WO2011086997A1 - 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置、及び、液晶表示装置 - Google Patents

感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置、及び、液晶表示装置 Download PDF

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WO2011086997A1
WO2011086997A1 PCT/JP2011/050295 JP2011050295W WO2011086997A1 WO 2011086997 A1 WO2011086997 A1 WO 2011086997A1 JP 2011050295 W JP2011050295 W JP 2011050295W WO 2011086997 A1 WO2011086997 A1 WO 2011086997A1
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group
resin composition
photosensitive resin
structural unit
methyl
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PCT/JP2011/050295
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English (en)
French (fr)
Japanese (ja)
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幸一 杉原
山田　悟
享平 崎田
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富士フイルム株式会社
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Priority to KR1020127018418A priority Critical patent/KR101650903B1/ko
Priority to CN201180005875.5A priority patent/CN102725692B/zh
Publication of WO2011086997A1 publication Critical patent/WO2011086997A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • 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
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Definitions

  • the present invention relates to a photosensitive resin composition, a method for forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device.
  • An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film.
  • photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
  • the interlayer insulating film in the display device is required to have high transparency in addition to the properties of the cured film such as insulation, solvent resistance, heat resistance, and indium tin oxide (ITO) sputtering suitability. For this reason, an attempt has been made to use an acrylic resin having excellent transparency as a film forming component.
  • micro lenses having a lens diameter of about 3 ⁇ m to 100 ⁇ m, or those micro lenses are defined.
  • An array of microlenses is used.
  • a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is as a lens, or by using the melt-flowed lens pattern as a mask and drying.
  • a method of transferring a lens shape to a base by etching is known.
  • a radiation sensitive resin composition is widely used for the formation of the lens pattern.
  • JP-A-5-165214 discloses (A) (a) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, and (b) a radical polymerizable having an epoxy group.
  • a photosensitive resin composition having a compound and (c) a resin soluble in an alkaline aqueous solution, which is a copolymer of other radical polymerizable compounds, and (B) a radiation-sensitive acid generating compound has been proposed.
  • JP-A-2009-98616 discloses (A) a structural unit having a specific structure containing an acid-dissociable group and a structural unit having a functional group that can react with a carboxyl group to form a covalent bond.
  • a resin that is insoluble or hardly soluble in alkali and becomes alkali-soluble when the acid-dissociable group is dissociated and (B) a compound that generates an acid upon irradiation with active light or radiation.
  • a positive photosensitive resin composition is described.
  • the photosensitive resin composition described in JP-A-5-165214 is insufficient in sensitivity and stability over time, and the cured film obtained from the photosensitive resin composition is highly colored by baking. There was a problem. In addition, sufficient sensitivity was not obtained for the photosensitive resin compositions described in JP-A-2004-264623 and JP-A-2009-98616.
  • An object of the present invention is to obtain a cured film having a high transmittance after curing and a small decrease in the transmittance even when heated, and is very high even when heating (PEB: post exposure baking) is not performed after exposure. It is providing the photosensitive resin composition which has a sensitivity. Moreover, the further subject of this invention is providing the cured film using the photosensitive resin composition of this invention, its manufacturing method, the organic electroluminescence display provided with this cured film, and a liquid crystal display device.
  • a photosensitive resin composition comprising (A) an acetal resin, (B) a photoacid generator, and (C) a solvent
  • the (A) acetal resin is a structural unit (a1) having a structure that generates a carboxyl group with an acid, a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, a structural unit having an epoxy group or an oxetanyl group (a3 And a polymer having a structural unit (a4) having a hydroxyl group or an alkyleneoxy group, and having an acetal structure or a ketal structure,
  • the structural unit (a1): the structural unit (a2) : Structural unit (a3): Structural unit (a4) 0.2 to 0.65: 0.02 to
  • (M) a development accelerator is contained, and the (M) development accelerator has at least one structure selected from a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group in the molecule, and has a molecular weight.
  • the photosensitive resin composition according to ⁇ 1> wherein is a compound in the range of 100 to 2000.
  • (B) photoacid generator is an oxime sulfonate compound.
  • the photoacid generator (B) is at least one selected from compounds represented by the following general formula (OS-3), general formula (OS-4), and general formula (OS-5)
  • R 1 represents an alkyl group, an aryl group, or a heteroaryl group
  • a plurality of R 2 are each independently a hydrogen atom, an alkyl group, or an aryl group.
  • a group or a halogen atom, and a plurality of R 6 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group
  • X represents O or S.
  • N represents 1 or 2
  • m represents an integer of 0-6.
  • the structural unit (a3) in the (A) acetal resin is any one of (3-ethyloxetane-3-yl) methyl acrylate and methyl (3-ethyloxetane-3-yl) methacrylate.
  • a curing sensitivity is high and a pattern of a favorable shape is formed even if it does not heat-process the cured film after exposure.
  • a microlens having a high transmittance can be formed.
  • ⁇ 11> (1) Applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10> on a substrate; (2) removing the solvent from the applied photosensitive resin composition; (3) exposing the applied photosensitive resin composition with actinic rays; (4) developing the exposed photosensitive resin composition with an aqueous developer; and (5) thermosetting the developed photosensitive resin composition;
  • a method for forming a cured film comprising:
  • ⁇ 12> A cured film formed by the method according to ⁇ 11>.
  • ⁇ 13> The cured film according to ⁇ 12>, which is an interlayer insulating film.
  • An organic EL display device comprising the cured film according to ⁇ 12> or ⁇ 13>.
  • ⁇ 15> A liquid crystal display device comprising the cured film according to ⁇ 12> or ⁇ 13>.
  • a cured film having a high transmittance after curing and a small decrease in transmittance even when heated can be obtained, and even when heating (PEB) is not performed after exposure, the sensitivity is very high.
  • the photosensitive resin composition which has this is provided.
  • the cured film using the said photosensitive resin composition, its manufacturing method, the organic electroluminescent display apparatus provided with this cured film, and a liquid crystal display device are provided.
  • the photosensitive resin composition of the present invention includes (A) an acetal resin, (B) a photoacid generator, and (C) a solvent, and the (A) acetal resin generates a carboxyl group with an acid.
  • the structural unit (a1): structural unit (a2): structural unit (a3): structural unit (a4) 0.2 to 0.65: 0.02 to 0 2: 0.2 to 0.6: 0.005 to 0.3
  • the content of the structural unit (a4) in the (A) acetal resin is in the range of 3 to 30% by mass. is there.
  • the photosensitive resin composition of the present invention is a positive photosensitive resin composition.
  • the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).
  • post exposure baking is referred to as PEB. May be called.
  • the photosensitive resin composition of the present invention becomes a photosensitive resin composition having very high sensitivity by containing the components (A) to (C). Moreover, the photosensitive resin composition which can obtain the cured film with the high transmittance
  • a property having a high transmittance after curing and a small decrease in the transmittance even when heated is referred to as “heat-resistant transparency”.
  • the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the photosensitive resin composition of the present invention contains (A) an acetal resin.
  • the (A) acetal resin contained in the photosensitive resin composition of the present invention includes a structural unit (a1) having a structure that generates a carboxyl group with an acid, a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group, and an epoxy.
  • the (A) acetal resin may further contain a structural unit (a5) having a structure other than the structural units (a1) to (a4).
  • the acetal resin is preferably a resin that is alkali-insoluble and becomes alkali-soluble when the acid-decomposable group in the structural unit (a1) having a structure that generates a carboxyl group with an acid is decomposed.
  • alkali-soluble in the present invention refers to a coating film (thickness 3 ⁇ m) of the compound (resin) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C. for 2 minutes. ) At 23 ° C. in a 0.4 mass% tetramethylammonium hydroxide aqueous solution is 0.01 ⁇ m / second or more. “Alkali insoluble” means that the compound (resin) coating film (thickness 3 ⁇ m) formed by applying a solution of the compound (resin) on a substrate and heating at 90 ° C.
