WO2017159873A1 - Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, and method for producing printed wiring board - Google Patents
Photosensitive resin composition, photosensitive element, method for producing substrate with resist pattern, and method for producing printed wiring board Download PDFInfo
- Publication number
- WO2017159873A1 WO2017159873A1 PCT/JP2017/011016 JP2017011016W WO2017159873A1 WO 2017159873 A1 WO2017159873 A1 WO 2017159873A1 JP 2017011016 W JP2017011016 W JP 2017011016W WO 2017159873 A1 WO2017159873 A1 WO 2017159873A1
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- WIPO (PCT)
- Prior art keywords
- group
- resist pattern
- substrate
- mass
- resin composition
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 78
- 239000000758 substrate Substances 0.000 title claims description 94
- 238000004519 manufacturing process Methods 0.000 title claims description 46
- -1 ethyleneoxy groups Chemical group 0.000 claims abstract description 75
- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000011230 binding agent Substances 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 81
- 238000007747 plating Methods 0.000 claims description 45
- 230000008569 process Effects 0.000 claims description 27
- 238000005530 etching Methods 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 8
- 239000000539 dimer Substances 0.000 claims description 7
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
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- 239000010410 layer Substances 0.000 description 118
- 239000000243 solution Substances 0.000 description 46
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- 239000000178 monomer Substances 0.000 description 16
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
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- 230000001235 sensitizing effect Effects 0.000 description 5
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 3
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- 239000003513 alkali Substances 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
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- 238000011088 calibration curve Methods 0.000 description 2
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- 125000001309 chloro group Chemical group Cl* 0.000 description 2
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- 239000011889 copper foil Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
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- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
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- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 2
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
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- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
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- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- UCSGWEMRGIONEW-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-bis(2-methoxyphenyl)-1h-imidazole Chemical class COC1=CC=CC=C1C1=C(C=2C(=CC=CC=2)OC)NC(C=2C(=CC=CC=2)Cl)=N1 UCSGWEMRGIONEW-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- 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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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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
- 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
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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
- 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
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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
- G03F7/20—Exposure; Apparatus therefor
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/18—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor the conductor being embedded in an insulating material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
Definitions
- the present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for manufacturing a substrate with a resist pattern, and a method for manufacturing a printed wiring board.
- a photosensitive resin composition is widely used as a resist material used when etching or plating is performed on a circuit forming substrate.
- a photosensitive resin composition includes a support and a layer (hereinafter also referred to as “photosensitive layer”) using the photosensitive resin composition provided on the support. ) Is often used.
- the printed wiring board is manufactured as follows, for example. First, a photosensitive layer is formed on a circuit forming substrate using a photosensitive element (photosensitive layer forming step). Next, the exposed portion is cured by irradiating a predetermined portion of the photosensitive layer with actinic rays (exposure step). Then, after peeling off and removing the support, a resist pattern made of a cured product of the photosensitive resin composition is formed on the circuit forming substrate by removing (developing) the unexposed portion of the photosensitive layer from the substrate. (Development process).
- the conductor pattern (circuit) is formed on the substrate by performing etching or plating on the substrate using the formed resist pattern as a resist (circuit formation process), the resist pattern is finally peeled off and removed. (Peeling step) to produce a printed wiring board.
- DLP Digital Light Processing
- LDI Laser Direct Imaging
- Patent Document 1 proposes a photosensitive resin composition that improves the above-described required characteristics by using a styrylpyridine compound as a sensitizing dye.
- Patent Documents 2 to 5 disclose photosensitive resin compositions that have improved the above-mentioned required characteristics by using a specific binder polymer, photopolymerizable compound, photopolymerization initiator, and sensitizing dye. Proposed.
- the resist pattern formed by the photosensitive resin composition is excellent in chemical resistance.
- plating dipping may occur.
- plating dive means a phenomenon in which a plating solution enters between the resist pattern and the substrate.
- the conductor pattern is connected and short-circuited when plating submergence occurs.
- the present disclosure relates to a photosensitive resin composition capable of forming a resist pattern excellent in chemical resistance with excellent sensitivity, a photosensitive element using the photosensitive resin composition, a method for manufacturing a substrate with a resist pattern, and a printed wiring board. It is an object to provide a manufacturing method.
- R 1 , R 2 , and R 3 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, An amino group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group, and a, b, and c are each independently 0 to 5 Indicates an integer. ]
- Ar 1 , Ar 2 , Ar 3 , and Ar 4 are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkoxy group.
- X 1 and X 2 each independently represents a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represents an integer of 1 to 5 Show.
- a photosensitive element comprising a support and a photosensitive layer using the photosensitive resin composition according to ⁇ 1> or ⁇ 2> provided on the support.
- ⁇ 4> a step of forming a photosensitive layer using the photosensitive resin composition according to ⁇ 1> or ⁇ 2> on a substrate; Irradiating at least a part of the photosensitive layer with actinic rays to photocuring the region to form a cured product region; Removing at least a portion of the photosensitive layer other than the cured product region from the substrate, and forming a resist pattern on the substrate.
- ⁇ 5> The method for producing a substrate with a resist pattern according to ⁇ 4>, wherein the wavelength of the actinic ray is in a range of 340 to 430 nm.
- a method for manufacturing a printed wiring board including a step of performing an etching process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern according to ⁇ 4> or ⁇ 5>.
- a method for manufacturing a printed wiring board including a step of performing a plating process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern according to ⁇ 4> or ⁇ 5>.
- a photosensitive resin composition capable of forming a resist pattern with excellent chemical resistance with excellent sensitivity, a photosensitive element using the photosensitive resin composition, a method for producing a substrate with a resist pattern, and a print A method for manufacturing a wiring board can be provided.
- (meth) acrylic acid means acrylic acid or methacrylic acid
- (meth) acrylate means acrylate or methacrylate
- (meth) acryloyl means acryloyl. Or methacryloyl.
- the “(poly) ethyleneoxy group” means at least one of an ethyleneoxy group (hereinafter also referred to as “EO group”) or a polyethyleneoxy group in which two or more ethylene groups are connected by an ether bond.
- EO group ethyleneoxy group
- (poly) propyleneoxy group” means at least one of a propyleneoxy group (hereinafter also referred to as “PO group”) or a polypropyleneoxy group in which two or more propylene groups are connected by an ether bond.
- PO group propyleneoxy group
- EO-modified means a compound having a (poly) ethyleneoxy group
- PO-modified means a compound having a (poly) propyleneoxy group
- EO ⁇ PO means a compound having both a (poly) ethyleneoxy group and a (poly) propyleneoxy group.
- the term “layer” is formed only in a part of the region in addition to the case where the layer is formed over the entire region when the region in which the layer is present is observed. Cases are also included.
- the term “stacked” indicates that the layers are stacked, and two or more layers may be bonded, or two or more layers may be detachable.
- the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term is used as long as the intended purpose of the process is achieved. include.
- numerical ranges indicated using “to” indicate ranges including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- the content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total amount of substance.
- the photosensitive resin composition of this embodiment comprises (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: bisphenol A having an EO group having less than 6 structural units.
- a photopolymerizable compound containing a type di (meth) acrylate hereinafter also referred to as “specific photopolymerizable compound”
- a styrylpyridine compound represented by formula (1)
- the said photosensitive resin composition may contain the other component as needed.
- a photosensitive resin composition capable of forming a resist pattern having excellent chemical solution resistance (particularly resistance to plating solution) with excellent sensitivity can be formed.
