WO2010095390A1 - 感光性樹脂組成物 - Google Patents

感光性樹脂組成物 Download PDF

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Publication number
WO2010095390A1
WO2010095390A1 PCT/JP2010/000759 JP2010000759W WO2010095390A1 WO 2010095390 A1 WO2010095390 A1 WO 2010095390A1 JP 2010000759 W JP2010000759 W JP 2010000759W WO 2010095390 A1 WO2010095390 A1 WO 2010095390A1
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group
carbon atoms
resin composition
photosensitive resin
general formula
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PCT/JP2010/000759
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English (en)
French (fr)
Japanese (ja)
Inventor
向井孝夫
榊原徳
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サンアプロ株式会社
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Priority to JP2011500489A priority Critical patent/JP5662929B2/ja
Priority to CN201080007012.7A priority patent/CN102307909B/zh
Publication of WO2010095390A1 publication Critical patent/WO2010095390A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording

Definitions

  • the present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition having excellent thick film curability.
  • Photosensitive resin composition suitably used for paints, printing inks, coating agents, casting materials (for example, materials for MEMS), resist materials, nanoimprint materials, adhesives, sealing agents, or molding materials for optical members or building materials It is.
  • thermosetting resins such as short-time curing and solvent-free.
  • Patent Document 1 a cationic polymerizable adhesive that cures at a low temperature by generating an acid from a photoacid generator by ultraviolet irradiation has been proposed (for example, Patent Document 1). In comparison, the curing rate was slow, and the metal member was corroded. Further, although a radical polymerizable adhesive that promotes radical generation from a thermal radical polymerization initiator by generating a base from a photobase generator by ultraviolet irradiation and cures quickly at a low temperature has been proposed (for example, Patent Document 2).
  • the photobase generator described above has a small absorption of 365 nm light, and is generally used for a wavelength of a high-pressure mercury lamp (i-line: 365 nm, h-line: 405 nm, g-line: 436 nm) which is a widely used light source.
  • a high-pressure mercury lamp i-line: 365 nm, h-line: 405 nm, g-line: 436 nm
  • the sensitivity is insufficient.
  • pigments for example, titanium oxide
  • binders with aromatic rings absorb the irradiation light. Therefore, for example, titanium oxide absorbs light of 380 nm or less, and an aromatic ring absorbs light near 365 nm. Therefore, a conventional photobase generator cannot generate a base.
  • An object of the present invention is to provide a photosensitive resin composition that is efficiently exposed to light having a wavelength of 350 nm to 500 nm and is excellent in thick film curability and deep part curability.
  • the present invention relates to a compound represented by the general formula (1) or the general formula (2), which generates a base by irradiation with actinic rays (A), a thermal radical polymerization initiator (B), and A photosensitive resin composition comprising a radically polymerizable substance (C).
  • Ar has at least one benzene skeleton, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an alkylthio group having 1 to 20 carbon atoms, a carbon number of 1 Selected from the group consisting of an alkylsilyl group having 20 carbon atoms, an acyl group having 1-20 carbon atoms, an amino group, a cyano group, an alkyl group having 1-20 carbon atoms, a phenyl group, a naphthyl group, a phenoxy group, and a phenylthio group.
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, or 1 to 20 carbon atoms.
  • alkyl group having 1 to carbon atoms which may be substituted with a group 20 selected, a phenyl group or a naphthyl group, R 3 - R 5 may be bonded to form a ring structure;
  • X - is Represents an anion.
  • the photosensitive resin composition of the present invention exhibits an effect that it is efficiently exposed to light having a wavelength of 350 nm to 500 nm and is excellent in deep part curability.
  • the photosensitive resin composition of the present invention contains a photobase generator (A), a thermal radical polymerization initiator (B), and a radical polymerizable substance (C).
  • the photobase generator (A) is a compound represented by the general formula (1) or the general formula (2), and Ar in the formula has at least one benzene skeleton, a halogen atom, a carbon number of 1 to 20 alkoxy groups, nitro group, carboxyl group, hydroxyl group, mercapto group, alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, An aromatic hydrocarbon group or a heterocyclic group which may be substituted with a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, a phenoxy group and a phenylthio group.