  • the dissolution rate with respect to a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. is less than 0.01 ⁇ m / second, preferably less than 0.005 ⁇ m / second.
  • the (A) acetal resin is preferably an acrylic polymer.
  • the “acrylic polymer” in the present invention is an addition polymerization type resin, is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof, and is derived from (meth) acrylic acid or an ester thereof. You may have structural units other than a structural unit, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. Moreover, you may include both the structural unit derived from (meth) acrylic acid and its ester.
  • the (A) acetal resin preferably contains 50 mol% or more of structural units derived from (meth) acrylic acid or its ester with respect to all structural units in the (A) acetal resin, and is 80 mol% or more. More preferably, it is a polymer consisting of only structural units derived from (meth) acrylic acid or its ester.
  • structural unit derived from (meth) acrylic acid or its ester is also referred to as “acrylic structural unit”.
  • (Meth) acrylic acid is a generic term for methacrylic acid and acrylic acid.
  • the (A) acetal-based resin has an acetal structure or a ketal structure, and may have both an acetal structure and a ketal structure.
  • the acetal structure or ketal structure is preferably a structure represented by the following general formula (I).
  • R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group. However, at least one of R 1 and R 2 represents an alkyl group or a cycloalkyl group.
  • R 3 represents a linear or branched alkyl group, a cycloalkyl group, or an aralkyl group.
  • R 1 and R 3 may be linked to form a cyclic ether, or R 2 and R 3 may be linked to form a cyclic ether.
  • R 1 and R 3 or R 2 and R 3 are linked to form a cyclic ether
  • R 1 and R 3 or R 2 and R 3 are linked to form a carbon number 2
  • the alkyl group, cycloalkyl group, and aralkyl group as R 3 may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. 6 or less is preferable.
  • R 7 in the acetal ester structure (—COOR 7 ) of carboxylic acid is, for example, 1-methoxyethyl group, 1-ethoxy Ethyl group, 1-n-propoxyethyl group, 1-i-propoxyethyl group, 1-n-butoxyethyl group, 1-i-butoxyethyl group, 1-sec-butoxyethyl group, 1-t-butoxyethyl group 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-norbornyloxyethyl group, 1-bornyloxyethyl, 1-benzyloxyethyl group, 1-phenethyloxyethyl group, (cyclohexyl) (methoxy) ) Methyl group, (cyclohexyl) (ethoxy) methyl group, (cyclohexyl)
  • R 8 in the ketal ester structure (—COOR 8 ) of carboxylic acid is, for example, a 1-methyl-1-methoxyethyl group 1-methyl-1-ethoxyethyl group, 1-methyl-1-n-propoxyethyl group, 1-methyl-1-i-propoxyethyl group, 1-methyl-1-n-butoxyethyl group, 1-methyl -1-i-butoxyethyl group, 1-methyl-1-sec-butoxyethyl group, 1-methyl-1-t-butoxyethyl group, 1-methyl-1-cyclopentyloxyethyl group, 1-methyl-1- Cyclohexyloxyethyl group, 1-methyl-1-norbornyloxyethyl group, 1-methyl-1-bornyloxyethyl group, 1-methyl-1-benzyloxyethyl 1-methyl-1-phenethyloxyethyl group, 1-cyclohex
  • R 7 in the acetal ester structure (—COOR 7 ) of carboxylic acid is preferably a 1-ethoxyethyl group, a 1-cyclohexyloxyethyl group, a 2-tetrahydrofuranyl group, or a 2-tetrahydropyranyl group, from the viewpoint of sensitivity.
  • a 1-ethoxyethyl group and a 1-cyclohexyloxyethyl group are particularly preferred.
  • Examples of the compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and ⁇ -methyl-p-carboxystyrene; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid.
  • Examples of the acid include acrylic acid and methacrylic acid.
  • a1 the structural unit derived from the carboxylic acid by which these carboxyl groups were protected can be mentioned as a preferable thing.
  • radical polymerizable monomer used for forming the structural unit (a1) include, for example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl methacrylate, 1-methoxyethyl acrylate.
  • R 6 represents a hydrogen atom or a methyl group
  • R 5 has the same meaning as R 3 in formula (I).
  • the structural unit (a1) can also be formed by reacting a carboxyl group with a vinyl ether compound after polymerizing the protected carboxyl group with the structural units (a2) to (a5) described later and precursors thereof. it can.
  • the specific example of the preferable structural unit formed in this way is the same as the structural unit derived from the preferable specific example of the said radical polymerizable monomer.
  • the structural unit (a1) is preferably a structural unit represented by the following general formula (5).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • L 1 represents a carbonyl group or a phenylene group
  • R 21 to R 27 each independently represents a hydrogen atom or a carbon number. Represents 1 to 4 alkyl groups.
  • structural unit (a1) the following structural units (a1-1) to (a1-8) can be exemplified. Of these, structural units represented by (a1-1) to (a1-4), (a1-7) and (a1-8) are particularly preferred.
  • the content of the structural unit (a1) is 20 to 60 mol%, more preferably 25 to 60 mol%, particularly preferably 25 to 55 mol%.
  • the acetal resin contains a structural unit (a2) having a carboxyl group or a phenolic hydroxyl group (hereinafter referred to as “structural unit (a2)” as appropriate).
  • structural unit (a2) having a carboxyl group
  • structural unit (a2) examples include unsaturated carboxylic acids having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid.
  • the structural unit derived from is mentioned.
  • the unsaturated polyvalent carboxylic acid used for obtaining the structural unit (a2-1) having a carboxyl group may be an acid anhydride thereof. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both terminals, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate and ⁇ -carboxypolycaprolactone monomethacrylate.
  • unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
  • Examples of the radical polymerizable monomer used to form the structural unit (a2-2) having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and ⁇ -methyl-p-hydroxystyrene, Compounds described in paragraphs [0011] to [0016] of Kokai 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs [0007] to [0010] of Japanese Patent No. 2888454, 4-hydroxybenzoic acid Preferred examples include an addition reaction product of glycidyl methacrylate and 4-hydroxybenzoic acid and glycidyl acrylate.
  • methacrylic acid, acrylic acid compounds described in paragraphs 0011 to 0016 of JP2008-40183A, and Japanese Patent No. 2888454 More preferred are 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate. From the viewpoint of properties, methacrylic acid and acrylic acid are particularly preferable. These structural units can be used singly or in combination of two or more.
  • the structural unit (a2) is preferably introduced as long as the (A) acetal resin is not alkali-soluble.
  • the content of the structural unit (a2) is 2 to 20 mol%, more preferably 2 to 15 mol%, particularly preferably 3 to 15 mol%. .
  • the acetal resin contains a structural unit (a3) having an epoxy group or an oxetanyl group (hereinafter, appropriately referred to as “structural unit (a3)”).
  • the structural unit (a3) may include both a structural unit having an epoxy group and an oxetanyl group.
  • the group having an epoxy group is not particularly limited as long as it has an epoxy ring, but preferred examples include a glycidyl group and a 3,4-epoxycyclohexylmethyl group.
  • the group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group is preferably exemplified.
  • the structural unit (a3) only needs to have at least one epoxy group or oxetanyl group in one structural unit, one or more epoxy groups and one or more oxetanyl groups, two or more epoxy groups, or It may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and has a total of 1 or 2 epoxy groups and / or oxetanyl groups. It is more preferable to have one epoxy group or oxetanyl group.
  • radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
  • radical polymerizable monomer used to form a structural unit having an oxetanyl group examples include those having an oxetanyl group described in paragraphs [0011] to [0016] of JP-A-2001-330953, for example ( And (meth) acrylic acid esters.
  • radical polymerizable monomer used to form the structural unit are preferably a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure.
  • glycidyl methacrylate glycidyl acrylate
  • compounds containing an alicyclic epoxy skeleton described in paragraphs [0034] to [0035] of Japanese Patent No. 4168443
  • Particularly preferred from the viewpoint of heat-resistant transparency is a structural unit derived from either (3-ethyloxetane-3-yl) methyl acrylate or methyl (3-ethyloxetane-3-yl) methacrylate. is there.
