JPWO2018088052A1 - Positive photosensitive resin composition and titanium black dispersion - Google Patents

Abstract

For example, the present invention provides a positive photosensitive resin composition that can be used for forming a black partition material of an organic EL display element and has high sensitivity and satisfactory developability, resolution, and heat resistance characteristics. The positive photosensitive resin composition comprises (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH / g or less, an acid value of 20 to 200 mgKOH / g, and (C) a solvent having a solubility parameter of 10.5 or more. , (D) a binder resin, and (E) a quinonediazide compound.

Description

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

  In a display device such as an organic EL display, a partition material is used at intervals of the colored pattern in the display region or at the edge of the peripheral portion of the display region in order to improve display characteristics. In the manufacture of the organic EL display device, in order to prevent the pixels of the organic material from coming into contact with each other, first, a partition is formed, and the pixel of the organic material is formed between the partitions. This partition is generally formed by photolithography using a photosensitive resin composition and has an insulating property. Specifically, the photosensitive resin composition is applied onto a substrate using a coating apparatus, and after removing volatile components by means of heating or the like, it is exposed through a mask. In the case of the positive type, development is performed by removing the exposed portion with a developer such as an alkaline aqueous solution, and the resulting pattern is heat-treated to form a partition (insulating film). Next, an organic material that emits light of three colors of red, green, and blue is formed 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, display devices have been downsized and the contents to be displayed have been diversified, so that high performance and high definition of pixels are required. For the purpose of increasing the contrast and improving the visibility in the display device, an attempt has been made to blacken the partition material using a colorant to provide light shielding properties. However, even if light shielding properties are provided, if the sensitivity is low with respect to the light to be reacted, the exposure time becomes long and the productivity is lowered. Therefore, it is important that the sensitivity is high. In order to meet the demand for higher definition, it is required that the pattern shape is excellent and the pattern surface is smooth in order to cope with the narrowing of the pattern pitch. In order to improve the visibility, it is required to make the blackened partition material closer to black, and since various processes are performed after the partition wall material is formed, it is heat resistant so as not to affect the peripheral members. It is required to be excellent.

  For example, Patent Document 1 proposes a method of blackening the partition wall material using carbon black. However, these radiation-sensitive resin compositions lack the light-shielding property of the cured film, and cannot improve the contrast.

  On the other hand, a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as disclosed in Patent Document 2 as a radiation-sensitive resin composition that has high resolution and exhibits high light-shielding properties by heat treatment after exposure. The composition which added titanium black to the thing is proposed. Although these compositions have sufficient sensitivity and light shielding properties, they are heated at a high temperature in the air in order to enhance the light shielding properties, and use coloration accompanied by oxidative degradation of the resin. This increases the outgas due to the deterioration of the resin, so that the heat resistance is inferior, and it is not suitable for manufacturing an organic EL display device and for stable driving. The properties of titanium black are not mentioned and it is difficult to say that the surface smoothness is sufficient.

  As the partition material, a polyimide resin having excellent insulating properties is generally used. However, in order to make this a light-shielding property, it needs to be blackened. However, it is difficult to form a blackened polyimide resin by a lithography method from the viewpoint of storage stability and cost of the photosensitive polyimide, and it is difficult to obtain a good resolution. For this reason, a material that blackens the partition material and satisfies the sensitivity, developability, resolution, and heat resistance has not yet been obtained.

JP 2002-116536 A JP 2001-281440 A

  In order to increase the contrast of the organic EL display element, efforts have been made to blacken the partition wall material, but a positive photosensitive resin composition that has high sensitivity and satisfies all the characteristics of developability, resolution, and heat resistance, and The production method has not been known so far.

  The present invention has been made based on the above-described circumstances, and the object thereof is positive photosensitivity that can satisfy high development characteristics, developability, resolution, and heat resistance in a blackened partition wall material. It is providing a resin composition and its manufacturing method.

  As a result of intensive studies, the present inventors have found that titanium black, a dispersant having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g, a solvent having a solubility parameter (SP value) of 10.5 or more, The present inventors have found that a positive photosensitive resin composition containing a binder resin and a quinonediazide compound can satisfy the characteristics of developability, resolution, and heat resistance with high sensitivity in a blackened partition wall material.

That is, the present invention includes the following aspects.
[1] (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,
A positive photosensitive resin composition comprising (D) a binder resin, and (E) a quinonediazide compound.

  [2] The composition according to [1], wherein the solvent (C) is γ-butyrolactone or n-methyl-2-pyrrolidone.

  [3] As described in [1] or [2], the dispersant (B) is 1 to 40 parts by mass and the solvent (C) is 250 to 600 parts by mass based on 100 parts by mass of the titanium black (A). Composition.

  [4] Any of [1] to [3], wherein titanium black (A) is 3 to 30 parts by mass and quinonediazide compound (E) is 3 to 20 parts by mass based on 100 parts by mass of binder resin (D). A composition according to claim 1.

[5] The binder resin (D) is
(D1) an alkali-soluble copolymer having an alkali-soluble group,
The composition according to any one of [1] to [4], comprising (d2) an alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and (d3) at least one selected from the group consisting of polyalkenylphenol resins. object.

[6] (A) Titanium black,
(B) A titanium black dispersion containing a dispersant having an amine value of 5 mg KOH / 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.

[7] (1) (A) Titanium black, (B) A dispersant having an amine value of 5 mgKOH / g or less, an acid value of 20 to 200 mgKOH / g, and (C) a solvent having a solubility parameter of 10.5 or more And a step of preparing a titanium black dispersion, and (2) production of a positive photosensitive resin composition comprising the steps of mixing the titanium black dispersion, (D) a binder resin and (E) a quinonediazide compound in this order. Method.

  [8] A cured product of the composition according to any one of [1] to [5].

[9] (I) An application step of applying the positive photosensitive resin composition according to any one of [1] to [5] to a substrate,
(II) a drying step for removing the solvent in the applied positive photosensitive resin composition;
(III) an exposure step of irradiating radiation through a photomask;
(IV) A method for producing a radiation lithographic structure, comprising: a development step of forming a pattern by alkali development; and (V) a heat treatment step of heating at a temperature of 100 to 350 ° C.

  [10] A partition wall of an organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [5].

  [11] An insulating film for an organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [5].

  [12] An organic EL device comprising a cured product of the positive photosensitive resin composition according to any one of [1] to [5].

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which can satisfy the characteristics of developability, resolution, and heat resistance with high sensitivity in the blackened partition material can be provided.

  The present invention is described in detail below.