- the reaction rate is increased while having low swelling.
- a resist pattern can be formed. This presumes that the cross-linking network in the resist pattern is further densified and the chemical resistance is improved.
- (A) component Binder polymer
- the said photosensitive resin composition contains the binder polymer (henceforth a "specific binder polymer") which has a structural unit derived from (meth) acrylic acid as (A) component.
- the component (A) may further contain a binder polymer other than the specific binder polymer as necessary.
- the content of the structural unit derived from (meth) acrylic acid is based on the total mass of the polymerizable monomer constituting the specific binder polymer (100% by mass) from the viewpoint of excellent balance between developability and resist pattern adhesion. The same applies hereinafter), and may be 15 to 40% by mass, 18 to 38% by mass, or 20 to 35% by mass. From the viewpoint of further improving developability, the content may be 15% by mass or more, 18% by mass or more, or 20% by mass or more. Further, from the viewpoint of further improving the adhesion of the resist pattern, the content may be 40% by mass or less, 38% by mass or less, or 35% by mass or less.
- the specific binder polymer may further have a structural unit derived from styrene or ⁇ -methylstyrene.
- the content of the structural unit derived from styrene or ⁇ -methylstyrene is from the viewpoint of further improving the adhesion and peelability of the resist pattern. Further, it may be 10 to 70% by mass, 15 to 60% by mass, or 20 to 55% by mass based on the total mass of the polymerizable monomers constituting the specific binder polymer. Good.
- the content may be 10% by mass or more, 15% by mass or more, or 20% by mass or more. Further, from the viewpoint of further improving the releasability of the resist pattern, the content may be 70% by mass or less, 60% by mass or less, or 55% by mass or less.
- the specific binder polymer may have other structural units other than the above structural units.
- Examples of the other structural units include structural units derived from the following other polymerizable monomers.
- polymerizable monomers can be polymerized with (meth) acrylic acid, styrene, or ⁇ -methylstyrene, and are different from (meth) acrylic acid, styrene, and ⁇ -methylstyrene. If so, there is no particular limitation.
- polymerizable monomers include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid benzyl, (meth) acrylic acid furfuryl, Tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meta ) Dicyclopentanyl acrylate Cyethyl
- the content of the other structural units is the total mass of the polymerizable monomer constituting the specific binder polymer from the viewpoint of further improving the resolution and releasability of the resist pattern.
- it may be 3 to 85% by mass, 5 to 75% by mass, 10 to 70% by mass, or 10 to 50% by mass.
- the specific binder polymer is, for example, (meth) acrylic acid as a polymerizable monomer (monomer), styrene or ⁇ -methylstyrene and other polymerizable monomers used as necessary, by a conventional method. It can be obtained by radical polymerization.
- a specific binder polymer may be used alone, or two or more specific binder polymers may be used in any combination. Moreover, you may use other binder polymers other than a specific binder polymer with a specific binder polymer.
- the acid value of the specific binder polymer may be 90 to 250 mgKOH / g, 100 to 240 mgKOH / g, or 120 to 235 mgKOH / g from the viewpoint of good balance between developability and resist pattern adhesion. Or 130 to 230 mg KOH / g. From the viewpoint of further shortening the development time, the acid value may be 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, or 130 mgKOH / g or more. May be.
- the acid value may be 250 mgKOH / g or less, 240 mgKOH / g or less, 235 mgKOH / g or less, or 230 mgKOH. / G or less.
- the weight average molecular weight (Mw) of the specific binder polymer is measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene), it is excellent in balance between developability and resist pattern adhesion. It may be 10,000 to 200,000, 15,000 to 100,000, 20,000 to 80,000, or 23,000 to 60,000. From the viewpoint of further shortening the development time, the weight average molecular weight may be 200000 or less, 100000 or less, 80000 or less, or 60000 or less. From the viewpoint of further improving the adhesion of the resist pattern, the weight average molecular weight may be 10,000 or more, 15000 or more, 20000 or more, 23000 or more, 25000 It may be the above.
- the degree of dispersion (weight average molecular weight / number average molecular weight) of the specific binder polymer may be 3.0 or less or 2.8 or less from the viewpoint of further improving the resolution and adhesion of the resist pattern. 2.5 or less.
- the specific binder polymer may have a characteristic group in its molecule that is sensitive to light having a wavelength in the range of 340 to 430 nm, if necessary.
- the characteristic group include a group constituted by removing at least one hydrogen atom from a sensitizing dye such as component (D) described later.
- the content of the component (A) in the photosensitive resin composition is 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of further improving the formability of the photosensitive layer, the sensitivity, and the resolution of the resist pattern.
- it may be 30 to 70 parts by mass, 35 to 65 parts by mass, or 40 to 60 parts by mass.
- the content may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more.
- the content may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less.
- the photosensitive resin composition is a bisphenol A type di (meth) acrylate having a number of structural units of the EO group of less than 6 (specific) as the photopolymerizable compound that is the component (B). At least one of photopolymerizable compounds).
- the component (B) may further contain a photopolymerizable compound other than the specific photopolymerizable compound as necessary.
- the number of structural units of the EO group is less than 6.
- the number of structural units of the EO group (structural unit) can be said to indicate how much the EO group is added in the molecule. Therefore, an integer value is shown for a single molecule.
- the number of structural units of the EO group may be less than 4 or less than 3 from the viewpoint of improving the chemical resistance of the resist pattern.
- the lower limit of the number of structural units of the EO group is 0 or more and may be 2 or more.
- the specific photopolymerizable compound may be a compound represented by the following formula (3).
- R 4 and R 5 each independently represent a hydrogen atom or a methyl group.
- XO each independently represents an EO group.
- (XO) m1 and (XO) m2 each represent a (poly) ethyleneoxy group.
- m1 and m2 can independently take a numerical value of 0 or more and less than 6.
- m1 + m2 is 0 or more and less than 6.
- m1 and m2 represent the number of structural units.
- the content of the specific photopolymerizable compound in the photosensitive resin composition is the component (A) and the component (B) from the viewpoint of suppressing swelling by suppressing molecular motion in the crosslinked network after curing and improving chemical resistance.
- the total amount may be 1 to 60 parts by mass, 5 to 55 parts by mass, or 10 to 50 parts by mass.
- the photosensitive resin composition may contain another photopolymerizable compound other than the specific photopolymerizable compound as the component (B).
- Other photopolymerizable compounds are not particularly limited as long as photopolymerization is possible.
- the other photopolymerizable compound may be a compound having an ethylenically unsaturated bond group.
- the compound having an ethylenically unsaturated bond group includes a compound having one ethylenically unsaturated bond group in the molecule, a compound having two ethylenically unsaturated bond groups in the molecule, and an ethylenically unsaturated bond in the molecule. Examples thereof include compounds having 3 or more groups.
- the total amount of component B) may be 1 to 60 parts by weight, 6 to 50 parts by weight, or 10 to 40 parts by weight.
- the component (B) may contain at least one compound having two ethylenically unsaturated bond groups in the molecule (excluding the specific photopolymerizable compound) as the other photopolymerizable compound.
- the content is 100 parts by mass of the total amount of the component (A) and the component (B).
- the amount may be 5 to 60 parts by mass, 5 to 55 parts by mass, or 10 to 50 parts by mass.