  • These structural units (a3) can be used individually by 1 type or in combination of 2 or more types.
  • the content of the structural unit (a3) in all structural units constituting the (A) acetal resin is 20 to 55 mol%, more preferably 25 to 55 mol%, and particularly preferably 25 to 50 mol%.
  • Structural unit (a4) having a hydroxyl group or an alkyleneoxy group The (A) acetal resin contains a structural unit (a4) having a hydroxyl group or an alkyleneoxy group (hereinafter, appropriately referred to as “structural unit (a4)”). Both structural units having a hydroxyl group and an alkyleneoxy group may be included.
  • the hydroxyl group in the structural unit (a4) refers to a hydroxyl group other than the phenolic hydroxyl group. Further, when the structural units (a1) to (a3) have a hydroxyl group, they are handled as the respective structural units (a1) to (a3) without being treated as the structural unit (a4).
  • any structural unit having a hydroxyl group and / or an alkyleneoxy group can be used, and preferred examples include a hydroxyl group-containing (meth) acrylate ester, an alkyl group-terminated polyester.
  • preferred examples include structural units derived from (meth) acrylic acid esters of alkylene glycol and (meth) acrylic acid esters of aryl-terminated polyalkylene glycol.
  • hydroxyl group-containing (meth) acrylic acid ester examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2,3 (meth) acrylic acid.
  • -Hydroxyalkyl esters of (meth) acrylic acid such as dihydroxypropyl and 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / propylene glycol)- Mono (meth) acrylate, polyethylene glycol / polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) -mono (meth) acrylate, poly (propylene glycol) Le tetramethylene glycol) - mono (meth) acrylate, propylene glycol polybutylene glycol - may be mentioned as preferred examples of the mono (meth) acrylate.
  • Examples of the (meth) acrylic acid ester of the alkyl group-terminated polyalkylene glycol include methoxypolyethylene glycol- (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, lauroxypolyethylene glycol- (meth) acrylate, stear
  • a preferred example is loxypolyethylene glycol- (meth) acrylate.
  • Examples of (meth) acrylic acid esters of aryl group-terminated polyalkylene glycols include phenoxy polyethylene glycol- (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol- (meth) acrylate, nonylphenoxy-polyethylene glycol- (meth) acrylate, and nonyl.
  • Preferred examples include phenoxy-polypropylene glycol- (meth) acrylate and nonylphenoxy-poly (ethylene glycol-propylene glycol)-(meth) acrylate.
  • hydroxyl group-containing (meth) acrylic acid esters alkyl group-terminated polyalkylene glycol (meth) acrylic acid esters and aryl group-terminated polyalkylene glycol (meth) acrylic acid esters can be used.
  • Blemmer E Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer P, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer 50 PEP-300, Blemmer 70 PEP- 350B, Blemmer 55PET-800, Blemmer PPT series, Blemmer 10PPB-500B, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer PME-100 , Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer 50POEP-800B, Blemmer PLE-200, Blemmer PSE-4 0, Blemmer PSE-1300, Blemmer PAE-50, Blemmer PAE-100, Blemmer 43PAPE-600B, Blemmer AME-400, Blemmer ALE
  • the number of hydroxyl groups is preferably 1 to 10, more preferably 1 to 5, and most preferably 1 to 3.
  • the number of repeating units of the alkyleneoxy group is preferably 1 to 25, more preferably 1 to 15, and most preferably 1 to 10.
  • Preferred specific structures of the structural unit (a4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 , 3-dihydroxypropyl, methoxypolyethylene glycol- (meth) acrylate having 2 to 10 ethylene glycol repeating units, methoxypolypropylene glycol- (meth) acrylate having 2 to 10 propylene glycol repeating units, ethylene glycol repeating units and propylene Methoxypolyethylene glycol-polypropylene glycol- (meth) acrylate having 2 to 10 glycol repeating units, and 2 to 10 ethylene glycol repeating units and propylene glycol repeating units.
  • Toxipolyethylene glycol-polypropylene glycol- (meth) acrylate polyethylene glycol mono (meth) acrylate having 2 to 10 ethylene glycol repeating units, polypropylene glycol mono (meth) acrylate having 2 to 10 propylene glycol repeating units, ethylene glycol Poly (ethylene glycol / propylene glycol) -mono (meth) acrylate having 3 to 10 repeating units and propylene glycol repeating units, polyethylene glycol having 3 to 10 ethylene glycol repeating units and propylene glycol repeating units Polypropylene glycol mono (meth) acrylate and the like, more preferably 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate having 2 to 10 ethylene glycol repeating units, ethylene glycol repeating units
  • the content of the structural unit (a4) in all structural units constituting the acetal resin is 0.5 to 30 mol%, more preferably 0.5 to 25 mol%, and preferably 1 to 25 mol%. Particularly preferred.
  • the content of the structural unit (a4) in all structural units constituting the (A) acetal resin is 3 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 25% by mass. .
  • the (A) acetal resin may contain a structure other than the structural units (a1) to (a4) (hereinafter, appropriately referred to as “structural unit (a5)”) as long as the effects of the present invention are not hindered. Good.
  • structural unit (a5) examples include compounds described in paragraphs [0021] to [0024] of JP-A No. 2004-264623 (provided that , Except for the structural units (a1) to (a4) described above).
  • (meth) acrylic acid esters having an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate are preferable from the viewpoint of improving electric characteristics.
  • methyl (meth) acrylate is preferred.
  • styrenes such as styrene and ⁇ -methylstyrene are preferable.
  • a structural unit (a5) can be used individually by 1 type or in combination of 2 or more types.
  • the content of the structural unit (a5) in all the structural units constituting the acetal resin is 0 to 40 mol%.
  • the content of the structural unit (a5) is preferably 1 to 40 mol% in all structural units constituting the (A) acetal resin. 30 mol% is more preferable, and 5 to 25 mol% is particularly preferable.
  • the weight average molecular weight of the (A) acetal resin in the present invention is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,000 to 12 , 000.
  • the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).
  • the method for introducing each structural unit contained in the (A) acetal resin used in the present invention may be a polymerization method or a polymer reaction method.
  • monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. That is, a radical comprising a structural unit (a1), a structural unit (a2), a structural unit (a3), a structural unit (a4), and a radical polymerizable monomer used to form the structural unit (a5) if necessary. It can be synthesized by polymerizing the polymerizable monomer mixture in an organic solvent using a radical polymerization initiator.
  • a necessary functional group is introduced into the structural unit using a reactive group contained in the structural unit of the obtained copolymer.
  • Introduction of the structural units (a1) to (a5) into the (A) acetal resin may be carried out by a polymerization method or a polymer reaction method, or these two methods may be used in combination.
  • the weight average molecular weight of the (A) acetal resin exemplified below is 2,000 to 30,000.
  • the composition ratio is shown in mol% in ().
  • the content of the structural unit (a4) in all structural units constituting the (A) acetal resin is 3 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 25% by mass. .
  • the content of the (A) acetal resin in the photosensitive resin composition of the present invention is preferably 20 to 99% by mass, and preferably 40 to 97% by mass with respect to the total solid content of the photosensitive resin composition. More preferred is 60 to 95% by mass. When the content is within this range, the pattern formability upon development is good.
  • the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
  • a resin other than the (A) acetal resin may be used in combination as long as the effects of the present invention are not hindered. However, the content of the resin other than the (A) acetal resin is preferably smaller than the content of the (A) acetal resin from the viewpoint of developability.
  • the photosensitive resin composition of the present invention contains (B) a photoacid generator.
  • the photoacid generator (B) used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is limited. is not.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.
  • the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity.
  • These photoacid generators can be used singly or in combination of two or more.
