WO2015046332A1 - Radiation sensitive composition and pattern forming method - Google Patents

Radiation sensitive composition and pattern forming method Download PDF

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Publication number
WO2015046332A1
WO2015046332A1 PCT/JP2014/075431 JP2014075431W WO2015046332A1 WO 2015046332 A1 WO2015046332 A1 WO 2015046332A1 JP 2014075431 W JP2014075431 W JP 2014075431W WO 2015046332 A1 WO2015046332 A1 WO 2015046332A1
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Prior art keywords
group
carbon atoms
substituent
sensitive composition
bis
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PCT/JP2014/075431
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French (fr)
Japanese (ja)
Inventor
信太　勝
照博 植松
Original Assignee
東京応化工業株式会社
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Application filed by 東京応化工業株式会社 filed Critical 東京応化工業株式会社
Priority to CN201480052348.3A priority Critical patent/CN105579907B/en
Priority to JP2015539332A priority patent/JP6195623B2/en
Priority to KR1020177034642A priority patent/KR102128155B1/en
Priority to KR1020167007028A priority patent/KR20160045094A/en
Publication of WO2015046332A1 publication Critical patent/WO2015046332A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

Definitions

  • the present invention relates to a radiation-sensitive composition and a pattern manufacturing method using the same.
  • radiation-sensitive compositions In the manufacture of integrated circuits, color filters, liquid crystal elements and the like, fine processing is required, and in order to satisfy this requirement, radiation-sensitive compositions have been conventionally used. Generally, there are positive and negative radiation-sensitive compositions. Usually, any of them is dissolved in a solvent and used in a solution state.
  • the radiation-sensitive composition is applied to a silicon substrate, glass substrate, or other substrate by a known coating method such as spin coating, roller coating, slit coating, or inkjet, and then pre-baked to form a radiation-sensitive composition film. Then, depending on the photosensitive wavelength range of the radiation-sensitive composition, it is exposed with particle beams such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams, developed, and then subjected to dry etching as necessary. A desired pattern is formed.
  • a known coating method such as spin coating, roller coating, slit coating, or inkjet
  • Various solvents have been conventionally used as a radiation-sensitive composition, and are selected and used in consideration of solubility, coatability, sensitivity, developability, pattern characteristics to be formed, and the like.
  • ethylene glycol monoethyl ether acetate is known as a solvent excellent in various properties such as solubility, coatability, and radiation-sensitive composition film-forming properties.
  • safety problems for the human body have been pointed out.
  • a solvent that has high safety is excellent in resin solubility and initiator solubility, and has improved performance such as radiation-sensitive composition film-forming properties.
  • the present invention has been made in view of the above situation, and is excellent in sensitivity, storage stability, applicability, developability, and safety, and has a pattern in which the generation of foreign matters is suppressed by exposure and development. It aims at providing the radiation sensitive composition which can be formed, and the pattern manufacturing method using the same.
  • the present inventors have found that the above problems can be solved by using a specific organic solvent, and have completed the present invention. Specifically, the present invention provides the following.
  • the first aspect of the present invention is a radiation-sensitive composition containing a compound represented by the following general formula (1).
  • R 1 represents a hydrogen atom or a hydroxyl group
  • R 2 and R 3 independently represent a hydrogen atom or a C 1 -C 3 alkyl group
  • R 4 and R 5 independently represent C 1 represents an alkyl group ⁇ C 3.
  • a radiation-sensitive composition film forming step of forming a radiation-sensitive composition film comprising the radiation-sensitive composition on a substrate, and the radiation-sensitive composition film are position-selective. It is a pattern manufacturing method including the exposure process exposed to 1 and the image development process which develops the exposed said radiation sensitive composition film
  • a radiation-sensitive composition excellent in sensitivity, storage stability, coatability, developability, and safety, and capable of forming a pattern in which the generation of foreign matter is suppressed by exposure and development, and the same A pattern manufacturing method using can be provided.
  • the radiation-sensitive composition according to the present invention contains at least the compound represented by the general formula (1).
  • the compound represented by the general formula (1) is used as a solvent in the radiation-sensitive composition according to the present invention.
  • the radiation-sensitive composition according to the present invention may contain only the compound represented by the general formula (1) as a solvent, or an organic solvent other than the compound represented by the general formula (1) ( Hereinafter, it may also contain “other organic solvent”. That is, the radiation-sensitive composition according to the present invention contains the compound represented by the general formula (1) as at least one kind of solvent.
  • the compound represented by the general formula (1) is a component other than the solvent (hereinafter referred to as “base component”) alone or in the form of a mixed solvent with another organic solvent. Is used as a solvent for dissolving and / or dispersing. Since the radiation-sensitive composition according to the present invention contains the compound represented by the general formula (1), it is excellent in sensitivity, storage stability, coatability, developability, and safety. A pattern in which the generation of foreign matter is suppressed can be formed.
  • the radiation-sensitive composition according to the present invention can be suitably used for producing, for example, a black matrix, a color filter, a black photo spacer, an integrated circuit, a liquid crystal element, and the like.
  • the compound represented by the general formula (1) is a solvent that can dissolve and / or disperse the base material component contained in the radiation-sensitive composition satisfactorily and is widely used in radiation-sensitive compositions in general. Can do. Among these, when the radiation-sensitive composition contains an oxime photopolymerization initiator, the compound represented by the general formula (1) has good solubility of the oxime photopolymerization initiator.
  • the compounds represented by the general formula (1) can be used alone or in combination of two or more.
  • the alkyl group of C 1 ⁇ C 3 represented an alkyl group of C 1 ⁇ C 3 represented by R 2 or R 3, and the R 4 or R 5, a methyl group
  • examples include an ethyl group, a propyl group, and an isopropyl group.
  • R 2 , R 3 , R 4 , and R 5 are preferably independently a methyl group or an ethyl group.
  • preferred specific examples include the compounds 1 to 4 used in the examples.
  • the compound 1, that is, the compound represented by the following formula (E1) is particularly preferred. preferable.
  • the compound represented by the following formula (E1) is not designated as a substance of very high concern (SVHC) and is a compound having low toxicity, and thus has a particularly high safety.
  • the content of the solvent is preferably such that the solid content concentration of the radiation-sensitive composition is 1 to 50% by mass, and more preferably 5 to 30% by mass. .
  • the mass ratio of the compound represented by the general formula (1) to the other organic solvent is 5:95 to 100: 0.
  • it is 20:80 to 100: 0.
  • the radiation sensitive composition according to the present invention may be either a negative type or a positive type.
  • a negative radiation sensitive composition a negative radiation sensitive composition containing a compound represented by the above general formula (1) and an alkali-soluble resin; a compound represented by the above general formula (1); , A radiation sensitive polyimide precursor composition containing a polyamic acid and a photosensitive component such as a photobase generator or a photoacid generator; a compound represented by the above general formula (1); and a polybenzoxazole precursor And a radiation-sensitive polybenzoxazole precursor composition containing a photosensitive component such as a photobase generator and a photoacid generator; a radiation-sensitive SOG containing a compound represented by the above general formula (1) ( Spin on glass) composition and the like.
  • a positive radiation sensitive composition containing a compound represented by the above general formula (1), an alkali-soluble resin, and a quinonediazide group-containing compound; the above general formula (1)
  • a radiation-sensitive polyimide composition comprising a compound represented by the formula: a polyimide resin; and a photosensitive component such as a photobase generator or a photoacid generator; a compound represented by the above general formula (1);
  • a chemically amplified positive radiation-sensitive composition containing a resin whose solubility in alkali is increased by the action of the above and a photoacid generator.
  • a negative radiation-sensitive composition (hereinafter referred to as “negative-type radiation-sensitive composition” containing the compound represented by the general formula (1) and an alkali-soluble resin. 1 ”), a radiation sensitive polyimide precursor composition containing a compound represented by the above general formula (1), a polyamic acid, and a photosensitive component such as a photobase generator and a photoacid generator ( Hereinafter, it is referred to as “negative radiation sensitive composition 2”), a compound represented by the above general formula (1), a polybenzoxazole precursor, a photobase generator, a photoacid generator, and other photosensitive components.
  • negative radiation sensitive composition 2 a compound represented by the above general formula (1), a polybenzoxazole precursor, a photobase generator, a photoacid generator, and other photosensitive components.
  • a radiation-sensitive polybenzoxazole precursor composition (hereinafter referred to as “negative radiation-sensitive composition 3”), a compound represented by the above general formula (1), an alkali-soluble resin, Containing a quinonediazide group-containing compound
  • the positive type radiation-sensitive composition (hereinafter, referred to as "positive-type radiation-sensitive composition 1".) Will be described in detail.
  • the negative radiation sensitive composition 1 contains the compound represented by the above general formula (1) and an alkali-soluble resin, and more specifically, represented by the above general formula (1). It contains a compound, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator.
  • the alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a 1 ⁇ m-thick resin film is formed on the substrate and placed in a 0.05% by mass KOH aqueous solution for 1 minute. When immersed, it means a film that dissolves 0.01 ⁇ m or more in thickness.
  • the alkali-soluble resin is not particularly limited as long as it is a resin exhibiting alkali solubility as described above, and a conventionally known alkali-soluble resin can be used.
  • the alkali-soluble resins can be used alone or in combination of two or more.
  • An example of a suitable alkali-soluble resin is (A1) a resin having a cardo structure.
  • the resin having a cardo structure is not particularly limited, and conventionally known resins can be used. Among these, a resin represented by the following formula (a-1) is preferable.
  • X a represents a group represented by the following formula (a-2).
  • R a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom
  • R a2 each independently represents a hydrogen atom or a methyl group
  • W a represents a single bond or a group represented by the following formula (a-3).
  • Y a represents a residue obtained by removing the acid anhydride group (—CO—O—CO—) from the dicarboxylic acid anhydride.
  • dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.
  • Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride.
  • tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
  • m represents an integer of 0 to 20.
  • the mass average molecular weight of the resin having a cardo structure is preferably 1000 to 40000, more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.
  • a mass average molecular weight means the value by polystyrene conversion measured by gel permeation chromatography (GPC).
  • a suitable alkali-soluble resin is (A2) an epoxy resin.
  • the epoxy resin is not particularly limited, and a conventionally known epoxy resin can be used, and it has an ethylenically unsaturated group even if it does not have an ethylenically unsaturated group. It may be.
  • epoxy resin having no ethylenically unsaturated group for example, a resin (A2-1) obtained by at least copolymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound can be used.
  • unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; It is done.
  • (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like.
  • unsaturated carboxylic acids can be used alone or in combination of two or more.
  • “(meth) acrylic acid” means both acrylic acid and methacrylic acid.
  • the proportion of the structural unit derived from the unsaturated carboxylic acid (the structural unit having a carboxyl group) in the resin (A2-1) is preferably 5 to 29% by mass, and more preferably 10 to 25% by mass. preferable. By setting it as the said range, the developability of the negative radiation sensitive composition 1 can be made moderate.
  • the epoxy group-containing unsaturated compound may have no alicyclic epoxy group or may have an alicyclic epoxy group, but more preferably has an alicyclic epoxy group.
  • Examples of the epoxy group-containing unsaturated compound having no alicyclic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl.
  • glycidyl (meth) acrylate 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoint of copolymerization reactivity, strength of cured resin, and the like.
  • Glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred.
  • the alicyclic group of the epoxy group-containing unsaturated compound having an alicyclic epoxy group may be monocyclic or polycyclic.
  • Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group.
  • Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.
  • examples of the epoxy group-containing unsaturated compound having an alicyclic epoxy group include compounds represented by the following formulas (a4-1) to (a4-16).
  • the compounds represented by the following formulas (a4-1) to (a4-6) are preferable in order to make the negative radiation-sensitive composition 1 have an appropriate developability, and the following formula (a4 The compounds represented by -1) to (a4-4) are more preferred.
  • R a3 represents a hydrogen atom or a methyl group
  • R a4 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms
  • R a5 represents a divalent hydrocarbon having 1 to 10 carbon atoms.
  • n represents an integer of 0 to 10.
  • R a4 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group.
  • R a5 for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH 2 —Ph—CH 2 — (Ph is A phenylene group) is preferred.
  • epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.
  • the proportion of the structural unit derived from the epoxy group-containing unsaturated compound (the structural unit having an epoxy group) in the resin (A2-1) is preferably 5 to 90% by mass, and preferably 15 to 75% by mass. Is more preferable. By setting it as the said range, it becomes easy to form a pattern of a favorable shape.
  • the resin (A2-1) is preferably obtained by further copolymerizing an alicyclic group-containing unsaturated compound.
  • the alicyclic group of the alicyclic group-containing unsaturated compound may be monocyclic or polycyclic.
  • Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group.
  • Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.
  • examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulas (a5-1) to (a5-8). Of these, compounds represented by the following formulas (a5-3) to (a5-8) are preferable in order to make the negative radiation-sensitive composition 1 have an appropriate developability, and the following formula (a5 -3) and compounds represented by (a5-4) are more preferred.
  • R a6 represents a hydrogen atom or a methyl group
  • R a7 represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms
  • R a8 represents a hydrogen atom or 1 to 5 carbon atoms.
  • R a7 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group.
  • R a8 for example, a methyl group and an ethyl group are preferable.
  • the proportion of the structural unit derived from the alicyclic group-containing unsaturated compound in the resin (A2-1) is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass.
  • the resin (A2-1) may be obtained by further copolymerizing other compounds than the above.
  • examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more.
  • (Meth) acrylic acid esters include linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc.
  • Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.
  • (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.
  • allyl compound examples include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.
  • the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether.
  • Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorofe And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.
  • Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl vinyl.
  • vinyl esters include enil acetate, vinyl acetoacetate, vinyl lactate, vinyl- ⁇ -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.
  • Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlor
  • the mass average molecular weight of the resin (A2-1) is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, there is a tendency that the film-forming ability and developability of the negative radiation-sensitive composition 1 are easily balanced.
  • an epoxy resin having an ethylenically unsaturated group for example, a carboxyl group of a resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, and an epoxy group of an epoxy group-containing unsaturated compound
  • Resin (A2-3) obtained by the reaction can be used.
  • the unsaturated carboxylic acid and the epoxy group-containing unsaturated compound include the compounds exemplified for the resin (A2-1). Therefore, the resin (A2-1) is exemplified as a resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound.
  • the proportion of the structural unit derived from the unsaturated carboxylic acid (the structural unit having a carboxyl group) in the resins (A2-2) and (A2-3) is preferably 5 to 60% by mass, and 10 to 40% by mass. % Is more preferable. By setting it as the said range, the developability of the negative radiation sensitive composition 1 can be made moderate.
  • the proportion of the structural unit derived from the epoxy group-containing unsaturated compound (structural unit having an epoxy group) in the resin (A2-2) or (A2-3) is preferably 5 to 90% by mass, More preferably, it is 15 to 75% by mass. By setting it as the said range, it becomes easy to form a pattern of a favorable shape.
  • the mass average molecular weights of the resins (A2-2) and (A2-3) are preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, there is a tendency that the film-forming ability and developability of the negative radiation-sensitive composition 1 are easily balanced.
  • (A2) epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, An epoxy (meth) acrylate resin obtained by reacting an epoxy group of an epoxy resin such as a polycarboxylic acid polyglycidyl ester, a polyol polyglycidyl ester, an amine epoxy resin, or a dihydroxybenzene type epoxy resin with (meth) acrylic acid, etc. It can also be used.
  • the content of the alkali-soluble resin is preferably 5 to 90% by mass, more preferably 10 to 85% by mass with respect to the solid content of the negative radiation-sensitive composition 1. By setting it as said range, there exists a tendency which is easy to balance the film formation ability of the negative radiation sensitive composition 1, and developability.
  • Photopolymerizable monomer It does not specifically limit as a photopolymerizable monomer, A conventionally well-known monofunctional monomer and a polyfunctional monomer can be used. A photopolymerizable monomer can be used individually or in combination of 2 or more types.
  • Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylic , Cyclohexyl (meth) acrylate, 2-hydroxyethyl
  • the content of the photopolymerizable monomer is preferably 1 to 45% by mass, more preferably 5 to 40% by mass with respect to the solid content of the negative radiation-sensitive composition 1.
  • Photopolymerization initiator It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used. A photoinitiator can be used individually or in combination of 2 or more types.
  • Specific photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Til, 4-dimethylamino-2-ethylhexy
  • oxime photopolymerization initiator examples include a photopolymerization initiator represented by the following formula (c-1).
  • R c1 represents a heterocyclic group, a condensed cyclic aromatic group, or an aromatic group, which may have a substituent.
  • R c2 to R c4 each independently represent a monovalent organic group.
  • heterocyclic group for R c1 examples include 5-membered or more, preferably 5- or 6-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom.
  • heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable.
  • This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group
  • Examples of the condensed cyclic aromatic group for R c1 include a naphthyl group, an anthryl group, and a phenanthryl group. Moreover, a phenyl group is mentioned as an aromatic group in Rc1 .
  • the heterocyclic group, the condensed cyclic aromatic group, or the aromatic group may have a substituent.
  • R c1 when R c1 is an aromatic group, it preferably has a substituent.
  • substituents include —NO 2 , —CN, —SO 2 R c5 , —COR c5 , —NR c6 R c7 , —R c8 , —OR c8 , —O—R c9 —O—R c10, etc. Is mentioned.
  • R c5 independently represents an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond.
  • the alkyl group in R c5 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
  • R c6 and R c7 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom, and among these, the alkylene group of the alkyl group and the alkoxy group is an ether bond, It may be interrupted by a thioether bond or an ester bond. R c6 and R c7 may be bonded to form a ring structure.
  • the alkyl group or alkoxy group in R c6 and R c7 preferably has 1 to 5 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, ethoxy group, A propoxy group etc. are mentioned.
  • a ring structure that can be formed by combining R c6 and R c7 includes a heterocyclic ring.
  • the heterocyclic ring include 5-membered or more, preferably 5- to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring.
  • the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like. Among these, a morpholine ring is preferable.
  • R c8 represents an alkyl group in which part or all of the hydrogen atoms may be substituted with a halogen atom.
  • the alkyl group for R c8 preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
  • R c9 and R c10 each independently represent an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond.
  • the preferred number of carbon atoms and specific examples thereof are the same as those described above for R c1 .
  • R c1 include a pyrrolyl group, a pyridyl group, a thienyl group, a thiopyralyl group, a benzothienyl group, a naphthyl group, and a phenyl group having a substituent.
  • R c2 represents a monovalent organic group.
  • the organic group is preferably a group represented by —R c11 , —OR c11 , —COR c11 , —SR c11 , —NR c11 R c12 .
  • R c11 and R c12 each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with a halogen atom, an alkyl group, or a heterocyclic group, Among them, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R c11 and R c12 may be bonded to form a ring structure with the nitrogen atom.
  • the alkyl group for R c11 and R c12 preferably has 1 to 20 carbon atoms, and more preferably has 1 to 5 carbon atoms.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl.
  • this alkyl group may have a substituent.
  • substituents include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
  • alkenyl group for R c11 and R c12 an alkenyl group having 1 to 20 carbon atoms is preferable, and an alkenyl group having 1 to 5 carbon atoms is more preferable.
  • alkenyl groups include linear or branched groups such as vinyl, allyl, butenyl, ethenyl, and propynyl groups.
  • this alkenyl group may have a substituent. Examples of those having a substituent include 2- (benzoxazol-2-yl) ethenyl group and the like.
  • the aryl group for R c11 and R c12 preferably has 6 to 20 carbon atoms, and more preferably has 6 to 10 carbon atoms.
  • Examples of the aryl group include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group and the like.
  • the aralkyl group in R c11 and R c12 is preferably one having 7 to 20 carbon atoms, and more preferably one having 7 to 12 carbon atoms.
  • Examples of the aralkyl group include benzyl group, ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.
  • heterocyclic group for R c11 and R c12 examples include 5-membered or more, preferably 5- to 7-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. This heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include pyrrolyl, pyridyl, pyrimidyl, furyl, and thienyl groups.
  • the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.
  • a ring structure that can be formed by combining R c11 and R c12 includes a heterocyclic ring.
  • the heterocyclic ring include 5-membered or more, preferably 5- to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring.
  • the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like.
  • R c2 is most preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.
  • R c3 represents a monovalent organic group.
  • the organic group include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (c-2), or a substituent.
  • the heterocyclic group which may have is preferable.
  • the substituent include the same groups as in R c1 above.
  • the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
  • R c13 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom.
  • alkylene group examples include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, an n-pentylene group, an isopentylene group, and a sec-pentylene group.
  • a linear or branched group is mentioned.
  • R c13 is most preferably an isopropylene group.
  • R c14 represents a monovalent organic group represented by —NR c15 R c16 (R c15 and R c16 each independently represents a monovalent organic group).
  • R c14 is represented by the following formula (c-3) because the solubility of the photopolymerization initiator can be improved.
  • R c17 and R c18 each independently represents an alkyl group having 1 to 5 carbon atoms.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec- Examples thereof include a pentyl group and a tert-pentyl group.
  • R c17 and R c18 are most preferably a methyl group.
  • heterocyclic group for R c3 examples include 5-membered or more, preferably 5-membered or 6-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom.
  • heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable.
  • This heterocyclic ring may contain a condensed ring. Examples of the hetero
  • heterocyclic group may have a substituent.
  • substituents include the same groups as in R c1 above.
  • R c4 represents a monovalent organic group.
  • an alkyl group having 1 to 5 carbon atoms is preferable.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec- Examples thereof include a pentyl group and a tert-pentyl group.
  • R c4 is most preferably a methyl group.
  • oxime photopolymerization initiator includes a photopolymerization initiator represented by the following formula (c-4) proposed in Japanese Patent Application Laid-Open No. 2010-15025.
  • R c21 and R c22 each independently represent R c31 , OR c31 , COR c31 , SR c31 , CONR c32 R c33 , or CN.
  • R c31 , R c32 , and R c33 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 20 heterocyclic groups are shown.
  • R c41, R c 42, and R c43 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon number of 2 to 20 heterocyclic groups are shown.
  • Methylene groups in the alkylene moiety of the substituents on the R c31, R c32, R c33 , R c41, R c42, and R c43 are unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or
  • the substituent may be interrupted 1 to 5 times, the alkyl part of the substituent may be branched or cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond.
  • R c32 and R c33, and R c 42 and R c43 may form a ring structure, respectively.
  • R c23 and R c24 each independently represent R c31 , OR c31 , COR c31 , SR c31 , CONR c32 R c33 , NR c31 COR c32 , OCOR c31 , COOR c31 , SCOR c31 , OCSR c31 , COSR c31 , CSOR c31 , CN, a halogen atom, or a hydroxyl group.
  • a and b each independently represent an integer of 0 to 4.
  • R c23 may be bonded to one of the adjacent carbon atoms of the benzene ring via —X c2 — to form a ring structure, and R c23 and R c24 are bonded to form a ring structure. May be.
  • X c1 represents a single bond or CO.
  • X c2 represents an oxygen atom, a sulfur atom, a selenium atom, CR c51 R c52 , CO, NR c53 , or PR c54 .
  • R c51 , R c52 , R c53 , and R c54 each independently represent R c31 , OR c31 , COR c31 , SR c31 , CONR c32 R c33 , or CN.
  • R c51 , R c53 , and R c54 may each independently form a ring structure together with any adjacent benzene ring.
  • the aryl group in R c31, R c32, R c33 , R c41, R c42, and R c43 a phenyl group, a tolyl group, xylyl group, ethylphenyl group, a chlorophenyl group, a naphthyl Group, anthryl group, phenanthrenyl group and the like.
  • the ring and R c32 and R c33 may be formed by combining the ring and the R c 42 and R c43 may be formed by bonding, and together with the benzene ring to which R c23 is adjacent
  • the ring that can be formed include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.
  • the photopolymerization initiator has a carbazole skeleton. Become.
  • the methylene group in the alkylene part of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond.
  • the linking group to be interrupted may be one type or two or more groups, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted continuously.
  • the alkyl part of the substituent may have a branched chain or may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.
  • Still another preferred example of the oxime photopolymerization initiator is an oxime ester compound represented by the following formula (2).
  • R d1 is a group selected from the group consisting of a monovalent organic group, amino group, halogen atom, nitro group, and cyano group, i is an integer of 0 to 4, and j is 0
  • R d2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent
  • R d3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. is there.
  • R d1 when R d1 is a monovalent organic group, R d1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups.
  • Preferred examples when R d1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent.
  • R d1 may be the same or different.
  • R d1 is an alkyl group
  • the carbon number thereof is preferably 1-20, and more preferably 1-6.
  • R d1 is an alkyl group, it may be linear or branched. Specific examples in the case where R d1 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group.
  • R d1 is an alkyl group
  • the alkyl group may contain an ether bond (—O—) in the carbon chain.
  • alkyl group having an ether bond in the carbon chain examples include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
  • R d1 is an alkoxy group
  • the carbon number thereof is preferably 1-20, and more preferably 1-6.
  • R d1 is an alkoxy group, it may be linear or branched.
  • Specific examples when R d1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octoxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy
  • R d1 is an alkoxy group
  • the alkoxy group may contain an ether bond (—O—) in the carbon chain.
  • the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.
  • R d1 is a cycloalkyl group or a cycloalkoxy group
  • the number of carbon atoms is preferably 3 to 10, and more preferably 3 to 6.
  • Specific examples in the case where R d1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • R d1 is a cycloalkoxy group
  • R d1 is a cycloalkoxy group
  • R d1 is a cycloalkoxy group
  • R d1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group
  • the carbon number thereof is preferably 2-20, and more preferably 2-7.
  • Specific examples of the case where R d1 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane group
  • Examples include a noyl group and an
  • R d1 is a saturated aliphatic acyloxy group
  • R d1 is a saturated aliphatic acyloxy group
  • R d1 is a saturated aliphatic acyloxy group
  • R d1 is a saturated aliphatic acyloxy group
  • R d1 is a saturated aliphatic acyloxy group
  • R d1 is an alkoxycarbonyl group
  • the carbon number thereof is preferably 2 to 20, and more preferably 2 to 7.
  • Specific examples of the case where R d1 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbon
  • R d1 is a phenylalkyl group
  • the carbon number thereof is preferably 7-20, and more preferably 7-10.
  • R d1 is a naphthylalkyl group
  • the carbon number thereof is preferably 11-20, and more preferably 11-14.
  • R d1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
  • R d1 is a naphthylalkyl group
  • R d1 is a naphthylalkyl group
  • R d1 may further have a substituent on the phenyl group or naphthyl group.
  • R d1 is a heterocyclyl group
  • the heterocyclyl group is a 5-membered or 6-membered monocycle in which the total number of N, S, and O is 1 or more, such monocycles, or such monocycles Is a heterocyclyl group in which a benzene ring is condensed.
  • the heterocyclyl group is a condensed ring, the ring number is up to 3.
  • heterocyclic ring constituting the heterocyclyl group examples include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline.
  • R d1 is a heterocyclyl group
  • the heterocyclyl group may further have a substituent.
  • R d1 is an amino group substituted with an organic group having 1 or 2
  • suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and 2 to 20 saturated aliphatic acyl groups, optionally substituted phenyl groups, optionally substituted benzoyl groups, optionally substituted C 7-20 phenylalkyl groups, substituents A naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group.
  • Specific examples of these suitable organic groups are the same as those for R d1 .
  • Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, and n-butyl.
  • examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to A saturated aliphatic acyl group having 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms And a dialkylamino group having an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.
  • the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable.
  • the phenyl group, naphthyl group, and heterocyclyl group included in R d1 have a plurality of substituents, the plurality of substituents may be the same or different.
  • R d1 since it is chemically stable, has few steric hindrances, is easy to synthesize an oxime ester compound, and has high solubility in a solvent, it has a nitro group and a carbon number of 1 Is preferably a group selected from the group consisting of an alkyl group having ⁇ 6, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms, more preferably a nitro group or an alkyl having 1 to 6 carbon atoms.
  • a nitro group or a methyl group is particularly preferable.
  • Position R d1 is bonded to the phenyl group, the phenyl group R d1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable.
  • i is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.
  • R d2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent.
  • R d2 is an optionally substituted carbazolyl group
  • the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.
  • the substituent that the phenyl group or carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired.
  • suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and cyclohexane having 3 to 10 carbon atoms.
  • R d2 is a carbazolyl group
  • suitable substituents that the carbazolyl group may have on the nitrogen atom include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, carbon atoms A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and a substituent.
  • an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
  • the substituent that the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent.
  • R It is the same as d1 .
  • Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent that the phenyl group or carbazolyl group has in R d2 further have a substituent include an alkyl group having 1 to 6 carbon atoms; Alkoxy group having 1 to 6 carbon atoms; saturated aliphatic acyl group having 2 to 7 carbon atoms; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; 1 to 6 carbon atoms; A monoalkylamino group having 1 to 6 carbon atoms; a dialkyla
  • the number of the substituent is not limited as long as the object of the present invention is not impaired. ⁇ 4 are preferred.
  • the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.
  • R d2 the group represented by the following formula (3) or (4) is preferable, and the group represented by the following formula (3) is more preferable because the negative radiation-sensitive composition 1 is excellent in sensitivity.
  • R d4 is a group selected from the group consisting of a monovalent organic group, amino group, halogen atom, nitro group, and cyano group, A is S or O, and k is an integer of 0-4. .
  • R d5 and R d6 are monovalent organic groups, which may be the same or different.
  • R d4 in the formula (3) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired.
  • R d4 when R d4 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, A benzoyl group substituted by a group selected from the group consisting of a piperazin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1
  • R d4 substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group
  • Benzoyl group nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.
  • k is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.
  • bond position of R d4, relative bond which the phenyl group R d4 are attached to atoms and bonds A, is preferably in the para position.
  • R d5 in formula (4) can be selected from various organic groups as long as the object of the present invention is not impaired.
  • R d5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, Phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, phenylalkyl having 7 to 20 carbon atoms which may have a substituent Group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted carbon number 11 to 20 Naphthylalkyl group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may be
  • an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
  • R d6 in formula (4) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups.
  • Specific examples of the group suitable as R d6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used.
  • R d6 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.
  • the substituent is an alkyl group having 1 to 6 carbon atoms, or a C 1 to 6 carbon group.
  • a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group are examples of the alkyl group having 1 to 6 carbon atoms.
  • the number of the substituent is not limited as long as the object of the present invention is not impaired, 1 to 4 are preferred.
  • the phenyl group, naphthyl group, and heterocyclyl group contained in R d4 , R d5 , or R d6 have a plurality of substituents, the plurality of substituents may be the same or different.
  • R d3 in the formula (2) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R d3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • the photopolymerization initiator composed of the compound represented by formula (2) is particularly excellent in sensitivity.
  • the oxime ester compound represented by the formula (2) can be synthesized according to the following scheme 1, for example. Specifically, an aromatic compound represented by the following formula (d1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (d1-2), and the following formula A ketone compound represented by (d1-3) is obtained, and the resulting ketone compound (d1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (d1-4), The oxime compound (d1-4) and an acid anhydride ((R d3 CO) 2 O) represented by the following formula (d1-5) or an acid halide (R) represented by the following formula (d1-6) An oxime ester compound represented by the following formula (d1-7) can be obtained by reacting with d3 COHal and Hal are halogen atoms.
  • an aromatic compound represented by the following formula (d1-1) is acylated by a Friedel-C
  • Hal is a halogen atom
  • the following formulas (d1-1), (d1-2), (d1-3), (d1-4), and (d1-7) , R d1 , R d2 , R d3 , and i are the same as those in the formula (2).
  • the oxime ester compound represented by the formula (2) can be synthesized, for example, according to the following scheme 2. Specifically, the ketone compound represented by the following formula (d2-1) is added to a nitrite ester (RONO, R represented by the following formula (d2-2) in the presence of hydrochloric acid in the presence of hydrochloric acid.
  • a compound represented by the following formula (d2-7) can also be synthesized by oximation and acylation in the same manner as in Scheme 1.
  • R d2 is the same as in formula (2).
  • oxime ester compounds represented by formula (2) particularly preferred compounds include compounds represented by the following formula.
  • Still another preferred example of the oxime photopolymerization initiator is “IRGACURE OXE01” (trade name, manufactured by BASF).
  • the content of the photopolymerization initiator is preferably 0.3 to 20% by mass, and more preferably 0.5 to 15% by mass with respect to the solid content of the negative radiation-sensitive composition 1.
  • the negative radiation sensitive composition 1 may contain a colorant.
  • the negative radiation-sensitive composition 1 is preferably used, for example, for forming a color filter of a liquid crystal display by containing a colorant.
  • the negative radiation sensitive composition 1 contains a light-shielding agent as a colorant, and thus is preferably used, for example, for forming a black matrix in a color filter or for forming a black photo spacer.
  • the colorants can be used alone or in combination of two or more.
  • C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 185; C. I.
  • Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, 73; C.
  • Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; C. I.
  • Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 : 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 : 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 166, 168, 170, 171, 172, 174, 175, 176, 177, 78, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215,
  • I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 66; C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37; C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28; C. I. Pigment black 1, C.I. I. Pigment Black 7.
  • Black pigments include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, etc.
  • Various pigments can be mentioned regardless of organic matter and inorganic matter. Among these, it is preferable to use carbon black having high light shielding properties.
  • carbon black known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.
  • Resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so when used as a black matrix for liquid crystal display, it produces less current leakage and produces a highly reliable display with low power consumption. it can.
  • the above organic pigment may be added as an auxiliary pigment.
  • a pigment and a dye may be used in combination.
  • dyes that can be used in combination with pigments include xanthene dyes, cyanine dyes, azo dyes, anthraquinone dyes, dioxazine dyes, and triphenylmethane dyes.
  • a dispersant may be further used.
  • a dispersant it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant.
  • carbon black it is preferable to use an acrylic resin-based dispersant as the dispersant.
  • the inorganic pigment and the organic pigment may be used alone or in combination.
  • the organic pigment is added in an amount of 10 to 10 parts per 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferably used in the range of 80 parts by mass, more preferably in the range of 20 to 40 parts by mass.
  • the content of the colorant is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, based on the solid content of the negative radiation-sensitive composition 1.
  • the negative radiation sensitive composition 1 may contain other organic solvents.
  • Other organic solvents can be used alone or in combination of two or more. Examples of other organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether
  • Alkyl 2-lactic acid esters ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Other esters such as
  • the content of the solvent is preferably such that the solid content concentration of the negative radiation sensitive composition 1 is 1 to 50% by mass, and more preferably 5 to 30% by mass. preferable.
  • the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0. 20:80 to 100: 0 is more preferable.
  • the negative radiation sensitive composition 1 may contain various additives as required.
  • the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.
  • the negative radiation sensitive composition 2 is a radiation sensitive polyimide precursor composition containing the compound represented by the general formula (1), a polyamic acid, and a photosensitive component.
  • the polyamic acid is not particularly limited as long as it is obtained by reacting tetracarboxylic dianhydride and diamine, and is appropriately selected from polyamic acids conventionally known as polyimide resin precursors.
  • the A polyamic acid can be used individually or in mixture of 2 or more types.
  • the polyamic acid represented by following formula (11) is mentioned, for example.
  • R 1A is a tetravalent organic group
  • R 2A is a divalent organic group
  • n is the number of repeating structural units shown in parentheses.
  • R 1A is a tetravalent organic group
  • R 2A is a divalent organic group
  • these organic groups preferably have 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms.
  • R 1A and R 2A may each be an aliphatic group, an aromatic group, or a group in which these structures are combined.
  • R 1A and R 2A may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to the carbon atom and the hydrogen atom.
  • R 1A and R 2A contain an oxygen atom, a nitrogen atom, or a sulfur atom
  • the oxygen atom, nitrogen atom, or sulfur atom represents a nitrogen-containing heterocyclic group, —CONH—, —NH—, —N ⁇ N—
  • R 1A and R 2A as a group selected from —CH ⁇ N—, —COO—, —O—, —CO—, —SO—, —SO 2 —, —S—, and —S—S—
  • a group selected from —O—, —CO—, —SO—, —SO 2 —, —S—, and —S—S— may be included in R 1A and R 2A. More preferred.
  • a polyimide resin represented by the following formula (12) is obtained by ring-closing the polyamic acid represented by the above formula (11) by heating or a catalyst. (Wherein R 1A and R 2A have the same meanings as in formula (11), and n is the number of repeating structural units shown in parentheses.)
  • the polyamic acid represented by the above formula (11) is obtained by reacting a tetracarboxylic dianhydride and a diamine in a solvent.
  • the tetracarboxylic dianhydride and diamine that are the raw materials for synthesizing the polyamic acid are not particularly limited as long as they can form a polyamic acid by the reaction of an acid anhydride group and an amino group.
  • the amount of tetracarboxylic dianhydride and diamine used in synthesizing the polyamic acid is not particularly limited, but 0.50 to 1.50 mol of diamine is used per 1 mol of tetracarboxylic dianhydride. Preferably, 0.60 to 1.30 mol is used, more preferably 0.70 to 1.20 mol.
  • the tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydrides conventionally used as a raw material for polyamic acid synthesis.
  • the tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. From the viewpoint of the heat resistance of the resulting polyimide resin, the aromatic tetracarboxylic dianhydride may be used. Carboxylic dianhydrides are preferred. Tetracarboxylic dianhydride may be used in combination of two or more.
  • aromatic tetracarboxylic dianhydride examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′.
  • -Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, and 3,3', 4,4'-diphenyl Examples include sulfonetetracarboxylic dianhydride.
  • 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the viewpoint of price and availability.
  • tetracarboxylic dianhydride and dicarboxylic anhydride may be used in combination.
  • carboxylic acid anhydrides are used in combination, the properties of the resulting polyimide resin may be further improved.
  • dicarboxylic acid anhydride examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro
  • examples thereof include phthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride and the like.
  • the diamine can be appropriately selected from diamines conventionally used as a raw material for synthesizing polyamic acid.
  • the diamine may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferred from the viewpoint of the heat resistance of the resulting polyimide resin. Two or more diamines may be used in combination.
  • aromatic diamine examples include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis ( Trifluoromethyl) biphenyl, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino Phenoxy)
  • the reaction between tetracarboxylic dianhydride and diamine is usually carried out in an organic solvent.
  • the organic solvent used for the reaction of tetracarboxylic dianhydride and diamine is not particularly limited as long as it can dissolve tetracarboxylic acid and diamine and does not react with tetracarboxylic dianhydride and diamine.
  • An organic solvent can be used individually or in mixture of 2 or more types.
  • organic solvents used in the reaction of tetracarboxylic dianhydride with diamine include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N Nitrogen-containing polar solvents such as N, N-diethylformamide, N-methylcaprolactam, and N, N, N ′, N′-tetramethylurea; ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valero Lactone polar solvents such as lactone, ⁇ -caprolactone, and ⁇ -caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve
  • N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N due to the solubility of the resulting polyamic acid and polyimide resin
  • Nitrogen-containing polar solvents such as N, N-diethylformamide, N-methylcaprolactam, and N, N, N ′, N′-tetramethylurea are preferred.
  • the photosensitive component is not particularly limited, and examples thereof include a compound (A) that decomposes by the action of light to generate at least one of a base and an acid, such as a photobase generator and a photoacid generator.
  • a photosensitive component can be used individually or in mixture of 2 or more types.
  • the compound (A) in the negative radiation sensitive composition 2 is decomposed to generate at least one of a base and an acid.
  • the base or acid thus generated acts as an imidization catalyst and promotes the ring closure of the polyamic acid in the negative radiation sensitive composition 2.
  • the compound (A) When the negative radiation sensitive composition 2 containing the compound (A) is exposed, the compound (A) is decomposed in the exposed area to generate at least one of a base and an acid.
  • the base or acid thus generated promotes the ring closure of the polyamic acid in the negative radiation sensitive composition 2, and the exposed portion becomes insoluble in the developer.
  • the unexposed portion since the unexposed portion is soluble in the developer, it can be removed by dissolving in the developer. Therefore, a desired pattern can be formed by selectively exposing the negative radiation sensitive composition 2.
  • Examples of the compound (A) include a compound (A-1) that decomposes by the action of light to generate an imidazole compound, and an oxime compound (A-2).
  • A-1 that decomposes by the action of light to generate an imidazole compound
  • A-2 an oxime compound
  • the compounds (A-1) and (A-2) will be described.
  • the imidazole compound generated from the compound (A-1) promotes ring closure of the polyamic acid in the negative radiation-sensitive composition 2 as a basic imidization catalyst.
  • the imidazole compound generated from the compound (A-1) may be an imidazole or a compound in which part or all of the hydrogen atoms bonded to the carbon atoms in the imidazole are substituted with a substituent. It is preferable that it is an imidazole compound represented by (3).
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphino group, (A phosphinyl group, a phosphonate group, or an organic group is shown.)
  • Examples of the organic group represented by R 1 , R 2 , or R 3 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a hetero atom.
  • the organic group may be linear, branched or cyclic. This organic group is usually monovalent, but may be divalent or higher when forming a cyclic structure.
  • R 1 and R 2 may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.
  • Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.
  • examples of the hetero atom include an oxygen atom, a nitrogen atom, and a silicon atom.
  • an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond, a carbonate bond, a sulfonyl bond, and a sulfinyl bond are preferable.
  • a hydrogen atom contained in a group other than an organic group represented by R 1 , R 2 , or R 3 may be substituted with a hydrocarbon group.
  • the hydrocarbon group may be linear, branched or cyclic.
  • R 1 , R 2 , and R 3 are each independently preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom.
  • a hydrogen atom is more preferable. Since imidazole in which R 1 , R 2 , and R 3 are all hydrogen atoms has a simple structure with little steric hindrance, it can easily act on a polyamic acid as an imidization catalyst.
  • the compound (A-1) is not particularly limited as long as it can be decomposed by the action of light to generate an imidazole compound, preferably an imidazole compound represented by the above formula (3).
  • the skeleton derived from amines generated during exposure is an imidazole compound, preferably an imidazole compound represented by the above formula (3)
  • the compound used as compound (A-1) is obtained by substituting the skeleton derived from
  • Suitable compound (A-1) includes a compound represented by the following formula (4).
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, phosphino group, sulfonate group
  • R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, or a sulfino group.
  • R 6 , R 7 , R 8 , R 9 , and R 10 are each independently a hydrogen atom or a halogen atom.
  • R 6 , R 7 , R 8 , R 9 , and R 10 are two or more of them May be bonded to form a cyclic structure and may contain a bond of a hetero atom.
  • R 1 , R 2 , and R 3 are the same as those described for the formula (3).
  • examples of the organic group represented by R 4 or R 5 include those exemplified for R 1 , R 2 , and R 3 .
  • This organic group may contain a hetero atom as in the case of R 1 , R 2 and R 3 .
  • the organic group may be linear, branched or cyclic.
  • R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, or an aryl having 7 to 16 carbon atoms.
  • Amino group is preferably a methylthio group. More preferably, both R 4 and R 5 are hydrogen atoms, or R 4
  • examples of the organic group represented by R 6 , R 7 , R 8 , R 9 , or R 10 include those exemplified for R 1 , R 2 , and R 3 .
  • This organic group may contain a hetero atom as in the case of R 1 and R 2 .
  • the organic group may be linear, branched or cyclic.
  • R 6 , R 7 , R 8 , R 9 , and R 10 may be bonded to form a cyclic structure, and may include a hetero atom bond.
  • the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.
  • R 6 , R 7 , R 8 , R 9 , and R 10 are two or more of them bonded to each other, and R 6 , R 7 , R 8 , R 9 , and R 10 are bonded to each other.
  • a ring atom may be shared to form a condensed ring such as naphthalene, anthracene, phenanthrene, and indene.
  • R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or a cyclohexane having 4 to 13 carbon atoms.
  • R 6 , R 7 , R 8 , R 9 , and R 10 two or more of them are bonded, and R 6 , R 7 , R 8 , R 9 , and R 10 are bonded.
  • a case where a condensed ring such as naphthalene, anthracene, phenanthrene, or indene is formed by sharing the atoms of the benzene ring is also preferable from the viewpoint of increasing the absorption wavelength.
  • a compound represented by the following formula (5) is preferable.
  • R 1 , R 2 , and R 3 have the same meanings as in formulas (3) and (4).
  • R 4 to R 9 have the same meanings as in formula (4).
  • R 11 is a hydrogen atom or Represents an organic group, and R 6 and R 7 do not become a hydroxyl group, and R 6 , R 7 , R 8 , and R 9 may combine with each other to form a cyclic structure. And may contain a heteroatom bond.
  • the compound represented by the formula (5) has a substituent —O—R 11 , it has excellent solubility in an organic solvent.
  • R 11 when R 11 is an organic group, examples of the organic group include those exemplified for R 1 , R 2 , and R 3 . This organic group may contain a hetero atom.
  • the organic group may be linear, branched or cyclic.
  • R 11 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.
  • Suitable compounds (A-1) also include compounds represented by the following formula (6).
  • R 1 , R 2 , and R 3 are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, phosphino group, sulfonate group, (A phosphinyl group, a phosphonato group, or an organic group.
  • R 12 represents an optionally substituted hydrocarbon group.
  • R 1 , R 2 , and R 3 are the same as those described for Formula (3).
  • R 12 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an optionally substituted 6 to 20 carbon atoms.
  • Examples thereof include an aryl group and an optionally substituted aralkyl group having 7 to 20 carbon atoms, and an optionally substituted aralkyl group having 7 to 20 carbon atoms is preferable.
  • the substituent include a halogen atom, a nitro group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • the compound represented by the formula (6) is a reaction between an imidazole compound represented by the formula (3) and a chloroformate represented by the following formula (7), an imidazole compound represented by the formula (3) and the following: It can synthesize
  • R 1 , R 2 , and R 3 have the same meaning as in formula (3).
  • R 12 has the same meaning as in formula (6).
  • the oxime compound (A-2) is decomposed by the action of light to generate at least one of a base and an acid. Ring closure of the polyamic acid in the negative radiation-sensitive composition 2 is promoted by the base or acid generated by the decomposition of the compound (A-2).
  • Suitable compound (A-2) includes a compound represented by the following formula (D1).
  • R d1 is an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted aryl group, or an optionally substituted carbazolyl group.
  • R d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aryl group which may have a substituent
  • R d3 is a hydrogen atom or a group represented by —CO—R d5
  • R d5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group which may have a substituent
  • p is 0 or 1.
  • R d1 in the above formula (D1) is an aryl group which may have a substituent
  • examples of the aryl group which may have a substituent include a phenyl group which may have a substituent.
  • a phenyl group which may have a substituent or a naphthyl group which may have a substituent is preferable, and a phenyl group which may have a substituent is more preferable.
  • the number of substituents bonded to the aryl group is not particularly limited.
  • the aryl group has a plurality of substituents, the plurality of substituents may be the same or different.
  • the type of substituent that the aryl group may have is not particularly limited as long as the object of the present invention is not impaired.
  • the substituent include an organic group, an amino group, a halogen atom, a nitro group, and a cyano group.
  • the type of the organic group is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups.
  • the organic group an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, It may have a phenoxy group that may have a substituent, a benzoyl group that may have a substituent, a phenoxycarbonyl group that may have a substituent, a benzoyloxy group that may have a substituent, and a substituent.
  • An optionally substituted phenylalkyl group, an optionally substituted naphthyl group, an optionally substituted naphthoxy group, an optionally substituted naphthoyl group, and an optionally substituted naphtho An oxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, 1 or 2 organic groups; Conversion amino groups, morpholin-1-yl group, and piperazine-1-yl group.
  • the carbon number of the substituent does not include the carbon number of the substituent that the substituent further has.
  • the carbon number is preferably 1-20, and more preferably 1-6. Further, when the organic group is an alkyl group, it may be linear or branched. Specific examples when the organic group is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.
  • the organic group is an alkyl group
  • the alkyl group may contain an ether bond (—O—) in the carbon chain.
  • alkyl group having an ether bond in the carbon chain examples include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
  • the carbon number is preferably 1-20, and more preferably 1-6. Further, when the organic group is an alkoxy group, it may be linear or branched. Specific examples when the organic group is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, iso
  • the alkoxy group may include an ether bond (—O—) in the carbon chain.
  • the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.
  • the organic group is a cycloalkyl group or a cycloalkoxy group
  • the carbon number thereof is preferably 3 to 10, more preferably 3 to 6.
  • Specific examples of the organic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • organic group is a cycloalkoxy group
  • organic group is a cycloalkoxy group
  • examples when the organic group is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
  • the carbon number thereof is preferably 2 to 20, and more preferably 2 to 7.
  • Specific examples when the organic group is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane group
  • Examples include a noyl group and an n-hexadecanoyl
  • organic group is a saturated aliphatic acyloxy group
  • organic group is a saturated aliphatic acyloxy group
  • examples when the organic group is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the
  • the carbon number is preferably 2 to 20, and more preferably 2 to 7.
  • Specific examples when the organic group is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl.
  • the carbon number thereof is preferably 7-20, and more preferably 7-10.
  • the organic group is a naphthylalkyl group
  • the carbon number thereof is preferably 11-20, and more preferably 11-14.
  • Specific examples in the case where the organic group is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
  • the organic group is a naphthylalkyl group
  • the organic group may further have a substituent on the phenyl group or naphthyl group.
  • the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group.
  • the heterocyclyl group is a condensed ring, the ring number is up to 3.
  • heterocyclic ring constituting the heterocyclyl group examples include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline.
  • the organic group is a heterocyclyl group
  • the heterocyclyl group may further have a substituent.
  • organic group is an amino group substituted with one or two organic groups
  • suitable examples of the organic group bonded to the nitrogen atom include alkyl groups having 1 to 20 carbon atoms and cycloalkyl groups having 3 to 10 carbon atoms.
  • a saturated aliphatic acyl group having 2 to 20 carbon atoms a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and a carbon group having 7 to 20 carbon atoms which may have a substituent.
  • a phenylalkyl group a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. It is done.
  • Specific examples of these suitable organic groups are the same as the specific examples of the organic group that the aryl group may have as a substituent when R d1 is an aryl group that may have a substituent. .
  • amino group substituted with one or two organic groups include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, and an isopropylamino group.
  • R d1 is an aryl group which may have a substituent
  • substitution in the case where the phenyl group, the naphthyl group, and the heterocyclyl group contained in the organic group bonded to the aryl group as a substituent further has a substituent
  • the group include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, and an alkyl group having 2 to 7 carbon atoms.
  • Saturated aliphatic acyloxy group monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen An atom, a nitro group, a cyano group, etc. are mentioned.
  • R d1 is an aryl group which may have a substituent
  • the phenyl group, naphthyl group and heterocyclyl group contained in the organic group bonded as a substituent to the aryl group further has a substituent
  • the number of substituents is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable.
  • R d1 is an aryl group which may have a substituent
  • the phenyl group, the naphthyl group, and the heterocyclyl group included in the organic group bonded as a substituent to the aryl group have a plurality of substituents.
  • the plurality of substituents may be the same or different.
  • R d1 is an aryl group which may have a substituent
  • the substituent that the aryl group has is that the substituent is chemically stable, has little steric hindrance, and has the formula (D1 )
  • a compound represented by the formula (D1) has high solubility in a solvent, etc., so that a nitro group, an alkyl group having 1 to 6 carbon atoms, a carbon number of 1 Is preferably a group selected from the group consisting of an alkoxy group having 6 to 6 carbon atoms and a saturated aliphatic acyl group having 2 to 7 carbon atoms, more preferably a nitro group or an alkyl group having 1 to 6 carbon atoms, a nitro group or a methyl group Is particularly preferred.
  • R d1 is an aryl group which may have a substituent
  • R d1 is preferably represented by the following formula (D1-1).
  • R d4 is a group selected from the group consisting of an organic group, an amino group, a halogen atom, a nitro group, and a cyano group, and q is an integer of 0 to 4.
  • R d4 is an organic group
  • a preferred example of the organic group is an organic group that the aryl group may have as a substituent when R d1 is an aryl group that may have a substituent. This is the same as the example.
  • R d1 is an aliphatic hydrocarbon group which may have a substituent
  • the carbon number thereof is 1 to 10. This carbon number does not include the carbon number of the substituent.
  • the aliphatic hydrocarbon group preferably has 1 to 9 carbon atoms, and more preferably 1 to 8 carbon atoms.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or a hydrocarbon group having an unsaturated bond.
  • the structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures, and is linear. Is preferred.
  • the substituent that the aliphatic hydrocarbon group has has an aryl group that may have a substituent, an aryloxy group that may have a substituent, an arylthio group that may have a substituent, and a substituent.
  • the aryl group contained in these groups includes a phenyl group, a naphthyl group, An anthryl group and a phenanthryl group are mentioned, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • R d1 is an aliphatic hydrocarbon group
  • substituents that the aliphatic hydrocarbon group may have are as follows.
  • d1 is an aryl group, it is the same as the substituent that the aryl group may have.
  • R d1 is an optionally substituted carbazolyl group
  • the type of substituent is not particularly limited as long as the object of the present invention is not impaired.
  • suitable substituents that the carbazolyl group may have on the carbon atom include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, carbon A cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, and a substituent.
  • phenyl group optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted phenylcarbonyl group, optionally substituted benzoyl group, substituted A phenoxycarbonyl group which may have a group, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a naphthyl which may have a substituent Group, substitution A naphthoxy group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent An optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclyl group, an optionally substituted hetero
  • R d1 is a carbazolyl group which may have a substituent
  • suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a carbon number of 3 A cycloalkyl group having 10 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted phenyl group, and an optionally substituted benzoyl group A phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, and a substituent.
  • It has a naphthoyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclyl group, and a substituent. Heterocycle And a rucarbonyl group. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
  • R d1 is substituted for an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with 1 or 2 organic groups.
  • an aryl group that may have a group the examples are the same as the examples of the substituent that the aryl group has.
  • Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of R d1 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; an alkyl group having 1 to 6 carbon atoms; A monoalkylamino group having 1 to 6 carbon atoms; a morpholin-1-yl group; a piperazin-1-yl
  • R d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aryl group which may have a substituent.
  • the aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or a hydrocarbon group having an unsaturated bond.
  • the structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures, and is linear. Is preferred.
  • R d2 is a linear aliphatic hydrocarbon group
  • R d2 is a linear aliphatic hydrocarbon group
  • methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Examples include a heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Of these, a methyl group is particularly preferred.
  • R d2 is an aryl group which may have a substituent
  • a substituent examples include a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent.
  • examples thereof include a good anthryl group and a phenanthrenyl group which may have a substituent.
  • a phenyl group which may have a substituent or a naphthyl group which may have a substituent is preferable, and a phenyl group which may have a substituent is more preferable.
  • R d1 is substituted for an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with 1 or 2 organic groups.
  • an aryl group that may have a group it is the same as the examples of the substituent that the aryl group may have.
  • Examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the aryl group in R d2 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; an alkyl group having 1 to 6 carbon atoms; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; a
  • the number of the substituent is not limited as long as the object of the present invention is not hindered. preferable.
  • the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.
