizers, rotary / Revolution mixer, etc. Among them, a ball type that can stably and finely disperse in a short period of time is preferred. Examples of the material used for the ball-type ball include glass, silicon nitride, aluminum oxide, zircon, zirconia, and steel. As the bead diameter, a general shape having a diameter of 0.03 to 25 mm can be used. In terms of miniaturization, a small diameter of 5 mm or less is preferred. [0112] The order of addition when preparing a dispersion is not particularly limited, but in order to obtain a good dispersion, the following order is preferred. [0113] First, the solvent (C) and the dispersant (B) are uniformly dispersed. If the solvent and the dispersant are not uniformly dispersed in advance, a region having a high concentration of the local dispersant will be generated, and defects such as agglomeration of particles are likely to occur. Next, the required amount of titanium black (A) is placed in a solution prepared in advance, and finally beads are placed. If titanium black is visible, it can be pre-dispersed. For the purpose of compatibility with the resin and suppressing re-aggregation of titanium black, a binder resin or other resin components may be used. [0114] [Manufacturing method of positive photosensitive resin composition] The positive photosensitive resin composition of the present invention is preferably: first, titanium black (A), a dispersant (B), and a solvent (C) are mixed to A titanium black dispersion is prepared, and thereafter, a binder resin (D), a quinonediazide compound (E), and an optional component (F) are further mixed to produce it. The method for preparing the titanium black dispersion is the same as described above. [0115] The order in which the titanium black dispersion is mixed with a binder resin, a quinonediazide compound, and any components is not particularly limited. For example, the binder resin is dissolved in a solvent other than the solvent (C) or (C). Then, the solution is mixed with additives such as quinonediazide compound, titanium black dispersion liquid, required thermal hardener, surfactant, etc. at a specified ratio, thereby preparing a positive photosensitive resin composition in a solution state. . [0116] When a titanium black dispersion is mixed with a binder resin, a quinonediazide compound, and any components, the mixer is not particularly limited, and examples thereof include a ball mill, a sand mill, a bead mill, a paint shaker, and a swing type. Ball types such as mills, kneaders, paddle mixers, planetary mixers, Henschel mixers, blade types, roll types such as triaxial roller mixers, etc., as other crushers, colloid mills, Ultrasound, homogenizer, rotary / revolution mixer, etc. When used at a laboratory level, mechanical stirrers are preferred because they are stable and can be mixed in a short period of time. The stirring wing used for stirring can be appropriately selected from fan type, propeller type, cross type, turbine type, and dragonfly type. A resin composition can be obtained by mixing a titanium black dispersion liquid, a binder resin solution, and the like, and stirring the mixture at room temperature for 1 to 10 minutes at a number of revolutions of 10 to 1000 rpm. [0117] The composition liquid prepared as described above is preferably filtered before use. Examples of the filtering means include a microporous filter having a pore diameter of 0.05 to 1.0 μm. [0118] The positive-type photosensitive resin composition of the present invention prepared in this manner is also excellent in storage stability over a long period of time. [Pattern Forming and Hardening Method] When the positive-type photosensitive resin composition of the present invention is used for radiation lithography, first, the positive-type photosensitive resin composition of the present invention is coated on the surface of a substrate, and The coating film can be formed by removing the solvent by means such as heating. The method for applying the positive photosensitive resin composition to the substrate surface is not particularly limited, and various methods such as a spray method, a roll coating method, a slit method, and a spin coating method can be used. [0120] After the positive photosensitive resin composition of the present invention is applied to the surface of a substrate, the solvent is usually dried by heating (pre-baking) to form a coating film. The heating conditions will vary depending on the type of each component, the blending ratio, etc., and usually heat treatment is performed at 70 to 130 ° C for a specified time (for example, 1 to 20 minutes on a hot plate and 3 to 60 minutes in an oven). Thereby, a coating film can be obtained. [0121] Next, the pre-baked coating film is irradiated with radiation (for example, visible light, ultraviolet rays, far ultraviolet rays, etc.), etc. (exposure step) through a mask of a specified pattern, and then developed with a developing solution, and will not be necessary. The part is removed to form a coating film of a specified pattern (development step). When naphthoquinonediazide sulfonate is used as the positive photosensitive compound, the preferable radiation is ultraviolet to visible light having a wavelength of 250 to 450 nm. [0122] As the developing solution, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia can be used; first amines such as ethylamine and n-propylamine can be used; Primary amines; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; dimethylethanolamine and triethanolamine And other alcohol amines; quaternary ammonium salts of tetramethylamine hydroxide, tetraethylamine hydroxide, choline, etc .; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7 -Alkaline aqueous solutions such as undecene, 1,5-diazabicyclo [4.3.0] -5-nonane and other cyclic amines. The concentration is not particularly limited, but is preferably 0.5 to 5.0% by mass. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol, a surfactant, and the like are added to the alkali aqueous solution to form an aqueous solution, and the aqueous solution may be used as a developing solution. The development time is usually 30 to 180 seconds, and the development method can be any of a dripping method, a rinsing method, and a dipping method. After development, rinse with running water for 30 to 90 seconds, remove unnecessary parts, and air dry with compressed air or compressed nitrogen to form a pattern. After that, the pattern can be heated by a heating device such as a hot plate or an oven at a predetermined temperature (for example, 120 to 350 ° C) for 20 to 200 minutes to obtain a coating film, but the temperature can also be increased in stages. (Heat treatment step). [0123] The present invention is applicable to a method for manufacturing a radiation lithographic structure, which includes (1) a coating step of coating the positive photosensitive resin composition on a substrate, and (II) coating the coated positive photosensitive resin composition. Drying step for removing the solvent in the type photosensitive resin composition, (III) exposure step for radiating radiation through a photomask, (IV) development step for pattern formation by alkali development, and (V) 100 to 350 The temperature is ℃ to perform the heat treatment step of heating. This method enables formation of a partition wall and an insulating film for an organic EL element. [0124] The present invention provides a partition wall of an organic EL element made of a cured product of the positive photosensitive resin composition. [0125] The present invention provides an insulating film of an organic EL element made of the cured product of the positive-type photosensitive resin composition. [0126] The present invention is an organic EL device including a cured product of the positive photosensitive resin composition. [Examples] [0127] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to the examples. (1) Synthesis of Binder Resin [Production Example 1] Production of alkali-soluble copolymer (d1) having an alkali-soluble group 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko Corporation) ) 76.8 g, 14.4-g N-phenylmaleimide (manufactured by Japan Catalyst), 14.4g N-cyclohexylmaleimide (manufactured by Japan Catalyst), as polymerization start V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 1.80 g of S-dodecyl-S '-(α, α'-dimethyl-α "-acetic acid) trithio as RAFT agent 1.95 g of carbonate ("723010" manufactured by Sigmaaldrich) was completely dissolved in 180 g of 1-methoxy-2-propyl acetate (manufactured by DAICEL). The obtained solution was dropped into a 500 mL three-necked flask over 1 hour, and 180 g of 1-methoxy-2-propyl acetate (made by DAICEL) heated to 85 ° C. under a nitrogen atmosphere, and thereafter The reaction was allowed to proceed at 85 ° C for 3 hours. The reaction solution cooled to room temperature was dropped into 1200 g of toluene to precipitate a polymer. The precipitated polymer was recovered by filtration and vacuum-dried at 80 ° C. for 7 hours to recover 104.4 g of a white powder. This was dissolved in γ-butyrolactone to obtain a resin liquid (resin