  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, an acid value of 20 to 200 mgKOH / g, and (C) a solubility parameter of 10.5 or more. Contains solvent.

  The positive photosensitive resin composition of the present invention has (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH / g or less, an acid value of 20 to 200 mgKOH / g, and (C) a solubility parameter of 10.5. The above solvent, (D) binder resin, and (E) quinonediazide compound are included.

(A) Titanium black Titanium black used in the present invention includes a method of heating and reducing a mixture of titanium dioxide and titanium metal in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), high-temperature hydrolysis of titanium tetrachloride. The method of reducing ultrafine titanium dioxide obtained in the above in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), and the method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-60). -65069, JP-A-61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (JP-A-61-201610). However, the present invention is not limited to these. Examples of commercially available titanium black include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13-MT, 16M, UF-8 manufactured by Mitsubishi Materials Corporation, and Tilac D manufactured by Ako Kasei Co., Ltd. Can be mentioned. These titanium blacks may be used alone or in combination of two or more.

  As for titanium black (A), 3-30 mass parts is preferable on the basis of 100 mass parts of binder resin (D), More preferably, it is 5-20 mass parts, More preferably, it is 8-15 mass parts. If content of titanium black (A) is 3-30 mass parts on the basis of 100 mass parts of binder resin (D), the target OD value (optical density) will be obtained.

  The average particle diameter D50 (volume basis) of titanium black (A) in the dispersion is preferably 5 to 100 nm. When the average particle diameter D50 is 5 to 100 nm, high light shielding properties can be obtained. The average particle size D50 can be measured using a laser diffraction / scattering 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 Dispersion having an amine value of 5 mgKOH / g or less and an acid value of 20 to 200 mgKOH / g used for dispersing the titanium black of the present invention Known agents can be used. For example, phosphates such as trade names DISPERBYK110, DISPERBYK111 (made by Big Chemie Japan Co., Ltd.), trade names such as Disparon PW-36, Disparon DA-375 (made by Enomoto Kasei Co., Ltd.), polyphosphates, phosphate polyester , Phosphoric acid dispersants such as polyether phosphates, carboxyl group-containing polymer dispersants such as Floren G-700, Floren G-900, and Floren GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.) Higher fatty acid ester-based dispersants such as the names Azisper PN411 and Azisper PA111 (Ajinomoto Fine Techno Co., Ltd.) can be mentioned. Among them, a dispersant having no graft chain in the skeleton, for example, trade names DISPERBYK110, DISPERBYK111 (manufactured by Big Chemie Japan Co., Ltd.) and the like are preferably used.

  The acid value of the dispersant is 20 to 200 mgKOH / g, preferably 30 to 180 mgKOH / g, 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, more preferably 3 mgKOH / g or less, and most preferably 0 mgKOH / g. When the acid value is 20 to 200 mgKOH / g and the amine value is 5 mgKOH / g or less, a good dispersion having an appropriate bond with titanium black can be easily obtained. These dispersants may be used alone or in combination of two or more.

  To the extent that the effects of the present invention are 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. Resin components having a functional group such as a hydroxyl group, a carboxyl group, an amino group, and a sulfo group can be used in combination for the purpose of improving compatibility with the binder resin, storage stability, various physical properties, and characteristics.

  The dispersant (B) is preferably contained in an amount of 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and further preferably 3 to 20 parts by mass with respect to 100 parts by mass of the titanium black (A). If a dispersing agent is 1-40 mass parts with respect to 100 mass parts of (A) titanium black, particle | grains can be disperse | distributed favorably.

  The amine value means the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize all basic nitrogen contained in 1 g of a sample, and the measurement method is as follows. A sample is dissolved in a mixed solvent of o-nitrotoluene and acetic acid, and titrated with a 0.1 mol / L perchloric acid acetic acid solution using a glass electrode and a reference electrode. The relationship between the reading of potentiometer or pH meter and the titration amount of 0.1 mol / L perchloric acid acetic acid solution corresponding to this is plotted, and the inflection point obtained in the titration curve is set as the end point. The total amine value is calculated by the amount of 0.1 mol / L perchloric acid acetic acid solution consumed.

  The acid value means the number of mg of potassium hydroxide required for neutralizing free fatty acid, resin acid, etc. contained in 1 g of a sample, and the measurement method includes neutralization titration method and potentiometric titration method. is there. In the case of the neutralization titration method, dissolve the sample in a solvent, add phenolphthalein as an indicator, and titrate with a potassium hydroxide ethanol solution to obtain the acid value.

(C) Solvent having a solubility parameter (SP value) of 10.5 or more As a dispersion solvent of the titanium black of the present invention, the SP value is 10.5 to 15.0, preferably 10.5 to 13.0. . More preferably, it does not contain a hydroxyl group. Specific examples of solvents 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), N , N-dimethylacetamide (10.8) and the like, among which N-methyl-2-pyrrolidone or γ-butyrolactone is more preferable, and γ-butyrolactone is still more preferable. By using a solvent having an SP value of 10.5 or more, the titanium black (A) can be uniformly dispersed. These solvents may be used alone or in combination of two or more.

  It is preferable that a solvent (C) contains 250-600 mass parts with respect to 100 mass parts of titanium black (A), More preferably, it is 300-500 mass parts, More preferably, it is 350-450 mass parts. If a solvent is 250-600 mass parts with respect to 100 mass parts of titanium black (A), moderate fluidity | liquidity will be acquired and a dispersion state will become favorable easily.

  The solubility parameter is defined by the square root of the cohesive energy density of the material and can be used as a measure to predict thermodynamic properties during sample mixing. It is possible to use numerical values described in Chemical Handbook Application (Revised 3rd edition, Maruzen, 1980) or 4th edition Experimental Chemistry Course (Maruzen, 1990, p. 186).

(D) Binder resin The binder resin (D) used in the positive photosensitive resin composition of the present invention is not particularly limited, but preferably has an alkali-soluble group and is alkali-soluble.

  The alkali-soluble group that the binder resin has is not particularly limited, and examples thereof include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, and an acid anhydride group. You may use resin to have. In the present invention, alkali-soluble means that it can be dissolved in an alkali solution, for example, a 2.38 mass% tetramethylammonium hydroxide aqueous solution.

  Examples of the binder resin include acrylic resin, styrene resin, epoxy resin, amide resin, phenol resin, polyamic acid resin, and those obtained by adding an alkali-soluble group to these resins. These can be used alone or in combination of two or more kinds of resins.