- the compound having two ethylenically unsaturated bond groups in the molecule includes bisphenol A type di (meth) acrylate, hydrogenated bisphenol A type di (meth) acrylate different from the specific photopolymerizable compound, and EO group in the molecule. And polyalkylene glycol di (meth) acrylate having at least one of PO groups, di (meth) acrylate having a urethane bond in the molecule, and trimethylolpropane di (meth) acrylate.
- Component (B) is a bisphenol A-type di (meth) acrylate or hydrogenated bisphenol A-type diester different from the specific photopolymerizable compound as another photopolymerizable compound from the viewpoint of improving the resolution and peelability of the resist pattern.
- Examples of the bisphenol A type di (meth) acrylate different from the specific photopolymerizable compound include compounds represented by the following formula (4).
- R 6 and R 7 each independently represent a hydrogen atom or a methyl group.
- XO and YO each independently represent an EO group or a PO group.
- (XO) x1 , (XO) x2 , (YO) y1 , and (YO) y2 each represent a (poly) ethyleneoxy group or a (poly) propyleneoxy group.
- x1, x2, y1, and y2 can each independently take a numerical value of 0 to 40.
- x1, x2, y1, and y2 indicate the number of structural units.
- the number of structural units of the PO group in the molecule may be 2 or more, or 3 or more from the viewpoint of improving the resolution of the resist pattern. Good. Further, the number of structural units of PO groups in the molecule may be 5 or less from the viewpoint of improving developability.
- the number of structural units of the EO group in the molecule may be 6 or more, or 8 or more from the viewpoint of improving developability.
- the number of structural units of the EO group in the molecule may be 16 or less or 14 or less from the viewpoint of improving the resolution of the resist pattern.
- the component (B) contains a bisphenol A type di (meth) acrylate that is different from the specific photopolymerizable compound, its content suppresses swelling by suppressing molecular motion in the crosslinked network after curing and improves chemical resistance.
- the total amount of the component (A) and the component (B) may be 1 to 65 parts by weight, 5 to 60 parts by weight, or 10 to 55 parts by weight. There may be.
- the content of the bisphenol A type di (meth) acrylate having a total number of structural units of EO groups and PO groups of 10 or less is (A) from the viewpoint of improving the resolution, adhesion, and chemical resistance of the resist pattern.
- the content of the bisphenol A type di (meth) acrylate having a total number of structural units of EO groups and PO groups of 10 or less is (B) from the viewpoint of improving the resolution, adhesion, and chemical resistance of the resist pattern. It may be 70 parts by weight or less, 65 parts by weight or less, 55 parts by weight or less, or 50 parts by weight or less with respect to 100 parts by weight of the total amount of components. It may be 45 parts by mass or less, or 40 parts by mass or less.
- Examples of the hydrogenated bisphenol A type di (meth) acrylate include 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane.
- the component (B) contains hydrogenated bisphenol A type di (meth) acrylate, the content thereof is suppressed from the viewpoint of suppressing swelling by suppressing molecular motion in the crosslinked network after curing, and improving chemical resistance (A )
- Component and (B) component may be 1 to 50 parts by mass or 5 to 40 parts by mass with respect to 100 parts by mass in total.
- Component (B) is a polyalkylene glycol diester having at least one of an EO group and a PO group in the molecule as another photopolymerizable compound from the viewpoint of improving the flexibility, resolution, and adhesion of the resist pattern in a balanced manner.
- You may contain at least 1 sort (s) of (meth) acrylate.
- the component (B) contains polyalkylene glycol di (meth) acrylate, the content thereof is based on 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoint of the resolution and flexibility of the resist pattern. It may be 1 to 30 parts by mass, 2 to 20 parts by mass, or 2 to 15 parts by mass.
- the polyalkylene glycol di (meth) acrylate may be EO / PO-modified polyalkylene glycol di (meth) acrylate.
- the (poly) ethyleneoxy group and the (poly) propyleneoxy group may be continuously present in a block manner or may be present randomly.
- the PO group in the (poly) propyleneoxy group may be either an n-propyleneoxy group or an isopropyleneoxy group.
- the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.
- Polyalkylene glycol di (meth) acrylate includes (poly) n-butyleneoxy group, (poly) isobutyleneoxy group, (poly) n-pentyleneoxy group, (poly) hexyleneoxy group, structural isomers thereof, etc. (Poly) alkyleneoxy group having about 4 to 6 carbon atoms and the like.
- the component (B) may contain at least one photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule as the other photopolymerizable compound.
- Examples of the compound having three or more ethylenically unsaturated bond groups include trimethylolpropane tri (meth) acrylate and EO-modified trimethylolpropane tri (meth) acrylate (one having 1 to 5 structural units of EO group).
- photopolymerizable compounds having three or more ethylenically unsaturated bond groups in the molecule include EO-modified trimethylolpropane trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., “TMPT21E” and “TMPT30E”), pentaerythritol tris.
- the amount may be 3 to 30 parts by mass, 5 to 25 parts by mass, or 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B). It may be.
- the component (B) is ethylene in the molecule as another photopolymerizable compound.
- a photopolymerizable compound having one polymerizable unsaturated bond group may be included.
- Examples of the photopolymerizable compound having one ethylenically unsaturated bond group in the molecule include nonylphenoxypolyethyleneoxy (meth) acrylate, phthalic acid compound, and (meth) acrylic acid alkyl ester.
- nonylphenoxypolyethyleneoxy (meth) acrylate or a phthalic acid compound may be included from the viewpoint of improving the resist pattern shape and the resolution, adhesion, and peelability of the resist pattern in a well-balanced manner.
- (B) component contains the photopolymerizable compound which has one ethylenically unsaturated bond group in a molecule
- the content is 1 with respect to 100 mass parts of total amounts of (A) component and (B) component. It may be ⁇ 20 parts by mass, 3 to 15 parts by mass, or 5 to 12 parts by mass.
- the content of the component (B) in the photosensitive resin composition may be 30 to 70 parts by weight, or 35 to 65 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). It may be.
- the content of the component (B) is 30 parts by mass or more, the sensitivity and the resolution of the resist pattern tend to be improved.
- the content of the component (B) is 70 parts by mass or less, a photosensitive layer is easily formed, and a good resist pattern shape tends to be easily obtained.
- Component (C) Photopolymerization initiator
- the photosensitive resin composition contains at least one photopolymerization initiator as the component (C).
- Component (C) is a 2,4,5-triarylimidazole compound represented by the following formula (2) from the viewpoint of improving sensitivity and resolution and adhesion of the resist pattern while maintaining the chemical resistance of the resist pattern. It may contain a mer.
- Ar 1 , Ar 2 , Ar 3 , and Ar 4 are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkoxy group.
- X 1 and X 2 each independently represents a halogen atom, an alkyl group, an alkenyl group or an alkoxy group, and p and q each independently represent an integer of 1 to 5 .
- p is 2 or more
- a plurality of X 1 may be the same or different
- q is 2 or more
- a plurality of X 2 may be the same or different.
- X 1 and X 2 are each independently a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be an alkoxy group. It is preferable that at least one of X 1 and X 2 is a chlorine atom.
- the substitution position of X 1 and X 2 is not particularly limited, and is preferably an ortho position or a para position.
- p and q are each independently an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1.
- Examples of the aryl group represented by Ar 1 , Ar 2 , Ar 3 , and Ar 4 include a phenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is preferable.