  • Ar is preferably an aromatic hydrocarbon group or a heterocyclic group having 1 to 4 benzene ring skeletons. More preferable ones will be described later.
  • R 1 and R 2 in the formula are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, carbon Alkylthio group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, alkyl group having 1 to 20 carbon atoms, phenyl group, naphthyl group, phenoxy group And a phenyl group which may be substituted with a group selected from the group of a phenylthio group, R 1 and R 2 may be bonded to each other to form a
  • M in the formula is an integer of 2 to 4, preferably 2 or 4.
  • R 3 to R 5 in the formula are each independently a halogen atom, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, a mercapto group, an alkylthio group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms.
  • a silyl group, an acyl group having 1 to 20 carbon atoms, an amino group, a cyano group, a phenoxy group and a phenylthio group, which may be substituted with a group selected from the group selected from the group consisting of a phenyl group, A naphthyl group, R 3 to R 5 may be bonded to each other to form a ring structure;
  • an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is particularly preferable.
  • X ⁇ in the formula represents an anion.
  • M in the general formula (6) is the same as m in the general formula (1), and preferable ones are also the same.
  • R 3 ⁇ R 5 in the general formula (7) are the same as R 3 ⁇ R 5 in the general formula (2), it is preferable also the same.
  • the photobase generator (A) may be used alone or in combination of two or more.
  • a base generated from the photobase generator (A) by irradiation with actinic rays (a tertiary amidine represented by the general formula (6) or a tertiary represented by the general formula (7)
  • the amine forms a redox initiator with the thermal radical polymerization initiator (B), so that decomposition of (B) proceeds rapidly. Radical generation from the redox initiator proceeds in a dark reaction, and as the base diffuses, photocuring is difficult with general photoradical initiators, where active light is attenuated or where it does not reach. Can be cured.
  • the general formula (6) will be described.
  • the general formula (6) is a compound having an amidine skeleton, and m is an integer of 2 to 4. Particularly preferred are 1,8-diazabicyclo [5.4.0] -7-undecene, where m is 4, and 1,5-diazabicyclo [4.3.0] -5-nonene, where m is 2.
  • the general formula (7) will be described.
  • the general formula (7) is a tertiary amine, particularly preferably triethylamine, tributylamine and 1-azabicyclo [2.2.2] octane.
  • Ar in the general formula (1) or general formula (2) is preferably an aromatic hydrocarbon group or heterocyclic group having 1 to 4 benzene ring skeletons, particularly preferably a general formula (3)
  • a monovalent residue obtained by removing any one of R 24 to R 33 from the compound represented by the general formula (5) is preferably an aromatic hydrocarbon group or heterocyclic group having 1 to 4 benzene ring skeletons, particularly preferably a general formula (3)
  • a monovalent residue obtained by removing any one of R 24 to R 33 from the compound represented by the general formula (5) is preferably an aromatic hydrocarbon group or heterocyclic group having 1 to 4 benzene ring skeletons,
  • the residue (Ar1) represented by the general formula (3) will be described.
  • (Ar1) is a residue having an anthracene skeleton, and is an example of a residue having a maximum absorption wavelength in the vicinity of i-line (365 nm).
  • Substituents R 6 to R 15 are modified in consideration of absorption wavelength adjustment, sensitivity adjustment, thermal stability, reactivity, decomposability, etc., and include hydrogen atoms, halogen atoms, alkoxy groups (from 1 to 20), nitro group, carboxyl group, hydroxyl group, mercapto group, silyl group (1-20 carbon atoms), acyl group (1-20 carbon atoms), amino group, cyano group, alkyl group (1-20 carbon atoms), A functional group selected from the group consisting of a phenyl group and a naphthyl group is modified depending on the purpose.
  • alkoxy group having 1 to 20 carbon atoms
  • examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, pentyloxy group, iso-pentyloxy group, neo- A pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and the like can be given.
  • Examples of the silyl group include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group.
  • the alkyl may be a linear structure or a branched structure.
  • acyl group examples include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, cyclohexylcarbonyl group and the like.
