WO2022145189A1 - 感光性樹脂組成物及び有機ｅｌ素子隔壁 - Google Patents

感光性樹脂組成物及び有機ｅｌ素子隔壁 Download PDF

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WO2022145189A1
WO2022145189A1 PCT/JP2021/045210 JP2021045210W WO2022145189A1 WO 2022145189 A1 WO2022145189 A1 WO 2022145189A1 JP 2021045210 W JP2021045210 W JP 2021045210W WO 2022145189 A1 WO2022145189 A1 WO 2022145189A1
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group
resin composition
mass
photosensitive resin
resin
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PCT/JP2021/045210
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English (en)
French (fr)
Japanese (ja)
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恭裕 石田
健太郎 古江
拓樹 倉本
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昭和電工株式会社
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Priority to JP2022572964A priority Critical patent/JPWO2022145189A1/ja
Publication of WO2022145189A1 publication Critical patent/WO2022145189A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels

Definitions

  • the present invention relates to a photosensitive resin composition containing a blackening agent, and an organic EL element partition wall, an organic EL element insulating film, and an organic EL element using the same.
  • a partition material is used at the interval portion of the coloring pattern in the display region or the edge of the peripheral portion of the display region in order to improve the display characteristics.
  • OLED organic EL display
  • a partition wall is first formed, and the pixels of the organic substance are formed between the partition walls.
  • the partition walls are generally formed by photolithography using a photosensitive resin composition and have insulating properties. Specifically, the photosensitive resin composition is applied onto the substrate using a coating device, the volatile components are removed by means such as heating, and then exposed through a mask, and then, in the case of a negative type, the unexposed portion is exposed.
  • the exposed portion is developed by removing it with a developing solution such as an alkaline aqueous solution, and the obtained pattern is heat-treated to form a partition wall (insulating film).
  • a developing solution such as an alkaline aqueous solution
  • an organic substance 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 pixels of an organic EL display device.
  • the partition material has a light-shielding property by using a colorant for the purpose of increasing the contrast in the display device and improving the visibility.
  • the photosensitive resin composition tends to have low sensitivity, and as a result, the exposure time may be long and the productivity may be lowered. Therefore, the photosensitive resin composition used for forming the partition wall material containing the colorant is required to have higher sensitivity.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2001-281440 describes a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting high light-shielding properties by heat treatment after exposure. The composition to which titanium black is added is described.
  • Patent Document 2 Japanese Unexamined Patent Publication No. 2002-116536 describes carbon black in a radiation-sensitive resin composition containing [A] an alkali-soluble resin, [B] 1,2-quinonediazide compound, and [C] a colorant. It describes a method of blackening a partition material using.
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2010-237310 describes a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits light-shielding properties by heat treatment after exposure. The composition to which the heat-sensitive dye is added is described.
  • the photosensitive resin composition used for forming the colored partition material it is necessary to use a considerable amount of a colorant in order to sufficiently enhance the light-shielding property of the cured film.
  • a colorant used in order to sufficiently enhance the light-shielding property of the cured film.
  • the radiation applied to the film of the photosensitive resin composition is absorbed by the colorant, so that the effective intensity of the radiation in the film is lowered, and the photosensitive resin composition is formed. Is not sufficiently exposed, and as a result, the pattern formability is deteriorated.
  • a thick film for example, a film having a thickness of 2 to 3 ⁇ m using a photosensitive resin composition containing a blackening agent
  • the bottom of the film of the exposed portion is absorbed by radiation by a radiation-sensitive compound in addition to the blackening agent.
  • the amount of radiation that reaches is significantly reduced. Therefore, in the positive type, the alkali solubility at the bottom of the film in the exposed portion is insufficient and a resin residue is generated during development, or a large amount of the photosensitive resin composition is consumed in order to obtain a film having a desired thickness.
  • the residual film ratio may decrease.
  • a photosensitive resin composition containing a blackening agent a photosensitive resin composition capable of increasing the thickness of the cured film while imparting a high optical density (OD value) to the cured film is eagerly desired.
  • An object of the present invention is to provide a highly sensitive photosensitive resin composition containing a blackening agent, which can form a thick film pattern having a high optical density (OD value).
  • the present inventors contain a blackening agent by using a first resin having an epoxy group and a phenolic hydroxyl group in combination with a second resin having a predetermined weight average molecular weight, phenolic hydroxyl group equivalent and carboxy group content. It has been found that a thick film pattern can be formed even when the photosensitive resin composition is used.
  • the present invention includes the following aspects.
  • a first resin having an epoxy group and a phenolic hydroxyl group (B) A second resin having a weight average molecular weight of 3000 to 80,000, a phenolic hydroxyl group equivalent of 250 to 700, and a carboxy group content of 0.0 to 0.5 mmol / g.
  • a photosensitive resin composition containing (D) a radiation-sensitive compound and (E) a blackening agent, wherein the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 ⁇ m of the film thickness.
  • a photosensitive resin composition A photosensitive resin composition.
  • the second resin is the formula (4).
  • R 3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 4 is a linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group having 3 to 20 carbon atoms.
  • the second resin is the formula (3).
  • R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b is an integer of 1 to 5).
  • the photosensitive resin composition according to any one of [1] to [3], which has a structural unit represented by.
  • the second resin is the formula (5).
  • R 5 and R 6 are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and fully or partially fluorinated fluoroalkyl groups having 1 to 3 carbon atoms.
  • the photosensitive resin composition according to any one of [1] to [4], which has a structural unit represented by. [6]
  • the first resin is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and has the formula (2).
  • a is an integer of 1 to 5, and * represents a bond portion of a compound having at least two epoxy groups in one molecule to a residue excluding the epoxy group involved in the reaction. .
  • the photosensitive resin composition according to [6], wherein the compound having at least two epoxy groups in one molecule is a novolak type epoxy resin.
  • the blackening agent is a dye defined by a color index (CI) of Solvent Black 27 to 47.
  • the photosensitive resin composition further contains (C) a third resin having a phenolic hydroxyl group, which is different from both the first resin and the second resin, and the phenolic hydroxyl group equivalent of the third resin is 107 to 240.
  • a highly sensitive photosensitive resin composition containing a blackening agent which can form a thick film pattern having a high optical density (OD value).
  • alkali-soluble means that the photosensitive resin composition or its components, or the film or cured film of the photosensitive resin composition can be dissolved in 2.38% by mass of an aqueous solution of tetramethylammonium hydroxide.
  • the "alkali-soluble functional group” means a group that imparts such alkali solubility to the photosensitive resin composition or a component thereof, or a film or a cured film of the photosensitive resin composition. Examples of the alkali-soluble functional group include a phenolic hydroxyl group, a carboxy group, a sulfo group, a phosphoric acid group, an acid anhydride group, a mercapto group and the like.
  • the "radical polymerizable functional group” means an ethylenically unsaturated group
  • the "radical polymerizable compound” means a compound having one or more ethylenically unsaturated groups.
  • the "structural unit” means an atomic group constituting a part of the basic structure of a polymer, and this atomic group may have a pendant atom or a pendant atomic group.
  • a radical (co) polymer it means a unit derived from a radically polymerizable compound used as a monomer, and in the case of a phenol novolac resin, one molecule of phenol (C 6 H 5 OH) and 1 molecule. It means the following units formed by the condensation reaction of molecular formaldehyde (HCHO).
  • a structural unit having a pendant group side group
  • a structural unit having a pendant group used for forming a cross-linking site or a group derived from the pendant group and a structural unit having a free pendant group not involved in the formation of a cross-linking site are considered to be different from each other.
  • a polymer having a branched molecular chain branched chain
  • the structural unit including the branch point (branched unit) and the structural unit contained in the linear molecular chain are considered to be different from each other.
  • (meth) acrylic means acrylic or methacrylic
  • (meth) acrylate means acrylate or methacrylate
  • (meth) acryloyl means acryloyl or methacryloyl.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin or polymer mean standard polystyrene-equivalent values measured by gel permeation chromatography (GPC).