  Examples of the binder resin having a phenolic hydroxyl group include known phenols such as phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, and phenol-dicyclopentadiene copolymer resin. Resin.

  In the present invention, the binder resin (D) preferably contains at least one selected from the following components (d1) to (d3).

(D1) Alkali-soluble copolymer of polymerizable monomer having alkali-soluble group and other polymerizable monomer Examples of the alkali-soluble group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, and a phosphate group. And an acid anhydride group. An alkali-soluble resin comprising a copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer is, for example, a polymerizable monomer having an alkali-soluble group and another polymerizable monomer. , A polymerization initiator and a RAFT agent (Reversible Addition Fragmentation Transfer; reversible addition-fragmentation chain transfer agent) or the like. The alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer may be one obtained by synthesizing a copolymer by radical polymerization and then adding an alkali-soluble group. .

Examples of the polymerizable functional group possessed by the polymerizable monomer include radically polymerizable functional groups. _{Specifically, CH 2 = CH-, CH 2} = C (CH 3) -, CH 2 = CHCO-, CH 2 = C (CH 3) CO -, - OC-CH = CH-CO- illustrate like it can. 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, β-furyl (meth). Acrylic acid, β-styryl (meth) acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid , Propiolic acid, 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 6-maleimidohexanoic acid Etc.

  Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene, acrylamide, acrylonitrile, vinyl n-butyl ether, and the like. Vinyl alcohol ethers, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester (Meth) acrylic acid ester such as 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, isobornyl (meth) acrylate, maleic anhydride, Feni Maleimides include N- substituted maleimide and cyclohexyl maleimide. Here, “(meth) acryl” means “acryl” and “methacryl”.

  It is particularly preferable to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having an alkali-soluble group and to use at least one selected from the group consisting of phenylmaleimide and cyclohexylmaleimide as the other polymerizable monomer. By using a resin obtained by radical polymerization of these polymerizable monomers, it is possible to improve shape maintainability and developability and contribute to reduction of outgas.

  The polymerization initiator for producing an alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble group and another polymerizable monomer by radical polymerization is not limited to the following, but 2,2 ′ -Azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovalerian) 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-butyl cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene ha Peroxide polymerization initiators such as dropper oxide having a 10-hour half-life temperature of 100 to 170 ° C., or benzoyl peroxide, lauroyl peroxide, 1,1′-di (t-butylperoxy) cyclohexane, t-butylperoxy A peroxide polymerization initiator such as pivalate can be used. 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, and 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer mixture. It is preferable that it is less than or equal to 15 parts by mass.

  The RAFT agent is not limited to the following, but thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, xanthates can be used. The RAFT agent can be used in the range of 0.005 to 20 parts by mass and preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers.

  As the binder resin (D) of the positive photosensitive resin composition of the present invention, a radical copolymer of 4-hydroxyphenyl methacrylate and phenylmaleimide and cyclohexylmaleimide or a radical copolymer of 4-hydroxyphenyl methacrylate and cyclohexylmaleimide is used. When used, the number average molecular weight is preferably in the range of 1000-30000, more preferably in the range of 3000-20000, and still more preferably in the range of 10000-15000. When the molecular weight is 1000 or more, the alkali solubility is appropriate, so that it is suitable as a resin for the photosensitive material. When the molecular weight is 30000 or less, the developability is good.

(D2) Alkali-soluble resin having epoxy group and phenolic hydroxyl group The alkali-soluble resin (d2) is, for example, a compound having at least two epoxy groups in one molecule (hereinafter referred to as “epoxy compound”). The epoxy group of (A) can be reacted with the carboxyl group of hydroxybenzoic acid. However, the reaction rate is adjusted so that the epoxy group remains.

  In the positive photosensitive resin composition of the present invention, since the alkali-soluble resin has an epoxy group, there is an advantage that chemical resistance, heat resistance, etc. are improved by reacting with a phenolic hydroxyl group during heating and crosslinking. Having a phenolic hydroxyl group has the advantage of being soluble in an alkaline aqueous solution.

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

  Examples of the compound having at least two epoxy groups in one molecule include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol type epoxy resins, biphenol type epoxy resins, naphthalene skeleton-containing epoxy resins, and alicyclic epoxy resins. And heterocyclic epoxy resins. These epoxy compounds only need to have two or more epoxy groups in one molecule and can be used alone, but may be used in combination of two or more. In addition, since these compounds are a thermosetting type, it cannot be uniquely described from the difference in the presence or absence of an epoxy group, the kind of functional group, a polymerization degree, etc. as common knowledge of those skilled in the art. An example of the structure of the novolac type epoxy resin is shown in Formula (1). In the formula (1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 50.

  Examples of the phenol novolac type epoxy resin include EPICLON (registered trademark) N-770 (manufactured by DIC Corporation), jER (registered trademark) -152 (manufactured by Mitsubishi Chemical Corporation), and the like.

  Examples of the cresol novolac type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation), EOCN (registered trademark) -102S (manufactured by Nippon Kayaku Co., Ltd.), and the like.

  Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), and YD-128 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). Bisphenol F type epoxy resins such as JER (registered trademark) 806 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and the like.

  Examples of the biphenol type epoxy resin include jER (registered trademark) YX-4000, jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation), and the like.

  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 Corporation), and the like.

  Examples of the alicyclic epoxy resin include EHPE (registered trademark) -3150 (manufactured by Daicel Chemical Industries, Ltd.).

  Examples of the heterocyclic epoxy resin include TEPIC (registered trademark), TEPIC (registered trademark) -L, TEPIC (registered trademark) -H, and TEPIC (registered trademark) -S (manufactured by Nissan Chemical Industries, Ltd.). .

  “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. For example, salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4 -Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy Examples include -4-nitrobenzoic acid and 4-hydroxy-3-nitrobenzoic acid, and dihydroxybenzoic acids are preferable in terms of enhancing alkali developability. These hydroxybenzoic acids can be used alone or in combination of two or more.

  The method for obtaining a compound having an alkali-soluble phenolic hydroxyl group from the epoxy compound and hydroxybenzoic acid is preferably 0.2 to 0.9 equivalent of hydroxybenzoic acid, more preferably 1 equivalent of epoxy group of the epoxy compound. 0.4 to 0.8 equivalent, more preferably 0.5 to 0.7 equivalent is used. If hydroxybenzoic acid is 0.2 equivalent or more, sufficient alkali solubility is expressed, and if it is 0.9 equivalent or less, increase in molecular weight due to side reaction can be suppressed.