  • R d5 is preferably a hydrogen atom, an acetyl group, a propionyl group, or a benzoyl group, and more preferably a hydrogen atom, an acetyl group, or a benzoyl group.
  • the compound represented by the formula (D1) is a fatty acid having 1 to 10 carbon atoms in which R d1 may have a substituent in the formula (D1) from the viewpoint of base generation efficiency or acid generation efficiency of this compound.
  • a compound having an aliphatic hydrocarbon group of 1 to 10 or an aryl group which may have a substituent, and R d2 being a group represented by the following formula (D1-2) is more preferable.
  • R d6 in the formula (D1-2) is an organic group
  • it can be selected from various organic groups as long as the object of the present invention is not impaired.
  • preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated aliphatic acyl having 2 to 7 carbon atoms.
  • alkoxy group having 2 to 7 carbon atoms saturated aliphatic acyloxy group having 2 to 7 carbon atoms
  • R d6 substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group
  • Benzoyl group nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.
  • the number of the substituent is not limited as long as the object of the present invention is not impaired, but is preferably 1 to 4.
  • the phenyl group, naphthyl group, and heterocyclyl group included in R d6 have a plurality of substituents, the plurality of substituents may be the same or different.
  • R d8 in the formula (12) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups.
  • Specific examples of the group suitable as R d8 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used.
  • R d8 among these groups, a phenyl group which may have a substituent and a naphthyl group which may have a substituent are more preferable, and a 2-methylphenyl group and a naphthyl group are particularly preferable.
  • the compound represented by the formula (D1) is synthesized according to the following scheme 1, for example, when p is 0, R d2 is an aryl group which may have a substituent, and R d3 is a hydrogen atom. be able to.
  • an aromatic compound represented by the following formula (1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (1-2), and the following formula:
  • a ketone compound represented by (1-3) is obtained, and the obtained ketone compound (1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (1-4).
  • Hal is a halogen atom.
  • R d1 and R d2 is the same as in formula (D1).
  • R d2 is an aryl group which may have a substituent
  • R d3 is a group represented by —CO—R d5
  • an oxime compound of the formula (1-4) obtained by the method described in Scheme 1 above
  • an oxime ester compound represented by the following formula (1-7) can be obtained by reacting with an acid halide represented by the following formula (1-6) (R d5 COHal, Hal is a halogen atom).
  • R d1 , R d2 , and R d5 are the same as those in formula (1).
  • R d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R d3 is a hydrogen atom
  • R d2 —CO—R d1 the ketone compound represented by can be oximed with hydroxylamine to obtain a compound represented by R d2 —C ( ⁇ N—OH) —R d1 .
  • R d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R d3 is a group represented by —CO—R d5.
  • the oxime compound represented by R d2 —C ( ⁇ N—OH) —R d1 is acylated according to the method described in Scheme 2 to yield R d2 —C ( ⁇ N—O—CO— It can be obtained as a compound represented by R d5 ) —R d1 .
  • the compound represented by the formula (D1) can be synthesized according to the following scheme 3, for example. Specifically, a ketone compound represented by the following formula (2-1) is added to a nitrite ester (RONO, R represents a carbon number of 1 to 6) represented by the following formula (2-2) in the presence of hydrochloric acid. The alkyl group.) Is reacted to obtain a ketoxime compound represented by the following formula (2-3), and then a ketoxime compound represented by the following formula (2-3) is obtained.
  • R d1 and R d2 are the same as those in the formula (D1).
  • the compound represented by the formula (D1) can be synthesized according to the following scheme 4 when p is 1 and R d3 is a group represented by —CO—R d5 .
  • an oxime compound of the formula (2-3) obtained by the method described in Scheme 3 above, an acid anhydride ((R d5 CO) 2 O) represented by the following formula (2-4),
  • an oxime ester compound represented by the following formula (2-6) can be obtained by reacting with an acid halide represented by the following formula (2-5) (R d5 COHal, Hal is a halogen atom).
  • R d1 , R d2 , and R d5 are the same as those in the formula (D1).
  • oxime compounds represented by the formula (D1) particularly preferred compounds include compounds represented by the following formula.
  • oxime compound (A-2) other oxime compounds other than the oxime compound represented by the above formula (D1) can also be used.
  • oxime compounds the oxime photopolymerization initiator described in the negative radiation-sensitive composition 1 can be used.
  • the content of the photosensitive component in the negative radiation sensitive composition 2 is not particularly limited as long as the object of the present invention is not impaired.
  • the content of the photosensitive component in the negative radiation sensitive composition 2 is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polyamic acid.
  • the negative radiation sensitive composition 2 may contain other organic solvents.
  • Other organic solvents can be used alone or in combination of two or more.
  • other organic solvents those exemplified in the negative radiation-sensitive composition 1 can be used.
  • the content of the solvent is preferably such that the solid concentration of the negative radiation sensitive composition 2 is 1 to 50% by mass, more preferably 5 to 40% by mass. preferable.
  • the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0. 20:80 to 100: 0 is more preferable.
  • the negative radiation sensitive composition 2 may contain various additives as necessary.
  • the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.
  • aromatic diamine diol In the present invention, a compound represented by the following formula (21) is used as the aromatic diamine diol.
  • One kind of aromatic diamine diol may be used alone, or two or more kinds may be used in combination.
  • R a1 is a tetravalent organic group containing one or more aromatic rings, and regarding the combination of two amino groups and a hydroxyl group contained in the aromatic diamine diol represented by the formula (21), respectively. In this combination, the amino group and the hydroxyl group are bonded to two adjacent carbon atoms on the aromatic ring contained in R a1 .
  • R a1 is a tetravalent organic group containing one or more aromatic rings, and preferably has 6 to 50 carbon atoms, more preferably 6 to 30 carbon atoms.
  • R a1 may be an aromatic group, and two or more aromatic groups may be an aliphatic hydrocarbon group or a halogenated aliphatic hydrocarbon group, or a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may be a group bonded through a bond including.
  • the aromatic ring contained in R a1 may be an aromatic heterocyclic ring.
  • the aromatic ring bonded to the amino group and hydroxyl group in R a1 is preferably a benzene ring.
  • the ring bonded to the amino group and hydroxyl group in R a1 is a condensed ring containing two or more rings, the ring bonded to the amino group and hydroxyl group in the condensed ring is preferably a benzene ring.
  • R a1 include groups represented by any of the following formulas (1-1) to (1-9).
  • X 1 represents an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, —O—, —S—, —SO—, —SO 2 —, One selected from the group consisting of —CO—, —COO—, —CONH—, and a single bond, wherein Y 1 s in the formulas (1-2) to (1-5) are the same or different; And may be one selected from the group consisting of —CH 2 —, —O—, —S—, —SO—, —SO 2 —, —CO—, and a single bond.
  • the group represented by any one of the above formulas (1-1) to (1-9) may have one or more substituents on the aromatic ring.
  • substituents include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkoxy having 1 to 6 carbon atoms. Groups are preferred.
  • the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
  • the compound represented by the above formula (21) include 2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, 2,5-diamino-3- Fluoro-1,4-benzenediol, 2,5-diamino-3,6-difluoro-1,4-benzenediol, 2,6-diamino-1,5-dihydroxynaphthalene, 1,5-diamino-2,6 -Dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5-dihydroxynaphthalene, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'- Diamino-4,4′-dihydroxybiphenyl, 2,3′-diamino-3,2′-dihydroxybiphenyl, 3,4′-d
  • 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferable because a polybenzoxazole resin having excellent transparency can be formed.
  • R a2 in formula (22) may be an aromatic group, an aliphatic group, or a group in which an aromatic group and an aliphatic group are combined.
  • R a2 is preferably a group containing an aromatic group and / or an alicyclic group from the viewpoint that the resulting polybenzoxazole resin has good heat resistance, mechanical properties, chemical resistance, and the like.
  • the aromatic group contained in R a2 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • one of the two A may be a hydrogen atom and the other may be a halogen atom, but both A are hydrogen atoms or both A are halogen atoms. preferable.
  • A is a halogen atom, as A, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a chlorine atom is more preferable.
  • the dialdehyde compound used as a raw material of the polybenzoxazole precursor is a compound represented by the following formula (2-1).
  • a dialdehyde compound may be used individually by 1 type, and may be used in combination of 2 or more type. (In the formula, R a2 is the same as in formula (22).)
  • Examples of the aromatic group or aromatic ring-containing group suitable as R a2 in formula (2-1) include the following groups.
  • X 2 represents an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, —O—, —S—, —SO—, —SO 2 —, —CO—, -COO -, - CONH-, and if .X 2 is one selected from the group consisting of a single bond is more, a plurality of X 2 are optionally be the same or different .Y 2, respectively, They may be the same or different, and are one selected from the group consisting of —CH 2 —, —O—, —S—, —SO—, —SO 2 —, —CO—, and a single bond.
  • q are each an integer of 0 to 3.
  • the aromatic ring or alicyclic ring contained in a group suitable as R a2 may have one or more substituents on the ring.
  • substituents include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkoxy having 1 to 6 carbon atoms. Groups are preferred.
  • the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
  • naphthalenedialdehydes include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene-3,7-dialdehyde, 2,3, 4,6,7,8-hexafluoronaphthalene-1,5-dialdehyde, 2,3,4,5,6,8-hexafluoronaphthalene-1,6-dialdehyde, 1,3,4,5 7,8-hexafluoronaphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-2,6-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene-2,6-dialdehyde, 1- Trifluoromethylnaphthalene-3,7-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene-3,7-dialdehyde, 1-
  • diphenyl ether dialdehydes include diphenyl ether-2,4′-dialdehyde, diphenyl ether-3,3′-dialdehyde, diphenyl ether-3,4′-dialdehyde, and diphenyl ether-4,4′-dialdehyde.
  • [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehydes include 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, 3,4′- [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, and the like.
  • 2,2-bis [4- (formylphenoxy) phenyl] propanes include 2,2-bis [4- (2-formylphenoxy) phenyl] propane, 2,2-bis [4- (3 -Formylphenoxy) phenyl] propane, 2,2-bis [4- (4-formylphenoxy) phenyl] propane, 2,2-bis [4- (3-formylphenoxy) phenyl] hexafluoropropane, and 2,2 -Bis [4- (4-formylphenoxy) phenyl] hexafluoropropane and the like.
  • bis [4- (formylphenoxy) phenyl] sulfides include bis [4- (3-formylphenoxy) phenyl] sulfide and bis [4- (4-formylphenoxy) phenyl] sulfide. .
  • bis [4- (formylphenoxy) phenyl] sulfone include bis [4- (3-formylphenoxy) phenyl] sulfone and bis [4- (4-formylphenoxy) phenyl] sulfone. .
  • diphenylalkanedialdehyde or diphenylfluoroalkanedialdehyde represented by the following formula can also be suitably used as the aromatic dialdehyde compound.
  • a compound having an imide bond represented by the following formula can also be suitably used as the aromatic dialdehyde compound.
  • dicarbonyl compound represented by the formula (2-1) is an alicyclic dialdehyde containing an alicyclic group
  • preferred examples thereof include cyclohexane-1,4-dialdehyde, cyclohexane-1,3.
  • isophthalaldehyde is preferred because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole resin having excellent heat resistance and mechanical properties.
  • Dicarboxylic acid dihalide used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (2-2).
  • Dicarboxylic acid dihalide may be used individually by 1 type, and may be used in combination of 2 or more type. (In the formula, R a2 is the same as in formula (22), and Hal is a halogen atom.)
  • a chlorine atom, a bromine atom and an iodine atom are preferable, and a chlorine atom is more preferable.
  • a compound suitable as the compound represented by the formula (2-2) a compound obtained by substituting two aldehyde groups of the aforementioned compound as a suitable example of a dialdehyde compound with a halocarbonyl group, preferably a chlorocarbonyl group. Is mentioned.
  • the polybenzoxazole precursor is produced by reacting the above-mentioned aromatic diamine diol with a dicarbonyl compound in a solvent according to a known method.
  • a production method in the case where the dicarbonyl compound is a dialdehyde compound and a production method in the case where the dicarbonyl compound is a dicarboxylic acid halide will be described.
  • the reaction of aromatic diamine diol and dialdehyde compound is carried out in a solvent.
  • the reaction between the aromatic diamine diol and the dialdehyde compound is a Schiff base formation reaction and can be performed according to a known method.
  • the reaction temperature is not particularly limited, but is usually preferably 20 to 200 ° C, more preferably 20 to 160 ° C, and particularly preferably 100 to 160 ° C.
  • the reaction between the aromatic diamine diol and the dialdehyde compound may be performed while adding an entrainer to the solvent and performing reflux dehydration.
  • the entrainer is not particularly limited, and is appropriately selected from organic solvents that form an azeotrope with water and form a two-phase system with water at room temperature. Suitable examples of entrainers include esters such as isobutyl acetate, allyl acetate, propionate-n-propyl, isopropyl propionate, n-butyl propionate, and isobutyl propionate; dichloromethyl ether, ethyl isoamyl ether, etc. Ethers; ketones such as ethyl propyl ketone; and aromatic hydrocarbons such as toluene.
  • reaction time between the aromatic diamine diol and the dialdehyde compound is not particularly limited, but it is typically preferably about 2 to 72 hours.
  • the amount of the dialdehyde compound used in the production of the polybenzoxazole precursor is preferably 0.5 to 1.5 mol, preferably 0.7 to 1.3 mol per mol of aromatic diamine diol. More preferably, it is a mole.
  • the amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dialdehyde compound proceeds favorably.
  • a solvent having a mass of 1 to 40 times, preferably 1.5 to 20 times the mass of the total mass of the aromatic diamine diol and the dialdehyde compound is used.
  • the reaction between the aromatic diamine diol and the dialdehyde compound is preferably carried out until the polybenzoxazole precursor to be produced has a number average molecular weight of 1000 to 20000, preferably 1200 to 5000.
  • the reaction of aromatic diamine diol and dicarboxylic acid dihalide is carried out in a solvent.
  • the reaction temperature is not particularly limited, but is usually preferably ⁇ 20 to 150 ° C., more preferably ⁇ 10 to 150 ° C., and particularly preferably ⁇ 5 to 70 ° C.
  • hydrogen halide is by-produced.
  • the amount of dicarboxylic acid dihalide used in the production of the polybenzoxazole precursor is preferably 0.5 to 1.5 mol, preferably 0.7 to 1.3 mol per mol of aromatic diamine diol. More preferably, it is a mole.
  • the amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide proceeds favorably.
  • the solvent is used in an amount of 1 to 40 times, preferably 1.5 to 20 times the weight of the sum of the weight of the aromatic diamine diol and the weight of the dicarboxylic acid dihalide.
  • the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide is preferably carried out until the number average molecular weight of the polybenzoxazole precursor to be produced is 1000 to 20000, preferably 1200 to 5000.
  • a polybenzoxazole precursor solution can be obtained.
  • the polybenzoxazole precursor solution can be used as it is.
  • Precursor pastes or solids can also be used.
  • an appropriate amount of a solvent or the like is added to the polybenzoxazole precursor solution obtained by the above reaction, and the solid concentration of the polybenzoxazole precursor solution is adjusted to that of the negative radiation-sensitive composition 3. It can also be used for preparation.
  • Examples of the organic solvent used in the reaction of the aromatic diamine diol with the dicarbonyl compound include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N Nitrogen-containing polar solvents such as N, N-diethylformamide, N, N, 2-trimethylpropionamide, N-methylcaprolactam, and N, N, N ′, N′-tetramethylurea; ⁇ -propiolactone, ⁇ - Lactone polar solvents such as butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, and ⁇ -caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether The Hexane, tetrahydr
  • N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N are used because of the solubility of the polybenzoxazole precursor and polybenzoxazole resin to be produced.
  • Nitrogen-containing polar solvents such as dimethylformamide, N, N-diethylformamide, N, N, 2-trimethylpropionamide, N-methylcaprolactam, and N, N, N ′, N′-tetramethylurea are preferred.
  • the photosensitive component is not particularly limited, and as in the case of the negative radiation-sensitive composition 2, for example, a photobase generator, a photoacid generator, or the like, which decomposes by the action of light to form a base and an acid.
  • the compound (A) which generates at least one is mentioned.
  • a photosensitive component can be used individually or in mixture of 2 or more types.
  • the compound (A) in the negative radiation sensitive composition 3 is decomposed to generate at least one of a base and an acid.
  • the base or acid thus generated acts on the polybenzoxazole precursor in the negative radiation-sensitive composition 3 and promotes conversion to a polybenzoxazole resin.
  • the compound (A) When the negative radiation sensitive composition 3 containing the compound (A) is exposed, the compound (A) is decomposed in the exposed area to generate at least one of a base and an acid. Conversion from the polybenzoxazole precursor to the polybenzoxazole resin in the negative radiation-sensitive composition 3 is promoted by the base or acid thus generated, and the exposed portion becomes insoluble in the developer. On the other hand, since the unexposed portion is soluble in the developer, it can be removed by dissolving in the developer. Therefore, a desired pattern can be formed by selectively exposing the negative radiation sensitive composition 3.
  • the content of the photosensitive component in the negative radiation sensitive composition 3 is not particularly limited as long as the object of the present invention is not impaired.
  • the content of the photosensitive component in the negative radiation-sensitive composition 3 is preferably 1 to 50 parts by mass and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor.
  • the negative radiation sensitive composition 3 may contain other organic solvents.
  • Other organic solvents can be used alone or in combination of two or more.
  • other organic solvents those exemplified in the negative radiation-sensitive composition 1 can be used.
  • the content of the solvent is preferably such that the solid content concentration of the negative radiation sensitive composition 3 is 1 to 50% by mass, and more preferably 5 to 40% by mass. preferable.
  • the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0. 20:80 to 100: 0 is more preferable.
  • the positive radiation sensitive composition 1 contains a compound represented by the general formula (1), an alkali-soluble resin, and a quinonediazide group-containing compound.
  • alkali-soluble resin As alkali-soluble resin, what was illustrated in the negative radiation sensitive composition 1 can be used.
  • the content of the alkali-soluble resin is preferably 5 to 90% by mass and more preferably 10 to 85% by mass with respect to the solid content of the positive radiation sensitive composition 1.
  • Examples of the compound having one or more phenolic hydroxyl groups include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone; Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, Bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5- Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, Bis (4-hydroxy-2,5-dimethylpheny
  • the content of the quinonediazide group-containing compound is preferably 10 to 95% by mass and more preferably 15 to 90% by mass with respect to the solid content of the positive radiation-sensitive composition 1. By setting it as said range, the sensitivity of the positive radiation sensitive composition 1 can be made favorable.
  • the positive radiation sensitive composition 1 may contain other organic solvents.
  • Other organic solvents can be used alone or in combination of two or more.
  • other organic solvents those exemplified in the negative radiation-sensitive composition 1 can be used.
  • the positive radiation sensitive composition 1 may contain other polymers.
  • Other polymers can be used alone or in combination of two or more.
  • examples of other polymers include the polyamic acid described in the negative radiation-sensitive composition 2, the polybenzoxazole precursor described in the negative radiation-sensitive composition 3, and the structure represented by the following general formula (31). The polymer which has as a main component is mentioned.
  • R 1 and R 2 may be the same or different and each represents a divalent to octavalent organic group having 2 or more carbon atoms.
  • R 3 and R 4 may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms.
  • l and m are integers of 0 to 2
  • p and q are integers of 0 to 4. However, p + q> 0.
  • R 1 represents a divalent to octavalent organic group having 2 or more carbon atoms, and represents an acid structural component.
  • acids in which R 1 is divalent include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid.
  • Etc examples of the acid in which R 1 is trivalent include tricarboxylic acids such as trimellitic acid and trimesic acid.
  • acids in which R 1 is tetravalent include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and other aromatic tetracarboxylic acids, butanetetracarboxylic acid, and cyclopentane.
  • acids in which R 1 is tetravalent include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and other aromatic tetracarboxylic acids, butanetetracarboxylic acid, and cyclopentane.
  • acids in which R 1 is tetravalent include pyromellitic acid, benzophenonetetracarboxylic acid
  • the acid which has hydroxyl groups such as a hydroxyphthalic acid and a hydroxy trimellitic acid, can also be mentioned. Two or more of these acid components may be used, but preferably contains 1 to 40 mol% of a tetracarboxylic acid residue. Moreover, it is preferable that the residue of the acid which has a hydroxyl group is contained 50 mol% or more from the point of the solubility with respect to an alkali developing solution, or a photosensitive point.
  • R 1 preferably has an aromatic ring from the viewpoint of heat resistance, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.
  • R 3 and R 4 in the general formula (31) each independently represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of solubility in an alkali developer and solution stability of the positive radiation sensitive composition 1, it is preferable that 10 mol% to 90 mol% of R 3 and R 4 are each hydrogen. Further, it is more preferable that R 3 and R 4 each contain at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.
  • l and m represent the number of carboxyl groups or ester groups, and each independently represents an integer of 0 to 2. Preferably it is 1 or 2.
  • p and q each independently represent an integer of 0 to 4, and p + q> 0.
  • the number of structural units represented by the general formula (31) is preferably in the range of 10 to 100,000, Is more preferably in the range of 000, and still more preferably in the range of 20 to 100.
  • the number of structural units represented by the general formula (31) can be easily calculated by measuring the mass average molecular weight by gel permeation chromatography (GPC), light scattering method, X-ray small angle scattering method or the like.
  • GPC gel permeation chromatography
  • the number of structural units represented by the general formula (31) Mm / M.
  • the number of structural units represented by the general formula (31) refers to a value calculated using the simplest GPC measurement in terms of polystyrene.
  • an aliphatic group having a siloxane structure may be copolymerized within a range in which the heat resistance is not lowered in order to improve adhesion to the substrate.
  • the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.
  • the content of the other polymer in the positive radiation sensitive composition 1 is not particularly limited as long as the object of the present invention is not impaired.
  • the content of the other polymer in the positive radiation sensitive composition 1 is preferably 1 to 300 parts by mass, more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  • the positive radiation sensitive composition 1 may contain various additives as necessary.
  • the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.
  • the radiation-sensitive composition according to the present invention is prepared by mixing the above components with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared radiation sensitive composition may become uniform.
  • a contact transfer type coating device such as a roll coater, a reverse coater or a bar coater
  • a non-contact type such as a spinner (rotary coating device) or a curtain flow coater
  • the radiation-sensitive composition according to the present invention is applied using a coating apparatus, and if necessary, the solvent is removed by drying to form a radiation-sensitive composition film.
  • a radiation-sensitive composition film made of the radiation-sensitive composition provided on the support film is attached to the substrate, thereby sensing the substrate on the substrate.
  • a radiation composition film can also be formed.
  • the dry film can be formed by applying the radiation-sensitive composition on a support film and drying it by a conventional method.
  • the radiation-sensitive composition film after exposure is developed with a developer to form a predetermined pattern.
  • the development method is not particularly limited, and an immersion method, a spray method, or the like can be used.
  • Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
  • Alkali-soluble resin Cardo resin 1 solid content 55% by mass (solvent: 3-methoxybutyl acetate, mass average molecular weight: 4,000)
  • Photopolymerizable monomer Photopolymerizable monomer 1: Dipentaerythritol hexaacrylate (DPHA)
  • Photopolymerization initiator 1 “NCI-831” (trade name, manufactured by ADEKA)
  • Photopolymerization initiator 3 “IRGACURE OXE01” (trade name, manufactured by BASF)
  • Colorant 1 Carbon dispersion “CF Black” (trade name, manufactured by Mikun
  • Colorant 4 From G36 (CI Pigment Green 36) / Y150 (CI Pigment Yellow 150) (mixing mass ratio: 70/30), in the same manner as Colorant 3, the average particle diameter of the pigment is Pigment dispersion prepared to be 90 to 190 nm (solid content: 18% by mass, solvent: propylene glycol monomethyl ether acetate) From the coloring agent 5: B156 (CI Pigment Blue 156) / V23 (CI Pigment Violet 23) (mixing mass ratio: 90/10), the average particle diameter of the pigment was determined in the same manner as the coloring agent 3.
  • the cardo resin 1 is synthesized according to the following formulation. First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid The solution was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was.
  • the negative radiation-sensitive composition was aged at 40 ° C. for 2 weeks, spin-coated on a 10 cm square glass substrate, the number of aggregated foreign matters was counted, and evaluation was performed according to the following criteria. The results are shown in Tables 4-8. ⁇ : 0 to 2, ⁇ : 3 to 10, x: 11 or more
  • BM represents Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-4
  • R represents Examples 3-1 to 3-7 and Comparative Example 3.
  • G represents Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-4
  • B represents Examples 5-1 to 5-7 and Comparative Example 5 -1 to 5-4
  • BPS represents Examples 6-1 to 6-7 and Comparative Examples 6-1 to 6-4.
  • the negative-type radiation-sensitive compositions of Examples containing the compound represented by the above general formula (1) are excellent in sensitivity, storage stability, and coatability, and are exposed to light. In addition, a pattern in which the generation of foreign matter was suppressed could be formed by development.
  • the negative radiation sensitive composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and more foreign matters in the pattern formed by exposure and development. Depending on the solvent used, the coating property was further inferior.
  • the negative type radiation sensitive composition of the comparative example containing a light-shielding agent as a colorant was inferior in sensitivity.
  • composition shown in Table 1 is 2 g of an esterification reaction product of 1 mol of 2,4,4,4′-tetrahydroxybenzophenone and 3 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride and 8 g of cresol novolac resin.
  • a positive radiation sensitive composition was prepared by dissolving in 40 g of the above solvent. The following evaluation tests were performed on the positive radiation sensitive composition thus obtained.
  • the prepared positive radiation sensitive composition is slit coated on a glass substrate and dried on a hot plate at 90 ° C. for 90 seconds to form a resist film having a film thickness of 1.3 ⁇ m. After being exposed through the mask, it was heated on a hot plate at 110 ° C. for 90 seconds, then developed with 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH), washed with water and dried for 30 seconds. The cross-sectional shape of the resist pattern was observed and evaluated according to the following criteria. The results are shown in Table 9.
  • ⁇ Preparation of polyamic acid-containing negative radiation sensitive resin composition In a 5 L separable flask equipped with a stirrer, a stirring blade, a reflux condenser, and a nitrogen gas inlet tube, 654.4 g of tetramellitic dianhydride, pyromellitic dianhydride (PMDA), and diamine 672.8 g of 4,4′-diaminodiphenyl ether (ODA) and a solvent having the composition shown in Table 10 were added. Nitrogen was introduced into the flask through a nitrogen gas introduction tube, and the atmosphere in the flask was changed to a nitrogen atmosphere.
  • PMDA pyromellitic dianhydride
  • ODA 4,4′-diaminodiphenyl ether
  • the negative radiation-sensitive resin compositions of Examples containing the compound represented by the above general formula (1) are excellent in storage stability and applicability, and are exposed and developed. A pattern in which the generation of foreign matter was suppressed could be formed.
  • the negative radiation sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and applicability, and is a pattern formed by exposure and development. More foreign material was generated.
  • ⁇ Preparation of a polybenzoxazole precursor-containing negative radiation sensitive resin composition After adding 2 mmol of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which is an aromatic diamine diol, and 1 mL of a solvent having the composition shown in Table 11 to an Erlenmeyer flask containing a rotor. The contents of the flask were stirred for 5 minutes using a magnetic stirrer. Thereafter, 2 mmol of isophthalaldehyde as a dicarbonyl compound was put in the flask, and the reaction was carried out by refluxing the contents of the flask for 3 hours under a nitrogen atmosphere.
  • the reaction solution was dehydrated by distillation under reduced pressure to obtain a polybenzoxazole precursor solution.
  • a polybenzoxazole precursor solution 0.5 mmol of “IRGACURE OXE02” (trade name, manufactured by BASF, oxime ester compound) as a photosensitive component is added and stirred, and a negative type having a solid content concentration of 30% by mass.
  • a radiation sensitive resin composition was prepared.
  • the obtained negative radiation-sensitive resin composition was evaluated for foreign matter, viscosity change, and coating unevenness in the same manner as in “Preparation of transparent resist”. The results are shown in Table 11.
  • the negative radiation-sensitive resin compositions of the examples containing the compound represented by the general formula (1) are excellent in storage stability and applicability, and are exposed and developed. A pattern in which the generation of foreign matter was suppressed could be formed.
  • the negative radiation sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and applicability, and is a pattern formed by exposure and development. More foreign material was generated.
  • the temperature of the oil bath was raised over 3 hours, and then the inside of the flask was decompressed to remove volatile components, and the dissolved resin was cooled to room temperature to obtain a polymer solid of Novolak Resin A.
  • the novolak resin A had a mass average molecular weight of 4,000.
  • D is H or 1,2-naphthoquinonediazide-5-sulfonyl group
  • the average esterification rate of D by 1,2-naphthoquinonediazide-5-sulfonyl group is 59.9%. Since the number of substitutions and substitution positions of D vary depending on the molecule, the average ratio (average esterification rate (%)) in which D is a 1,2-naphthoquinonediazide-5-sulfonyl group is shown as described above. same as below. ]
  • the positive-type radiation-sensitive resin compositions of Examples containing the compound represented by the general formula (1) are excellent in storage stability and applicability, and are exposed and developed. A pattern in which the generation of foreign matter was suppressed could be formed.
  • the positive type radiation sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and coatability, and is a pattern formed by exposure and development. More foreign material was generated.
  • ⁇ Preparation 2 of a polyamic acid-containing positive radiation-sensitive resin composition > 6 g of polymer A solid, 4 g of novolak resin A, 2 g of quinonediazide compound B represented by the following formula, 6.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-PC (trade name, Asahi Organic Materials Co., Ltd.) 1 g and 0.3 g of vinyltrimethoxysilane were measured and dissolved in a solvent having the composition shown in Table 13 to obtain a positive radiation sensitive resin composition having a solid content concentration of 30% by mass. .
  • the polymer A and the novolak resin A are those obtained in “Preparation 1 of a polyamic acid-containing positive radiation-sensitive resin composition”.
  • the resulting positive radiation sensitive resin composition was evaluated for foreign matter, viscosity change, and coating unevenness in the same manner as in “Preparation of transparent resist”. The results are shown in Table 13.
  • D is H or 1,2-naphthoquinonediazide-5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazide-5-sulfonyl group is 54.7%.
  • the positive-type radiation-sensitive resin compositions of Examples containing the compound represented by the general formula (1) are excellent in storage stability and applicability, and are exposed and developed. A pattern in which the generation of foreign matter was suppressed could be formed.
  • the positive type radiation sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and coatability, and is a pattern formed by exposure and development. More foreign material was generated.

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Abstract

Provided are: a radiation sensitive composition which has excellent sensitivity, storage stability, coatability, developability and safety and is capable of forming a pattern that is suppressed in the occurrence of foreign materials by exposure and development; and a pattern forming method which uses this radiation sensitive composition. A radiation sensitive composition according to the present invention contains a compound represented by general formula (1). In the formula, R1 represents a hydrogen atom or a hydroxyl group; each of R2 and R3 independently represents a hydrogen atom or a C1-C3 alkyl group; and each of R4 and R5 independently represents a C1-C3 alkyl group.

Description

感放射線性組成物及びパターン製造方法Radiation-sensitive composition and pattern manufacturing method
　本発明は、感放射線性組成物及びそれを用いたパターン製造方法に関する。 The present invention relates to a radiation-sensitive composition and a pattern manufacturing method using the same.
　集積回路、カラーフィルタ、液晶素子等の製造においては微細加工が要求されるが、この要求を満たすため、従来より感放射線性組成物が利用されている。一般的に感放射線性組成物にはポジ型とネガ型とがあり、通常、いずれのものも溶剤に溶解されて溶液状態で用いられる。 In the manufacture of integrated circuits, color filters, liquid crystal elements and the like, fine processing is required, and in order to satisfy this requirement, radiation-sensitive compositions have been conventionally used. Generally, there are positive and negative radiation-sensitive compositions. Usually, any of them is dissolved in a solvent and used in a solution state.
　感放射線性組成物は、シリコン基板、ガラス基板等の基板上にスピンコート、ローラーコート、スリットコート、インクジェット等の公知の塗布法により塗布された後、プリベークされて感放射線性組成物膜が形成され、その後、感放射線性組成物の感光波長域に応じて、紫外線、遠紫外線、Ｘ線、電子線等の粒子線等により露光され、現像された後、必要に応じドライエッチングが施されて、所望のパターンが形成される。 The radiation-sensitive composition is applied to a silicon substrate, glass substrate, or other substrate by a known coating method such as spin coating, roller coating, slit coating, or inkjet, and then pre-baked to form a radiation-sensitive composition film. Then, depending on the photosensitive wavelength range of the radiation-sensitive composition, it is exposed with particle beams such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams, developed, and then subjected to dry etching as necessary. A desired pattern is formed.
　感放射線性組成物に用いられる溶媒としては、従来から種々のものが用いられており、溶解性、塗布性、感度、現像性、形成されるパターン特性等を考慮して選択、使用されている。例えば、溶解性、塗布性、感放射線性組成物膜形成特性等の諸特性に優れた溶剤としてエチレングリコールモノエチルエーテルアセテートが知られているが、近年、人体に対する安全性の問題が指摘されており、安全性が高くしかも樹脂溶解性、開始剤溶解性に優れ、感放射線性組成物膜形成特性等の性能の改善された溶媒が求められてきている。 Various solvents have been conventionally used as a radiation-sensitive composition, and are selected and used in consideration of solubility, coatability, sensitivity, developability, pattern characteristics to be formed, and the like. . For example, ethylene glycol monoethyl ether acetate is known as a solvent excellent in various properties such as solubility, coatability, and radiation-sensitive composition film-forming properties. However, in recent years, safety problems for the human body have been pointed out. Thus, there is a need for a solvent that has high safety, is excellent in resin solubility and initiator solubility, and has improved performance such as radiation-sensitive composition film-forming properties.
　これらの解決策として、エチレングリコールモノエチルエーテルアセテートに替わる溶媒としてプロピレングリコールモノメチルエーテルアセテート等が提案されている（例えば特許文献１）。 As these solutions, propylene glycol monomethyl ether acetate or the like has been proposed as a solvent in place of ethylene glycol monoethyl ether acetate (for example, Patent Document 1).
特公平３－１６５９号公報Japanese Patent Publication No.3-1659
　しかし、エチレングリコールモノエチルエーテルアセテートに比べて安全性が高いとされているこれらの溶剤を用いた従来の感放射線性組成物には、感度、保存安定性、塗布性、もしくは現像性が十分ではなく、又は、このような感放射線性組成物を露光及び現像して得られるパターンには異物が発生しやすいという問題がある。 However, conventional radiation-sensitive compositions using these solvents, which are considered to be safer than ethylene glycol monoethyl ether acetate, do not have sufficient sensitivity, storage stability, coatability, or developability. Or a pattern obtained by exposing and developing such a radiation-sensitive composition has a problem that foreign matters are likely to be generated.
　本発明は、以上のような状況に鑑みてなされたものであり、感度、保存安定性、塗布性、現像性、及び安全性に優れ、露光及び現像により、異物の発生が抑制されたパターンを形成することができる感放射線性組成物及びそれを用いたパターン製造方法を提供することを目的とする。 The present invention has been made in view of the above situation, and is excellent in sensitivity, storage stability, applicability, developability, and safety, and has a pattern in which the generation of foreign matters is suppressed by exposure and development. It aims at providing the radiation sensitive composition which can be formed, and the pattern manufacturing method using the same.
　本発明者らは、上記課題を解決するため鋭意研究を重ねた結果、特定の有機溶剤を用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。具体的には、本発明は以下のものを提供する。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific organic solvent, and have completed the present invention. Specifically, the present invention provides the following.
　本発明の第一の態様は、下記一般式（１）で表される化合物を含有する感放射線性組成物である。 The first aspect of the present invention is a radiation-sensitive composition containing a compound represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ１は、水素原子又はヒドロキシル基を表し、Ｒ２及びＲ３は、独立に水素原子又はＣ１～Ｃ３のアルキル基を表し、Ｒ４及びＲ５は、独立にＣ１～Ｃ３のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000003
 (Wherein R 1 represents a hydrogen atom or a hydroxyl group, R 2 and R 3 independently represent a hydrogen atom or a C 1 -C 3 alkyl group, and R 4 and R 5 independently represent C 1 represents an alkyl group ~ C 3.)
　本発明の第二の態様は、上記感放射線性組成物からなる感放射線性組成物膜を基板上に形成する感放射線性組成物膜形成工程と、上記感放射線性組成物膜を位置選択的に露光する露光工程と、露光された上記感放射線性組成物膜を現像する現像工程とを含むパターン製造方法である。 In a second aspect of the present invention, a radiation-sensitive composition film forming step of forming a radiation-sensitive composition film comprising the radiation-sensitive composition on a substrate, and the radiation-sensitive composition film are position-selective. It is a pattern manufacturing method including the exposure process exposed to 1 and the image development process which develops the exposed said radiation sensitive composition film | membrane.
　本発明によれば、感度、保存安定性、塗布性、現像性、及び安全性に優れ、露光及び現像により、異物の発生が抑制されたパターンを形成することができる感放射線性組成物及びそれを用いたパターン製造方法を提供することができる。 According to the present invention, a radiation-sensitive composition excellent in sensitivity, storage stability, coatability, developability, and safety, and capable of forming a pattern in which the generation of foreign matter is suppressed by exposure and development, and the same A pattern manufacturing method using can be provided.
≪感放射線性組成物≫
　本発明に係る感放射線性組成物は、上記一般式（１）で表される化合物を少なくとも含有する。上記一般式（１）で表される化合物は、本発明に係る感放射線性組成物において、溶剤として用いられる。本発明に係る感放射線性組成物は、溶剤として、上記一般式（１）で表される化合物のみを含有してもよいし、上記一般式（１）で表される化合物以外の有機溶剤（以下、「その他の有機溶剤」ともいう。）を更に含有してもよい。即ち、本発明に係る感放射線性組成物は、上記一般式（１）で表される化合物を溶剤の少なくとも１種として含有する。上記一般式（１）で表される化合物は、本発明に係る感放射線性組成物において、単独で又はその他の有機溶剤との混合溶剤の形態で、溶剤以外の成分（以下、「基材成分」という。）を溶解及び／又は分散する溶剤として用いられる。本発明に係る感放射線性組成物は、上記一般式（１）で表される化合物を含有するため、感度、保存安定性、塗布性、現像性、及び安全性に優れ、露光及び現像により、異物の発生が抑制されたパターンを形成することができる。本発明に係る感放射線性組成物は、例えば、ブラックマトリクス、カラーフィルタ、ブラックフォトスペーサ、集積回路、液晶素子等の製造に好適に用いることができる。 ≪Radiosensitive composition≫
The radiation-sensitive composition according to the present invention contains at least the compound represented by the general formula (1). The compound represented by the general formula (1) is used as a solvent in the radiation-sensitive composition according to the present invention. The radiation-sensitive composition according to the present invention may contain only the compound represented by the general formula (1) as a solvent, or an organic solvent other than the compound represented by the general formula (1) ( Hereinafter, it may also contain “other organic solvent”. That is, the radiation-sensitive composition according to the present invention contains the compound represented by the general formula (1) as at least one kind of solvent. In the radiation-sensitive composition according to the present invention, the compound represented by the general formula (1) is a component other than the solvent (hereinafter referred to as “base component”) alone or in the form of a mixed solvent with another organic solvent. Is used as a solvent for dissolving and / or dispersing. Since the radiation-sensitive composition according to the present invention contains the compound represented by the general formula (1), it is excellent in sensitivity, storage stability, coatability, developability, and safety. A pattern in which the generation of foreign matter is suppressed can be formed. The radiation-sensitive composition according to the present invention can be suitably used for producing, for example, a black matrix, a color filter, a black photo spacer, an integrated circuit, a liquid crystal element, and the like.
［一般式（１）で表される化合物］
　上記一般式（１）で表される化合物は、感放射線性組成物に含まれる基材成分を良好に溶解及び／又は分散することができる溶剤であり、広く感放射線性組成物一般において用いることができる。中でも、感放射線性組成物がオキシム系光重合開始剤を含む場合、上記一般式（１）で表される化合物は、オキシム系光重合開始剤の溶解性が良好である。上記一般式（１）で表される化合物は、単独で又は２種以上組み合わせて用いることができる。 [Compound represented by general formula (1)]
The compound represented by the general formula (1) is a solvent that can dissolve and / or disperse the base material component contained in the radiation-sensitive composition satisfactorily and is widely used in radiation-sensitive compositions in general. Can do. Among these, when the radiation-sensitive composition contains an oxime photopolymerization initiator, the compound represented by the general formula (1) has good solubility of the oxime photopolymerization initiator. The compounds represented by the general formula (1) can be used alone or in combination of two or more.
　上記一般式（１）において、Ｒ２又はＲ３により表されるＣ１～Ｃ３のアルキル基、及びＲ４又はＲ５により表されるＣ１～Ｃ３のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基が挙げられる。
　Ｒ２、Ｒ３、Ｒ４、及びＲ５は、独立にメチル基又はエチル基であることが好ましい。 In the general formula (1), the alkyl group of C 1 ~ C 3 represented an alkyl group of C 1 ~ C 3 represented by R 2 or R 3, and the R 4 or R 5, a methyl group, Examples include an ethyl group, a propyl group, and an isopropyl group.
R 2 , R 3 , R 4 , and R 5 are preferably independently a methyl group or an ethyl group.
　上記一般式（１）で表される化合物の具体例としては、下記の各式で表される化合物が挙げられる。 Specific examples of the compound represented by the general formula (1) include compounds represented by the following formulas.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　上記一般式（１）で表される化合物のうち、好ましい具体例としては、実施例で用いられる化合物１～４が挙げられ、化合物１、即ち、下記式（Ｅ１）で表される化合物が特に好ましい。下記式（Ｅ１）で表される化合物は、高懸念物質（ＳＶＨＣ）に指定されておらず、毒性の低い化合物であるため、安全性が特に高い。 Among the compounds represented by the general formula (1), preferred specific examples include the compounds 1 to 4 used in the examples. The compound 1, that is, the compound represented by the following formula (E1) is particularly preferred. preferable. The compound represented by the following formula (E1) is not designated as a substance of very high concern (SVHC) and is a compound having low toxicity, and thus has a particularly high safety.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　本発明に係る感放射線性組成物において、溶剤の含有量は、上記感放射線性組成物の固形分濃度が１～５０質量％となる量が好ましく、５～３０質量％となる量がより好ましい。また、本発明に係る感放射線性組成物に含まれる溶剤において、上記一般式（１）で表される化合物とその他の有機溶剤との質量比は、５：９５～１００：０であることが好ましく、２０：８０～１００：０であることがより好ましい。溶剤の含有量及び上記一般式（１）で表される化合物とその他の有機溶剤との質量比を上記の範囲とすることにより、得られる感放射線性組成物は、感度、保存安定性、塗布性、現像性、及び安全性に優れたものとなりやすく、この感放射線性組成物を露光及び現像することにより形成されるパターンは、異物の発生が抑制されたものとなりやすい。なお、その他の有機溶剤については後述する。 In the radiation-sensitive composition according to the present invention, the content of the solvent is preferably such that the solid content concentration of the radiation-sensitive composition is 1 to 50% by mass, and more preferably 5 to 30% by mass. . In the solvent contained in the radiation-sensitive composition according to the present invention, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is 5:95 to 100: 0. Preferably, it is 20:80 to 100: 0. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) and the other organic solvent within the above ranges, the resulting radiation-sensitive composition has a sensitivity, storage stability, coating The pattern formed by exposing and developing this radiation-sensitive composition is likely to be suppressed in the generation of foreign matters. Other organic solvents will be described later.
＜感放射線性組成物の例＞
　本発明に係る感放射線性組成物は、ネガ型及びポジ型のいずれであってもよい。ネガ型感放射線性組成物としては、上記一般式（１）で表される化合物と、アルカリ可溶性樹脂とを含有するネガ型感放射線性組成物；上記一般式（１）で表される化合物と、ポリアミック酸と、光塩基発生剤、光酸発生剤等の感光性成分とを含有する感放射線性ポリイミド前駆体組成物；上記一般式（１）で表される化合物と、ポリベンゾオキサゾール前駆体と、光塩基発生剤、光酸発生剤等の感光性成分とを含有する感放射線性ポリベンゾオキサゾール前駆体組成物；上記一般式（１）で表される化合物を含有する感放射線性ＳＯＧ（スピンオングラス）組成物等が挙げられる。ポジ型感放射線性組成物としては、上記一般式（１）で表される化合物と、アルカリ可溶性樹脂と、キノンジアジド基含有化合物とを含有するポジ型感放射線性組成物；上記一般式（１）で表される化合物と、ポリイミド樹脂と、光塩基発生剤、光酸発生剤等の感光性成分とを含有する感放射線性ポリイミド組成物；上記一般式（１）で表される化合物と、酸の作用によりアルカリに対する溶解性が増大する樹脂と、光酸発生剤とを含有する化学増幅型ポジ型感放射線性組成物等が挙げられる。以下、これらの感放射線性組成物のうち、上記一般式（１）で表される化合物と、アルカリ可溶性樹脂とを含有するネガ型感放射線性組成物（以下、「ネガ型感放射線性組成物１」という。）、上記一般式（１）で表される化合物と、ポリアミック酸と、光塩基発生剤、光酸発生剤等の感光性成分とを含有する感放射線性ポリイミド前駆体組成物（以下、「ネガ型感放射線性組成物２」という。）、上記一般式（１）で表される化合物と、ポリベンゾオキサゾール前駆体と、光塩基発生剤、光酸発生剤等の感光性成分とを含有する感放射線性ポリベンゾオキサゾール前駆体組成物（以下、「ネガ型感放射線性組成物３」という。）、及び上記一般式（１）で表される化合物と、アルカリ可溶性樹脂と、キノンジアジド基含有化合物とを含有するポジ型感放射線性組成物（以下、「ポジ型感放射線性組成物１」という。）について詳細に説明する。 <Examples of radiation-sensitive composition>
The radiation sensitive composition according to the present invention may be either a negative type or a positive type. As a negative radiation sensitive composition, a negative radiation sensitive composition containing a compound represented by the above general formula (1) and an alkali-soluble resin; a compound represented by the above general formula (1); , A radiation sensitive polyimide precursor composition containing a polyamic acid and a photosensitive component such as a photobase generator or a photoacid generator; a compound represented by the above general formula (1); and a polybenzoxazole precursor And a radiation-sensitive polybenzoxazole precursor composition containing a photosensitive component such as a photobase generator and a photoacid generator; a radiation-sensitive SOG containing a compound represented by the above general formula (1) ( Spin on glass) composition and the like. As a positive radiation sensitive composition, a positive radiation sensitive composition containing a compound represented by the above general formula (1), an alkali-soluble resin, and a quinonediazide group-containing compound; the above general formula (1) A radiation-sensitive polyimide composition comprising a compound represented by the formula: a polyimide resin; and a photosensitive component such as a photobase generator or a photoacid generator; a compound represented by the above general formula (1); And a chemically amplified positive radiation-sensitive composition containing a resin whose solubility in alkali is increased by the action of the above and a photoacid generator. Hereinafter, among these radiation-sensitive compositions, a negative radiation-sensitive composition (hereinafter referred to as “negative-type radiation-sensitive composition” containing the compound represented by the general formula (1) and an alkali-soluble resin. 1 ”), a radiation sensitive polyimide precursor composition containing a compound represented by the above general formula (1), a polyamic acid, and a photosensitive component such as a photobase generator and a photoacid generator ( Hereinafter, it is referred to as “negative radiation sensitive composition 2”), a compound represented by the above general formula (1), a polybenzoxazole precursor, a photobase generator, a photoacid generator, and other photosensitive components. A radiation-sensitive polybenzoxazole precursor composition (hereinafter referred to as “negative radiation-sensitive composition 3”), a compound represented by the above general formula (1), an alkali-soluble resin, Containing a quinonediazide group-containing compound The positive type radiation-sensitive composition (hereinafter, referred to as "positive-type radiation-sensitive composition 1".) Will be described in detail.
＜ネガ型感放射線性組成物１＞
　ネガ型感放射線性組成物１は、上記一般式（１）で表される化合物と、アルカリ可溶性樹脂とを含有するものであり、より具体的には、上記一般式（１）で表される化合物と、アルカリ可溶性樹脂と、光重合性モノマーと、光重合開始剤とを含有するものである。 <Negative type radiation sensitive composition 1>
The negative radiation sensitive composition 1 contains the compound represented by the above general formula (1) and an alkali-soluble resin, and more specifically, represented by the above general formula (1). It contains a compound, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator.
［一般式（１）で表される化合物］
　一般式（１）で表される化合物としては、感放射線性組成物の一般的な説明において例示したものを用いることができる。上記一般式（１）で表される化合物は、単独で又は２種以上組み合わせて用いることができる。 [Compound represented by general formula (1)]
As the compound represented by the general formula (1), those exemplified in the general description of the radiation-sensitive composition can be used. The compounds represented by the general formula (1) can be used alone or in combination of two or more.
［アルカリ可溶性樹脂］
　アルカリ可溶性樹脂とは、樹脂濃度２０質量％の樹脂溶液（溶媒：プロピレングリコールモノメチルエーテルアセテート）により、膜厚１μｍの樹脂膜を基板上に形成し、濃度０．０５質量％のＫＯＨ水溶液に１分間浸漬した際に、膜厚０．０１μｍ以上溶解するものをいう。 [Alkali-soluble resin]
The alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a 1 μm-thick resin film is formed on the substrate and placed in a 0.05% by mass KOH aqueous solution for 1 minute. When immersed, it means a film that dissolves 0.01 μm or more in thickness.
　アルカリ可溶性樹脂としては、上述のアルカリ可溶性を示す樹脂であれば特に限定されず、従来公知のアルカリ可溶性樹脂を用いることができる。アルカリ可溶性樹脂は、単独で又は２種以上組み合わせて用いることができる。 The alkali-soluble resin is not particularly limited as long as it is a resin exhibiting alkali solubility as described above, and a conventionally known alkali-soluble resin can be used. The alkali-soluble resins can be used alone or in combination of two or more.
　好適なアルカリ可溶性樹脂の一例としては、（Ａ１）カルド構造を有する樹脂が挙げられる。（Ａ１）カルド構造を有する樹脂としては、特に限定されるものではなく、従来公知の樹脂を用いることができる。その中でも、下記式（ａ－１）で表される樹脂が好ましい。 An example of a suitable alkali-soluble resin is (A1) a resin having a cardo structure. (A1) The resin having a cardo structure is not particularly limited, and conventionally known resins can be used. Among these, a resin represented by the following formula (a-1) is preferable.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記式（ａ－１）中、Ｘａは、下記式（ａ－２）で表される基を示す。 In the above formula (a-1), X a represents a group represented by the following formula (a-2).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　上記式（ａ－２）中、Ｒａ１は、それぞれ独立に水素原子、炭素数１～６の炭化水素基、又はハロゲン原子を示し、Ｒａ２は、それぞれ独立に水素原子又はメチル基を示し、Ｗａは、単結合又は下記式（ａ－３）で表される基を示す。 In the above formula (a-2), R a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R a2 each independently represents a hydrogen atom or a methyl group, W a represents a single bond or a group represented by the following formula (a-3).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　また、上記式（ａ－１）中、Ｙａは、ジカルボン酸無水物から酸無水物基（－ＣＯ－Ｏ－ＣＯ－）を除いた残基を示す。ジカルボン酸無水物の例としては、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水メチルエンドメチレンテトラヒドロフタル酸、無水クロレンド酸、メチルテトラヒドロ無水フタル酸、無水グルタル酸等が挙げられる。 In the formula (a-1), Y a represents a residue obtained by removing the acid anhydride group (—CO—O—CO—) from the dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.
　また、上記式（ａ－１）中、Ｚａは、テトラカルボン酸二無水物から２個の酸無水物基を除いた残基を示す。テトラカルボン酸二無水物の例としては、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物、ビフェニルエーテルテトラカルボン酸二無水物等が挙げられる。
　また、上記式（ａ－１）中、ｍは、０～２０の整数を示す。 Further, in the above formula (a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
In the formula (a-1), m represents an integer of 0 to 20.
　（Ａ１）カルド構造を有する樹脂の質量平均分子量は、１０００～４００００であることが好ましく、２０００～３００００であることがより好ましい。上記の範囲とすることにより、良好な現像性を得ながら、十分な耐熱性、膜強度を得ることができる。なお、本明細書において、質量平均分子量とは、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定されたポリスチレン換算による値をいう。 (A1) The mass average molecular weight of the resin having a cardo structure is preferably 1000 to 40000, more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability. In addition, in this specification, a mass average molecular weight means the value by polystyrene conversion measured by gel permeation chromatography (GPC).
　また、好適なアルカリ可溶性樹脂の他の例としては、（Ａ２）エポキシ樹脂が挙げられる。（Ａ２）エポキシ樹脂としては、特に限定されるものではなく、従来公知のエポキシ樹脂を用いることができ、エチレン性不飽和基を有さないものであっても、エチレン性不飽和基を有するものであってもよい。 Further, another example of a suitable alkali-soluble resin is (A2) an epoxy resin. (A2) The epoxy resin is not particularly limited, and a conventionally known epoxy resin can be used, and it has an ethylenically unsaturated group even if it does not have an ethylenically unsaturated group. It may be.
　エチレン性不飽和基を有さないエポキシ樹脂としては、例えば、不飽和カルボン酸とエポキシ基含有不飽和化合物とを少なくとも共重合させて得られる樹脂（Ａ２－１）を用いることができる。 As the epoxy resin having no ethylenically unsaturated group, for example, a resin (A2-1) obtained by at least copolymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound can be used.
　不飽和カルボン酸としては、（メタ）アクリル酸、クロトン酸等のモノカルボン酸；マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸等のジカルボン酸；これらジカルボン酸の無水物；等が挙げられる。これらの中でも、共重合反応性、得られる樹脂のアルカリ溶解性、入手の容易性等の点から、（メタ）アクリル酸及び無水マレイン酸が好ましい。これらの不飽和カルボン酸は、単独又は２種以上組み合わせて用いることができる。
　なお、本明細書において、「（メタ）アクリル酸」は、アクリル酸とメタクリル酸との両方を意味する。 Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; It is done. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.
In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid.
　上記樹脂（Ａ２－１）に占める不飽和カルボン酸由来の構成単位（カルボキシル基を有する構成単位）の割合は、５～２９質量％であることが好ましく、１０～２５質量％であることがより好ましい。上記範囲とすることにより、ネガ型感放射線性組成物１の現像性を適度なものとすることができる。 The proportion of the structural unit derived from the unsaturated carboxylic acid (the structural unit having a carboxyl group) in the resin (A2-1) is preferably 5 to 29% by mass, and more preferably 10 to 25% by mass. preferable. By setting it as the said range, the developability of the negative radiation sensitive composition 1 can be made moderate.
　エポキシ基含有不飽和化合物は、脂環式エポキシ基を有さないものであっても、脂環式エポキシ基を有するものであってもよいが、脂環式エポキシ基を有するものがより好ましい。 The epoxy group-containing unsaturated compound may have no alicyclic epoxy group or may have an alicyclic epoxy group, but more preferably has an alicyclic epoxy group.