- Examples of the substituent that Ar 1 , Ar 2 , Ar 3 , and Ar 4 may have include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. And at least one substituent selected from the group consisting of groups.
- the number of substituents is preferably 1 to 5, more preferably 1 to 3, More preferably it is.
- the substitution position is not particularly limited, and is preferably the ortho position or the para position.
- Ar 1 , Ar 2 , Ar 3 , and Ar 4 are preferably all unsubstituted.
- Examples of the 2,4,5-triarylimidazole dimer represented by the formula (2) include 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2-chlorophenyl)- 4,5-di (methoxyphenyl) imidazole dimer, 2- (2-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2-methoxyphenyl) -4,5-diphenylimidazole dimer And 2- (4-methoxyphenyl) -4,5-diphenylimidazole dimer.
- substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently give asymmetric compounds.
- 2,4,5-triarylimidazole dimer represented by the formula (2) one kind may be used alone, or two or more kinds may be used in combination.
- the component (C) contains the 2,4,5-triarylimidazole dimer represented by the formula (2)
- the content thereof is 25 parts by mass with respect to 100 parts by mass of the total component (C).
- the above may be sufficient, 50 mass parts or more may be sufficient, and 75 mass parts or more may be sufficient.
- the photopolymerization initiator that is component (C) may contain other commonly used photopolymerization initiators in addition to the 2,4,5-triarylimidazole dimer represented by the formula (2). Good.
- Other photopolymerization initiators include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2- Aromatic ketones such as morpholino-propanone-1; quinone compounds such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 9-phenylacridine, 1 , 7- (9,9′-acridinyl) heptane and the like.
- the content of the component (C) in the photosensitive resin composition may be 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be part by mass, 2 to 6 parts by mass, or 3 to 5 parts by mass.
- the content of the component (C) is 0.1 parts by mass or more, the sensitivity, the resolution of the resist pattern, and the adhesiveness tend to be improved.
- the content of the component (C) is 10 parts by mass or less, a good resist pattern shape tends to be easily obtained.
- Component (D) styrylpyridine compound represented by formula (1)
- the photosensitive resin composition contains at least one styrylpyridine compound represented by the following formula (1) as the component (D).
- a component may be used individually by 1 type and may be used in combination of 2 or more type.
- R 1 , R 2 , and R 3 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, amino Group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group, and a, b, and c are each independently an integer of 0 to 5 Indicates.
- a is 2 or more
- a plurality of R 1 may be the same or different
- b is 2 or more
- a plurality of R 2 may be the same or different
- c is 2 or more
- a plurality of R 3 may be the same or different.
- carbon number of an alkyl ester group means carbon number of an alkyl part.
- R 1 , R 2 , and R 3 in formula (1) are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 carbon atom. It may be an alkyl ester group having 6 to 6, an amino group, or an alkylamino group having 1 to 20 carbon atoms.
- A, b and c each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2.
- Examples of the styrylpyridine compound represented by the formula (1) include 3,5-dibenzylidenedicyclopentano [b, e] -4-phenylpyridine, 3,5-bis (4-methylbenzylidenedicyclopentano). [B, e])-4- (4-methylphenyl) pyridine, 3,5-bis (4-methoxybenzylidenedicyclopentano [b, e])-4- (4-methoxyphenyl) pyridine, 3, 5-bis (4-aminobenzylidenedicyclopentano [b, e])-4- (4-aminophenyl) pyridine, 3,5-bis (4-dimethylaminobenzylidenedicyclopentano [b, e]) -4- (4-dimethylaminophenyl) pyridine, 3,5-bis (4-carboxybenzylidenedicyclopentano [b, e])-4- (4-carboxyphenyl) pyrid 3,5-bis (4
- the styrylpyridine compound represented by the formula (1) can be synthesized, for example, by a condensation reaction of a benzaldehyde derivative, a cyclic alkyl ketone, and ammonium acetate.
- the content of the component (D) in the photosensitive resin composition may be 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be ⁇ 5 parts by mass, or 0.08 to 3 parts by mass.
- the content of the component (D) is 0.01 parts by mass or more, the sensitivity and the resolution of the resist pattern are improved, and a resist pattern excellent in chemical resistance tends to be obtained.
- the content of the component (D) is 10 parts by mass or less, a good resist pattern shape tends to be obtained.
- (E) component amine compound
- the said photosensitive resin composition may contain at least 1 sort (s) of an amine compound as (E) component.
- examples of the amine compound include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leuco crystal violet. These amine compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content may be 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be 0.05 to 5 parts by mass, or 0.1 to 2 parts by mass.
- the content of component (E) is 0.01 parts by mass or more, sufficient sensitivity tends to be obtained.
- the content of the component (E) is 10 parts by mass or less, it tends to be suppressed that the excessive component (E) is deposited as a foreign substance after the formation of the photosensitive layer.
- the photosensitive resin composition may be used in addition to a photopolymerizable compound (oxetane compound, etc.) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, and a component (D) as necessary.
- a photopolymerizable compound oxetane compound, etc.
- Sensitizing dyes dyes such as malachite green, Victoria pure blue, brilliant green and methyl violet
- photochromic agents such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline and 2-chloroaniline
- thermal coloring Inhibitors plasticizers such as 4-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, perfumes, imaging agents, heat
- plasticizers such as 4-toluenesulfonamide
- pigments such as fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, perfumes, imaging agents, heat
- Other components such as a crosslinking agent may be contained. These other components may be used alone or in combination of two or more for each component.
- the content thereof is about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It may be.
- the photosensitive resin composition may further contain at least one organic solvent.
- Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide.
- These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.
- Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, it can be used as a solution having a solid content of about 30 to 60 mass% by adding an organic solvent to the photosensitive resin composition.
- the photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”.
- a photosensitive layer which is a coating film of the photosensitive resin composition, can be formed by applying the coating solution on the surface of a support, a metal plate or the like described later and drying it. It does not restrict
- the metal plate include metal plates such as copper, copper alloys, iron alloys such as nickel, chromium, iron, and stainless steel.
- metal plates such as copper, a copper alloy, and an iron alloy, are mentioned.
- the thickness of the photosensitive layer to be formed is not particularly limited and can be appropriately selected depending on its use.
- the thickness after drying may be about 1 to 100 ⁇ m.
- the surface of the photosensitive layer may be covered with a protective layer.
- the protective layer include polymer films such as polyethylene and polypropylene.
- the said photosensitive resin composition can be applied to formation of the photosensitive layer of the photosensitive element mentioned later. That is, another embodiment of the present disclosure relates to (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: bisphenol A in which the number of structural units of the EO group is less than 6.
- Photosensitive resin composition comprising a photopolymerizable compound containing a di (meth) acrylate, a component (C): a photopolymerization initiator, and a component (D): a styrylpyridine compound represented by formula (1)
- the said photosensitive resin composition can be used for the manufacturing method of the board
- Photosensitive resin composition comprising a photopolymerizable compound containing a di (meth) acrylate, a component (C): a photopolymerization initiator, and a component (D): a styrylpyridine compound represented by formula (1)
- the photosensitive element of this embodiment is equipped with a support body and the photosensitive layer which uses the said photosensitive resin composition provided on this support body.
- a photosensitive layer is a coating film formed using the said photosensitive resin composition, Comprising:
- the said photosensitive resin composition is a thing of an unhardened state.
- the photosensitive element may have other layers, such as a protective layer, as needed.