  A catalyst may be used to accelerate the reaction. The usage-amount of a catalyst is 0.1-10 mass parts with respect to 100 mass parts of reaction raw material mixtures which consist of an epoxy compound and hydroxybenzoic acids. 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, and zirconium octoate.

  The number average molecular weight of the 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 in the range of 2000 to 3500. More preferably it is. If the molecular weight is 500 or more, the solubility in an alkaline aqueous solution is appropriate, so that the resin of the photosensitive material is good. If the molecular weight is 8000 or less, the coatability and developability are good.

(D3) Polyalkenyl phenol resin A polyalkenyl phenol resin is obtained by converting a hydroxyl group of a known phenol resin into an alkenyl ether, and further subjecting the alkenyl ether group to Claisen rearrangement. The polyalkenylphenol resin preferably has the structure of the formula (2). By containing such a resin, it is possible to improve the development characteristics of the resulting photosensitive resin composition and to contribute to the reduction of outgas.

In the 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, the formula (3)

(In Formula (3), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or carbon. Represents an aryl group having 6 to 12 atoms, * in formula (3) represents a bond with a carbon atom constituting an aromatic ring.
Represents an alkenyl group represented by formula (1), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by formula (3). Q is an alkylene group represented by the formula —CR ⁴ R ⁵ —, a cycloalkylene 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 R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a cyclohexane having 5 to 10 carbon atoms. An alkyl group or an aryl group having 6 to 12 carbon atoms is represented. When two or more structures of the formula (2) are present in one molecule, the structures of the formula (2) may be the same or different.

R ¹ , R ² and R ^{3 in} formula (2) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by formula (3), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group And at least one of R ¹ , R ² and R ³ is an alkenyl group represented by formula (3).

In R ¹ , R ² and R ³ of formula (2), specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group and the like can be mentioned. 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 the formula (3), R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 5 to 10 carbon atoms. A cycloalkyl group or an aryl group having 6 to 12 carbon atoms, but specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group and the like, and examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group and the like. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, and a naphthyl group. Door can be. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferable examples of the alkenyl group represented by the formula (3) include an allyl group and a methallyl group from the viewpoint of reactivity, and more preferred is an allyl group. And it is most preferable that any one of R ¹ , R ² and R ³ is an allyl group or a methallyl group, and the other two are hydrogen atoms.

Q in the formula (2) is an alkylene group represented by the formula —CR ⁴ R ⁵ —, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, or an alicyclic condensed ring. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or the number of carbon atoms. It represents a 5-10 cycloalkyl group or an aryl group having 6-12 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like. Can be mentioned. Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group and the like. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cycloheptyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, and a naphthyl group. R ⁴ and R ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom.

  Here, specific examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, and a cycloheptylene group. Specific examples of the divalent organic group having an aromatic ring include a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, a 4,4′-methylenediphenyl group, and a formula (4). And the like.

  Specific examples of the divalent organic group having an alicyclic fused ring include a dicyclopentadienylene group.

When a polyalkenylphenol resin is used for the binder resin (D) used in the photosensitive resin composition of the present invention, Q in formula (2) is —CH as a particularly preferred polyalkenylphenol resin from the viewpoint of alkali developability and outgassing. _{What is 2-,} that is, one having a structure represented by the formula (5).

In the formula (5), R ¹ , R ² and R ³ are the same as in the formula (2).

Preferred ^R 1, ^{R 2} and ^{R 3} are the same as the preferred ^R 1, ^{R 2} and ^{R 3} in Formula (2).

  The structural unit represented by the formula (2) or the formula (5) is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, further preferably 85 to 85 mol% in the polyalkenylphenol resin. 100 mol%. If the structural unit represented by Formula (2) or Formula (5) is 50 mol% or more in the polyalkenylphenol resin, the heat resistance is improved, which is preferable. Since the phenolic hydroxyl group in the polyalkenyl phenol resin is ionized in the presence of a basic compound and can be dissolved in water, it is necessary that the phenolic hydroxyl group is in a certain amount or more from the viewpoint of alkali developability. Therefore, the polyalkenylphenol resin including the structure of the formula (5) is particularly preferably a polyalkenylphenol resin having a structural unit represented by the formula (5) and a structural unit represented by the formula (6).

In Formula (6), R ^1a , R ^2a and R ^3a each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

  In the polyalkenylphenol resin having the structural unit represented by the formula (5) and the structural unit represented by the formula (6), the number of the structural units represented by the formula (5) is x, and the formula (6) When the number of structural units represented is y, 0.5 ≦ x / (x + y) <1, 0 <y / (x + y) ≦ 0.5, and (x + y) is preferably 2 to 3000, More preferably, it is 2-2000, More preferably, it is 2-1000.

  When using a polyalkenylphenol resin as the binder resin (D), the preferred number average molecular weight is 500 to 5000, more preferably 800 to 3000, and still more preferably 1000 to 1500. If the number average molecular weight is 500 or more, the alkali development speed is appropriate, the resolution is good because the difference in dissolution rate between the exposed and unexposed areas is sufficient, and if it is 5000 or less, the alkali developability is good.

  As the binder resin, one type of resin may be used alone, or two or more types of resins may be used in combination. Among these, at least one selected from resin components (d1) to (d3) is preferably included, and at least (d1) and (d2) are more preferably included. The total amount of one or more selected from (d1) to (d3) with respect to 100 parts by mass of the binder resin (D) is preferably 1 to 100 parts by mass, more preferably 10 to 100 parts by mass, Preferably it is 30-100 mass parts. If the total amount of one or more components selected from (d1) to (d3) with respect to 100 parts by mass of the binder resin (D) is 1 to 100 parts by mass, the resin composition has good heat resistance.

  The binder resin (D) can be arbitrarily combined, for example, using the resin components (d1) and (d2) together, and a plurality of the components (d1) to (d3) can also be used in combination.

  For example, 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) may be used in combination. When three types are used in combination, the proportion of the alkali-soluble copolymer (d1) having an alkali-soluble group in the binder resin (D) is 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 polyalkenylphenol resin (d3) is preferably 5 to 60% by mass.

  In addition, when the alkali-soluble copolymer (d1) having an alkali-soluble group also corresponds to the alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group, the alkali-soluble copolymer (d1) having an alkali-soluble group Shall be treated as When the alkali-soluble copolymer (d1) having an alkali-soluble group also corresponds to the polyalkenylphenol resin (d3), it is handled as an alkali-soluble copolymer (d1) having an alkali-soluble group. That is, the alkali-soluble resin (d2) and polyalkenylphenol resin (d3) having an epoxy group and a phenolic hydroxyl group exclude those corresponding to the alkali-soluble copolymer (d1) having an alkali-soluble group.