  • photoacid generators include the following: As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy- ⁇ -styryl) -bis (4,6-trichloromethyl) -s -Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -bis (4
  • diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl-4- (2′-hydroxy-1 '-Tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-) Tetradecaoxy) phenyliodonium p-toluenesulfonate, etc .;
  • Triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoro Romethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, etc .;
  • quaternary ammonium salts tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate and the like;
  • diazomethane derivative examples include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like;
  • imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-ene-dicarboximide, succinimide trifluoromethyl sulfonate, phthalimido trifluoromethyl sulfonate, N-hydroxynaphthalimide methane sulfonate, N-hydroxy -5-norbornene-2,3-dicarboximidopropane sulfonate and the like.
  • the photosensitive resin composition of the present invention preferably contains (B) an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following structure (1) as a photoacid generator.
  • the compound having at least one oxime sulfonate residue represented by the structure (1) is represented by the following general formula (OS-3), general formula (OS-4), or general formula (OS-5).
  • An oxime sulfonate compound is preferred.
  • R 1 represents an alkyl group, an aryl group, or a heteroaryl group
  • a plurality of R 2 are each independently a hydrogen atom, an alkyl group, an aryl group,
  • a plurality of R 6 each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group
  • X represents O or S
  • m represents an integer of 0 to 6.
  • the alkyl group, aryl group or heteroaryl group represented by R 1 may have a substituent.
  • the alkyl group represented by R 1 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
  • the substituent that the alkyl group represented by R 1 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned.
  • examples of the alkyl group represented by R 1 include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s- Butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group Etc.
  • the aryl group represented by R 1 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • substituent that the aryl group represented by R 1 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples thereof include an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.
  • the aryl group represented by R 1 is preferably a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
  • the heteroaryl group represented by R 1 may be at least one heteroaromatic ring.
  • a heteroaromatic ring and a benzene ring are condensed. You may do it.
  • the heteroaryl group represented by R 1 may have a thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring, and benzimidazole ring, which may have a substituent.
  • a group obtained by removing one hydrogen atom from a ring selected from the group consisting of:
  • R 2 is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
  • one or two of R 2 present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. It is more preferably a group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.
  • the alkyl group or aryl group represented by R 2 may have a substituent.
  • substituents that the alkyl group or aryl group represented by R 2 may have include the same groups as the substituent that the alkyl group or aryl group in R 1 may have.
  • the alkyl group represented by R 2 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, It is more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.
  • Examples of the alkyl group represented by R 2 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, A chloromethyl group, a bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group.
  • a group is more preferable, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is particularly preferable.
  • the aryl group represented by R 2 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • the aryl group represented by R 2 is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
  • the halogen atom represented by R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.
  • X represents O or S, and is preferably O.
  • the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
  • n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n Is preferably 2.
  • the alkyl group and alkyloxy group represented by R 6 may have a substituent.
  • the alkyl group represented by R 6 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
  • the substituent that the alkyl group represented by R 6 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned.
  • examples of the alkyl group represented by R 6 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s- Butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group Is preferred.
  • the alkyloxy group represented by R 6 is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. preferable.
  • substituents that the alkyloxy group represented by R 6 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl. Groups.
  • the alkyloxy group represented by R 6 includes a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group. Group or ethoxyethyloxy group is preferred.
  • the aminosulfonyl group for R 6 include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
  • alkoxysulfonyl group represented by R 6 examples include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.
  • m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, It is particularly preferred that
  • the compound represented by the general formula (OS-3) is particularly preferably a compound represented by the following general formula (OS-6), (OS-10) or (OS-11),
  • the compound represented by the general formula (OS-4) is particularly preferably a compound represented by the following general formula (OS-7), and the compound represented by the general formula (OS-5) is A compound represented by the general formula (OS-8) or (OS-9) is particularly preferable.
  • R 1 represents an alkyl group, an aryl group or a heteroaryl group
  • R 7 represents a hydrogen atom or a bromine atom
  • R 8 represents a hydrogen atom
  • a carbon number represents an alkyl group of 1 to 8, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group
  • R 9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
  • 10 represents a hydrogen atom or a methyl group.
  • R 1 in the general formulas (OS-6) to (OS-11) has the same meaning as R 1 in the general formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
  • R 7 in the general formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
  • R 8 in the general formulas (OS-6) to (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, or a phenyl group.
  • a chlorophenyl group preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferably, it is particularly preferably a methyl group.
  • R 9 in the general formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
  • R 10 in the general formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • the oxime steric structure (E, Z) may be either one or a mixture.
  • oxime sulfonate compounds represented by the general formulas (OS-3) to (OS-5) include the following exemplary compounds, but the present invention is not limited thereto.
  • oxime sulfonate compound having at least one oxime sulfonate group represented by the structure (1) a compound represented by the following general formula (OS-1) may be mentioned.
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or hetero Represents an aryl group.
  • R 2 represents an alkyl group or an aryl group.
  • R 21 to R 24 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group, Or represents an aryl group. Two of R 21 to R 24 may be bonded to each other to form a ring.
  • R 21 to R 24 are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R 21 to R 24 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 21 to R 24 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the above-described substituents may further have a substituent.
  • the compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).
  • R 1 , R 2, R 21 ⁇ R 24 are respectively synonymous with R 1, R 2, R 21 ⁇ R 24 in the general formula (OS-1), preferred examples The same is true.
  • R 1 in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the general formula (OS-2), and R 1
  • is a cyano group, a phenyl group or a naphthyl group is most preferred.
  • the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
  • b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.
  • the oxime sulfonate compound having at least one oxime sulfonate residue represented by the structure (1) is preferably a compound represented by the following general formula (2).
  • R 1A represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or 2-thienyl.
  • Group, an alkoxy group having 1 to 4 carbon atoms or a cyano group and when R 1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom, a hydroxyl group, or a carbon atom having 1 carbon atom.
  • R 2A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, an anthranyl group which may be substituted with W, a dialkylamino group, a morpholino group, or a cyano group.
  • R 2A and R 1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be bonded to a benzene ring.
  • R 3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, It represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W.
  • W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.
  • the alkyl group having 1 to 6 carbon atoms represented by R 1A may be a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- Examples thereof include a butyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, and a 2-ethylbutyl group.
  • Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R 1A include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.
  • Examples of the alkoxy group having 1 to 4 carbon atoms represented by R 1A include a methoxy group and an ethoxy group.
  • R 1A represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group
  • these groups are a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, a carbon atom having 1 to 4 carbon atoms.
  • Alkyl groups eg, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl
  • alkoxy groups having 1 to 4 carbon atoms eg, methoxy, ethoxy, etc.
  • a nitro group may be substituted.
  • alkyl group having 1 to 10 carbon atoms represented by R 2A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl.
  • alkoxy group having 1 to 10 carbon atoms represented by R 2A include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an n-amyloxy group, and an n-octyl group. Examples thereof include an oxy group and an n-decyloxy group.
  • halogenated alkyl group having 1 to 5 carbon atoms represented by R 2A include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, a perfluoro group, And fluoro-n-amyl group.
  • halogenated alkoxy group having 1 to 5 carbon atoms represented by R 2A include trifluoromethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoro-n-butoxy group, perfluoro group, And fluoro-n-amyloxy group.
  • phenyl group optionally substituted by W represented by R 2A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M- Methoxyphenyl group, p-methoxyphenyl group
  • naphthyl group optionally substituted by W represented by R 2A include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.
  • anthranyl group optionally substituted with W represented by R 2A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.
  • dialkylamino group represented by R 2A examples include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.
  • alkyl group having 1 to 10 carbon atoms represented by R 3A include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl.
  • alkoxy group having 1 to 10 carbon atoms represented by R 3A include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyl group. Examples thereof include an oxy group and an n-decyloxy group.
  • halogenated alkyl group having 1 to 5 carbon atoms represented by R 3A include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group, And fluoro-n-amyl group.
  • halogenated alkoxy group having 1 to 5 carbon atoms represented by R 3A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, a perfluoro group, And fluoro-n-amyloxy group.