liquid 1) having a solid content of 20% by mass. The number average molecular weight of the obtained reactant was 14,100, and the weight average molecular weight was 24,900. [Production Example 2] Production of alkali-soluble resin (d2) having epoxy group and phenolic hydroxyl group A 300 mL three-necked flask was charged with γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent. 60 g, 42 g of EPICLON (registered trademark) N-695 (cresol novolac epoxy resin, epoxy equivalent 210 made by DIC) is a compound having at least two epoxy groups in one molecule, under a nitrogen environment Dissolve at 60 ° C. To this, 15.5 g (0.10 mol, 0.5 equivalent to 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as hydroxybenzoic acids are added as a reaction catalyst. 0.2 g (0.76 mmol) of phenylphosphine (produced by Beixing Chemical Industry Co., Ltd.) was reacted at 110 ° C. for 12 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 recover 260 g (resin solution 2). The number average molecular weight of the obtained reactant was 2,400, and the weight average molecular weight was 5,600. [Production Example 3] Production of polyallylphenol resin (d3) was placed in a 1000 mL three-necked flask: 100 g of pure water was dissolved in 201 g (1.45 mol) of potassium carbonate (manufactured by Soda Co., Ltd.) ), 100.0 g of phenol novolac resin "SHONOL (registered trademark) BRN-5834Y" (manufactured by Aica SDK Phenol), 16 g of isopropanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the reactor Replace with nitrogen and heat to 85 ° C. Under a nitrogen stream, 84 g (0.84 mol) of allyl acetate (manufactured by Showa Denko Corporation) and 50% water content of a 5% -Pd / C-STD type (dispersed metal palladium in activated carbon at a content of 5% by mass) were added. In addition, the stabilized allylation reaction catalyst obtained by dissolving activated carbon in which the aforementioned metal palladium is dispersed so as to be 50% by mass, manufactured by NECHEMCAT (stock) 0.40 g (palladium: 0.188 mmol) And 2.45 g (9.4 mmol) of triphenylphosphine (the activator of the aforementioned palladium-containing allylation reaction catalyst, manufactured by Beixing Chemical Industry Co., Ltd.), in a nitrogen environment, the temperature was raised to 105 ° C. and allowed to react 4 Hours, after which 14 g (0.14 mol) of allyl acetate was added to ¹ H-NMR was used to confirm the formation of allyl ether groups while heating was continued for 10 hours. Thereafter, the stirring was stopped, and the organic layer and the aqueous layer were separated into two layers by standing. Pure water (200 g) was added until the precipitated salt was dissolved, and then 200 g of toluene was added. The temperature was maintained at 80 ° C or higher, and no white precipitate was precipitated. After that, filtration (using a 1 μm membrane filter (manufactured by ADVANTEC) KST-142-JA) was pressurized (0.3 MPa)) to recover Pd / C. This filter residue was washed with 100 g of toluene, and the aqueous layer was separated. The organic layer was washed twice with 200 g of water, and it was confirmed that the aqueous layer was neutral. The organic layer was separated, and then concentrated under reduced pressure to obtain a phenol novolak-type polyallyl ether resin as a brown oil. [0131] Next, 125 g of a phenol novolak-type polyallyl ether resin was placed in a 500 mL flask equipped with a mechanical stirrer, and diluted with 130 g of γ-butyrolactone (manufactured by Wako Pure Chemical Industries, Ltd.). The temperature was raised to 170 ° C while stirring at 300 rpm. ¹ H-NMR was used to confirm the decrease in the allyl ether group, and the Claisen rearrangement reaction was allowed to proceed for 30 hours. After the reaction, the solution was returned to room temperature and diluted with γ-butyrolactone to a solid content of 20% by mass to obtain a phenol novolac polyallylphenol resin solution (resin solution 3). The solid content of this polyallyl phenol resin was 132, the number average molecular weight was 1,100, and the weight average molecular weight was 9,900. The resin is a polyalkenyl phenol resin having a structural unit represented by the formula (5) and a structural unit represented by the formula (6), in the formula (5), R ¹ , R ² , R ³ One of them is an allyl group, and the other is a hydrogen atom. In the formula (6), R ^1a , R ^2a , R ^3a Is a hydrogen atom, x / (x + y) is 0.85, and y / (x + y) is 0.15. [0133] The weight average molecular weight and the number average molecular weight were calculated using the following