(E) Quinonediazide compound The positive photosensitive resin composition of this invention contains a quinonediazide compound as a radiation sensitive compound. As quinonediazide compounds, quinonediazide sulfonic acid is bonded to a polyhydroxy compound with an ester, quinonediazide sulfonic acid is bonded to a polyamino compound, and a quinonediazide sulfonic acid is bonded to a polyhydroxypolyamino compound. Or those having an ester bond and a sulfonamide bond. From the viewpoint of the contrast between the exposed area and the unexposed area, it is preferable that 20 to 100 mol% of the functional groups of these polyhydroxy compound or polyamino compound are substituted with quinonediazide. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, 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 (above, trade name, 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 (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (quotient Name, but include the Honshu Chemical Industry Co., Ltd.), and the like, but is not limited to these.

  Specific examples of the quinonediazide compound include 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound.

  When exposed to ultraviolet light or the like, the quinonediazide compound generates a carboxyl group through the reaction shown in the following reaction formula 2. Generation | occurrence | production of a carboxyl group enables it to melt | dissolve the exposed part (film | membrane) with respect to an alkaline solution, and alkali developability expresses.

  Although content of the quinonediazide compound in the photosensitive resin composition in this invention changes with quinonediazide compounds to be used, 3-20 mass parts is preferable on the basis of 100 mass parts of binder resin (D), More preferably, 5-5 mass parts is preferable. 15 parts by mass, more preferably 7 to 10 parts by mass. Alkali developability is favorable in it being 3 mass parts or more on the basis of 100 mass parts of binder resin (D). If it is 20 parts by mass or less, the rate of decrease in heating at 300 ° C. or higher is difficult to increase.

(F) Optional component In the positive photosensitive resin composition of the present invention, a thermosetting agent, a surfactant, a colorant other than (A), a solvent other than (C), and the like can be added as optional components. . The optional component (F) is defined as not applicable to any of (A) to (E).

(F1) Thermosetting agent As the thermosetting agent, a thermal radical generator can be used. Preferable thermal radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl. Organic peroxides such as cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and the like having a 10-hour half-life temperature of 100 to 170 ° C. Can be mentioned.

  As for content of a thermosetting agent, 5 mass parts or less are preferable with respect to 100 mass parts of binder resin (D), More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less.

(F2) Surfactant The positive photosensitive resin composition of the present invention further contains a surfactant as an optional component, for example, in order to improve coatability or developability of the coating film. Can do.

  Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene dilaurate, nonoxy surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene distearate, etc .; Megafac (registered trademark) F-251, F-281 F-430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558 (above, product names) , Manufactured by DIC Corporation), Surflon ( (Registered trademark) S-242, S-243, S-385, S-386, S-420, S-611 (above, trade name, manufactured by ACG Seimi Chemical Co., Ltd.) Agents; organosiloxane polymers KP323, KP326, KP341 (above, trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

  Such a surfactant is blended in an amount of 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 based on 100 parts by mass of the binder resin (D).

(F3) Other colorant The positive photosensitive resin composition of the present invention may further contain a colorant other than titanium black (A) as an optional component. Examples of such a colorant include dyes, organic pigments, and inorganic pigments, which can be used according to the purpose. However, the content of the colorant other than titanium black (A) is within a range that does not impair the effects of the present invention.

  Specific examples of the dye include azo dye, benzoquinone dye, naphthoquinone dye, anthraquinone dye, cyanine dye, squarylium dye, croconium dye, merocyanine dye, stilbene dye, diphenylmethane dye, triphenylmethane dye, fluorane dye, spiropyran dye, phthalocyanine dye, Examples include indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

  Examples of the pigment include black pigments such as carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, and C.I. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Pigment orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Pigment green 7, C.I. I. And CI pigment brown 23, 25, 26.

(F4) Other solvent The positive photosensitive resin composition of the present invention is dissolved in a solvent and used in a solution state. The positive photosensitive resin composition of the present invention can be adjusted to a viscosity suitable for various coating methods depending on the amount of solvent. Depending on the purpose of use, an appropriate solid content concentration can be adopted. For example, the solid content concentration can 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 can be added at 5 mass% or less of the total solvent.

  Other solvents include, for example, glycol ethers such as ethylene glycol dimethyl ether and ethylene glycol methyl ethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl. Diethylene glycols such as methyl ether, propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydride Ketones such as xyl-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate Esters such as methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate Kind. These solvents may be used alone or in combination of two or more.

[Production method of titanium black dispersion]
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, an acid value of 20 to 200 mgKOH / g, and (C) a solubility parameter of 10.5 or more. It can manufacture by mixing a solvent as an essential component.

  The disperser for crushing and dispersing titanium black is not particularly limited, and ball types such as a ball mill, sand mill, bead mill, paint shaker, rocking mill, kneader, paddle mixer, planetary mixer, Henschel mixer, etc. Examples of the roll type such as a blade type and a three-roll mixer, and other examples include a crushing machine, a colloid mill, an ultrasonic wave, a homogenizer, and a rotation / revolution mixer. Among these, a ball type that can stably and finely disperse in a short time is preferable. Examples of the material of the ball used in the ball mold include glass, silicon nitride, alumina, zircon, zirconia, and steel. As a bead diameter, a general shape having a diameter of 0.03 to 25 mm can be used, but a small diameter of 5 mm or less is preferable from the viewpoint of miniaturization.

  The order of addition when preparing the dispersion is not particularly limited, but the following order is desirable in order to obtain a good dispersion.

  First, a solvent (C) and a dispersing agent (B) are disperse | distributed uniformly. In the case where the solvent and the dispersant are not uniformly dispersed in advance, an area with a high concentration of the dispersant is partially generated, and problems such as particle aggregation tend to occur. The required amount of titanium black (A) is then placed in the previously prepared solution and finally the beads. When aggregation is observed in titanium black, preliminary dispersion may be performed. A binder resin or other resin component may be used for the purpose of compatibility with the resin and suppression of reaggregation of titanium black.

[Method for producing positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention is prepared by first mixing a titanium black (A), a dispersant (B), and a solvent (C) to prepare a titanium black dispersion, and then binder resin (D), quinonediazide. It is preferable that the compound (E) and the optional component (F) are further mixed and produced. The method for preparing the titanium black dispersion is as described above.