- FIG. 1 shows an example of a photosensitive element.
- the support body 2, the photosensitive layer 3, and the protective layer 4 are laminated
- the photosensitive element 1 can be obtained as follows, for example.
- a coating solution which is the photosensitive resin composition containing an organic solvent, is applied to form a coating layer, which is dried to form the photosensitive layer 3.
- the surface of the photosensitive layer 3 opposite to the support 2 is covered with a protective layer 4, thereby laminating the support 2, the photosensitive layer 3 formed on the support 2, and the photosensitive layer 3.
- the photosensitive element 1 provided with the protective layer 4 obtained is obtained.
- the photosensitive element 1 does not necessarily have to include the protective layer 4.
- a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.
- the thickness of the support 2 may be 1 to 100 ⁇ m, 5 to 50 ⁇ m, or 5 to 30 ⁇ m. When the thickness of the support 2 is 1 ⁇ m or more, the support 2 tends to be prevented from being broken when the support 2 is peeled off. Moreover, it exists in the tendency for the fall of the resolution to be suppressed as the thickness of the support body 2 is 100 micrometers or less.
- the protective layer 4 is preferably such that the adhesive force of the photosensitive layer 3 to the protective layer 4 is smaller than the adhesive force of the photosensitive layer 3 to the support 2.
- a low fish eye film is preferred.
- fish eye means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.
- the protective layer 4 a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene can be used.
- Commercially available products include Alfane MA-410 and E-200 manufactured by Oji Paper Co., Ltd., polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and PS series polyethylene terephthalate films such as PS-25 manufactured by Teijin Limited. It is done.
- the protective layer 4 may be the same as the support 2.
- the thickness of the protective layer 4 may be 1 to 100 ⁇ m, 5 to 50 ⁇ m, 5 to 30 ⁇ m, or 15 to 30 ⁇ m.
- the thickness of the protective layer 4 is 1 ⁇ m or more, the protective layer 4 tends to be prevented from being broken when the photosensitive layer 3 and the support 2 are laminated on the substrate while peeling off the protective layer 4.
- the thickness of the protective layer 4 is 100 ⁇ m or less, the handling property and the inexpensiveness tend to be excellent.
- the photosensitive element can be produced, for example, as follows.
- a photosensitive element can be manufactured with the manufacturing method including.
- Application of the coating liquid onto the support 2 can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.
- the drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer.
- the coating layer is preferably dried at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive layer 3 may be 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.
- the thickness of the photosensitive layer 3 in the photosensitive element can be appropriately selected depending on the application.
- the thickness of the photosensitive layer 3 after drying may be 1 to 100 ⁇ m, 1 to 50 ⁇ m, or 5 to 40 ⁇ m.
- the thickness of the photosensitive layer 3 is 1 ⁇ m or more, industrial coating tends to be facilitated.
- the thickness of the photosensitive layer 3 is 100 ⁇ m or less, sufficient adhesion and resolution of the resist pattern tend to be obtained.
- the transmittance of the photosensitive layer 3 with respect to ultraviolet rays may be 5 to 75%, 10 to 65%, or 15 to 55% with respect to ultraviolet rays in the wavelength range of 350 to 420 nm. Good. When the transmittance is 5% or more, the resist pattern tends to have sufficient adhesion. If the transmittance is 75% or less, the resolution of the resist pattern tends to be sufficiently obtained.
- the transmittance can be measured with an ultraviolet spectrometer. Examples of the ultraviolet spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.
- the photosensitive element may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
- an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
- an intermediate layer described in JP-A-2006-098982 can be applied to this embodiment.
- the form of the obtained photosensitive element is not particularly limited.
- the photosensitive element may be in the form of a sheet, or may be in the form of a roll wound around a core.
- the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
- plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
- end face separator it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance.
- As a packaging method it is preferable to wrap and package in a black sheet with low moisture permeability.
- the photosensitive element can be suitably used, for example, in a method for manufacturing a substrate with a resist pattern described later.
- a substrate with a resist pattern can be produced using the photosensitive resin composition.
- the method for manufacturing a substrate with a resist pattern according to this embodiment includes (i) a step of forming a photosensitive layer using the photosensitive resin composition on the substrate (photosensitive layer forming step), and (ii) the photosensitive layer. Irradiating at least a part of the actinic ray to photocuring the region to form a cured product region (exposure step); and (iii) at least a part of the photosensitive layer other than the cured product region. Is removed from the substrate and a resist pattern is formed on the substrate (development step).
- substrate with a resist pattern may have another process further as needed.
- the photosensitive layer 3 is formed on a board
- a substrate for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.
- a glass epoxy material is mentioned, for example.
- An example of the conductor layer is copper foil.
- the photosensitive layer 3 is formed on the substrate by removing the protective layer 4 and then heating the photosensitive layer 3 of the photosensitive element. This is done by pressure bonding to the substrate. Thereby, a laminate in which the substrate, the photosensitive layer 3 and the support 2 are laminated in this order is obtained.
- This photosensitive layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability.
- Heating to at least one of the photosensitive layer 3 and the substrate at the time of pressure bonding is preferably performed at a temperature of 70 to 130 ° C., and the pressure bonding is performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm 2 ). It is preferable. These conditions are not particularly limited, and are appropriately selected as necessary. If the photosensitive layer 3 is heated to 70 to 130 ° C., the substrate need not be preheated. Adhesion and follow-up can be further improved by pre-heating the substrate.
- (Ii) Exposure Step In the exposure step, the exposed portion irradiated with the actinic ray is photocured by irradiating at least a part of the photosensitive layer 3 formed on the substrate as described above with the actinic ray. Thus, a latent image is formed.
- the support 2 existing on the photosensitive layer 3 is transparent to the active light, the active light can be irradiated through the support 2.
- the support 2 shows a light-shielding property against actinic rays
- the photosensitive layer 3 is irradiated with actinic rays after the support 2 is removed.
- Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Further, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.
- a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.
- the light source for active light is not particularly limited, and a known light source can be used. Specifically, carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid state lasers such as YAG lasers, semiconductor lasers, ultraviolet rays such as gallium nitride blue-violet lasers, visible light, etc. What emits effectively is used.
- the wavelength of the actinic ray may be in the range of 340 to 430 nm or in the range of 350 to 420 nm.
- development step the uncured portion of the photosensitive layer 3 is removed from the substrate by development processing, whereby a resist pattern, which is a cured product obtained by photocuring the photosensitive layer 3, is formed on the substrate. .
- development processing includes wet development and dry development, and wet development is widely used.
- development is performed by a known development method using a developer corresponding to the photosensitive resin composition.
- the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.
- the developer is appropriately selected according to the configuration of the photosensitive resin composition.
- the developer include an alkaline aqueous solution and an organic solvent developer.
- An alkaline aqueous solution is safe and stable when used as a developer, and has good operability.
- Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate Alkali metal phosphates such as sodium pyrophosphate and potassium pyrophosphate, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2 -Amino-2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like are used.
- Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, a dilute solution of 0.1 to 5% by mass of sodium hydroxide, A dilute solution of 1 to 5% by mass sodium tetraborate is preferred.
- the pH of the alkaline aqueous solution is preferably in the range of 9-11.
- the temperature is adjusted according to the alkali developability of the photosensitive layer 3.
- the alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like.
- the alkaline aqueous solution may contain one or more organic solvents.