measurement conditions using a polystyrene standard material to create a calibration curve. Device 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 [0134 (2) The raw materials were used as (D) binder resins. Resin methods 1 to 3 synthesized in Production Examples 1 to 3 and novolac phenol resin BRM-595M (manufactured by Aica SDK Phenol) were used for the reprecipitation method. The low-molecular-weight component was removed, and a resin liquid 4 prepared by using γ-butyrolactone to have a solid content of 20% by mass was used. Table 1 shows materials other than the (D) binder resin. [0135] (3) Production of titanium black dispersion [Example 1] 39 g of γ-butyrolactone and 1 g of dispersant DISPERBYK-111 were added and mixed in a 150 cc integral spiral storage container (made of stainless steel). Here, 10 g of titanium black UF-8 with a primary particle diameter of 20 nm was placed and mixed, and then zirconia beads (trade name: YTZ ball, Nikkato) 200 g), sealed so as not to leak, install this in a paint shaker (manufactured by Asada Iron Works Co., Ltd.), and disperse it for 10 hours. The obtained dispersion was filtered through a microporous filter having a pore diameter of 0.45 μm and 0.22 μm to obtain a titanium black dispersion. Hereinafter, the obtained titanium black dispersion is referred to as dispersion liquid 1. [Examples 2 to 5, Comparative Examples 1 to 5] A titanium black dispersion was obtained in the same procedure as in Example 1 in accordance with the preparations described in Table 2 and the diameter of the zirconia beads. Hereinafter, the titanium black dispersion liquids obtained in Examples 2 to 5 are referred to as dispersion liquids 2 to 5, and the titanium black dispersion liquids obtained in Comparative Examples 1 to 5 are hereinafter referred to as dispersion liquids C1 to C5. (4) Production of positive-type photosensitive resin composition [Example 6] 50 parts by mass of the resin solution 1 and 125 parts by mass of the resin solution 2 were added as the quinonediazide compound obtained in Production Examples 1 to 2. 15 parts by mass of TS-130A and 100 parts by mass of the titanium black dispersion 1 obtained in Example 1 and 7.5 parts by mass of a 1% by mass solution (diluted with γ-butyrolactone) of SurflonS-386 as a surfactant, and Further mixing. After visually confirming a uniform state, filtration was performed using a microporous filter having a pore size of 0.22 μm to prepare a positive-type photosensitive resin composition having a solid content concentration of 24%. [Examples 7 to 12 and Comparative Examples 6 to 8] A positive photosensitive resin composition was prepared in the same procedure as in Example 6 by blending as shown in Table 3. (5) Evaluation For the titanium black dispersions produced in Examples 1 to 5 and Comparative Examples 1 to 5, the average particle diameter of the titanium black was evaluated. However, since the titanium black dispersion liquid systems of Comparative Examples 1 and 5 could be visually confirmed to aggregate, they were not measured. The results are shown in Table 2. [0141] [Average particle diameter of titanium black] 20 g of γ-butyrolactone was weighed, one drop of the dispersion was added, and the laser diffraction / scattering type particle size distribution measuring apparatus Nanotrac wave was added after mixing for 1 minute with ultrasonic waves. The cells of (Ex) (Nikkiso Co., Ltd.) were filled to measure the average particle diameter D50 of the dispersed titanium black. [0142] The positive-type photosensitive resin compositions produced in Examples 6 to 12 and Comparative Examples 6 to 8 were subjected to alkali developability, pattern formation, pattern linearity, light-shielding property (OD value), and prebaking. Evaluation of appearance, surface roughness Ra, and heat resistance (weight reduction rate) after baking. The results are shown in Table 3. The evaluation method is as follows. [Alkali developability, pattern formation, pattern linearity] The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated so that the dry film thickness became about 1.5 μm. It was placed on a glass substrate (size 100 mm × 100 mm × 1 mm), and the solvent was dried at 120 ° C. for 80 seconds. Furthermore, an exposure device (trade name Multilight ML-251A / B, manufactured by Ushio Electric Co., Ltd.) equipped with an ultra-high pressure mercury lamp was further used, and a photomask made of quartz (patterned to 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200μm, 500μm line width & pitch mask), 100mJ / cm ² Exposure. The exposure amount was measured using an integrated ultraviolet light meter (brand name: UIT-150, light receiving unit UVD-S365, manufactured by Ushio Electric Co., Ltd.). The exposed coating film was subjected to alkaline development with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 60 seconds using a rotary developing device (AD-1200, manufactured by Takisawa Industries, Ltd.) to evaluate the alkali developability . Observation was performed using an optical microscope (VH-Z250, manufactured by Keyence Co., Ltd.), and it was judged that there was no residue after the alkali development, and that the residue was judged to be bad. [0144] The pattern formability was evaluated by measuring the line width of the pattern after alkali development. Using an optical microscope (VH-Z250, manufactured by Keyence Co., Ltd.), the line width of the photomask and the pitch pattern of the pattern were set at 10 μm, and the magnification was confirmed using a microscope with a magnification of 1000 times. As long as the line width of the pattern after the alkali development and the line width of the spaced pattern is 1: 1, it is judged to be good, and the line width of the line part is within ± 10%, and the others are judged to be acceptable. Defective to evaluate pattern formation. [0145] The linearity of the pattern was evaluated by determining that the pattern was straight, that the pattern was good, that the waveform was acceptable, and that the other patterns were bad. [0146] [OD value] The positive-type photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated on a glass substrate (100 mm × 100 mm × 1 mm) so as to be about 1.5 μm, The solvent was dried by heating on a hot plate at 120 ° C. for 80 seconds. Thereafter, a coating film was obtained by hardening it at 250 ° C. for 60 minutes in a nitrogen atmosphere. The hardened glass coating film was measured using a penetration densitometer (BMT-1, manufactured by SAKATA INX ENG.), And was corrected by using only the OD value of the glass, and converted into an OD value per 1 μm of the coating film thickness. . The thickness of the coating film was measured using a surface roughness meter (SURFCOM 130A, manufactured by Tokyo Precision Co., Ltd.). [Appearance after Pre-Baking] The positive-type photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were spin-coated on a glass substrate (size 100 mm × 100 mm ×) so as to be about 1.5 μm. 1 mm), the solvent was dried by heating on a hot plate at 120 ° C. for 80 seconds. The appearance evaluation after pre-baking is based on visual observation of the dried coating film surface. Those who have a uniform gloss surface are judged to be good, those with uneven gloss are judged to be acceptable, and those who have light penetrable holes are judged to be acceptable. As bad. [Surface Roughness Ra] The positive photosensitive resin composition of Examples 6 to 12 and Comparative Examples 6 to 8 was spin-coated on a glass substrate (size 100 mm × 100 mm) so that the dry film thickness was about 1.5 μm. × 1 mm), the solvent was dried at 120 ° C for 80 seconds. Further, an exposure device (trade name Multilight ML-251A / B, manufactured by Ushio Electric Co., Ltd.) equipped with an ultra-high pressure mercury lamp was further used, and 100 mJ / cm was passed through a quartz mask. ² Exposure. The exposure amount was measured using an integrated ultraviolet light meter (brand name: UIT-150, light receiving unit UVD-S365, manufactured by Ushio Electric Co., Ltd.). The exposed coating film was subjected to alkaline development using a rotary developing device (AD-1200, manufactured by Takizawa Industry Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Thereafter, the coating film was patterned by being cured at 250 ° C. for 60 minutes in a nitrogen atmosphere. A surface roughness meter (SURFCOM 130A, manufactured by Tokyo Precision Co., Ltd.) was used to measure the surface roughness of the pattern (width 10 μm) of the coating film after curing. [Weight Reduction Rate] The positive-type photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were placed in an aluminum cup, and dried at 60 ° C for 30 minutes in a nitrogen atmosphere, and then in a nitrogen atmosphere. It was hardened by heating at 250 ° C for 60 minutes. Using this hardened product, TG / DTA7200 (manufactured by Hitachi-hightech) was used, and the temperature was raised from room temperature to 300 ° C under a nitrogen flow at a temperature increase rate of 10 ° C / min. It was measured that the temperature was maintained