  • phenyl group optionally substituted by W represented by R 3A include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-methoxyphenyl group, p-methoxyphenyl group
  • anthranyl group optionally substituted by W represented by R 3A examples include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.
  • an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy having 1 to 5 carbon atoms represented by W Examples include an alkyl group having 1 to 10 carbon atoms represented by R 2A or R 3A , an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and 1 carbon atom. Examples similar to those listed as specific examples of the halogenated alkoxy groups of 5 to 5 are mentioned.
  • R 2A and R 1A may be bonded to each other to form a 5-membered ring or a 6-membered ring.
  • examples of the 5-membered ring or 6-membered ring include carbocyclic groups and heterocyclic ring groups. It may be a cyclopentane, cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring.
  • the 5-membered ring or 6-membered ring may be bonded to an optionally substituted benzene ring, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thiol. Xanthene ring system.
  • the 5-membered or 6-membered ring may contain a carbonyl group, examples of which include cyclohexadienone, naphthalenone and anthrone ring systems.
  • One preferred embodiment of the compound represented by the general formula (2) is a compound represented by the following general formula (2-1).
  • the compound represented by the general formula (2-1) is a compound in which R 2A and R 1A in the general formula (2) are bonded to form a 5-membered ring.
  • R 3A has the same meaning as R 3A in General Formula (2), X represents an alkyl group, an alkoxy group, or a halogen atom, and t represents an integer of 0 to 3. And when t is 2 or 3, the plurality of X may be the same or different.
  • the alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • As the halogen atom represented by X a chlorine atom or a fluorine atom is preferable.
  • t is preferably 0 or 1.
  • t is 1, X is a methyl group, the substitution position of X is an ortho position, R 3A is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
  • R 1A represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group, or an anthranyl group
  • R 2A represents a cyano group
  • R 3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group
  • the compound represented by the general formula (2) is preferably a compound represented by the following general formula (2-2).
  • R 4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and l is 0 to 5 Represents an integer.
  • R 3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, Represents a phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, and W represents a halogen atom, a cyano group, a nitro group, a carbon atom number of 1 to Represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.
  • R 3A in the general formula (2-2) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl.
  • Group, perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group, preferably methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group Is particularly preferred.
  • the halogen atom represented by R 4A is preferably a fluorine atom, a chlorine atom or a bromine atom.
  • the alkyl group having 1 to 4 carbon atoms represented by R 4A is preferably a methyl group or an ethyl group.
  • the alkoxy group having 1 to 4 carbon atoms represented by R 4A is preferably a methoxy group or an ethoxy group.
  • l is preferably from 0 to 2, particularly preferably from 0 to 1.
  • preferred embodiments of the compounds included in the photoacid generator represented by the general formula (2-2) include R in the general formula (2) 1A represents a phenyl group or 4-methoxyphenyl group, R 2A represents a cyano group, and R 3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 4-tolyl group. is there.
  • the photosensitive resin composition of the present invention preferably does not contain a 1,2-quinonediazide compound as a photoacid generator (B) sensitive to actinic rays. This is because the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less, and is less sensitive than the oxime sulfonate compound.
  • the oxime sulfonate compound acts as a catalyst for the deprotection of the acidic group protected in response to the actinic ray, so that the acid generated by the action of one photon Contributing to the deprotection reaction, the quantum yield exceeds 1, for example, a large value such as a power of 10, and it is assumed that high sensitivity is obtained as a result of so-called chemical amplification.
  • the photoacid generator (B) is preferably used in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the (A) acetal resin, 0.5 to 10 It is more preferable to use parts by mass.
  • the photosensitive resin composition of the present invention contains (C) a solvent.
  • the photosensitive resin composition of the present invention comprises (A) an acetal-based resin as an essential component, (B) a photoacid generator, and optional components of various additives described later as preferred components in (C) a solvent. It is preferably prepared as a dissolved solution.
  • solvent (C) used in the photosensitive resin composition of the present invention known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene.
  • Examples of the solvent (C) used in the photosensitive resin composition of the present invention include (1) ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and the like.
  • ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether; (3) ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether Ethylene glycol monoalkyl ethers such as acetate and ethylene glycol monobutyl ether acetate Acetates; (4) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; (5) propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl Propylene glycol dialkyl ethers such as ether and diethylene glycol monoethyl ether;
  • Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; (7) diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl Diethylene glycol dialkyl ethers such as methyl ether; (8) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, etc.
  • Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
  • Dipropylene glycol dimethyl ether Dipropylene glycol dialkyl ethers such as dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;
  • Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate; (12) methyl lactate, lactic acid Lactic acid esters such as ethyl, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, N-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl prop
  • Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
  • N-methylformamide, N, N-dimethyl examples include amides such as formamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and (17) lactones such as ⁇ -butyrolactone.
  • Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.
  • diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate are particularly preferable.
  • the solvent that can be used in the present invention is a single type or a combination of two types, preferably a combination of two types, and a combination of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. More preferably.
  • the content of the solvent (C) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by mass, and 100 to 2,000 parts by mass per 100 parts by mass of the (A) acetal resin. More preferred is 150 to 1,500 parts by mass.
  • the photosensitive resin composition of the present invention preferably contains other components.
  • (N) a sensitizer it is preferable to add (N) a sensitizer.
  • the photosensitive resin composition of the present invention preferably contains (F) an adhesion improver from the viewpoint of substrate adhesion, and preferably contains (G) a basic compound from the viewpoint of liquid storage stability.
  • a surfactant such as a fluorine-based surfactant or a silicon-based surfactant.
  • the photosensitive resin composition of the present invention includes (D) an antioxidant, (I) a plasticizer, (J) a thermal radical generator, (K) a thermal acid generator, ( L) Known additives such as acid proliferating agents, ultraviolet absorbers, thickeners, and organic or inorganic suspending agents can be added.
  • (N) Sensitizer In the photosensitive resin composition of the present invention, it is preferable to add (N) a sensitizer in order to promote the decomposition in the combination with the above-mentioned (B) photoacid generator.
  • the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise
  • Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
  • sensitizers include polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone) Thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (for example, thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), acridones (eg, acridone, 10-
  • a sensitizer that absorbs actinic rays or radiation to be in an electronically excited state and has an electron transfer action to the photoacid generator is preferred, and in particular, polycyclic aromatics, acridones, coumarins, Base styryls are preferred. Of these, anthracene compounds are most preferable.
  • a commercially available sensitizer may be used, or it may be synthesized by a known synthesis method.
  • the addition amount of the sensitizer is preferably 20 to 300 parts by mass, and particularly preferably 30 to 200 parts by mass with respect to 100 parts by mass of the (B) photoacid generator, from the viewpoint of both sensitivity and transparency.
  • the photosensitive resin composition of the present invention preferably contains (M) a development accelerator.
  • M a development accelerator.
  • the development accelerator any compound having a development promotion effect can be used, but a compound having at least one structure selected from the group of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group is preferable. A compound having a carboxyl group or a phenolic hydroxyl group is more preferred, and a compound having a phenolic hydroxyl group is most preferred.
  • the molecular weight of the (M) development accelerator is preferably 100 to 2000, more preferably 150 to 1500, and most preferably 150 to 1000.
  • Examples of development accelerators having an alkyleneoxy group include polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester, polybutylene glycol, Examples thereof include polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, and compounds described in JP-A-9-222724. Examples of compounds having a carboxyl group include compounds described in JP-A 2000-66406, JP-A 9-6001, JP-A 10-20501, JP-A 11-338150, and the like.
  • Examples of those having a phenolic hydroxyl group include JP-A-2005-346024, JP-A-10-133366, JP-A-9-194415, JP-A-9-222724, JP-A-11-171810, Examples thereof include compounds described in JP-A-2007-121766, JP-A-9-297396, JP-A-2003-43679, and the like.
  • a phenol compound having 2 to 10 benzene rings is preferable, and a phenol compound having 2 to 5 benzene rings is more preferable.