  • Phenolic hydroxyl group equivalent (Epoxy equivalent of raw material + molecular weight of carboxylic acid to be added) / (number of phenolic hydroxyl groups of carboxylic acid) Means the value calculated by.
  • the "resin component” means the first resin (A), the second resin (B), and the third resin (C) as an optional component.
  • the "solid content” includes an optional component such as a resin component, a radiation-sensitive compound (D), a blackening agent (E), and a dissolution accelerator (F), and is a liquid basic compound (G) and a solvent. It means the total mass of the components excluding (H).
  • the photosensitive resin composition of one embodiment is a first resin (A) having an epoxy group and a phenolic hydroxyl group, having a weight average molecular weight of 3000 to 80,000, a phenolic hydroxyl group equivalent of 250 to 700, and a carboxy group. It contains a second resin (B) having a content of 0.0 to 0.5 mmol / g, a radiation-sensitive compound (D), and a blackening agent (E).
  • the first resin (A) is a resin having an epoxy group and a phenolic hydroxyl group.
  • the resin having an epoxy group and a phenolic hydroxyl group is, for example, an epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter, may be referred to as “epoxy compound”) and a hydroxybenzoic acid compound. It can be obtained by reacting the carboxy group of.
  • epoxy compound an epoxy group of a compound having at least two epoxy groups in one molecule
  • a hydroxybenzoic acid compound a compound having at least two epoxy groups in one molecule
  • It can be obtained by reacting the carboxy group of.
  • a crosslink can be formed by a reaction with the phenolic hydroxyl group at the time of heating, and the chemical resistance and heat resistance of the coating film can be improved.
  • the phenolic hydroxyl group imparts alkali solubility during development to the resin.
  • reaction formula 1 shows an example of a reaction in which one of the epoxy groups of the epoxy compound reacts with the carboxy group of the hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group.
  • Examples of the compound having at least two epoxy groups in one molecule include a novolak type epoxy resin such as a phenol novolac type epoxy resin and a cresol novolak type epoxy resin, a bisphenol type epoxy resin, a biphenol type epoxy resin, and a naphthalene skeleton-containing epoxy.
  • Examples thereof include a resin, an alicyclic epoxy resin, and a heterocyclic epoxy resin.
  • These epoxy compounds may have two or more epoxy groups in one molecule, and may be used alone or in combination of two or more. Since these compounds are thermosetting, it is not possible to unambiguously describe their structures due to differences in the presence or absence of epoxy groups, the types of functional groups, the degree of polymerization, and the like, as is common knowledge of those skilled in the art.
  • R 1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a hydroxyl group having 1 to 2 carbon atoms, and m is an integer of 1 to 50.
  • Examples of the phenol novolac type epoxy resin include EPICLON (registered trademark) N-770 (manufactured by DIC Corporation) and jER (registered trademark) -152 (manufactured by Mitsubishi Chemical Corporation).
  • Examples of the cresol novolac type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) and EOCN (registered trademark) -102S (manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of the bisphenol type epoxy resin include bisphenol A type such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Co., Ltd.), and YD-128 (trade name, manufactured by Nittetsu Chemical & Materials Co., Ltd.).
  • Examples thereof include epoxy resins, bisphenol F type epoxy resins such as jER (registered trademark) 806 (manufactured by Mitsubishi Chemical Co., Ltd.) and YDF-170 (trade name, manufactured by Nittetsu Chemical & Materials Co., Ltd.).
  • Examples of the biphenol type epoxy resin include jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation).
  • Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (trade name, manufactured by DIC Corporation).
  • 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-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.) and the like.
  • the compound having at least two epoxy groups in one molecule is preferably a novolak type epoxy resin, and more preferably a cresol novolak type epoxy resin.
  • a photosensitive resin composition containing a novolak type epoxy resin, particularly a resin having an epoxy group and a phenolic hydroxyl group derived from a cresol novolak type epoxy resin, has excellent pattern forming properties, and its alkali solubility can be easily adjusted. There is little outgas.
  • the hydroxybenzoic acid compound is a compound in which at least one of the 2 to 6 positions 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-4-nitro Examples thereof include benzoic acid and 4-hydroxy-3-nitrobenzoic acid, and a dihydroxybenzoic acid compound is preferable from the viewpoint of enhancing alkali developability. These hydroxybenzoic acid compounds may be used alone or in combination of two or more.
  • the resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and formula (2).
  • a is an integer of 1 to 5
  • * represents a bond portion of a compound having at least two epoxy groups in one molecule to a residue excluding the epoxy group involved in the reaction.
  • 0.2 to 1.0 equivalent of the hydroxy benzoic acid compound can be used with respect to 1 equivalent of the epoxy group of the epoxy compound. It can be used, preferably 0.3 to 0.9 equivalents, and more preferably 0.4 to 0.8 equivalents. If the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and if it is 1.0 equivalent or less, an increase in molecular weight due to a side reaction can be suppressed.
  • a catalyst may be used to accelerate the reaction between the epoxy compound and the hydroxybenzoic acid compound.
  • the amount of the catalyst used can be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture composed of the epoxy compound and the hydroxybenzoic acid compound.
  • the reaction temperature can be 60 to 150 ° C. and the reaction time can be 3 to 30 hours.
  • Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanate, zirconium octanate and the like.
  • the number average molecular weight of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and further preferably 1000 to 5000.
  • the weight average molecular weight of the resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 30,000, more preferably 2000 to 25,000, and further preferably 3000 to 20000.
  • the alkali development speed is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good.
  • the number average molecular weight is 8000 or less, or the weight average molecular weight is 30,000 or less, the coatability and the alkali developability are good.
  • the phenolic hydroxyl group equivalent of the resin having an epoxy group and a phenolic hydroxyl group is preferably 60 to 300, more preferably 80 to 250, and further preferably 100 to 200.
  • the phenolic hydroxyl group equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 60 or more, the film thickness of the unexposed portion can be sufficiently maintained during alkaline development.
  • the phenolic hydroxyl group equivalent of the resin having an epoxy group and a phenolic hydroxyl group is 300 or less, the desired alkali solubility can be obtained.
  • the phenolic hydroxyl group equivalents of the first resin (A), the second resin (B) described later, and the third resin (C) of the optional component described later are after exposure to the photosensitive resin composition and before development. Means the value at the time. Whether or not there is a change between the original phenolic hydroxyl group equivalents of these resins and the phenolic hydroxyl group equivalents after exposure to the photosensitive resin composition and before development can be determined by the following procedure using NMR. You can judge. To 100 parts by mass of the resin to be measured, 30 parts by mass of the radiation-sensitive compound used in the photosensitive resin composition and 1 part by mass of methyltriphenylsilane as an internal standard are added and mixed in DMSO-d6.
  • the content of the first resin (A) in the photosensitive resin composition is preferably 5 to 60% by mass, based on the total mass of the resin component, the radiation-sensitive compound (D), and the blackening agent (E). It is preferably 10 to 55% by mass, more preferably 10 to 50% by mass.
  • the content of the first resin (A) is 5% by mass or more based on the total mass, the residual film ratio, heat resistance, sensitivity and the like are appropriate.
  • the optical density (OD value) of the cured film can be 0.5 or more per 1 ⁇ m of the film thickness. , The light-shielding property can be maintained even after curing.
  • the photosensitive resin composition preferably contains the first resin (A) in an amount of 20% by mass to 90% by mass, more preferably 25% by mass to 70% by mass, and more preferably 30% by mass, based on the total mass of the resin components. It is more preferable to contain% to 55% by mass. If the content of the first resin (A) is 20% by mass or more based on the total mass of the resin components, the desired alkali solubility can be obtained. When the content of the first resin (A) is 90% by mass or less based on the total mass of the resin components, high sensitivity can be imparted to the photosensitive resin composition.
  • the second resin (B) is a resin having a weight average molecular weight of 3000 to 80,000, a phenolic hydroxyl group equivalent of 250 to 700, and a carboxy group content of 0.0 to 0.5 mmol / g.
  • the second resin (B) is not particularly limited as long as it is different from the first resin (A).
  • "different" means that the structures of the structural units of one resin and another resin are different from each other, or when a certain resin contains one or more common structural units with another resin, the common structural units are summed up. It means that it contains less than 70 mol%, and resins having different molecular weights are regarded as the same resin.