　脂環式エポキシ基を有さないエポキシ基含有不飽和化合物としては、グリシジル（メタ）アクリレート、２－メチルグリシジル（メタ）アクリレート、３，４－エポキシブチル（メタ）アクリレート、６，７－エポキシヘプチル（メタ）アクリレート、３，４－エポキシシクロヘキシル（メタ）アクリレート等の（メタ）アクリル酸エポキシアルキルエステル類；α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、α－エチルアクリル酸６，７－エポキシヘプチル等のα－アルキルアクリル酸エポキシアルキルエステル類；ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル等のグリシジルエーテル類；等が挙げられる。これらの中でも、共重合反応性、硬化後の樹脂の強度等の点から、グリシジル（メタ）アクリレート、２－メチルグリシジル（メタ）アクリレート、６，７－エポキシヘプチル（メタ）アクリレート、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、及びｐ－ビニルベンジルグリシジルエーテルが好ましい。 Examples of the epoxy group-containing unsaturated compound having no alicyclic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl. (Meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and other (meth) acrylic acid epoxy alkyl esters; α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate Α-alkylacrylic acid epoxy alkyl esters such as glycidyl and α-ethylacrylic acid 6,7-epoxyheptyl; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether ; Etc. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoint of copolymerization reactivity, strength of cured resin, and the like. Glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred.
　脂環式エポキシ基を有するエポキシ基含有不飽和化合物の脂環式基は、単環であっても多環であってもよい。単環の脂環式基としては、シクロペンチル基、シクロヘキシル基等が挙げられる。また、多環の脂環式基としては、ノルボルニル基、イソボルニル基、トリシクロノニル基、トリシクロデシル基、テトラシクロドデシル基等が挙げられる。 The alicyclic group of the epoxy group-containing unsaturated compound having an alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.
　具体的に、脂環式エポキシ基を有するエポキシ基含有不飽和化合物としては、例えば下記式（ａ４－１）～（ａ４－１６）で表される化合物が挙げられる。これらの中でも、ネガ型感放射線性組成物１の現像性を適度なものとするためには、下記式（ａ４－１）～（ａ４－６）で表される化合物が好ましく、下記式（ａ４－１）～（ａ４－４）で表される化合物がより好ましい。 Specifically, examples of the epoxy group-containing unsaturated compound having an alicyclic epoxy group include compounds represented by the following formulas (a4-1) to (a4-16). Among these, the compounds represented by the following formulas (a4-1) to (a4-6) are preferable in order to make the negative radiation-sensitive composition 1 have an appropriate developability, and the following formula (a4 The compounds represented by -1) to (a4-4) are more preferred.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記式中、Ｒａ３は水素原子又はメチル基を示し、Ｒａ４は炭素数１～６の２価の脂肪族飽和炭化水素基を示し、Ｒａ５は炭素数１～１０の２価の炭化水素基を示し、ｎは０～１０の整数を示す。Ｒａ４としては、直鎖状又は分枝鎖状のアルキレン基、例えばメチレン基、エチレン基、プロピレン基、テトラメチレン基、エチルエチレン基、ペンタメチレン基、ヘキサメチレン基が好ましい。Ｒａ５としては、例えばメチレン基、エチレン基、プロピレン基、テトラメチレン基、エチルエチレン基、ペンタメチレン基、ヘキサメチレン基、フェニレン基、シクロヘキシレン基、－ＣＨ２－Ｐｈ－ＣＨ２－（Ｐｈはフェニレン基を示す）が好ましい。 In the above formula, R a3 represents a hydrogen atom or a methyl group, R a4 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R a5 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R a4 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R a5 , for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH 2 —Ph—CH 2 — (Ph is A phenylene group) is preferred.
　これらのエポキシ基含有不飽和化合物は、単独又は２種以上組み合わせて用いることができる。 These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.
　上記樹脂（Ａ２－１）に占めるエポキシ基含有不飽和化合物由来の構成単位（エポキシ基を有する構成単位）の割合は、５～９０質量％であることが好ましく、１５～７５質量％であることがより好ましい。上記範囲とすることにより、良好な形状のパターンを形成しやすくなる。 The proportion of the structural unit derived from the epoxy group-containing unsaturated compound (the structural unit having an epoxy group) in the resin (A2-1) is preferably 5 to 90% by mass, and preferably 15 to 75% by mass. Is more preferable. By setting it as the said range, it becomes easy to form a pattern of a favorable shape.
　上記樹脂（Ａ２－１）は、脂環式基含有不飽和化合物を更に共重合させたものであることが好ましい。 The resin (A2-1) is preferably obtained by further copolymerizing an alicyclic group-containing unsaturated compound.
　脂環式基含有不飽和化合物の脂環式基は、単環であっても多環であってもよい。単環の脂環式基としては、シクロペンチル基、シクロヘキシル基等が挙げられる。また、多環の脂環式基としては、アダマンチル基、ノルボルニル基、イソボルニル基、トリシクロノニル基、トリシクロデシル基、テトラシクロドデシル基等が挙げられる。 The alicyclic group of the alicyclic group-containing unsaturated compound may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.
　具体的に、脂環式基含有不飽和化合物としては、例えば下記式（ａ５－１）～（ａ５－８）で表される化合物が挙げられる。これらの中でも、ネガ型感放射線性組成物１の現像性を適度なものとするためには、下記式（ａ５－３）～（ａ５－８）で表される化合物が好ましく、下記式（ａ５－３）、（ａ５－４）で表される化合物がより好ましい。 Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulas (a5-1) to (a5-8). Of these, compounds represented by the following formulas (a5-3) to (a5-8) are preferable in order to make the negative radiation-sensitive composition 1 have an appropriate developability, and the following formula (a5 -3) and compounds represented by (a5-4) are more preferred.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　上記式中、Ｒａ６は水素原子又はメチル基を示し、Ｒａ７は単結合又は炭素数１～６の２価の脂肪族飽和炭化水素基を示し、Ｒａ８は水素原子又は炭素数１～５のアルキル基を示す。Ｒａ７としては、単結合、直鎖状又は分枝鎖状のアルキレン基、例えばメチレン基、エチレン基、プロピレン基、テトラメチレン基、エチルエチレン基、ペンタメチレン基、ヘキサメチレン基が好ましい。Ｒａ８としては、例えばメチル基、エチル基が好ましい。 In the above formula, R a6 represents a hydrogen atom or a methyl group, R a7 represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R a8 represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R a7 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R a8 , for example, a methyl group and an ethyl group are preferable.
　上記樹脂（Ａ２－１）に占める脂環式基含有不飽和化合物由来の構成単位の割合は、１～４０質量％であることが好ましく、５～３０質量％であることがより好ましい。 The proportion of the structural unit derived from the alicyclic group-containing unsaturated compound in the resin (A2-1) is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass.
　また、上記樹脂（Ａ２－１）は、上記以外の他の化合物を更に共重合させたものであってもよい。このような他の化合物としては、（メタ）アクリル酸エステル類、（メタ）アクリルアミド類、アリル化合物、ビニルエーテル類、ビニルエステル類、スチレン類等が挙げられる。これらの化合物は、単独又は２種以上組み合わせて用いることができる。 Further, the resin (A2-1) may be obtained by further copolymerizing other compounds than the above. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more.
　（メタ）アクリル酸エステル類としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、アミル（メタ）アクリレート、ｔ－オクチル（メタ）アクリレート等の直鎖状又は分岐鎖状のアルキル（メタ）アクリレート；クロロエチル（メタ）アクリレート、２，２－ジメチルヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、トリメチロールプロパンモノ（メタ）アクリレート、ベンジル（メタ）アクリレート、フルフリル（メタ）アクリレート；等が挙げられる。 (Meth) acrylic acid esters include linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.
　（メタ）アクリルアミド類としては、（メタ）アクリルアミド、Ｎ－アルキル（メタ）アクリルアミド、Ｎ－アリール（メタ）アクリルアミド、Ｎ，Ｎ－ジアルキル（メタ）アクリルアミド、Ｎ，Ｎ－アリール（メタ）アクリルアミド、Ｎ－メチル－Ｎ－フェニル（メタ）アクリルアミド、Ｎ－ヒドロキシエチル－Ｎ－メチル（メタ）アクリルアミド等が挙げられる。 (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.
　アリル化合物としては、酢酸アリル、カプロン酸アリル、カプリル酸アリル、ラウリン酸アリル、パルミチン酸アリル、ステアリン酸アリル、安息香酸アリル、アセト酢酸アリル、乳酸アリル等のアリルエステル類；アリルオキシエタノール；等が挙げられる。 Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.
　ビニルエーテル類としては、ヘキシルビニルエーテル、オクチルビニルエーテル、デシルビニルエーテル、エチルヘキシルビニルエーテル、メトキシエチルビニルエーテル、エトキシエチルビニルエーテル、クロルエチルビニルエーテル、１－メチル－２，２－ジメチルプロピルビニルエーテル、２－エチルブチルビニルエーテル、ヒドロキシエチルビニルエーテル、ジエチレングリコールビニルエーテル、ジメチルアミノエチルビニルエーテル、ジエチルアミノエチルビニルエーテル、ブチルアミノエチルビニルエーテル、ベンジルビニルエーテル、テトラヒドロフルフリルビニルエーテル等のアルキルビニルエーテル；ビニルフェニルエーテル、ビニルトリルエーテル、ビニルクロルフェニルエーテル、ビニル－２，４－ジクロルフェニルエーテル、ビニルナフチルエーテル、ビニルアントラニルエーテル等のビニルアリールエーテル；等が挙げられる。 The vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether. Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorofe And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.
　ビニルエステル類としては、ビニルブチレート、ビニルイソブチレート、ビニルトリメチルアセテート、ビニルジエチルアセテート、ビニルバレート、ビニルカプロエート、ビニルクロルアセテート、ビニルジクロルアセテート、ビニルメトキシアセテート、ビニルブトキシアセテート、ビニルフエニルアセテート、ビニルアセトアセテート、ビニルラクテート、ビニル－β－フェニルブチレート、安息香酸ビニル、サリチル酸ビニル、クロル安息香酸ビニル、テトラクロル安息香酸ビニル、ナフトエ酸ビニル等が挙げられる。 Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl vinyl. Examples thereof include enil acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.
　スチレン類としては、スチレン；メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、イソプロピルスチレン、ブチルスチレン、ヘキシルスチレン、シクロヘキシルスチレン、デシルスチレン、ベンジルスチレン、クロルメチルスチレン、トリフルオロメチルスチレン、エトキシメチルスチレン、アセトキシメチルスチレン等のアルキルスチレン；メトキシスチレン、４－メトキシ－３－メチルスチレン、ジメトキシスチレン等のアルコキシスチレン；クロロスチレン、ジクロロスチレン、トリクロロスチレン、テトラクロロスチレン、ペンタクロロスチレン、ブロモスチレン、ジブロモスチレン、ヨードスチレン、フルオロスチレン、トリフルオロスチレン、２－ブロモ－４－トリフルオロメチルスチレン、４－フルオロ－３－トリフルオロメチルスチレン等のハロスチレン；等が挙げられる。 Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluorome Rusuchiren, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.
　樹脂（Ａ２－１）の質量平均分子量は、２０００～５００００であることが好ましく、５０００～３００００であることがより好ましい。上記の範囲とすることにより、ネガ型感放射線性組成物１の膜形成能、現像性のバランスがとりやすい傾向がある。 The mass average molecular weight of the resin (A2-1) is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, there is a tendency that the film-forming ability and developability of the negative radiation-sensitive composition 1 are easily balanced.
　一方、エチレン性不飽和基を有するエポキシ樹脂としては、例えば、不飽和カルボン酸とエポキシ基含有不飽和化合物とを少なくとも重合させて得られる樹脂のカルボキシル基と、エポキシ基含有不飽和化合物のエポキシ基とを反応させて得られる樹脂（Ａ２－２）、あるいは、不飽和カルボン酸とエポキシ基含有不飽和化合物とを少なくとも重合させて得られる樹脂のエポキシ基と、不飽和カルボン酸のカルボキシル基とを反応させて得られる樹脂（Ａ２－３）を用いることができる。 On the other hand, as an epoxy resin having an ethylenically unsaturated group, for example, a carboxyl group of a resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, and an epoxy group of an epoxy group-containing unsaturated compound An epoxy group of a resin obtained by polymerizing at least a unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, and a carboxyl group of an unsaturated carboxylic acid. Resin (A2-3) obtained by the reaction can be used.
　不飽和カルボン酸、エポキシ基含有不飽和化合物としては、上記樹脂（Ａ２－１）で例示した化合物が挙げられる。したがって、不飽和カルボン酸とエポキシ基含有不飽和化合物とを少なくとも重合させて得られる樹脂としては、上記樹脂（Ａ２－１）が例示される。 Examples of the unsaturated carboxylic acid and the epoxy group-containing unsaturated compound include the compounds exemplified for the resin (A2-1). Therefore, the resin (A2-1) is exemplified as a resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound.
　上記樹脂（Ａ２－２）、（Ａ２－３）に占める不飽和カルボン酸由来の構成単位（カルボキシル基を有する構成単位）の割合は、５～６０質量％であることが好ましく、１０～４０質量％であることがより好ましい。上記範囲とすることにより、ネガ型感放射線性組成物１の現像性を適度なものとすることができる。 The proportion of the structural unit derived from the unsaturated carboxylic acid (the structural unit having a carboxyl group) in the resins (A2-2) and (A2-3) is preferably 5 to 60% by mass, and 10 to 40% by mass. % Is more preferable. By setting it as the said range, the developability of the negative radiation sensitive composition 1 can be made moderate.
　また、上記樹脂（Ａ２－２）、（Ａ２－３）に占めるエポキシ基含有不飽和化合物由来の構成単位（エポキシ基を有する構成単位）の割合は、５～９０質量％であることが好ましく、１５～７５質量％であることがより好ましい。上記範囲とすることにより、良好な形状のパターンを形成しやすくなる。 Further, the proportion of the structural unit derived from the epoxy group-containing unsaturated compound (structural unit having an epoxy group) in the resin (A2-2) or (A2-3) is preferably 5 to 90% by mass, More preferably, it is 15 to 75% by mass. By setting it as the said range, it becomes easy to form a pattern of a favorable shape.
　樹脂（Ａ２－２）、（Ａ２－３）の質量平均分子量は、２０００～５００００であることが好ましく、５０００～３００００であることがより好ましい。上記の範囲とすることにより、ネガ型感放射線性組成物１の膜形成能、現像性のバランスがとりやすい傾向がある。 The mass average molecular weights of the resins (A2-2) and (A2-3) are preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, there is a tendency that the film-forming ability and developability of the negative radiation-sensitive composition 1 are easily balanced.
　上記のほか、（Ａ２）エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノール又はクレゾールノボラック型エポキシ樹脂、レゾール型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ポリカルボン酸ポリグリシジルエステル、ポリオールポリグリシジルエステル、アミンエポキシ樹脂、ジヒドロキシベンゼン型エポキシ樹脂等のエポキシ樹脂のエポキシ基と、（メタ）アクリル酸とを反応させて得られるエポキシ（メタ）アクリレート樹脂等を用いることもできる。 In addition to the above, (A2) epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, An epoxy (meth) acrylate resin obtained by reacting an epoxy group of an epoxy resin such as a polycarboxylic acid polyglycidyl ester, a polyol polyglycidyl ester, an amine epoxy resin, or a dihydroxybenzene type epoxy resin with (meth) acrylic acid, etc. It can also be used.
　アルカリ可溶性樹脂の含有量は、ネガ型感放射線性組成物１の固形分に対して５～９０質量％であることが好ましく、１０～８５質量％であることがより好ましい。上記の範囲とすることにより、ネガ型感放射線性組成物１の膜形成能、現像性のバランスをとりやすい傾向がある。 The content of the alkali-soluble resin is preferably 5 to 90% by mass, more preferably 10 to 85% by mass with respect to the solid content of the negative radiation-sensitive composition 1. By setting it as said range, there exists a tendency which is easy to balance the film formation ability of the negative radiation sensitive composition 1, and developability.
［光重合性モノマー］
　光重合性モノマーとしては、特に限定されず、従来公知の単官能モノマー、多官能モノマーを用いることができる。光重合性モノマーは、単独で又は２種以上組み合わせて用いることができる。 [Photopolymerizable monomer]
It does not specifically limit as a photopolymerizable monomer, A conventionally well-known monofunctional monomer and a polyfunctional monomer can be used. A photopolymerizable monomer can be used individually or in combination of 2 or more types.
　単官能モノマーとしては、（メタ）アクリルアミド、メチロール（メタ）アクリルアミド、メトキシメチル（メタ）アクリルアミド、エトキシメチル（メタ）アクリルアミド、プロポキシメチル（メタ）アクリルアミド、ブトキシメトキシメチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ヒドロキシメチル（メタ）アクリルアミド、（メタ）アクリル酸、フマル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、シトラコン酸、無水シトラコン酸、クロトン酸、２－アクリルアミド－２－メチルプロパンスルホン酸、ｔｅｒｔ－ブチルアクリルアミドスルホン酸、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－フェノキシ－２－ヒドロキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシ－２－ヒドロキシプロピルフタレート、グリセリンモノ（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ジメチルアミノ（メタ）アクリレート、グリシジル（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、フタル酸誘導体のハーフ（メタ）アクリレート等が挙げられる。これらの単官能モノマーは、単独又は２種以上組み合わせて用いることができる。 Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylic , Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2 -(Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl Examples include (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.
　一方、多官能モノマーとしては、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６－ヘキサングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、２，２－ビス（４－（メタ）アクリロキシジエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロキシポリエトキシフェニル）プロパン、２－ヒドロキシ－３－（メタ）アクリロイルオキシプロピル（メタ）アクリレート、エチレングリコールジグリシジルエーテルジ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、フタル酸ジグリシジルエステルジ（メタ）アクリレート、グリセリントリアクリレート、グリセリンポリグリシジルエーテルポリ（メタ）アクリレート、ウレタン（メタ）アクリレート（即ち、トリレンジイソシアネート）、トリメチルヘキサメチレンジイソシアネートとヘキサメチレンジイソシアネートと２－ヒドロキシエチル（メタ）アクリレートとの反応物、メチレンビス（メタ）アクリルアミド、（メタ）アクリルアミドメチレンエーテル、多価アルコールとＮ－メチロール（メタ）アクリルアミドとの縮合物等の多官能モノマーや、トリアクリルホルマール等が挙げられる。これらの多官能モノマーは、単独又は２種以上組み合わせて用いることができる。 On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (medium ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy Diethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) ) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether (Meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide Examples thereof include polyfunctional monomers such as methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.
　光重合性モノマーの含有量は、ネガ型感放射線性組成物１の固形分に対して１～４５質量％であることが好ましく、５～４０質量％であることがより好ましい。上記の範囲とすることにより、感度、現像性、解像性のバランスがとりやすい傾向がある。 The content of the photopolymerizable monomer is preferably 1 to 45% by mass, more preferably 5 to 40% by mass with respect to the solid content of the negative radiation-sensitive composition 1. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.
［光重合開始剤］
　光重合開始剤としては、特に限定されず、従来公知の光重合開始剤を用いることができる。光重合開始剤は、単独で又は２種以上組み合わせて用いることができる。 [Photopolymerization initiator]
It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used. A photoinitiator can be used individually or in combination of 2 or more types.
　光重合開始剤として具体的には、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－〔４－（２－ヒドロキシエトキシ）フェニル〕－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－ドデシルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、ビス（４－ジメチルアミノフェニル）ケトン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド、４－ベンゾイル－４’－メチルジメチルスルフィド、４－ジメチルアミノ安息香酸、４－ジメチルアミノ安息香酸メチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸ブチル、４－ジメチルアミノ－２－エチルヘキシル安息香酸、４－ジメチルアミノ－２－イソアミル安息香酸、ベンジル－β－メトキシエチルアセタール、ベンジルジメチルケタール、１－フェニル－１，２－プロパンジオン－２－（ｏ－エトキシカルボニル）オキシム、ｏ－ベンゾイル安息香酸メチル、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、１－クロロ－４－プロポキシチオキサントン、チオキサンテン、２－クロロチオキサンテン、２，４－ジエチルチオキサンテン、２－メチルチオキサンテン、２－イソプロピルチオキサンテン、２－エチルアントラキノン、オクタメチルアントラキノン、１，２－ベンズアントラキノン、２，３－ジフェニルアントラキノン、アゾビスイソブチロニトリル、ベンゾイルパーオキシド、クメンパーオキシド、２－メルカプトベンゾイミダール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾチアゾール、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、２，４，５－トリアリールイミダゾール二量体、ベンゾフェノン、２－クロロベンゾフェノン、４，４’－ビスジメチルアミノベンゾフェノン（即ち、ミヒラーズケトン）、４，４’－ビスジエチルアミノベンゾフェノン（即ち、エチルミヒラーズケトン）、４，４’－ジクロロベンゾフェノン、３，３－ジメチル－４－メトキシベンゾフェノン、ベンジル、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンゾインイソブチルエーテル、ベンゾインブチルエーテル、アセトフェノン、２，２－ジエトキシアセトフェノン、ｐ－ジメチルアセトフェノン、ｐ－ジメチルアミノプロピオフェノン、ジクロロアセトフェノン、トリクロロアセトフェノン、ｐ－ｔｅｒｔ－ブチルアセトフェノン、ｐ－ジメチルアミノアセトフェノン、ｐ－ｔｅｒｔ－ブチルトリクロロアセトフェノン、ｐ－ｔｅｒｔ－ブチルジクロロアセトフェノン、α，α－ジクロロ－４－フェノキシアセトフェノン、チオキサントン、２－メチルチオキサントン、２－イソプロピルチオキサントン、ジベンゾスベロン、ペンチル－４－ジメチルアミノベンゾエート、９－フェニルアクリジン、１，７－ビス－（９－アクリジニル）ヘプタン、１，５－ビス－（９－アクリジニル）ペンタン、１，３－ビス－（９－アクリジニル）プロパン、ｐ－メトキシトリアジン、２，４，６－トリス（トリクロロメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－［２－（５－メチルフラン－２－イル）エテニル］－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－［２－（フラン－２－イル）エテニル］－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－［２－（４－ジエチルアミノ－２－メチルフェニル）エテニル］－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－［２－（３，４－ジメトキシフェニル）エテニル］－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－ｎ－ブトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－ビス－トリクロロメチル－６－（３－ブロモ－４－メトキシ）フェニル－ｓ－トリアジン、２，４－ビス－トリクロロメチル－６－（２－ブロモ－４－メトキシ）フェニル－ｓ－トリアジン、２，４－ビス－トリクロロメチル－６－（３－ブロモ－４－メトキシ）スチリルフェニル－ｓ－トリアジン、２，４－ビス－トリクロロメチル－６－（２－ブロモ－４－メトキシ）スチリルフェニル－ｓ－トリアジン、「ＩＲＧＡＣＵＲＥ　ＯＸＥ０２」、「ＩＲＧＡＣＵＲＥ　ＯＸＥ０１」、「ＩＲＧＡＣＵＲＥ　３６９」、「ＩＲＧＡＣＵＲＥ　６５１」、「ＩＲＧＡＣＵＲＥ　９０７」（商品名、ＢＡＳＦ製）、「ＮＣＩ－８３１」（商品名、ＡＤＥＫＡ製）等が挙げられる。これらの光重合開始剤は、単独又は２種以上組み合わせて用いることができる。 Specific photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Til, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- ( o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisiso Butyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- ( o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4 ' -Bisdimethylaminobenzophenone (ie Michler's ketone), 4, '-Bisdiethylaminobenzophenone (ie ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -N-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p- Dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetopheno , Α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9- Acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-to Azine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo -4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-triazine Chloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, “IRGACURE OXE02 ”,“ IRGACURE OXE01 ”,“ IRGACURE 369 ”,“ IRGACURE 651 ”,“ IRGACURE 907 ”(trade name, manufactured by BASF),“ NCI-831 ”(trade name, manufactured by ADEKA), and the like. These photopolymerization initiators can be used alone or in combination of two or more.
　これらの中でも、オキシム系光重合開始剤を用いることが感度の面で特に好ましい。
　オキシム系光重合開始剤の好ましい例としては、下記式（ｃ－１）で表される光重合開始剤が挙げられる。 Among these, it is particularly preferable in terms of sensitivity to use an oxime photopolymerization initiator.
Preferable examples of the oxime photopolymerization initiator include a photopolymerization initiator represented by the following formula (c-1).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記式（ｃ－１）中、Ｒｃ１は、置換基を有していてもよい、複素環基、縮合環式芳香族基、又は芳香族基を示す。Ｒｃ２～Ｒｃ４はそれぞれ独立に１価の有機基を示す。 In the above formula (c-1), R c1 represents a heterocyclic group, a condensed cyclic aromatic group, or an aromatic group, which may have a substituent. R c2 to R c4 each independently represent a monovalent organic group.
　Ｒｃ１における複素環基としては、窒素原子、硫黄原子、及び酸素原子の少なくとも１つの原子を含む５員環以上、好ましくは５員環又は６員環の複素環基が挙げられる。複素環基の例としては、ピロリル基、イミダゾリル基、ピラゾリル基等の含窒素５員環基；ピリジル基、ピラジニル基、ピリミジル基、ピリダジニル基等の含窒素６員環基；チアゾリル基、イソチアゾリル基等の含窒素含硫黄基；オキサゾリル基、イソオキサゾリル基等の含窒素含酸素基；チエニル基、チオピラニル基等の含硫黄基；フリル基、ピラニル基等の含酸素基；等が挙げられる。この中でも、窒素原子又は硫黄原子を１つ含むものが好ましい。この複素環には縮合環が含まれていてもよい。縮合環が含まれる複素環基の例としてはベンゾチエニル基等が挙げられる。 Examples of the heterocyclic group for R c1 include 5-membered or more, preferably 5- or 6-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group.
　Ｒｃ１における縮合環式芳香族基としては、ナフチル基、アントリル基、フェナントリル基等が挙げられる。また、Ｒｃ１における芳香族基としては、フェニル基が挙げられる。 Examples of the condensed cyclic aromatic group for R c1 include a naphthyl group, an anthryl group, and a phenanthryl group. Moreover, a phenyl group is mentioned as an aromatic group in Rc1 .
　複素環基、縮合環式芳香族基、又は芳香族基は、置換基を有していてもよい。特にＲｃ１が芳香族基である場合には、置換基を有していることが好ましい。このような置換基としては、－ＮＯ２、－ＣＮ、－ＳＯ２Ｒｃ５、－ＣＯＲｃ５、－ＮＲｃ６Ｒｃ７、－Ｒｃ８、－ＯＲｃ８、－Ｏ－Ｒｃ９－Ｏ－Ｒｃ１０等が挙げられる。 The heterocyclic group, the condensed cyclic aromatic group, or the aromatic group may have a substituent. In particular, when R c1 is an aromatic group, it preferably has a substituent. Such substituents include —NO 2 , —CN, —SO 2 R c5 , —COR c5 , —NR c6 R c7 , —R c8 , —OR c8 , —O—R c9 —O—R c10, etc. Is mentioned.
　Ｒｃ５は、それぞれ独立にアルキル基を示し、これらはハロゲン原子で置換されていてもよく、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよい。Ｒｃ５におけるアルキル基は、炭素数１～５であることが好ましく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等が挙げられる。 R c5 independently represents an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond. The alkyl group in R c5 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
　Ｒｃ６及びＲｃ７は、それぞれ独立に水素原子、アルキル基、又はアルコキシ基を示し、これらはハロゲン原子で置換されていてもよく、これらのうちアルキル基及びアルコキシ基のアルキレン部分は、エーテル結合、チオエーテル結合、又はエステル結合により中断されていてもよい。また、Ｒｃ６とＲｃ７とが結合して環構造を形成していてもよい。Ｒｃ６及びＲｃ７におけるアルキル基又はアルコキシ基は、炭素数１～５であることが好ましく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。 R c6 and R c7 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom, and among these, the alkylene group of the alkyl group and the alkoxy group is an ether bond, It may be interrupted by a thioether bond or an ester bond. R c6 and R c7 may be bonded to form a ring structure. The alkyl group or alkoxy group in R c6 and R c7 preferably has 1 to 5 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, ethoxy group, A propoxy group etc. are mentioned.
　Ｒｃ６とＲｃ７とが結合して形成し得る環構造としては、複素環が挙げられる。この複素環としては、少なくとも窒素原子を含む５員環以上、好ましくは５～７員環の複素環が挙げられる。この複素環には縮合環が含まれていてもよい。複素環の例としては、ピペリジン環、モルホリン環、チオモルホリン環等が挙げられる。これらの中でも、モルホリン環が好ましい。 A ring structure that can be formed by combining R c6 and R c7 includes a heterocyclic ring. Examples of the heterocyclic ring include 5-membered or more, preferably 5- to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like. Among these, a morpholine ring is preferable.
　Ｒｃ８は、水素原子の一部又は全部がハロゲン原子で置換されていてもよいアルキル基を示す。Ｒｃ８におけるアルキル基は、炭素数１～６であることが好ましく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等が挙げられる。 R c8 represents an alkyl group in which part or all of the hydrogen atoms may be substituted with a halogen atom. The alkyl group for R c8 preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
　Ｒｃ９及びＲｃ１０は、それぞれ独立にアルキル基を示し、これらはハロゲン原子で置換されていてもよく、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよい。好ましい炭素数やその具体例は、上記Ｒｃ１の説明と同様である。 R c9 and R c10 each independently represent an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond. The preferred number of carbon atoms and specific examples thereof are the same as those described above for R c1 .
　これらの中でも、Ｒｃ１としては、ピロリル基、ピリジル基、チエニル基、チオピラリル基、ベンゾチエニル基、ナフチル基、置換基を有するフェニル基が好ましい例として挙げられる。 Among these, preferable examples of R c1 include a pyrrolyl group, a pyridyl group, a thienyl group, a thiopyralyl group, a benzothienyl group, a naphthyl group, and a phenyl group having a substituent.
　上記式（ｃ－１）中、Ｒｃ２は、一価の有機基を示す。この有機基としては、－Ｒｃ１１、－ＯＲｃ１１、－ＣＯＲｃ１１、－ＳＲｃ１１、－ＮＲｃ１１Ｒｃ１２で表される基が好ましい。Ｒｃ１１及びＲｃ１２は、それぞれ独立にアルキル基、アルケニル基、アリール基、アラルキル基、又は複素環基を示し、これらはハロゲン原子、アルキル基、又は複素環基で置換されていてもよく、これらのうちアルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよい。また、Ｒｃ１１とＲｃ１２とが結合して窒素原子とともに環構造を形成していてもよい。 In the above formula (c-1), R c2 represents a monovalent organic group. The organic group is preferably a group represented by —R c11 , —OR c11 , —COR c11 , —SR c11 , —NR c11 R c12 . R c11 and R c12 each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with a halogen atom, an alkyl group, or a heterocyclic group, Among them, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R c11 and R c12 may be bonded to form a ring structure with the nitrogen atom.
　Ｒｃ１１及びＲｃ１２におけるアルキル基としては、炭素数１～２０のものが好ましく、炭素数１～５のものがより好ましい。アルキル基の例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、イソオクチル基、ｓｅｃ－オクチル基、ｔｅｒｔ－オクチル基、ｎ－ノニル基、イソノニル基、ｎ－デシル基、イソデシル基等の直鎖状又は分枝鎖状の基が挙げられる。また、このアルキル基は置換基を有していてもよい。置換基を有するものの例としては、メトキシエトキシエチル基、エトキシエトキシエチル基、プロピロキシエトキシエチル基、メトキシプロピル基等が挙げられる。 The alkyl group for R c11 and R c12 preferably has 1 to 20 carbon atoms, and more preferably has 1 to 5 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl. Group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group And a straight chain or branched chain group such as Moreover, this alkyl group may have a substituent. Examples of those having a substituent include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
　Ｒｃ１１及びＲｃ１２におけるアルケニル基としては、炭素数１～２０のものが好ましく、炭素数１～５のものがより好ましい。アルケニル基の例としては、ビニル基、アリル基、ブテニル基、エテニル基、プロピニル基等の直鎖状又は分枝鎖状の基が挙げられる。また、このアルケニル基は置換基を有していてもよい。置換基を有するものの例としては、２－（ベンゾオキサゾール－２－イル）エテニル基等が挙げられる。 As the alkenyl group for R c11 and R c12, an alkenyl group having 1 to 20 carbon atoms is preferable, and an alkenyl group having 1 to 5 carbon atoms is more preferable. Examples of alkenyl groups include linear or branched groups such as vinyl, allyl, butenyl, ethenyl, and propynyl groups. Moreover, this alkenyl group may have a substituent. Examples of those having a substituent include 2- (benzoxazol-2-yl) ethenyl group and the like.
　Ｒｃ１１及びＲｃ１２におけるアリール基としては、炭素数６～２０のものが好ましく、炭素数６～１０のものがより好ましい。アリール基の例としては、フェニル基、トリル基、キシリル基、エチルフェニル基、ナフチル基、アントリル基、フェナントリル基等が挙げられる。 The aryl group for R c11 and R c12 preferably has 6 to 20 carbon atoms, and more preferably has 6 to 10 carbon atoms. Examples of the aryl group include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group and the like.
　Ｒｃ１１及びＲｃ１２におけるアラルキル基としては、炭素数７～２０のものが好ましく、炭素数７～１２のものがより好ましい。アラルキル基の例としては、ベンジル基、α－メチルベンジル基、α，α－ジメチルベンジル基、フェニルエチル基、フェニルエテニル基等が挙げられる。 The aralkyl group in R c11 and R c12 is preferably one having 7 to 20 carbon atoms, and more preferably one having 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.
　Ｒｃ１１及びＲｃ１２における複素環基としては、窒素原子、硫黄原子、及び酸素原子の少なくとも１つの原子を含む５員環以上、好ましくは５～７員環の複素環基が挙げられる。この複素環基には縮合環が含まれていてもよい。複素環基の例としては、ピロリル基、ピリジル基、ピリミジル基、フリル基、チエニル基等が挙げられる。 Examples of the heterocyclic group for R c11 and R c12 include 5-membered or more, preferably 5- to 7-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. This heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include pyrrolyl, pyridyl, pyrimidyl, furyl, and thienyl groups.
　これらのＲｃ１１及びＲｃ１２のうち、アルキル基及びアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよい。 Among these R c11 and R c12 , the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.
　また、Ｒｃ１１とＲｃ１２とが結合して形成し得る環構造としては、複素環が挙げられる。この複素環としては、少なくとも窒素原子を含む５員環以上、好ましくは５～７員環の複素環が挙げられる。この複素環には縮合環が含まれていてもよい。複素環の例としては、ピペリジン環、モルホリン環、チオモルホリン環等が挙げられる。 A ring structure that can be formed by combining R c11 and R c12 includes a heterocyclic ring. Examples of the heterocyclic ring include 5-membered or more, preferably 5- to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like.
　これらの中でも、Ｒｃ２としては、メチル基、エチル基、プロピル基、フェニル基であることが最も好ましい。 Among these, R c2 is most preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.
　上記式（ｃ－１）中、Ｒｃ３は、１価の有機基を示す。この有機基としては、炭素数１～６のアルキル基、置換基を有していてもよい炭素数６～１２のアリール基、下記式（ｃ－２）で表される基、又は置換基を有していてもよい複素環基が好ましい。置換基としては、上記Ｒｃ１の場合と同様の基が挙げられる。炭素数６～１２のアリール基としては、フェニル基、ナフチル基、アントリル基、フェナントリル基等が挙げられる。 In the above formula (c-1), R c3 represents a monovalent organic group. Examples of the organic group include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (c-2), or a substituent. The heterocyclic group which may have is preferable. Examples of the substituent include the same groups as in R c1 above. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　上記式（ｃ－２）中、Ｒｃ１３は、酸素原子で中断されていてもよい炭素数１～５のアルキレン基を示す。このようなアルキレン基としては、メチレン基、エチレン基、ｎ－プロピレン基、イソプロピレン基、ｎ－ブチレン基、イソブチレン基、ｓｅｃ－ブチレン基、ｎ－ペンチレン基、イソペンチレン基、ｓｅｃ－ペンチレン基等の直鎖状又は分枝鎖状の基が挙げられる。これらの中でも、Ｒｃ１３はイソプロピレン基であることが最も好ましい。 In the above formula (c-2), R c13 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of such an alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, an n-pentylene group, an isopentylene group, and a sec-pentylene group. A linear or branched group is mentioned. Among these, R c13 is most preferably an isopropylene group.
　上記式（ｃ－２）中、Ｒｃ１４は、－ＮＲｃ１５Ｒｃ１６で表される１価の有機基を示す（Ｒｃ１５及びＲｃ１６は、それぞれ独立に１価の有機基を示す）。そのような有機基の中でも、Ｒｃ１４の構造が下記式（ｃ－３）で表されるものであれば、光重合開始剤の溶解性を向上することができる点で好ましい。 In the above formula (c-2), R c14 represents a monovalent organic group represented by —NR c15 R c16 (R c15 and R c16 each independently represents a monovalent organic group). Among such organic groups, it is preferable that the structure of R c14 is represented by the following formula (c-3) because the solubility of the photopolymerization initiator can be improved.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記式（ｃ－３）中、Ｒｃ１７及びＲｃ１８は、それぞれ独立に炭素数１～５のアルキル基を示す。このようなアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基等が挙げられる。これらの中でも、Ｒｃ１７及びＲｃ１８はメチル基であることが最も好ましい。 In the above formula (c-3), R c17 and R c18 each independently represents an alkyl group having 1 to 5 carbon atoms. Such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec- Examples thereof include a pentyl group and a tert-pentyl group. Among these, R c17 and R c18 are most preferably a methyl group.
　Ｒｃ３における複素環基としては、窒素原子、硫黄原子、及び酸素原子の少なくとも１つの原子を含む５員環以上、好ましくは５員環又は６員環の複素環基が挙げられる。複素環基の例としては、ピロリル基、イミダゾリル基、ピラゾリル基等の含窒素５員環基；ピリジル基、ピラジニル基、ピリミジル基、ピリダジニル基等の含窒素６員環基；チアゾリル基、イソチアゾリル基等の含窒素含硫黄基；オキサゾリル基、イソオキサゾリル基等の含窒素含酸素基；チエニル基、チオピラニル基等の含硫黄基；フリル基、ピラニル基等の含酸素基；等が挙げられる。この中でも、窒素原子又は硫黄原子を１つ含むものが好ましい。この複素環には縮合環が含まれていてもよい。縮合環が含まれる複素環基の例としてはベンゾチエニル基等が挙げられる。 Examples of the heterocyclic group for R c3 include 5-membered or more, preferably 5-membered or 6-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group.
　また、複素環基は置換基を有していてもよい。置換基としては、上記Ｒｃ１の場合と同様の基が挙げられる。 Moreover, the heterocyclic group may have a substituent. Examples of the substituent include the same groups as in R c1 above.
　上記式（ｃ－１）中、Ｒｃ４は、１価の有機基を示す。この中でも、炭素数１～５のアルキル基であることが好ましい。このようなアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基等が挙げられる。これらの中でも、Ｒｃ４はメチル基であることが最も好ましい。 In the above formula (c-1), R c4 represents a monovalent organic group. Among these, an alkyl group having 1 to 5 carbon atoms is preferable. Such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec- Examples thereof include a pentyl group and a tert-pentyl group. Among these, R c4 is most preferably a methyl group.
　また、オキシム系光重合開始剤の好ましい他の例としては、特開２０１０－１５０２５号公報で提案されている下記式（ｃ－４）で表される光重合開始剤が挙げられる。 Further, another preferred example of the oxime photopolymerization initiator includes a photopolymerization initiator represented by the following formula (c-4) proposed in Japanese Patent Application Laid-Open No. 2010-15025.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記式（ｃ－４）中、Ｒｃ２１及びＲｃ２２は、それぞれ独立に、Ｒｃ３１、ＯＲｃ３１、ＣＯＲｃ３１、ＳＲｃ３１、ＣＯＮＲｃ３２Ｒｃ３３、又はＣＮを示す。 In the formula (c-4), R c21 and R c22 each independently represent R c31 , OR c31 , COR c31 , SR c31 , CONR c32 R c33 , or CN.
　Ｒｃ３１、Ｒｃ３２、及びＲｃ３３は、それぞれ独立に水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は炭素数２～２０の複素環基を示す。アルキル基、アリール基、アリールアルキル基、及び複素環基の水素原子は、更にＯＲｃ４１、ＣＯＲｃ４１、ＳＲｃ４１、ＮＲｃ４２Ｒｃ４３、ＣＯＮＲｃ４２Ｒｃ４３、－ＮＲｃ４２－ＯＲｃ４３、－ＮＣＯＲｃ４２－ＯＣＯＲｃ４３、－Ｃ（＝Ｎ－ＯＲｃ４１）－Ｒｃ４２、－Ｃ（＝Ｎ－ＯＣＯＲｃ４１）－Ｒｃ４２、ＣＮ、ハロゲン原子、－ＣＲｃ４１＝ＣＲｃ４２Ｒｃ４３、－ＣＯ－ＣＲｃ４１＝ＣＲｃ４２Ｒｃ４３、カルボキシル基、又はエポキシ基で置換されていてもよい。Ｒｃ４１、Ｒｃ４２、及びＲｃ４３は、それぞれ独立に水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基、又は炭素数２～２０の複素環基を示す。 R c31 , R c32 , and R c33 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 20 heterocyclic groups are shown. Alkyl group, aryl group, arylalkyl group, and a hydrogen atom of the heterocyclic group, further OR c41, COR c41, SR c41 , NR c42 R c43, CONR c42 R c43, -NR c42 -OR c43, -NCOR c42 - OCOR c43, -C (= N- OR c41) -R c42, -C (= N-OCOR c41) -R c42, CN, halogen atom, -CR c41 = CR c42 R c43 , -CO-CR c41 = CR It may be substituted with c42 R c43 , a carboxyl group, or an epoxy group. R c41, R c 42, and R c43 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon number of 2 to 20 heterocyclic groups are shown.
　上記Ｒｃ３１、Ｒｃ３２、Ｒｃ３３、Ｒｃ４１、Ｒｃ４２、及びＲｃ４３における置換基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合、又はウレタン結合により１～５回中断されていてもよく、上記置換基のアルキル部分は分岐鎖があってもよく、環状アルキルであってもよく、上記置換基のアルキル末端は不飽和結合であってもよく、また、Ｒｃ３２とＲｃ３３、及びＲｃ４２とＲｃ４３はそれぞれ結合して環構造を形成していてもよい。 Methylene groups in the alkylene moiety of the substituents on the R c31, R c32, R c33 , R c41, R c42, and R c43 are unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or The substituent may be interrupted 1 to 5 times, the alkyl part of the substituent may be branched or cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. At best, also, R c32 and R c33, and R c 42 and R c43 may form a ring structure, respectively.
　上記式（ｃ－４）中、Ｒｃ２３及びＲｃ２４は、それぞれ独立に、Ｒｃ３１、ＯＲｃ３１、ＣＯＲｃ３１、ＳＲｃ３１、ＣＯＮＲｃ３２Ｒｃ３３、ＮＲｃ３１ＣＯＲｃ３２、ＯＣＯＲｃ３１、ＣＯＯＲｃ３１、ＳＣＯＲｃ３１、ＯＣＳＲｃ３１、ＣＯＳＲｃ３１、ＣＳＯＲｃ３１、ＣＮ、ハロゲン原子、又は水酸基を示す。ａ及びｂは、それぞれ独立に０～４の整数を示す。
　Ｒｃ２３は、－Ｘｃ２－を介して隣接するベンゼン環の炭素原子の１つと結合して環構造を形成していてもよく、Ｒｃ２３とＲｃ２４とが結合して環構造を形成していてもよい。 In the above formula (c-4), R c23 and R c24 each independently represent R c31 , OR c31 , COR c31 , SR c31 , CONR c32 R c33 , NR c31 COR c32 , OCOR c31 , COOR c31 , SCOR c31 , OCSR c31 , COSR c31 , CSOR c31 , CN, a halogen atom, or a hydroxyl group. a and b each independently represent an integer of 0 to 4.
R c23 may be bonded to one of the adjacent carbon atoms of the benzene ring via —X c2 — to form a ring structure, and R c23 and R c24 are bonded to form a ring structure. May be.
　上記式（ｃ－４）中、Ｘｃ１は、単結合又はＣＯを示す。 In the above formula (c-4), X c1 represents a single bond or CO.
　上記式（ｃ－４）中、Ｘｃ２は、酸素原子、硫黄原子、セレン原子、ＣＲｃ５１Ｒｃ５２、ＣＯ、ＮＲｃ５３、又はＰＲｃ５４を示す。Ｒｃ５１、Ｒｃ５２、Ｒｃ５３、及びＲｃ５４は、それぞれ独立に、Ｒｃ３１、ＯＲｃ３１、ＣＯＲｃ３１、ＳＲｃ３１、ＣＯＮＲｃ３２Ｒｃ３３、又はＣＮを示す。Ｒｃ５１、Ｒｃ５３、及びＲｃ５４は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環構造を形成していてもよい。 In the above formula (c-4), X c2 represents an oxygen atom, a sulfur atom, a selenium atom, CR c51 R c52 , CO, NR c53 , or PR c54 . R c51 , R c52 , R c53 , and R c54 each independently represent R c31 , OR c31 , COR c31 , SR c31 , CONR c32 R c33 , or CN. R c51 , R c53 , and R c54 may each independently form a ring structure together with any adjacent benzene ring.
　上記式（ｃ－４）中、Ｒｃ３１、Ｒｃ３２、Ｒｃ３３、Ｒｃ４１、Ｒｃ４２、及びＲｃ４３におけるアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基等が挙げられる。 In the formula (c-4), as the alkyl group in R c31, R c32, R c33 , R c41, R c42, and R c43, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group and the like.
　上記式（ｃ－４）中、Ｒｃ３１、Ｒｃ３２、Ｒｃ３３、Ｒｃ４１、Ｒｃ４２、及びＲｃ４３におけるアリール基としては、フェニル基、トリル基、キシリル基、エチルフェニル基、クロロフェニル基、ナフチル基、アンスリル基、フェナンスレニル基等が挙げられる。 In the formula (c-4), the aryl group in R c31, R c32, R c33 , R c41, R c42, and R c43, a phenyl group, a tolyl group, xylyl group, ethylphenyl group, a chlorophenyl group, a naphthyl Group, anthryl group, phenanthrenyl group and the like.
　上記式（ｃ－４）中、Ｒｃ３１、Ｒｃ３２、Ｒｃ３３、Ｒｃ４１、Ｒｃ４２、及びＲｃ４３におけるアリールアルキル基としては、ベンジル基、クロロベンジル基、α－メチルベンジル基、α，α－ジメチルベンジル基、フェニルエチル基、フェニルエテニル基等が挙げられる。 In the formula (c-4), the aryl group in R c31, R c32, R c33 , R c41, R c42, and R c43, benzyl group, chlorobenzyl group, alpha-methylbenzyl, alpha, alpha -Dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.
　上記式（ｃ－４）中、Ｒｃ３１、Ｒｃ３２、Ｒｃ３３、Ｒｃ４１、Ｒｃ４２、及びＲｃ４３における複素環基としては、ピリジル基、ピリミジル基、フリル基、チエニル基、テトラヒドロフリル基、ジオキソラニル基、ベンゾオキサゾール－２－イル基、テトラヒドロピラニル基、ピロリジル基、イミダゾリジル基、ピラゾリジル基、チアゾリジル基、イソチアゾリジル基、オキサゾリジル基、イソオキサゾリジル基、ピペリジル基、ピペラジル基、モルホリニル基等の５～７員環が好ましく挙げられる。 In the formula (c-4), as the heterocyclic group in R c31, R c32, R c33 , R c41, R c42, and R c43, pyridyl group, pyrimidyl group, furyl group, a thienyl group, a tetrahydrofuryl group, Dioxolanyl group, benzooxazol-2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidyl group, pyrazolidyl group, thiazolidyl group, isothiazolidyl group, oxazolidyl group, isoxazolidyl group, piperidyl group, piperazyl group, morpholinyl group, etc. A 5- to 7-membered ring is preferred.
　上記式（ｃ－４）中、Ｒｃ３２とＲｃ３３とが結合して形成し得る環、Ｒｃ４２とＲｃ４３とが結合して形成し得る環、及びＲｃ２３が隣接するベンゼン環と一緒になって形成し得る環としては、シクロペンタン環、シクロヘキサン環、シクロペンテン環、ベンゼン環、ピペリジン環、モルホリン環、ラクトン環、ラクタム環等の５～７員環が挙げられる。
　なお、Ｘｃ２がＮＲｃ５３であり、Ｒｃ２３が隣接するベンゼン環の炭素原子の１つと結合して、Ｘｃ２とともに５員環構造を形成する場合、光重合開始剤はカルバゾール骨格を有することになる。 In the formula (c-4), the ring and R c32 and R c33 may be formed by combining the ring and the R c 42 and R c43 may be formed by bonding, and together with the benzene ring to which R c23 is adjacent Examples of the ring that can be formed include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.
When X c2 is NR c53 and R c23 is bonded to one of the adjacent carbon atoms of the benzene ring to form a 5-membered ring structure together with X c2 , the photopolymerization initiator has a carbazole skeleton. Become.
　上記式（ｃ－４）中、Ｒｃ３１、Ｒｃ３２、Ｒｃ３３、Ｒｃ４１、Ｒｃ４２、及びＲｃ４３を置換してもよいハロゲン原子、及びＲｃ２４、Ｒｃ２５におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 In the formula (c-4), as the halogen atom in R c31, R c32, R c33 , R c41, R c42, and R c43 which may be substituted halogen atoms, and R c24, R c25, fluorine atom , Chlorine atom, bromine atom and iodine atom.
　上記置換基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合、又はウレタン結合により１～５回中断されていてもよい。この場合、中断する結合基は１種又は２種以上の基でもよく、連続して中断し得る基の場合は２つ以上連続して中断してもよい。また、上記置換基のアルキル部分は分岐鎖があってもよく、環状アルキルであってもよく、上記置換基のアルキル末端は不飽和結合であってもよい。 The methylene group in the alkylene part of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond. In this case, the linking group to be interrupted may be one type or two or more groups, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted continuously. In addition, the alkyl part of the substituent may have a branched chain or may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.
　オキシム系光重合開始剤の好ましい更に他の例としては、下記式（２）で表されるオキシムエステル化合物が挙げられる。 Still another preferred example of the oxime photopolymerization initiator is an oxime ester compound represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000018
 （式中、Ｒｄ１は、１価の有機基、アミノ基、ハロゲン原子、ニトロ基、及びシアノ基からなる群より選択される基であり、ｉは０～４の整数であり、ｊは０又は１であり、Ｒｄ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、Ｒｄ３は、水素原子又は炭素数１～６のアルキル基である。）
Figure JPOXMLDOC01-appb-C000018
 Wherein R d1 is a group selected from the group consisting of a monovalent organic group, amino group, halogen atom, nitro group, and cyano group, i is an integer of 0 to 4, and j is 0 Or R d2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent, and R d3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. is there.)
　上記式（２）中、Ｒｄ１が１価の有機基である場合、Ｒｄ１は、本発明の目的を阻害しない範囲で特に限定されず、種々の有機基から適宜選択される。Ｒｄ１が有機基である場合の好適な例としては、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、飽和脂肪族アシル基、アルコキシカルボニル基、飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよいフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよいナフチルアルキル基、置換基を有してもよいヘテロシクリル基、１又は２の有機基で置換されたアミノ基、モルホリン－１－イル基、及びピペラジン－１－イル基等が挙げられる。ｉが２～４の整数である場合、Ｒｄ１は同一であっても異なっていてもよい。また、置換基の炭素数には、置換基が更に有する置換基の炭素数は含まない。 In the above formula (2), when R d1 is a monovalent organic group, R d1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples when R d1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthoxycarbonyl group which may have, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, Or an amino group substituted with two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. When i is an integer of 2 to 4, R d1 may be the same or different. Moreover, the carbon number of the substituent does not include the carbon number of the substituent that the substituent further has.
　Ｒｄ１がアルキル基である場合、その炭素数は１～２０が好ましく、１～６がより好ましい。また、Ｒｄ１がアルキル基である場合、直鎖であっても、分岐鎖であってもよい。Ｒｄ１がアルキル基である場合の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、イソオクチル基、ｓｅｃ－オクチル基、ｔｅｒｔ－オクチル基、ｎ－ノニル基、イソノニル基、ｎ－デシル基、及びイソデシル基等が挙げられる。また、Ｒｄ１がアルキル基である場合、アルキル基は炭素鎖中にエーテル結合（－Ｏ－）を含んでいてもよい。炭素鎖中にエーテル結合を有するアルキル基の例としては、メトキシエチル基、エトキシエチル基、メトキシエトキシエチル基、エトキシエトキシエチル基、プロピルオキシエトキシエチル基、及びメトキシプロピル基等が挙げられる。 When R d1 is an alkyl group, the carbon number thereof is preferably 1-20, and more preferably 1-6. Further, when R d1 is an alkyl group, it may be linear or branched. Specific examples in the case where R d1 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples include n-decyl group and isodecyl group. When R d1 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
　Ｒｄ１がアルコキシ基である場合、その炭素数は１～２０が好ましく、１～６がより好ましい。また、Ｒｄ１がアルコキシ基である場合、直鎖であっても、分岐鎖であってもよい。Ｒｄ１がアルコキシ基である場合の具体例としては、メトキシ基、エトキシ基、ｎ－プロピルオキシ基、イソプロピルオキシ基、ｎ－ブチルオキシ基、イソブチルオキシ基、ｓｅｃ－ブチルオキシ基、ｔｅｒｔ－ブチルオキシ基、ｎ－ペンチルオキシ基、イソペンチルオキシ基、ｓｅｃ－ペンチルオキシ基、ｔｅｒｔ－ペンチルオキシ基、ｎ－ヘキシルオキシ基、ｎ－ヘプチルオキシ基、ｎ－オクチルオキシ基、イソオクチルオキシ基、ｓｅｃ－オクチオキシル基、ｔｅｒｔ－オクチルオキシ基、ｎ－ノニルオキシ基、イソノニルオキシ基、ｎ－デシルオキシ基、及びイソデシルオキシ基等が挙げられる。また、Ｒｄ１がアルコキシ基である場合、アルコキシ基は炭素鎖中にエーテル結合（－Ｏ－）を含んでいてもよい。炭素鎖中にエーテル結合を有するアルコキシ基の例としては、メトキシエトキシ基、エトキシエトキシ基、メトキシエトキシエトキシ基、エトキシエトキシエトキシ基、プロピルオキシエトキシエトキシ基、及びメトキシプロピルオキシ基等が挙げられる。 When R d1 is an alkoxy group, the carbon number thereof is preferably 1-20, and more preferably 1-6. Further, when R d1 is an alkoxy group, it may be linear or branched. Specific examples when R d1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octoxyl group, Examples thereof include a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. When R d1 is an alkoxy group, the alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.