  • Particularly preferred is a phenolic compound disclosed as a dissolution accelerator in JP-A-10-133366.
  • a development accelerator may be used individually by 1 type, and it is also possible to use 2 or more types together.
  • the addition amount of the (M) development accelerator in the photosensitive resin composition of the present invention is 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) acetal resin from the viewpoint of sensitivity and residual film ratio. Is preferable, 0.2 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
  • the photosensitive resin composition of this invention contains (E) crosslinking agent as needed.
  • the crosslinking agent include a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, or at least one ethylenically unsaturated double bond. The compound which has can be added.
  • these crosslinking agents particularly preferred are compounds having two or more epoxy groups or oxetanyl groups in the molecule.
  • Compounds having two or more epoxy groups or oxetanyl groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenol novolac type epoxy resins. , Cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
  • bisphenol A type epoxy resin JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051
  • the bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, trade name, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above).
  • bisphenol A type epoxy resin preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin.
  • a bisphenol A type epoxy resin is particularly preferable.
  • the compound having two or more oxetanyl groups in the molecule Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, trade name, manufactured by Toagosei Co., Ltd.) may be used. it can.
  • the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an epoxy group.
  • the addition amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to the photosensitive resin composition is preferably 1 to 50 parts by mass when the total amount of the (A) acetal resin component is 100 parts by mass. 3 to 30 parts by mass is more preferable.
  • Alkoxymethyl group-containing crosslinking agent As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively.
  • the type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.
  • a methoxymethyl group is preferred.
  • crosslinkable compounds alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferable crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
  • alkoxymethyl group-containing crosslinking agents are available as commercial products.
  • Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, trade name, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalac MX-750, -032, -706, -708, -40, -31, -270, -280,- 290, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390 (trade name, manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.
  • the addition amount of the alkoxymethyl group-containing crosslinking agent is 0.05 to 50 masses per 100 mass parts of the (A) acetal resin component. Part is preferable, and 0.5 to 10 parts by mass is more preferable. By adding within this range, preferable alkali solubility during development and excellent solvent resistance of the cured film can be obtained.
  • Compound having at least one ethylenically unsaturated double bond As a compound having at least one ethylenically unsaturated double bond, monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or more ( (Meth) acrylate compounds such as (meth) acrylate can be suitably used.
  • Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl.
  • Examples include -2-hydroxypropyl phthalate.
  • bifunctional (meth) acrylate examples include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
  • Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
  • the proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is 50 parts by mass or less with respect to 100 parts by mass of the (A) acetal resin component. Preferably, it is 30 parts by mass or less.
  • the photosensitive resin composition of the present invention preferably contains (F) an adhesion improving agent.
  • the adhesion improver (F) that can be used in the photosensitive resin composition of the present invention is insulated from inorganic substances that serve as substrates, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, and aluminum. It is a compound that improves the adhesion to the film. Specific examples include silane coupling agents and thiol compounds.
  • the silane coupling agent as the (F) adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
  • Preferred examples of the silane coupling agent include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ - Methacryloxypropyltrialkoxysilane, ⁇ -methacryloxypropylalkyldialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, and ⁇ -glycidoxypropyltrialkoxysilane is more preferable.
  • the content of the (F) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) acetal resin component. Part is more preferred.
  • the photosensitive resin composition of this invention contains the (G) basic compound.
  • G As a basic compound, it can select and use arbitrarily from the compounds used with a chemically amplified resist. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
  • aliphatic amines examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene.
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.
  • the content of the basic compound (G) in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the (A) acetal resin component, and 0.002 It is more preferable that the amount is 0.2 parts by mass.
  • the photosensitive resin composition of the present invention preferably contains (H) a surfactant (such as a fluorine-based surfactant or a silicon-based surfactant).
  • a surfactant such as a fluorine-based surfactant or a silicon-based surfactant.
  • a copolymer (3) containing the repeating unit A and the repeating unit B shown below can be given as a preferred example.
  • the weight average molecular weight (Mw) of the copolymer is 1000 or more and 10,000 or less, and preferably 1500 or more and 5000 or less.
  • the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.
  • R 21 and R 23 each independently represent a hydrogen atom or a methyl group
  • R 22 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 24 represents a hydrogen atom or carbon number
  • 1 represents an alkyl group having 4 or less
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p represents a numerical value of 10% to 80% by mass
  • Q represents a numerical value of 20% by mass to 90% by mass
  • r represents an integer of 1 to 18, and n represents an integer of 1 to 10.
  • L in the repeating unit B is preferably an alkylene group represented by the following formula (4).
  • R 25 represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3.
  • fluorine-based surfactants and silicon-based surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. , JP 63-34540, JP 7-230165, JP 8-62834, JP 9-54432, JP 9-5988, JP 2001-330953, etc.
  • An activator can be mentioned and a commercially available surfactant can also be used.
  • Examples of commercially available surfactants that can be used include F-top EF301, EF303 (above, trade name, manufactured by Shin-Akita Kasei Co., Ltd.), FLORARD FC430, 431 (above, trade name, manufactured by Sumitomo 3M Limited), Mega Fuck F171, F173, F176, F189, R08 (above, trade name, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, trade name, manufactured by Asahi Glass Co., Ltd.) ), PolyFox series (trade name, manufactured by OMNOVA) or the like.
  • Polysiloxane polymer KP-341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.
  • the addition amount of (H) surfactant is based on 100 parts by mass of (A) acetal resin component.
  • the amount is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass, and still more preferably 0.01 to 1 part by mass.
  • the content of the antioxidant is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 0.5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
  • additives other than antioxidants various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.
  • the photosensitive resin composition of the present invention may contain (I) a plasticizer.
  • plasticizers include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
  • the content of the plasticizer (I) in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) acetal resin component, and 1 to 10 parts by mass. More preferably, it is a part.
  • the photosensitive resin composition of the present invention may contain (J) a thermal radical generator, such as a compound having at least one ethylenically unsaturated double bond as described above. When it contains an ethylenically unsaturated compound, it is preferable to further contain (J) a thermal radical generator.
  • a thermal radical generator such as a compound having at least one ethylenically unsaturated double bond as described above.
  • a thermal radical generator such as a compound having at least one ethylenically unsaturated double bond as described above.
  • a thermal radical generator such as a compound having at least one ethylenically unsaturated double bond as described above.
  • a thermal radical generator such as a compound having at least one ethylenically unsaturated double bond as described above.
  • a thermal radical generator such as a compound having at least one ethylenically unsaturated double bond as described above.
  • a thermal radical generator such as a compound having at least one
  • thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.
  • a thermal radical generator may be used individually by 1 type, and can also use 2 or more types together.
  • the content of the (J) thermal radical generator in the photosensitive resin composition of the present invention is from 0.01 to 50 parts by mass, based on 100 parts by mass of the (A) acetal resin, from the viewpoint of improving film properties.
  • 0.1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
  • (K) Thermal acid generator In the present invention, (K) a thermal acid generator may be used in order to improve film physical properties and the like in low-temperature curing.
  • the thermal acid generator of the present invention is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C to 250 ° C, preferably 150 ° C to 220 ° C. It is a compound that generates a low nucleophilic acid such as sulfonic acid, carboxylic acid, disulfonylimide and the like.
  • the generated acid sulfonic acid, an alkyl carboxylic acid substituted with an electron withdrawing group or an aryl carboxylic acid, a disulfonylimide substituted with an electron withdrawing group, and the like having a strong pKa of 2 or less are preferable.
  • the electron withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
  • a sulfonic acid ester that does not substantially generate an acid by exposure to exposure light and generates an acid by heat.
  • the fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by measuring IR spectrum and NMR spectrum before and after exposure of the compound.
  • the molecular weight of the sulfonate ester is generally 230 to 1000, preferably 230 to 800.
  • the sulfonic acid ester usable in the present invention a commercially available one may be used, or one synthesized by a known method may be used.