  • Examples of the second resin (B) include acrylic resin, polystyrene resin, epoxy resin, polyamide resin, phenol resin, polyimide resin, polyamic acid resin, polybenzoxazole resin, polybenzoxazole resin precursor, silicone resin, and cyclic olefin. Examples thereof include polymers, cardo resins, and derivatives of these resins, and those having an alkali-soluble functional group bonded to these resins.
  • a homopolymer or a copolymer of a polymerizable monomer having a phenolic hydroxyl group can also be used.
  • any one of these resins can be used alone, or two or more of these resins can be used in combination.
  • the second resin (B) may have a radically polymerizable functional group.
  • the second resin (B) has a (meth) acryloyloxy group, an allyl group or a methallyl group as a radically polymerizable functional group.
  • the weight average molecular weight of the second resin (B) is 3000 to 80000, preferably 4000 to 30000, and more preferably 5000 to 15000. Since the weight average molecular weight is 3000 to 80,000, the alkaline development speed is appropriate and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so that the pattern resolution is good, and the coatability and alkali developability are also good. Is.
  • the number average molecular weight of the second resin (B) is preferably 1000 to 20000, more preferably 1500 to 15000, and further preferably 2000 to 10000. When the number average molecular weight is 1000 or more, the alkaline development rate is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good. When the number average molecular weight is 20000 or less, the coatability and the alkali developability are good.
  • the polydispersity (Mw / Mn) of the second resin (B) is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2. It is 8.8. By setting the degree of polydispersity within the above range, a photosensitive resin composition having excellent pattern forming property and alkali developability can be obtained.
  • the phenolic hydroxyl group equivalent of the second resin (B) is 250 to 700, preferably 260 to 600, and more preferably 270 to 550.
  • the second resin (B) having a phenolic hydroxyl group equivalent of 250 to 700 suppresses excessive dissolution in the unexposed portion as a resin component having low alkali solubility during development, while the exposed portion has high alkali solubility. Since it is released from the coating film into the developing solution as the resin component and any dissolution accelerator are dissolved, the sensitivity and residual film ratio of the photosensitive resin composition can be increased. As a result, the content of the radiation-sensitive compound (D) in the photosensitive resin composition can be reduced depending on the application, and as a result, the photosensitive resin composition can be made suitable for forming a thick film. can.
  • the carboxy group content of the second resin (B) is 0.0 to 0.5 mmol / g, preferably 0.0 to 0.1 mmol / g, and more preferably 0.00 to 0.05 mmol / g. Is. Since the carboxy group has higher alkali solubility than the phenolic hydroxyl group, it is not desirable that the carboxy group is contained in a large amount in the second resin (B), which is an alkali low solubility component. When the carboxy group content of the second resin (B) is 0.0 to 0.5 mmol / g, the alkali dissolution rate of the second resin (B), which is a low alkali solubility component, can be precisely controlled. ..
  • the second resin (B) is preferably a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer.
  • a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer can be obtained, for example, by radically polymerizing the polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. Can be manufactured. After synthesizing the copolymer by radical polymerization, a derivative to which a phenolic hydroxyl group is added may be used. Examples of the polymerizable monomer having a phenolic hydroxyl group include 4-hydroxystyrene, 4-hydroxyphenylmethacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide and the like. Can be mentioned.
  • polymerizable monomers examples include polymerizable styrene derivatives such as styrene, vinyltoluene, ⁇ -methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl-n-butyl ether and the like.
  • Ether compounds of vinyl alcohol methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl ( Meta) acrylate, tert-butyl (meth) acrylate, phenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2 , 2-Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (me
  • the copolymer of the polymerizable monomer having a phenolic hydroxyl group and the other polymerizable monomer has an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic ring structure, and the like. It is preferable to have one or more kinds of cyclic structures such as a heterocyclic structure.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • b is an integer of 1 to 5.
  • the polymerizable monomer having such a phenolic hydroxyl group 4-hydroxyphenyl methacrylate is particularly preferable.
  • R 3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 4 is a linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group having 3 to 20 carbon atoms.
  • a polymerizable monomer forming a structural unit represented by is preferable.
  • the acidic functional group is a group exhibiting an acid-base reaction with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, and specifically, a phenolic hydroxyl group, a carboxy group, a sulfo group, and a phosphoric acid. Groups include groups, acid anhydride groups, and mercapto groups.
  • alkyl group having 1 to 5 carbon atoms in R 3 of the formula (4) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and tert-. Butyl group, n-pentyl group and the like can be mentioned.
  • R 3 is preferably a methyl group.
  • the linear alkyl group having 1 to 20 carbon atoms and the branched alkyl group having 3 to 20 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
  • N-butyl group isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n -Dodecyl group, n-hexadecyl group and the like can be mentioned.
  • Examples of the cyclic alkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an isobornyl group, an adamantyl group and a dicyclopentanyl group.
  • aryl group having 6 to 20 carbon atoms examples include a phenyl group, a 4- (benzyloxymethoxy) phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, an anthrasenyl group, a phenanthrenyl group and the like.
  • R4 is preferably a tert-butyl group, a cyclohexyl group, an isobornyl group, a dicyclopentanyl group, a phenyl group, or a 4- (benzyloxymethoxy) phenyl group.
  • R 5 and R 6 are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and fully or partially fluorinated fluoroalkyl groups having 1 to 3 carbon atoms, respectively. Alternatively, it is a halogen atom, and R 7 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, and 1 to 6 carbon atoms.
  • R 5 and R 6 are preferably hydrogen atoms.
  • R 7 is preferably a cyclic alkyl group or a phenyl group having 3 to 12 carbon atoms. Phenylmaleimide and cyclohexylmaleimide are particularly preferred as such other polymerizable monomers.
  • 4-Hydroxyphenyl methacrylate is used as the polymerizable monomer having a phenolic hydroxyl group, and tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentanyl methacrylate, phenyl methacrylate and other polymerizable monomers are used. It is particularly preferable to use at least one selected from the group consisting of 4- (benzyloxymethoxy) phenylmethacrylate and at least one selected from the group consisting of phenylmaleimide and cyclohexylmaleimide in combination.
  • a resin obtained by radically polymerizing these polymerizable monomers as a second resin (B) having low alkali solubility, shape retention can be improved and outgas can be reduced.
  • the polymerization initiator for producing a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer by radical polymerization is not limited to the following, but is 2,2'-azo.
  • a product polymerization initiator or a peroxide polymerization initiator such as benzoyl peroxide, lauroyl peroxide, 1,1'-di (tert-butylperoxy) cyclohexane, and tert-butylperoxypivalate can be used.
  • the amount of the polymerization initiator used is generally 0.01 part by mass or more, 0.05 part by mass or more or 0.5 part by mass or more, 40 parts by mass or less, 20 parts by mass with respect to 100 parts by mass of the mixture of the polymerizable monomer. It is preferably parts by mass or less or 15 parts by mass or less.
  • a RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with a polymerization initiator.
  • the RAFT agent is not limited to the following, and thiocarbonylthio compounds such as dithioester, dithiocarbamate, trithiocarbonate, and xantate can be used.
  • the RAFT agent can be used in the 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 is preferably used in the range of 0.01 to 10 parts by mass.
  • the second resin (B) is represented by the formula (4).
  • R 3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 4 is a linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group having 3 to 20 carbon atoms.
  • the second resin (B) is represented by the formula (3).
  • R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b is an integer of 1 to 5). It has a structural unit represented by.
  • R2 is preferably a methyl group.
  • b is preferably 1.
  • the OH group is preferably at the 4-position.
  • the second resin (B) is represented by the formula (5).
  • R 5 and R 6 are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and completely or partially fluorinated fluoroalkyl groups having 1 to 3 carbon atoms. , Or a halogen atom, where R 7 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, and 1 to 6 carbon atoms.
  • R 5 and R 6 are preferably hydrogen atoms.
  • R 7 is preferably a phenyl group or a cyclohexyl group.