  The order of mixing the titanium black dispersion and the binder resin, the quinonediazide compound, and the optional component is not particularly limited. For example, the binder resin is dissolved in a solvent (C) or a solvent other than (C), , A quinonediazide compound, a titanium black dispersion, and if necessary, additives such as a thermosetting agent and a surfactant can be mixed at a predetermined ratio to prepare a positive photosensitive resin composition in a solution state. .

  The stirrer for mixing the titanium black dispersion with the binder resin, the quinonediazide compound, and the optional components is not particularly limited. Ball types such as ball mill, sand mill, bead mill, paint shaker, rocking mill, kneader, paddle Examples include a blade type such as a mixer, a planetary mixer, a Henschel mixer, a roll type such as a three-roll mixer, and a crushing machine, a colloid mill, an ultrasonic wave, a homogenizer, a rotation / revolution mixer, and a mechanical stirrer. When used at a laboratory level, a mechanical stirrer is preferable because it can be stably mixed in a short time. The stirring blade used at the time of stirring can be appropriately selected from a fan, a propeller, a cross, a turbine, a dragonfly type, and the like. A resin composition can be obtained by mixing a titanium black dispersion or a binder resin solution and stirring at room temperature for 1 to 10 minutes at a rotation speed of 10 to 1000 rpm.

  It is preferable to filter the composition liquid prepared as described above before use. Examples of the filtering means include a Millipore filter having a pore diameter of 0.05 to 1.0 μm.

  The positive photosensitive resin composition of the present invention thus prepared is also excellent in long-term storage stability.

[Pattern formation and curing method]
When the positive photosensitive resin composition of the present invention is used for radiation lithography, first, the positive photosensitive resin composition of the present invention is applied to the substrate surface, the solvent is removed by means such as heating, and the coating is performed. A film can be formed. 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 employed.

  After applying the positive photosensitive resin composition of the present invention to the substrate surface, the solvent is usually dried by heating (pre-baking) to form a coating film. The heating conditions vary depending on the type of each component, the blending ratio, etc., but it is usually applied by heating at 70 to 130 ° C. for a predetermined time, for example, 1 to 20 minutes on a hot plate, or 3 to 60 minutes in an oven. A membrane can be obtained.

  Next, the pre-baked coating film is irradiated with radiation (eg, visible light, ultraviolet light, far ultraviolet light, etc.) through a mask having a predetermined pattern (exposure process), and then developed with a developer to remove unnecessary portions. To form a predetermined patterned coating film (development process). When naphthoquinone diazide sulfonic acid ester is used as a positive photosensitive compound, preferable radiation is ultraviolet to visible light having a wavelength of 250 to 450 nm.

  Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline Quaternary ammonium salts such as pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane, and other cyclic amines Using an aqueous solution of an alkali such as Kill. Although there is no restriction | limiting in particular in a density | concentration, 0.5-5.0 mass% is preferable. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like to the alkaline aqueous solution can also be used as a developer. The development time is usually 30 to 180 seconds, and the development method may be any of a liquid piling method, a shower method, a dipping method, and the like. After the development, washing with running water is performed for 30 to 90 seconds, unnecessary portions are removed, and the pattern is formed by air drying with compressed air or compressed nitrogen. After that, the coating film can be obtained by heating the pattern at a predetermined temperature, for example, 120 to 350 ° C. for 20 to 200 minutes with a heating device such as a hot plate or an oven. (Heat treatment process).

  The present invention includes (I) a coating step of applying the positive photosensitive resin composition to a substrate, (II) a drying step of removing a solvent in the applied positive photosensitive resin composition, and (III) radiation. A method of manufacturing a radiation lithographic structure, including an exposure step of irradiating through a photomask, (IV) a development step of forming a pattern by alkali development, and (V) a heat treatment step of heating at a temperature of 100 to 350 ° C. be able to. This method can be used for forming the partition walls and the insulating film of the organic EL element.

  The present invention can provide a partition wall of an organic EL device comprising a cured product of the positive photosensitive resin composition.

  In the present invention, an insulating film of an organic EL element comprising a cured product of the positive photosensitive resin composition can be obtained.

  The present invention can provide an organic EL device containing a cured product of the positive photosensitive resin composition.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to this Example.

(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 KK) 76.8 g, N-phenylmaleimide (Made by Nippon Shokubai Co., Ltd.) 14.4 g, N-cyclohexylmaleimide (made by Nippon Shokubai Co., Ltd.) 14.4 g, V-601 (made by Wako Pure Chemical Industries, Ltd.) 1.80 g as a polymerization initiator, S as RAFT agent -1.95 g of dodecyl-S ′-(α, α′-dimethyl-α ″ -acetic acid) trithiocarbonate (“723010” manufactured by Sigma-Aldrich), 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) It was completely dissolved in 180 g. The obtained solution was added dropwise to 180 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) heated to 85 ° C. in a 500 mL three-necked flask under a nitrogen gas atmosphere over 1 hour, and then 85 The reaction was carried out at 0 ° 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 collected by filtration and vacuum dried at 80 ° C. for 7 hours to collect 104.4 g of a white powder. This was dissolved in γ-butyrolactone to obtain a resin liquid having a solid content of 20% by mass (resin liquid 1). The number average molecular weight of the obtained reaction product was 14100, and the weight average molecular weight was 24900.

[Production Example 2] Production of alkali-soluble resin (d2) having an epoxy group and a phenolic hydroxyl group 60 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent in a 300 mL three-neck flask is at least two in one molecule. 42 g of EPICLON (registered trademark) N-695 (a cresol novolac type epoxy resin manufactured by DIC Corporation, epoxy equivalent 210) was charged as a compound having an epoxy group, and dissolved at 60 ° C. in a nitrogen atmosphere. There, 15.5 g (0.10 mol, 0.5 equivalent to 1 equivalent of epoxy) 3,5-dihydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as hydroxybenzoic acid, and triphenylphosphine ( 0.2 g (0.76 mmol) was added, and the reaction was carried out 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 reaction product was 2400, and the weight average molecular weight was 5600.