　Ｒｄ１がシクロアルキル基又はシクロアルコキシ基である場合、その炭素数は３～１０が好ましく、３～６がより好ましい。Ｒｄ１がシクロアルキル基である場合の具体例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、及びシクロオクチル基等が挙げられる。Ｒｄ１がシクロアルコキシ基である場合の具体例としては、シクロプロピルオキシ基、シクロブチルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロヘプチルオキシ基、及びシクロオクチルオキシ基等が挙げられる。 When R d1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 to 10, and more preferably 3 to 6. Specific examples in the case where R d1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples in the case where R d1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, and the like.
　Ｒｄ１が飽和脂肪族アシル基又は飽和脂肪族アシルオキシ基である場合、その炭素数は２～２０が好ましく、２～７がより好ましい。Ｒｄ１が飽和脂肪族アシル基である場合の具体例としては、アセチル基、プロパノイル基、ｎ－ブタノイル基、２－メチルプロパノイル基、ｎ－ペンタノイル基、２，２－ジメチルプロパノイル基、ｎ－ヘキサノイル基、ｎ－ヘプタノイル基、ｎ－オクタノイル基、ｎ－ノナノイル基、ｎ－デカノイル基、ｎ－ウンデカノイル基、ｎ－ドデカノイル基、ｎ－トリデカノイル基、ｎ－テトラデカノイル基、ｎ－ペンタデカノイル基、及びｎ－ヘキサデカノイル基等が挙げられる。Ｒｄ１が飽和脂肪族アシルオキシ基である場合の具体例としては、アセチルオキシ基、プロパノイルオキシ基、ｎ－ブタノイルオキシ基、２－メチルプロパノイルオキシ基、ｎ－ペンタノイルオキシ基、２，２－ジメチルプロパノイルオキシ基、ｎ－ヘキサノイルオキシ基、ｎ－ヘプタノイルオキシ基、ｎ－オクタノイルオキシ基、ｎ－ノナノイルオキシ基、ｎ－デカノイルオキシ基、ｎ－ウンデカノイルオキシ基、ｎ－ドデカノイルオキシ基、ｎ－トリデカノイルオキシ基、ｎ－テトラデカノイルオキシ基、ｎ－ペンタデカノイルオキシ基、及びｎ－ヘキサデカノイルオキシ基等が挙げられる。 When R d1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the carbon number thereof is preferably 2-20, and more preferably 2-7. Specific examples of the case where R d1 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane group Examples include a noyl group and an n-hexadecanoyl group. Specific examples in the case where R d1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.
　Ｒｄ１がアルコキシカルボニル基である場合、その炭素数は２～２０が好ましく、２～７がより好ましい。Ｒｄ１がアルコキシカルボニル基である場合の具体例としては、メトキシカルボニル基、エトキシカルボニル基、ｎ－プロピルオキシカルボニル基、イソプロピルオキシカルボニル基、ｎ－ブチルオキシカルボニル基、イソブチルオキシカルボニル基、ｓｅｃ－ブチルオキシカルボニル基、ｔｅｒｔ－ブチルオキシカルボニル基、ｎ－ペンチルオキシカルボニル基、イソペンチルオキシカルボニル基、ｓｅｃ－ペンチルオキシカルボニル基、ｔｅｒｔ－ペンチルオキシカルボニル基、ｎ－ヘキシルオキシカルボニル基、ｎ－ヘプチルオキシカルボニル基、ｎ－オクチルオキシカルボニル基、イソオクチルオキシカルボニル基、ｓｅｃ－オクチオキシルカルボニル基、ｔｅｒｔ－オクチルオキシカルボニル基、ｎ－ノニルオキシカルボニル基、イソノニルオキシカルボニル基、ｎ－デシルオキシカルボニル基、及びイソデシルオキシカルボニル基等が挙げられる。 When R d1 is an alkoxycarbonyl group, the carbon number thereof is preferably 2 to 20, and more preferably 2 to 7. Specific examples of the case where R d1 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.
　Ｒｄ１がフェニルアルキル基である場合、その炭素数は７～２０が好ましく、７～１０がより好ましい。またＲｄ１がナフチルアルキル基である場合、その炭素数は１１～２０が好ましく、１１～１４がより好ましい。Ｒｄ１がフェニルアルキル基である場合の具体例としては、ベンジル基、２－フェニルエチル基、３－フェニルプロピル基、及び４－フェニルブチル基が挙げられる。Ｒｄ１がナフチルアルキル基である場合の具体例としては、α－ナフチルメチル基、β－ナフチルメチル基、２－（α－ナフチル）エチル基、及び２－（β－ナフチル）エチル基が挙げられる。Ｒｄ１が、フェニルアルキル基又はナフチルアルキル基である場合、Ｒｄ１は、フェニル基又はナフチル基上に更に置換基を有していてもよい。 When R d1 is a phenylalkyl group, the carbon number thereof is preferably 7-20, and more preferably 7-10. Further, when R d1 is a naphthylalkyl group, the carbon number thereof is preferably 11-20, and more preferably 11-14. Specific examples when R d1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R d1 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R d1 is a phenylalkyl group or a naphthylalkyl group, R d1 may further have a substituent on the phenyl group or naphthyl group.
　Ｒｄ１がヘテロシクリル基である場合、ヘテロシクリル基は、Ｎ、Ｓ、及びＯの合計の個数が１個以上である５員又は６員の単環であるか、かかる単環同士、又はかかる単環とベンゼン環とが縮合したヘテロシクリル基である。ヘテロシクリル基が縮合環である場合は、環数３までのものとする。かかるヘテロシクリル基を構成する複素環としては、フラン、チオフェン、ピロール、オキサゾール、イソオキサゾール、チアゾール、チアジアゾール、イソチアゾール、イミダゾール、ピラゾール、トリアゾール、ピリジン、ピラジン、ピリミジン、ピリダジン、ベンゾフラン、ベンゾチオフェン、インドール、イソインドール、インドリジン、ベンゾイミダゾール、ベンゾトリアゾール、ベンゾオキサゾール、ベンゾチアゾール、カルバゾール、プリン、キノリン、イソキノリン、キナゾリン、フタラジン、シンノリン、及びキノキサリン等が挙げられる。Ｒｄ１がヘテロシクリル基である場合、ヘテロシクリル基は更に置換基を有していてもよい。 When R d1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle in which the total number of N, S, and O is 1 or more, such monocycles, or such monocycles Is a heterocyclyl group in which a benzene ring is condensed. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R d1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.
　Ｒｄ１が１又は２の有機基で置換されたアミノ基である場合、有機基の好適な例は、炭素数１～２０のアルキル基、炭素数３～１０のシクロアルキル基、炭素数２～２０の飽和脂肪族アシル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、及びヘテロシクリル基等が挙げられる。これらの好適な有機基の具体例は、Ｒｄ１と同様である。１又は２の有機基で置換されたアミノ基の具体例としては、メチルアミノ基、エチルアミノ基、ジエチルアミノ基、ｎ－プロピルアミノ基、ジ－ｎ－プロピルアミノ基、イソプロピルアミノ基、ｎ－ブチルアミノ基、ジ－ｎ－ブチルアミノ基、ｎ－ペンチルアミノ基、ｎ－ヘキシルアミノ基、ｎ－ヘプチルアミノ基、ｎ－オクチルアミノ基、ｎ－ノニルアミノ基、ｎ－デシルアミノ基、フェニルアミノ基、ナフチルアミノ基、アセチルアミノ基、プロパノイルアミノ基、ｎ－ブタノイルアミノ基、ｎ－ペンタノイルアミノ基、ｎ－ヘキサノイルアミノ基、ｎ－ヘプタノイルアミノ基、ｎ－オクタノイルアミノ基、ｎ－デカノイルアミノ基、ベンゾイルアミノ基、α－ナフトイルアミノ基、及びβ－ナフトイルアミノ基等が挙げられる。 When R d1 is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and 2 to 20 saturated aliphatic acyl groups, optionally substituted phenyl groups, optionally substituted benzoyl groups, optionally substituted C 7-20 phenylalkyl groups, substituents A naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these suitable organic groups are the same as those for R d1 . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, and n-butyl. Amino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthyl Amino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-deca Examples include a noylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.
　Ｒｄ１に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合の置換基としては、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～７の飽和脂肪族アシル基、炭素数２～７のアルコキシカルボニル基、炭素数２～７の飽和脂肪族アシルオキシ基、炭素数１～６のアルキル基を有するモノアルキルアミノ基、炭素数１～６のアルキル基を有するジアルキルアミノ基、モルホリン－１－イル基、ピペラジン－１－イル基、ハロゲン原子、ニトロ基、及びシアノ基等が挙げられる。Ｒｄ１に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合、その置換基の数は、本発明の目的を阻害しない範囲で限定されないが、１～４が好ましい。Ｒｄ１に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が、複数の置換基を有する場合、複数の置換基は、同一であっても異なっていてもよい。 In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R d1 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to A saturated aliphatic acyl group having 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms And a dialkylamino group having an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R d1 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R d1 have a plurality of substituents, the plurality of substituents may be the same or different.
　Ｒｄ１の中では、化学的に安定であることや、立体的な障害が少なく、オキシムエステル化合物の合成が容易であることや、溶媒に対する溶解性が高いこと等から、ニトロ基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、及び炭素数２～７の飽和脂肪族アシル基からなる群より選択される基が好ましく、ニトロ基又は炭素数１～６のアルキルがより好ましく、ニトロ基又はメチル基が特に好ましい。 Among R d1 , since it is chemically stable, has few steric hindrances, is easy to synthesize an oxime ester compound, and has high solubility in a solvent, it has a nitro group and a carbon number of 1 Is preferably a group selected from the group consisting of an alkyl group having ˜6, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms, more preferably a nitro group or an alkyl having 1 to 6 carbon atoms. Preferably, a nitro group or a methyl group is particularly preferable.
　Ｒｄ１がフェニル基に結合する位置は、Ｒｄ１が結合するフェニル基について、フェニル基とオキシムエステル化合物の主骨格との結合手の位置を１位とし、メチル基の位置を２位とする場合に、４位又は５位が好ましく、５位がよりに好ましい。また、ｉは、０～３の整数が好ましく、０～２の整数がより好ましく、０又は１が特に好ましい。 Position R d1 is bonded to the phenyl group, the phenyl group R d1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. Further, i is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.
　Ｒｄ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基である。また、Ｒｄ２が置換基を有してもよいカルバゾリル基である場合、カルバゾリル基上の窒素原子は、炭素数１～６のアルキル基で置換されていてもよい。 R d2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. In addition, when R d2 is an optionally substituted carbazolyl group, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.
　Ｒｄ２において、フェニル基又はカルバゾリル基が有する置換基は、本発明の目的を阻害しない範囲で特に限定されない。フェニル基又はカルバゾリル基が、炭素原子上に有してもよい好適な置換基の例としては、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数３～１０のシクロアルキル基、炭素数３～１０のシクロアルコキシ基、炭素数２～２０の飽和脂肪族アシル基、炭素数２～２０のアルコキシカルボニル基、炭素数２～２０の飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいフェニルチオ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、置換基を有してもよいヘテロシクリルカルボニル基、アミノ基、１又は２の有機基で置換されたアミノ基、モルホリン－１－イル基、及びピペラジン－１－イル基、ハロゲン原子、ニトロ基、及びシアノ基等が挙げられる。 In R d2 , the substituent that the phenyl group or carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and cyclohexane having 3 to 10 carbon atoms. An alkyl group, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, and a substituent. Phenyl group which may have, phenoxy group which may have substituent, phenylthio group which may have substituent, benzoyl group which may have substituent, phenoxy which may have substituent A carbonyl group, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Good naphthoxy A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, 20 naphthylalkyl groups, optionally substituted heterocyclyl groups, optionally substituted heterocyclylcarbonyl groups, amino groups, amino groups substituted with 1 or 2 organic groups, morpholin-1-yl Group, piperazin-1-yl group, halogen atom, nitro group, cyano group and the like.
　Ｒｄ２がカルバゾリル基である場合、カルバゾリル基が窒素原子上に有してもよい好適な置換基の例としては、炭素数１～２０のアルキル基、炭素数３～１０のシクロアルキル基、炭素数２～２０の飽和脂肪族アシル基、炭素数２～２０のアルコキシカルボニル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、及び置換基を有してもよいヘテロシクリルカルボニル基等が挙げられる。これらの置換基の中では、炭素数１～２０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、エチル基が特に好ましい。 When R d2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, carbon atoms A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and a substituent. A good phenoxycarbonyl group, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent A naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, etc. Is I can get lost. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
　フェニル基又はカルバゾリル基が有してもよい置換基の具体例について、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、飽和脂肪族アシル基、アルコキシカルボニル基、飽和脂肪族アシルオキシ基、置換基を有してもよいフェニルアルキル基、置換基を有してもよいナフチルアルキル基、置換基を有してもよいヘテロシクリル基、及び１又は２の有機基で置換されたアミノ基に関しては、Ｒｄ１と同様である。 Specific examples of the substituent that the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. For a phenylalkyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted with one or two organic groups, R It is the same as d1 .
　Ｒｄ２において、フェニル基又はカルバゾリル基が有する置換基に含まれるフェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合の置換基の例としては、炭素数１～６のアルキル基；炭素数１～６のアルコキシ基；炭素数２～７の飽和脂肪族アシル基；炭素数２～７のアルコキシカルボニル基；炭素数２～７の飽和脂肪族アシルオキシ基；フェニル基；ナフチル基；ベンゾイル基；ナフトイル基；炭素数１～６のアルキル基、モルホリン－１－イル基、ピペラジン－１－イル基、及びフェニル基からなる群より選択される基により置換されたベンゾイル基；炭素数１～６のアルキル基を有するモノアルキルアミノ基；炭素数１～６のアルキル基を有するジアルキルアミノ基；モルホリン－１－イル基；ピペラジン－１－イル基；ハロゲン原子；ニトロ基；シアノ基が挙げられる。フェニル基又はカルバゾリル基が有する置換基に含まれるフェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合、その置換基の数は、本発明の目的を阻害しない範囲で限定されないが、１～４が好ましい。フェニル基、ナフチル基、及びヘテロシクリル基が、複数の置換基を有する場合、複数の置換基は、同一であっても異なっていてもよい。 Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent that the phenyl group or carbazolyl group has in R d2 further have a substituent include an alkyl group having 1 to 6 carbon atoms; Alkoxy group having 1 to 6 carbon atoms; saturated aliphatic acyl group having 2 to 7 carbon atoms; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; 1 to 6 carbon atoms; A monoalkylamino group having 1 to 6 carbon atoms; a dialkylamino group having 1 to 6 carbon atoms; a morpholin-1-yl group; a piperazine-1- Yl group; halogen atom; nitro group; cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent that the phenyl group or carbazolyl group has further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. ~ 4 are preferred. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.
　Ｒｄ２の中では、ネガ型感放射線性組成物１が感度に優れる点から、下記式（３）又は（４）で表される基が好ましく、下記式（３）で表される基がより好ましく、下記式（３）で表される基であって、ＡがＳである基が特に好ましい。 Among R d2, the group represented by the following formula (3) or (4) is preferable, and the group represented by the following formula (3) is more preferable because the negative radiation-sensitive composition 1 is excellent in sensitivity. A group represented by the following formula (3), in which A is S, is particularly preferable.
Figure JPOXMLDOC01-appb-C000019
 （Ｒｄ４は、１価の有機基、アミノ基、ハロゲン原子、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｋは、０～４の整数である。）
Figure JPOXMLDOC01-appb-C000019
 (R d4 is a group selected from the group consisting of a monovalent organic group, amino group, halogen atom, nitro group, and cyano group, A is S or O, and k is an integer of 0-4. .)
Figure JPOXMLDOC01-appb-C000020
 （Ｒｄ５及びＲｄ６は、１価の有機基であり、同一であっても異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000020
 (R d5 and R d6 are monovalent organic groups, which may be the same or different.)
　式（３）におけるＲｄ４が有機基である場合、本発明の目的を阻害しない範囲で、種々の有機基から選択できる。式（３）においてＲｄ４が有機基である場合の好適な例としては、炭素数１～６のアルキル基；炭素数１～６のアルコキシ基；炭素数２～７の飽和脂肪族アシル基；炭素数２～７のアルコキシカルボニル基；炭素数２～７の飽和脂肪族アシルオキシ基；フェニル基；ナフチル基；ベンゾイル基；ナフトイル基；炭素数１～６のアルキル基、モルホリン－１－イル基、ピペラジン－１－イル基、及びフェニル基からなる群より選択される基により置換されたベンゾイル基；炭素数１～６のアルキル基を有するモノアルキルアミノ基；炭素数１～６のアルキル基を有するジアルキルアミノ基；モルホリン－１－イル基；ピペラジン－１－イル基；ハロゲン原子；ニトロ基；シアノ基が挙げられる。 When R d4 in the formula (3) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. In the formula (3), when R d4 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, A benzoyl group substituted by a group selected from the group consisting of a piperazin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms A dialkylamino group; a morpholin-1-yl group; a piperazin-1-yl group; a halogen atom; a nitro group; and a cyano group.
　Ｒｄ４の中では、ベンゾイル基；ナフトイル基；炭素数１～６のアルキル基、モルホリン－１－イル基、ピペラジン－１－イル基、及びフェニル基からなる群より選択される基により置換されたベンゾイル基；ニトロ基が好ましく、ベンゾイル基；ナフトイル基；２－メチルフェニルカルボニル基；４－（ピペラジン－１－イル）フェニルカルボニル基；４－（フェニル）フェニルカルボニル基がより好ましい。 In R d4 , substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.
　また、式（３）において、ｋは、０～３の整数が好ましく、０～２の整数がより好ましく、０又は１であるのが特に好ましい。ｋが１である場合、Ｒｄ４の結合する位置は、Ｒｄ４が結合するフェニル基が原子Ａと結合する結合手に対して、パラ位であるのが好ましい。 In the formula (3), k is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. when k is 1, bond position of R d4, relative bond which the phenyl group R d4 are attached to atoms and bonds A, is preferably in the para position.
　式（４）におけるＲｄ５は、本発明の目的を阻害しない範囲で、種々の有機基から選択できる。Ｒｄ５の好適な例としては、炭素数１～２０のアルキル基、炭素数３～１０のシクロアルキル基、炭素数２～２０の飽和脂肪族アシル基、炭素数２～２０のアルコキシカルボニル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、及び置換基を有してもよいヘテロシクリルカルボニル基等が挙げられる。 R d5 in formula (4) can be selected from various organic groups as long as the object of the present invention is not impaired. Preferable examples of R d5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, Phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, phenylalkyl having 7 to 20 carbon atoms which may have a substituent Group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted carbon number 11 to 20 Naphthylalkyl group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, and the like.
　Ｒｄ５の中では、炭素数１～２０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、エチル基が特に好ましい。 Among R d5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
　式（４）におけるＲｄ６は、本発明の目的を阻害しない範囲で特に限定されず、種々の有機基から選択できる。Ｒｄ６として好適な基の具体例としては、炭素数１～２０のアルキル基、置換基を有してもよいフェニル基、置換基を有してもよいナフチル基、及び置換基を有してもよいヘテロシクリル基が挙げられる。Ｒｄ６として、これらの基の中では置換基を有してもよいフェニル基がより好ましく、２－メチルフェニル基が特に好ましい。 R d6 in formula (4) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of the group suitable as R d6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. Among these groups, R d6 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.
　Ｒｄ４、Ｒｄ５、又はＲｄ６に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合の置換基としては、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～７の飽和脂肪族アシル基、炭素数２～７のアルコキシカルボニル基、炭素数２～７の飽和脂肪族アシルオキシ基、炭素数１～６のアルキル基を有するモノアルキルアミノ基、炭素数１～６のアルキル基を有するジアルキルアミノ基、モルホリン－１－イル基、ピペラジン－１－イル基、ハロゲン原子、ニトロ基、及びシアノ基等が挙げられる。Ｒｄ４、Ｒｄ５、又はＲｄ６に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合、その置換基の数は、本発明の目的を阻害しない範囲で限定されないが、１～４が好ましい。Ｒｄ４、Ｒｄ５、又はＲｄ６に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が、複数の置換基を有する場合、複数の置換基は、同一であっても異なっていてもよい。 When the phenyl group, naphthyl group, and heterocyclyl group contained in R d4 , R d5 , or R d6 further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, or a C 1 to 6 carbon group. Monoalkylamino having an alkoxy group, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R d4 , R d5 , or R d6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, 1 to 4 are preferred. When the phenyl group, naphthyl group, and heterocyclyl group contained in R d4 , R d5 , or R d6 have a plurality of substituents, the plurality of substituents may be the same or different.
　式（２）におけるＲｄ３は、水素原子又は炭素数１～６のアルキル基である。Ｒｄ３としては、メチル基又はエチル基が好ましく、メチル基がより好ましい。Ｒｄ３がメチル基である場合、式（２）で表される化合物からなる光重合開始剤は、特に感度に優れる。 R d3 in the formula (2) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R d3 is preferably a methyl group or an ethyl group, and more preferably a methyl group. When R d3 is a methyl group, the photopolymerization initiator composed of the compound represented by formula (2) is particularly excellent in sensitivity.
　式（２）で表されるオキシムエステル化合物は、ｊが０である場合、例えば、下記スキーム１に従って合成することができる。具体的には、下記式（ｄ１－１）で表される芳香族化合物を、下記式（ｄ１－２）で表されるハロカルボニル化合物を用いて、フリーデルクラフツ反応によりアシル化して、下記式（ｄ１－３）で表されるケトン化合物を得、得られたケトン化合物（ｄ１－３）を、ヒドロキシルアミンによりオキシム化して下記式（ｄ１－４）で表されるオキシム化合物を得、次いで式（ｄ１－４）のオキシム化合物と、下記式（ｄ１－５）で表される酸無水物（（Ｒｄ３ＣＯ）２Ｏ）、又は下記式（ｄ１－６）で表される酸ハライド（Ｒｄ３ＣＯＨａｌ、Ｈａｌはハロゲン原子。）とを反応させて、下記式（ｄ１－７）で表されるオキシムエステル化合物を得ることができる。なお、下記式（ｄ１－２）において、Ｈａｌはハロゲン原子であり、下記式（ｄ１－１）、（ｄ１－２）、（ｄ１－３）、（ｄ１－４）、及び（ｄ１－７）において、Ｒｄ１、Ｒｄ２、Ｒｄ３、及びｉは、式（２）と同様である。 When j is 0, the oxime ester compound represented by the formula (2) can be synthesized according to the following scheme 1, for example. Specifically, an aromatic compound represented by the following formula (d1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (d1-2), and the following formula A ketone compound represented by (d1-3) is obtained, and the resulting ketone compound (d1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (d1-4), The oxime compound (d1-4) and an acid anhydride ((R d3 CO) 2 O) represented by the following formula (d1-5) or an acid halide (R) represented by the following formula (d1-6) An oxime ester compound represented by the following formula (d1-7) can be obtained by reacting with d3 COHal and Hal are halogen atoms. In the following formula (d1-2), Hal is a halogen atom, and the following formulas (d1-1), (d1-2), (d1-3), (d1-4), and (d1-7) , R d1 , R d2 , R d3 , and i are the same as those in the formula (2).
＜スキーム１＞
Figure JPOXMLDOC01-appb-C000021
 <Scheme 1>
Figure JPOXMLDOC01-appb-C000021
　式（２）で表されるオキシムエステル化合物は、ｊが１である場合、例えば、下記スキーム２に従って合成することができる。具体的には、下記式（ｄ２－１）で表されるケトン化合物に、塩酸の存在下に下記式（ｄ２－２）で表される亜硝酸エステル（ＲＯＮＯ、Ｒは炭素数１～６のアルキル基。）を反応させて、下記式（ｄ２－３）で表されるケトオキシム化合物を得、次いで、下記式（ｄ２－３）で表されるケトオキシム化合物と、下記式（ｄ２－４）で表される酸無水物（（Ｒｄ３ＣＯ）２Ｏ）、又は下記式（ｄ２－５）で表される酸ハライド（Ｒｄ３ＣＯＨａｌ、Ｈａｌはハロゲン原子。）とを反応させて、下記式（ｄ２－６）で表されるオキシムエステル化合物を得ることができる。なお、下記式（ｄ２－１）、（ｄ２－３）、（ｄ２－４）、（ｄ２－５）、及び（ｄ２－６）において、Ｒｄ１、Ｒｄ２、Ｒｄ３、及びｉは、式（２）と同様である。 When j is 1, the oxime ester compound represented by the formula (2) can be synthesized, for example, according to the following scheme 2. Specifically, the ketone compound represented by the following formula (d2-1) is added to a nitrite ester (RONO, R represented by the following formula (d2-2) in the presence of hydrochloric acid in the presence of hydrochloric acid. Alkyl group.) To obtain a ketoxime compound represented by the following formula (d2-3), and then a ketoxime compound represented by the following formula (d2-3) and the following formula (d2-4) By reacting with an acid anhydride ((R d3 CO) 2 O) or an acid halide (R d3 COHal, Hal is a halogen atom) represented by the following formula (d2-5): An oxime ester compound represented by d2-6) can be obtained. In the following formulas (d2-1), (d2-3), (d2-4), (d2-5), and (d2-6), R d1 , R d2 , R d3 , and i are the formulas Same as (2).
＜スキーム２＞
Figure JPOXMLDOC01-appb-C000022
 <Scheme 2>
Figure JPOXMLDOC01-appb-C000022
　また、式（２）で表されるオキシムエステル化合物は、ｊが１であり、Ｒｄ１がメチル基であって、Ｒｄ１が結合するベンゼン環に結合するメチル基に対して、Ｒｄ１がパラ位に結合する場合、例えば、下記式（ｄ２－７）で表される化合物を、スキーム１と同様の方法で、オキシム化及びアシル化することによって合成することもできる。なお、下記式（ｄ２－７）において、Ｒｄ２は、式（２）と同様である。 In the oxime ester compound represented by the formula (2), j is 1, R d1 is a methyl group, and R d1 is a para group with respect to a methyl group bonded to a benzene ring to which R d1 is bonded. In the case of bonding to a position, for example, a compound represented by the following formula (d2-7) can also be synthesized by oximation and acylation in the same manner as in Scheme 1. In the following formula (d2-7), R d2 is the same as in formula (2).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（２）で表されるオキシムエステル化合物の中でも特に好適な化合物としては、下記式の化合物が挙げられる。 Among the oxime ester compounds represented by formula (2), particularly preferred compounds include compounds represented by the following formula.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　オキシム系光重合開始剤の好ましい更に他の例としては、「ＩＲＧＡＣＵＲＥ　ＯＸＥ０１」（商品名、ＢＡＳＦ製）が挙げられる。 Still another preferred example of the oxime photopolymerization initiator is “IRGACURE OXE01” (trade name, manufactured by BASF).
　光重合開始剤の含有量は、ネガ型感放射線性組成物１の固形分に対して０．３～２０質量％であることが好ましく、０．５～１５質量％であることがより好ましい。上記の範囲とすることにより、十分な耐熱性、耐薬品性を得ることができ、また塗膜形成能を向上させ、硬化不良を抑制することができる。 The content of the photopolymerization initiator is preferably 0.3 to 20% by mass, and more preferably 0.5 to 15% by mass with respect to the solid content of the negative radiation-sensitive composition 1. By setting it as said range, sufficient heat resistance and chemical-resistance can be acquired, a coating-film formation ability can be improved, and hardening failure can be suppressed.
［着色剤］
　ネガ型感放射線性組成物１は、着色剤を含有してもよい。ネガ型感放射線性組成物１は、着色剤を含有することにより、例えば、液晶表示ディスプレイのカラーフィルタ形成用に好ましく使用される。また、ネガ型感放射線性組成物１は、着色剤として遮光剤を含むことにより、例えば、カラーフィルタにおけるブラックマトリクス形成用や、ブラックフォトスペーサ形成用に好ましく使用される。着色剤は、単独で又は２種以上組み合わせて用いることができる。 [Colorant]
The negative radiation sensitive composition 1 may contain a colorant. The negative radiation-sensitive composition 1 is preferably used, for example, for forming a color filter of a liquid crystal display by containing a colorant. Moreover, the negative radiation sensitive composition 1 contains a light-shielding agent as a colorant, and thus is preferably used, for example, for forming a black matrix in a color filter or for forming a black photo spacer. The colorants can be used alone or in combination of two or more.
　着色剤としては、特に限定されないが、例えば、カラーインデックス（Ｃ．Ｉ．；Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ社発行）においてピグメント（Ｐｉｇｍｅｎｔ）に分類されている化合物、具体的には、下記のようなカラーインデックス（Ｃ．Ｉ．）番号が付されているものを用いることが好ましい。 Although it does not specifically limit as a coloring agent, For example, the compound classified as the pigment (Pigment) in the color index (CI; The Society of Dyers and Colorists company), for example, the following It is preferable to use a color index (CI) number.
　Ｃ．Ｉ．ピグメントイエロー１（以下、「Ｃ．Ｉ．ピグメントイエロー」は同様であり、番号のみを記載する。）、３、１１、１２、１３、１４、１５、１６、１７、２０、２４、３１、５３、５５、６０、６１、６５、７１、７３、７４、８１、８３、８６、９３、９５、９７、９８、９９、１００、１０１、１０４、１０６、１０８、１０９、１１０、１１３、１１４、１１６、１１７、１１９、１２０、１２５、１２６、１２７、１２８、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５１、１５２、１５３、１５４、１５５、１５６、１６６、１６７、１６８、１７５、１８０、１８５；
　Ｃ．Ｉ．ピグメントオレンジ１（以下、「Ｃ．Ｉ．ピグメントオレンジ」は同様であり、番号のみを記載する。）、５、１３、１４、１６、１７、２４、３４、３６、３８、４０、４３、４６、４９、５１、５５、５９、６１、６３、６４、７１、７３；
　Ｃ．Ｉ．ピグメントバイオレット１（以下、「Ｃ．Ｉ．ピグメントバイオレット」は同様であり、番号のみを記載する。）、１９、２３、２９、３０、３２、３６、３７、３８、３９、４０、５０；
　Ｃ．Ｉ．ピグメントレッド１（以下、「Ｃ．Ｉ．ピグメントレッド」は同様であり、番号のみを記載する。）、２、３、４、５、６、７、８、９、１０、１１、１２、１４、１５、１６、１７、１８、１９、２１、２２、２３、３０、３１、３２、３７、３８、４０、４１、４２、４８：１、４８：２、４８：３、４８：４、４９：１、４９：２、５０：１、５２：１、５３：１、５７、５７：１、５７：２、５８：２、５８：４、６０：１、６３：１、６３：２、６４：１、８１：１、８３、８８、９０：１、９７、１０１、１０２、１０４、１０５、１０６、１０８、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４９、１５０、１５１、１５５、１６６、１６８、１７０、１７１、１７２、１７４、１７５、１７６、１７７、１７８、１７９、１８０、１８５、１８７、１８８、１９０、１９２、１９３、１９４、２０２、２０６、２０７、２０８、２０９、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、２４２、２４３、２４５、２５４、２５５、２６４、２６５；
　Ｃ．Ｉ．ピグメントブルー１（以下、「Ｃ．Ｉ．ピグメントブルー」は同様であり、番号のみを記載する。）、２、１５、１５：３、１５：４、１５：６、１６、２２、６０、６４、６６；
　Ｃ．Ｉ．ピグメントグリーン７、Ｃ．Ｉ．ピグメントグリーン３６、Ｃ．Ｉ．ピグメントグリーン３７；
　Ｃ．Ｉ．ピグメントブラウン２３、Ｃ．Ｉ．ピグメントブラウン２５、Ｃ．Ｉ．ピグメントブラウン２６、Ｃ．Ｉ．ピグメントブラウン２８；
　Ｃ．Ｉ．ピグメントブラック１、Ｃ．Ｉ．ピグメントブラック７。 C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 185;
C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same, and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 : 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 : 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 166, 168, 170, 171, 172, 174, 175, 176, 177, 78, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment black 1, C.I. I. Pigment Black 7.
　また、着色剤を遮光剤とする場合、遮光剤としては黒色顔料を用いることが好ましい。黒色顔料としては、カーボンブラック、チタンブラック、銅、鉄、マンガン、コバルト、クロム、ニッケル、亜鉛、カルシウム、銀等の金属酸化物、複合酸化物、金属硫化物、金属硫酸塩、金属炭酸塩等、有機物、無機物を問わず各種の顔料を挙げることができる。これらの中でも、高い遮光性を有するカーボンブラックを用いることが好ましい。 Further, when a colorant is used as a light shielding agent, it is preferable to use a black pigment as the light shielding agent. Black pigments include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, etc. Various pigments can be mentioned regardless of organic matter and inorganic matter. Among these, it is preferable to use carbon black having high light shielding properties.
　カーボンブラックとしては、チャンネルブラック、ファーネスブラック、サーマルブラック、ランプブラック等の公知のカーボンブラックを用いることができるが、遮光性に優れるチャンネルブラックを用いることが好ましい。また、樹脂被覆カーボンブラックを使用してもよい。 As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.
　樹脂被覆カーボンブラックは、樹脂被覆のないカーボンブラックに比べて導電性が低いことから、液晶表示ディスプレイのブラックマトリクスとして使用した場合に電流のリークが少なく、信頼性の高い低消費電力のディスプレイを製造できる。 Resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so when used as a black matrix for liquid crystal display, it produces less current leakage and produces a highly reliable display with low power consumption. it can.
　また、カーボンブラックの色調を調整するために、補助顔料として上記の有機顔料を適宜添加してもよい。 In addition, in order to adjust the color tone of carbon black, the above organic pigment may be added as an auxiliary pigment.
　また、着色剤として顔料を用いる場合、顔料と染料とを併用してもよい。顔料と併用可能な染料としては、キサンテン系染料、シアニン系染料、アゾ系染料、アントラキノン系染料、ジオキサジン系染料、トリフェニルメタン系染料等が挙げられる。 Further, when a pigment is used as a colorant, a pigment and a dye may be used in combination. Examples of dyes that can be used in combination with pigments include xanthene dyes, cyanine dyes, azo dyes, anthraquinone dyes, dioxazine dyes, and triphenylmethane dyes.
　また、着色剤を感放射線性樹脂組成物において均一に分散させるために、更に分散剤を使用してもよい。このような分散剤としては、ポリエチレンイミン系、ウレタン樹脂系、アクリル樹脂系の高分子分散剤を用いることが好ましい。特に、着色剤としてカーボンブラックを用いる場合には、分散剤としてアクリル樹脂系の分散剤を用いることが好ましい。 Further, in order to uniformly disperse the colorant in the radiation sensitive resin composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.
　また、無機顔料及び有機顔料は、それぞれ単独で用いてもよく、併用してもよいが、併用する場合には、無機顔料と有機顔料との総量１００質量部に対して、有機顔料を１０～８０質量部の範囲で用いることが好ましく、２０～４０質量部の範囲で用いることがより好ましい。 In addition, the inorganic pigment and the organic pigment may be used alone or in combination. When used in combination, the organic pigment is added in an amount of 10 to 10 parts per 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferably used in the range of 80 parts by mass, more preferably in the range of 20 to 40 parts by mass.
　着色剤の含有量は、ネガ型感放射線性組成物１の固形分に対して、５～９０質量％が好ましく、１０～８０質量％がより好ましい。 The content of the colorant is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, based on the solid content of the negative radiation-sensitive composition 1.
［その他の有機溶剤（一般式（１）で表される化合物以外の有機溶剤）］
　ネガ型感放射線性組成物１は、その他の有機溶剤を含有してもよい。その他の有機溶剤は、単独で又は２種以上組み合わせて用いることができる。その他の有機溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコール－ｎ－プロピルエーテル、エチレングリコールモノ－ｎ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－プロピルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－プロピルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ－ｎ－プロピルエーテル、ジプロピレングリコールモノ－ｎ－ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル等の（ポリ）アルキレングリコールモノアルキルエーテル類；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の（ポリ）アルキレングリコールモノアルキルエーテルアセテート類；ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等の他のエーテル類；メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン等のケトン類；２－ヒドロキシプロピオン酸メチル、２－ヒドロキシプロピオン酸エチル等の乳酸アルキルエステル類；２－ヒドロキシ－２－メチルプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチル部炭酸メチル、３－メチル－３－メトキシブチルアセテート、３－メチル－３－メトキシブチルプロピオネート、酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸イソブチル、蟻酸ｎ－ペンチル、酢酸イソペンチル、プロピオン酸ｎ－ブチル、酪酸エチル、酪酸ｎ－プロピル、酪酸イソプロピル、酪酸ｎ－ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸ｎ－プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸エチル等の他のエステル類；トルエン、キシレン等の芳香族炭化水素類等が挙げられる。 [Other organic solvents (organic solvents other than the compound represented by formula (1))]
The negative radiation sensitive composition 1 may contain other organic solvents. Other organic solvents can be used alone or in combination of two or more. Examples of other organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Diethylene glycol Other ethers such as methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Other esters such as ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene.
　ネガ型感放射線性組成物１において、溶剤の含有量は、ネガ型感放射線性組成物１の固形分濃度が１～５０質量％となる量が好ましく、５～３０質量％となる量がより好ましい。また、ネガ型感放射線性組成物１に含まれる溶剤において、上記一般式（１）で表される化合物とその他の有機溶剤との質量比は、５：９５～１００：０であることが好ましく、２０：８０～１００：０であることがより好ましい。溶剤の含有量及び上記一般式（１）で表される化合物とその他の有機溶剤との質量比を上記の範囲とすることにより、ネガ型感放射線性組成物１は、感度、保存安定性、塗布性、現像性、及び安全性に優れたものとなりやすく、ネガ型感放射線性組成物１を露光及び現像することにより形成されるパターンは、異物の発生が抑制されたものとなりやすい。 In the negative radiation sensitive composition 1, the content of the solvent is preferably such that the solid content concentration of the negative radiation sensitive composition 1 is 1 to 50% by mass, and more preferably 5 to 30% by mass. preferable. In the solvent contained in the negative radiation-sensitive composition 1, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0. 20:80 to 100: 0 is more preferable. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) and the other organic solvent within the above range, the negative radiation-sensitive composition 1 has sensitivity, storage stability, A pattern formed by exposing and developing the negative radiation-sensitive composition 1 is likely to be excellent in applicability, developability, and safety, and generation of foreign matters is likely to be suppressed.
［その他の成分］
　ネガ型感放射線性組成物１は、必要に応じて、各種の添加剤を含有していてもよい。添加剤としては、増感剤、硬化促進剤、充填剤、密着促進剤、酸化防止剤、凝集防止剤、熱重合禁止剤、消泡剤、界面活性剤等が挙げられる。 [Other ingredients]
The negative radiation sensitive composition 1 may contain various additives as required. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.
＜ネガ型感放射線性組成物２＞
　ネガ型感放射線性組成物２は、上記一般式（１）で表される化合物と、ポリアミック酸と、感光性成分とを含有する感放射線性ポリイミド前駆体組成物である。 <Negative type radiation sensitive composition 2>
The negative radiation sensitive composition 2 is a radiation sensitive polyimide precursor composition containing the compound represented by the general formula (1), a polyamic acid, and a photosensitive component.
［一般式（１）で表される化合物］
　一般式（１）で表される化合物としては、感放射線性組成物の一般的な説明において例示したものを用いることができる。上記一般式（１）で表される化合物は、単独で又は２種以上組み合わせて用いることができる。 [Compound represented by general formula (1)]
As the compound represented by the general formula (1), those exemplified in the general description of the radiation-sensitive composition can be used. The compounds represented by the general formula (1) can be used alone or in combination of two or more.
［ポリアミック酸］
　本発明において、ポリアミック酸は、テトラカルボン酸二無水物及びジアミンを反応させて得られるものであれば、特に限定されず、従来からポリイミド樹脂の前駆体として知られているポリアミック酸から適宜選択される。ポリアミック酸は単独で又は２種以上を混合して用いることができる。 [Polyamic acid]
In the present invention, the polyamic acid is not particularly limited as long as it is obtained by reacting tetracarboxylic dianhydride and diamine, and is appropriately selected from polyamic acids conventionally known as polyimide resin precursors. The A polyamic acid can be used individually or in mixture of 2 or more types.
　好適なポリアミック酸としては、例えば、下記式（１１）で表されるポリアミック酸が挙げられる。
Figure JPOXMLDOC01-appb-C000025
 （式中、Ｒ１Ａは４価の有機基であり、Ｒ２Ａは２価の有機基であり、ｎは括弧内に示される構成単位の繰り返し数である。） As a suitable polyamic acid, the polyamic acid represented by following formula (11) is mentioned, for example.
Figure JPOXMLDOC01-appb-C000025
 (In the formula, R 1A is a tetravalent organic group, R 2A is a divalent organic group, and n is the number of repeating structural units shown in parentheses.)
　式（１１）中、Ｒ１Ａは４価の有機基であり、Ｒ２Ａは２価の有機基であり、これら有機基の炭素数は２～５０が好ましく、２～３０がより好ましい。Ｒ１Ａ及びＲ２Ａは、それぞれ、脂肪族基であっても、芳香族基であっても、これらの構造を組合せた基であってもよい。Ｒ１Ａ及びＲ２Ａは、炭素原子、及び水素原子の他に、ハロゲン原子、酸素原子、及び硫黄原子を含んでいてもよい。Ｒ１Ａ及びＲ２Ａが酸素原子、窒素原子、又は硫黄原子を含む場合、酸素原子、窒素原子、又は硫黄原子は、含窒素複素環基、－ＣＯＮＨ－、－ＮＨ－、－Ｎ＝Ｎ－、－ＣＨ＝Ｎ－、－ＣＯＯ－、－Ｏ－、－ＣＯ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－Ｓ－Ｓ－から選択される基として、Ｒ１Ａ及びＲ２Ａに含まれてもよく、－Ｏ－、－ＣＯ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－Ｓ－Ｓ－から選択される基として、Ｒ１Ａ及びＲ２Ａに含まれるのがより好ましい。 In the formula (11), R 1A is a tetravalent organic group, R 2A is a divalent organic group, and these organic groups preferably have 2 to 50 carbon atoms, more preferably 2 to 30 carbon atoms. R 1A and R 2A may each be an aliphatic group, an aromatic group, or a group in which these structures are combined. R 1A and R 2A may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to the carbon atom and the hydrogen atom. When R 1A and R 2A contain an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom represents a nitrogen-containing heterocyclic group, —CONH—, —NH—, —N═N—, R 1A and R 2A as a group selected from —CH═N—, —COO—, —O—, —CO—, —SO—, —SO 2 —, —S—, and —S—S— A group selected from —O—, —CO—, —SO—, —SO 2 —, —S—, and —S—S— may be included in R 1A and R 2A. More preferred.
　上記式（１１）で表されるポリアミック酸を加熱や触媒によって閉環させることにより、下記式（１２）で表されるポリイミド樹脂が得られる。
Figure JPOXMLDOC01-appb-C000026
 （式中、Ｒ１Ａ及びＲ２Ａは式（１１）と同義であり、ｎは括弧内に示される構成単位の繰り返し数である。） A polyimide resin represented by the following formula (12) is obtained by ring-closing the polyamic acid represented by the above formula (11) by heating or a catalyst.
Figure JPOXMLDOC01-appb-C000026
 (Wherein R 1A and R 2A have the same meanings as in formula (11), and n is the number of repeating structural units shown in parentheses.)
　上記式（１１）で表されるポリアミック酸は、溶剤中で、テトラカルボン酸二無水物と、ジアミンとを反応させることにより得られる。ポリアミック酸の合成原料となるテトラカルボン酸二無水物、及びジアミンは、酸無水物基とアミノ基との反応によりポリアミック酸を形成可能なものであれば特に限定されない。 The polyamic acid represented by the above formula (11) is obtained by reacting a tetracarboxylic dianhydride and a diamine in a solvent. The tetracarboxylic dianhydride and diamine that are the raw materials for synthesizing the polyamic acid are not particularly limited as long as they can form a polyamic acid by the reaction of an acid anhydride group and an amino group.
　ポリアミック酸を合成する際の、テトラカルボン酸二無水物及びジアミンの使用量は特に限定されないが、テトラカルボン酸二無水物１モルに対して、ジアミンを０．５０～１．５０モル用いるのが好ましく、０．６０～１．３０モル用いるのがより好ましく、０．７０～１．２０モル用いるのが特に好ましい。 The amount of tetracarboxylic dianhydride and diamine used in synthesizing the polyamic acid is not particularly limited, but 0.50 to 1.50 mol of diamine is used per 1 mol of tetracarboxylic dianhydride. Preferably, 0.60 to 1.30 mol is used, more preferably 0.70 to 1.20 mol.
　テトラカルボン酸二無水物は、従来からポリアミック酸の合成原料として使用されているテトラカルボン酸二無水物から適宜選択することができる。テトラカルボン酸二無水物は、芳香族テトラカルボン酸二無水物であっても、脂肪族テトラカルボン酸二無水物であってもよいが、得られるポリイミド樹脂の耐熱性の点から、芳香族テトラカルボン酸二無水物が好ましい。テトラカルボン酸二無水物は、２種以上を組合せて用いてもよい。 The tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydrides conventionally used as a raw material for polyamic acid synthesis. The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. From the viewpoint of the heat resistance of the resulting polyimide resin, the aromatic tetracarboxylic dianhydride may be used. Carboxylic dianhydrides are preferred. Tetracarboxylic dianhydride may be used in combination of two or more.
　芳香族テトラカルボン酸二無水物の好適な具体例としては、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、４，４’－オキシジフタル酸二無水物、及び３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物等が挙げられる。これらの中では、価格、入手容易性等から、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、及びピロメリット酸二無水物が好ましい。 Preferable specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′. -Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, and 3,3', 4,4'-diphenyl Examples include sulfonetetracarboxylic dianhydride. Among these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the viewpoint of price and availability.
　なお、ポリアミック酸を合成する際に、テトラカルボン酸二無水物とジカルボン酸無水物とを併用してもよい。これらのカルボン酸無水物を併用すると、得られるポリイミド樹脂の特性が更に良好となる場合がある。ジカルボン酸無水物としては、例えば、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水メチルエンドメチレンテトラヒドロフタル酸、無水クロレンド酸、メチルテトラヒドロ無水フタル酸、無水グルタル酸、ｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物等が挙げられる。 In addition, when synthesizing polyamic acid, tetracarboxylic dianhydride and dicarboxylic anhydride may be used in combination. When these carboxylic acid anhydrides are used in combination, the properties of the resulting polyimide resin may be further improved. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride and the like.
　ジアミンは、従来からポリアミック酸の合成原料として使用されているジアミンから適宜選択することができる。ジアミンは、芳香族ジアミンであっても、脂肪族ジアミンであってもよいが、得られるポリイミド樹脂の耐熱性の点から、芳香族ジアミンが好ましい。ジアミンは、２種以上を組合せて用いてもよい。 The diamine can be appropriately selected from diamines conventionally used as a raw material for synthesizing polyamic acid. The diamine may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferred from the viewpoint of the heat resistance of the resulting polyimide resin. Two or more diamines may be used in combination.
　芳香族ジアミンの好適な具体例としては、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、２，４－ジアミノトルエン、４，４’－ジアミノビフェニル、４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニル、３，３’－ジアミノジフェニルスルフォン、４，４’－ジアミノジフェニルスルフォン、４，４’－ジアミノジフェニルスルフィド、４，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、３，３’－ジアミノジフェニルエーテル、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン、４，４’－ビス（４－アミノフェノキシ）ビフェニル、ビス［４－（４－アミノフェノキシ）フェニル］スルフォン、ビス［４－（３－アミノフェノキシ）フェニル］スルフォン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、９，９－ビス（４－アミノフェニル）フルオレン、９，９－ビス（４－アミノ－３－メチルフェニル）フルオレン、及び４，４’－［１，４－フェニレンビス（１－メチルエタン－１，１－ジイル）］ジアニリン等が挙げられる。これらの中では、価格、入手容易性等から、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、２，４－ジアミノトルエン、及び４，４’－ジアミノジフェニルエーテルが好ましい。 Preferable specific examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis ( Trifluoromethyl) biphenyl, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino Phenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, and 4, And 4 ′-[1,4-phenylenebis (1-methylethane-1,1-diyl)] dianiline. Of these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the viewpoint of price and availability.
　テトラカルボン酸二無水物とジアミンとの反応は、通常、有機溶剤中で行われる。テトラカルボン酸二無水物とジアミンとの反応に使用される有機溶剤は、テトラカルボン酸及びジアミンを溶解させることができ、テトラカルボン酸二無水物及びジアミンと反応しないものであれば特に限定されない。有機溶剤は単独で又は２種以上を混合して用いることができる。 The reaction between tetracarboxylic dianhydride and diamine is usually carried out in an organic solvent. The organic solvent used for the reaction of tetracarboxylic dianhydride and diamine is not particularly limited as long as it can dissolve tetracarboxylic acid and diamine and does not react with tetracarboxylic dianhydride and diamine. An organic solvent can be used individually or in mixture of 2 or more types.
　テトラカルボン酸二無水物とジアミンとの反応に用いる有機溶剤の例としては、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ－メチルカプロラクタム、及びＮ，Ｎ，Ｎ’，Ｎ’－テトラメチルウレア等の含窒素極性溶剤；β－プロピオラクトン、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、γ－カプロラクトン、及びε－カプロラクトン等のラクトン系極性溶剤；ジメチルスルホキシド；アセトニトリル；乳酸エチル、及び乳酸ブチル等の脂肪酸エステル類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジオキサン、テトラヒドロフラン、メチルセルソルブアセテート、及びエチルセルソルブアセテート等のエーテル類が挙げられる。 Examples of organic solvents used in the reaction of tetracarboxylic dianhydride with diamine include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N Nitrogen-containing polar solvents such as N, N-diethylformamide, N-methylcaprolactam, and N, N, N ′, N′-tetramethylurea; β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valero Lactone polar solvents such as lactone, γ-caprolactone, and ε-caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve Tate, and ethers such as ethyl cellosolve acetate.
　これらの有機溶剤の中では、生成するポリアミック酸やポリイミド樹脂の溶解性から、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ－メチルカプロラクタム、及びＮ，Ｎ，Ｎ’，Ｎ’－テトラメチルウレア等の含窒素極性溶剤が好ましい。 Among these organic solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, due to the solubility of the resulting polyamic acid and polyimide resin Nitrogen-containing polar solvents such as N, N-diethylformamide, N-methylcaprolactam, and N, N, N ′, N′-tetramethylurea are preferred.
［感光性成分］
　感光性成分としては、特に限定されず、例えば、光塩基発生剤、光酸発生剤等の、光の作用により分解して塩基及び酸の少なくとも一方を発生する化合物（Ａ）が挙げられる。感光性成分は単独で又は２種以上を混合して用いることができる。 [Photosensitive component]
The photosensitive component is not particularly limited, and examples thereof include a compound (A) that decomposes by the action of light to generate at least one of a base and an acid, such as a photobase generator and a photoacid generator. A photosensitive component can be used individually or in mixture of 2 or more types.
　化合物（Ａ）を含有するネガ型感放射線性組成物２を露光することにより、ネガ型感放射線性組成物２中の化合物（Ａ）は分解して、塩基及び酸の少なくとも一方を発生する。このようにして発生した塩基又は酸は、イミド化触媒として作用して、ネガ型感放射線性組成物２中のポリアミック酸の閉環を促進する。 By exposing the negative radiation sensitive composition 2 containing the compound (A), the compound (A) in the negative radiation sensitive composition 2 is decomposed to generate at least one of a base and an acid. The base or acid thus generated acts as an imidization catalyst and promotes the ring closure of the polyamic acid in the negative radiation sensitive composition 2.
　化合物（Ａ）を含有するネガ型感放射線性組成物２を露光すると、露光部において化合物（Ａ）が分解して塩基及び酸の少なくとも一方を発生する。このようにして発生した塩基又は酸により、ネガ型感放射線性組成物２中のポリアミック酸の閉環が促進され、露光部は現像液に対して不溶となる。一方、未露光部は、現像液に対して可溶であるため、現像液に溶解させて除去することができる。よって、ネガ型感放射線性組成物２を選択的に露光することにより、所望のパターンを形成することができる。 When the negative radiation sensitive composition 2 containing the compound (A) is exposed, the compound (A) is decomposed in the exposed area to generate at least one of a base and an acid. The base or acid thus generated promotes the ring closure of the polyamic acid in the negative radiation sensitive composition 2, and the exposed portion becomes insoluble in the developer. On the other hand, since the unexposed portion is soluble in the developer, it can be removed by dissolving in the developer. Therefore, a desired pattern can be formed by selectively exposing the negative radiation sensitive composition 2.
　化合物（Ａ）としては、例えば、光の作用により分解してイミダゾール化合物を発生する化合物（Ａ－１）や、オキシム化合物（Ａ－２）が挙げられる。以下、化合物（Ａ－１）及び（Ａ－２）について説明する。 Examples of the compound (A) include a compound (A-1) that decomposes by the action of light to generate an imidazole compound, and an oxime compound (A-2). Hereinafter, the compounds (A-1) and (A-2) will be described.
（光の作用により分解してイミダゾール化合物を発生する化合物（Ａ－１））
　化合物（Ａ－１）が発生するイミダゾール化合物は、塩基性のイミド化触媒として、ネガ型感放射線性組成物２中のポリアミック酸の閉環を促進する。化合物（Ａ－１）が発生するイミダゾール化合物は、イミダゾールであっても、イミダゾール中の炭素原子に結合した水素原子の一部又は全部が置換基で置換された化合物であってもよく、下記式（３）で表されるイミダゾール化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000027
 （式中、Ｒ１、Ｒ２、及びＲ３は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を示す。） (Compound capable of decomposing by the action of light to generate an imidazole compound (A-1))
The imidazole compound generated from the compound (A-1) promotes ring closure of the polyamic acid in the negative radiation-sensitive composition 2 as a basic imidization catalyst. The imidazole compound generated from the compound (A-1) may be an imidazole or a compound in which part or all of the hydrogen atoms bonded to the carbon atoms in the imidazole are substituted with a substituent. It is preferable that it is an imidazole compound represented by (3).
Figure JPOXMLDOC01-appb-C000027
 (Wherein R 1 , R 2 , and R 3 are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphino group, (A phosphinyl group, a phosphonate group, or an organic group is shown.)
　Ｒ１、Ｒ２、又はＲ３により示される有機基としては、アルキル基、アルケニル基、シクロアルキル基、シクロアルケニル基、アリール基、アラルキル基等が挙げられる。この有機基は、ヘテロ原子を含んでいてもよい。また、この有機基は、直鎖状、分岐鎖状、環状のいずれでもよい。この有機基は、通常は１価であるが、環状構造を形成する場合等には、２価以上となり得る。 Examples of the organic group represented by R 1 , R 2 , or R 3 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a hetero atom. The organic group may be linear, branched or cyclic. This organic group is usually monovalent, but may be divalent or higher when forming a cyclic structure.