  • the alkyl group includes methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and iso-pentyl group. , Neo-pentyl group, hexyl group, heptyl group, octyl group and the like.
  • halogen atom fluorine and chlorine are preferable.
  • Preferred examples of the substituent include a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferable examples include a cyano group, a phenyl group, and a carbon group.
  • examples thereof include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, and an acyl group having 1 to 15 carbon atoms.
  • Particularly preferred are an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms.
  • the alkyl moiety may be linear, branched or cyclic.
  • the residue (Ar2) represented by the general formula (4) will be described.
  • (Ar2) is a residue having a thioxanthone skeleton, and is an example of a compound having a maximum absorption wavelength in the vicinity of i-line (365 nm).
  • Examples of the substituents R 16 to R 23 include the same ones as the substituents R 6 to R 15 of the above (Ar1), and preferred ones are also the same.
  • the residue (Ar3) represented by the general formula (5) will be described.
  • (Ar3) is a residue having a benzophenone skeleton, and is an example of a residue having a maximum absorption wavelength near the i-line (365 nm).
  • Examples of the substituents R 24 to R 33 include the same ones as the substituents R 6 to R 15 of the above (Ar1), and preferred ones are also the same.
  • the residue (Ar1) and the residue (Ar2) are preferable.
  • the thermal radical polymerization initiator (B) contained in the photosensitive resin composition of the present invention represents a compound that generates radicals by heat, unlike a photo radical initiator that generates radicals by irradiation with actinic rays such as electron beams, ultraviolet rays, and visible rays. It is preferable to use known compounds such as organic peroxides (hydroperoxides, dialkyl peroxides, diacyl peroxides, etc.) known from azo compounds and azo compounds. From the viewpoint of stability and reactivity, a thermal radical polymerization initiator having a 10-hour half-life temperature of 70 ° C to 250 ° C is more preferable. Specifically, the following (B1) and (B2) are mentioned. (B) may be used alone or in combination of two or more.
  • thermal radical polymerization initiator (B1) having a 10-hour half-life temperature of 70 ° C. or higher and lower than 150 ° C.
  • B11 Peroxide-based polymerization initiator: benzoyl peroxide (half-life temperature 74 ° C.), t-butyl peroxyacetate (half-life temperature 102 ° C.), 2,2-di- (t-butylperoxy) butane ( Half-life temperature 103 ° C), t-butyl peroxybenzoate (half-life temperature 104 ° C), n-butyl 4,4-di- (t-butylperoxy) valerate (half-life temperature 105 ° C), di- (2 -T-butylperoxyisopropyl) benzene (half-life temperature 119 ° C), dicumyl peroxide (half-life temperature 116 ° C), di-t-hexyl peroxide (half-life temperature 116 ° C)
  • thermal radical polymerization initiator (B2) having a 10-hour half-life temperature of 150 ° C. or higher and 250 ° C. or lower include the following.
  • B21 Peroxide-based polymerization initiator: 1,1,3,3-tetramethylbutyl hydroperoxide (half-life temperature 153 ° C.), cumene hydroperoxide (half-life temperature 158 ° C.), t-butyl hydroper Oxide (half-life temperature 167 ° C.), t-butyltrimethylsilyl peroxide (half-life temperature 176 ° C.) and the like.
  • B22 Others: 2,3-dimethyl-2,3-diphenylbutane (half-life temperature 210 ° C.) and the like.
  • the radically polymerizable substance (C) contained in the photosensitive resin composition of the present invention will be described.
  • any known compound can be used as long as it is a compound that is polymerized by radicals.
  • an N-vinyl compound, a monofunctional (meth) acrylate monomer, a (meth) acryloyl group (hereinafter, referred to as “C”) can be used.
  • Multifunctional (meth) acrylate oligomers and maleimide compounds having two or more (meth) acryloyl groups in the molecule are preferred, and (meth) acrylate monomers and polyfunctional (meth) acrylate oligomers are more preferred.
  • N-vinyl compound examples include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, and the like.