  • the second resin (B) is a copolymer containing a structural unit represented by the above formula (3), a structural unit represented by the formula (4), and a structural unit represented by the formula (5). Is preferable.
  • the photosensitive resin composition preferably contains the second resin (B) in an amount of 5% by mass to 50% by mass, more preferably 8% by mass to 45% by mass, and 10% by mass, based on the total mass of the resin components. It is more preferable to contain% to 40% by mass.
  • the content of the second resin (B) is 5% by mass or more based on the total mass of the resin components, a sufficient contrast due to the difference in dissolution rate from the first resin (A) can be obtained.
  • the content of the second resin (B) is 50% by mass or less based on the total mass of the resin components, the dissolution of the coating film during development can be made more uniform microscopically, and as a result, the coating surface surface. Roughness can be effectively suppressed.
  • the photosensitive resin composition may further contain, as an optional component, a third resin (C) having a phenolic hydroxyl group, which is different from both the first resin (A) and the second resin (B).
  • the phenolic hydroxyl group equivalent of the third resin (C) is 107 to 240, preferably 140 to 235, and more preferably 170 to 230. Since the third resin (C) having a phenolic hydroxyl group equivalent of 107 to 240 has higher alkali solubility than the second resin (B), the dissolution rate of the exposed portion and the unexposed portion of the cured film can be adjusted. It can be made, and thereby the pattern forming property can be enhanced.
  • the third resin (C) is preferably a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer.
  • the method for producing a polymerizable monomer having a phenolic hydroxyl group, another polymerizable monomer, and a copolymer of the polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer is described in the second method.
  • the resin (B) is as described above.
  • the third resin (C) 4-hydroxyphenylmethacrylate is used as the polymerizable monomer having a phenolic hydroxyl group, and at least selected from the group consisting of phenylmaleimide and cyclohexylmaleimide as the other polymerizable monomer. It is particularly preferable to use one.
  • a resin obtained by radically polymerizing these polymerizable monomers as the third resin (C)
  • shape retention and developability can be improved and outgas can be reduced.
  • the third resin (C) is represented by the formula (3).
  • R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • b is an integer of 1 to 5.
  • Structural unit represented by and formula (5) In the formula (5), R 5 and R 6 are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and completely or partially fluorinated fluoroalkyl groups having 1 to 3 carbon atoms.
  • R 7 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, and 1 to 6 carbon atoms. It is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.) It has a structural unit represented by.
  • the third resin (C) preferably does not contain the structural unit represented by the formula (4).
  • the number average molecular weight of the third resin (C) is preferably 1000 to 30,000, more preferably 1500 to 25,000, and even more preferably 2000 to 20000.
  • the weight average molecular weight of the third resin (C) is preferably 3000 to 80000, more preferably 4000 to 70,000, and further preferably 5000 to 60,000.
  • the alkali development speed is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good.
  • the number average molecular weight is 30,000 or less or the weight average molecular weight is 80,000 or less, the coatability and the alkali developability are good.
  • the polydispersity (Mw / Mn) of the third resin (C) is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2. It is 8.8. By setting the degree of polydispersity within the above range, a photosensitive resin composition having excellent pattern forming property and alkali developability can be obtained.
  • the photosensitive resin composition preferably contains the third resin (C) in an amount of 5% by mass to 50% by mass, more preferably 8% by mass to 45% by mass, and 10% by mass, based on the total mass of the resin components. It is more preferable to contain% to 40% by mass.
  • the content of the third resin (C) is 5% by mass or more based on the total mass of the resin components, the dissolution of the coating film during development can be made microscopically more uniform, and as a result, the coating surface can be made uniform. Roughness can be effectively suppressed.
  • the content of the third resin (C) was 50% by mass or less based on the total mass of the resin components, the contrast due to the difference in dissolution rate between the first resin (A) and the second resin (B) was maintained. A pattern can be formed.
  • a photoacid generator As the radiation-sensitive compound (D), a photoacid generator, a photobase generator or a photopolymerization initiator can be used.
  • a photoacid generator is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, ⁇ -rays, and electron beams. Since the photoacid generator increases the solubility of the irradiated portion in the alkaline aqueous solution, it can be used in a positive photosensitive resin composition in which the portion is dissolved.
  • a photobase generator is a compound that generates a base when irradiated with radiation.
  • a photopolymerization initiator is a compound that generates radicals when irradiated with radiation.
  • the photopolymerization initiator is a radical polymerization functional group or a radically polymerizable compound of the binder resin of the portion irradiated with radiation when the photosensitive resin composition contains a binder resin or a radically polymerizable compound having a radically polymerizable functional group. It can be used in a negative photosensitive resin composition in which radical polymerization of the above progresses and a polymer insoluble in an alkaline aqueous solution is formed in the portion thereof.
  • the radiation-sensitive compound (D) is preferably a photoacid generator in that a pattern with high sensitivity and high resolution can be obtained.
  • the photoacid generator at least one selected from the group consisting of a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt can be used.
  • the photoacid generator is a compound or salt that is sensitive to i-rays (365 nm).
  • the quinone-diazide compound includes a polyhydroxy compound in which quinone-diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone-diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone-diazide sulfonic acid is ester-bonded or a sulfonamide-bond. And so on. From the viewpoint of the contrast between the exposed portion and the unexposed portion, it is preferable that 20 mol% or more of the total functional group of the polyhydroxy compound or the polyamino compound is substituted with quinonediazide.
  • polyhydroxy compound examples 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, Methyltris-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 (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIRC-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-
  • polyamino compound examples include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diamino.
  • examples thereof include, but are not limited to, diphenyl sulfide.
  • polyhydroxypolyamino compound examples include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-dihydroxybenzidine and the like.
  • the quinone diazide compound is preferably a 1,2-naphthoquinone diazide-4-sulfonic acid ester or a 1,2-naphthoquinone diazide-5-sulfonic acid ester of a polyhydroxy compound.
  • the quinone diazide compound When the quinone diazide compound is irradiated with ultraviolet light or the like, it produces a carboxy group through the reaction shown in the following reaction formula 2. By generating a carboxy group, the exposed portion (coating) becomes soluble in an alkaline aqueous solution, and alkaline developability occurs in that portion.
  • the content of the photoacid generator in the photosensitive resin composition shall be 1 to 40 parts by mass based on a total of 100 parts by mass of the resin components. It is preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass.
  • the content of the photoacid generator is 1 part by mass or more based on the total of 100 parts by mass, the alkali developability is good, and when it is 40 parts by mass or less, the film is reduced by heating at 300 ° C. or higher. Can be suppressed.
  • a photobase generator may be used as the radiation-sensitive compound (D).
  • the photobase generator at least one selected from the group consisting of an amide compound and an ammonium salt can be used.
  • the photobase generator is a compound or salt that is sensitive to i-rays (365 nm).
  • Examples of the amide compound include 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate, 9-anthrylmethyl-N, N-dimethylcarbamate and 1- (anthraquinone-2-yl) ethylimidazole carboxylate. , (E) -1- [3- (2-Hydroxyphenyl) -2-propenoyl] piperidine and the like.
  • ammonium salt examples include 1,2-diisopropyl-3- (bisdimethylamino) methylene) guanididium 2- (3-benzoylphenyl) propionate, (Z)- ⁇ [bis (dimethylamino) methylidene] amino ⁇ -N. -Cyclohexylamino) methaminium tetrakis (3-fluorophenyl) borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate and the like.
  • the content of the photobase generator in the photosensitive resin composition shall be 1 to 40 parts by mass based on a total of 100 parts by mass of the resin components. It is preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass.
  • the content of the photobase generator is 1 part by mass or more based on the total of 100 parts by mass, the alkali developability is good, and when it is 40 parts by mass or less, the film is reduced by heating at 300 ° C. or higher. Can be suppressed.
  • a photopolymerization initiator may be used as the radiation-sensitive compound (D).
  • the photopolymerization initiator comprises a benzyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine oxide compound, an oxime ester compound, an acridine compound, a benzophenone compound, an acetophenone compound, an aromatic ketoester compound and a benzoic acid ester compound. At least one selected from the group can be used.