　Ｒ１及びＲ２は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。環状構造としては、ヘテロシクロアルキル基、ヘテロアリール基等が挙げられ、縮合環であってもよい。 R 1 and R 2 may be bonded to each other to form a cyclic structure, and may include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.
　Ｒ１、Ｒ２、又はＲ３により示される有機基がヘテロ原子を含む場合、そのヘテロ原子としては、例えば、酸素原子、窒素原子、珪素原子が挙げられる。ヘテロ原子を含む結合の具体例としては、エーテル結合、チオエーテル結合、カルボニル結合、チオカルボニル結合、エステル結合、アミド結合、ウレタン結合、イミノ結合（－Ｎ＝Ｃ（－Ｒ）－又は－Ｃ（＝ＮＲ）－（ただし、Ｒは水素原子又は有機基を示す）。以下、同じ）、カーボネート結合、スルホニル結合、スルフィニル結合、アゾ結合等が挙げられる。中でも、イミダゾール化合物の耐熱性の観点から、エーテル結合、チオエーテル結合、カルボニル結合、チオカルボニル結合、エステル結合、アミド結合、ウレタン結合、イミノ結合、カーボネート結合、スルホニル結合、スルフィニル結合が好ましい。 When the organic group represented by R 1 , R 2 , or R 3 contains a hetero atom, examples of the hetero atom include an oxygen atom, a nitrogen atom, and a silicon atom. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (—N═C (—R) — or —C (= NR)-(wherein R represents a hydrogen atom or an organic group, hereinafter the same), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like. Among these, from the viewpoint of heat resistance of the imidazole compound, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond, a carbonate bond, a sulfonyl bond, and a sulfinyl bond are preferable.
　Ｒ１、Ｒ２、又はＲ３により示される、有機基以外の基に含まれる水素原子は、炭化水素基によって置換されていてもよい。この炭化水素基は、直鎖状、分岐鎖状、及び環状のいずれでもよい。 A hydrogen atom contained in a group other than an organic group represented by R 1 , R 2 , or R 3 may be substituted with a hydrocarbon group. The hydrocarbon group may be linear, branched or cyclic.
　Ｒ１、Ｒ２、及びＲ３としては、それぞれ独立に水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアリール基、炭素数１～１２のアルコキシ基、及びハロゲン原子が好ましく、水素原子がより好ましい。Ｒ１、Ｒ２、及びＲ３がいずれも水素原子であるイミダゾールは、立体的な障害の少ない単純な構造であるため、イミド化触媒としてポリアミック酸に容易に作用することができる。 R 1 , R 2 , and R 3 are each independently preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom. A hydrogen atom is more preferable. Since imidazole in which R 1 , R 2 , and R 3 are all hydrogen atoms has a simple structure with little steric hindrance, it can easily act on a polyamic acid as an imidization catalyst.
　化合物（Ａ－１）は、光の作用により分解してイミダゾール化合物、好ましくは上記式（３）で表されるイミダゾール化合物を発生させることができる化合物であれば特に限定されない。従来から感光性組成物に配合されている、光の作用によりアミンを発生する化合物について、露光時に発生するアミンに由来する骨格を、イミダゾール化合物、好ましくは上記式（３）で表されるイミダゾール化合物に由来する骨格に置換することにより、化合物（Ａ－１）として使用される化合物が得られる。 The compound (A-1) is not particularly limited as long as it can be decomposed by the action of light to generate an imidazole compound, preferably an imidazole compound represented by the above formula (3). Regarding compounds that have been conventionally blended in photosensitive compositions and generate amines by the action of light, the skeleton derived from amines generated during exposure is an imidazole compound, preferably an imidazole compound represented by the above formula (3) The compound used as compound (A-1) is obtained by substituting the skeleton derived from
　好適な化合物（Ａ－１）としては、下記式（４）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000028
 （式中、Ｒ１、Ｒ２、及びＲ３は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、ホスフィノ基、スルホナト基、ホスフィニル基、ホスホナト基、又は有機基を示す。Ｒ４及びＲ５は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基を示す。Ｒ６、Ｒ７、Ｒ８、Ｒ９、及びＲ１０は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基を示す。Ｒ６、Ｒ７、Ｒ８、Ｒ９、及びＲ１０は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。） Suitable compound (A-1) includes a compound represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000028
 (Wherein R 1 , R 2 , and R 3 are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, phosphino group, sulfonate group, R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, or a sulfino group. , Sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, or organic group R 6 , R 7 , R 8 , R 9 , and R 10 are each independently a hydrogen atom or a halogen atom. , Hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group , Sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, or organic group, R 6 , R 7 , R 8 , R 9 , and R 10 are two or more of them May be bonded to form a cyclic structure and may contain a bond of a hetero atom.)
　式（４）において、Ｒ１、Ｒ２、及びＲ３は、式（３）について説明したものと同様である。 In the formula (4), R 1 , R 2 , and R 3 are the same as those described for the formula (3).
　式（４）において、Ｒ４又はＲ５により示される有機基としては、Ｒ１、Ｒ２、及びＲ３について例示したものが挙げられる。この有機基は、Ｒ１、Ｒ２、及びＲ３の場合と同様に、ヘテロ原子を含んでいてもよい。また、この有機基は、直鎖状、分岐鎖状、環状のいずれでもよい。 In the formula (4), examples of the organic group represented by R 4 or R 5 include those exemplified for R 1 , R 2 , and R 3 . This organic group may contain a hetero atom as in the case of R 1 , R 2 and R 3 . The organic group may be linear, branched or cyclic.
　Ｒ４及びＲ５としては、それぞれ独立に水素原子、炭素数１～１０のアルキル基、炭素数４～１３のシクロアルキル基、炭素数４～１３のシクロアルケニル基、炭素数７～１６のアリールオキシアルキル基、炭素数７～２０のアラルキル基、シアノ基を有する炭素数２～１１のアルキル基、水酸基を有する炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数２～１１のアミド基、炭素数１～１０のアルキルチオ基、炭素数１～１０のアシル基、炭素数２～１１のエステル基（－ＣＯＯＲ又は－ＯＣＯＲ（ただし、Ｒは炭化水素基を示す。））、炭素数６～２０のアリール基、電子供与性基及び／又は電子吸引性基が置換した炭素数６～２０のアリール基、電子供与性基及び／又は電子吸引性基が置換したベンジル基、シアノ基、メチルチオ基であることが好ましい。より好ましくは、Ｒ４及びＲ５の両方が水素原子であるか、又はＲ４がメチル基であり、Ｒ５が水素原子である。 R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, or an aryl having 7 to 16 carbon atoms. An oxyalkyl group, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, 2 carbon atoms An amide group having ˜11, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, and an ester group having 2 to 11 carbon atoms (—COOR or —OCOR (where R represents a hydrocarbon group)) ), Aryl groups having 6 to 20 carbon atoms, electron donating groups and / or electron withdrawing groups substituted aryl groups having 6 to 20 carbon atoms, electron donating groups and / or electron withdrawing groups substituted benzyl groups , Amino group is preferably a methylthio group. More preferably, both R 4 and R 5 are hydrogen atoms, or R 4 is a methyl group and R 5 is a hydrogen atom.
　式（４）において、Ｒ６、Ｒ７、Ｒ８、Ｒ９、又はＲ１０により示される有機基としては、Ｒ１、Ｒ２、及びＲ３において例示したものが挙げられる。この有機基は、Ｒ１及びＲ２の場合と同様に、ヘテロ原子を含んでいてもよい。また、この有機基は、直鎖状、分岐鎖状、環状のいずれでもよい。 In the formula (4), examples of the organic group represented by R 6 , R 7 , R 8 , R 9 , or R 10 include those exemplified for R 1 , R 2 , and R 3 . This organic group may contain a hetero atom as in the case of R 1 and R 2 . The organic group may be linear, branched or cyclic.
　Ｒ６、Ｒ７、Ｒ８、Ｒ９、及びＲ１０は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。環状構造としては、ヘテロシクロアルキル基、ヘテロアリール基等が挙げられ、縮合環であってもよい。例えば、Ｒ６、Ｒ７、Ｒ８、Ｒ９、及びＲ１０は、それらの２つ以上が結合して、Ｒ６、Ｒ７、Ｒ８、Ｒ９、及びＲ１０が結合しているベンゼン環の原子を共有してナフタレン、アントラセン、フェナントレン、インデン等の縮合環を形成してもよい。 Two or more of R 6 , R 7 , R 8 , R 9 , and R 10 may be bonded to form a cyclic structure, and may include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring. For example, R 6 , R 7 , R 8 , R 9 , and R 10 are two or more of them bonded to each other, and R 6 , R 7 , R 8 , R 9 , and R 10 are bonded to each other. A ring atom may be shared to form a condensed ring such as naphthalene, anthracene, phenanthrene, and indene.
　Ｒ６、Ｒ７、Ｒ８、Ｒ９、及びＲ１０としては、それぞれ独立に水素原子、炭素数１～１０のアルキル基、炭素数４～１３のシクロアルキル基、炭素数４～１３のシクロアルケニル基、炭素数７～１６のアリールオキシアルキル基、炭素数７～２０のアラルキル基、シアノ基を有する炭素数２～１１のアルキル基、水酸基を有する炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数２～１１のアミド基、炭素数１～１０のアルキルチオ基、炭素数１～１０のアシル基、炭素数２～１１のエステル基、炭素数６～２０のアリール基、電子供与性基及び／又は電子吸引性基が置換した炭素数６～２０のアリール基、電子供与性基及び／又は電子吸引性基が置換したベンジル基、シアノ基、メチルチオ基、ニトロ基であることが好ましい。 R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or a cyclohexane having 4 to 13 carbon atoms. Alkenyl group, aryloxyalkyl group having 7 to 16 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having a cyano group, alkyl group having 1 to 10 carbon atoms having a hydroxyl group, carbon number An alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, and an aryl having 6 to 20 carbon atoms Group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, methylthio group, nitro group Is Door is preferable.
　また、Ｒ６、Ｒ７、Ｒ８、Ｒ９、及びＲ１０としては、それらの２つ以上が結合して、Ｒ６、Ｒ７、Ｒ８、Ｒ９、及びＲ１０が結合しているベンゼン環の原子を共有してナフタレン、アントラセン、フェナントレン、インデン等の縮合環を形成している場合も、吸収波長が長波長化する点から好ましい。 In addition, as R 6 , R 7 , R 8 , R 9 , and R 10 , two or more of them are bonded, and R 6 , R 7 , R 8 , R 9 , and R 10 are bonded. A case where a condensed ring such as naphthalene, anthracene, phenanthrene, or indene is formed by sharing the atoms of the benzene ring is also preferable from the viewpoint of increasing the absorption wavelength.
　上記式（４）で表される化合物の中では、下記式（５）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000029
 （式中、Ｒ１、Ｒ２、及びＲ３は、式（３）及び（４）と同義である。Ｒ４～Ｒ９は式（４）と同義である。Ｒ１１は、水素原子又は有機基を示す。Ｒ６及びＲ７が水酸基となることはない。Ｒ６、Ｒ７、Ｒ８、及びＲ９は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。） Among the compounds represented by the above formula (4), a compound represented by the following formula (5) is preferable.
Figure JPOXMLDOC01-appb-C000029
 (Wherein R 1 , R 2 , and R 3 have the same meanings as in formulas (3) and (4). R 4 to R 9 have the same meanings as in formula (4). R 11 is a hydrogen atom or Represents an organic group, and R 6 and R 7 do not become a hydroxyl group, and R 6 , R 7 , R 8 , and R 9 may combine with each other to form a cyclic structure. And may contain a heteroatom bond.)
　式（５）で表される化合物は、置換基－Ｏ－Ｒ１１を有するため、有機溶剤に対する溶解性に優れる。 Since the compound represented by the formula (5) has a substituent —O—R 11 , it has excellent solubility in an organic solvent.
　式（５）において、Ｒ１１が有機基である場合、その有機基としては、Ｒ１、Ｒ２、及びＲ３において例示したものが挙げられる。この有機基は、ヘテロ原子を含んでいてもよい。また、この有機基は、直鎖状、分岐鎖状、環状のいずれでもよい。Ｒ１１としては、水素原子、又は炭素数１～１２のアルキル基が好ましく、メチル基がより好ましい。 In the formula (5), when R 11 is an organic group, examples of the organic group include those exemplified for R 1 , R 2 , and R 3 . This organic group may contain a hetero atom. The organic group may be linear, branched or cyclic. R 11 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.
　好適な化合物（Ａ－１）としては、下記式（６）で表される化合物も挙げられる。
Figure JPOXMLDOC01-appb-C000030
 （式中、Ｒ１、Ｒ２、及びＲ３は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、ホスフィノ基、スルホナト基、ホスフィニル基、ホスホナト基、又は有機基を示す。Ｒ１２は、置換されていてもよい炭化水素基を示す。） Suitable compounds (A-1) also include compounds represented by the following formula (6).
Figure JPOXMLDOC01-appb-C000030
 (Wherein R 1 , R 2 , and R 3 are each independently a hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, phosphino group, sulfonate group, (A phosphinyl group, a phosphonato group, or an organic group. R 12 represents an optionally substituted hydrocarbon group.)
　式（６）において、Ｒ１、Ｒ２、及びＲ３は、式（３）について説明したものと同様である。 In Formula (6), R 1 , R 2 , and R 3 are the same as those described for Formula (3).
　式（６）において、Ｒ１２としては、炭素数１～２０のアルキル基、炭素数２～２０のアルケニル基、炭素数２～２０のアルキニル基、置換されていてもよい炭素数６～２０のアリール基、置換されていてもよい炭素数７～２０のアラルキル基が挙げられ、置換されていてもよい炭素数７～２０のアラルキル基が好ましい。上記アリール基又はアラルキル基が置換されている場合、置換基としては、ハロゲン原子、ニトロ基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基が挙げられる。 In the formula (6), R 12 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an optionally substituted 6 to 20 carbon atoms. Examples thereof include an aryl group and an optionally substituted aralkyl group having 7 to 20 carbon atoms, and an optionally substituted aralkyl group having 7 to 20 carbon atoms is preferable. When the aryl group or aralkyl group is substituted, examples of the substituent include a halogen atom, a nitro group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
　式（６）で表される化合物は、式（３）で表されるイミダゾール化合物と下記式（７）で表されるクロロギ酸エステルとの反応、式（３）で表されるイミダゾール化合物と下記式（８）で表されるジカーボネートとの反応、又は下記式（９）で表されるカルボニルジイミダゾール化合物と下記式（１０）で表されるアルコールとの反応により合成することができる。
Figure JPOXMLDOC01-appb-C000031
 （式（７）～（１０）中、Ｒ１、Ｒ２、及びＲ３は、式（３）と同義である。Ｒ１２は式（６）と同義である。） The compound represented by the formula (6) is a reaction between an imidazole compound represented by the formula (3) and a chloroformate represented by the following formula (7), an imidazole compound represented by the formula (3) and the following: It can synthesize | combine by reaction with the dicarbonate represented by Formula (8), or the reaction of the carbonyldiimidazole compound represented by following formula (9), and the alcohol represented by following formula (10).
Figure JPOXMLDOC01-appb-C000031
 (In formulas (7) to (10), R 1 , R 2 , and R 3 have the same meaning as in formula (3). R 12 has the same meaning as in formula (6).)
　化合物（Ａ－１）として特に好適な化合物の具体例を以下に示す。
Figure JPOXMLDOC01-appb-C000032
 Specific examples of the compound particularly suitable as the compound (A-1) are shown below.
Figure JPOXMLDOC01-appb-C000032
（オキシム化合物（Ａ－２））
　オキシム化合物（Ａ－２）は、光の作用により分解して塩基及び酸の少なくとも一方を発生する。化合物（Ａ－２）が分解して発生した塩基又は酸により、ネガ型感放射線性組成物２中のポリアミック酸の閉環が促進される。 (Oxime compound (A-2))
The oxime compound (A-2) is decomposed by the action of light to generate at least one of a base and an acid. Ring closure of the polyamic acid in the negative radiation-sensitive composition 2 is promoted by the base or acid generated by the decomposition of the compound (A-2).
　好適な化合物（Ａ－２）としては、下記式（Ｄ１）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000033
 （式中、Ｒｄ１は、置換基を有してもよい炭素数１～１０の脂肪族炭化水素基、置換基を有してもよいアリール基、又は置換基を有してもよいカルバゾリル基であり、Ｒｄ２は、炭素数１～１０の脂肪族炭化水素基、又は置換基を有してもよいアリール基であり、Ｒｄ３は水素原子、又は－ＣＯ－Ｒｄ５で表される基であり、Ｒｄ５は、水素原子、炭素数１～６のアルキル基、又は置換基を有していてもよいアリール基であり、ｐは０又は１である。） Suitable compound (A-2) includes a compound represented by the following formula (D1).
Figure JPOXMLDOC01-appb-C000033
 (Wherein R d1 is an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted aryl group, or an optionally substituted carbazolyl group. R d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aryl group which may have a substituent, and R d3 is a hydrogen atom or a group represented by —CO—R d5 R d5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group which may have a substituent, and p is 0 or 1.)
　上記式（Ｄ１）中のＲｄ１が置換基を有していてもよいアリール基である場合、置換基を有してもよいアリール基の例としては、置換基を有してもよいフェニル基、置換基を有してもよいナフチル基、置換基を有してもよいアントリル基、及び置換基を有してもよいフェナントレニル基が挙げられる。これらの基の中では、置換基を有してもよいフェニル基、又は置換基を有してもよいナフチル基が好ましく、置換基を有してもよいフェニル基がより好ましい。 In the case where R d1 in the above formula (D1) is an aryl group which may have a substituent, examples of the aryl group which may have a substituent include a phenyl group which may have a substituent. , A naphthyl group which may have a substituent, an anthryl group which may have a substituent, and a phenanthrenyl group which may have a substituent. Among these groups, a phenyl group which may have a substituent or a naphthyl group which may have a substituent is preferable, and a phenyl group which may have a substituent is more preferable.
　アリール基が置換基を有する場合、アリール基に結合する置換基の数は特に限定されない。アリール基が複数の置換基を有する場合、当該複数の置換基は、同一であっても異なっていてもよい。アリール基が有してもよい置換基の種類は、本発明の目的を阻害しない範囲で特に限定されない。置換基の好適な例としては、有機基、アミノ基、ハロゲン原子、ニトロ基、及びシアノ基が挙げられる。 When the aryl group has a substituent, the number of substituents bonded to the aryl group is not particularly limited. When the aryl group has a plurality of substituents, the plurality of substituents may be the same or different. The type of substituent that the aryl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include an organic group, an amino group, a halogen atom, a nitro group, and a cyano group.
　置換基が有機基である場合、当該有機基の種類は本発明の目的を阻害しない範囲で特に限定されず、種々の有機基から適宜選択される。有機基の好適な例としては、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、飽和脂肪族アシル基、アルコキシカルボニル基、飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよいフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよいナフチルアルキル基、置換基を有してもよいヘテロシクリル基、１、又は２の有機基で置換されたアミノ基、モルホリン－１－イル基、及びピペラジン－１－イル基等が挙げられる。置換基の炭素数には、置換基が更に有する置換基の炭素数は含まない。 When the substituent is an organic group, the type of the organic group is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. As preferable examples of the organic group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, It may have a phenoxy group that may have a substituent, a benzoyl group that may have a substituent, a phenoxycarbonyl group that may have a substituent, a benzoyloxy group that may have a substituent, and a substituent. An optionally substituted phenylalkyl group, an optionally substituted naphthyl group, an optionally substituted naphthoxy group, an optionally substituted naphthoyl group, and an optionally substituted naphtho An oxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, 1 or 2 organic groups; Conversion amino groups, morpholin-1-yl group, and piperazine-1-yl group. The carbon number of the substituent does not include the carbon number of the substituent that the substituent further has.
　有機基がアルキル基である場合、その炭素数は１～２０が好ましく、１～６がより好ましい。また、有機基がアルキル基である場合、直鎖状であっても、分岐鎖状であってもよい。有機基がアルキル基である場合の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、イソオクチル基、ｓｅｃ－オクチル基、ｔｅｒｔ－オクチル基、ｎ－ノニル基、イソノニル基、ｎ－デシル基、及びイソデシル基等が挙げられる。また、有機基がアルキル基である場合、アルキル基は炭素鎖中にエーテル結合（－Ｏ－）を含んでいてもよい。炭素鎖中にエーテル結合を有するアルキル基の例としては、メトキシエチル基、エトキシエチル基、メトキシエトキシエチル基、エトキシエトキシエチル基、プロピルオキシエトキシエチル基、及びメトキシプロピル基等が挙げられる。 When the organic group is an alkyl group, the carbon number is preferably 1-20, and more preferably 1-6. Further, when the organic group is an alkyl group, it may be linear or branched. Specific examples when the organic group is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples include n-decyl group and isodecyl group. When the organic group is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.
　有機基がアルコキシ基である場合、その炭素数は１～２０が好ましく、１～６がより好ましい。また、有機基がアルコキシ基である場合、直鎖状であっても、分岐鎖状であってもよい。有機基がアルコキシ基である場合の具体例としては、メトキシ基、エトキシ基、ｎ－プロピルオキシ基、イソプロピルオキシ基、ｎ－ブチルオキシ基、イソブチルオキシ基、ｓｅｃ－ブチルオキシ基、ｔｅｒｔ－ブチルオキシ基、ｎ－ペンチルオキシ基、イソペンチルオキシ基、ｓｅｃ－ペンチルオキシ基、ｔｅｒｔ－ペンチルオキシ基、ｎ－ヘキシルオキシ基、ｎ－ヘプチルオキシ基、ｎ－オクチルオキシ基、イソオクチルオキシ基、ｓｅｃ－オクチルオキシ基、ｔｅｒｔ－オクチルオキシ基、ｎ－ノニルオキシ基、イソノニルオキシ基、ｎ－デシルオキシ基、及びイソデシルオキシ基等が挙げられる。また、有機基がアルコキシ基である場合、アルコキシ基は炭素鎖中にエーテル結合（－Ｏ－）を含んでいてもよい。炭素鎖中にエーテル結合を有するアルコキシ基の例としては、メトキシエトキシ基、エトキシエトキシ基、メトキシエトキシエトキシ基、エトキシエトキシエトキシ基、プロピルオキシエトキシエトキシ基、及びメトキシプロピルオキシ基等が挙げられる。 When the organic group is an alkoxy group, the carbon number is preferably 1-20, and more preferably 1-6. Further, when the organic group is an alkoxy group, it may be linear or branched. Specific examples when the organic group is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. When the organic group is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.
　有機基がシクロアルキル基、又はシクロアルコキシ基である場合、その炭素数は３～１０が好ましく、３～６がより好ましい。有機基シクロアルキル基である場合の具体例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、及びシクロオクチル基等が挙げられる。有機基がシクロアルコキシ基である場合の具体例としては、シクロプロピルオキシ基、シクロブチルオキシ基、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロヘプチルオキシ基、及びシクロオクチルオキシ基等が挙げられる。 In the case where the organic group is a cycloalkyl group or a cycloalkoxy group, the carbon number thereof is preferably 3 to 10, more preferably 3 to 6. Specific examples of the organic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when the organic group is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.
　有機基が飽和脂肪族アシル基、又は飽和脂肪族アシルオキシ基である場合、その炭素数は２～２０が好ましく、２～７がより好ましい。有機基が飽和脂肪族アシル基である場合の具体例としては、アセチル基、プロパノイル基、ｎ－ブタノイル基、２－メチルプロパノイル基、ｎ－ペンタノイル基、２，２－ジメチルプロパノイル基、ｎ－ヘキサノイル基、ｎ－ヘプタノイル基、ｎ－オクタノイル基、ｎ－ノナノイル基、ｎ－デカノイル基、ｎ－ウンデカノイル基、ｎ－ドデカノイル基、ｎ－トリデカノイル基、ｎ－テトラデカノイル基、ｎ－ペンタデカノイル基、及びｎ－ヘキサデカノイル基等が挙げられる。有機基が飽和脂肪族アシルオキシ基である場合の具体例としては、アセチルオキシ基、プロパノイルオキシ基、ｎ－ブタノイルオキシ基、２－メチルプロパノイルオキシ基、ｎ－ペンタノイルオキシ基、２，２－ジメチルプロパノイルオキシ基、ｎ－ヘキサノイルオキシ基、ｎ－ヘプタノイルオキシ基、ｎ－オクタノイルオキシ基、ｎ－ノナノイルオキシ基、ｎ－デカノイルオキシ基、ｎ－ウンデカノイルオキシ基、ｎ－ドデカノイルオキシ基、ｎ－トリデカノイルオキシ基、ｎ－テトラデカノイルオキシ基、ｎ－ペンタデカノイルオキシ基、及びｎ－ヘキサデカノイルオキシ基等が挙げられる。 When the organic group is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the carbon number thereof is preferably 2 to 20, and more preferably 2 to 7. Specific examples when the organic group is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when the organic group is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.
　有機基がアルコキシカルボニル基である場合、その炭素数は２～２０が好ましく、２～７がより好ましい。有機基がアルコキシカルボニル基である場合の具体例としては、メトキシカルボニル基、エトキシカルボニル基、ｎ－プロピルオキシカルボニル基、イソプロピルオキシカルボニル基、ｎ－ブチルオキシカルボニル基、イソブチルオキシカルボニル基、ｓｅｃ－ブチルオキシカルボニル基、ｔｅｒｔ－ブチルオキシカルボニル基、ｎ－ペンチルオキシカルボニル基、イソペンチルオキシカルボニル基、ｓｅｃ－ペンチルオキシカルボニル基、ｔｅｒｔ－ペンチルオキシカルボニル基、ｎ－ヘキシルオキシカルボニル基、ｎ－ヘプチルオキシカルボニル基、ｎ－オクチルオキシカルボニル基、イソオクチルオキシカルボニル基、ｓｅｃ－オクチルオキシカルボニル基、ｔｅｒｔ－オクチルオキシカルボニル基、ｎ－ノニルオキシカルボニル基、イソノニルオキシカルボニル基、ｎ－デシルオキシカルボニル基、及びイソデシルオキシカルボニル基等が挙げられる。 When the organic group is an alkoxycarbonyl group, the carbon number is preferably 2 to 20, and more preferably 2 to 7. Specific examples when the organic group is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Seo nonyloxycarbonyl group, n- decyl oxycarbonyl group, and the like isodecyl oxycarbonyl group.
　有機基がフェニルアルキル基である場合、その炭素数は７～２０が好ましく、７～１０がより好ましい。また有機基がナフチルアルキル基である場合、その炭素数は１１～２０が好ましく、１１～１４がより好ましい。有機基がフェニルアルキル基である場合の具体例としては、ベンジル基、２－フェニルエチル基、３－フェニルプロピル基、及び４－フェニルブチル基が挙げられる。有機基がナフチルアルキル基である場合の具体例としては、α－ナフチルメチル基、β－ナフチルメチル基、２－（α－ナフチル）エチル基、及び２－（β－ナフチル）エチル基が挙げられる。有機基がフェニルアルキル基、又はナフチルアルキル基である場合、有機基はフェニル基、又はナフチル基上に更に置換基を有していてもよい。 When the organic group is a phenylalkyl group, the carbon number thereof is preferably 7-20, and more preferably 7-10. In addition, when the organic group is a naphthylalkyl group, the carbon number thereof is preferably 11-20, and more preferably 11-14. Specific examples in the case where the organic group is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when the organic group is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When the organic group is a phenylalkyl group or a naphthylalkyl group, the organic group may further have a substituent on the phenyl group or naphthyl group.
　有機基がヘテロシクリル基である場合、ヘテロシクリル基は、１以上のＮ、Ｓ、Ｏを含む５員又は６員の単環であるか、かかる単環同士、又はかかる単環とベンゼン環とが縮合したヘテロシクリル基である。ヘテロシクリル基が縮合環である場合は、環数３までのものとする。かかるヘテロシクリル基を構成する複素環としては、フラン、チオフェン、ピロール、オキサゾール、イソオキサゾール、チアゾール、チアジアゾール、イソチアゾール、イミダゾール、ピラゾール、トリアゾール、ピリジン、ピラジン、ピリミジン、ピリダジン、ベンゾフラン、ベンゾチオフェン、インドール、イソインドール、インドリジン、ベンゾイミダゾール、ベンゾトリアゾール、ベンゾオキサゾール、ベンゾチアゾール、カルバゾール、プリン、キノリン、イソキノリン、キナゾリン、フタラジン、シンノリン、及びキノキサリン等が挙げられる。有機基がヘテロシクリル基である場合、ヘテロシクリル基は更に置換基を有していてもよい。 When the organic group is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When the organic group is a heterocyclyl group, the heterocyclyl group may further have a substituent.
　有機基が、１又は２の有機基で置換されたアミノ基である場合、窒素原子に結合する有機基の好適な例は、炭素数１～２０のアルキル基、炭素数３～１０のシクロアルキル基、炭素数２～２０の飽和脂肪族アシル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、及びヘテロシクリル基等が挙げられる。これらの好適な有機基の具体例は、Ｒｄ１が置換基を有してもよいアリール基である場合に、当該アリール基が置換基として有してもよい有機基の具体例と同様である。１又は２の有機基で置換されたアミノ基の具体例としては、メチルアミノ基、ジメチルアミノ基、エチルアミノ基、ジエチルアミノ基、ｎ－プロピルアミノ基、ジ－ｎ－プロピルアミノ基、イソプロピルアミノ基、ｎ－ブチルアミノ基、ジ－ｎ－ブチルアミノ基、ｎ－ペンチルアミノ基、ｎ－ヘキシルアミノ基、ｎ－ヘプチルアミノ基、ｎ－オクチルアミノ基、ｎ－ノニルアミノ基、ｎ－デシルアミノ基、フェニルアミノ基、ナフチルアミノ基、アセチルアミノ基、プロパノイルアミノ基、ｎ－ブタノイルアミノ基、ｎ－ペンタノイルアミノ基、ｎ－ヘキサノイルアミノ基、ｎ－ヘプタノイルアミノ基、ｎ－オクタノイルアミノ基、ｎ－デカノイルアミノ基、ベンゾイルアミノ基、α－ナフトイルアミノ基、及びβ－ナフトイルアミノ基等が挙げられる。 When the organic group is an amino group substituted with one or two organic groups, suitable examples of the organic group bonded to the nitrogen atom include alkyl groups having 1 to 20 carbon atoms and cycloalkyl groups having 3 to 10 carbon atoms. Group, a saturated aliphatic acyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, and a carbon group having 7 to 20 carbon atoms which may have a substituent. And a phenylalkyl group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. It is done. Specific examples of these suitable organic groups are the same as the specific examples of the organic group that the aryl group may have as a substituent when R d1 is an aryl group that may have a substituent. . Specific examples of the amino group substituted with one or two organic groups include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, and an isopropylamino group. N-butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenyl Amino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group N-decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group, etc. I can get lost.
　Ｒｄ１が置換基を有してもよいアリール基である場合に、アリール基に置換基として結合する有機基に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合の置換基としては、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～７の飽和脂肪族アシル基、炭素数２～７のアルコキシカルボニル基、炭素数２～７の飽和脂肪族アシルオキシ基、炭素数１～６のアルキル基を有するモノアルキルアミノ基、炭素数１～６のアルキル基を有するジアルキルアミノ基、モルホリン－１－イル基、ピペラジン－１－イル基、ハロゲン原子、ニトロ基、及びシアノ基等が挙げられる。 When R d1 is an aryl group which may have a substituent, the substitution in the case where the phenyl group, the naphthyl group, and the heterocyclyl group contained in the organic group bonded to the aryl group as a substituent further has a substituent Examples of the group include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, and an alkyl group having 2 to 7 carbon atoms. Saturated aliphatic acyloxy group, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen An atom, a nitro group, a cyano group, etc. are mentioned.
　Ｒｄ１が置換基を有してもよいアリール基である場合に、アリール基に置換基として結合する有機基に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合、その置換基の数は、本発明の目的を阻害しない範囲で限定されないが、１～４が好ましい。Ｒｄ１が置換基を有してもよいアリール基である場合に、アリール基に置換基として結合する有機基に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が、複数の置換基を有する場合、複数の置換基は、同一であっても異なっていてもよい。 When R d1 is an aryl group which may have a substituent, when the phenyl group, naphthyl group and heterocyclyl group contained in the organic group bonded as a substituent to the aryl group further has a substituent, The number of substituents is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When R d1 is an aryl group which may have a substituent, the phenyl group, the naphthyl group, and the heterocyclyl group included in the organic group bonded as a substituent to the aryl group have a plurality of substituents. The plurality of substituents may be the same or different.
　Ｒｄ１が置換基を有してもよいアリール基である場合に、アリール基が有する置換基としては、当該置換基が化学的に安定であることや、立体的な障害が少なく、式（Ｄ１）で表される化合物の合成が容易であることや、式（Ｄ１）で表される化合物の溶媒に対する溶解性が高いこと等から、ニトロ基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、及び炭素数２～７の飽和脂肪族アシル基からなる群より選択される基が好ましく、ニトロ基、又は炭素数１～６のアルキルがより好ましく、ニトロ基、又はメチル基が特に好ましい。 In the case where R d1 is an aryl group which may have a substituent, the substituent that the aryl group has is that the substituent is chemically stable, has little steric hindrance, and has the formula (D1 ), A compound represented by the formula (D1) has high solubility in a solvent, etc., so that a nitro group, an alkyl group having 1 to 6 carbon atoms, a carbon number of 1 Is preferably a group selected from the group consisting of an alkoxy group having 6 to 6 carbon atoms and a saturated aliphatic acyl group having 2 to 7 carbon atoms, more preferably a nitro group or an alkyl group having 1 to 6 carbon atoms, a nitro group or a methyl group Is particularly preferred.
　Ｒｄ１が置換基を有してもよいアリール基である場合、Ｒｄ１は、下記式（Ｄ１－１）であるのが好ましい。
Figure JPOXMLDOC01-appb-C000034
 （式（Ｄ１－１）中、Ｒｄ４は、有機基、アミノ基、ハロゲン原子、ニトロ基、及びシアノ基からなる群より選択される基であり、ｑは０～４の整数である。） When R d1 is an aryl group which may have a substituent, R d1 is preferably represented by the following formula (D1-1).
Figure JPOXMLDOC01-appb-C000034
 (In formula (D1-1), R d4 is a group selected from the group consisting of an organic group, an amino group, a halogen atom, a nitro group, and a cyano group, and q is an integer of 0 to 4.)
　Ｒｄ４が有機基である場合、当該有機基の好適な例は、Ｒｄ１が置換基を有してもよいアリール基である場合に、当該アリール基が置換基として有してもよい有機基の例と同様である。 When R d4 is an organic group, a preferred example of the organic group is an organic group that the aryl group may have as a substituent when R d1 is an aryl group that may have a substituent. This is the same as the example.
　Ｒｄ４がフェニル基に結合する位置は、Ｒｄ４が結合するフェニル基について、フェニル基とオキシム化合物の主骨格との結合手の位置を１位とし、メチル基の位置を２位とする場合に、４位、又は５位が好ましく、５位がよりに好ましい。また、ｑは、０～３の整数が好ましく、０～２の整数がより好ましく、０又は１が特に好ましい。 Position R d4 is bonded to the phenyl group, the phenyl group R d4 are attached the position of the bond to the main chain of the phenyl group and the oxime compound is the 1-position, in the case of a two-position the location of the methyl group The 4th or 5th position is preferable, and the 5th position is more preferable. Further, q is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.
　上記式（Ｄ１）中、Ｒｄ１が置換基を有してもよい脂肪族炭化水素基である場合、その炭素数は１～１０である。この炭素数には、置換基の炭素数は含まれない。当該脂肪族炭化水素基の炭素数は、１～９が好ましく、１～８がより好ましい。当該脂肪族炭化水素基は、飽和脂肪族炭化水素基であってもよく、不飽和結合を有する炭化水素基であってもよい。当該脂肪族炭化水素基の構造は、直鎖状であっても、分岐鎖状であっても、環状であっても、これらの構造を組み合わせた構造であってもよく、直鎖状であるのが好ましい。 In the above formula (D1), when R d1 is an aliphatic hydrocarbon group which may have a substituent, the carbon number thereof is 1 to 10. This carbon number does not include the carbon number of the substituent. The aliphatic hydrocarbon group preferably has 1 to 9 carbon atoms, and more preferably 1 to 8 carbon atoms. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or a hydrocarbon group having an unsaturated bond. The structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures, and is linear. Is preferred.
　上記式（Ｄ１）中、Ｒｄ１が直鎖状の脂肪族炭化水素基である場合の好適な例としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－へプチル基、ｎ－オクチル基、ｎ－ノニル基、及びｎ－デシル基が挙げられる。
　Ｒｄ１が環状の脂肪族炭化水素基である場合の好適な例としてはシクロペンチル基、シクロへキシル基が挙げられる。
　Ｒｄ１が直鎖状の脂肪族炭化水素基と環状の脂肪族炭化水素基とを組み合わせた構造である場合の好適な例としては、シクロヘキシルメチル基、シクロペンチルメチル基、２－シクロヘキシルエチル基、２－シクロペンチルエチル基、３－シクロヘキシル－ｎ－プロピル基、及び３－シクロペンチル－ｎ－プロピル基が挙げられ、これらの基の中では２－シクロヘキシルエチル基、及び２－シクロペンチルエチル基が好ましい。 In the above formula (D1), preferred examples when R d1 is a linear aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, Examples include an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.
Preferable examples when R d1 is a cyclic aliphatic hydrocarbon group include a cyclopentyl group and a cyclohexyl group.
Preferable examples in the case where R d1 has a structure in which a linear aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group are combined include a cyclohexylmethyl group, a cyclopentylmethyl group, a 2-cyclohexylethyl group, 2 -Cyclopentylethyl group, 3-cyclohexyl-n-propyl group, and 3-cyclopentyl-n-propyl group can be mentioned, and among these groups, 2-cyclohexylethyl group and 2-cyclopentylethyl group are preferable.
　Ｒｄ１が脂肪族炭化水素基である場合に、当該脂肪族炭化水素基が有していてもよい置換基としては、水酸基、ハロゲン原子、シアノ基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、置換基を有してもよいアリール基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアリールチオ基、炭素数２～１０の飽和脂肪族アシル基、置換基を有していてもよいアリールカルボニル基、アミノ基、１又は２の炭素数１～６のアルキルで置換されたアミノ基、及び１又は２の置換基を有してもよいアリール基で置換されたアミノ基が挙げられる。なお、これらの置換基の炭素数は、脂肪族炭化水素基の炭素数には含まれない。 When R d1 is an aliphatic hydrocarbon group, examples of the substituent that the aliphatic hydrocarbon group may have include a hydroxyl group, a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, 1-10 alkylthio groups, aryl groups optionally having substituents, aryloxy groups optionally having substituents, arylthio groups optionally having substituents, saturated aliphatic groups having 2 to 10 carbon atoms It may have an acyl group, an arylcarbonyl group which may have a substituent, an amino group, an amino group substituted with 1 or 2 alkyl having 1 to 2 carbon atoms, and a substituent having 1 or 2 An amino group substituted with an aryl group can be mentioned. The carbon number of these substituents is not included in the carbon number of the aliphatic hydrocarbon group.
　脂肪族炭化水素基が有する置換基が、置換基を有してもよいアリール基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアリールチオ基、置換基を有していてもよいアリールカルボニル基、及び１又は２の置換基を有してもよいアリール基で置換されたアミノ基である場合、これらの基に含まれるアリール基としては、フェニル基、ナフチル基、アントリル基、及びフェナントリル基が挙げられ、フェニル基、及びナフチル基が好ましく、フェニル基がより好ましい。 The substituent that the aliphatic hydrocarbon group has has an aryl group that may have a substituent, an aryloxy group that may have a substituent, an arylthio group that may have a substituent, and a substituent. In the case of an arylcarbonyl group which may be optionally substituted and an amino group substituted with an aryl group which may have one or two substituents, the aryl group contained in these groups includes a phenyl group, a naphthyl group, An anthryl group and a phenanthryl group are mentioned, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
　脂肪族炭化水素基が有する置換基が、置換基を有してもよいアリール基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアリールチオ基、置換基を有していてもよいアリールカルボニル基、及び１又は２の置換基を有してもよいアリール基で置換されたアミノ基である場合、これらの基に含まれるアリール基が有してもよい置換基としては、水酸基、ハロゲン原子、シアノ基、ニトロ基、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、及び炭素数２～７の飽和脂肪族アシル基等が挙げられる。 The substituent that the aliphatic hydrocarbon group has has an aryl group that may have a substituent, an aryloxy group that may have a substituent, an arylthio group that may have a substituent, and a substituent. In the case of an arylcarbonyl group which may be substituted and an amino group substituted with an aryl group which may have 1 or 2 substituents, the aryl group contained in these groups may have a substituent Examples thereof include a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms.
　Ｒｄ１が脂肪族炭化水素基である場合に当該脂肪族炭化水素基が有していてもよい置換基として説明した以上の置換基の具体例は、以上説明した炭素数の範囲内において、Ｒｄ１がアリール基である場合に当該アリール基が有してもよい置換基と同様である。 When R d1 is an aliphatic hydrocarbon group, specific examples of the above-described substituents as the substituents that the aliphatic hydrocarbon group may have are as follows. When d1 is an aryl group, it is the same as the substituent that the aryl group may have.
　Ｒｄ１が置換基を有してもよいカルバゾリル基である場合、置換基の種類は本発明の目的を阻害しない範囲で特に限定されない。カルバゾリル基が炭素原子上に有してもよい好適な置換基の例としては、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数３～１０のシクロアルキル基、炭素数３～１０のシクロアルコキシ基、炭素数２～２０の飽和脂肪族アシル基、炭素数２～２０のアルコキシカルボニル基、炭素数２～２０の飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいフェニルチオ基、置換基を有してもよいフェニルカルボニル基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフチルカルボニル基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、置換基を有してもよいヘテロシクリルカルボニル基、アミノ基、１又は２の有機基で置換されたアミノ基、モルホリン－１－イル基、及びピペラジン－１－イル基、ハロゲン原子、ニトロ基、及びシアノ基等が挙げられる。 When R d1 is an optionally substituted carbazolyl group, the type of substituent is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the carbazolyl group may have on the carbon atom include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, carbon A cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, and a substituent. Good phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted phenylcarbonyl group, optionally substituted benzoyl group, substituted A phenoxycarbonyl group which may have a group, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a naphthyl which may have a substituent Group, substitution A naphthoxy group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent An optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, amino And an amino group substituted by an organic group of 1 or 2, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.
　Ｒｄ１が置換基を有してもよいカルバゾリル基である場合、カルバゾリル基が窒素原子上に有してもよい好適な置換基の例としては、炭素数１～２０のアルキル基、炭素数３～１０のシクロアルキル基、炭素数２～２０の飽和脂肪族アシル基、炭素数２～２０のアルコキシカルボニル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、及び置換基を有してもよいヘテロシクリルカルボニル基等が挙げられる。これらの置換基の中では、炭素数１～２０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、エチル基が特に好ましい。 When R d1 is a carbazolyl group which may have a substituent, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a carbon number of 3 A cycloalkyl group having 10 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted phenyl group, and an optionally substituted benzoyl group A phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, and a substituent. It has a naphthoyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclyl group, and a substituent. Heterocycle And a rucarbonyl group. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
　カルバゾリル基が有してもよい置換基の具体例について、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、飽和脂肪族アシル基、アルコキシカルボニル基、飽和脂肪族アシルオキシ基、置換基を有してもよいフェニルアルキル基、置換基を有してもよいナフチルアルキル基、置換基を有してもよいヘテロシクリル基、及び１又は２の有機基で置換されたアミノ基に関しては、Ｒｄ１が置換基を有してもよいアリール基である場合の、アリール基が有する置換基の例と同様である。 Specific examples of the substituent that the carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. R d1 is substituted for an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with 1 or 2 organic groups. In the case of an aryl group that may have a group, the examples are the same as the examples of the substituent that the aryl group has.
　Ｒｄ１において、カルバゾリル基が有する置換基に含まれるフェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合の置換基の例としては、炭素数１～６のアルキル基；炭素数１～６のアルコキシ基；炭素数２～７の飽和脂肪族アシル基；炭素数２～７のアルコキシカルボニル基；炭素数２～７の飽和脂肪族アシルオキシ基；フェニル基；ナフチル基；ベンゾイル基；ナフトイル基；炭素数１～６のアルキル基、モルホリン－１－イル基、ピペラジン－１－イル基、及びフェニル基からなる群より選択される基により置換されたベンゾイル基；炭素数１～６のアルキル基を有するモノアルキルアミノ基；炭素数１～６のアルキル基を有するジアルキルアミノ基；モルホリン－１－イル基；ピペラジン－１－イル基；ハロゲン；ニトロ基；シアノ基が挙げられる。カルバゾリル基が有する置換基に含まれるフェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合、その置換基の数は、本発明の目的を阻害しない範囲で限定されないが、１～４が好ましい。フェニル基、ナフチル基、及びヘテロシクリル基が、複数の置換基を有する場合、複数の置換基は、同一であっても異なっていてもよい。 Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of R d1 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; an alkyl group having 1 to 6 carbon atoms; A monoalkylamino group having 1 to 6 carbon atoms; a morpholin-1-yl group; a piperazin-1-yl group; a halogen Nitro group; cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituent of the carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.
　Ｒｄ２は、炭素数１～１０の脂肪族炭化水素基、又は置換基を有してもよいアリール基である。
　Ｒｄ２が脂肪族炭化水素基である場合、当該脂肪族炭化水素基の炭素数は、１～６が好ましく、１がより好ましい。当該脂肪族炭化水素基は、飽和脂肪族炭化水素基であってもよく、不飽和結合を有する炭化水素基であってもよい。当該脂肪族炭化水素基の構造は、直鎖状であっても、分岐鎖状であっても、環状であっても、これらの構造を組み合わせた構造であってもよく、直鎖状であるのが好ましい。 R d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aryl group which may have a substituent.
When R d2 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or a hydrocarbon group having an unsaturated bond. The structure of the aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination of these structures, and is linear. Is preferred.
　Ｒｄ２が直鎖状の脂肪族炭化水素基である場合の好適な例としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－へプチル基、ｎ－オクチル基、ｎ－ノニル基、及びｎ－デシル基が挙げられる。これらの中では、メチル基が特に好ましい。 Preferable examples when R d2 is a linear aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Examples include a heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Of these, a methyl group is particularly preferred.
　Ｒｄ２が置換基を有してもよいアリール基である場合の例としては、置換基を有してもよいフェニル基、置換基を有してもよいナフチル基、置換基を有してもよいアントリル基、及び置換基を有してもよいフェナントレニル基が挙げられる。これらの基の中では、置換基を有してもよいフェニル基、又は置換基を有してもよいナフチル基が好ましく、置換基を有してもよいフェニル基がより好ましい。 Examples of the case where R d2 is an aryl group which may have a substituent include a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Examples thereof include a good anthryl group and a phenanthrenyl group which may have a substituent. Among these groups, a phenyl group which may have a substituent or a naphthyl group which may have a substituent is preferable, and a phenyl group which may have a substituent is more preferable.
　Ｒｄ２において、アリール基が有する置換基は、本発明の目的を阻害しない範囲で特に限定されない。アリール基が、炭素原子上に有してもよい好適な置換基の例としては、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシ基、炭素数３～１０のシクロアルキル基、炭素数３～１０のシクロアルコキシ基、炭素数２～２０の飽和脂肪族アシル基、炭素数２～２０のアルコキシカルボニル基、炭素数２～２０の飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいフェニルチオ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、置換基を有してもよいヘテロシクリルカルボニル基、アミノ基、１又は２の有機基で置換されたアミノ基、モルホリン－１－イル基、及びピペラジン－１－イル基、ハロゲン原子、ニトロ基、及びシアノ基等が挙げられる。 In R d2 , the substituent that the aryl group has is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the aryl group may have on the carbon atom include alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, Having a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, Benzoyloxy group which may have a substituent, phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, naphthyl group which may have a substituent, naphthoxy which may have a substituent Group, with substituent A good naphthoyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a substituent A heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and piperazin-1-yl Group, halogen atom, nitro group, cyano group and the like.
　アリール基が有してもよい置換基の具体例について、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、飽和脂肪族アシル基、アルコキシカルボニル基、飽和脂肪族アシルオキシ基、置換基を有してもよいフェニルアルキル基、置換基を有してもよいナフチルアルキル基、置換基を有してもよいヘテロシクリル基、及び１又は２の有機基で置換されたアミノ基に関しては、Ｒｄ１が置換基を有してもよいアリール基である場合に、アリール基が有してもよい置換基についての例示と同様である。 Specific examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. R d1 is substituted for an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with 1 or 2 organic groups. In the case of an aryl group that may have a group, it is the same as the examples of the substituent that the aryl group may have.
　Ｒｄ２において、アリール基が有する置換基に含まれるフェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合の置換基の例としては、炭素数１～６のアルキル基；炭素数１～６のアルコキシ基；炭素数２～７の飽和脂肪族アシル基；炭素数２～７のアルコキシカルボニル基；炭素数２～７の飽和脂肪族アシルオキシ基；フェニル基；ナフチル基；ベンゾイル基；ナフトイル基；炭素数１～６のアルキル基、モルホリン－１－イル基、ピペラジン－１－イル基、及びフェニル基からなる群より選択される基により置換されたベンゾイル基；炭素数１～６のアルキル基を有するモノアルキルアミノ基；炭素数１～６のアルキル基を有するジアルキルアミノ基；モルホリン－１－イル基；ピペラジン－１－イル基；ハロゲン原子；ニトロ基；シアノ基が挙げられる。アリール基が有する置換基に含まれるフェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合、その置換基の数は、本発明の目的を阻害しない範囲で限定されないが、１～４が好ましい。フェニル基、ナフチル基、及びヘテロシクリル基が、複数の置換基を有する場合、複数の置換基は、同一であっても異なっていてもよい。 Examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the aryl group in R d2 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; an alkyl group having 1 to 6 carbon atoms; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; a piperazin-1-yl group; Child; nitro group; cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the aryl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not hindered. preferable. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.
　式（Ｄ１）におけるＲｄ３は、水素原子、又は－ＣＯ－Ｒｄ５で表される基である。－ＣＯ－Ｒｄ５で表される基において、Ｒｄ５は、水素原子、炭素数１～６のアルキル基、又は置換基を有してもよいアリール基である。Ｒｄ５が置換基を有してもよいアリール基である場合、アリール基が有してもよい置換基は、前述のＲｄ１が置換基を有してもよいアリール基である場合に、当該アリール基が有してもよい置換基と同様である。Ｒｄ５が置換基を有してもよいアリール基である場合、アリール基は２以上の置換基を有していてもよい。この場合、アリール基が有する置換基は同一であっても異なっていてもよい。Ｒｄ５としては、水素原子、アセチル基、プロピオニル基、及びベンゾイル基が好ましく、水素原子、アセチル基、及びベンゾイル基がより好ましい。 R d3 in the formula (D1) is a hydrogen atom or a group represented by —CO—R d5 . In the group represented by —CO—R d5 , R d5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group which may have a substituent. When R d5 is an aryl group that may have a substituent, the substituent that the aryl group may have is the above when R d1 is an aryl group that may have a substituent. This is the same as the substituent that the aryl group may have. When R d5 is an aryl group which may have a substituent, the aryl group may have two or more substituents. In this case, the substituents that the aryl group has may be the same or different. R d5 is preferably a hydrogen atom, an acetyl group, a propionyl group, or a benzoyl group, and more preferably a hydrogen atom, an acetyl group, or a benzoyl group.
　式（Ｄ１）で表される化合物としては、この化合物の塩基発生効率又は酸発生効率の点から、式（Ｄ１）において、Ｒｄ１が置換基を有してもよい炭素数１～１０の脂肪族炭化水素基、又は置換基を有してもよいアリール基であり、Ｒｄ２が下記式（Ｄ１－２）で表される基である化合物、又は、式（Ｄ１）において、Ｒｄ１が下記式（Ｄ１－３）で表される基である化合物が好ましく、着色が抑制され透明性の高い樹脂が得られる点から、式（Ｄ１）において、Ｒｄ１が置換基を有してもよい炭素数１～１０の脂肪族炭化水素基、又は置換基を有してもよいアリール基であり、Ｒｄ２が下記式（Ｄ１－２）で表される基である化合物がより好ましい。 The compound represented by the formula (D1) is a fatty acid having 1 to 10 carbon atoms in which R d1 may have a substituent in the formula (D1) from the viewpoint of base generation efficiency or acid generation efficiency of this compound. A group hydrocarbon group or an aryl group which may have a substituent, wherein R d2 is a group represented by the following formula (D1-2), or in formula (D1), R d1 is A compound that is a group represented by the formula (D1-3) is preferable, and in the formula (D1), R d1 is a carbon that may have a substituent from the viewpoint that coloring is suppressed and a highly transparent resin is obtained. A compound having an aliphatic hydrocarbon group of 1 to 10 or an aryl group which may have a substituent, and R d2 being a group represented by the following formula (D1-2) is more preferable.
Figure JPOXMLDOC01-appb-C000035
 （式（Ｄ１－２）中、Ｒｄ６は、１価の有機基、アミノ基、ハロゲン原子、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｒは、０～４の整数である。）
Figure JPOXMLDOC01-appb-C000035
 (In the formula (D1-2), R d6 is a group selected from the group consisting of a monovalent organic group, amino group, halogen atom, nitro group, and cyano group, A is S or O, r is an integer of 0 to 4.)
　式（Ｄ１－２）におけるＲｄ６が有機基である場合、本発明の目的を阻害しない範囲で、種々の有機基から選択できる。式（Ｄ１－２）においてＲｄ６が有機基である場合の好適な例としては、炭素数１～６のアルキル基；炭素数１～６のアルコキシ基；炭素数２～７の飽和脂肪族アシル基；炭素数２～７のアルコキシカルボニル基；炭素数２～７の飽和脂肪族アシルオキシ基；フェニル基；ナフチル基；ベンゾイル基；ナフトイル基；炭素数１～６のアルキル基、モルホリン－１－イル基、ピペラジン－１－イル基、及びフェニル基からなる群より選択される基により置換されたベンゾイル基；炭素数１～６のアルキル基を有するモノアルキルアミノ基；炭素数１～６のアルキル基を有するジアルキルアミノ基；モルホリン－１－イル基；ピペラジン－１－イル基；ハロゲン原子；ニトロ基；シアノ基が挙げられる。 When R d6 in the formula (D1-2) is an organic group, it can be selected from various organic groups as long as the object of the present invention is not impaired. In the formula (D1-2), when R d6 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated aliphatic acyl having 2 to 7 carbon atoms. Group: alkoxy group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; alkyl group having 1 to 6 carbon atoms; morpholin-1-yl A benzoyl group substituted by a group selected from the group consisting of a group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms Morpholin-1-yl group; piperazin-1-yl group; halogen atom; nitro group; cyano group.