  • Examples of the (meth) acrylate monomer include alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.]; alicyclic group-containing (meth) acrylate [dicyclopentanyl (meth) acrylate, sidiclopentenyl (meth) Acrylate and isobornyl (meth) acrylate, etc.], hydroxyalkyl (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate
  • Polyfunctional (meth) acrylate oligomers include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and trimethylolpropane tri (meth) acrylate.
  • the maleimide compound includes at least two maleimide groups in the molecule.
  • the addition amount of the thermal radical polymerization initiator (B) is 0.05 to 30 parts, preferably 0.000, relative to 100 parts of the radical polymerizable substance (C) from the viewpoint of photocurability and storage stability. 1 to 20 parts.
  • the addition amount of the photobase generator (A) is preferably 1 to 150 parts by weight with respect to 100 parts by weight of the thermal radical initiator (B), from the viewpoint of radical generation efficiency and physical properties of the cured product, and 5 to 100 parts by weight. Is more preferable.
  • the photosensitive resin composition in the present invention may contain a solvent, a sensitizer, an adhesion-imparting agent (such as a silane coupling agent) and the like.
  • Solvents include glycol ethers (such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone), and esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether).
  • Acetate and propylene glycol alkyl ether acetate aromatic hydrocarbons (toluene, xylene and the like), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol and the like) and ethers (tetrahydrofuran and the like). These may be used alone or in combination.
  • the solvent is preferably added so that the solid content concentration of the photosensitive resin composition is 1 to 100% by weight, more preferably 5 to 80% by weight, and particularly preferably 10 to 60% by weight.
  • sensitizer examples include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene.
  • the content of the sensitizer is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight with respect to the photosensitive resin composition.
  • adhesion-imparting agent examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, vinyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, urea
  • examples thereof include propyltriethoxysilane, tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate and the like.
  • the content of the adhesion-imparting agent is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight with respect to the photosensitive resin composition.
  • inorganic fine particles, pigments, dispersants, antifoaming agents, leveling agents, thixotropy imparting agents, slip agents, flame retardants, antistatic agents, oxidations are further selected according to the purpose of use.
  • An inhibitor and an ultraviolet absorber may be added and contained.
  • the photosensitive resin composition of the present invention can be photocured by irradiation with an actinic ray of 350 to 500 nm, in addition to a commonly used high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, etc. (UV ⁇ Latest trends in EB curing technology, edited by Radtech Research Association, CM Publishing, 138 pages, 2006) can be used. Heating may be performed at the time of irradiation with actinic rays and / or for the purpose of diffusing the base generated from the photobase generator after irradiation. The heating temperature varies depending on the application, but is usually 30 ° C. to 200 ° C., preferably 35 ° C. to 150 ° C., more preferably 40 ° C. to 120 ° C.
  • the photosensitive resin composition of the present invention is hard to be photocured with a general photoradical initiator due to generation of radicals from a redox initiator, and cures at a portion where active light is attenuated or does not reach. Therefore, it can be used for paints, printing inks, coating agents, casting materials (for example, materials for MEMS), resist materials, nanoimprint materials, adhesives or sealants, or molding materials for optical members or building materials.
  • the reaction solution was added dropwise to an aqueous solution consisting of 4.0 g of sodium tetraphenylborate salt and 40 g of water in a 100 ml eggplant flask, and the mixture was further stirred for 1 hour at room temperature (about 25 ° C.). And the organic layer was washed three times with water. The organic layer was concentrated with an evaporator to obtain 5.4 g of a white solid. This white solid was recrystallized from acetonitrile to obtain 4.7 g of a photobase generator (A1-1) (white solid).
  • A1-1 photobase generator
  • the reaction solution was added dropwise to a dispersion composed of 3.0 g of silver phenylglyoxylate and 20 g of methanol placed in a 100 ml eggplant flask, and further stirred for 1 hour at room temperature (about 25 ° C.).
  • the filtrate removed by the above step was concentrated with an evaporator to obtain 4.5 g of a brown solid.
  • This brown solid was recrystallized with ether / hexane to obtain 2.6 g of the photobase generator (A1-4) (yellow solid) of the present invention.
  • the organic layer was washed 3 times with 30 g of water.
  • the organic layer was concentrated with an evaporator to obtain a yellow solid.