- the organic solvent to be used include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and the like. These are used alone or in combination of two or more.
- the alkaline aqueous solution contains an organic solvent
- the content of the organic solvent is preferably 2 to 90% by mass based on the total amount of the alkaline aqueous solution.
- organic solvent used in the organic solvent developer examples include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and ⁇ -butyrolactone.
- water in an amount of 1 to 20% by mass to these organic solvents to obtain an organic solvent developer.
- the above-described method for producing a substrate with a resist pattern comprises removing a non-exposed portion and then performing heating at 60 to 250 ° C. or exposure with an energy amount of 0.2 to 10 J / cm 2 as necessary. You may have further the process of further hardening.
- the method for manufacturing a printed wiring board according to the present embodiment includes a step of performing at least one of an etching process and a plating process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern. That is, the method for manufacturing a printed wiring board according to the first embodiment includes a step of performing an etching process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern. Moreover, the method for manufacturing a printed wiring board according to the second embodiment includes a step of performing a plating process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern.
- a substrate for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer is preferably used.
- the method for manufacturing a printed wiring board may have other steps such as a resist removal step as necessary.
- the etching process and the plating process of the substrate are performed on the conductor layer of the substrate using the formed resist pattern as a mask.
- the conductor layer of the circuit forming substrate that is not covered with the cured resist is removed by etching to form a conductor pattern.
- the etching method is appropriately selected according to the conductor layer to be removed.
- the etching solution include a cupric chloride aqueous solution, a ferric chloride aqueous solution, an alkali etching solution, and a hydrogen peroxide etching solution.
- the plating process copper, solder, or the like is plated on the conductor layer of the circuit forming substrate that is not covered with the cured resist, using the resist pattern (cured resist) formed on the substrate as a mask. After the plating treatment, the hardened resist is removed, and the conductor layer covered with the hardened resist is etched to form a conductor pattern.
- the method of plating treatment may be electrolytic plating treatment or electroless plating treatment.
- Plating treatment includes copper plating such as copper sulfate plating, copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, soft Examples thereof include gold plating such as gold plating.
- the resist pattern on the substrate is removed (peeled).
- the removal of the resist pattern can be performed, for example, using a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step.
- a stronger alkaline aqueous solution a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used.
- a 1 to 10% by mass sodium hydroxide aqueous solution or a 1 to 10% by mass potassium hydroxide aqueous solution is preferably used, and a 1 to 5% by mass sodium hydroxide aqueous solution or a 1 to 5% by mass potassium hydroxide aqueous solution is more preferably used.
- Examples of a method for applying a strong alkaline aqueous solution to a resist pattern include an immersion method and a spray method, and these may be used alone or in combination of two or more.
- a desired printed wiring board can be manufactured by further removing the conductor layer covered with the cured resist by the etching treatment and forming the conductor pattern.
- the etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.
- the above-described printed wiring board manufacturing method can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small diameter through hole.
- the said photosensitive resin composition can be used conveniently for manufacture of a printed wiring board. That is, in one preferred embodiment, component (A): a binder polymer having a structural unit derived from (meth) acrylic acid, and component (B): bisphenol A having an EO group having less than 6 structural units Photosensitive resin composition comprising a photopolymerizable compound containing a di (meth) acrylate, a component (C): a photopolymerization initiator, and a component (D): a styrylpyridine compound represented by formula (1) Application to the production of printed wiring boards.
- component (A) a binder polymer having a structural unit derived from (meth) acrylic acid
- component (B) bisphenol A having an EO group having less than 6 structural units
- Photosensitive resin composition comprising a photopolymerizable compound containing a di (meth) acrylate, a component (C): a photopolymerization initiator, and a component (D): a s
- a more preferred embodiment is application of the photosensitive resin composition to the production of a high-density package substrate, and application of the photosensitive resin composition to a semi-additive construction method.
- FIG. 2 An example of the manufacturing process of the wiring board by a semi-additive construction method is demonstrated, referring FIG.
- the size of the members in FIG. 2 is conceptual, and the relative relationship between the sizes of the members is not limited to this.
- FIG. 2A a substrate (circuit forming substrate) in which the conductor layer 10 is formed on the insulating layer 15 is prepared.
- the conductor layer 10 is, for example, a metal copper layer.
- FIG. 2B the photosensitive layer 32 is formed on the conductor layer 10 of the substrate by the photosensitive layer forming step.
- FIG.2 (c) the mask 20 is arrange
- a region other than the photocured portion in the photosensitive layer 32 is removed from the substrate by a developing process, thereby forming a resist pattern 30 that is a photocured portion on the substrate.
- a plating layer 42 is formed on the conductor layer 10 by plating using the resist pattern 30 that is a photocured portion as a mask.
- FIG. 2F after the resist pattern 30 which is a photocured portion is peeled off with a strong alkaline aqueous solution, a part of the plating layer 42 and the conductor layer 10 masked by the resist pattern 30 are removed by flash etching.
- the conductor pattern 40 is formed by removing.
- the conductor layer 10 and the plating layer 42 may be made of the same material or different materials.
- Examples 1 to 6 and Comparative Examples 1 to 4 ⁇ Preparation of solution of photosensitive resin composition>
- Each component shown in Table 2 and Table 3 was mixed with 9 g of acetone, 5 g of toluene, and 5 g of methanol in the blending amount (unit: g) shown in the same table, whereby Examples 1 to 6 and Comparative Examples 1 to 4 were mixed.
- Each solution of the photosensitive resin composition was prepared.
- the blending amount of the component (A) shown in Tables 2 and 3 is the mass (solid content) of the nonvolatile content. Details of each component shown in Tables 2 and 3 are as follows. “-” Means not blended.
- Binder polymer [synthesis of binder polymer (A-1)] A polymerizable monomer (monomer) 81 g of methacrylic acid, 135 g of styrene, 69 g of benzyl methacrylate, and 15 g of methyl methacrylate (mass ratio: 27/45/23/5) and 1.5 g of azobisisobutyronitrile A solution obtained by mixing the above was designated as “Solution a”.
- Solution b A solution obtained by dissolving 0.5 g of azobisisobutyronitrile in 100 g of a mixed solution (mass ratio: 3: 2) of 60 g of methyl cellosolve and 40 g of toluene was designated as “Solution b”.
- a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube was charged with 300 g of a mixed solution of 180 g of methyl cellosolve and 120 g of toluene (mass ratio: 3: 2), and nitrogen was introduced into the flask.
- the mixture was heated with stirring while blowing gas, and the temperature was raised to 80 ° C.
- the solution a was added dropwise to the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring.
- the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a solution of binder polymer (A-1).
- the non-volatile content (solid content) of the binder polymer (A-1) was 41.5% by mass, the weight average molecular weight was 44000, the acid value was 176 mgKOH / g, and the degree of dispersion was 2.2.
- the weight average molecular weight was measured by a gel permeation chromatography (GPC) method and was derived by conversion using a standard polystyrene calibration curve.
- GPC gel permeation chromatography
- GPC condition Pump Hitachi L-6000 type (manufactured by Hitachi, Ltd.) Column: 3 in total, column specifications: 10.7 mm ⁇ x 300 mm Gelpack GL-R440 Gelpack GL-R450 Gelpack GL-R400M (Hitachi Chemical Co., Ltd.) Eluent: Tetrahydrofuran (THF) Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.