　Ｒｄ６の中では、ベンゾイル基；ナフトイル基；炭素数１～６のアルキル基、モルホリン－１－イル基、ピペラジン－１－イル基、及びフェニル基からなる群より選択される基により置換されたベンゾイル基；ニトロ基が好ましく、ベンゾイル基；ナフトイル基；２－メチルフェニルカルボニル基；４－（ピペラジン－１－イル）フェニルカルボニル基；４－（フェニル）フェニルカルボニル基がより好ましい。 In R d6 , substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.
　また、式（Ｄ１－２）において、ｒは、０～３の整数が好ましく、０～２の整数がより好ましく、０又は１であるのが特に好ましい。ｒが１である場合、Ｒｄ６の結合する位置は、Ｒｄ６が結合するフェニル基が酸素原子又は硫黄原子と結合する結合手に対して、パラ位であるのが好ましい。
　式（Ｄ１－２）において、ＡはＳであるのが好ましい。 In the formula (D1-2), r is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When r is 1, the binding position of R d6 are, with respect to bond the phenyl group R d6 are attached is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.
In the formula (D1-2), A is preferably S.
　Ｒｄ６に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合の置換基としては、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～７の飽和脂肪族アシル基、炭素数２～７のアルコキシカルボニル基、炭素数２～７の飽和脂肪族アシルオキシ基、炭素数１～６のアルキル基を有するモノアルキルアミノ基、炭素数１～６のアルキル基を有するジアルキルアミノ基、モルホリン－１－イル基、ピペラジン－１－イル基、ハロゲン原子、ニトロ基、及びシアノ基等が挙げられる。Ｒｄ６に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合、その置換基の数は、本発明の目的を阻害しない範囲で限定されないが、１～４が好ましい。Ｒｄ６に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が、複数の置換基を有する場合、複数の置換基は、同一であっても異なっていてもよい。 In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R d6 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to A saturated aliphatic acyl group having 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms And a dialkylamino group having an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R d6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group included in R d6 have a plurality of substituents, the plurality of substituents may be the same or different.
Figure JPOXMLDOC01-appb-C000036
 （式（Ｄ１－３）中、Ｒｄ７及びＲｄ８は、それぞれ１価の有機基であり、ｓは０又は１である。）
Figure JPOXMLDOC01-appb-C000036
 (In the formula (D1-3), R d7 and R d8 are each a monovalent organic group, and s is 0 or 1.)
　式（１２）におけるＲｄ７は、本発明の目的を阻害しない範囲で、種々の有機基から選択できる。Ｒｄ７の好適な例としては、炭素数１～２０のアルキル基、炭素数３～１０のシクロアルキル基、炭素数２～２０の飽和脂肪族アシル基、炭素数２～２０のアルコキシカルボニル基、置換基を有してもよいフェニル基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよい炭素数７～２０のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよい炭素数１１～２０のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、及び置換基を有してもよいヘテロシクリルカルボニル基等が挙げられる。 R d7 in formula (12) can be selected from various organic groups as long as the object of the present invention is not impaired . Preferable examples of R d7 include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, saturated aliphatic acyl groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, Phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, phenylalkyl having 7 to 20 carbon atoms which may have a substituent Group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted carbon number 11 to 20 Naphthylalkyl group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, and the like.
　Ｒｄ７の中では、炭素数１～２０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、エチル基が特に好ましい。 Among R d7 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
　式（１２）におけるＲｄ８は、本発明の目的を阻害しない範囲で特に限定されず、種々の有機基から選択できる。Ｒｄ８として好適な基の具体例としては、炭素数１～２０のアルキル基、置換基を有してもよいフェニル基、置換基を有してもよいナフチル基、及び置換基を有してもよいヘテロシクリル基が挙げられる。Ｒｄ８として、これらの基の中では置換基を有してもよいフェニル基、及び置換基を有してもよいナフチル基がより好ましく、２－メチルフェニル基及びナフチル基が特に好ましい。 R d8 in the formula (12) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of the group suitable as R d8 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. As R d8 , among these groups, a phenyl group which may have a substituent and a naphthyl group which may have a substituent are more preferable, and a 2-methylphenyl group and a naphthyl group are particularly preferable.
　Ｒｄ７又はＲｄ８に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合の置換基としては、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数２～７の飽和脂肪族アシル基、炭素数２～７のアルコキシカルボニル基、炭素数２～７の飽和脂肪族アシルオキシ基、炭素数１～６のアルキル基を有するモノアルキルアミノ基、炭素数１～６のアルキル基を有するジアルキルアミノ基、モルホリン－１－イル基、ピペラジン－１－イル基、ハロゲン、ニトロ基、及びシアノ基等が挙げられる。Ｒｄ７又はＲｄ８に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が更に置換基を有する場合、その置換基の数は、本発明の目的を阻害しない範囲で限定されないが、１～４が好ましい。Ｒｄ７又はＲｄ８に含まれる、フェニル基、ナフチル基、及びヘテロシクリル基が、複数の置換基を有する場合、複数の置換基は、同一であっても異なっていてもよい。 In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R d7 or R d8 further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a carbon number Examples include a dialkylamino group having 1 to 6 alkyl groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R d7 or R d8 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R d7 or R d8 have a plurality of substituents, the plurality of substituents may be the same or different.
　式（Ｄ１）で表される化合物は、ｐが０であり、Ｒｄ２が置換基を有してもよいアリール基であり、Ｒｄ３が水素原子である場合、例えば、下記スキーム１に従って合成することができる。具体的には、下記式（１－１）で表される芳香族化合物を、下記式（１－２）で表されるハロカルボニル化合物を用いて、フリーデルクラフツ反応によりアシル化して、下記式（１－３）で表されるケトン化合物を得、得られたケトン化合物（１－３）を、ヒドロキシルアミンによりオキシム化して下記式（１－４）で表されるオキシム化合物が得られる。なお、下記式（１－２）において、Ｈａｌはハロゲン原子であり、下記式（１－１）、（１－２）、（１－３）、及び（１－４）において、Ｒｄ１、及びＲｄ２は、式（Ｄ１）と同様である。 The compound represented by the formula (D1) is synthesized according to the following scheme 1, for example, when p is 0, R d2 is an aryl group which may have a substituent, and R d3 is a hydrogen atom. be able to. Specifically, an aromatic compound represented by the following formula (1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (1-2), and the following formula: A ketone compound represented by (1-3) is obtained, and the obtained ketone compound (1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (1-4). In the following formula (1-2), Hal is a halogen atom. In the following formulas (1-1), (1-2), (1-3), and (1-4), R d1 and R d2 is the same as in formula (D1).
＜スキーム１＞
Figure JPOXMLDOC01-appb-C000037
 <Scheme 1>
Figure JPOXMLDOC01-appb-C000037
　式（Ｄ１）で表される化合物は、ｐが０であり、Ｒｄ２が置換基を有してもよいアリール基であり、Ｒｄ３が－ＣＯ－Ｒｄ５で表される基である場合、下記スキーム２に従って合成することができる。具体的には、上記スキーム１に記載の方法で得られる式（１－４）のオキシム化合物と、下記式（１－５）で表される酸無水物（（Ｒｄ５ＣＯ）２Ｏ）、又は下記式（１－６）で表される酸ハライド（Ｒｄ５ＣＯＨａｌ、Ｈａｌはハロゲン原子。）とを反応させて、下記式（１－７）で表されるオキシムエステル化合物を得ることができる。なお、下記式（１－４）、（１－５）、（１－６）、及び（１－７）において、Ｒｄ１、Ｒｄ２、及びＲｄ５は式（１）と同様である。 In the compound represented by the formula (D1), when p is 0, R d2 is an aryl group which may have a substituent, and R d3 is a group represented by —CO—R d5 , It can be synthesized according to the following scheme 2. Specifically, an oxime compound of the formula (1-4) obtained by the method described in Scheme 1 above, an acid anhydride ((R d5 CO) 2 O) represented by the following formula (1-5), Alternatively, an oxime ester compound represented by the following formula (1-7) can be obtained by reacting with an acid halide represented by the following formula (1-6) (R d5 COHal, Hal is a halogen atom). . In the following formulas (1-4), (1-5), (1-6), and (1-7), R d1 , R d2 , and R d5 are the same as those in formula (1).
＜スキーム２＞
Figure JPOXMLDOC01-appb-C000038
 <Scheme 2>
Figure JPOXMLDOC01-appb-C000038
　式（Ｄ１）で表される化合物は、ｐが０であり、Ｒｄ２が炭素数１～１０の脂肪族炭化水素基であり、Ｒｄ３が水素原子である場合、Ｒｄ２－ＣＯ－Ｒｄ１で表されるケトン化合物を、スキーム１に記載の方法に従って、ヒドロキシルアミンによりオキシム化して、Ｒｄ２－Ｃ（＝Ｎ－ＯＨ）－Ｒｄ１で表される化合物として得ることができる。
　また、式（Ｄ１）で表される化合物は、ｐが０であり、Ｒｄ２が炭素数１～１０の脂肪族炭化水素基であり、Ｒｄ３が－ＣＯ－Ｒｄ５で表される基である場合、Ｒｄ２－Ｃ（＝Ｎ－ＯＨ）－Ｒｄ１で表されるオキシム化合物を、スキーム２に記載される方法に従ってアシル化することで、Ｒｄ２－Ｃ（＝Ｎ－Ｏ－ＣＯ－Ｒｄ５）－Ｒｄ１で表される化合物として得ることができる。 In the compound represented by the formula (D1), when p is 0, R d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R d3 is a hydrogen atom, R d2 —CO—R d1 In accordance with the method described in Scheme 1, the ketone compound represented by can be oximed with hydroxylamine to obtain a compound represented by R d2 —C (═N—OH) —R d1 .
In the compound represented by the formula (D1), p is 0, R d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R d3 is a group represented by —CO—R d5. In some cases, the oxime compound represented by R d2 —C (═N—OH) —R d1 is acylated according to the method described in Scheme 2 to yield R d2 —C (═N—O—CO— It can be obtained as a compound represented by R d5 ) —R d1 .
　式（Ｄ１）で表される化合物は、ｐが１であり、Ｒｄ３が水素原子である場合、例えば、下記スキーム３に従って合成することができる。具体的には、下記式（２－１）で表されるケトン化合物に、塩酸の存在下に下記式（２－２）で表される亜硝酸エステル（ＲＯＮＯ、Ｒは炭素数１～６のアルキル基。）を反応させて、下記式（２－３）で表されるケトオキシム化合物を得、次いで、下記式（２－３）で表されるケトオキシム化合物が得られる。なお、下記式（２－１）、及び（２－３）において、Ｒｄ１、及びＲｄ２は、式（Ｄ１）と同様である。 When p is 1 and R d3 is a hydrogen atom, the compound represented by the formula (D1) can be synthesized according to the following scheme 3, for example. Specifically, a ketone compound represented by the following formula (2-1) is added to a nitrite ester (RONO, R represents a carbon number of 1 to 6) represented by the following formula (2-2) in the presence of hydrochloric acid. The alkyl group.) Is reacted to obtain a ketoxime compound represented by the following formula (2-3), and then a ketoxime compound represented by the following formula (2-3) is obtained. In the following formulas (2-1) and (2-3), R d1 and R d2 are the same as those in the formula (D1).
＜スキーム３＞
Figure JPOXMLDOC01-appb-C000039
 <Scheme 3>
Figure JPOXMLDOC01-appb-C000039
　式（Ｄ１）で表される化合物は、ｐが１であり、Ｒｄ３が－ＣＯ－Ｒｄ５で表される基である場合、下記スキーム４に従って合成することができる。具体的には、上記スキーム３に記載の方法で得られる式（２－３）のオキシム化合物と、下記式（２－４）で表される酸無水物（（Ｒｄ５ＣＯ）２Ｏ）、又は下記式（２－５）で表される酸ハライド（Ｒｄ５ＣＯＨａｌ、Ｈａｌはハロゲン原子。）とを反応させて、下記式（２－６）で表されるオキシムエステル化合物を得ることができる。なお、下記式（２－３）、（２－４）、（２－５）、及び（２－６）において、Ｒｄ１、Ｒｄ２、及びＲｄ５は、式（Ｄ１）と同様である。 The compound represented by the formula (D1) can be synthesized according to the following scheme 4 when p is 1 and R d3 is a group represented by —CO—R d5 . Specifically, an oxime compound of the formula (2-3) obtained by the method described in Scheme 3 above, an acid anhydride ((R d5 CO) 2 O) represented by the following formula (2-4), Alternatively, an oxime ester compound represented by the following formula (2-6) can be obtained by reacting with an acid halide represented by the following formula (2-5) (R d5 COHal, Hal is a halogen atom). . In the following formulas (2-3), (2-4), (2-5), and (2-6), R d1 , R d2 , and R d5 are the same as those in the formula (D1).
＜スキーム４＞
Figure JPOXMLDOC01-appb-C000040
 <Scheme 4>
Figure JPOXMLDOC01-appb-C000040
　式（Ｄ１）で表されるオキシム化合物の中でも特に好適な化合物としては、下記式の化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000041
 Among the oxime compounds represented by the formula (D1), particularly preferred compounds include compounds represented by the following formula.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　オキシム化合物（Ａ－２）としては、上記式（Ｄ１）で表されるオキシム化合物以外のその他のオキシム化合物を用いることもできる。その他のオキシム化合物としては、ネガ型感放射線性組成物１において記載したオキシム系光重合開始剤を用いることができる。 As the oxime compound (A-2), other oxime compounds other than the oxime compound represented by the above formula (D1) can also be used. As other oxime compounds, the oxime photopolymerization initiator described in the negative radiation-sensitive composition 1 can be used.
　ネガ型感放射線性組成物２における感光性成分の含有量は、本発明の目的を阻害しない範囲で特に限定されない。ネガ型感放射線性組成物２における感光性成分の含有量は、ポリアミック酸１００質量に対して１～５０質量部が好ましく、１～３０質量部がより好ましい。 The content of the photosensitive component in the negative radiation sensitive composition 2 is not particularly limited as long as the object of the present invention is not impaired. The content of the photosensitive component in the negative radiation sensitive composition 2 is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polyamic acid.
［その他の有機溶剤（一般式（１）で表される化合物以外の有機溶剤）］
　ネガ型感放射線性組成物２は、その他の有機溶剤を含有してもよい。その他の有機溶剤は、単独で又は２種以上組み合わせて用いることができる。その他の有機溶剤としては、ネガ型感放射線性組成物１において例示したものを用いることができる。 [Other organic solvents (organic solvents other than the compound represented by formula (1))]
The negative radiation sensitive composition 2 may contain other organic solvents. Other organic solvents can be used alone or in combination of two or more. As other organic solvents, those exemplified in the negative radiation-sensitive composition 1 can be used.
　ネガ型感放射線性組成物２において、溶剤の含有量は、ネガ型感放射線性組成物２の固形分濃度が１～５０質量％となる量が好ましく、５～４０質量％となる量がより好ましい。また、ネガ型感放射線性組成物２に含まれる溶剤において、上記一般式（１）で表される化合物とその他の有機溶剤との質量比は、５：９５～１００：０であることが好ましく、２０：８０～１００：０であることがより好ましい。溶剤の含有量及び上記一般式（１）で表される化合物とその他の有機溶剤との質量比を上記の範囲とすることにより、ネガ型感放射線性組成物２は、感度、保存安定性、塗布性、現像性、及び安全性に優れたものとなりやすく、ネガ型感放射線性組成物２を露光及び現像することにより形成されるパターンは、異物の発生が抑制されたものとなりやすい。 In the negative radiation sensitive composition 2, the content of the solvent is preferably such that the solid concentration of the negative radiation sensitive composition 2 is 1 to 50% by mass, more preferably 5 to 40% by mass. preferable. In the solvent contained in the negative radiation-sensitive composition 2, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0. 20:80 to 100: 0 is more preferable. By making the content of the solvent and the mass ratio of the compound represented by the general formula (1) and the other organic solvent within the above range, the negative radiation-sensitive composition 2 has sensitivity, storage stability, A pattern formed by exposing and developing the negative radiation-sensitive composition 2 is likely to be excellent in applicability, developability, and safety, and generation of foreign matters is likely to be suppressed.
［その他の成分］
　ネガ型感放射線性組成物２は、必要に応じて、各種の添加剤を含有していてもよい。添加剤としては、増感剤、硬化促進剤、充填剤、密着促進剤、酸化防止剤、凝集防止剤、熱重合禁止剤、消泡剤、界面活性剤等が挙げられる。 [Other ingredients]
The negative radiation sensitive composition 2 may contain various additives as necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.
＜ネガ型感放射線性組成物３＞
　ネガ型感放射線性組成物３は、上記一般式（１）で表される化合物と、ポリベンゾオキサゾール前駆体と、感光性成分とを含有する感放射線性ポリベンゾオキサゾール前駆体組成物である。 <Negative type radiation sensitive composition 3>
The negative radiation sensitive composition 3 is a radiation sensitive polybenzoxazole precursor composition containing the compound represented by the general formula (1), a polybenzoxazole precursor, and a photosensitive component.
［一般式（１）で表される化合物］
　一般式（１）で表される化合物としては、感放射線性組成物の一般的な説明において例示したものを用いることができる。上記一般式（１）で表される化合物は、単独で又は２種以上組み合わせて用いることができる。 [Compound represented by general formula (1)]
As the compound represented by the general formula (1), those exemplified in the general description of the radiation-sensitive composition can be used. The compounds represented by the general formula (1) can be used alone or in combination of two or more.
［ポリベンゾオキサゾール前駆体］
　ポリベンゾオキサゾール前駆体は、単独で又は２種以上を混合して用いることができる。ポリベンゾオキサゾール前駆体の合成原料としては、芳香族ジアミンジオールと、特定の構造のジカルボニル化合物とを用いる。以下、芳香族ジアミンジオールと、ジカルボニル化合物とについて説明する。 [Polybenzoxazole precursor]
A polybenzoxazole precursor can be used individually or in mixture of 2 or more types. As a synthesis raw material for the polybenzoxazole precursor, an aromatic diamine diol and a dicarbonyl compound having a specific structure are used. Hereinafter, the aromatic diamine diol and the dicarbonyl compound will be described.
（芳香族ジアミンジオール）
　本発明では、芳香族ジアミンジオールとして下記式（２１）で表される化合物を用いる。芳香族ジアミンジオールは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Figure JPOXMLDOC01-appb-C000051
 （式中、Ｒａ１は１以上の芳香環を含む４価の有機基であり、式（２１）で表される芳香族ジアミンジオールに含まれる２組のアミノ基と水酸基との組み合わせに関して、それぞれの組み合わせでは、アミノ基と水酸基とは、Ｒａ１に含まれる芳香環上の隣接する２つの炭素原子に結合している。） (Aromatic diamine diol)
In the present invention, a compound represented by the following formula (21) is used as the aromatic diamine diol. One kind of aromatic diamine diol may be used alone, or two or more kinds may be used in combination.
Figure JPOXMLDOC01-appb-C000051
 (In the formula, R a1 is a tetravalent organic group containing one or more aromatic rings, and regarding the combination of two amino groups and a hydroxyl group contained in the aromatic diamine diol represented by the formula (21), respectively. In this combination, the amino group and the hydroxyl group are bonded to two adjacent carbon atoms on the aromatic ring contained in R a1 .)
　式（２１）中、Ｒａ１は、１以上の芳香環を含む４価の有機基であり、その炭素数は６～５０が好ましく、６～３０がより好ましい。Ｒａ１は、芳香族基であってもよく、２以上の芳香族基が、脂肪族炭化水素基及びハロゲン化脂肪族炭化水素基や、酸素原子、硫黄原子、及び窒素原子等のヘテロ原子を含む結合を介して結合された基であってもよい。Ｒａ１に含まれる、酸素原子、硫黄原子、及び窒素原子等のヘテロ原子を含む結合としては、－ＣＯＮＨ－、－ＮＨ－、－Ｎ＝Ｎ－、－ＣＨ＝Ｎ－、－ＣＯＯ－、－Ｏ－、－ＣＯ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－Ｓ－Ｓ－等が挙げられ、－Ｏ－、－ＣＯ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－Ｓ－Ｓ－が好ましい。 In the formula (21), R a1 is a tetravalent organic group containing one or more aromatic rings, and preferably has 6 to 50 carbon atoms, more preferably 6 to 30 carbon atoms. R a1 may be an aromatic group, and two or more aromatic groups may be an aliphatic hydrocarbon group or a halogenated aliphatic hydrocarbon group, or a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may be a group bonded through a bond including. Examples of the bond containing a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom contained in R a1 include —CONH—, —NH—, —N═N—, —CH═N—, —COO—, — O—, —CO—, —SO—, —SO 2 —, —S—, —S—S— and the like can be mentioned, and —O—, —CO—, —SO—, —SO 2 —, —S -And -SS- are preferred.
　Ｒａ１に含まれる芳香環は、芳香族複素環であってもよい。Ｒａ１中のアミノ基及び水酸基と結合する芳香環はベンゼン環であるのが好ましい。Ｒａ１中のアミノ基及び水酸基と結合する環が２以上の環を含む縮合環である場合、当該縮合環中のアミノ基及び水酸基と結合する環はベンゼン環であるのが好ましい。 The aromatic ring contained in R a1 may be an aromatic heterocyclic ring. The aromatic ring bonded to the amino group and hydroxyl group in R a1 is preferably a benzene ring. When the ring bonded to the amino group and hydroxyl group in R a1 is a condensed ring containing two or more rings, the ring bonded to the amino group and hydroxyl group in the condensed ring is preferably a benzene ring.
　Ｒａ１の好適な例としては、下記式（１－１）～（１－９）のいずれかで表される基が挙げられる。
Figure JPOXMLDOC01-appb-C000052
 （式（１－１）中、Ｘ１は、炭素数１～１０のアルキレン基、炭素数１～１０のフッ素化アルキレン基、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、及び単結合からなる群より選択される１種である。式（１－２）～（１－５）中、Ｙ１は、それぞれ、同一でも異なっていてもよく、－ＣＨ２－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、及び単結合からなる群より選択される１種である。） Preferable examples of R a1 include groups represented by any of the following formulas (1-1) to (1-9).
Figure JPOXMLDOC01-appb-C000052
 (In the formula (1-1), X 1 represents an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, —O—, —S—, —SO—, —SO 2 —, One selected from the group consisting of —CO—, —COO—, —CONH—, and a single bond, wherein Y 1 s in the formulas (1-2) to (1-5) are the same or different; And may be one selected from the group consisting of —CH 2 —, —O—, —S—, —SO—, —SO 2 —, —CO—, and a single bond.
　上記式（１－１）～（１－９）のいずれかで表される基は、芳香環上に１又は複数の置換基を有していてもよい。置換基の好適な例としては、フッ素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数１～６のフッ素化アルキル基、炭素数１～６のフッ素化アルコキシ基が好ましい。置換基がフッ素化アルキル基又はフッ素化アルコキシ基である場合、パーフルオロアルキル基又はパーフルオロアルコキシ基であるのが好ましい。 The group represented by any one of the above formulas (1-1) to (1-9) may have one or more substituents on the aromatic ring. Preferable examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkoxy having 1 to 6 carbon atoms. Groups are preferred. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
　上記式（２１）で表される化合物の具体例としては、２，４－ジアミノ－１，５－ベンゼンジオール、２，５－ジアミノ－１，４－ベンゼンジオール、２，５－ジアミノ－３－フルオロ－１，４－ベンゼンジオール、２，５－ジアミノ－３，６－ジフルオロ－１，４－ベンゼンジオール、２，６－ジアミノ－１，５－ジヒドロキシナフタレン、１，５－ジアミノ－２，６－ジヒドロキシナフタレン、２，６－ジアミノ－３，７－ジヒドロキシナフタレン、１，６－ジアミノ－２，５－ジヒドロキシナフタレン、４，４’－ジアミノ－３，３’－ジヒドロキシビフェニル、３，３’－ジアミノ－４，４’－ジヒドロキシビフェニル、２，３’－ジアミノ－３，２’－ジヒドロキシビフェニル、３，４’－ジアミノ－４，３’－ジヒドロキシビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシ－６，６’－ジトリフルオロメチルビフェニル、３，３’－ジアミノ－４，４’－ジヒドロキシ－６，６’－ジトリフルオロメチルビフェニル、２，３’－ジアミノ－３，２’－ジヒドロキシ－６，６’－ジトリフルオロメチルビフェニル、３，４’－ジアミノ－４，３’－ジヒドロキシ－６，６’－ジトリフルオロメチルビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシ－５，５’－ジトリフルオロメチルビフェニル、３，３’－ジアミノ－４，４’－ジヒドロキシ－５，５’－ジトリフルオロメチルビフェニル、２，３’－ジアミノ－３，２’－ジヒドロキシ－５，５’－ジトリフルオロメチルビフェニル、３，４’－ジアミノ－４，３’－ジヒドロキシ－５，５’－ジトリフルオロメチルビフェニル、ビス（４－アミノ－３－ヒドロキシフェニル）メタン、ビス（３－アミノ－４－ヒドロキシフェニル）メタン、３，４’－ジアミノ－４，３’－ジヒドロキシジフェニルメタン、ビス（４－アミノ－３－ヒドロキシ－６－トリフルオロメチル）メタン、ビス（３－アミノ－４－ヒドロキシ－６－トリフルオロメチル）メタン、３，４’－ジアミノ－４，３’－ジヒドロキシ－６，６’－ジトリフルオロメチルジフェニルメタン、ビス（４－アミノ－３－ヒドロキシフェニル）ジフルオロメタン、ビス（３－アミノ－４－ヒドロキシフェニル）ジフルオロメタン、３，４’－ジアミノ－４，３’－ジヒドロキシジフェニルジフルオロメタン、ビス（４－アミノ－３－ヒドロキシ－６－トリフルオロメチルフェニル）ジフルオロメタン、ビス（３－アミノ－４－ヒドロキシ－６－トリフルオロメチルフェニル）ジフルオロメタン、３，４’－ジアミノ－４，３’－ジヒドロキシ－６，６’－ジトリフルオロメチルジフェニルジフルオロメタン、ビス（４－アミノ－３－ヒドロキシフェニル）エーテル、ビス（３－アミノ－４－ヒドロキシフェニル）エーテル、３，４’－ジアミノ－４，３’－ジヒドロキシジフェニルエーテル、ビス（４－アミノ－３－ヒドロキシ－６－トリフルオロメチルフェニル）エーテル、ビス（３－アミノ－４－ヒドロキシ－６－トリフルオロメチルフェニル）エーテル、３，４’－ジアミノ－４，３’－ジヒドロキシ－６，６’－ジトリフルオロメチルジフェニルエーテル、ビス（４－アミノ－３－ヒドロキシフェニル）ケトン、ビス（３－アミノ－４－ヒドロキシフェニル）ケトン、３，４’－ジアミノ－４，３’－ジヒドロキシジフェニルケトン、ビス（４－アミノ－３－ヒドロキシ－６－トリフルオロメチル）ケトン、ビス（３－アミノ－４－ヒドロキシ－６－トリフルオロメチル）ケトン、３，４’－ジアミノ－４，３’－ジヒドロキシ－６，６’－ジトリフルオロメチルジフェニルケトン、２，２－ビス（４－アミノ－３－ヒドロキシフェニル）プロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、２－（３－アミノ－４－ヒドロキシフェニル）－２－（４’－アミノ－３’－ヒドロキシフェニル）プロパン、２，２－ビス（４－アミノ－３－ヒドロキシ－６－トリフルオロメチルフェニル）プロパン、２，２－ビス（３－アミノ－４－ヒドロキシ－６－トリフルオロメチルフェニル）プロパン、２－（３－アミノ－４－ヒドロキシ－６－トリフルオロメチルフェニル）－２－（４’－アミノ－３’－ヒドロキシ－６’－トリフルオロメチルフェニル）プロパン、２，２－ビス（３－アミノ－４－ヒドロキシ－５－トリフルオロメチルフェニル）プロパン、２，２－ビス（４－アミノ－３－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、２－（３－アミノ－４－ヒドロキシフェニル）－２－（４’－アミノ－３’－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス（４－アミノ－３－ヒドロキシ－６－トリフルオロメチルフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－ヒドロキシ－６－トリフルオロメチルフェニル）ヘキサフルオロプロパン、２－（３－アミノ－４－ヒドロキシ－６－トリフルオロメチルフェニル）－２－（４’－アミノ－３’－ヒドロキシ－６’－トリフルオロメチルフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－ヒドロキシ－５－トリフルオロメチルフェニル）ヘキサフルオロプロパン、ビス（４－アミノ－３－ヒドロキシフェニル）スルホン、ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、３，４’－ジアミノ－４，３’－ジヒドロキシジフェニルスルホン、ビス（４－アミノ－３－ヒドロキシ－６－トリフルオロメチル）スルホン、ビス（３－アミノ－４－ヒドロキシ－６－トリフルオロメチル）スルホン、３，４’－ジアミノ－４，３’－ジヒドロキシ－６，６’－ジトリフルオロメチルジフェニルスルホン、ビス（４－アミノ－３－ヒドロキシフェニル）スルフィド、ビス（３－アミノ－４－ヒドロキシフェニル）スルフィド、３，４’－ジアミノ－４，３’－ジヒドロキシジフェニルスルフィド、ビス（４－アミノ－３－ヒドロキシ－６－トリフルオロメチル）スルフィド、ビス（３－アミノ－４－ヒドロキシ－６－トリフルオロメチル）スルフィド、３，４’－ジアミノ－４，３’－ジヒドロキシ－６，６’－ジトリフルオロメチルジフェニルスルフィド、（４－アミノ－３－ヒドロキシフェニル）４－アミノ－３－ヒドロキシフェニルベンゾエート、（３－アミノ－４－ヒドロキシフェニル）３－アミノ４－ヒドロキシフェニルベンゾエート、（３－アミノ－４－ヒドロキシフェニル）４－アミノ－３－ヒドロキシフェニルベンゾエート、（４－アミノ－３－ヒドロキシフェニル）３－アミノ－４－ヒドロキシフェニルベンゾエート、Ｎ－（４－アミノ－３－ヒドロキシフェニル）４－アミノ－３－ヒドロキシベンズアミド、Ｎ－（３－アミノ－４－ヒドロキシフェニル）３－アミノ４－ヒドロキシフェニルベンズアミド、Ｎ－（３－アミノ－４－ヒドロキシフェニル）４－アミノ－３－ヒドロキシフェニルベンズアミド、Ｎ－（４－アミノ－３－ヒドロキシフェニル）３－アミノ－４－ヒドロキシフェニルベンズアミド、２，４’－ビス（４－アミノ－３－ヒドロキシフェノキシ）ビフェニル、２，４’－ビス（３－アミノ－４－ヒドロキシフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－３－ヒドロキシフェノキシ）ビフェニル、４，４’－ビス（３－アミノ－４－ヒドロキシフェノキシ）ビフェニル、ジ［４－（４－アミノ－３－ヒドロキシフェノキシ）フェニル］エーテル、ジ［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］エーテル、２，４’－ビス（４－アミノ－３－ヒドロキシフェノキシ）ベンゾフェノン、２，４’－ビス（３－アミノ－４－ヒドロキシフェノキシ）ベンゾフェノン、４，４’－ビス（４－アミノ－３－ヒドロキシフェノキシ）ベンゾフェノン、４，４’－ビス（３－アミノ－４－ヒドロキシフェノキシ）ベンゾフェノン、２，４’－ビス（４－アミノ－３－ヒドロキシフェノキシ）オクタフルオロビフェニル、２，４’－ビス（３－アミノ－４－ヒドロキシフェノキシ）オクタフルオロビフェニル、４，４’－ビス（４－アミノ－３－ヒドロキシフェノキシ）オクタフルオロビフェニル、４，４’－ビス（３－アミノ－４－ヒドロキシフェノキシ）オクタフルオロビフェニル、２，４’－ビス（４－アミノ－３－ヒドロキシフェノキシ）オクタフルオロベンゾフェノン、２，４’－ビス（３－アミノ－４－ヒドロキシフェノキシ）オクタフルオロベンゾフェノン、４，４’－ビス（４－アミノ－３－ヒドロキシフェノキシ）オクタフルオロベンゾフェノン、４，４’－ビス（３－アミノ－４－ヒドロキシフェノキシ）オクタフルオロベンゾフェノン、２，２－ビス［４－（４－アミノ－３－ヒドロキシフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノ－３－ヒドロキシフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］ヘキサフルオロプロパン、２，８－ジアミノ－３，７－ジヒドロキシジベンゾフラン、２，８－ジアミノ－３，７－ジヒドロキシフルオレン、２，６－ジアミノ－３，７－ジヒドロキシキサンテン、９，９－ビス－（４－アミノ－３－ヒドロキシフェニル）フルオレン、及び９，９－ビス－（３－アミノ－４－ヒドロキシフェニル）フルオレンが挙げられる。 Specific examples of the compound represented by the above formula (21) include 2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, 2,5-diamino-3- Fluoro-1,4-benzenediol, 2,5-diamino-3,6-difluoro-1,4-benzenediol, 2,6-diamino-1,5-dihydroxynaphthalene, 1,5-diamino-2,6 -Dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5-dihydroxynaphthalene, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'- Diamino-4,4′-dihydroxybiphenyl, 2,3′-diamino-3,2′-dihydroxybiphenyl, 3,4′-diamino-4,3′-dihydroxybiphenyl Phenyl, 4,4′-diamino-3,3′-dihydroxy-6,6′-ditrifluoromethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-6,6′-ditrifluoromethylbiphenyl, 2,3′-diamino-3,2′-dihydroxy-6,6′-ditrifluoromethylbiphenyl, 3,4′-diamino-4,3′-dihydroxy-6,6′-ditrifluoromethylbiphenyl, 4, 4'-diamino-3,3'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 2,3 ' -Diamino-3,2'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-5,5'- Trifluoromethylbiphenyl, bis (4-amino-3-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) methane, 3,4'-diamino-4,3'-dihydroxydiphenylmethane, bis (4- Amino-3-hydroxy-6-trifluoromethyl) methane, bis (3-amino-4-hydroxy-6-trifluoromethyl) methane, 3,4'-diamino-4,3'-dihydroxy-6,6 ' -Ditrifluoromethyldiphenylmethane, bis (4-amino-3-hydroxyphenyl) difluoromethane, bis (3-amino-4-hydroxyphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxydiphenyldifluoromethane Bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) D) Difluoromethane, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyldifluoromethane Bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) ether, 3,4'-diamino-4,3'-dihydroxydiphenyl ether, bis (4-amino-3- Hydroxy-6-trifluoromethylphenyl) ether, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) ether, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditri Fluoromethyldiphenyl ether, bis (4-amino-3-hydroxyphenyl) keto Bis (3-amino-4-hydroxyphenyl) ketone, 3,4'-diamino-4,3'-dihydroxydiphenylketone, bis (4-amino-3-hydroxy-6-trifluoromethyl) ketone, bis ( 3-amino-4-hydroxy-6-trifluoromethyl) ketone, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl ketone, 2,2-bis (4-amino) -3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2- (3-amino-4-hydroxyphenyl) -2- (4'-amino-3'-hydroxy) Phenyl) propane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) propane, 2,2-bis (3-amino) 4-hydroxy-6-trifluoromethylphenyl) propane, 2- (3-amino-4-hydroxy-6-trifluoromethylphenyl) -2- (4′-amino-3′-hydroxy-6′-trifluoro) Methylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2 -Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (3-amino-4-hydroxyphenyl) -2- (4'-amino-3'-hydroxyphenyl) hexafluoropropane, 2,2 -Bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis ( 3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-6-trifluoromethylphenyl) -2- (4′-amino-3′-hydroxy -6′-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) sulfone Bis (3-amino-4-hydroxyphenyl) sulfone, 3,4'-diamino-4,3'-dihydroxydiphenylsulfone, bis (4-amino-3-hydroxy-6-trifluoromethyl) sulfone, bis ( 3-Amino-4-hydroxy-6-trifluoromethyl) sulfone, 3,4'-diamino 4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl sulfone, bis (4-amino-3-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfide, 3,4'-diamino -4,3'-dihydroxydiphenyl sulfide, bis (4-amino-3-hydroxy-6-trifluoromethyl) sulfide, bis (3-amino-4-hydroxy-6-trifluoromethyl) sulfide, 3,4 ' -Diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl sulfide, (4-amino-3-hydroxyphenyl) 4-amino-3-hydroxyphenylbenzoate, (3-amino-4-hydroxyphenyl) ) 3-amino 4-hydroxyphenyl benzoate, (3-amino 4-hydroxyphenyl) 4-amino-3-hydroxyphenylbenzoate, (4-amino-3-hydroxyphenyl) 3-amino-4-hydroxyphenylbenzoate, N- (4-amino-3-hydroxyphenyl) 4-amino -3-hydroxybenzamide, N- (3-amino-4-hydroxyphenyl) 3-amino-4-hydroxyphenylbenzamide, N- (3-amino-4-hydroxyphenyl) 4-amino-3-hydroxyphenylbenzamide, N -(4-amino-3-hydroxyphenyl) 3-amino-4-hydroxyphenylbenzamide, 2,4'-bis (4-amino-3-hydroxyphenoxy) biphenyl, 2,4'-bis (3-amino- 4-hydroxyphenoxy) biphenyl, 4,4'-bis (4-amino) -3-hydroxyphenoxy) biphenyl, 4,4′-bis (3-amino-4-hydroxyphenoxy) biphenyl, di [4- (4-amino-3-hydroxyphenoxy) phenyl] ether, di [4- (3 -Amino-4-hydroxyphenoxy) phenyl] ether, 2,4′-bis (4-amino-3-hydroxyphenoxy) benzophenone, 2,4′-bis (3-amino-4-hydroxyphenoxy) benzophenone, 4, 4'-bis (4-amino-3-hydroxyphenoxy) benzophenone, 4,4'-bis (3-amino-4-hydroxyphenoxy) benzophenone, 2,4'-bis (4-amino-3-hydroxyphenoxy) Octafluorobiphenyl, 2,4'-bis (3-amino-4-hydroxyphenoxy) octaful Robiphenyl, 4,4′-bis (4-amino-3-hydroxyphenoxy) octafluorobiphenyl, 4,4′-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 2,4′-bis ( 4-Amino-3-hydroxyphenoxy) octafluorobenzophenone, 2,4′-bis (3-amino-4-hydroxyphenoxy) octafluorobenzophenone, 4,4′-bis (4-amino-3-hydroxyphenoxy) octa Fluorobenzophenone, 4,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobenzophenone, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-Amino-4-hydroxyphenoxy) phenyl] propane 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, 2, 8-diamino-3,7-dihydroxydibenzofuran, 2,8-diamino-3,7-dihydroxyfluorene, 2,6-diamino-3,7-dihydroxyxanthene, 9,9-bis- (4-amino-3- Hydroxyphenyl) fluorene, and 9,9-bis- (3-amino-4-hydroxyphenyl) fluorene.
　これらの中では、透明性が優れるポリベンゾオキサゾール樹脂を形成できる点から、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパンが好ましい。 Among these, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferable because a polybenzoxazole resin having excellent transparency can be formed.
（ジカルボニル化合物）
　ポリベンゾオキサゾール前駆体の合成原料としては、以上説明した芳香族ジアミンジオールとともに、下記式（２２）で表されるジカルボニル化合物を用いる。前述の芳香族ジアミンジオールと、下記式（２２）で表されるジカルボニル化合物とを縮合させることにより、ポリベンゾオキサゾール前駆体が得られる。
Figure JPOXMLDOC01-appb-C000053
 （式中、Ｒａ２は２価の有機基であり、Ａは水素原子又はハロゲン原子を表す。） (Dicarbonyl compound)
As a synthesis raw material for the polybenzoxazole precursor, a dicarbonyl compound represented by the following formula (22) is used together with the aromatic diamine diol described above. A polybenzoxazole precursor is obtained by condensing the aromatic diamine diol described above and a dicarbonyl compound represented by the following formula (22).
Figure JPOXMLDOC01-appb-C000053
 (In the formula, R a2 is a divalent organic group, and A represents a hydrogen atom or a halogen atom.)
　式（２２）中のＲａ２は、芳香族基であってもよく、脂肪族基であってもよく、芳香族基と脂肪族基とを組み合わせた基であってもよい。得られるポリベンゾオキサゾール樹脂の耐熱性、機械的特性、耐薬品性等が良好である点から、Ｒａ２は、芳香族基及び／又は脂環式基を含む基であるのが好ましい。Ｒａ２に含まれる芳香族基は、芳香族炭化水素基であってもよく、芳香族複素環基であってもよい。 R a2 in formula (22) may be an aromatic group, an aliphatic group, or a group in which an aromatic group and an aliphatic group are combined. R a2 is preferably a group containing an aromatic group and / or an alicyclic group from the viewpoint that the resulting polybenzoxazole resin has good heat resistance, mechanical properties, chemical resistance, and the like. The aromatic group contained in R a2 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
　Ｒａ２は、炭素原子、及び水素原子の他に、ハロゲン原子、酸素原子、及び硫黄原子を含んでいてもよい。Ｒａ２が酸素原子、窒素原子、又は硫黄原子を含む場合、酸素原子、窒素原子、又は硫黄原子は、２価の含窒素複素環基、－ＣＯＮＨ－、－ＮＨ－、－Ｎ＝Ｎ－、－ＣＨ＝Ｎ－、－ＣＯＯ－、－Ｏ－、－ＣＯ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－Ｓ－Ｓ－から選択される基として、Ｒａ２に含まれてもよく、－Ｏ－、－ＣＯ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－Ｓ－Ｓ－から選択される基として、Ｒａ２に含まれるのがより好ましい。 R a2 may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to the carbon atom and the hydrogen atom. When R a2 contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom is a divalent nitrogen-containing heterocyclic group, —CONH—, —NH—, —N═N—, Included in R a2 as a group selected from —CH═N—, —COO—, —O—, —CO—, —SO—, —SO 2 —, —S—, and —S—S—. More preferably, R a2 is more preferably included as a group selected from —O—, —CO—, —SO—, —SO 2 —, —S—, and —S—S—.
　式（２２）中、２つのＡの一方が水素原子であり、他方がハロゲン原子であってもよいが、２つのＡがともに水素原子であるか、２つのＡがともにハロゲン原子であるのが好ましい。Ａがハロゲン原子である場合、Ａとして塩素原子、臭素原子、及びヨウ素原子が好ましく、塩素原子がより好ましい。 In formula (22), one of the two A may be a hydrogen atom and the other may be a halogen atom, but both A are hydrogen atoms or both A are halogen atoms. preferable. When A is a halogen atom, as A, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a chlorine atom is more preferable.
　式（２２）で表されるジカルボニル化合物として、２つのＡがともに水素原子であるジアルデヒド化合物を用いる場合、下記式（１０）で表されるポリベンゾオキサゾール中間体が製造される。
Figure JPOXMLDOC01-appb-C000054
 （式中、Ｒａ１及びＲａ２は、式（２１）及び式（２２）と同様であり、ｎは式（１０）で表される単位の繰り返し数である。） When a dialdehyde compound in which two A are both hydrogen atoms is used as the dicarbonyl compound represented by the formula (22), a polybenzoxazole intermediate represented by the following formula (10) is produced.
Figure JPOXMLDOC01-appb-C000054
 (In the formula, R a1 and R a2 are the same as those in the formulas (21) and (22), and n is the number of repeating units represented by the formula (10).)
　式（２２）で表されるジカルボニル化合物として、２つのＡがともにハロゲン原子であるジカルボン酸ジハライドを用いる場合、下記式（２０）で表されるポリベンゾオキサゾール中間体が製造される。
Figure JPOXMLDOC01-appb-C000055
 （式中、Ｒａ１及びＲａ２は、式（２１）及び式（２２）と同様であり、ｎは式（２０）で表される単位の繰り返し数である。） When a dicarboxylic acid dihalide in which two A are both halogen atoms is used as the dicarbonyl compound represented by the formula (22), a polybenzoxazole intermediate represented by the following formula (20) is produced.
Figure JPOXMLDOC01-appb-C000055
 (In the formula, R a1 and R a2 are the same as in formula (21) and formula (22), and n is the number of repeating units represented by formula (20).)
　以下、ジカルボニル化合物として好適な化合物である、ジアルデヒド化合物と、ジカルボン酸ジハライドとについて説明する。 Hereinafter, the dialdehyde compound and the dicarboxylic acid dihalide, which are suitable compounds as the dicarbonyl compound, will be described.
・ジアルデヒド化合物
　ポリベンゾオキサゾール前駆体の原料として用いるジアルデヒド化合物は、下記式（２－１）で表される化合物である。ジアルデヒド化合物は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Figure JPOXMLDOC01-appb-C000056
 （式中、Ｒａ２は、式（２２）と同様である。） -Dialdehyde compound The dialdehyde compound used as a raw material of the polybenzoxazole precursor is a compound represented by the following formula (2-1). A dialdehyde compound may be used individually by 1 type, and may be used in combination of 2 or more type.
Figure JPOXMLDOC01-appb-C000056
 (In the formula, R a2 is the same as in formula (22).)
　式（２－１）中のＲａ２として好適な芳香族基又は芳香環含有基としては、以下の基が挙げられる。
Figure JPOXMLDOC01-appb-C000057
 （上記式中、Ｘ２は、炭素数１～１０のアルキレン基、炭素数１～１０のフッ素化アルキレン基、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、及び単結合からなる群より選択される１種である。Ｘ２が複数である場合、複数のＸ２は同一でも異なっていてもよい。Ｙ２は、それぞれ、同一でも異なっていてもよく、－ＣＨ２－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、及び単結合からなる群より選択される１種である。ｐ及びｑは、それぞれ０～３の整数である。） Examples of the aromatic group or aromatic ring-containing group suitable as R a2 in formula (2-1) include the following groups.
Figure JPOXMLDOC01-appb-C000057
 (In the above formula, X 2 represents an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, —O—, —S—, —SO—, —SO 2 —, —CO—, -COO -, - CONH-, and if .X 2 is one selected from the group consisting of a single bond is more, a plurality of X 2 are optionally be the same or different .Y 2, respectively, They may be the same or different, and are one selected from the group consisting of —CH 2 —, —O—, —S—, —SO—, —SO 2 —, —CO—, and a single bond. And q are each an integer of 0 to 3.)
　式（２－１）中のＲａ２として好適な脂環式基又は脂環含有基としては、以下の基が挙げられる。
Figure JPOXMLDOC01-appb-C000058
 （上記式中、Ｘ２は、炭素数１～１０のアルキレン基、炭素数１～１０のフッ素化アルキレン基、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、及び単結合からなる群より選択される１種である。Ｘ２が複数である場合、複数のＸ２は同一でも異なっていてもよい。Ｙ２は、それぞれ、同一でも異なっていてもよく、－ＣＨ２－、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、及び単結合からなる群より選択される１種である。Ｚは、－ＣＨ２－、－ＣＨ２ＣＨ２－、及び－ＣＨ＝ＣＨ－からなる群より選択される１種である。ｐは、それぞれ０～３の整数である。） As the alicyclic group or alicyclic group-containing group suitable as R a2 in formula (2-1), the following groups may be mentioned.
Figure JPOXMLDOC01-appb-C000058
 (In the above formula, X 2 represents an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, —O—, —S—, —SO—, —SO 2 —, —CO—, -COO -, - CONH-, and if .X 2 is one selected from the group consisting of a single bond is more, a plurality of X 2 are optionally be the same or different .Y 2, respectively, They may be the same or different, and are one selected from the group consisting of —CH 2 —, —O—, —S—, —SO—, —SO 2 —, —CO—, and a single bond. is, -CH 2 -, - CH 2 CH 2 -, .p and is one selected from the group consisting of -CH = CH- are each an integer of 0 to 3).
　上記のＲａ２として好適な基に含まれる芳香環又は脂環は、その環上に１又は複数の置換基を有していてもよい。置換基の好適な例としては、フッ素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数１～６のフッ素化アルキル基、炭素数１～６のフッ素化アルコキシ基が好ましい。置換基がフッ素化アルキル基又はフッ素化アルコキシ基である場合、パーフルオロアルキル基又はパーフルオロアルコキシ基であるのが好ましい。 The aromatic ring or alicyclic ring contained in a group suitable as R a2 may have one or more substituents on the ring. Preferable examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkoxy having 1 to 6 carbon atoms. Groups are preferred. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
　式（２－１）で表されるジアルデヒド化合物が芳香族ジアルデヒドである場合、その好適な例としては、ベンゼンジアルデヒド類、ピリジンジアルデヒド類、ピラジンジアルデヒド類、ピリミジンジアルデヒド類、ナフタレンジアルデヒド類、ビフェニルジアルデヒド類、ジフェニルエーテルジアルデヒド類、ジフェニルスルホンジアルデヒド類、ジフェニルスルフィドジアルデヒド類、ビス（ホルミルフェノキシ）ベンゼン類、［１，４－フェニレンビス（１－メチルエチリデン）］ビスベンズアルデヒド類、２，２－ビス［４－（ホルミルフェノキシ）フェニル］プロパン類、ビス［４－（ホルミルフェノキシ）フェニル］スルフィド類、ビス［４－（ホルミルフェノキシ）フェニル］スルホン類、及び含フルオレンジアルデヒドが挙げられる。 When the dialdehyde compound represented by the formula (2-1) is an aromatic dialdehyde, preferred examples thereof include benzenedialdehydes, pyridinedialdehydes, pyrazinedialdehydes, pyrimidinedialdehydes, naphthalene. Dialdehydes, biphenyl dialdehydes, diphenyl ether dialdehydes, diphenyl sulfone dialdehydes, diphenyl sulfide dialdehydes, bis (formylphenoxy) benzenes, [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde 2,2-bis [4- (formylphenoxy) phenyl] propanes, bis [4- (formylphenoxy) phenyl] sulfides, bis [4- (formylphenoxy) phenyl] sulfones, and fluorenedialdehyde Is It is.
　ベンゼンジアルデヒド類の具体例としては、フタルアルデヒド、イソフタルアルデヒド、テレフタルアルデヒド、３－フルオロフタルアルデヒド、４－フルオロフタルアルデヒド、２－フルオロイソフタルアルデヒド、４－フルオロイソフタルアルデヒド、５－フルオロイソフタルアルデヒド、２－フルオロテレフタルアルデヒド、３－トリフルオロメチルフタルアルデヒド、４－トリフルオロメチルフタルアルデヒド、２－トリフルオロメチルイソフタルアルデヒド、４－トリフルオロメチルイソフタルアルデヒド、５－トリフルオロメチルイソフタルアルデヒド、２－トリフルオロメチルテレフタルアルデヒド、３，４，５，６－テトラフルオロフタルアルデヒド、２，４，５，６－テトラフルオロイソフタルアルデヒド、及び２，３，５，６－テトラフルオロテレフタルアルデヒド等が挙げられる。 Specific examples of benzenedialdehydes include phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 3-fluorophthalaldehyde, 4-fluorophthalaldehyde, 2-fluoroisophthalaldehyde, 4-fluoroisophthalaldehyde, 5-fluoroisophthalaldehyde, 2 -Fluoroterephthalaldehyde, 3-trifluoromethylphthalaldehyde, 4-trifluoromethylphthalaldehyde, 2-trifluoromethylisophthalaldehyde, 4-trifluoromethylisophthalaldehyde, 5-trifluoromethylisophthalaldehyde, 2-trifluoromethyl Terephthalaldehyde, 3,4,5,6-tetrafluorophthalaldehyde, 2,4,5,6-tetrafluoroisophthalaldehyde, and 2,3 5,6-tetrafluoro terephthalaldehyde and the like.
　ピリジンジアルデヒド類の具体例としては、ピリジン－２，３－ジアルデヒド、ピリジン－３，４－ジアルデヒド、及びピリジン－３，５－ジアルデヒド等が挙げられる。
　ピラジンジアルデヒド類の具体例としては、ピラジン－２，３－ジアルデヒド、ピラジン－２，５－ジアルデヒド、及びピラジン－２，６－ジアルデヒド等が挙げられる。
　ピリミジンジアルデヒド類の具体例としては、ピリミジン－２，４－ジアルデヒド、ピリミジン－４，５－ジアルデヒド、及びピリミジン－４，６－ジアルデヒド等が挙げられる。 Specific examples of pyridinedialdehydes include pyridine-2,3-dialdehyde, pyridine-3,4-dialdehyde, and pyridine-3,5-dialdehyde.
Specific examples of pyrazine dialdehydes include pyrazine-2,3-dialdehyde, pyrazine-2,5-dialdehyde, pyrazine-2,6-dialdehyde and the like.
Specific examples of pyrimidine dialdehydes include pyrimidine-2,4-dialdehyde, pyrimidine-4,5-dialdehyde, and pyrimidine-4,6-dialdehyde.
　ナフタレンジアルデヒド類の具体例としては、ナフタレン－１，５－ジアルデヒド、ナフタレン－１，６－ジアルデヒド、ナフタレン－２，６－ジアルデヒド、ナフタレン－３，７－ジアルデヒド、２，３，４，６，７，８－ヘキサフルオロナフタレン－１，５－ジアルデヒド、２，３，４，５，６，８－ヘキサフルオロナフタレン－１，６－ジアルデヒド、１，３，４，５，７，８－ヘキサフルオロナフタレン－２，６－ジアルデヒド、１－トリフルオロメチルナフタレン－２，６－ジアルデヒド、１，５－ビス（トリフルオロメチル）ナフタレン－２，６－ジアルデヒド、１－トリフルオロメチルナフタレン－３，７－ジアルデヒド、１，５－ビス（トリフルオロメチル）ナフタレン－３，７－ジアルデヒド、１－トリフルオロメチル－２，４，５，６，８－ペンタフルオロナフタレン－３，７－ジアルデヒド、１－ビス（トリフルオロメチル）メトキシ－２，４，５，６，８－ペンタフルオロナフタレン－３，７－ジアルデヒド、１，５－ビス（トリフルオロメチル）－２，４，６，８－テトラフルオロナフタレン－３，７－ジアルデヒド、及び１，５－ビス［ビス（トリフルオロメチル）メトキシ］－２，４，６，８－テトラフルオロナフタレン－３，７－ジアルデヒド等が挙げられる。 Specific examples of naphthalenedialdehydes include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene-3,7-dialdehyde, 2,3, 4,6,7,8-hexafluoronaphthalene-1,5-dialdehyde, 2,3,4,5,6,8-hexafluoronaphthalene-1,6-dialdehyde, 1,3,4,5 7,8-hexafluoronaphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-2,6-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene-2,6-dialdehyde, 1- Trifluoromethylnaphthalene-3,7-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene-3,7-dialdehyde, 1-trifluoromethyl 2,4,5,6,8-pentafluoronaphthalene-3,7-dialdehyde, 1-bis (trifluoromethyl) methoxy-2,4,5,6,8-pentafluoronaphthalene-3,7-di Aldehydes, 1,5-bis (trifluoromethyl) -2,4,6,8-tetrafluoronaphthalene-3,7-dialdehyde, and 1,5-bis [bis (trifluoromethyl) methoxy] -2, Examples include 4,6,8-tetrafluoronaphthalene-3,7-dialdehyde.