[Production Example 3] Production of polyallylphenol resin (d3) A solution of 201 g (1.45 mol) of potassium carbonate (manufactured by Nippon Soda Co., Ltd.) in 100 g of pure water in a 1000 mL three-necked flask, phenol novolac resin “Shonol (registered trademark) BRN-5835Y” (manufactured by Aika SDK Phenol Co., Ltd.) 100.0 g and isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) 16 g were charged, the reactor was purged with nitrogen gas and heated to 85 ° C. . Under a nitrogen gas stream, 84 g (0.84 mol) of allyl acetate (manufactured by Showa Denko KK), 50% water content 5% -Pd / C-STD type (metal palladium is dispersed in activated carbon at a content of 5% by mass, The activated carbon in which the metallic palladium is dispersed is mixed with water so as to be 50% by mass and stabilized by an allylation reaction catalyst, manufactured by N.E. Chemcat Co., Ltd.) 0.40 g (palladium: 0.188 mmol) and tri 2.45 g (9.4 mmol) of phenylphosphine (activator of the above-mentioned palladium-containing allylation reaction catalyst, manufactured by Hokuko Chemical Co., Ltd.) is added, and the reaction is performed for 4 hours by raising the temperature to 105 ° C. in a nitrogen atmosphere. Thereafter, 14 g (0.14 mol) of allyl acetate was added, and heating was continued for 10 hours while confirming the formation of allyl ether groups by ¹ H-NMR. Thereafter, the stirring was stopped, and the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After adding pure water (200 g) until the precipitated salt is dissolved, 200 g of toluene is added, and the temperature is kept at 80 ° C. or higher, and it is confirmed that no white precipitate is deposited. Then, Pd / C Was recovered by filtration (pressure (0.3 MPa) using a 1 μm membrane filter (KST-142-JA manufactured by Advantech Co., Ltd.). The filter cake was washed with 100 g of toluene and the aqueous layer was separated. The organic layer was separated and concentrated under reduced pressure to obtain a brown oily phenol novolac-type polyallyl ether resin.

Subsequently, 125 g of phenol novolac-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.). While stirring at 300 rpm, the temperature was raised to 170 ° C., and the Claisen rearrangement reaction was carried out for 30 hours while confirming the reduction of allyl ether groups by ¹ H-NMR. 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-type polyallylphenol resin solution (resin solution 3). The polyallylphenol resin had a hydroxyl group equivalent of 132, a number average molecular weight of 1100, and a weight average molecular weight of 9,900.

This resin is a polyalkenylphenol resin having a structural unit represented by the formula (5) and a structural unit represented by the formula (6). In the formula (5), among R ¹ , R ² and R ³ , One is an allyl group and the other is a hydrogen atom. In Formula (6), R ^1a , R ^2a , and R ^3a are hydrogen atoms, x / (x + y) is 0.85, and y / (x + y) Was 0.15.

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

(2) Raw material (D) Resin liquids 1 to 3 synthesized according to Production Examples 1 to 3 and novolak phenol resin BRM-595M (manufactured by Aika SDK Phenol Co., Ltd.) as a binder resin are low molecular weight components by a reprecipitation method. Then, a resin liquid 4 prepared with γ-butyrolactone to a solid content of 20% by mass was used.
(D) Table 1 shows materials other than the binder resin.

(3) Production of titanium black dispersion [Example 1]
1 g of γ-butyrolactone 39 g and a dispersant DISPERBYK-111 were added to a 150 cc total drawn screw storage container (made of stainless steel) and mixed. Then, 10 g of titanium black UF-8 with a primary particle size of 20 nm was added and mixed, and then 200 g of zirconia beads for pulverization / dispersion treatment with a diameter of 0.3 mm (trade name: YTZ ball, manufactured by Nikkato Corporation) were added. It was sealed so as not to leak, and this was set on a paint shaker (manufactured by Asada Tekko Co., Ltd.) and dispersed for 10 hours. The obtained dispersion was filtered through a Millipore filter having a pore size of 0.45 μm and 0.22 μm to obtain a titanium black dispersion. The resulting titanium black dispersion is hereinafter referred to as Dispersion 1.

[Examples 2 to 5, Comparative Examples 1 to 5]
A titanium black dispersion was obtained in the same procedure as in Example 1 according to the formulation shown in Table 2 and the diameter of the zirconia beads. The titanium black dispersions obtained in Examples 2 to 5 are hereinafter referred to as dispersions 2 to 5, and the titanium black dispersions obtained in Comparative Examples 1 to 5 are hereinafter referred to as dispersions C1 to C5.

(4) Production of positive photosensitive resin composition [Example 6]
50 parts by mass of the resin liquid 1 obtained in Production Examples 1 and 2, 125 parts by mass of the resin liquid 2, 15 parts by mass of TS-130A as a quinonediazide compound, and the titanium black dispersion obtained in Example 1 100 parts by mass of 1 and 7.5 parts by mass of a 1% by mass solution of Surflon S-386 (diluted with γ-butyrolactone) as a surfactant were added and further mixed. After confirming that it became uniform, it was filtered through a Millipore filter having a pore diameter of 0.22 μm to prepare a positive 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 by the same procedure as in Example 6 as shown in Table 3.

(5) Evaluation About the titanium black dispersion liquid manufactured in Examples 1-5 and Comparative Examples 1-5, evaluation of the average particle diameter of titanium black was performed. However, the titanium black dispersions of Comparative Examples 1 and 5 were not measured because aggregation was confirmed visually. The results are shown in Table 2.

[Average particle size of titanium black]
Weigh 20 g of γ-butyrolactone, add 1 drop of the dispersion to it, mix with ultrasonic waves for 1 minute, and fill the cell of laser diffraction / scattering particle size distribution measuring device Nanotrac wave (Ex) (Nikkiso Co., Ltd.). The average particle diameter D50 of the dispersed titanium black was measured.

  About positive photosensitive resin composition manufactured in Examples 6-12 and Comparative Examples 6-8, alkali developability, pattern formability, pattern linearity, light shielding property (OD value), appearance after pre-baking, surface roughness Ra and heat resistance (weight reduction rate) were evaluated. The results are shown in Table 3. The evaluation method is as follows.

[Alkali developability, pattern formability, pattern linearity]
The positive 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 × 1 mm) so that the dry film thickness was about 1.5 μm, and 120 ° C. The solvent was dried at 80 seconds. Furthermore, quartz photomasks (5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, 500 μm lines) are used in an exposure apparatus (trade name Multilight ML-251A / B, manufactured by USHIO INC.) Incorporating an ultra-high pressure mercury lamp. 100 mJ / cm < ² > was exposed through the one where the space was patterned. The amount of exposure was measured using an ultraviolet integrated light meter (trade name: UIT-150 light receiving unit UVD-S365, manufactured by USHIO INC.). The exposed coating film was subjected to alkali development with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), and evaluated for alkali developability. In observation using an optical microscope (VH-Z250, manufactured by Keyence Corporation), a case where there was no residue after alkali development was judged good, and a case where there was a residue was judged as defective.