- THF Tetrahydrofuran
- Binder Polymer (A-2) A polymerizable monomer (monomer) 81 g of methacrylic acid, 9 g of 2-hydroxyethyl methacrylate, 141 g of styrene, 69 g of benzyl methacrylate (mass ratio: 27/3/47/23), and azobisisobutyronitrile The solution obtained by mixing 2.4 g was designated as “solution c”, and the binder polymer (A-1) was obtained in the same manner as in the case of obtaining the solution of the binder polymer (A-1) except that the solution c was used instead of the solution a. A solution of (A-2) was obtained.
- the binder polymer (A-2) had a nonvolatile content (solid content) of 41.7% by mass, a weight average molecular weight of 38000, an acid value of 176 mgKOH / g, and a dispersity of 1.8.
- Table 1 shows the mass ratio (%), the acid value, the weight average molecular weight, and the dispersity of the polymerizable monomers (monomers) for the binder polymers (A-1) and (A-2). “-” Means not blended.
- H-MOP-DSP 4,6-bis (4-methoxybenzylidenedicyclohexano [b, e])-5- (4-methoxyphenyl) ) Pyridine
- the photosensitive resin composition solution obtained above was applied onto a 16 ⁇ m thick polyethylene terephthalate film (“FB-40”, manufactured by Toray Industries, Inc.) (support), and hot air at 70 ° C. and 110 ° C. A drying process was sequentially performed with a convection dryer to form a photosensitive layer having a dried film thickness of 25 ⁇ m.
- a polyethylene film (“E-200K” manufactured by Oji Paper Co., Ltd.) (protective layer) was bonded onto the photosensitive layer to obtain a photosensitive element in which a support, a photosensitive layer, and a protective layer were sequentially laminated.
- a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., “MCL-E-679F”) (hereinafter referred to as “substrate”) (hereinafter referred to as “substrate”) composed of a glass epoxy material and copper foil (thickness 16 ⁇ m) formed on both sides thereof.
- the photosensitive elements according to Examples 1 to 6 and Comparative Examples 1 to 4 were laminated (laminated) on the copper surface of the substrate.
- the obtained laminated substrate was allowed to cool to 23 ° C.
- the support was peeled from the laminated substrate to expose the photosensitive layer, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 60 seconds to remove unexposed portions.
- the resist pattern which consists of hardened
- the sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining steps (step number) of the step tablet obtained as a resist pattern (cured film). Sensitivity is indicated by the above step number when exposed at 100 mJ / cm 2 , and the higher this value, the better the sensitivity. The results are shown in Tables 4 and 5.
- the space portion (unexposed portion) is removed cleanly, and the line portion (exposed portion) is the minimum of the line width / space width values in the resist pattern formed without causing meandering, chipping, or other defects.
- the resolution and adhesion were evaluated based on the values. The smaller this value, the better the resolution and adhesion of the resist pattern.
- the obtained resist pattern was observed with an optical microscope at a magnification of 1000 times to confirm the presence or absence of defects. The results are shown in Tables 4 and 5.
- a glass phototool having a wiring pattern with L / S of 5/5, 8/8, 10/10, and 15/15 (unit: ⁇ m) is brought into close contact with the support of the evaluation laminate and developed.
- the exposure was performed with an energy amount that resulted in 14 remaining steps.
- the support was peeled off, and an unexposed portion was removed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. to obtain a substrate for evaluation.
- the development time was a time corresponding to twice the shortest development time (the shortest time for removing the unexposed area).
- the substrate for evaluation was immersed in a degreasing solution (Meltex Co., Ltd., “PC-455”, 25 mass%) for 5 minutes, washed with water, immersed in a soft etch solution (ammonium persulfate 150 g / L) for 2 minutes, and washed with water. Pretreatment was sequentially performed in the order of immersion in 10% by mass sulfuric acid for 1 minute.
- Copper sulfate plating solution copper sulfate 75 g / L, sulfuric acid 190 g / L, chloride ion 50 mass ppm, made by Meltex Co., Ltd., “Capper Grime PCM”, 5 mL / L
- Copper plating treatment was performed until the plating thickness reached 12 ⁇ m.
- the substrate for evaluation after the copper plating treatment was washed with water and dried, and then the resist pattern was peeled off by dipping in a stripping solution (Mitsubishi Gas Chemical Co., Ltd., “R-100”, 0.2% by volume) at 50 ° C.
- the base copper was etched with an aqueous solution containing 0.1% by mass sulfuric acid and 0.1% by mass hydrogen peroxide.
- the plating latent was confirmed from above using an optical microscope, and “A (excellent)” was evaluated when the plating latent was not generated, and “C (defect)” was evaluated when the plating latent was generated.
- plating submergence arises the metal copper which precipitated by copper plating in the area
- photopolymerization includes a binder polymer having a structural unit derived from (meth) acrylic acid and a bisphenol A type di (meth) acrylate having an EO group having a number of structural units of less than 6.
- Examples 1 to 6 using a photosensitive resin composition containing a photosensitive compound, a photopolymerization initiator, and a styrylpyridine compound represented by the formula (1) are sensitive to the sensitivity of the photosensitive resin composition and the resist. It was excellent in all of the resolution of a pattern, adhesiveness, and chemical
- Comparative Example 1 using a photosensitive resin composition containing no bisphenol A type di (meth) acrylate having less than 6 EO group structural units was excellent in the sensitivity of the photosensitive resin composition.
- the resolution, adhesion, and chemical resistance of the resist pattern were inferior to those of Examples 1-6.
- Comparative Examples 2 to 4 using the photosensitive resin composition not containing the styrylpyridine compound represented by the formula (1) the sensitivity of the photosensitive resin composition and the chemical resistance of the resist pattern are higher than those of Examples 1 to 6.
- Comparative Examples 3 to 4 were also inferior in the resolution and adhesion of the resist pattern.
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Abstract
Description
<1> (メタ)アクリル酸に由来する構造単位を有するバインダーポリマーと、
エチレンオキシ基の構造単位数が6未満であるビスフェノールA型ジ(メタ)アクリレートを含む光重合性化合物と、
光重合開始剤と、
下記式(1)で示されるスチリルピリジン化合物と、を含有する感光性樹脂組成物。 Specific means for solving the above problems include the following embodiments.
<1> a binder polymer having a structural unit derived from (meth) acrylic acid;
A photopolymerizable compound containing a bisphenol A-type di (meth) acrylate having an ethyleneoxy group having less than 6 structural units;
A photopolymerization initiator;
The photosensitive resin composition containing the styryl pyridine compound shown by following formula (1).
前記感光層の少なくとも一部の領域に活性光線を照射して、前記領域を光硬化させて硬化物領域を形成する工程と、
前記感光層の前記硬化物領域以外の少なくとも一部を前記基板上から除去して、前記基板上にレジストパターンを形成する工程と、を有するレジストパターン付き基板の製造方法。 <4> a step of forming a photosensitive layer using the photosensitive resin composition according to <1> or <2> on a substrate;
Irradiating at least a part of the photosensitive layer with actinic rays to photocuring the region to form a cured product region;
Removing at least a portion of the photosensitive layer other than the cured product region from the substrate, and forming a resist pattern on the substrate.
また、本明細書において、「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。
また、本明細書において、「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
また、本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計量を意味する。 In this specification, the term “layer” is formed only in a part of the region in addition to the case where the layer is formed over the entire region when the region in which the layer is present is observed. Cases are also included. The term “stacked” indicates that the layers are stacked, and two or more layers may be bonded, or two or more layers may be detachable.