　ビフェニルジアルデヒド類の具体例としては、ビフェニル－２，２’－ジアルデヒド、ビフェニル－２，４’－ジアルデヒド、ビフェニル－３，３’－ジアルデヒド、ビフェニル－４，４’－ジアルデヒド、６，６’－ジフルオロビフェニル－３，４’－ジアルデヒド、６，６’－ジフルオロビフェニル－２，４’－ジアルデヒド、６，６’－ジフルオロビフェニル－３，３’－ジアルデヒド、６，６’－ジフルオロビフェニル－３，４’－ジアルデヒド、６，６’－ジフルオロビフェニル－４，４’－ジアルデヒド、６，６’－ジトリフルオロメチルビフェニル－２，２’－ジアルデヒド、６，６’－ジトリフルオロメチルビフェニル－２，４’－ジアルデヒド、６，６’－ジトリフルオロメチルビフェニル－３，３’－ジアルデヒド、６，６’－ジトリフルオロメチルビフェニル－３，４’－ジアルデヒド、及び６，６’－ジトリフルオロメチルビフェニル－４，４’－ジアルデヒド等が挙げられる。 Specific examples of biphenyldialdehydes include biphenyl-2,2′-dialdehyde, biphenyl-2,4′-dialdehyde, biphenyl-3,3′-dialdehyde, biphenyl-4,4′-dialdehyde, 6,6′-difluorobiphenyl-3,4′-dialdehyde, 6,6′-difluorobiphenyl-2,4′-dialdehyde, 6,6′-difluorobiphenyl-3,3′-dialdehyde, 6, 6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-4,4'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-2,2'-dialdehyde, 6, 6′-ditrifluoromethylbiphenyl-2,4′-dialdehyde, 6,6′-ditrifluoromethylbiphenyl-3,3′-dialdehyde, , 6'-ditrifluoromethyl-biphenyl-3,4'-dialdehyde, and 6,6'-ditrifluoromethyl-4,4'-dialdehyde, and the like.
　ジフェニルエーテルジアルデヒド類の具体例としては、ジフェニルエーテル－２，４’－ジアルデヒド、ジフェニルエーテル－３，３’－ジアルデヒド、ジフェニルエーテル－３，４’－ジアルデヒド、及びジフェニルエーテル－４，４’－ジアルデヒド等が挙げられる。 Specific examples of diphenyl ether dialdehydes include diphenyl ether-2,4′-dialdehyde, diphenyl ether-3,3′-dialdehyde, diphenyl ether-3,4′-dialdehyde, and diphenyl ether-4,4′-dialdehyde. Etc.
　ジフェニルスルホンジアルデヒド類の具体例としては、ジフェニルスルホン－３，３’－ジアルデヒド、ジフェニルスルホン－３，４’－ジアルデヒド、及びジフェニルスルホン－４，４’－ジアルデヒド等が挙げられる。 Specific examples of diphenylsulfonedialdehydes include diphenylsulfone-3,3'-dialdehyde, diphenylsulfone-3,4'-dialdehyde, and diphenylsulfone-4,4'-dialdehyde.
　ジフェニルスルフィドジアルデヒド類の具体例としては、ジフェニルスルフィド－３，３’－ジアルデヒド、ジフェニルスルフィド－３，４’－ジアルデヒド、及びジフェニルスルフィド－４，４’－ジアルデヒド等が挙げられる。 Specific examples of diphenyl sulfide dialdehydes include diphenyl sulfide-3,3'-dialdehyde, diphenyl sulfide-3,4'-dialdehyde, and diphenyl sulfide-4,4'-dialdehyde.
　ジフェニルケトンジアルデヒド類の具体例としては、ジフェニルケトン－３，３’－ジアルデヒド、ジフェニルケトン－３，４’－ジアルデヒド、及びジフェニルケトン－４，４’－ジアルデヒド等が挙げられる。 Specific examples of diphenyl ketone dialdehydes include diphenyl ketone-3,3'-dialdehyde, diphenyl ketone-3,4'-dialdehyde, and diphenyl ketone-4,4'-dialdehyde.
　ビス（ホルミルフェノキシ）ベンゼン類の具体例としては、ベンゼン１，３－ビス（３－ホルミルフェノキシ）ベンゼン、１，４－ビス（３－ホルミルフェノキシ）ベンゼン、及び１，４－ビス（４－ホルミルフェノキシ）ベンゼン等が挙げられる。 Specific examples of bis (formylphenoxy) benzenes include benzene 1,3-bis (3-formylphenoxy) benzene, 1,4-bis (3-formylphenoxy) benzene, and 1,4-bis (4-formyl). And phenoxy) benzene.
　［１，４－フェニレンビス（１－メチルエチリデン）］ビスベンズアルデヒド類の具体例としては、３，３’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスベンズアルデヒド、３，４’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスベンズアルデヒド、及び４，４’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスベンズアルデヒド等が挙げられる。 Specific examples of [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehydes include 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, 3,4′- [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, and the like.
　２，２－ビス［４－（ホルミルフェノキシ）フェニル］プロパン類の具体例としては、２，２－ビス［４－（２－ホルミルフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－ホルミルフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－ホルミルフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－ホルミルフェノキシ）フェニル］ヘキサフルオロプロパン、及び２，２－ビス［４－（４－ホルミルフェノキシ）フェニル］ヘキサフルオロプロパン等が挙げられる。 Specific examples of 2,2-bis [4- (formylphenoxy) phenyl] propanes include 2,2-bis [4- (2-formylphenoxy) phenyl] propane, 2,2-bis [4- (3 -Formylphenoxy) phenyl] propane, 2,2-bis [4- (4-formylphenoxy) phenyl] propane, 2,2-bis [4- (3-formylphenoxy) phenyl] hexafluoropropane, and 2,2 -Bis [4- (4-formylphenoxy) phenyl] hexafluoropropane and the like.
　ビス［４－（ホルミルフェノキシ）フェニル］スルフィド類の具体例としては、ビス［４－（３－ホルミルフェノキシ）フェニル］スルフィド、及びビス［４－（４－ホルミルフェノキシ）フェニル］スルフィド等が挙げられる。 Specific examples of bis [4- (formylphenoxy) phenyl] sulfides include bis [4- (3-formylphenoxy) phenyl] sulfide and bis [4- (4-formylphenoxy) phenyl] sulfide. .
　ビス［４－（ホルミルフェノキシ）フェニル］スルホン類の具体例としては、ビス［４－（３－ホルミルフェノキシ）フェニル］スルホン、及びビス［４－（４－ホルミルフェノキシ）フェニル］スルホン等が挙げられる。 Specific examples of bis [4- (formylphenoxy) phenyl] sulfone include bis [4- (3-formylphenoxy) phenyl] sulfone and bis [4- (4-formylphenoxy) phenyl] sulfone. .
　含フルオレンジアルデヒドの具体例としては、フルオレン－２，６－ジアルデヒド、フルオレン－２，７－ジアルデヒド、ジベンゾフラン－３，７－ジアルデヒド、９，９－ビス（４－ホルミルフェニル）フルオレン、９，９－ビス（３－ホルミルフェニル）フルオレン、及び９－（３－ホルミルフェニル）－９－（４’－ホルミルフェニル）フルオレン等が挙げられる Specific examples of the fluorinated aldehydes include fluorene-2,6-dialdehyde, fluorene-2,7-dialdehyde, dibenzofuran-3,7-dialdehyde, 9,9-bis (4-formylphenyl) fluorene, 9,9-bis (3-formylphenyl) fluorene, 9- (3-formylphenyl) -9- (4′-formylphenyl) fluorene, etc.
　また、下記式で表される、ジフェニルアルカンジアルデヒド又はジフェニルフルオロアルカンジアルデヒドも、芳香族ジアルデヒド化合物として好適に使用できる。
Figure JPOXMLDOC01-appb-C000059
 Further, diphenylalkanedialdehyde or diphenylfluoroalkanedialdehyde represented by the following formula can also be suitably used as the aromatic dialdehyde compound.
Figure JPOXMLDOC01-appb-C000059
　更に、下記式で表されるイミド結合を有する化合物も、芳香族ジアルデヒド化合物として好適に使用することができる。
Figure JPOXMLDOC01-appb-C000060
 Furthermore, a compound having an imide bond represented by the following formula can also be suitably used as the aromatic dialdehyde compound.
Figure JPOXMLDOC01-appb-C000060
　式（２－１）で表されるジカルボニル化合物が脂環式基を含む脂環式ジアルデヒドである場合、その好適な例としては、シクロヘキサン－１，４－ジアルデヒド、シクロヘキサン－１，３－ジアルデヒド、ビシクロ［２．２．１］ヘプタン－２，５－ジアルデヒド、ビシクロ［２．２．２］オクタン－２，５－ジアルデヒド、ビシクロ［２．２．２］オクタ－７－エン－２，５－ジアルデヒド、ビシクロ［２．２．１］ヘプタン－２，３－ジアルデヒド、ビシクロ［２．２．１］ヘプタ－５－エン－２，３－ジアルデヒド、トリシクロ［５．２．１．０２，６］デカン－３，４－ジアルデヒド、トリシクロ［５．２．１．０２，６］デカ－４－エン－８，９－ジアルデヒド、ペルヒドロナフタレン－２，３－ジアルデヒド、ペルヒドロナフタレン－１，４－ジアルデヒド、ペルヒドロナフタレン－１，６－ジアルデヒド、ペルヒドロ－１，４－メタノナフタレン－２，３－ジアルデヒド、ペルヒドロ－１，４－メタノナフタレン－２，７－ジアルデヒド、ペルヒドロ－１，４－メタノナフタレン－７，８－ジアルデヒド、ペルヒドロ－１，４：５，８－ジメタノナフタレン－２，３－ジアルデヒド、ペルヒドロ－１，４：５，８－ジメタノナフタレン－２，７－ジアルデヒド、ペルヒドロ－１，４：５，８：９，１０－トリメタノアントラセン－２，３－ジアルデヒド、ビシクロヘキシル－４，４’－ジアルデヒド、ジシクロヘキシルエーテル－３，４’－ジアルデヒド、ジシクロヘキシルメタン－３，３’－ジアルデヒド、ジシクロヘキシルメタン－３，４’－ジアルデヒド、ジシクロヘキシルメタン－４，４’－ジアルデヒド、ジシクロヘキシルジフルオロメタン－３，３’－ジアルデヒド、ジシクロヘキシルジフルオロメタン－３，４’－ジアルデヒド、ジシクロヘキシルジフルオロメタン－４，４’－ジアルデヒド、ジシクロヘキシルスルホン－３，３’－ジアルデヒド、ジシクロヘキシルスルホン－３，４’－ジアルデヒド、ジシクロヘキシルスルホン－４，４’－ジアルデヒド、ジシクロヘキシルスルフィド－３，３’－ジアルデヒド、ジシクロヘキシルスルフィド－３，４’－ジアルデヒド、ジシクロヘキシルスルフィド－４，４’－ジアルデヒド、ジシクロヘキシルケトン－３，３’－ジアルデヒド、ジシクロヘキシルケトン－３，４’－ジアルデヒド、ジシクロヘキシルケトン－４，４’－ジアルデヒド、２，２－ビス（３－ホルミルシクロヘキシル）プロパン、２，２－ビス（４－ホルミルシクロヘキシル）プロパン、２，２－ビス（３－ホルミルシクロヘキシル）ヘキサフルオロプロパン、２，２－ビス（４－ホルミルシクロヘキシル）ヘキサフルオロプロパン、１，３－ビス（３－ホルミルシクロヘキシル）ベンゼン、１，４－ビス（３－ホルミルシクロヘキシル）ベンゼン、１，４－ビス（４－ホルミルシクロヘキシル）ベンゼン、３，３’－［１，４－シクロヘキシレンビス（１－メチルエチリデン）］ビスシクロヘキサンカルバルデヒド、３，４’－［１，４－シクロヘキシレンビス（１－メチルエチリデン）］ビスシクロヘキサンカルバルデヒド、４，４’－［１，４－シクロヘキシレンビス（１－メチルエチリデン）］ビスシクロヘキサンカルバルデヒド、２，２－ビス［４－（３－ホルミルシクロヘキシル）シクロヘキシル］プロパン、２，２－ビス［４－（４－ホルミルシクロヘキシル）シクロヘキシル］プロパン、２，２－ビス［４－（３－ホルミルシクロヘキシル）シクロヘキシル］ヘキサフルオロプロパン、２，２－ビス［４－（４－ホルミルフェノキシ）シクロヘキシル］ヘキサフルオロプロパン、ビス［４－（３－ホルミルシクロヘキシルオキシ）シクロヘキシル］スルフィド、ビス［４－（４－ホルミルシクロヘキシルオキシ）シクロヘキシル］スルフィド、ビス［４－（３－ホルミルシクロヘキシルオキシ）シクロヘキシル］スルホン、ビス［４－（４－ホルミルシクロヘキシルオキシ）シクロヘキシル］スルホン、２，２’－ビシクロ［２．２．１］ヘプタン－５，６’－ジアルデヒド、２，２’－ビシクロ［２．２．１］ヘプタン－６，６’－ジアルデヒド、及び１，３－ジホルミルアダマンタン等が挙げられる。 When the dicarbonyl compound represented by the formula (2-1) is an alicyclic dialdehyde containing an alicyclic group, preferred examples thereof include cyclohexane-1,4-dialdehyde, cyclohexane-1,3. -Dialdehyde, bicyclo [2.2.1] heptane-2,5-dialdehyde, bicyclo [2.2.2] octane-2,5-dialdehyde, bicyclo [2.2.2] oct-7- En-2,5-dialdehyde, bicyclo [2.2.1] heptane-2,3-dialdehyde, bicyclo [2.2.1] hept-5-ene-2,3-dialdehyde, tricyclo [5 .2.1.0 2,6 ] decane-3,4-dialdehyde, tricyclo [5.2.1.0 2,6 ] dec-4-ene-8,9-dialdehyde, perhydronaphthalene-2 , 3-Dialdehyde, perhydronaphth Talen-1,4-dialdehyde, perhydronaphthalene-1,6-dialdehyde, perhydro-1,4-methanonaphthalene-2,3-dialdehyde, perhydro-1,4-methanonaphthalene-2,7-di Aldehyde, perhydro-1,4-methanonaphthalene-7,8-dialdehyde, perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dialdehyde, perhydro-1,4: 5,8-dialdehyde Methanonaphthalene-2,7-dialdehyde, perhydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dialdehyde, bicyclohexyl-4,4'-dialdehyde, dicyclohexyl ether-3 , 4'-dialdehyde, dicyclohexylmethane-3,3'-dialdehyde, dicyclohexylmethane-3,4'-dialdehyde, dicyclo Rohexylmethane-4,4′-dialdehyde, dicyclohexyldifluoromethane-3,3′-dialdehyde, dicyclohexyldifluoromethane-3,4′-dialdehyde, dicyclohexyldifluoromethane-4,4′-dialdehyde, dicyclohexylsulfone -3,3'-dialdehyde, dicyclohexylsulfone-3,4'-dialdehyde, dicyclohexylsulfone-4,4'-dialdehyde, dicyclohexylsulfide-3,3'-dialdehyde, dicyclohexylsulfide-3,4'- Dialdehyde, dicyclohexyl sulfide-4,4′-dialdehyde, dicyclohexylketone-3,3′-dialdehyde, dicyclohexylketone-3,4′-dialdehyde, dicyclohexylketone-4,4′-dialdehyde, 2,2 -Bis (3- Formylcyclohexyl) propane, 2,2-bis (4-formylcyclohexyl) propane, 2,2-bis (3-formylcyclohexyl) hexafluoropropane, 2,2-bis (4-formylcyclohexyl) hexafluoropropane, 1, 3-bis (3-formylcyclohexyl) benzene, 1,4-bis (3-formylcyclohexyl) benzene, 1,4-bis (4-formylcyclohexyl) benzene, 3,3 ′-[1,4-cyclohexylenebis (1-Methylethylidene)] biscyclohexanecarbaldehyde, 3,4 '-[1,4-cyclohexylenebis (1-methylethylidene)] biscyclohexanecarbaldehyde, 4,4'-[1,4-cyclohexylenebis (1-Methylethylidene)] biscyclohexanecarbaldehyde 2,2-bis [4- (3-formylcyclohexyl) cyclohexyl] propane, 2,2-bis [4- (4-formylcyclohexyl) cyclohexyl] propane, 2,2-bis [4- (3-formylcyclohexyl) ) Cyclohexyl] hexafluoropropane, 2,2-bis [4- (4-formylphenoxy) cyclohexyl] hexafluoropropane, bis [4- (3-formylcyclohexyloxy) cyclohexyl] sulfide, bis [4- (4-formyl) Cyclohexyloxy) cyclohexyl] sulfide, bis [4- (3-formylcyclohexyloxy) cyclohexyl] sulfone, bis [4- (4-formylcyclohexyloxy) cyclohexyl] sulfone, 2,2′-bicyclo [2.2.1] Heptane-5,6'-di Examples include aldehyde, 2,2′-bicyclo [2.2.1] heptane-6,6′-dialdehyde, 1,3-diformyladamantane, and the like.
　以上説明したジアルデヒド化合物の中では、合成や入手が容易であることや、耐熱性及び機械的性質に優れるポリベンゾオキサゾール樹脂を得やすいことから、イソフタルアルデヒドが好ましい。 Of the dialdehyde compounds described above, isophthalaldehyde is preferred because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole resin having excellent heat resistance and mechanical properties.
・ジカルボン酸ジハライド
　ポリベンゾオキサゾール前駆体の原料として用いるジカルボン酸ジハライドは、下記式（２－２）で表される化合物である。ジカルボン酸ジハライドは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Figure JPOXMLDOC01-appb-C000061
 （式中、Ｒａ２は、式（２２）と同様であり、Ｈａｌはハロゲン原子である。） Dicarboxylic acid dihalide The dicarboxylic acid dihalide used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (2-2). Dicarboxylic acid dihalide may be used individually by 1 type, and may be used in combination of 2 or more type.
Figure JPOXMLDOC01-appb-C000061
 (In the formula, R a2 is the same as in formula (22), and Hal is a halogen atom.)
　式（２－２）中、Ｈａｌとしては、塩素原子、臭素原子、及びヨウ素原子が好ましく、塩素原子がより好ましい。 In the formula (2-2), as Hal, a chlorine atom, a bromine atom and an iodine atom are preferable, and a chlorine atom is more preferable.
　式（２－２）で表される化合物として好適な化合物としては、ジアルデヒド化合物の好適な例として前述した化合物が有する２つのアルデヒド基を、ハロカルボニル基、好ましくはクロロカルボニル基に置換した化合物が挙げられる。 As a compound suitable as the compound represented by the formula (2-2), a compound obtained by substituting two aldehyde groups of the aforementioned compound as a suitable example of a dialdehyde compound with a halocarbonyl group, preferably a chlorocarbonyl group. Is mentioned.
　以上説明したジカルボン酸ジハライドの中では、合成や入手が容易であることや、耐熱性及び機械的性質に優れるポリベンゾオキサゾール樹脂を得やすいことから、テレフタル酸二クロライドが好ましい。 Among the dicarboxylic acid dihalides described above, terephthalic acid dichloride is preferred because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole resin excellent in heat resistance and mechanical properties.
（ポリベンゾオキサゾール前駆体の製造方法）
　本発明において、ポリベンゾオキサゾール前駆体は、前述の芳香族ジアミンジオールと、ジカルボニル化合物とを、溶剤中で、周知の方法に従って反応させることによって製造される。以下、ポリベンゾオキサゾール前駆体の製造方法の代表的な例として、ジカルボニル化合物がジアルデヒド化合物である場合の製造方法と、ジカルボニル化合物がジカルボン酸ハライドである場合の製造方法とについて説明する。 (Method for producing polybenzoxazole precursor)
In the present invention, the polybenzoxazole precursor is produced by reacting the above-mentioned aromatic diamine diol with a dicarbonyl compound in a solvent according to a known method. Hereinafter, as a representative example of a method for producing a polybenzoxazole precursor, a production method in the case where the dicarbonyl compound is a dialdehyde compound and a production method in the case where the dicarbonyl compound is a dicarboxylic acid halide will be described.
・芳香族ジアミンジオールとジアルデヒド化合物との反応
　芳香族ジアミンジオールとジアルデヒド化合物との反応は、溶剤中で行われる。芳香族ジアミンジオールとジアルデヒド化合物との反応はシッフ塩基の形成反応であり、周知の方法に従って行うことができる。反応温度は特に限定されないが、通常、２０～２００℃が好ましく、２０～１６０℃がより好ましく、１００～１６０℃が特に好ましい。 -Reaction of aromatic diamine diol and dialdehyde compound The reaction of aromatic diamine diol and dialdehyde compound is carried out in a solvent. The reaction between the aromatic diamine diol and the dialdehyde compound is a Schiff base formation reaction and can be performed according to a known method. The reaction temperature is not particularly limited, but is usually preferably 20 to 200 ° C, more preferably 20 to 160 ° C, and particularly preferably 100 to 160 ° C.
　芳香族ジアミンジオールとジアルデヒド化合物との反応は、溶剤にエントレーナーを添加し、還流脱水しながら行われてもよい。エントレーナーとしては、特に限定されず、水と共沸混合物を形成し、室温にて水と二相系を形成する有機溶剤から適宜選択される。エントレーナーの好適な例としては、酢酸イソブチル、酢酸アリル、プロピオン酸－ｎ－プロピル、プロピオン酸イソプロピル、プロピオン酸－ｎ－ブチル、及びプロピオン酸イソブチル等のエステル；ジクロロメチルエーテル、及びエチルイソアミルエーテル等のエーテル類；エチルプロピルケトン等のケトン類；トルエン等の芳香族炭化水素が挙げられる。 The reaction between the aromatic diamine diol and the dialdehyde compound may be performed while adding an entrainer to the solvent and performing reflux dehydration. The entrainer is not particularly limited, and is appropriately selected from organic solvents that form an azeotrope with water and form a two-phase system with water at room temperature. Suitable examples of entrainers include esters such as isobutyl acetate, allyl acetate, propionate-n-propyl, isopropyl propionate, n-butyl propionate, and isobutyl propionate; dichloromethyl ether, ethyl isoamyl ether, etc. Ethers; ketones such as ethyl propyl ketone; and aromatic hydrocarbons such as toluene.
　芳香族ジアミンジオールとジアルデヒド化合物との反応時間は特に限定されないが、典型的には２～７２時間程度が好ましい。 The reaction time between the aromatic diamine diol and the dialdehyde compound is not particularly limited, but it is typically preferably about 2 to 72 hours.
　ポリベンゾオキサゾール前駆体を製造する際の、ジアルデヒド化合物の使用量は、芳香族ジアミンジオール１モルに対して、０．５～１．５モルであるのが好ましく、０．７～１．３モルであるのがより好ましい。 The amount of the dialdehyde compound used in the production of the polybenzoxazole precursor is preferably 0.5 to 1.5 mol, preferably 0.7 to 1.3 mol per mol of aromatic diamine diol. More preferably, it is a mole.
　溶剤の使用量は、芳香族ジアミンジオールとジアルデヒド化合物との反応が良好に進行する限り特に限定されない。典型的には、芳香族ジアミンジオールの質量と、ジアルデヒド化合物の質量との合計に対して、１～４０倍、好ましくは１．５～２０倍の質量の溶剤が使用される。 The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dialdehyde compound proceeds favorably. Typically, a solvent having a mass of 1 to 40 times, preferably 1.5 to 20 times the mass of the total mass of the aromatic diamine diol and the dialdehyde compound is used.
　芳香族ジアミンジオールとジアルデヒド化合物との反応は、生成するポリベンゾオキサゾール前駆体の数平均分子量が、１０００～２００００、好ましくは１２００～５０００となるまで行われるのが好ましい。 The reaction between the aromatic diamine diol and the dialdehyde compound is preferably carried out until the polybenzoxazole precursor to be produced has a number average molecular weight of 1000 to 20000, preferably 1200 to 5000.
・芳香族ジアミンジオールとジカルボン酸ジハライドとの反応
　芳香族ジアミンジオールとジカルボン酸ジハライドとの反応は、溶剤中で行われる。反応温度は特に限定されないが、通常、－２０～１５０℃が好ましく、－１０～１５０℃がより好ましく、－５～７０℃が特に好ましい。芳香族ジアミンジオールとジカルボン酸ジハライドとの反応ではハロゲン化水素が副生する。かかるハロゲン化水素を中和するために、トリエチルアミン、ピリジン、及びＮ，Ｎ－ジメチル－４－アミノピリジン等の有機塩基や、水酸化ナトリウム及び水酸化カリウム等のアルカリ金属水酸化物を、反応液中に少量加えてもよい。 -Reaction of aromatic diamine diol and dicarboxylic acid dihalide The reaction of aromatic diamine diol and dicarboxylic acid dihalide is carried out in a solvent. The reaction temperature is not particularly limited, but is usually preferably −20 to 150 ° C., more preferably −10 to 150 ° C., and particularly preferably −5 to 70 ° C. In the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide, hydrogen halide is by-produced. In order to neutralize the hydrogen halide, an organic base such as triethylamine, pyridine and N, N-dimethyl-4-aminopyridine, or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used as a reaction solution. A small amount may be added inside.
　芳香族ジアミンジオールとジカルボン酸ジハライドとの反応時間は特に限定されないが、典型的には２～７２時間程度が好ましい。 The reaction time between the aromatic diamine diol and the dicarboxylic acid dihalide is not particularly limited, but is typically preferably about 2 to 72 hours.
　ポリベンゾオキサゾール前駆体を製造する際の、ジカルボン酸ジハライドの使用量は、芳香族ジアミンジオール１モルに対して、０．５～１．５モルであるのが好ましく、０．７～１．３モルであるのがより好ましい。 The amount of dicarboxylic acid dihalide used in the production of the polybenzoxazole precursor is preferably 0.5 to 1.5 mol, preferably 0.7 to 1.3 mol per mol of aromatic diamine diol. More preferably, it is a mole.
　溶剤の使用量は、芳香族ジアミンジオールとジカルボン酸ジハライドとの反応が良好に進行する限り特に限定されない。典型的には、芳香族ジアミンジオールの質量と、ジカルボン酸ジハライドの質量との合計に対して、１～４０倍、好ましくは１．５～２０倍の質量の溶剤が使用される。 The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide proceeds favorably. Typically, the solvent is used in an amount of 1 to 40 times, preferably 1.5 to 20 times the weight of the sum of the weight of the aromatic diamine diol and the weight of the dicarboxylic acid dihalide.
　芳香族ジアミンジオールとジカルボン酸ジハライドとの反応は、生成するポリベンゾオキサゾール前駆体の数平均分子量が、１０００～２００００、好ましくは１２００～５０００となるまで行われるのが好ましい。 The reaction between the aromatic diamine diol and the dicarboxylic acid dihalide is preferably carried out until the number average molecular weight of the polybenzoxazole precursor to be produced is 1000 to 20000, preferably 1200 to 5000.
　以上説明した方法により、ポリベンゾオキサゾール前駆体の溶液が得られる。ネガ型感放射線性組成物３を調製する場合には、ポリベンゾオキサゾール前駆体の溶液をそのまま用いることができる。また、減圧下に、ポリベンゾオキサゾール前駆体からポリベンゾオキサゾール樹脂への変換が生じない程度の低温で、ポリベンゾオキサゾール前駆体の溶液から溶剤の少なくとも一部を除去して得られる、ポリベンゾオキサゾール前駆体のペースト又は固体を用いることもできる。また、上記の反応により得られるポリベンゾオキサゾール前駆体の溶液に対して、溶剤等を適量加えて、固形分濃度が調整されたポリベンゾオキサゾール前駆体の溶液をネガ型感放射線性組成物３の調製に用いることもできる。 By the method described above, a polybenzoxazole precursor solution can be obtained. When preparing the negative radiation sensitive composition 3, the polybenzoxazole precursor solution can be used as it is. In addition, polybenzoxazole obtained by removing at least a part of the solvent from the polybenzoxazole precursor solution at a low temperature at which conversion from the polybenzoxazole precursor to the polybenzoxazole resin does not occur under reduced pressure. Precursor pastes or solids can also be used. In addition, an appropriate amount of a solvent or the like is added to the polybenzoxazole precursor solution obtained by the above reaction, and the solid concentration of the polybenzoxazole precursor solution is adjusted to that of the negative radiation-sensitive composition 3. It can also be used for preparation.
　芳香族ジアミンジオールとジカルボニル化合物との反応に用いる有機溶剤の例としては、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ，２－トリメチルプロピオンアミド、Ｎ－メチルカプロラクタム、及びＮ，Ｎ，Ｎ’，Ｎ’－テトラメチルウレア等の含窒素極性溶剤；β－プロピオラクトン、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、γ－カプロラクトン、及びε－カプロラクトン等のラクトン系極性溶剤；ジメチルスルホキシド；アセトニトリル；乳酸エチル、及び乳酸ブチル等の脂肪酸エステル類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジオキサン、テトラヒドロフラン、メチルセルソルブアセテート、及びエチルセルソルブアセテート等のエーテル類が挙げられる。 Examples of the organic solvent used in the reaction of the aromatic diamine diol with the dicarbonyl compound include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N Nitrogen-containing polar solvents such as N, N-diethylformamide, N, N, 2-trimethylpropionamide, N-methylcaprolactam, and N, N, N ′, N′-tetramethylurea; β-propiolactone, γ- Lactone polar solvents such as butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether The Hexane, tetrahydrofuran, ethers such as methyl cellosolve acetate, and ethyl cellosolve acetate.
　これらの有機溶剤の中では、生成するポリベンゾオキサゾール前駆体やポリベンゾオキサゾール樹脂の溶解性から、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ，２－トリメチルプロピオンアミド、Ｎ－メチルカプロラクタム、及びＮ，Ｎ，Ｎ’，Ｎ’－テトラメチルウレア等の含窒素極性溶剤が好ましい。 Among these organic solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N are used because of the solubility of the polybenzoxazole precursor and polybenzoxazole resin to be produced. Nitrogen-containing polar solvents such as dimethylformamide, N, N-diethylformamide, N, N, 2-trimethylpropionamide, N-methylcaprolactam, and N, N, N ′, N′-tetramethylurea are preferred.
［感光性成分］
　感光性成分としては、特に限定されず、ネガ型感放射線性組成物２の場合と同様に、例えば、光塩基発生剤、光酸発生剤等の、光の作用により分解して塩基及び酸の少なくとも一方を発生する化合物（Ａ）が挙げられる。感光性成分は単独で又は２種以上を混合して用いることができる。 [Photosensitive component]
The photosensitive component is not particularly limited, and as in the case of the negative radiation-sensitive composition 2, for example, a photobase generator, a photoacid generator, or the like, which decomposes by the action of light to form a base and an acid. The compound (A) which generates at least one is mentioned. A photosensitive component can be used individually or in mixture of 2 or more types.
　化合物（Ａ）を含有するネガ型感放射線性組成物３を露光することにより、ネガ型感放射線性組成物３中の化合物（Ａ）は分解して、塩基及び酸の少なくとも一方を発生する。このようにして発生した塩基又は酸は、ネガ型感放射線性組成物３中のポリベンゾオキサゾール前駆体に作用して、ポリベンゾオキサゾール樹脂への変換を促進する。 When the negative radiation sensitive composition 3 containing the compound (A) is exposed, the compound (A) in the negative radiation sensitive composition 3 is decomposed to generate at least one of a base and an acid. The base or acid thus generated acts on the polybenzoxazole precursor in the negative radiation-sensitive composition 3 and promotes conversion to a polybenzoxazole resin.
　化合物（Ａ）を含有するネガ型感放射線性組成物３を露光すると、露光部において化合物（Ａ）が分解して塩基及び酸の少なくとも一方を発生する。このようにして発生した塩基又は酸により、ネガ型感放射線性組成物３中のポリベンゾオキサゾール前駆体からポリベンゾオキサゾール樹脂への変換が促進され、露光部は現像液に対して不溶となる。一方、未露光部は、現像液に対して可溶であるため、現像液に溶解させて除去することができる。よって、ネガ型感放射線性組成物３を選択的に露光することにより、所望のパターンを形成することができる。 When the negative radiation sensitive composition 3 containing the compound (A) is exposed, the compound (A) is decomposed in the exposed area to generate at least one of a base and an acid. Conversion from the polybenzoxazole precursor to the polybenzoxazole resin in the negative radiation-sensitive composition 3 is promoted by the base or acid thus generated, and the exposed portion becomes insoluble in the developer. On the other hand, since the unexposed portion is soluble in the developer, it can be removed by dissolving in the developer. Therefore, a desired pattern can be formed by selectively exposing the negative radiation sensitive composition 3.
　化合物（Ａ）としては、ネガ型感放射線性組成物２の場合と同様に、例えば、光の作用により分解してイミダゾール化合物を発生する化合物（Ａ－１）や、オキシム化合物（Ａ－２）が挙げられる。化合物（Ａ－１）が発生するイミダゾール化合物は、ネガ型感放射線性組成物３中のポリベンゾオキサゾール前駆体からポリベンゾオキサゾール樹脂への変換を促進する。また、化合物（Ａ－２）が分解して発生した塩基又は酸により、ネガ型感放射線性組成物３中のポリベンゾオキサゾール前駆体からポリベンゾオキサゾール樹脂への変換が促進される。化合物（Ａ－１）及び化合物（Ａ－２）の詳細は、ネガ型感放射線性組成物２について説明したのと同様である。 As the compound (A), as in the case of the negative radiation sensitive composition 2, for example, a compound (A-1) that decomposes by the action of light to generate an imidazole compound, or an oxime compound (A-2) Is mentioned. The imidazole compound generated from the compound (A-1) promotes the conversion of the polybenzoxazole precursor in the negative radiation-sensitive composition 3 to the polybenzoxazole resin. Further, the conversion from the polybenzoxazole precursor in the negative radiation-sensitive composition 3 to the polybenzoxazole resin is promoted by the base or acid generated by the decomposition of the compound (A-2). The details of the compound (A-1) and the compound (A-2) are the same as those described for the negative radiation-sensitive composition 2.
　ネガ型感放射線性組成物３における感光性成分の含有量は、本発明の目的を阻害しない範囲で特に限定されない。ネガ型感放射線性組成物３における感光性成分の含有量は、ポリベンゾオキサゾール前駆体１００質量に対して１～５０質量部が好ましく、１～３０質量部がより好ましい。 The content of the photosensitive component in the negative radiation sensitive composition 3 is not particularly limited as long as the object of the present invention is not impaired. The content of the photosensitive component in the negative radiation-sensitive composition 3 is preferably 1 to 50 parts by mass and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor.
［その他の有機溶剤（一般式（１）で表される化合物以外の有機溶剤）］
　ネガ型感放射線性組成物３は、その他の有機溶剤を含有してもよい。その他の有機溶剤は、単独で又は２種以上組み合わせて用いることができる。その他の有機溶剤としては、ネガ型感放射線性組成物１において例示したものを用いることができる。 [Other organic solvents (organic solvents other than the compound represented by formula (1))]
The negative radiation sensitive composition 3 may contain other organic solvents. Other organic solvents can be used alone or in combination of two or more. As other organic solvents, those exemplified in the negative radiation-sensitive composition 1 can be used.
　ネガ型感放射線性組成物３において、溶剤の含有量は、ネガ型感放射線性組成物３の固形分濃度が１～５０質量％となる量が好ましく、５～４０質量％となる量がより好ましい。また、ネガ型感放射線性組成物３に含まれる溶剤において、上記一般式（１）で表される化合物とその他の有機溶剤との質量比は、５：９５～１００：０であることが好ましく、２０：８０～１００：０であることがより好ましい。溶剤の含有量及び上記一般式（１）で表される化合物とその他の有機溶剤との質量比を上記の範囲とすることにより、ネガ型感放射線性組成物３は、感度、保存安定性、塗布性、現像性、及び安全性に優れたものとなりやすく、ネガ型感放射線性組成物３を露光及び現像することにより形成されるパターンは、異物の発生が抑制されたものとなりやすい。 In the negative radiation sensitive composition 3, the content of the solvent is preferably such that the solid content concentration of the negative radiation sensitive composition 3 is 1 to 50% by mass, and more preferably 5 to 40% by mass. preferable. In the solvent contained in the negative radiation-sensitive composition 3, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0. 20:80 to 100: 0 is more preferable. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) and the other organic solvent within the above range, the negative radiation-sensitive composition 3 has sensitivity, storage stability, The pattern formed by exposing and developing the negative radiation-sensitive composition 3 is likely to be suppressed in the generation of foreign matters.
［その他の成分］
　ネガ型感放射線性組成物３は、必要に応じて、各種の添加剤を含有していてもよい。添加剤としては、増感剤、硬化促進剤、充填剤、密着促進剤、酸化防止剤、凝集防止剤、熱重合禁止剤、消泡剤、界面活性剤等が挙げられる。 [Other ingredients]
The negative radiation sensitive composition 3 may contain various additives as required. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.
＜ポジ型感放射線性組成物１＞
　ポジ型感放射線性組成物１は、上記一般式（１）で表される化合物と、アルカリ可溶性樹脂と、キノンジアジド基含有化合物とを含有するものである。 <Positive radiation sensitive composition 1>
The positive radiation sensitive composition 1 contains a compound represented by the general formula (1), an alkali-soluble resin, and a quinonediazide group-containing compound.
［一般式（１）で表される化合物］
　一般式（１）で表される化合物としては、感放射線性組成物の一般的な説明において例示したものを用いることができる。上記一般式（１）で表される化合物は、単独で又は２種以上組み合わせて用いることができる。 [Compound represented by general formula (1)]
As the compound represented by the general formula (1), those exemplified in the general description of the radiation-sensitive composition can be used. The compounds represented by the general formula (1) can be used alone or in combination of two or more.
［アルカリ可溶性樹脂］
　アルカリ可溶性樹脂としては、ネガ型感放射線性組成物１において例示したものを用いることができる。 [Alkali-soluble resin]
As alkali-soluble resin, what was illustrated in the negative radiation sensitive composition 1 can be used.
　アルカリ可溶性樹脂の含有量は、ポジ型感放射線性組成物１の固形分に対して５～９０質量％であることが好ましく、１０～８５質量％であることがより好ましい。上記の範囲とすることにより、ポジ型感放射線性組成物１の膜形成能、現像性のバランスをとりやすい傾向にある。 The content of the alkali-soluble resin is preferably 5 to 90% by mass and more preferably 10 to 85% by mass with respect to the solid content of the positive radiation sensitive composition 1. By setting it as the above range, the film forming ability and developability of the positive radiation sensitive composition 1 tend to be easily balanced.
［キノンジアジド基含有化合物］
　キノンジアジド基含有化合物としては、特に限定されないが、フェノール性水酸基を１つ以上有する化合物と、キノンジアジド基含有スルホン酸との完全エステル化物や部分エステル化物が好ましい。このようなキノンジアジド基含有化合物は、フェノール性水酸基を１つ以上有する化合物とキノンジアジド基含有スルホン酸とを、ジオキサン等の適当な溶剤中において、トリエタノールアミン、炭酸アルカリ、炭酸水素アルカリ等のアルカリの存在下で縮合させ、完全エステル化又は部分エステル化することにより得ることができる。キノンジアジド基含有化合物は、単独で又は２種以上組み合わせて用いることができる。 [Quinonediazide group-containing compound]
Although it does not specifically limit as a quinonediazide group containing compound, The complete esterification thing and partial esterification thing of the compound which has one or more phenolic hydroxyl groups, and a quinonediazide group containing sulfonic acid are preferable. Such a quinonediazide group-containing compound is obtained by combining a compound having one or more phenolic hydroxyl groups and a quinonediazide group-containing sulfonic acid in an appropriate solvent such as dioxane with an alkali such as triethanolamine, alkali carbonate, or alkali hydrogencarbonate. It can be obtained by condensation in the presence and complete esterification or partial esterification. A quinonediazide group containing compound can be used individually or in combination of 2 or more types.
　上記フェノール性水酸基を１つ以上有する化合物としては、例えば、２，３，４－トリヒドロキシベンゾフェノン、２，３，４，４’－テトラヒドロキシベンゾフェノン等のポリヒドロキシベンゾフェノン類；
トリス（４－ヒドロシキフェニル）メタン、ビス（４－ヒドロキシ－３－メチルフェニル）－２－ヒドロキシフェニルメタン、ビス（４－ヒドロキシ－２，３，５－トリメチルフェニル）－２－ヒドロキシフェニルメタン、ビス（４－ヒドロキシ－３，５－ジメチルフェニル）－４－ヒドロキシフェニルメタン、ビス（４－ヒドロキシ－３，５－ジメチルフェニル）－３－ヒドロキシフェニルメタン、ビス（４－ヒドロキシ－３，５－ジメチルフェニル）－２－ヒドロキシフェニルメタン、ビス（４－ヒドロキシ－２，５－ジメチルフェニル）－４－ヒドロキシフェニルメタン、ビス（４－ヒドロキシ－２，５－ジメチルフェニル）－３－ヒドロキシフェニルメタン、ビス（４－ヒドロキシ－２，５－ジメチルフェニル）－２－ヒドロキシフェニルメタン、ビス（４－ヒドロキシ－３，５－ジメチルフェニル）－３，４－ジヒドロキシフェニルメタン、ビス（４－ヒドロキシ－２，５－ジメチルフェニル）－３，４－ジヒドロキシフェニルメタン、ビス（４－ヒドロキシ－２，５－ジメチルフェニル）－２，４－ジヒドロキシフェニルメタン、ビス（４－ヒドロキシフェニル）－３－メトキシ－４－ヒドロキシフェニルメタン、ビス（５－シクロヘキシル－４－ヒドロキシ－２－メチルフェニル）－４－ヒドロキシフェニルメタン、ビス（５－シクロヘキシル－４－ヒドロキシ－２－メチルフェニル）－３－ヒドロキシフェニルメタン、ビス（５－シクロヘキシル－４－ヒドロキシ－２－メチルフェニル）－２－ヒドロキシフェニルメタン、ビス（５－シクロヘキシル－４－ヒドロキシ－２－メチルフェニル）－３，４－ジヒドロキシフェニルメタン等のトリスフェノール型化合物；
２，４－ビス（３，５－ジメチル－４－ヒドロキシベンジル）－５－ヒドロキシフェノール、２，６－ビス（２，５－ジメチル－４－ヒドロキシベンジル）－４－メチルフェノール等のリニア型３核体フェノール化合物；
１，１－ビス〔３－（２－ヒドロキシ－５－メチルベンジル）－４－ヒドロキシ－５－シクロヘキシルフェニル〕イソプロパン、ビス［２，５－ジメチル－３－（４－ヒドロキシ－５－メチルベンジル）－４－ヒドロキシフェニル］メタン、ビス［２，５－ジメチル－３－（４－ヒドロキシベンジル）－４－ヒドロキシフェニル］メタン、ビス［３－（３，５－ジメチル－４－ヒドロキシベンジル）－４－ヒドロキシ－５－メチルフェニル］メタン、ビス［３－（３，５－ジメチル－４－ヒドロキシベンジル）－４－ヒドロキシ－５－エチルフェニル］メタン、ビス［３－（３，５－ジエチル－４－ヒドロキシベンジル）－４－ヒドロキシ－５－メチルフェニル］メタン、ビス［３－（３，５－ジエチル－４－ヒドロキシベンジル）－４－ヒドロキシ－５－エチルフェニル］メタン、ビス［２－ヒドロキシ－３－（３，５－ジメチル－４－ヒドロキシベンジル）－５－メチルフェニル］メタン、ビス［２－ヒドロキシ－３－（２－ヒドロキシ－５－メチルベンジル）－５－メチルフェニル］メタン、ビス［４－ヒドロキシ－３－（２－ヒドロキシ－５－メチルベンジル）－５－メチルフェニル］メタン、ビス［２，５－ジメチル－３－（２－ヒドロキシ－５－メチルベンジル）－４－ヒドロキシフェニル］メタン等のリニア型４核体フェノール化合物；
２，４－ビス［２－ヒドロキシ－３－（４－ヒドロキシベンジル）－５－メチルベンジル］－６－シクロヘキシルフェノール、２，４－ビス［４－ヒドロキシ－３－（４－ヒドロキシベンジル）－５－メチルベンジル］－６－シクロヘキシルフェノール、２，６－ビス［２，５－ジメチル－３－（２－ヒドロキシ－５－メチルベンジル）－４－ヒドロキシベンジル］－４－メチルフェノール等のリニア型５核体フェノール化合物；
ビス（２，３，４－トリヒドロキシフェニル）メタン、ビス（２，４－ジヒドロキシフェニル）メタン、２，３，４－トリヒドロキシフェニル－４’－ヒドロキシフェニルメタン、２－（２，３，４－トリヒドロキシフェニル）－２－（２’，３’，４’－トリヒドロキシフェニル）プロパン、２－（２，４－ジヒドロキシフェニル）－２－（２’，４’－ジヒドロキシフェニル）プロパン、２－（４－ヒドロキシフェニル）－２－（４’－ヒドロキシフェニル）プロパン、２－（３－フルオロ－４－ヒドロキシフェニル）－２－（３’－フルオロ－４’－ヒドロキシフェニル）プロパン、２－（２，４－ジヒドロキシフェニル）－２－（４’－ヒドロキシフェニル）プロパン、２－（２，３，４－トリヒドロキシフェニル）－２－（４’－ヒドロキシフェニル）プロパン、２－（２，３，４－トリヒドロキシフェニル）－２－（４’－ヒドロキシ－３’，５’－ジメチルフェニル）プロパン、４，４’－［１－［４－［１－（４－ヒドロキシフェニル）－１－メチルエチル］フェニル］エチリデン］ビスフェノール等のビスフェノール型化合物；
１－［１－（４－ヒドロキシフェニル）イソプロピル］－４－［１，１－ビス（４－ヒドロキシフェニル）エチル］ベンゼン、１－［１－（３－メチル－４－ヒドロキシフェニル）イソプロピル］－４－［１，１－ビス（３－メチル－４－ヒドロキシフェニル）エチル］ベンゼン等の多核枝分かれ型化合物；
１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン等の縮合型フェノール化合物；等が挙げられる。 Examples of the compound having one or more phenolic hydroxyl groups include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone;
Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, Bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5- Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, Bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyl Nylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4- Hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) ) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl Methane, bis (5-cyclohexyl-4-hydro Shi-2-methylphenyl) -3,4-trisphenol compounds such dihydroxyphenyl methane;
Linear type 3, such as 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol and 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Nuclear phenolic compounds;
1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) ) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl)- 4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl- 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Roxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy- 5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl-3- ( Linear tetranuclear phenolic compounds such as 2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;
2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5 Linear type 5 such as -methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol Nuclear phenolic compounds;
Bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4′-hydroxyphenylmethane, 2- (2,3,4) -Trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2 -(4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxyphenyl) ) Propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxy-3 ′, 5′-dimethylphenyl) propane, 4,4 ′-[1- [4- [1 Bisphenol type compounds such as-(4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol;
1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl]- Polynuclear branched compounds such as 4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;
And a condensed phenol compound such as 1,1-bis (4-hydroxyphenyl) cyclohexane.
　上記キノンジアジド基含有スルホン酸としては、ナフトキノン－１，２－ジアジド－５－スルホン酸、ナフトキノン－１，２－ジアジド－４－スルホン酸、オルトアントラキノンジアジドスルホン酸等が挙げられる。 Examples of the quinonediazide group-containing sulfonic acid include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and orthoanthraquinonediazidesulfonic acid.
　キノンジアジド基含有化合物の含有量は、ポジ型感放射線性組成物１の固形分に対して、１０～９５質量％であることが好ましく、１５～９０質量％であることがより好ましい。上記の範囲とすることにより、ポジ型感放射線性組成物１の感度を良好なものとすることができる。 The content of the quinonediazide group-containing compound is preferably 10 to 95% by mass and more preferably 15 to 90% by mass with respect to the solid content of the positive radiation-sensitive composition 1. By setting it as said range, the sensitivity of the positive radiation sensitive composition 1 can be made favorable.
［その他の有機溶剤（一般式（１）で表される化合物以外の有機溶剤）］
　ポジ型感放射線性組成物１は、その他の有機溶剤を含有してもよい。その他の有機溶剤は、単独で又は２種以上組み合わせて用いることができる。その他の有機溶剤としては、ネガ型感放射線性組成物１において例示したものを用いることができる。 [Other organic solvents (organic solvents other than the compound represented by formula (1))]
The positive radiation sensitive composition 1 may contain other organic solvents. Other organic solvents can be used alone or in combination of two or more. As other organic solvents, those exemplified in the negative radiation-sensitive composition 1 can be used.
　ポジ型感放射線性組成物１において、溶剤の含有量は、ポジ型感放射線性組成物１の固形分濃度が１～５０質量％となる量が好ましく、５～３０質量％となる量がより好ましい。また、ポジ型感放射線性組成物１に含まれる溶剤において、上記一般式（１）で表される化合物とその他の有機溶剤との質量比は、５：９５～１００：０であることが好ましく、２０：８０～１００：０であることがより好ましい。溶剤の含有量及び上記一般式（１）で表される化合物とその他の有機溶剤との質量比を上記の範囲とすることにより、ポジ型感放射線性組成物１は、感度、保存安定性、塗布性、現像性、及び安全性に優れたものとなりやすく、ポジ型感放射線性組成物１を露光及び現像することにより形成されるパターンは、異物の発生が抑制されたものとなりやすい。 In the positive radiation sensitive composition 1, the content of the solvent is preferably such that the solid concentration of the positive radiation sensitive composition 1 is 1 to 50% by mass, and more preferably 5 to 30% by mass. preferable. In the solvent contained in the positive radiation sensitive composition 1, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0. 20:80 to 100: 0 is more preferable. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) and the other organic solvent within the above range, the positive radiation-sensitive composition 1 has a sensitivity, storage stability, A pattern formed by exposing and developing the positive radiation-sensitive composition 1 is likely to be excellent in applicability, developability, and safety, and generation of foreign matters is likely to be suppressed.
［その他のポリマー］
　ポジ型感放射線性組成物１は、その他のポリマーを含有してもよい。その他のポリマーは、単独で又は２種以上組み合わせて用いることができる。その他のポリマーとしては、ネガ型感放射線性組成物２において説明したポリアミック酸や、ネガ型感放射線性組成物３において説明したポリベンゾオキサゾール前駆体や、下記一般式（３１）で表される構造を主成分とするポリマーが挙げられる。 [Other polymers]
The positive radiation sensitive composition 1 may contain other polymers. Other polymers can be used alone or in combination of two or more. Examples of other polymers include the polyamic acid described in the negative radiation-sensitive composition 2, the polybenzoxazole precursor described in the negative radiation-sensitive composition 3, and the structure represented by the following general formula (31). The polymer which has as a main component is mentioned.
　一般式（３１）で表される構造を主成分とするポリマーは、加熱又は適当な触媒により、イミド環、オキサゾール環、その他の環状構造を有するポリマーとなり得るものである。好ましくはポリイミド前駆体のポリアミック酸又はポリアミック酸エステル、ポリベンゾオキサゾール前駆体のポリヒドロキシアミドである。ここで、主成分とは、一般式（３１）で表される構成単位を、ポリマーの全構成単位の５０モル％以上有することを意味する。７０モル％以上含有することが好ましく、９０モル％以上含有することがより好ましい。 The polymer having the structure represented by the general formula (31) as a main component can be a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. Preferred are polyamic acid or polyamic acid ester of polyimide precursor, and polyhydroxyamide of polybenzoxazole precursor. Here, the main component means that the structural unit represented by the general formula (31) has 50 mol% or more of all the structural units of the polymer. It is preferable to contain 70 mol% or more, and it is more preferable to contain 90 mol% or more.
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
　一般式（３１）中、Ｒ１、Ｒ２はそれぞれ同一でも異なっていてもよく炭素数２以上の２価～８価の有機基を示す。Ｒ３、Ｒ４はそれぞれ同一でも異なっていてもよく、水素又は炭素数１～２０の１価の有機基を示す。ｌ、ｍは０～２の整数、ｐ、ｑは０～４の整数を示す。ただしｐ＋ｑ＞０である。 In general formula (31), R 1 and R 2 may be the same or different and each represents a divalent to octavalent organic group having 2 or more carbon atoms. R 3 and R 4 may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms. l and m are integers of 0 to 2, and p and q are integers of 0 to 4. However, p + q> 0.
　上記一般式（３１）中、Ｒ１は炭素数２以上の２価～８価の有機基を示し、酸の構造成分を表している。Ｒ１が２価となる酸としては、テレフタル酸、イソフタル酸、ジフェニルエーテルジカルボン酸、ナフタレンジカルボン酸、ビス（カルボキシフェニル）プロパン等の芳香族ジカルボン酸、シクロヘキサンジカルボン酸、アジピン酸等の脂肪族ジカルボン酸等を挙げることができる。Ｒ１が３価となる酸としては、トリメリット酸、トリメシン酸等のトリカルボン酸等を挙げることができる。Ｒ１が４価となる酸としてはピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、ジフェニルエーテルテトラカルボン酸、ジフェニルスルホンテトラカルボン酸等の芳香族テトラカルボン酸や、ブタンテトラカルボン酸、シクロペンタンテトラカルボン酸等の脂肪族テトラカルボン酸、これらのカルボキシル基２個の水素原子をメチル基やエチル基にしたジエステル化合物等を挙げることができる。また、ヒドロキシフタル酸、ヒドロキシトリメリット酸等の水酸基を有する酸も挙げることができる。これら酸成分を２種以上用いてもかまわないが、テトラカルボン酸の残基を１～４０モル％含むことが好ましい。また、アルカリ現像液に対する溶解性や感光性の点から、水酸基を有する酸の残基を５０モル％以上含むことが好ましい。 In the general formula (31), R 1 represents a divalent to octavalent organic group having 2 or more carbon atoms, and represents an acid structural component. Examples of acids in which R 1 is divalent include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid. Etc. Examples of the acid in which R 1 is trivalent include tricarboxylic acids such as trimellitic acid and trimesic acid. Examples of acids in which R 1 is tetravalent include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and other aromatic tetracarboxylic acids, butanetetracarboxylic acid, and cyclopentane. Examples thereof include aliphatic tetracarboxylic acids such as tetracarboxylic acid, diester compounds in which two hydrogen atoms of these carboxyl groups are converted into a methyl group or an ethyl group. Moreover, the acid which has hydroxyl groups, such as a hydroxyphthalic acid and a hydroxy trimellitic acid, can also be mentioned. Two or more of these acid components may be used, but preferably contains 1 to 40 mol% of a tetracarboxylic acid residue. Moreover, it is preferable that the residue of the acid which has a hydroxyl group is contained 50 mol% or more from the point of the solubility with respect to an alkali developing solution, or a photosensitive point.
　Ｒ１は、耐熱性の点から芳香族環を有することが好ましく、炭素数６～３０の３価又は４価の有機基が更に好ましい。 R 1 preferably has an aromatic ring from the viewpoint of heat resistance, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.