  • the photopolymerization initiator is a compound that is highly sensitive to i-rays (365 nm).
  • the photopolymerization initiator is highly sensitive at the time of exposure, the photopolymerization initiator is preferably an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine oxide compound, an oxime ester compound, an acridine compound or a benzophenone compound, and an ⁇ -aminoketone compound.
  • An acylphosphine oxide compound, or an oxime ester compound is more preferable.
  • Examples of the benzyl ketal compound include 2,2-dimethoxy-1,2-diphenylethane-1-one.
  • Examples of the ⁇ -hydroxyketone compound include 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -Hydroxycyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one or 2-hydroxy-1- [4- [4- (2-hydroxy-) 2-Methylpropionyl) benzyl] phenyl] -2-methylpropan-1-one can be mentioned.
  • Examples of the ⁇ -aminoketone compound include 2-dimethylamino-2-methyl-1-phenylpropane-1-one, 2-diethylamino-2-methyl-1-phenylpropane-1-one, and 2-methyl-2-one.
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide or bis (2,6-dimethoxybenzoyl)-(2). , 4,4-trimethylpentyl) phosphine oxide.
  • oxime ester compound examples include 1-phenylpropane-1,2-dione-2- (O-ethoxycarbonyl) oxime, 1-phenylbutane-1,2-dione-2- (O-methoxycarbonyl) oxime, and the like.
  • 1,3-Diphenylpropane-1,2,3-trion-2- (O-ethoxycarbonyl) oxime 1- [4- (phenylthio) phenyl] octane-1,2-dione-2- (O-benzoyl) Oxime, 1- [4- [4- (carboxyphenyl) thio] phenyl] Propane-1,2-dione-2- (O-acetyl) oxime, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-Carbazole-3-yl] Etanone-1- (O-acetyl) oxime, 1- [9-ethyl-6- [2-methyl-4- [1- (2,2-dimethyl-1,3-) Dioxolan-4-yl) methyloxy] benzoyl] -9H-carbazole-3-yl] etanone-1- (O-acetyl) oxime.
  • Examples of the acridine compound include 1,7-bis (acridine-9-yl) -n-heptane.
  • Examples of the benzophenone compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone, and alkyl.
  • Benzophenones, 3,3', 4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenones, 4-methylbenzophenones, dibenzylketones or fluorenones can be mentioned.
  • Examples of the acetophenone compound include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-tert-butyldichloroacetophenone, benzalacetophenone or 4-azidobenzalacetophenone.
  • Examples of the aromatic ketoester compound include 2-phenyl-2-methyl oxyacetate.
  • Examples of the benzoic acid ester compound include ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-ethyl) hexyl, ethyl 4-diethylaminobenzoate or methyl 2-benzoylbenzoate.
  • the photopolymerization initiator is used.
  • a photocationic polymerization initiator that generates a cationic species or Lewis acid by light can be used.
  • the photocationic polymerization initiator include triphenylsulfonium, sulfonium such as diphenyl-4- (phenylthio) phenylsulfonate, iodonium such as diphenyliodonium and bis (dodecylphenyl) iodinenium, and diazonium such as phenyldiazonium.
  • Fe such as 1-benzyl-2-cyanopyridinium, pyridinium such as 1- (naphthylmethyl) -2-cyanopyridinium, (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe. It is a cation, and the anionic moiety is composed of BF 4- , PF 6- , SbF 6- , [BX 4 ]- ( X is a phenyl group substituted with at least two or more fluorine atoms or a trifluoromethyl group) and the like.
  • the onium salt to be added is mentioned.
  • the content of the photopolymerization initiator in the photosensitive resin composition shall be 1 to 40 parts by mass based on a total of 100 parts by mass of the resin components. It is preferably 1.5 to 35 parts by mass, and more preferably 2 to 30 parts by mass.
  • the content of the photopolymerization initiator is 1 part by mass or more based on the total of 100 parts by mass, the alkali developability is good, and when it is 40 parts by mass or less, the film is reduced by heating at 300 ° C. or higher. Can be suppressed.
  • the photosensitive resin composition may further contain a radically polymerizable compound.
  • Resins and compounds having a plurality of ethylenically unsaturated groups as radically polymerizable compounds can crosslink the coating film to increase its hardness.
  • a compound having a plurality of (meth) acrylic groups as the radically polymerizable compound from the viewpoint of reactivity at the time of exposure, hardness of the film, heat resistance and the like.
  • Such compounds include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylol.
  • the content of the radically polymerizable compound in the photosensitive resin composition can be 15 parts by mass to 65 parts by mass and 20 parts by mass to 60 parts by mass with respect to 100 parts by mass of the total resin components. Is preferable, and 25 parts by mass to 50 parts by mass is more preferable.
  • the content of the radically polymerizable compound is in the above range, the alkali developability is good, and the heat resistance of the cured film can be improved.
  • the blackening agent (E) is selected from the group consisting of black dyes and black pigments. A black dye and a black pigment may be used in combination. By forming a black partition wall on the organic EL element using the photosensitive resin composition containing the blackening agent (E), the visibility of a display device such as an organic EL display can be improved.
  • the black agent (E) contains a black dye.
  • a black dye a dye specified by the color index (CI) of Solvent Black 27 to 47 can be used.
  • the black dye is preferably C.I. I. It is specified in. Solvent Black 27-47 C.I. I.
  • the photosensitive resin composition containing a black dye has less residual colorant during development as compared with the photosensitive resin composition containing a black pigment, and can form a high-definition pattern on the film.
  • the content of the black dye in the photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 10 parts by mass, based on a total of 100 parts by mass of the resin components. It is 15 to 100 parts by mass, more preferably 20 to 80 parts by mass.
  • the content of the black dye is 10 parts by mass or more based on the total of 100 parts by mass, the light-shielding property of the film after curing can be maintained.
  • the content of the black dye is 150 parts by mass or less based on the total of 100 parts by mass, the residual film ratio, heat resistance, sensitivity and the like are appropriate.
  • a black pigment may be used as the blackening agent (E).
  • the black pigment include carbon black, carbon nanotube, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigment, lactam pigment and the like. Those having a surface treatment applied to these black pigments can also be used.
  • Examples of commercially available perylene-based pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, 34, etc. manufactured by BASF.
  • Examples of commercially available lactam pigments include Irgaphor® Black S0100CF manufactured by BASF.
  • the black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene-based pigments, and lactam-based pigments.
  • the black agent (E) is a black pigment that does not easily inhibit the polymerization.
  • the content of the black pigment in the photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 10 parts by mass, based on a total of 100 parts by mass of the resin components. It is 15 to 100 parts by mass, more preferably 20 to 80 parts by mass.
  • the content of the black pigment is 10 parts by mass or more based on the total of 100 parts by mass, sufficient light-shielding property can be obtained.
  • the content of the black pigment is 150 parts by mass or less based on the total of 100 parts by mass, the residual film ratio, sensitivity and the like are appropriate.
  • the total amount of the black dye and the black pigment in the photosensitive resin composition is preferably 10 to 150 based on a total of 100 parts by mass of the resin components. It is by mass, more preferably 15 to 100 parts by mass, and even more preferably 20 to 80 parts by mass. When the total amount of the black dye and the black pigment is 10 parts by mass or more based on the total 100 parts by mass, sufficient light-shielding property can be obtained. If the total amount of the black dye and the black pigment is 150 parts by mass or less based on the total 100 parts by mass, the residual film ratio, sensitivity and the like are appropriate.
  • the photosensitive resin composition contains, as optional components, a dissolution accelerator (F), a basic compound (G), a solvent (H), a thermosetting agent, a surfactant, a second colorant other than the blackening agent (E), and the like.
  • a dissolution accelerator F
  • G basic compound
  • H solvent
  • thermosetting agent thermosetting agent
  • surfactant a second colorant other than the blackening agent
  • E second colorant other than the blackening agent
  • the optional component is defined as not applicable to any of (A) to (E).
  • the photosensitive resin composition may contain a dissolution accelerator (F), for example, in order to improve the solubility of the alkali-soluble portion during development.