  • the sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
  • the content of the sulfonic acid ester in the photosensitive resin composition is preferably 0.5 to 20 parts by mass, particularly preferably 1 to 15 parts by mass, with 100 parts by mass of the (A) acetal resin component. .
  • the photosensitive resin composition of the present invention can use (L) an acid proliferating agent for the purpose of improving sensitivity.
  • the acid proliferating agent used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here.
  • the acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
  • acid proliferating agent examples include JP-A-10-1508 [0203] to [0223], JP-A-10-282642 [0016] to [0055], and JP-A-9-512498.
  • JP-A-10-1508 [0203] to [0223]
  • JP-A-10-282642 [0016] to [0055]
  • JP-A-9-512498 The compounds described on page 12 line to page 47 line 2 can be mentioned.
  • Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
  • the content of the acid proliferating agent in the photosensitive resin composition is 10 to 1000 parts by mass with respect to 100 parts by mass of the (B) photoacid generator, in view of the dissolution contrast between the exposed and unexposed areas. And more preferably 20 to 500 parts by mass.
  • the method for forming a cured film in the present invention includes the following steps (1) to (5): (1) Applying the photosensitive resin composition of the present invention on a substrate (application process); (2) removing the solvent from the applied photosensitive resin composition (solvent removal step); (3) Exposing the applied photosensitive resin composition with actinic rays (exposure step); (4) Developing the exposed photosensitive resin composition with an aqueous developer (developing step); (5) Thermosetting the developed photosensitive resin composition (post-baking step). Each step will be described below in order.
  • the obtained coating film is irradiated with an actinic ray having a wavelength of 300 nm to 450 nm.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group in the structural unit (a1) contained in the (A) acetal resin is decomposed to generate a carboxyl group.
  • PEB post-exposure heat treatment
  • PEB can be performed as necessary in order to accelerate the decomposition reaction.
  • PEB can promote the generation of a carboxyl group from an acid-decomposable group.
  • the acid-decomposable group in the structural unit (a1) in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to produce a carboxyl group
  • PEB is necessarily performed.
  • a positive image can be formed by development.
  • hydrolysis of an acid-decomposable group can be promoted without causing a crosslinking reaction.
  • the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 90 ° C. or lower.
  • the (A) acetal resin having a liberated carboxyl group is developed using an alkaline developer.
  • a positive image is formed by removing an exposed area containing a resin composition having a carboxyl group that is easily dissolved in an alkaline developer.
  • the obtained positive image is heated to thermally decompose the acid-decomposable group in the structural unit (a1) to generate a carboxyl group, which is crosslinked with an epoxy group and / or an oxetanyl group. By doing so, a cured film can be formed.
  • This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C.
  • the heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.
  • a resin composition is prepared. For example, after preparing a solution in which (A) an acetal resin or (B) a photoacid generator is previously dissolved in (C) a solvent, these are mixed at a predetermined ratio to prepare a photosensitive resin composition. You can also The solution of the photosensitive resin composition prepared as described above can be used after being filtered using a filter having a pore size of 0.1 ⁇ m or the like.
  • a desired dry coating film can be formed by applying the resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking).
  • the substrate include a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as necessary, and a transparent conductive circuit layer, for example, in the production of a liquid crystal display device.
  • substrate is not specifically limited, For example, methods, such as a slit coat method, a spray method, a roll coat method, a spin coat method, can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate.
  • the large substrate means a substrate having a side of 1 m or more on each side.
  • the heating conditions in the solvent removal step are as follows: the acid-decomposable group is decomposed in the structural unit (a1) in the (A) acetal resin in the unexposed area, and (A) the acetal tree is alkalinized.
  • the range is not soluble in the developer, and varies depending on the type and blending ratio of each component, but is preferably about 70 to 120 ° C. for about 30 to 300 seconds.
  • Exposure Step (3) the substrate provided with the dried coating film is irradiated with an actinic ray having a predetermined pattern. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. After the exposure process, PEB is performed as necessary.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, or the like can be used.
  • actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used.
  • Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.
  • 343 nm and 355 nm are used in a solid (YAG) laser, 351 nm (XeF) is used in an excimer laser, and 375 in a semiconductor laser.
  • nm and 405 nm are used. Among these, 355 nm and 405 nm are more preferable from the viewpoint of stability and cost.
  • the coating can be irradiated with the laser once or a plurality of times.
  • the energy density per pulse of the laser is preferably 0.1 mJ / cm 2 or more and 10,000 mJ / cm 2 or less.
  • mJ / cm 2 more preferably 0.3 mJ / cm 2 or more, and most preferably from 0.5 mJ / cm 2 or more, in so as not to degrade the coating film by ablation phenomenon, 1000 mJ / cm 2 The following is more preferable, and 100 mJ / cm 2 or less is most preferable.
  • the pulse width is preferably 0.1 nsec or more and 30000 nsec or less.
  • 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable.
  • 1000 nsec or less is more preferable, and 50 nsec or less. Is most preferred.
  • the frequency of the laser is preferably 1 to 50000 Hz, more preferably 10 to 1000 Hz.
  • the exposure processing time increases.
  • the laser frequency exceeds 50000 Hz, the alignment accuracy decreases during the scan exposure.
  • the frequency of the laser is preferably 1 Hz or more and 50000 Hz or less. In order to shorten the exposure processing time, 10 Hz or more is more preferable, and 100 Hz or more is most preferable. In order to improve the alignment accuracy in the scan exposure, 10000 Hz or less is more preferable, and 1000 Hz or less is most preferable.
  • a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
  • the exposure apparatus that can be used in the present invention is not particularly limited, but commercially available exposure apparatuses include Callisto (trade name, manufactured by Buoy Technology Co., Ltd.), AEGIS (trade name, manufactured by Buoy Technology Co., Ltd.), and DF2200G ( Product name, manufactured by Dainippon Screen Co., Ltd.) can be used. Further, devices other than those described above are also preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • spectral filters such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • development Step (4) In the development step, an exposed portion area is removed using a basic developer to form an image pattern.
  • the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used.
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is usually 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, a shower method, and the like. After the development, washing with running water is performed for 10 to 90 seconds to form a desired pattern.
  • Post bake process For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or an oven, for a predetermined time at a predetermined temperature, for example, 180 to 250 ° C., for example, 5 to 60 minutes on the hot plate, In the case of an oven, heat treatment is performed for 30 to 90 minutes to decompose (A) the acid-decomposable group in the acetal resin to generate a carboxyl group, and (A) the epoxy group in the acetal resin and / or Alternatively, by reacting with a crosslinkable group that is an oxetanyl group and crosslinking, a protective film or an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed.
  • a heating device such as a hot plate or an oven
  • the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable.
  • a preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm 2 .
  • the photosensitive resin composition of the present invention provides a cured film having excellent insulation and high transparency even when baked at high temperatures, and is useful as an interlayer insulating film. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
  • the organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that a cured film formed using the photosensitive resin composition of the present invention is used as a planarizing film or an interlayer insulating film. Examples include various known organic EL display devices and liquid crystal display devices having a simple structure.
  • the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
  • a bottom emission type organic EL element is formed on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the first electrode 5 corresponds to the anode of the organic EL element.
  • An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. Further, although not shown in FIG.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate.
  • An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
  • An EL display device is obtained.
  • FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • a PGMEA solution of polymer A-1 (solid content concentration: 40%) was obtained by reacting at 70 ° C. for 4 hours.
  • the obtained polymer A-1 had a weight average molecular weight of 8,000 as measured by gel permeation chromatography (GPC).
  • Table 1 shows the monomers used in the synthesis of Polymer A-1.
  • the structural units (a1) to (a5) are changed to those shown in Table 1, and the amount of each structural unit is changed to that shown in Table 1.
  • A-2 to 19, A-30, A-31, A-34 to A-36, and A′-20 to 29 were synthesized, respectively.
  • the amount of radical polymerization initiator V-65 added was adjusted so as to have the molecular weight shown in Table 1.