  • This yellow solid was recrystallized from acetonitrile / ether to obtain 1.3 g of a photobase generator (A1-6) (slightly yellow powder).
  • DNCDP ⁇ [(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl ⁇ -2,6-dimethylpiperidine
  • Non-Patent Document 1 Micromolecules A. Mochizuki, Vol. 28, No. 1, 1995
  • the obtained DNCDP had a yield of 65% and a melting point of 132.8 ° C., and the elemental analysis results were C; 58.12, H; 6.90, N; 7.94, O; .
  • DNCDP is a compound that generates a secondary amine when irradiated with actinic rays.
  • a quaternary ammonium salt as a photobase generator was synthesized in the same manner as in the production example of Patent Document 2. That is, p-nitrophenacyl bromide (2.00 g, 8.2 mmol) was dissolved in acetone (20 g), and N, N-dimethylbenzylamine (1.10 g, 8.8) dissolved in acetone (5 g) was dissolved therein. 2 mmol) was slowly added, and then stirred at room temperature for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain white crystals (yield 1.59 g).
  • diethylthioxanthone Wako Pure Chemical Industries, Ltd., 2,4-diethyl-9H-thioxanthen-9-one
  • Comparative photobase generators H-1) to (H-2) 3 parts, dipentaerythritol pentaacrylate (manufactured by Sanyo Chemical Industries, Neomer DA-600), titanium oxide (Ishihara Sangyo, Tyco A-200) 40 parts of pigment dispersant (Bic Chemie, Disperyk-111, 0.5 part) was mixed to obtain a pigment dispersion, and then 3 parts of benzoyl peroxide (manufactured by NOF Corporation, Nyper BW) was mixed for photosensitivity. Resin compositions Q′-1 to Q′-2 were produced.
  • Comparative Examples 4-6 Comparative photobase generators (H-1) to (H-2) 3 parts, diethylthioxanthone (Wako Pure Chemical Industries, Ltd., 2,4-diethyl-9H-thioxanthen-9-one) 1 part, dipentaerythritol 100 parts of pentaacrylate (manufactured by Sanyo Chemical Industries, Neomer DA-600), 40 parts of titanium oxide (manufactured by Ishihara Sangyo, Type A-200), 0.5 parts of pigment dispersant (manufactured by Big Chemie, Disperyk-111) are mixed.
  • Measurement method About 50 mg of a measurement sample (photobase generator) was precisely weighed into a 50 mL volumetric flask, about 20 g of acetonitrile was added and dissolved, and then acetonitrile was added to match the marked line. 1 mL of this solution was taken into a 20 mL volumetric flask with a measuring pipette, and acetonitrile was added to the marked line for dilution to obtain an acetonitrile solution having a predetermined concentration. This solution was put in a quartz cell (optical path length: 1 cm), and an absorption spectrum in a wavelength range of 200 to 500 nm was measured with a spectrophotometer (Shimadzu Corporation, UV-2550). From the absorbance obtained from the spectrum, the molar extinction coefficient was calculated by the following equation.
  • each photosensitive resin composition obtained in the examples and comparative examples was applied to a PET steel plate obtained by thermocompression bonding of a 12 ⁇ m thick homo-PET (polyethylene terephthalate) sheet to a 0.20 mm thick tin-free steel plate.
  • the film thickness was changed and applied, photocured under the following irradiation conditions, the pencil hardness (JIS K5400 (1990)) of the coating film was measured, and the film thickness at which the pencil hardness could be maintained at 2H or higher was measured.
  • the results are shown in Table 1.
  • a belt conveyor type UV irradiator (I Graphics Co., Ltd., ECS-151U) uses a filter (I Graphics Co., Ltd., 365 filter) that transmits light with a wavelength of 300 to 450 nm to control the exposure wavelength. Used for exposure. Exposure was about 12 J / cm 2 as approximately 0.6 J / cm 2, 405 nm as 365 nm.
  • the photosensitive resin compositions Q-1 to Q-9 of the present invention all have good film thicknesses of 50 ⁇ m or more that maintain a pencil hardness of 2H or more, and the photosensitive resin compositions Q ′ of the comparative examples are good.