  • a dissolution accelerator (F) a small molecule compound having an alkali-soluble functional group is used. Of these, a compound having at least one group selected from a carboxy group and a phenolic hydroxyl group is preferable.
  • low molecular weight compounds having a carboxy group include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and capric acid; oxalic acid and malon. Acids, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc.
  • aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and capric acid
  • Aliphatic dicarboxylic acids such as aliphatic tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimertic acid, and mesitylic acid; phthalic acid, isophthalic acid, Aromatic polycarboxylic acids such as terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid and gallic acid; phenylacetic acid, hydroatropic acid, hydrocay Examples thereof include other carboxylic acids such as dermal acid, mandelic acid, phenylsuccinic acid, atropic acid, silicic acid, methyl silicate, benzyl silicate, cinnamyldenacetic acid, kumalic acid and umberic acid.
  • Low-molecular-weight compounds having a phenolic hydroxyl group include catechol, resorcinol, hydroquinone, propyl gallate, dihydroxynaphthalene, leukokinizarin, 1,2,4-benzenetriol, anthracentriol, pyrogallol, fluoroglucinol, tetrahydroxybenzophenone, and phenolphthal.
  • Rain, phenolphthalin, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, ⁇ , ⁇ , ⁇ '-tris (4-hydroxyphenyl) -1-ethyl-4 -Isopropylbenzene and the like can be mentioned.
  • the content of the dissolution accelerator (F) can be 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, and more preferably 3 to 3 parts by mass, based on 100 parts by mass of the total resin components. It is 12 parts by mass. If the content of the dissolution accelerator (F) is 0.1 parts by mass or more based on the total of 100 parts by mass, the dissolution of the resin component can be effectively promoted, and if it is 20 parts by mass or less. Excessive dissolution of the resin component can be suppressed, and the pattern formability of the coating film, surface quality and the like can be improved.
  • the photosensitive resin composition can contain a basic compound (G) in order to ensure the long-term reliability of the organic EL device.
  • the basic compound (G) acts as a quencher of an acidic component or moiety such as a carboxylic acid or a phenolic hydroxyl group contained in the photosensitive resin composition, or an acidic gas generated from a photoacid generator.
  • the use of the basic compound (G) can prevent a decrease in emission luminance, pixel shrinkage, generation of dark spots, and the like.
  • Examples of the basic compound (G) include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, 3- (2-ethylhexyloxy) propylamine, and di-n-.
  • the content of the basic compound (G) is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 3 parts by mass, based on 100 parts by mass of the total solid content excluding the basic compound (G). It is 2 parts by mass or less.
  • the photosensitive resin composition can be used in a solution state (however, when a black pigment is contained, the pigment is in a dispersed state) by dissolving it in a solvent.
  • a radiation-sensitive compound (D) and a blackening agent are added to a solution obtained by dissolving a first resin (A), a second resin (B), and an optional third resin (C) in a solvent (H).
  • E if necessary, a solution-state photosensitive resin composition by mixing an arbitrary component such as a dissolution accelerator (F), a basic compound (G), a thermosetting agent, and a surfactant in a predetermined ratio. You can prepare things.
  • the photosensitive resin composition can be adjusted to a viscosity suitable for the coating method used by changing the amount of the solvent.
  • Examples of the solvent (H) include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol.
  • glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether
  • ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate
  • diethylene glycol diethylene glycol.
  • Diethylene glycol compounds such as monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol monoalkyl ether acetate compounds such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and cyclohexanone; ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropion Methyl acid, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbut
  • thermosetting agent As the thermosetting agent, a thermal radical generator can be used.
  • Preferred thermal radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl.
  • the content of the thermosetting agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the thermosetting agent. ..
  • the photosensitive resin composition may contain a surfactant, for example, in order to improve the coatability, the smoothness of the coating film, or the developability of the coating film.
  • a surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and poly such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether.
  • Oxyethylene aryl ethers Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafuck® F-251, F-281, F 430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559 (above, Product name, manufactured by DIC Co., Ltd., Surfron (registered trademark) S-242, S-243, S-386, S-420, S-611 (above, product name, manufactured by AGC Seimi Chemical Co., Ltd.) Fluorobased surfactants such as; organosiloxane polymers KP323, KP326, KP341 (above, trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned. These may be used alone, or two or more kinds may be used.
  • the content of the surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 part by mass or less, based on 100 parts by mass of the total solid content excluding the surfactant. Is.
  • the photosensitive resin composition can contain a second colorant other than the blackening agent (E).
  • the second colorant include dyes, organic pigments, inorganic pigments and the like, which can be used according to the purpose.
  • the second colorant can be used in a content that does not impair the effects of the present invention.
  • dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilben dyes, diphenylmethane dyes, and triphenylmethane dyes.
  • dyes include dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, flugide dyes, nickel complex dyes, and azulene dyes.
  • 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. Pigment Brown 23, 25, 26 and the like can be mentioned.
  • the photosensitive resin composition comprises a first resin (A), a second resin (B), an optional third resin (C), a radiation-sensitive compound (D), a blackening agent (E), and if necessary, dissolved. It can be prepared by dissolving or dispersing the above optional components such as the accelerator (F) and the basic compound (G) in the solvent (H) and mixing them.
  • the solid content concentration of the photosensitive resin composition can be appropriately determined.
  • the solid content concentration of the photosensitive resin composition may be 1 to 60% by mass, 3 to 50% by mass, or 5 to 40% by mass.
  • a known method can be used as the dispersion mixing method when a pigment is used.
  • ball type such as ball mill, sand mill, bead mill, paint shaker, rocking mill, blade type such as kneader, paddle mixer, planetary mixer, henschel mixer, roll type such as 3-roll mixer, etc.
  • An ultrasonic wave, a homogenizer, a rotation / revolution mixer, or the like may be used. It is preferable to use a bead mill from the viewpoint of dispersion efficiency and fine dispersion.
  • the prepared photosensitive resin composition is usually filtered before use.
  • the filtering means include a millipore filter having a pore size of 0.05 to 1.0 ⁇ m.
  • the photosensitive resin composition prepared in this way is also excellent in long-term storage stability.
  • the photosensitive resin composition When the photosensitive resin composition is used for radiation lithography, first, the photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition can be applied to the surface of the substrate and the solvent can be removed by means such as heating to form a film.
  • the method for applying the coating composition to the substrate surface is not particularly limited, and for example, a spray method, a roll coating method, a slit method, a spin coating method, or the like can be used.
  • the solvent is usually removed by heating to form a film (pre-bake).
  • the heating conditions vary depending on the type of each component, the mixing ratio, etc., but a film is usually obtained by heat-treating at 70 to 130 ° C., for example, for 30 seconds to 20 minutes on a hot plate and 1 to 60 minutes in an oven. be able to.
  • the thickness of the formed coating is 2-3 ⁇ m.
  • the prebaked film is irradiated with radiation (for example, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, gamma ray, synchrotron radiation, etc.) through a photomask having a predetermined pattern (exposure step).
  • radiation for example, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, gamma ray, synchrotron radiation, etc.
  • the preferred radiation is ultraviolet or visible light having a wavelength of 250-450 nm.
  • the radiation is i-ray.
  • the radiation is ghi rays.
  • the film is developed by contacting it with a developing solution, unnecessary parts are removed, and a pattern is formed on the film (development process).
  • a developing solution examples include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di-.
  • Secondary amines such as n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alkaline amines such as dimethylethanolamine and triethanolamine; Fourth such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline Secondary ammonium salts; of alkaline compounds such as pyrrol, piperidine, cyclic amines such as 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane.
  • An aqueous solution can be used.
  • 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 an alkaline aqueous solution can also be used as a developer.
  • the development time is usually 30 to 180 seconds.
  • the developing method may be any of a liquid filling method, a shower method, a dipping method and the like. After development, a pattern can be formed on the film by washing with running water for 30 to 90 seconds, removing unnecessary portions, and air-drying with compressed air or compressed nitrogen.
  • a cured film can be obtained by heat-treating the patterned film with a heating device such as a hot plate or an oven at 100 to 350 ° C. for 20 to 200 minutes (post-baking, heat treatment). Process).