  Evaluation of pattern formability was performed by measuring the line width of the pattern after alkali development. Using an optical microscope (VH-Z250, manufactured by Keyence Corporation), the location where the line width of the photomask line & space pattern was 10 μm was confirmed with a microscope having a magnification of 1000 times. Evaluation of pattern formability is good if the line width of the line & space pattern of the pattern after alkali development is 1: 1, the line width of the line portion is within ± 10% is acceptable, and the others are defective. Went.

  In the evaluation of the linearity of the pattern, a pattern having a linear shape was good, a pattern having a wavy pattern was acceptable, and a pattern other than that was regarded as defective.

[OD value]
A glass substrate (size 100 mm × 100 mm × 1 mm) was spin-coated with the positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 so as to have a thickness of about 1.5 μm. The solvent was dried by heating for 80 seconds. Then, the coating film was obtained by making it harden | cure at 250 degreeC under nitrogen gas atmosphere for 60 minutes. The cured glass coating film was measured with a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.), corrected with the OD value of only the glass, and converted to an OD value per 1 μm thickness of the coating film. In addition, the thickness of the coating film was measured using a surface roughness meter (Surfcom 130A, manufactured by Tokyo Seimitsu Co., Ltd.).

[Appearance after pre-baking]
A glass substrate (size 100 mm × 100 mm × 1 mm) was spin-coated with the positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 so as to have a thickness of about 1.5 μm. The solvent was dried by heating for 80 seconds. Appearance evaluation after pre-baking was performed by visually observing the surface of the coating after drying, with a uniform glossy surface being good, uneven glossiness being acceptable, and light-transmitting holes being defective. .

[Surface roughness Ra]
The positive 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 × 1 mm) so that the dry film thickness was about 1.5 μm, and 120 ° C. The solvent was dried at 80 seconds. Furthermore, 100 mJ / cm < ² > exposure was performed through the photomask made from quartz with the exposure apparatus (Brand name Multilight ML-251A / B, Ushio Electric Co., Ltd. product) incorporating the ultra high pressure mercury lamp. The amount of exposure was measured using an ultraviolet integrated light meter (trade name: UIT-150 light receiving unit UVD-S365, manufactured by USHIO INC.). The exposed coating film was subjected to alkali development with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). Thereafter, a patterned coating film was obtained by curing at 250 ° C. for 60 minutes in a nitrogen gas atmosphere. The surface roughness of the 10 μm wide pattern of the cured coating film was measured using a surface roughness meter (Surfcom 130A, manufactured by Tokyo Seimitsu Co., Ltd.).

[Weight reduction rate]
The positive photosensitive resin compositions of Examples 6 to 12 and Comparative Examples 6 to 8 were put in an aluminum cup, dried at 60 ° C. for 30 minutes in a nitrogen gas atmosphere, and then heated at 250 ° C. for 60 minutes in a nitrogen gas atmosphere. Cured. Using the cured product, TG / DTA7200 (manufactured by Hitachi High-Tech Science Co., Ltd.) was used, and the temperature was raised from room temperature to 300 ° C. under a temperature increase rate of 10 ° C./min in a nitrogen gas stream. The weight reduction rate (%) when held was measured.

  From Examples 1 to 5 in Table 2, titanium black dispersion using a dispersant having an amine value of 5 mgKOH / g or less, an acid value of 20 to 200 mgKOH / g, and a solvent having a solubility parameter (SP value) of 10.5 or more. The liquid had an average particle diameter D50 after the dispersion treatment of 100 nm or less and good dispersibility.

  In Examples 6 to 12, which are positive photosensitive resin compositions using the titanium black dispersions of Examples 1 to 5, the appearance after prebaking, alkali developability, pattern formability, pattern linearity, and surface roughness Ra It was found that all points of weight reduction rate were excellent in a well-balanced manner.

  On the other hand, a titanium black dispersion 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 a comparative example using no dispersant 5 and Comparative Examples 6 to 8 were found to be difficult to apply to the blackened partition wall material for which developability and high resolution are required.

  The black positive photosensitive resin composition of the present invention can be suitably used for positive radiation lithography. The organic EL element provided with the partition and the insulating film formed from the black positive photosensitive resin composition of the present invention is suitably used as an electronic component of a display device exhibiting good contrast.

Claims (12)

(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,
A positive photosensitive resin composition comprising (D) a binder resin, and (E) a quinonediazide compound.   The composition according to claim 1, wherein the solvent (C) is γ-butyrolactone or n-methyl-2-pyrrolidone.   The composition according to claim 1 or 2, wherein the dispersant (B) is 1 to 40 parts by mass and the solvent (C) is 250 to 600 parts by mass based on 100 parts by mass of the titanium black (A).   The titanium black (A) is 3 to 30 parts by mass and the quinonediazide compound (E) is 3 to 20 parts by mass based on 100 parts by mass of the binder resin (D). Composition. Binder resin (D)
(D1) an alkali-soluble copolymer having an alkali-soluble group,
The composition according to any one of claims 1 to 4, comprising (d2) an alkali-soluble resin having an epoxy group and a phenolic hydroxyl group, and (d3) at least one selected from the group consisting of polyalkenylphenol resins. object. (A) Titanium black,
(B) A titanium black dispersion containing a dispersant having an amine value of 5 mg KOH / 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. (1) (A) titanium black, (B) a dispersant having an amine value of 5 mgKOH / g or less, an acid value of 20 to 200 mgKOH / g, and (C) a solvent having a solubility parameter of 10.5 or more are mixed, A method for producing a positive photosensitive resin composition comprising a step of preparing a titanium black dispersion, and (2) a step of mixing the titanium black dispersion, (D) a binder resin, and (E) a quinonediazide compound in this order.   Hardened | cured material of the composition of any one of Claims 1-5. (I) The application | coating process which apply | coats the positive photosensitive resin composition of any one of Claims 1-5 to a base material,
(II) a drying step for removing the solvent in the applied positive photosensitive resin composition;
(III) an exposure step of irradiating radiation through a photomask;
(IV) A method for producing a radiation lithographic structure, comprising: a development step of forming a pattern by alkali development; and (V) a heat treatment step of heating at a temperature of 100 to 350 ° C.   The partition of the organic EL element which consists of hardened | cured material of the positive photosensitive resin composition of any one of Claims 1-5.   The insulating film of the organic EL element which consists of hardened | cured material of the positive type photosensitive resin composition of any one of Claims 1-5.   The organic EL element containing the hardened | cured material of the positive photosensitive resin composition of any one of Claims 1-5.