at 300 ° C for 90 minutes Weight reduction rate (%) at the time. [0150] [0151] [0152] As can be seen from Examples 1 to 5 in Table 2, a dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g and a solvent having a solubility parameter (SP value) of 10.5 or more were used. The resulting titanium black dispersion had an average particle diameter D50 after the dispersion treatment of 100 nm or less, and the dispersibility was good. [0153] Examples 6 to 12 of the positive-type photosensitive resin composition using the titanium black dispersions of Examples 1 to 5 show the appearance, alkali developability, and pattern formation property after pre-baking. All aspects of the pattern linearity, surface roughness Ra, and weight reduction rate are good and excellent. On the other hand, the titanium black dispersions of Comparative Examples 1 to 4 using a dispersant having an amine value of 5 mgKOH / g or more, or a solvent having a solubility parameter (SP value) of less than 10.5, and an unused dispersion The positive photosensitive resin compositions of Comparative Example 5 and Comparative Examples 6 to 8 were found to be difficult to apply to blackened partition materials that require developability and high resolution. [Industrial Applicability] [0155] The black positive-type photosensitive resin composition system of the present invention can suitably use positive-type radiation lithography. An organic EL element including a partition wall and an insulating film formed of the black positive photosensitive resin composition of the present invention is suitable for use as an electronic component in a display device that exhibits good contrast.

Claims (12)

A positive photosensitive resin composition comprising (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, and (C) a solubility parameter of 10.5 or more A solvent, (D) a binder resin, and (E) a quinonediazide compound. The positive-type photosensitive resin composition according to claim 1, wherein the solvent (C) is γ-butyrolactone or n-methyl-2-pyrrolidone. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the titanium black (A) is 100 parts by mass, the dispersant (B) is 1 to 40 parts by mass, and the solvent (C) is 250 to 600. Parts by mass. The positive-type photosensitive resin composition according to claim 1 or 2, wherein based on 100 parts by mass of the binder resin (D), titanium black (A) is 3 to 30 parts by mass, and the quinone diazide compound (E ) Is 3 to 20 parts by mass. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the binder resin (D) comprises an alkali-soluble copolymer selected from (d1) having an alkali-soluble group, and (d2) having an epoxy group and phenol. At least one of the group consisting of an alkali-soluble resin having a hydroxyl group and (d3) a polyalkenyl phenol resin. A titanium black dispersion containing (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, and (C) a solvent having a solubility parameter of 10.5 or more. A method for producing a positive photosensitive resin composition, which comprises (1) a dispersant comprising (A) titanium black, (B) an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, And (C) a step of mixing a titanium black dispersion with a solvent having a solubility parameter of 10.5 or more, and (2) a step of mixing the aforementioned titanium black dispersion, (D) a binder resin, and (E) a quinone diazide compound . The hardened | cured material is a hardened | cured material of the positive photosensitive resin composition as described in any one of Claims 1-5. A method for producing a radiation lithographic structure, comprising (I) a coating step of applying a positive-type photosensitive resin composition according to any one of claims 1 to 5 to a substrate, and (II) applying the coated Drying step for removing the solvent in the positive photosensitive resin composition, (III) an exposure step for radiating radiation through a photomask, (IV) a development step for pattern formation by alkali development, and (V) 100% ~ 350 ° C to perform the heat treatment step of heating. A partition wall of an organic EL element, which is formed of a cured product of the positive-type photosensitive resin composition according to any one of claims 1 to 5. An insulating film for an organic EL element, which is made of a cured product of the positive-type photosensitive resin composition according to any one of claims 1 to 5. An organic EL device comprising a cured product of the positive-type photosensitive resin composition according to any one of claims 1 to 5.