  • a heating device such as a hot plate or an oven at 100 to 350 ° C. for 20 to 200 minutes.
  • the temperature may be kept constant, the temperature may be continuously increased, or the temperature may be increased stepwise.
  • the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 ⁇ m film thickness. Thereby, sufficient light-shielding property can be obtained.
  • the OD value of the cured film of the photosensitive resin composition is preferably 0.7 or more, more preferably 1.0 or more.
  • One embodiment is to prepare a coating composition by dissolving or dispersing a photosensitive resin composition in a solvent, applying the coating composition to a substrate to form a film, and removing the solvent contained in the film. To dry the film, to expose the film by irradiating the dried film through a photomask, to develop the exposed film by contacting it with a developing solution, and to form a pattern on the film.
  • a method for producing an organic EL element partition wall or an organic EL element insulating film which comprises heat-treating a film on which a pattern is formed at a temperature of 100 ° C. to 350 ° C. to form an organic EL element partition wall or an organic EL element insulating film. Is.
  • Organic EL element partition wall One embodiment is an organic EL device partition wall containing a cured product of a photosensitive resin composition.
  • Organic EL element insulating film One embodiment is an organic EL device insulating film containing a cured product of a photosensitive resin composition.
  • Organic EL element One embodiment is an organic EL device containing a cured product of a photosensitive resin composition.
  • TMAH tetramethylammonium hydroxide
  • polystyrene is standard under the following measurement conditions. It was calculated using a calibration line prepared using a substance.
  • Device name Shodex® GPC-101
  • Mobile phase Tetrahydrofuran Flow rate: 1.0 mL / min
  • Detector Chromatography (registered trademark) RI-71 Temperature: 40 ° C
  • First resin (A) Production of resin (N770OH70) having an epoxy group and a phenolic hydroxyl group 75.2 g of ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as a solvent in a 300 mL three-necked flask. 37.6 g of EPICLON (registered trademark) N-770 (phenol novolak type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 188) was charged as a compound having at least two epoxy groups in one molecule, and the temperature was 60 ° C. under a nitrogen gas atmosphere. Dissolved in.
  • the reaction solution was returned to room temperature, diluted with ⁇ -butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain a solution of 286.5 g of a resin having an epoxy group and a phenolic hydroxyl group (N770OH70).
  • the obtained reactants had a number average molecular weight of 2400, a weight average molecular weight of 5400, an epoxy equivalent of 2000, a phenolic hydroxyl group equivalent of 142, and a carboxy group content of 0 mmol / g.
  • First resin (A) Production of resin (N695OH70) having an epoxy group and a phenolic hydroxyl group 75.2 g of ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as a solvent in a 300 mL three-necked flask. 37.8 g of EPICLON (registered trademark) N-695 (cresol novolac type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 214) was charged as a compound having at least two epoxy groups in one molecule, and the temperature was 60 ° C. under a nitrogen gas atmosphere. Dissolved in.
  • the reaction solution was returned to room temperature, diluted with ⁇ -butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain a solution of 274.2 g of a resin having an epoxy group and a phenolic hydroxyl group (N695OH70).
  • the obtained reactants had a number average molecular weight of 3000, a weight average molecular weight of 5100, an epoxy equivalent of 2200, a phenolic hydroxyl group equivalent of 161 and a carboxy group content of 0 mmol / g.
  • Second Resin (B) Production of Second Resin (B-TBMA 42.5%) Having a Phenolic Hydroxyl Group 4-Hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 17.3 g, N -Cycloxyl maleimide (manufactured by Nippon Catalyst Co., Ltd.) 6.15 g and tert-butyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester TB”) 13.8 g, and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent.
  • PQMA Phenolic Hydroxyl Group 4-Hydroxyphenyl methacrylate
  • the reaction solution cooled to room temperature was added dropwise to a mixture of 1000 g of hexane and toluene at 80:20 to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 80 ° C. for 5 hours to recover 36.5 g of white powder.
  • the obtained second resin B-TBMA 42.5% having a phenolic hydroxyl group had a number average molecular weight of 4100, a weight average molecular weight of 7600, a phenolic hydroxyl group equivalent of 384, and a carboxy group content of 0 mmol / g.
  • Second resin (B) Production of second resin (B-PhMA 41%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 17.0 g, N-cyclohexyl Maleimide (manufactured by Nippon Catalyst Co., Ltd.) 5.83 g and phenylmethacrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH”) 14.4 g, and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 60.0 g as a solvent.
  • PQMA phenolic hydroxyl group 4-hydroxyphenyl methacrylate
  • N-cyclohexyl Maleimide manufactured by Nippon Catalyst Co., Ltd.
  • phenylmethacrylate manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH”
  • the reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 80 ° C. for 5 hours to recover 36.5 g of white powder.
  • the obtained second resin B-PhMA 41% having a phenolic hydroxyl group had a number average molecular weight of 4300, a weight average molecular weight of 7800, a phenolic hydroxyl group equivalent of 390, and a carboxy group content of 0 mmol / g.
  • Second Resin (B) Production of Second Resin (B-PhMA53%) Having a Phenolic Hydroxyl Group 4-Hydroxyphenylmethacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 12.5 g, N-cyclohexyl Maleimide (manufactured by Nippon Catalyst Co., Ltd.) 5.90 g and phenylmethacrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH”) 18.9 g, and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 56.0 g as a solvent.
  • PQMA Phenolic Hydroxyl Group 4-Hydroxyphenylmethacrylate
  • the reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 80 ° C. for 5 hours to recover 36.5 g of white powder.
  • the obtained second resin having a phenolic hydroxyl group (B-PhMA53%) had a number average molecular weight of 4400, a weight average molecular weight of 7500, a phenolic hydroxyl group equivalent of 531 and a carboxy group content of 0 mmol / g.
  • Second resin (B) Production of second resin (B-PhMA 20%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 24.6 g, N-cyclohexyl Maleimide (manufactured by Nippon Catalyst Co., Ltd.) 5.71 g and phenylmethacrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH”) 6.89 g, and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 55.8 g as a solvent.
  • PQMA phenolic hydroxyl group 4-hydroxyphenyl methacrylate
  • PQMA phenolic hydroxyl group 4-hydroxyphenyl methacrylate
  • N-cyclohexyl Maleimide manufactured by Nippon Catalyst Co., Ltd.
  • phenylmethacrylate manufactured by Mitsubishi Chemical Co
  • the reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 80 ° C. for 5 hours to recover 36.4 g of white powder.
  • the obtained second resin B-PhMA 20% having a phenolic hydroxyl group had a number average molecular weight of 3600, a weight average molecular weight of 7200, a phenolic hydroxyl group equivalent of 270, and a carboxy group content of 0 mmol / g.
  • V-601 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • 14.6 g of 1-methoxy-2-propyl acetate manufactured by Daicel Co., Ltd.
  • the two obtained solutions were simultaneously placed in 61.2 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) heated to 85 ° C. in a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. The mixture was added dropwise, and then the reaction was carried out at 85 ° C. for 3 hours.
  • the reaction solution cooled to room temperature was added dropwise to 815 g of toluene to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 90 ° C. for 4 hours to recover 32.4 g of white powder.
  • the obtained polymerizable monomer having a phenolic hydroxyl group and other polymerizable monomer copolymer PCX-02e has a number average molecular weight of 3100, a weight average molecular weight of 6700, a phenolic hydroxyl group equivalent of 210, and a carboxy group. The content was 0 mmol / g.
  • GMA-MAA glycidyl methacrylate and methacrylic acid
  • PGME solution having a solid content of 30% by mass. Since the obtained GMA-MAA has a carboxy group and an epoxy group in the molecule, it has high self-reactivity, that is, ring-opening polymerization of the epoxy group easily proceeds. Therefore, when reprecipitation and vacuum drying are performed, the molecular weight is high. It became epoxide and could not be isolated.
  • the PGME solution of GMA-MAA had low stability, and the viscosity of the solution increased as the molecular weight increased over time.