  • -1 to Q′-6 were found to have a film thickness of 25 ⁇ m or less maintaining a pencil hardness of 2H or more. In order to maintain the pencil hardness of 2H or more, the coating film needs to be deeply cured to the surface of the PET steel plate.
  • a photosensitive resin composition having excellent thick film curability can be obtained by using the photosensitive resin composition of the present invention. Paints, printing inks, coating agents, resist materials, etc. containing fillers such as coloring materials such as dyes and pigments and inorganic particles that attenuate actinic light and do not cure sufficiently to the deep part. It is particularly useful for adhesives, casting materials (eg, MEMS materials), nanoimprint materials, sealing agents, or molding materials that need to be cured with a thick film that does not reach and does not fully cure deep.
  • the photosensitive resin composition of the present invention is a paint, printing ink, coating agent, casting material (for example, a material for MEMS), resist material, nanoimprint material, adhesive or sealing agent, in which thick film curability and deep curability are useful. Or it is used suitably for the molding material of an optical member or a building material.

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Cited By (17)

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Publication number Priority date Publication date Assignee Title
JP2012168526A (ja) * 2011-01-26 2012-09-06 Sanyo Chem Ind Ltd 感光性組成物
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JP2016142753A (ja) * 2015-01-29 2016-08-08 三菱化学株式会社 感光性樹脂組成物、それで構成される硬化部材、及びそれを備えた画像表示装置
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005275258A (ja) * 2004-03-26 2005-10-06 Fuji Photo Film Co Ltd ホログラム記録材料、ホログラム記録方法及び光記録媒体
JP2007045900A (ja) * 2005-08-09 2007-02-22 Hitachi Chem Co Ltd 回路接続材料並びに回路端子の接続構造体及び接続方法
JP2009244745A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd 感光性樹脂組成物、およびこれを用いた物品、及びネガ型パターン形成方法
JP2009265294A (ja) * 2008-04-24 2009-11-12 Sanyo Chem Ind Ltd 感光性樹脂組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08211604A (ja) * 1995-02-02 1996-08-20 Konica Corp 感光性組成物、感光性平版印刷版及びその現像方法
JP2000169821A (ja) 1998-09-30 2000-06-20 Three Bond Co Ltd 紫外線硬化性異方導電接着剤
JP4201778B2 (ja) * 2005-03-24 2008-12-24 株式会社ノリタケスーパーアブレーシブ ワイヤソー
EP1975710B1 (en) * 2007-03-30 2013-10-23 FUJIFILM Corporation Plate-making method of lithographic printing plate precursor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005275258A (ja) * 2004-03-26 2005-10-06 Fuji Photo Film Co Ltd ホログラム記録材料、ホログラム記録方法及び光記録媒体
JP2007045900A (ja) * 2005-08-09 2007-02-22 Hitachi Chem Co Ltd 回路接続材料並びに回路端子の接続構造体及び接続方法
JP2009244745A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd 感光性樹脂組成物、およびこれを用いた物品、及びネガ型パターン形成方法
JP2009265294A (ja) * 2008-04-24 2009-11-12 Sanyo Chem Ind Ltd 感光性樹脂組成物

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KR101710319B1 (ko) 2011-03-07 2017-02-24 산요가세이고교 가부시키가이샤 감광성 조성물, 경화물, 및, 활성 광선 경화물의 제조 방법
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KR101666263B1 (ko) 2011-03-07 2016-10-13 산요가세이고교 가부시키가이샤 감광성 조성물, 경화물, 및, 활성 광선 경화물의 제조 방법
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EP2980180A4 (en) * 2013-03-28 2016-09-14 San Apro Ltd PHOTO BASE GENERATOR
WO2015008709A1 (ja) 2013-07-18 2015-01-22 セメダイン株式会社 光硬化性組成物
WO2015088021A1 (ja) 2013-12-13 2015-06-18 セメダイン株式会社 接着性を有する光硬化性組成物
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US10100070B2 (en) 2014-01-24 2018-10-16 Fujifilm Wako Pure Chemical Corporation Borate-based base generator, and base-reactive composition comprising such base generator
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