　一般式（３１）中、Ｒ２は炭素数２個以上の２価～８価の有機基を示し、ジアミンの構造成分を表している。Ｒ２は、耐熱性の点から芳香族環を有することが好ましい。ジアミンの具体的な例としては、フェニレンジアミン、ジアミノジフェニルエーテル、アミノフェノキシベンゼン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ビス（トリフルオロメチル）ベンチジン、ビス（アミノフェノキシフェニル）プロパン、ビス（アミノフェノキシフェニル）スルホン、ビス（アミノ－ヒドロキシ－フェニル）ヘキサフルオロプロパン、ジアミノジヒドロキシピリミジン、ジアミノジヒドロキシピリジン、ヒドロキシ－ジアミノ－ピリミジン、ジアミノフェノール、ジヒドロキシベンチジン、ジアミノ安息香酸、ジアミノテレフタル酸、これらの芳香族環の水素の少なくとも一部をアルキル基やハロゲン原子で置換した化合物や、脂肪族のシクロヘキシルジアミン、メチレンビスシクロヘキシルアミン、ヘキサメチレンジアミンを挙げることができる。これらジアミン成分を２種以上用いてもかまわないが、アルカリ現像液に対する溶解性の点から、水酸基を有するジアミンの残基を６０モル％以上含むことが好ましい。 In general formula (31), R 2 represents a divalent to octavalent organic group having 2 or more carbon atoms and represents a structural component of diamine. R 2 preferably has an aromatic ring from the viewpoint of heat resistance. Specific examples of diamines include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, Bis (amino-hydroxy-phenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, at least hydrogen of these aromatic rings Compounds partially substituted with alkyl groups or halogen atoms, aliphatic cyclohexyl diamine, methylene bis cyclohexyl amine , Mention may be made of hexamethylene diamine. Two or more of these diamine components may be used, but from the viewpoint of solubility in an alkaline developer, it is preferable that the residue of a diamine having a hydroxyl group is 60 mol% or more.
　一般式（３１）のＲ３及びＲ４はそれぞれ独立して、水素又は炭素数１～２０の１価の有機基を示す。アルカリ現像液に対する溶解性と、ポジ型感放射線性組成物１の溶液安定性の点から、Ｒ３及びＲ４のそれぞれ１０モル％～９０モル％が水素であることが好ましい。更に、Ｒ３及びＲ４がそれぞれ炭素数１～１６の１価の炭化水素基を少なくとも１つ以上含有し、その他は水素原子であることがより好ましい。 R 3 and R 4 in the general formula (31) each independently represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of solubility in an alkali developer and solution stability of the positive radiation sensitive composition 1, it is preferable that 10 mol% to 90 mol% of R 3 and R 4 are each hydrogen. Further, it is more preferable that R 3 and R 4 each contain at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.
　また、一般式（３１）のｌ及びｍはカルボキシル基又はエステル基の数を示し、それぞれ独立に０～２の整数を示す。好ましくは１又は２である。一般式（３１）のｐ及びｑはそれぞれ独立に０～４の整数を示し、ｐ＋ｑ＞０である。 In the general formula (31), l and m represent the number of carboxyl groups or ester groups, and each independently represents an integer of 0 to 2. Preferably it is 1 or 2. In the general formula (31), p and q each independently represent an integer of 0 to 4, and p + q> 0.
　一般式（３１）で表される構造を主成分とするポリマーにおける、一般式（３１）で表される構成単位の数は、１０～１００，０００の範囲であることが好ましく、１５～１，０００の範囲であることがより好ましく、２０～１００の範囲であることが更に好ましい。 In the polymer having the structure represented by the general formula (31) as a main component, the number of structural units represented by the general formula (31) is preferably in the range of 10 to 100,000, Is more preferably in the range of 000, and still more preferably in the range of 20 to 100.
　一般式（３１）で表される構成単位の数は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）や光散乱法、Ｘ線小角散乱法等で質量平均分子量を測定することで容易に算出できる。繰り返し単位の分子量をＭ、ポリマーの質量平均分子量をＭｍとすると、一般式（３１）で表される構成単位の数＝Ｍｍ／Ｍである。一般式（３１）で表される構成単位の数は、最も簡便なポリスチレン換算によるＧＰＣ測定を用いて算出する値をいう。 The number of structural units represented by the general formula (31) can be easily calculated by measuring the mass average molecular weight by gel permeation chromatography (GPC), light scattering method, X-ray small angle scattering method or the like. When the molecular weight of the repeating unit is M and the mass average molecular weight of the polymer is Mm, the number of structural units represented by the general formula (31) = Mm / M. The number of structural units represented by the general formula (31) refers to a value calculated using the simplest GPC measurement in terms of polystyrene.
　更に、例えば、基板との接着性を向上させるために、耐熱性を低下させない範囲でシロキサン構造を有する脂肪族の基を共重合してもよい。具体的には、ジアミン成分として、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（ｐ－アミノ－フェニル）オクタメチルペンタシロキサン等を１～１０モル％共重合したもの等が挙げられる。 Furthermore, for example, an aliphatic group having a siloxane structure may be copolymerized within a range in which the heat resistance is not lowered in order to improve adhesion to the substrate. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.
　ポジ型感放射線性組成物１におけるその他のポリマーの含有量は、本発明の目的を阻害しない範囲で特に限定されない。ポジ型感放射線性組成物１におけるその他のポリマーの含有量は、アルカリ可溶性樹脂１００質量に対して１～３００質量部が好ましく、１～２００質量部がより好ましい。 The content of the other polymer in the positive radiation sensitive composition 1 is not particularly limited as long as the object of the present invention is not impaired. The content of the other polymer in the positive radiation sensitive composition 1 is preferably 1 to 300 parts by mass, more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
［その他の成分］
　ポジ型感放射線性組成物１は、必要に応じて、各種の添加剤を含有していてもよい。添加剤としては、増感剤、硬化促進剤、充填剤、密着促進剤、酸化防止剤、凝集防止剤、熱重合禁止剤、消泡剤、界面活性剤等が挙げられる。 [Other ingredients]
The positive radiation sensitive composition 1 may contain various additives as necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, and a surfactant.
＜感放射線性組成物の調製方法＞
　本発明に係る感放射線性組成物は、上記の各成分を撹拌機で混合することにより調製される。なお、調製された感放射線性組成物が均一なものとなるよう、メンブランフィルタ等を用いて濾過してもよい。 <Method for preparing radiation-sensitive composition>
The radiation-sensitive composition according to the present invention is prepared by mixing the above components with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared radiation sensitive composition may become uniform.
≪パターン製造方法≫
　本発明に係るレジストパターンの製造方法は、本発明に係る感放射線性組成物からなる感放射線性組成物膜を基板上に形成する感放射線性組成物膜形成工程と、上記感放射線性組成物膜を位置選択的に露光する露光工程と、露光された上記感放射線性組成物膜を現像する現像工程とを含むものである。 ≪Pattern manufacturing method≫
The method for producing a resist pattern according to the present invention includes a radiation-sensitive composition film forming step of forming a radiation-sensitive composition film comprising the radiation-sensitive composition according to the present invention on a substrate, and the radiation-sensitive composition. An exposure process for selectively exposing the film and a development process for developing the exposed radiation-sensitive composition film are included.
　まず、感放射線性組成物膜形成工程では、例えば、基板上に、ロールコーター、リバースコーター、バーコーター等の接触転写型塗布装置やスピンナー（回転式塗布装置）、カーテンフローコーター等の非接触型塗布装置を用いて本発明に係る感放射線性組成物を塗布し、必要に応じて、乾燥により溶媒を除去して、感放射線性組成物膜を形成する。 First, in the radiation-sensitive composition film forming step, for example, a contact transfer type coating device such as a roll coater, a reverse coater or a bar coater, a non-contact type such as a spinner (rotary coating device) or a curtain flow coater is formed on a substrate. The radiation-sensitive composition according to the present invention is applied using a coating apparatus, and if necessary, the solvent is removed by drying to form a radiation-sensitive composition film.
　また、感放射線性組成物膜形成工程では、支持フィルム上に設けられた上記感放射線性組成物からなる感放射線性組成物膜（ドライフィルム）を基板に貼り付けることにより、上記基板上に感放射線性組成物膜を形成することもできる。ドライフィルムは、常法により、上記感放射線性組成物を支持フィルム上に塗布した後、乾燥させることで形成することができる。 In the radiation-sensitive composition film forming step, a radiation-sensitive composition film (dry film) made of the radiation-sensitive composition provided on the support film is attached to the substrate, thereby sensing the substrate on the substrate. A radiation composition film can also be formed. The dry film can be formed by applying the radiation-sensitive composition on a support film and drying it by a conventional method.
　次いで、露光工程では、所定パターンのマスクを介して、感放射線性組成物膜に紫外線、エキシマレーザー光等の放射線を照射し、感放射線性組成物膜を位置選択的に露光する。露光には、例えば、高圧水銀灯、超高圧水銀灯、キセノンランプ、カーボンアーク灯等の紫外線を発する光源を用いることができる。露光量は感放射線性組成物の組成によっても異なるが、例えば１０～６００ｍＪ／ｃｍ２程度が好ましい。 Next, in the exposure step, the radiation-sensitive composition film is irradiated with radiation such as ultraviolet rays and excimer laser light through a mask having a predetermined pattern, and the radiation-sensitive composition film is exposed selectively. For the exposure, for example, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The exposure amount varies depending on the composition of the radiation-sensitive composition, but is preferably about 10 to 600 mJ / cm 2 , for example.
　次いで、現像工程では、露光後の感放射線性組成物膜を現像液で現像することにより、所定のパターンを形成する。現像方法は特に限定されず、浸漬法、スプレー法等を用いることができる。現像液の具体例としては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の有機系のものや、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、アンモニア、４級アンモニウム塩等の水溶液が挙げられる。 Next, in the development step, the radiation-sensitive composition film after exposure is developed with a developer to form a predetermined pattern. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.
　以下、実施例を示して本発明を更に具体的に説明するが、本発明の範囲は、これらの実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.
＜材料＞
　実施例及び比較例で用いた各成分の詳細は下記の通りである。
・アルカリ可溶性樹脂
　カルド樹脂１：固形分５５質量％（溶剤：３－メトキシブチルアセテート、質量平均分子量：４，０００）
　アクリル樹脂１：メタクリル酸（ＭＡＡ）とメタクリル酸トリシクロデカニル（ＴＣＤＭＡ）とメタクリル酸２，３－エポキシシクロヘキシルメチル（ＥＣＨＭ）とメタクリル酸グリシジル（ＧＭＡ）とをＭＡＡ／ＴＣＤＭＡ／ＥＣＨＭ／ＧＭＡ＝１５／２０／４０／２５（質量比）で混合し、常法により付加重合して得た、下記式で表される構成単位を有するアクリル樹脂（質量平均分子量１０，０００） <Material>
Details of each component used in Examples and Comparative Examples are as follows.
Alkali-soluble resin Cardo resin 1: solid content 55% by mass (solvent: 3-methoxybutyl acetate, mass average molecular weight: 4,000)
Acrylic resin 1: Methacrylic acid (MAA), tricyclodecanyl methacrylate (TCDMA), 2,3-epoxycyclohexylmethyl methacrylate (ECHM), and glycidyl methacrylate (GMA) are MAA / TCDMA / ECHM / GMA = 15 / 20/40/25 (mass ratio), an acrylic resin having a constitutional unit represented by the following formula (mass average molecular weight 10,000) obtained by addition polymerization by a conventional method
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
　アクリル樹脂２：メタクリル酸ベンジル（ＢｚＭＡ）とメタクリル酸（ＭＡＡ）とをＢｚＭＡ／ＭＡＡ＝８０／２０（質量比）で混合し、常法により付加重合して得たアクリル樹脂（質量平均分子量１５，０００）
・光重合性モノマー
　光重合性モノマー１：ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）
・光重合開始剤
　光重合開始剤１：「ＮＣＩ－８３１」（商品名、ＡＤＥＫＡ製）
　光重合開始剤２：２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾ－ル二量体
　光重合開始剤３：「ＩＲＧＡＣＵＲＥ　ＯＸＥ０１」（商品名、ＢＡＳＦ製）
　光重合開始剤４：「ＩＲＧＡＣＵＲＥ　ＯＸＥ０２」（商品名、ＢＡＳＦ製）
　着色剤１：カーボン分散液「ＣＦブラック」（商品名、御国色素社製、固形分２５％、溶剤：３－メトキシブチルアセテート）
　着色剤２：黒色顔料Ｅｘｐｅｒｉｍｅｎｔａｌ　Ｂｌａｃｋ　５８２（商品名、ＢＡＳＦ製）を、分散剤を用い、定法によってビーズミルで分散させて、顔料の平均粒子径が９０～１９０ｎｍとなるように製造した顔料分散液（固形分１５質量％、溶剤：プロピレングリコールモノメチルエーテルアセテート）
　着色剤３：Ｒ２５４（Ｃ．Ｉ．ピグメントレッド２５４）／Ｙ１３９（Ｃ．Ｉ．ピグメントイエロー）（混合質量比：８５／１５）を、分散剤とアクリル樹脂２（対顔料固形分比率：１０質量％）とを併用し、定法によってビーズミルで分散させて、顔料の平均粒子径が９０～１９０ｎｍとなるように製造した顔料分散液（固形分１８質量％、溶剤：プロピレングリコールモノメチルエーテルアセテート）
　着色剤４：Ｇ３６（Ｃ．Ｉ．ピグメントグリーン３６）／Ｙ１５０（Ｃ．Ｉ．ピグメントイエロー１５０）（混合質量比：７０／３０）から、着色剤３と同様にして、顔料の平均粒子径が９０～１９０ｎｍとなるように製造した顔料分散液（固形分１８質量％、溶剤：プロピレングリコールモノメチルエーテルアセテート）
　着色剤５：Ｂ１５６（Ｃ．Ｉ．ピグメントブルー１５６）／Ｖ２３（Ｃ．Ｉ．ピグメントバイオレット２３）（混合質量比：９０／１０）から、着色剤３と同様にして、顔料の平均粒子径が９０～１９０ｎｍとなるように製造した顔料分散液（固形分１５質量％、溶剤：プロピレングリコールモノメチルエーテルアセテート）
・界面活性剤
　界面活性剤１：「グラノール４４０」（商品名、共栄社化学株式会社）
・化合物１～４：それぞれ下記式（Ｅ１）～（Ｅ４）で表される化合物 Acrylic resin 2: acryl methacrylate (BzMA) and methacrylic acid (MAA) were mixed at BzMA / MAA = 80/20 (mass ratio) and subjected to addition polymerization by a conventional method (mass average molecular weight 15, 000)
Photopolymerizable monomer Photopolymerizable monomer 1: Dipentaerythritol hexaacrylate (DPHA)
Photopolymerization initiator Photopolymerization initiator 1: “NCI-831” (trade name, manufactured by ADEKA)
Photopolymerization initiator 2: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer Photopolymerization initiator 3: “IRGACURE OXE01” (trade name, manufactured by BASF)
Photopolymerization initiator 4: “IRGACURE OXE02” (trade name, manufactured by BASF)
Colorant 1: Carbon dispersion “CF Black” (trade name, manufactured by Mikuni Color Co., Ltd., solid content 25%, solvent: 3-methoxybutyl acetate)
Colorant 2: Black pigment Experimental Black 582 (trade name, manufactured by BASF) was dispersed in a bead mill by a conventional method using a dispersant, and a pigment dispersion produced so that the average particle size of the pigment was 90 to 190 nm ( Solid content 15% by weight, solvent: propylene glycol monomethyl ether acetate)
Colorant 3: R254 (CI Pigment Red 254) / Y139 (CI Pigment Yellow) (mixing mass ratio: 85/15), dispersant and acrylic resin 2 (to pigment solid content ratio: 10 mass) And a pigment dispersion (solid content: 18% by mass, solvent: propylene glycol monomethyl ether acetate) produced by dispersing with a bead mill by a conventional method so that the average particle size of the pigment is 90 to 190 nm.
Colorant 4: From G36 (CI Pigment Green 36) / Y150 (CI Pigment Yellow 150) (mixing mass ratio: 70/30), in the same manner as Colorant 3, the average particle diameter of the pigment is Pigment dispersion prepared to be 90 to 190 nm (solid content: 18% by mass, solvent: propylene glycol monomethyl ether acetate)
From the coloring agent 5: B156 (CI Pigment Blue 156) / V23 (CI Pigment Violet 23) (mixing mass ratio: 90/10), the average particle diameter of the pigment was determined in the same manner as the coloring agent 3. Pigment dispersion prepared to be 90 to 190 nm (solid content 15% by mass, solvent: propylene glycol monomethyl ether acetate)
・ Surfactant Surfactant 1: “Granol 440” (trade name, Kyoeisha Chemical Co., Ltd.)
Compounds 1 to 4: Compounds represented by the following formulas (E1) to (E4), respectively
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
・その他の有機溶剤
　ＭＢＡ：３－メトキシブチルアセテート
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
　ＥＥＰ：３－エトキシプロピオン酸エチル
　ＥＬ：乳酸エチル
　ＮＭＰ：Ｎ－メチル－２－ピロリドン
　ＧＢＬ：γ－ブチロラクトン Other organic solvents MBA: 3-methoxybutyl acetate PGMEA: propylene glycol monomethyl ether acetate EEP: ethyl 3-ethoxypropionate EL: ethyl lactate NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone
　カルド樹脂１は、以下の処方に従って合成したものである。
　まず、５００ｍｌ四つ口フラスコ中に、ビスフェノールフルオレン型エポキシ樹脂（エポキシ当量２３５）２３５ｇ、テトラメチルアンモニウムクロライド１１０ｍｇ、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール１００ｍｇ、及びアクリル酸７２．０ｇを仕込み、これに２５ｍｌ／分の速度で空気を吹き込みながら９０～１００℃で加熱溶解した。次に、溶液が白濁した状態のまま徐々に昇温し、１２０℃に加熱して完全溶解させた。この際、溶液は次第に透明粘稠になったが、そのまま撹拌を継続した。この間、酸価を測定し、１．０ｍｇＫＯＨ／ｇ未満になるまで加熱撹拌を続けた。酸価が目標値に達するまで１２時間を要した。そして室温まで冷却し、無色透明で固体状の下記構造式（ａ－４）で表されるビスフェノールフルオレン型エポキシアクリレートを得た。 The cardo resin 1 is synthesized according to the following formulation.
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid The solution was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature, and a bisphenolfluorene type epoxy acrylate represented by the following structural formula (a-4) was obtained as a colorless and transparent solid.
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
　次いで、このようにして得られた上記のビスフェノールフルオレン型エポキシアクリレート３０７．０ｇに３－メトキシブチルアセテート６００ｇを加えて溶解した後、ベンゾフェノンテトラカルボン酸二無水物８０．５ｇ及び臭化テトラエチルアンモニウム１ｇを混合し、徐々に昇温して１１０～１１５℃で４時間反応させた。酸無水物基の消失を確認した後、１，２，３，６－テトラヒドロ無水フタル酸３８．０ｇを混合し、９０℃で６時間反応させ、カルド樹脂１を得た。酸無水物基の消失はＩＲスペクトルにより確認した。このカルド樹脂１は、前述の一般式（ａ－１）で表される化合物に相当する。 Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, gradually warmed and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 3,8.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain cardo resin 1. The disappearance of the acid anhydride group was confirmed by IR spectrum. This cardo resin 1 corresponds to the compound represented by the general formula (a-1).
＜透明レジストの作製＞
　表１に記載の組成及び配合量（単位：質量部）に従って、アルカリ可溶性樹脂、光重合性モノマー、光重合開始剤、及び界面活性剤を、表２に示す組成の溶剤と混合して、固形分濃度２０質量％のネガ型感放射線性組成物を調製した。 <Preparation of transparent resist>
According to the composition and blending amount (unit: part by mass) described in Table 1, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a surfactant are mixed with a solvent having the composition shown in Table 2 to obtain a solid. A negative radiation sensitive composition having a partial concentration of 20% by mass was prepared.
［異物］
　６８０ｍｍ×８８０ｍｍ×０．７ｍｍ厚のガラス基材にネガ型感放射線性組成物をスピン塗布し、塗膜を１００℃で１２０秒間乾燥させて、厚さ１．２μｍの感光性樹脂層を形成した。次いで、露光量１００ｍＪ／ｃｍ２で、感光性樹脂層を露光した。次いで、ＫＯＨ０．０４質量％と界面活性剤エマルゲンＡ６０（花王製）０．１質量％とを含む水溶液を現像液として用い、２３℃にて６０秒間シャワー現像を行い、得られたパターン中の異物を自動光学検査装置（タカノ製）でカウントした。結果を表２に示す。 [Foreign matter]
A negative radiation-sensitive composition was spin-coated on a glass substrate having a thickness of 680 mm × 880 mm × 0.7 mm, and the coating film was dried at 100 ° C. for 120 seconds to form a photosensitive resin layer having a thickness of 1.2 μm. . Next, the photosensitive resin layer was exposed with an exposure amount of 100 mJ / cm 2 . Subsequently, using an aqueous solution containing 0.04% by mass of KOH and 0.1% by mass of surfactant Emulgen A60 (manufactured by Kao) as a developing solution, shower development is performed at 23 ° C. for 60 seconds, and foreign matters in the obtained pattern Were counted with an automatic optical inspection device (manufactured by Takano). The results are shown in Table 2.
［感度］
　６８０ｍｍ×８８０ｍｍ×０．７ｍｍ厚のガラス基材にネガ型感放射線性組成物をスピン塗布し、塗膜を１００℃で１２０秒間乾燥させて、厚さ１．２μｍの感光性樹脂層を形成した。次いで、ラインアンドスペースパターンのマスクを用いて、種々の露光量で、感光性樹脂層を露光した。次いで、ＫＯＨ０．０４質量％と界面活性剤エマルゲンＡ６０（花王製）０．１質量％とを現像液として用い、２３℃にて６０秒間シャワー現像を行った。得られたラインパターンのＣＤ（Ｃｒｉｔｉｃａｌ　Ｄｉｍｅｎｓｉｏｎ）がマスクのＣＤ＋１μｍとなる露光量を求め、以下の基準で評価した。結果を表２に示す。
　○：１００ｍＪ／ｃｍ２未満、△：１００～１４０ｍＪ／ｃｍ２、×：１４０ｍＪ／ｃｍ２超 [sensitivity]
A negative radiation-sensitive composition was spin-coated on a glass substrate having a thickness of 680 mm × 880 mm × 0.7 mm, and the coating film was dried at 100 ° C. for 120 seconds to form a photosensitive resin layer having a thickness of 1.2 μm. . Next, the photosensitive resin layer was exposed with various exposure amounts using a line and space pattern mask. Next, shower development was performed at 23 ° C. for 60 seconds using 0.04% by mass of KOH and 0.1% by mass of surfactant Emulgen A60 (manufactured by Kao) as a developer. The exposure amount at which the CD (Critical Dimension) of the obtained line pattern was CD + 1 μm of the mask was determined and evaluated according to the following criteria. The results are shown in Table 2.
○: less than 100 mJ / cm 2 , Δ: 100 to 140 mJ / cm 2 , x: over 140 mJ / cm 2
［析出物］
　－５℃で２週間、ネガ型感放射線性組成物をエージング処理した後、１０ｃｍ角のガラス基材にスピン塗布し、析出した異物の個数をカウントして、以下の基準で評価した。結果を表２に示す。
　○：０～２個、△：３～１０個、×：１１個以上 [Precipitate]
The negative radiation sensitive composition was aged at −5 ° C. for 2 weeks, spin-coated on a 10 cm square glass substrate, the number of deposited foreign matters was counted, and evaluated according to the following criteria. The results are shown in Table 2.
○: 0 to 2, △: 3 to 10, x: 11 or more
［粘度変化］
　４０℃で２週間、エージング処理したネガ型感放射線性組成物の粘度を測定し、初期粘度５ｍＰａ・ｓからの変化量を求めて、以下の基準で評価した。結果を表２に示す。
　○：変化量が０．５ｍＰａ・ｓ未満、△：変化量が０．５～２ｍＰａ・ｓ、×：変化量が２ｍＰａ・ｓ超 [Viscosity change]
The viscosity of the negative radiation sensitive composition aged at 40 ° C. for 2 weeks was measured, and the amount of change from the initial viscosity of 5 mPa · s was determined and evaluated according to the following criteria. The results are shown in Table 2.
○: Change is less than 0.5 mPa · s, Δ: Change is from 0.5 to 2 mPa · s, ×: Change is more than 2 mPa · s
［塗布むら］
　６８０ｍｍ×８８０ｍｍ×０．７ｍｍ厚のガラス基材にネガ型感放射線性組成物をスピン塗布し、塗膜を１００℃で１２０秒間乾燥させた際に、ピンむらや放射むら等の塗布むらが発生したか否かを目視で確認し、以下の基準で評価した。結果を表２に示す。
　○：塗布むらは発生しなかった、△：局所的に塗布むらが発生した、×：全面で塗布むらが発生した [Coating unevenness]
When a negative radiation sensitive composition is spin-coated on a 680 mm x 880 mm x 0.7 mm thick glass substrate and the coating film is dried at 100 ° C. for 120 seconds, uneven coating such as pin unevenness and radiation unevenness occurs. It was visually confirmed whether or not, and the following criteria were evaluated. The results are shown in Table 2.
○: Application unevenness did not occur, Δ: Application unevenness occurred locally, X: Application unevenness occurred over the entire surface
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
　表２から分かるように、上記一般式（１）で表される化合物を含有する実施例のネガ型感放射線性組成物は、感度、保存安定性、及び塗布性に優れており、露光及び現像により、異物の発生が抑制されたパターンを形成することができた。
　これに対し、上記一般式（１）で表される化合物を含有しない比較例のネガ型感放射線性組成物は、感度及び保存安定性に劣り、用いる溶剤によっては、更に、塗布性に劣り、及び／又は、露光及び現像により形成されたパターン中でより多くの異物が発生した。 As can be seen from Table 2, the negative radiation-sensitive compositions of Examples containing the compound represented by the general formula (1) are excellent in sensitivity, storage stability, and coating properties, and are exposed and developed. Thus, it was possible to form a pattern in which the generation of foreign matter was suppressed.
On the other hand, the negative type radiation sensitive composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in sensitivity and storage stability, and further inferior in coatability depending on the solvent used. And / or more foreign matter was generated in the pattern formed by exposure and development.
＜ブラックマトリクス用レジスト、カラーフィルタ用レジスト、及びブラックフォトスペーサ用レジストの作製＞
　表３に記載の組成及び配合量（単位：質量部）に従って、アルカリ可溶性樹脂、光重合性モノマー、光重合開始剤、着色剤、及び界面活性剤を、表４～８に示す組成の溶剤と混合して（着色剤の配合量は固形分換算）、固形分濃度１８質量％のネガ型感放射線性組成物を調製した。
　得られたネガ型感放射線性組成物について、上記「透明レジストの作製」と同様にして、異物、感度、粘度変化、及び塗布むらの評価を行った。結果を表４～８に示す。 <Preparation of black matrix resist, color filter resist, and black photo spacer resist>
In accordance with the composition and blending amount (unit: parts by mass) described in Table 3, the alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, colorant, and surfactant were mixed with the solvents having the compositions shown in Tables 4-8. By mixing (the amount of the colorant blended in terms of solid content), a negative radiation-sensitive composition having a solid content concentration of 18% by mass was prepared.
The obtained negative radiation-sensitive composition was evaluated for foreign matter, sensitivity, viscosity change, and coating unevenness in the same manner as in “Preparation of transparent resist”. The results are shown in Tables 4-8.
［凝集物］
　４０℃で２週間、ネガ型感放射線性組成物をエージング処理した後、１０ｃｍ角のガラス基材にスピン塗布し、凝集した異物の個数をカウントして、以下の基準で評価した。結果を表４～８に示す。
　○：０～２個、△：３～１０個、×：１１個以上 [Agglomerate]
The negative radiation-sensitive composition was aged at 40 ° C. for 2 weeks, spin-coated on a 10 cm square glass substrate, the number of aggregated foreign matters was counted, and evaluation was performed according to the following criteria. The results are shown in Tables 4-8.
○: 0 to 2, △: 3 to 10, x: 11 or more
Figure JPOXMLDOC01-appb-T000068
Figure JPOXMLDOC01-appb-T000068
　なお、表３の最上段において、ＢＭは、実施例２－１～２－１１及び比較例２－１～２－４を表し、Ｒは、実施例３－１～３－７及び比較例３－１～３－４を表し、Ｇは、実施例４－１～４－７及び比較例４－１～４－４を表し、Ｂは、実施例５－１～５－７及び比較例５－１～５－４を表し、ＢＰＳは、実施例６－１～６－７及び比較例６－１～６－４を表す。 In Table 3, BM represents Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-4, and R represents Examples 3-1 to 3-7 and Comparative Example 3. -1 to 3-4, G represents Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-4, and B represents Examples 5-1 to 5-7 and Comparative Example 5 -1 to 5-4, and BPS represents Examples 6-1 to 6-7 and Comparative Examples 6-1 to 6-4.
Figure JPOXMLDOC01-appb-T000069
Figure JPOXMLDOC01-appb-T000069
Figure JPOXMLDOC01-appb-T000070
Figure JPOXMLDOC01-appb-T000070
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000073
　表４～８から分かるように、上記一般式（１）で表される化合物を含有する実施例のネガ型感放射線性組成物は、感度、保存安定性、及び塗布性に優れており、露光及び現像により、異物の発生が抑制されたパターンを形成することができた。
　これに対し、上記一般式（１）で表される化合物を含有しない比較例のネガ型感放射線性組成物は、保存安定性に劣り、露光及び現像により形成されたパターン中でより多くの異物が発生し、用いる溶剤によっては、更に、塗布性に劣っていた。また、着色剤として遮光剤を含有する比較例のネガ型感放射線性組成物は、感度に劣っていた。 As can be seen from Tables 4 to 8, the negative-type radiation-sensitive compositions of Examples containing the compound represented by the above general formula (1) are excellent in sensitivity, storage stability, and coatability, and are exposed to light. In addition, a pattern in which the generation of foreign matter was suppressed could be formed by development.
On the other hand, the negative radiation sensitive composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and more foreign matters in the pattern formed by exposure and development. Depending on the solvent used, the coating property was further inferior. Moreover, the negative type radiation sensitive composition of the comparative example containing a light-shielding agent as a colorant was inferior in sensitivity.
＜ポジ型感放射線性組成物の調製＞
　２，４，４，４’－テトラヒドロキシベンゾフェノン１モルとナフトキノン－１，２－ジアジド－５－スルホニルクロリド３モルとのエステル化反応生成物２ｇとクレゾールノボラック樹脂８ｇとを、表１に示す組成の溶剤４０ｇに溶解して、ポジ型感放射線性組成物を調製した。このようにして得たポジ型感放射線性組成物について、以下の評価試験を行った。 <Preparation of positive radiation sensitive composition>
The composition shown in Table 1 is 2 g of an esterification reaction product of 1 mol of 2,4,4,4′-tetrahydroxybenzophenone and 3 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride and 8 g of cresol novolac resin. A positive radiation sensitive composition was prepared by dissolving in 40 g of the above solvent. The following evaluation tests were performed on the positive radiation sensitive composition thus obtained.
［析出物の有無］
　調製したポジ型感放射線性組成物を０．２μｍメンブレンフィルターで濾過したものを４０℃で静置し、２ヶ月経過時点でのポジ型感放射線性組成物中の析出物の有無について調べた。結果を表９に示す。 [Presence of precipitates]
The prepared positive radiation sensitive composition filtered through a 0.2 μm membrane filter was allowed to stand at 40 ° C., and the presence or absence of precipitates in the positive radiation sensitive composition after 2 months was examined. The results are shown in Table 9.
［感度変化］
　３ヶ月後のポジ型感放射線性組成物の感度変化の有無について調べた。即ち、調製直後のポジ型感放射線性組成物を基材に塗布して乾燥させた場合と、調製して３ヶ月経過したポジ型感放射線性組成物を基材に塗布して乾燥させた場合の最小露光量（感度）を比較し、全く変化のなかった場合を「○」、感度が低下した場合を「×」とした。結果を表９に示す。 [Change in sensitivity]
The presence or absence of the sensitivity change of the positive radiation sensitive composition after 3 months was examined. That is, when a positive radiation sensitive composition immediately after preparation is applied to a substrate and dried, and when a positive radiation sensitive composition that has been prepared for three months has been applied to a substrate and dried The minimum exposure amount (sensitivity) was compared, and the case where there was no change at all was indicated by “◯”, and the case where the sensitivity decreased was indicated by “X”. The results are shown in Table 9.
［断面形状］
　調製したポジ型感放射線性組成物をガラス基板上にスリットコートし、ホットプレートで９０℃、９０秒間乾燥して膜厚１．３μｍのレジスト膜を形成し、この膜にステッパーを用いて、所定のマスクを介して露光した後、ホットプレート上で１１０℃、９０秒間加熱し、ついで２．３８質量％の水酸化テトラメチルアンモニウム水溶液（ＴＭＡＨ）で現像し、３０秒間水洗・乾燥して得られたレジストパターンの断面形状を観察し、以下の基準で評価した。結果を表９に示す。なお、アンダーカットとは、レジストパターンの断面において、ガラス基板と接触するレジストパターン最下部の幅がレジストパターン最上部の幅よりも狭くなっていることをいう。
　○：ガラス基板とレジストパターンとの接触部分にアンダーカットが生じていない。
　×：ガラス基板とレジストパターンとの接触部分にアンダーカットが生じている。 [Cross-sectional shape]
The prepared positive radiation sensitive composition is slit coated on a glass substrate and dried on a hot plate at 90 ° C. for 90 seconds to form a resist film having a film thickness of 1.3 μm. After being exposed through the mask, it was heated on a hot plate at 110 ° C. for 90 seconds, then developed with 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH), washed with water and dried for 30 seconds. The cross-sectional shape of the resist pattern was observed and evaluated according to the following criteria. The results are shown in Table 9. The undercut means that the width of the lowermost portion of the resist pattern that contacts the glass substrate is narrower than the width of the uppermost portion of the resist pattern in the cross section of the resist pattern.
○: No undercut occurs at the contact portion between the glass substrate and the resist pattern.
X: Undercut has occurred in the contact portion between the glass substrate and the resist pattern.
［塗布状態］
　調製したポジ型感放射線性組成物をガラス基板上にスリットコートし、ホットプレートで９０℃、９０秒間乾燥したものの膜厚を測定し、面内で均一に塗布されている場合を「良好」、面内で均一に塗布されていないものを「不良」とした。結果を表９に示す。 [Application state]
Slit coat the prepared positive radiation sensitive composition on a glass substrate, measure the film thickness of what was dried at 90 ° C. for 90 seconds on a hot plate, and “good” when the film is uniformly applied in the plane, Those that were not uniformly applied in the plane were defined as “bad”. The results are shown in Table 9.
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000074
　表９から分かるように、上記一般式（１）で表される化合物を含有する実施例のポジ型感放射線性組成物は、保存安定性、現像性、及び塗布性に優れていた。
　これに対し、上記一般式（１）で表される化合物を含有しない比較例のポジ型感放射線性組成物は、保存安定性、現像性、及び塗布性に劣っていた。 As can be seen from Table 9, the positive-type radiation-sensitive compositions of Examples containing the compound represented by the general formula (1) were excellent in storage stability, developability, and coatability.
On the other hand, the positive type radiation sensitive composition of the comparative example which does not contain the compound represented by the said General formula (1) was inferior in storage stability, developability, and applicability | paintability.
＜ポリアミック酸含有ネガ型感放射線性樹脂組成物の調製＞
　撹拌機、撹拌羽根、還流冷却機、窒素ガス導入管を備えた容量５Ｌのセパラブルフラスコに、テトラカルボン酸二無水物であるピロメリット酸二無水物（ＰＭＤＡ）６５４．４ｇと、ジアミンである４，４’－ジアミノジフェニルエーテル（ＯＤＡ）６７２．８ｇと、表１０に示す組成の溶剤とを投入した。窒素ガス導入管よりフラスコ内に窒素を導入し、フラスコ内を窒素雰囲気とした。次いで、フラスコの内容物を撹拌しながら、５０℃で２０時間、上記テトラカルボン酸二無水物と上記ジアミンとを反応させて、ポリアミック酸溶液を得た。得られたポリアミック酸溶液に、感光性成分である「ＩＲＧＡＣＵＲＥ　ＯＸＥ０２」（商品名、ＢＡＳＦ製、オキシムエステル化合物）２７８ｇを添加し撹拌して、固形分濃度３０質量％のネガ型感放射線性樹脂組成物を調製した。
　得られたネガ型感放射線性樹脂組成物について、「透明レジストの作製」と同様にして、異物、粘度変化、及び塗布むらの評価を行った。結果を表１０に示す。 <Preparation of polyamic acid-containing negative radiation sensitive resin composition>
In a 5 L separable flask equipped with a stirrer, a stirring blade, a reflux condenser, and a nitrogen gas inlet tube, 654.4 g of tetramellitic dianhydride, pyromellitic dianhydride (PMDA), and diamine 672.8 g of 4,4′-diaminodiphenyl ether (ODA) and a solvent having the composition shown in Table 10 were added. Nitrogen was introduced into the flask through a nitrogen gas introduction tube, and the atmosphere in the flask was changed to a nitrogen atmosphere. Next, while stirring the contents of the flask, the tetracarboxylic dianhydride and the diamine were reacted at 50 ° C. for 20 hours to obtain a polyamic acid solution. To the obtained polyamic acid solution, 278 g of a photosensitive component “IRGACURE OXE02” (trade name, manufactured by BASF, oxime ester compound) is added and stirred, and a negative radiation sensitive resin composition having a solid content concentration of 30 mass%. A product was prepared.
The obtained negative radiation-sensitive resin composition was evaluated for foreign matter, viscosity change, and coating unevenness in the same manner as in “Preparation of transparent resist”. The results are shown in Table 10.
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000075
　表１０から分かるように、上記一般式（１）で表される化合物を含有する実施例のネガ型感放射線性樹脂組成物は、保存安定性及び塗布性に優れており、露光及び現像により、異物の発生が抑制されたパターンを形成することができた。
　これに対し、上記一般式（１）で表される化合物を含有しない比較例のネガ型感放射線性樹脂組成物は、保存安定性及び塗布性が劣っており、露光及び現像により形成されたパターン中でより多くの異物が発生した。 As can be seen from Table 10, the negative radiation-sensitive resin compositions of Examples containing the compound represented by the above general formula (1) are excellent in storage stability and applicability, and are exposed and developed. A pattern in which the generation of foreign matter was suppressed could be formed.
On the other hand, the negative radiation sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and applicability, and is a pattern formed by exposure and development. More foreign material was generated.
＜ポリベンゾオキサゾール前駆体含有ネガ型感放射線性樹脂組成物の調製＞
　回転子を入れた三角フラスコに、芳香族ジアミンジオールである２，２'－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン２ｍｍｏｌと、表１１に示す組成の溶剤１ｍＬとを加えた後、マグネッチックスターラーを用いてフラスコの内容物５分間撹拌した。その後、ジカルボニル化合物であるイソフタルアルデヒド２ｍｍｏｌをフラスコ内に入れ、窒素雰囲気下でフラスコの内容物を３時間還流させて反応を行った。次いで、減圧蒸留にて、反応液を脱水し、ポリベンゾオキサゾール前駆体溶液を得た。
　得られたポリベンゾオキサゾール前駆体溶液に、感光性成分である「ＩＲＧＡＣＵＲＥ　ＯＸＥ０２」（商品名、ＢＡＳＦ製、オキシムエステル化合物）０．５ｍｍｏｌを添加し撹拌して、固形分濃度３０質量％のネガ型感放射線性樹脂組成物を調製した。
　得られたネガ型感放射線性樹脂組成物について、「透明レジストの作製」と同様にして、異物、粘度変化、及び塗布むらの評価を行った。結果を表１１に示す。 <Preparation of a polybenzoxazole precursor-containing negative radiation sensitive resin composition>
After adding 2 mmol of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, which is an aromatic diamine diol, and 1 mL of a solvent having the composition shown in Table 11 to an Erlenmeyer flask containing a rotor. The contents of the flask were stirred for 5 minutes using a magnetic stirrer. Thereafter, 2 mmol of isophthalaldehyde as a dicarbonyl compound was put in the flask, and the reaction was carried out by refluxing the contents of the flask for 3 hours under a nitrogen atmosphere. Next, the reaction solution was dehydrated by distillation under reduced pressure to obtain a polybenzoxazole precursor solution.
To the obtained polybenzoxazole precursor solution, 0.5 mmol of “IRGACURE OXE02” (trade name, manufactured by BASF, oxime ester compound) as a photosensitive component is added and stirred, and a negative type having a solid content concentration of 30% by mass. A radiation sensitive resin composition was prepared.
The obtained negative radiation-sensitive resin composition was evaluated for foreign matter, viscosity change, and coating unevenness in the same manner as in “Preparation of transparent resist”. The results are shown in Table 11.
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000076
　表１１から分かるように、上記一般式（１）で表される化合物を含有する実施例のネガ型感放射線性樹脂組成物は、保存安定性及び塗布性に優れており、露光及び現像により、異物の発生が抑制されたパターンを形成することができた。
　これに対し、上記一般式（１）で表される化合物を含有しない比較例のネガ型感放射線性樹脂組成物は、保存安定性及び塗布性が劣っており、露光及び現像により形成されたパターン中でより多くの異物が発生した。 As can be seen from Table 11, the negative radiation-sensitive resin compositions of the examples containing the compound represented by the general formula (1) are excellent in storage stability and applicability, and are exposed and developed. A pattern in which the generation of foreign matter was suppressed could be formed.
On the other hand, the negative radiation sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and applicability, and is a pattern formed by exposure and development. More foreign material was generated.
＜ポリアミック酸含有ポジ型感放射線性樹脂組成物の調製１＞
［ヒドロキシル基含有酸無水物（ａ）の合成］
　窒素気流下、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン（ＢＡＨＦ）１８．３ｇ（０．０５ｍｏｌ）とアリルグリシジルエーテル３４．２ｇ（０．３ｍｏｌ）をＧＢＬ１００ｇに溶解させ、－１０℃に冷却した。ここにＧＢＬ５０ｇに溶解させた無水トリメリット酸クロリド２２．１ｇ（０．１１ｍｏｌ）を滴下した。このとき反応液の温度が０℃を越えないように滴下速度を調整した。滴下終了後、０℃で５時間撹拌した。この溶液をロータリーエバポレーターで濃縮し、トルエン１Ｌに投入して、下記式で表されるヒドロキシル基含有酸無水物（ａ）を得た。 <Preparation 1 of a polyamic acid-containing positive radiation-sensitive resin composition>
[Synthesis of hydroxyl group-containing acid anhydride (a)]
Under a nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and 34.2 g (0.3 mol) of allyl glycidyl ether were dissolved in 100 g of GBL. And cooled to -10 ° C. Here, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added dropwise. At this time, the dropping rate was adjusted so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the mixture was stirred at 0 ° C. for 5 hours. This solution was concentrated with a rotary evaporator and charged into 1 L of toluene to obtain a hydroxyl group-containing acid anhydride (a) represented by the following formula.
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
［ポリマーＡの合成］
　窒素気流下、４，４’－ジアミノフェニルエーテル４．４０ｇ（０．０２２ｍｏｌ）、１，３－ビス（３－アミノプロピル）テトラメチルジシロキサン１．２４ｇ（０．００５ｍｏｌ）をＮＭＰ５０ｇに溶解させた。ここに合成例１で得られたヒドロキシル基含有酸無水物（ａ）２１．４ｇ（０．０３０モル）を加えて、２０℃で１時間反応させ、次いで４０℃で２時間反応させた。その後、４－アミノフェノール０．６５ｇ（０．００６ｍｏｌ）を加え、更に４０℃で４５分間反応させた。その後、Ｎ、Ｎ－ジメチルホルムアミドジメチルアセタール７．１４ｇ（０．０６ｍｏｌ）をＮＭＰ５ｇで希釈した溶液を１０分かけて滴下した。滴下後、４０℃で３時間撹拌した。反応終了後、溶液を水２Ｌに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を４５℃の真空乾燥機で８０時間乾燥し、ポリイミド前駆体であるポリマーＡを得た。ＧＰＣにより、ポリマーＡの質量平均分子量を測定し、上記一般式（３１）で表される構成単位の数が１０～５００の範囲内であることを確認した。 [Synthesis of Polymer A]
Under a nitrogen stream, 4.40 g (0.022 mol) of 4,4′-diaminophenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 50 g of NMP. . 21.4 g (0.030 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto and reacted at 20 ° C. for 1 hour and then at 40 ° C. for 2 hours. Thereafter, 0.65 g (0.006 mol) of 4-aminophenol was added, and the mixture was further reacted at 40 ° C. for 45 minutes. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 45 ° C. for 80 hours to obtain polymer A as a polyimide precursor. The mass average molecular weight of the polymer A was measured by GPC, and it was confirmed that the number of structural units represented by the general formula (31) was in the range of 10 to 500.
［ノボラック樹脂Ａの合成］
　窒素気流下、ｍ－クレゾール７０．２ｇ（０．６５ｍｏｌ）、ｐ－クレゾール３７．８ｇ（０．３５ｍｏｌ）、３７重量％ホルムアルデヒド水溶液７５．５ｇ（ホルムアルデヒド０．９３ｍｏｌ）、シュウ酸二水和物０．６３ｇ（０．００５ｍｏｌ）、メチルイソブチルケトン２６４ｇを仕込んだ後、油浴中に浸し、反応液を還流させながら、４時間重縮合反応を行った。その後、油浴の温度を３時間かけて昇温し、その後、フラスコ内を減圧し、揮発分を除去し、溶解している樹脂を室温まで冷却して、ノボラック樹脂Ａのポリマー固体を得た。ＧＰＣによると、ノボラック樹脂Ａの質量平均分子量は４，０００であった。 [Synthesis of Novolak Resin A]
Under a nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g of a 37 wt% aqueous formaldehyde solution (0.93 mol of formaldehyde), oxalic acid dihydrate 0 Then, .63 g (0.005 mol) and 264 g of methyl isobutyl ketone were charged, followed by immersion in an oil bath, and a polycondensation reaction was performed for 4 hours while refluxing the reaction solution. Thereafter, the temperature of the oil bath was raised over 3 hours, and then the inside of the flask was decompressed to remove volatile components, and the dissolved resin was cooled to room temperature to obtain a polymer solid of Novolak Resin A. . According to GPC, the novolak resin A had a mass average molecular weight of 4,000.
［組成物の調製］
　ポリマーＡの固体６ｇ、ノボラック樹脂Ａ４ｇ、下記式で表されるキノンジアジド化合物Ａ２ｇ、ＨＭＯＭ－ＴＰＨＡＰ（商品名、本州化学工業（株）製）６．０ｇ、ＢＩＲ－ＰＣ（商品名、旭有機材工業（株）製）１ｇ、ビニルトリメトキシシラン０．３ｇを測りとり、それらを表１２に示す組成の溶剤に溶解させて、固形分濃度３０質量％のポジ型感放射線性樹脂組成物を得た。
　得られたポジ型感放射線性樹脂組成物について、「透明レジストの作製」と同様にして、異物、粘度変化、及び塗布むらの評価を行った。結果を表１２に示す。 [Preparation of composition]
6 g of polymer A solid, 4 g of novolac resin A, 2 g of quinonediazide compound A2 represented by the following formula, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 6.0 g, BIR-PC (trade name, Asahi Organic Materials Co., Ltd.) 1 g and 0.3 g of vinyltrimethoxysilane were measured and dissolved in a solvent having a composition shown in Table 12 to obtain a positive radiation sensitive resin composition having a solid content concentration of 30% by mass. .
The resulting positive radiation sensitive resin composition was evaluated for foreign matter, viscosity change, and coating unevenness in the same manner as in “Preparation of transparent resist”. The results are shown in Table 12.
Figure JPOXMLDOC01-appb-C000078
 ［上記式中、ＤはＨ又は１，２－ナフトキノンジアジド－５－スルホニル基であり、Ｄの１，２－ナフトキノンジアジド－５－スルホニル基による平均エステル化率は５９．９％である。なお、分子によりＤの置換数や置換位置にばらつきがあるため、上記の通り、Ｄが１，２－ナフトキノンジアジド－５－スルホニル基である平均割合（平均エステル化率（％））を示す。以下、同じ。］
Figure JPOXMLDOC01-appb-C000078
 [In the above formula, D is H or 1,2-naphthoquinonediazide-5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazide-5-sulfonyl group is 59.9%. Since the number of substitutions and substitution positions of D vary depending on the molecule, the average ratio (average esterification rate (%)) in which D is a 1,2-naphthoquinonediazide-5-sulfonyl group is shown as described above. same as below. ]
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000079
　表１２から分かるように、上記一般式（１）で表される化合物を含有する実施例のポジ型感放射線性樹脂組成物は、保存安定性及び塗布性に優れており、露光及び現像により、異物の発生が抑制されたパターンを形成することができた。
　これに対し、上記一般式（１）で表される化合物を含有しない比較例のポジ型感放射線性樹脂組成物は、保存安定性及び塗布性が劣っており、露光及び現像により形成されたパターン中でより多くの異物が発生した。 As can be seen from Table 12, the positive-type radiation-sensitive resin compositions of Examples containing the compound represented by the general formula (1) are excellent in storage stability and applicability, and are exposed and developed. A pattern in which the generation of foreign matter was suppressed could be formed.
On the other hand, the positive type radiation sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and coatability, and is a pattern formed by exposure and development. More foreign material was generated.
＜ポリアミック酸含有ポジ型感放射線性樹脂組成物の調製２＞
　ポリマーＡの固体６ｇ、ノボラック樹脂Ａ４ｇ、下記式で表されるキノンジアジド化合物Ｂ２ｇ、ＨＭＯＭ－ＴＰＨＡＰ（商品名、本州化学工業（株）製）６．０ｇ、ＢＩＲ－ＰＣ（商品名、旭有機材工業（株）製）１ｇ、ビニルトリメトキシシラン０．３ｇを測りとり、それらを表１３に示す組成の溶剤に溶解させて、固形分濃度３０質量％のポジ型感放射線性樹脂組成物を得た。なお、ポリマーＡ及びノボラック樹脂Ａは、「ポリアミック酸含有ポジ型感放射線性樹脂組成物の調製１」で得たものである。
　得られたポジ型感放射線性樹脂組成物について、「透明レジストの作製」と同様にして、異物、粘度変化、及び塗布むらの評価を行った。結果を表１３に示す。 <Preparation 2 of a polyamic acid-containing positive radiation-sensitive resin composition>
6 g of polymer A solid, 4 g of novolak resin A, 2 g of quinonediazide compound B represented by the following formula, 6.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-PC (trade name, Asahi Organic Materials Co., Ltd.) 1 g and 0.3 g of vinyltrimethoxysilane were measured and dissolved in a solvent having the composition shown in Table 13 to obtain a positive radiation sensitive resin composition having a solid content concentration of 30% by mass. . In addition, the polymer A and the novolak resin A are those obtained in “Preparation 1 of a polyamic acid-containing positive radiation-sensitive resin composition”.
The resulting positive radiation sensitive resin composition was evaluated for foreign matter, viscosity change, and coating unevenness in the same manner as in “Preparation of transparent resist”. The results are shown in Table 13.
Figure JPOXMLDOC01-appb-C000080
 ［上記式中、ＤはＨ又は１，２－ナフトキノンジアジド－５－スルホニル基であり、Ｄの１，２－ナフトキノンジアジド－５－スルホニル基による平均エステル化率は５４．７％である。］
Figure JPOXMLDOC01-appb-C000080
 [In the above formula, D is H or 1,2-naphthoquinonediazide-5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazide-5-sulfonyl group is 54.7%. ]
Figure JPOXMLDOC01-appb-T000081
Figure JPOXMLDOC01-appb-T000081
　表１３から分かるように、上記一般式（１）で表される化合物を含有する実施例のポジ型感放射線性樹脂組成物は、保存安定性及び塗布性に優れており、露光及び現像により、異物の発生が抑制されたパターンを形成することができた。
　これに対し、上記一般式（１）で表される化合物を含有しない比較例のポジ型感放射線性樹脂組成物は、保存安定性及び塗布性が劣っており、露光及び現像により形成されたパターン中でより多くの異物が発生した。 As can be seen from Table 13, the positive-type radiation-sensitive resin compositions of Examples containing the compound represented by the general formula (1) are excellent in storage stability and applicability, and are exposed and developed. A pattern in which the generation of foreign matter was suppressed could be formed.
On the other hand, the positive type radiation sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) is inferior in storage stability and coatability, and is a pattern formed by exposure and development. More foreign material was generated.

Claims (4)

  1. 　下記一般式（１）で表される化合物を含有する感放射線性組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は、水素原子又はヒドロキシル基を表し、Ｒ２及びＲ３は、独立に水素原子又はＣ１～Ｃ３のアルキル基を表し、Ｒ４及びＲ５は、独立にＣ１～Ｃ３のアルキル基を表す。）     The radiation sensitive composition containing the compound represented by following General formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 represents a hydrogen atom or a hydroxyl group, R 2 and R 3 independently represent a hydrogen atom or a C 1 -C 3 alkyl group, and R 4 and R 5 independently represent C 1 represents an alkyl group ~ C 3.)
  2. 　前記一般式（１）で表される化合物が、下記式（Ｅ１）～（Ｅ４）の各式で表される化合物の少なくとも１種である請求項１に記載の感放射線性組成物。
    Figure JPOXMLDOC01-appb-C000002
         The radiation-sensitive composition according to claim 1, wherein the compound represented by the general formula (1) is at least one compound represented by the following formulas (E1) to (E4).
    Figure JPOXMLDOC01-appb-C000002
  3. 　前記一般式（１）で表される化合物を溶剤の少なくとも１種として含有する請求項１又は２に記載の感放射線性組成物。 The radiation sensitive composition of Claim 1 or 2 which contains the compound represented by the said General formula (1) as at least 1 sort (s) of a solvent.
  4. 　請求項１から３のいずれか１項に記載の感放射線性組成物からなる感放射線性組成物膜を基板上に形成する感放射線性組成物膜形成工程と、
    　前記感放射線性組成物膜を位置選択的に露光する露光工程と、
    　露光された前記感放射線性組成物膜を現像する現像工程とを含むパターン製造方法。     A radiation-sensitive composition film forming step of forming a radiation-sensitive composition film comprising the radiation-sensitive composition according to any one of claims 1 to 3 on a substrate;
    An exposure step of selectively exposing the radiation-sensitive composition film;
    The pattern manufacturing method including the image development process which develops the exposed said radiation sensitive composition film | membrane.
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JP6195623B2 (en) 2017-09-13
TW201524943A (en) 2015-07-01
CN105579907B (en) 2019-12-17
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KR20170136653A (en) 2017-12-11

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