  • Second resin (B) Production of second resin (B-CHMA 20%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 24.5 g, N-cyclohexyl 7.11 g of maleimide (manufactured by Nippon Catalyst Co., Ltd.) and 5.68 g of cyclohexyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) were added to 69.3 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent, as a polymerization initiator.
  • PQMA phenolic hydroxyl group 4-hydroxyphenyl methacrylate
  • the reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 80 ° C. for 5 hours to recover 39.1 g of white powder.
  • the obtained second resin B-CHMA 20% having a phenolic hydroxyl group had a number average molecular weight of 3500, a weight average molecular weight of 7200, a phenolic hydroxyl group equivalent of 271, and a carboxy group content of 0 mmol / g.
  • Second resin (B) Production of second resin (B-CHMA 40%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 17.14 g, N-cyclohexyl 14.39 g of maleimide (manufactured by Nippon Catalyst Co., Ltd.) and 5.75 g of cyclohexyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) are added to 69.3 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent, as a polymerization initiator.
  • PQMA phenolic hydroxyl group 4-hydroxyphenyl methacrylate
  • the reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 80 ° C. for 5 hours to recover 39.1 g of white powder.
  • the obtained second resin B-CHMA 40% having a phenolic hydroxyl group had a number average molecular weight of 3900, a weight average molecular weight of 7500, a phenolic hydroxyl group equivalent of 387, and a carboxy group content of 0 mmol / g.
  • Second resin (B) Production of second resin (B-BOM 32%) having a phenolic hydroxyl group 4-Hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko KK) 17.3 g, N, N -Diisopropylethylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 29.0 g, tetrahydrofuran (dehydrated) (manufactured by Kanto Chemical Co., Ltd.) 160 g in a 500 mL three-necked flask until the solid is completely dissolved in a nitrogen gas atmosphere. Stirred.
  • PQMA phenolic hydroxyl group 4-Hydroxyphenyl methacrylate
  • the obtained second resin B-BOM having a phenolic hydroxyl group had a number average molecular weight of 3600, a weight average molecular weight of 6900, a phenolic hydroxyl group equivalent of 431, and a carboxy group content of 0 mmol / g.
  • Second resin (B) Production of second resin (B-IBMA 20%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 23.1 g, N-cyclohexyl Polymerization of 8.86 g of maleimide (manufactured by Nippon Catalyst Co., Ltd.) and 5.35 g of isobornyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) with 69.2 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent.
  • PQMA phenolic hydroxyl group 4-hydroxyphenyl methacrylate
  • the reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 80 ° C. for 5 hours to recover 39.1 g of white powder.
  • the obtained second resin B-IBMA 20% having a phenolic hydroxyl group had a number average molecular weight of 3600, a weight average molecular weight of 7100, a phenolic hydroxyl group equivalent of 288, and a carboxy group content of 0 mmol / g.
  • Second resin (B) Production of second resin (B-TCDMA 20%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 23.1 g, N-cyclohexyl 8.79 g of maleimide (manufactured by Nippon Catalyst Co., Ltd.) and 5.37 g of dicyclopentanyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) were added to 69.2 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent.
  • PQMA phenolic hydroxyl group 4-hydroxyphenyl methacrylate
  • the reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer.
  • the precipitated copolymer was recovered by filtration and vacuum dried at 80 ° C. for 5 hours to recover 39.1 g of white powder.
  • the obtained second resin B-TCDMA 20% having a phenolic hydroxyl group had a number average molecular weight of 3800, a weight average molecular weight of 8000, a phenolic hydroxyl group equivalent of 287, and a carboxy group content of 0 mmol / g.
  • Table 1 shows the structural unit ratio of the resin, the phenolic hydroxyl group equivalent, the carboxy group content, the alkali dissolution rate, and the weight average molecular weight (Mw).
  • PQMA represents a structural unit derived from 4-hydroxyphenylmethacrylate
  • CHMI represents a structural unit derived from N-cyclohexylmaleimide.
  • TS-150A (4,4'-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (TrisP-), which is a quinonediazide compound, is used.
  • TrisP- which is a quinonediazide compound
  • PA an ester of 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonic acid), manufactured by Toyo Synthetic Industry Co., Ltd.
  • the structure of TS-150A is shown below.
  • Black agent (E) As the blackening agent, VALIFAST (registered trademark) BLACK 3820 (black dye specified by CI of Solvent Black 27, manufactured by Orient Chemical Industry Co., Ltd.), which is a black dye, was used.
  • VALIFAST registered trademark
  • BLACK 3820 black dye specified by CI of Solvent Black 27, manufactured by Orient Chemical Industry Co., Ltd.
  • an exposure device incorporating an ultra-high pressure mercury lamp (trade name: Multilight ML-251A / B, Ushio Denki Co., Ltd.) Band pass filter for mercury exposure (trade name HB0365, manufactured by Asahi Spectrometry Co., Ltd.) and photomask made of quartz (5 ⁇ m, 10 ⁇ m, 20 ⁇ m, 50 ⁇ m, 100 ⁇ m, 200 ⁇ m, 500 ⁇ m line & space (L / S)) It was exposed at 100 mJ / cm 2 through the one having a pattern).
  • the exposure amount was measured using an ultraviolet integrated photometer (trade name UIT-150 light receiving unit UVD-S365, manufactured by Ushio, Inc.). Then, using a spin developer (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), alkaline development was performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution in the range of 20 seconds to 200 seconds until the film on the exposed portion disappeared. rice field. Therefore, in Table 2, the solubility of the exposed part is expressed as 2.70 ⁇ m (more than 2.70 ⁇ m because the pattern was peeled off only in Comparative Example 2) together with the development time.
  • the photosensitive resin composition was bar-coated on a glass substrate (size 100 mm ⁇ 100 mm ⁇ 1 mm) so that the dry film thickness was 2.7 ⁇ m, and heated on a hot plate at 120 ° C. for 120 seconds to dry the solvent (pre-bake). .. After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, manufactured by Filmometrics Co., Ltd.), 2.38% by mass hydroxylation using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). Alkaline development was carried out with an aqueous solution of tetramethylammonium for the same development time as the solubility in the exposed part.
  • an optical film thickness measuring device F20-NIR, manufactured by Filmometrics Co., Ltd.
  • AD-1200 manufactured by Takizawa Sangyo Co., Ltd.
  • the film thickness after alkaline development was measured again using an optical film thickness measuring device (F20-NIR, manufactured by Filmometrics Co., Ltd.), and the film thickness ( ⁇ m) dissolved before and after development was calculated as the unexposed portion solubility. ..
  • ⁇ Difference in solubility was obtained by subtracting the solubility ( ⁇ m) in the unexposed portion from the solubility ( ⁇ m) in the exposed portion. The larger the solubility difference, the higher the sensitivity and the better the pattern forming property.
  • the photosensitive resin composition was spin-coated on a glass substrate (size 100 mm ⁇ 100 mm ⁇ 1 mm) so that the dry film thickness was about 1.5 ⁇ m, and heated on a hot plate at 120 ° C. for 120 seconds to dry the solvent. Then, a film was obtained by curing at 250 ° C. for 60 minutes in a nitrogen gas atmosphere.
  • the OD value of the cured film was measured with a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.), corrected by the OD value of glass only, and converted into an OD value per 1 ⁇ m of the film thickness.
  • the film thickness was measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmometrics Co., Ltd.).
  • Table 2 also shows the alkali dissolution rate of the photosensitive resin composition.
  • Table 2 shows the evaluation results of the photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4. In Comparative Example 3, pattern peeling occurred during development, and accurate solubility could not be measured. Therefore, the numerical values related to solubility in Table 2 are shown in parentheses. Comparative Example 4 could not be evaluated because the stability of the PGME solution of GMA-MAA was low.
  • the photosensitive resin composition of the present disclosure can be suitably used for radiation lithography for forming a partition wall or an insulating film of an organic EL element.
  • An organic EL device provided with a partition wall or an insulating film formed from the photosensitive resin composition of the present disclosure is suitably used as an electronic component of a display device showing good contrast.

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WO2018186494A1 (ja) * 2017-04-07 2018-10-11 昭和電工株式会社 感光性樹脂組成物
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