  • the molar ratios shown in Table 1 are copolymerization ratios of the respective structural units, and (a4) mass% of the structural units is (a-4) mass% of the structural units in the polymer.
  • “-” indicates that the structural unit is not used.
  • (a4) 10 mol% of HEMA and 1 mol% of PME-400 are used as the structural unit.
  • CHOEMA and MATHF were synthesized in the same manner as 1-ethoxyethyl methacrylate.
  • Ph-2 was synthesized by the following method. 4-hydroxybenzoic acid (2-hydroxyethyl) ester To a solution of 21 g of acetonitrile in 100 ml of acetonitrile, 20 ml of N, N-dimethylacetamide was added with stirring, and 20 g of methacrylic acid chloride was further added. After reacting with stirring at 35 ° C.
  • the weight average molecular weight measured by (GPC) was 7,500.
  • the mass% of the (a4) structural unit was 22%.
  • Examples 1 to 119, Comparative Examples 1 to 11, Comparative Example 14 (1) Preparation of photosensitive resin composition Each component shown in Table 2 below was mixed to obtain a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.1 ⁇ m. Solutions of photosensitive resin compositions of 1 to 119, Comparative Examples 1 to 11 and Comparative Example 14 were prepared. In Tables 2 to 5, in Example 30, Example 70, and Example 107, two types of polymers A′-32 and A-33 were used. Moreover, what was described 2 types in a table
  • B1 CGI1397 (trade name, the following structure, manufactured by Ciba Japan Co., Ltd.)
  • B2 CGI1325 (trade name, the following structure, manufactured by Ciba Japan Co., Ltd.)
  • B3 PAI-1001 (trade name, the following structure, manufactured by Midori Chemical Co., Ltd.)
  • B4 PAI-101 (trade name, following structure, manufactured by Midori Chemical Co., Ltd.)
  • B5 ⁇ - (p-Toluenesulfonyloxyimino) phenylacetonitrile (the synthesis method is shown below)
  • B6 The following compound B7: The following compound B8: The following compound B9: The following compound N1: NBCA (trade name, the following structure, manufactured by Kurokin Kasei Co., Ltd.)
  • N2 DBA (trade name, 9,10-dibutoxyanthracene, the following structure, Kawasaki Chemical Industries)
  • C1 Propylene glycol mono
  • the reaction solution was poured into 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid, and then 30 g of polyphosphoric acid was added and reacted at 170 ° C. for 30 minutes.
  • the reaction solution was poured into water (300 mL), and ethyl acetate (300 mL) was added for liquid separation, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).
  • Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to a suspension of the resulting ketone compound (10.0 g) and methanol (100 mL) for 24 hours. Heated to reflux. After standing to cool, water (150 mL) and ethyl acetate (150 mL) were added for liquid separation, and the organic layer was separated four times with 80 mL of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g). Got. The obtained oxime (3.1 g) was sulfonated in the same manner as B7 to obtain B8 (3.2 g).
  • B9 B9 was synthesized in the same manner as B7 except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in the synthesis of B7.
  • composition used in Comparative Example 12 is the composition described in Example 1 of JP-A-2004-264623.
  • the composition used in Comparative Example 13 is the composition described in Example 7 of JP-A-2009-98616.
  • the composition used in Comparative Example 14 is the composition described in Example 1 of JP-A-10-26829.
  • the optimum exposure amount (Eopt) when resolving 10 ⁇ m line and space at 1: 1 was defined as sensitivity.
  • the sensitivity can be said to be high when the exposure dose is lower than 70 mJ / cm 2 .
  • Tables 6 and 7. “**” in the sensitivity (no PEB) column indicates that peeling occurred during development and patterning could not be performed, and “*” indicates 200 mJ / It shows that pattern formation could not be performed at cm 2 .
  • the value of the minimum light transmittance is converted into a value per 2 ⁇ m of film thickness after heating at 230 ° C. for 2 hours. 0: 92% or more 1: 87% or more and less than 92% 2: 85% or more and less than 87% 3: 82% or more and less than 85% 4: less than 82%
  • the photosensitive resin composition of the present invention has very high sensitivity, good heat-resistant transparency, and excellent ITO sputtering resistance even when PEB is not performed. Moreover, although the photosensitive resin composition of this invention has very high sensitivity even if PEB is not performed, it turns out that sensitivity becomes still higher by performing PEB. On the other hand, it can be seen that the comparative example not using the present invention has low sensitivity when PEB is not performed, and the sensitivity is lower than that of the embodiment of the present invention even when PEB is performed.
  • UV-LED exposure Further, with respect to the photosensitive resin compositions of Examples 1 to 119, except that the exposure was changed from an i-line stepper to a UV-LED light source exposure machine (2-1) When the same evaluation as the sensitivity evaluation (without PEB) was performed, it was found that all patterns could be formed.
  • Example 120 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
  • a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
  • a wiring 2 (height of 1.0 ⁇ m) connected to the TFT 1 through the contact hole was formed on the insulating film 3.
  • the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
  • the planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 11 on the substrate, pre-baking (90 ° C. ⁇ 2 minutes) on a hot plate, and then applying high pressure from above the mask. After irradiating i-line (365 nm) with 25 mJ / cm 2 (illuminance 20 mW / cm 2 ) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average level difference of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2.000 nm.
  • a bottom emission type organic EL element was formed on the obtained flattening film 4.
  • a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
  • pattern processing was performed by wet etching using an ITO etchant.
  • the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
  • the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
  • an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
  • the insulating film 8 was formed by using the photosensitive resin composition of Example 12 and the same method as described above.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
  • a second electrode made of Al was formed on the entire surface above the substrate.
  • substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
  • Example 121 In Example 120, the photosensitive resin composition of Example 11 for forming the planarizing film 4 and the photosensitive resin composition of Example 12 for forming the insulating film 8 are both the photosensitive resin composition of Example 43.
  • An organic EL display device was produced in the same manner as in Example 120 except that the above was changed. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
  • Example 122 In Example 120, the photosensitive resin composition of Example 11 for forming the planarizing film 4 and the photosensitive resin composition of Example 12 for forming the insulating film 8 are both photosensitive resin compositions of Example 80.
  • An organic EL display device was produced in the same manner as in Example 120 except that the above was changed. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
  • Example 123 In Example 120, the photosensitive resin composition of Example 11 for forming the planarizing film 4 and the photosensitive resin composition of Example 12 for forming the insulating film 8 are both the photosensitive resin composition of Example 119.
  • An organic EL display device was produced in the same manner as in Example 120 except that the above was changed. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
  • Example 124 In the active matrix liquid crystal display device shown in FIGS. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 124 was obtained. That is, using the photosensitive resin composition of Example 11, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 120. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 125 A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 43. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
  • Example 126 A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 80. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
  • Example 127 A liquid crystal display device was produced in the same manner as in Example 124 except that the photosensitive resin composition of Example 11 was changed to the photosensitive resin composition of Example 119. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
  • Example 128 In the liquid crystal display device shown in FIG. 2 of JP-A-2008-146004, the protective film 141 was formed using the photosensitive resin composition of Example 119, and the liquid crystal display device of Example 128 was obtained. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 129 In the liquid crystal display device shown in FIG. 1 of JP-A-2000-267073, the overcoat 15 was formed using the photosensitive resin composition of Example 119, and the liquid crystal display device of Example 129 was obtained. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

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PCT/JP2011/050295 2010-01-15 2011-01-11 感光性樹脂組成物、硬化膜の形成方法、硬化膜、有機ｅｌ表示装置、及び、液晶表示装置 WO2011086997A1 (ja)

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KR20130025338A (ko) * 2011-09-01 2013-03-11 제이에스알 가부시끼가이샤 어레이 기판, 액정 표시 소자 및 어레이 기판의 제조 방법
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KR101747769B1 (ko) 2013-09-30 2017-06-15 후지필름 가부시키가이샤 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 유기 el 표시 장치 및 액정 표시 장치
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