In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term is used as long as the intended purpose of the process is achieved. include.
In this specification, numerical ranges indicated using “to” indicate ranges including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In addition, in the present specification, the content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total amount of substance.
本実施形態の感光性樹脂組成物は、(A)成分:(メタ)アクリル酸に由来する構造単位を有するバインダーポリマーと、(B)成分:EO基の構造単位数が6未満であるビスフェノールA型ジ(メタ)アクリレート(以下、「特定光重合性化合物」ともいう。)を含む光重合性化合物と、(C)成分:光重合開始剤と、(D)成分:式(1)で示されるスチリルピリジン化合物と、を含有する。上記感光性樹脂組成物は、必要に応じてその他の成分を含有していてもよい。 <Photosensitive resin composition>
The photosensitive resin composition of this embodiment comprises (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: bisphenol A having an EO group having less than 6 structural units. A photopolymerizable compound containing a type di (meth) acrylate (hereinafter also referred to as “specific photopolymerizable compound”), a component (C): a photopolymerization initiator, and a component (D): represented by formula (1) A styrylpyridine compound. The said photosensitive resin composition may contain the other component as needed.
上記感光性樹脂組成物は、(A)成分として、(メタ)アクリル酸に由来する構造単位を有するバインダーポリマー(以下、「特定バインダーポリマー」ともいう。)を含む。(A)成分は、必要に応じて特定バインダーポリマー以外のバインダーポリマーを更に含んでいてもよい。 (A) component: Binder polymer The said photosensitive resin composition contains the binder polymer (henceforth a "specific binder polymer") which has a structural unit derived from (meth) acrylic acid as (A) component. The component (A) may further contain a binder polymer other than the specific binder polymer as necessary.
上記感光性樹脂組成物は、(B)成分である光重合性化合物として、EO基の構造単位数が6未満であるビスフェノールA型ジ(メタ)アクリレート(特定光重合性化合物)の少なくとも1種を含む。(B)成分は、必要に応じて、特定光重合性化合物以外の光重合性化合物を更に含んでいてもよい。 (B) Component: Photopolymerizable Compound The photosensitive resin composition is a bisphenol A type di (meth) acrylate having a number of structural units of the EO group of less than 6 (specific) as the photopolymerizable compound that is the component (B). At least one of photopolymerizable compounds). The component (B) may further contain a photopolymerizable compound other than the specific photopolymerizable compound as necessary.
また、特定光重合性化合物において、EO基の構造単位数は、レジストパターンの薬液耐性を向上させる観点から、4未満であってもよく、3未満であってもよい。また、EO基の構造単位数の下限値は、0以上であり、2以上であってもよい。 In the specific photopolymerizable compound, the number of structural units of the EO group is less than 6. Here, the number of structural units of the EO group (structural unit) can be said to indicate how much the EO group is added in the molecule. Therefore, an integer value is shown for a single molecule. Hereinafter, the same applies to the number of structural units.
In the specific photopolymerizable compound, the number of structural units of the EO group may be less than 4 or less than 3 from the viewpoint of improving the chemical resistance of the resist pattern. Further, the lower limit of the number of structural units of the EO group is 0 or more and may be 2 or more.
(B)成分が水添ビスフェノールA型ジ(メタ)アクリレートを含む場合、その含有量は、硬化後に架橋ネットワーク中の分子運動の抑制により膨潤を抑制させ、薬液耐性を向上させる観点から、(A)成分及び(B)成分の総量100質量部に対して、1~50質量部であってもよく、5~40質量部であってもよい。 Examples of the hydrogenated bisphenol A type di (meth) acrylate include 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane.
In the case where the component (B) contains hydrogenated bisphenol A type di (meth) acrylate, the content thereof is suppressed from the viewpoint of suppressing swelling by suppressing molecular motion in the crosslinked network after curing, and improving chemical resistance (A ) Component and (B) component may be 1 to 50 parts by mass or 5 to 40 parts by mass with respect to 100 parts by mass in total.
上記感光性樹脂組成物は、(C)成分として、光重合開始剤の少なくとも1種を含有する。(C)成分は、レジストパターンの薬液耐性を維持しつつ、感度、並びにレジストパターンの解像度及び密着性を向上させる点から、下記式(2)で示される2,4,5-トリアリールイミダゾール二量体を含んでいてもよい。 Component (C): Photopolymerization initiator The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). Component (C) is a 2,4,5-triarylimidazole compound represented by the following formula (2) from the viewpoint of improving sensitivity and resolution and adhesion of the resist pattern while maintaining the chemical resistance of the resist pattern. It may contain a mer.
X1及びX2の置換位置は特に限定されず、オルト位又はパラ位であることが好ましい。
p及びqは、それぞれ独立に、1~5の整数であり、1~3の整数であることが好ましく、1であることがより好ましい。 X 1 and X 2 are each independently a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may be an alkoxy group. It is preferable that at least one of X 1 and X 2 is a chlorine atom.
The substitution position of X 1 and X 2 is not particularly limited, and is preferably an ortho position or a para position.
p and q are each independently an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1.
Ar1、Ar2、Ar3、及びAr4が有していてもよい置換基としては、炭素数1~6のアルキル基、炭素数2~6のアルケニル基、及び炭素数1~6のアルコキシ基からなる群より選択される少なくとも1種の置換基が挙げられる。Ar1、Ar2、Ar3、及びAr4が、それぞれ独立に上記置換基を有する場合、置換基の数は1~5であることが好ましく、1~3であることがより好ましく、1であることが更に好ましい。また、Ar1、Ar2、Ar3、及びAr4が、それぞれ独立に上記置換基を有する場合、その置換位置は特に限定されず、オルト位又はパラ位であることが好ましい。Ar1、Ar2、Ar3、及びAr4は、いずれも無置換であることが好ましい。 Examples of the aryl group represented by Ar 1 , Ar 2 , Ar 3 , and Ar 4 include a phenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is preferable.
Examples of the substituent that Ar 1 , Ar 2 , Ar 3 , and Ar 4 may have include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. And at least one substituent selected from the group consisting of groups. When Ar 1 , Ar 2 , Ar 3 , and Ar 4 each independently have the above substituent, the number of substituents is preferably 1 to 5, more preferably 1 to 3, More preferably it is. Further, when Ar 1 , Ar 2 , Ar 3 , and Ar 4 each independently have the above substituent, the substitution position is not particularly limited, and is preferably the ortho position or the para position. Ar 1 , Ar 2 , Ar 3 , and Ar 4 are preferably all unsubstituted.
上記感光性樹脂組成物は、(D)成分として、下記式(1)で示されるスチリルピリジン化合物の少なくとも1種を含有する。(D)成分は、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。 Component (D): styrylpyridine compound represented by formula (1) The photosensitive resin composition contains at least one styrylpyridine compound represented by the following formula (1) as the component (D). (D) A component may be used individually by 1 type and may be used in combination of 2 or more type.
なお、アルキルエステル基の炭素数は、アルキル部分の炭素数を意味する。 In the formula (1), R 1 , R 2 , and R 3 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, amino Group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group, and a, b, and c are each independently an integer of 0 to 5 Indicates. However, when a is 2 or more, a plurality of R 1 may be the same or different, and when b is 2 or more, a plurality of R 2 may be the same or different, and c is 2 or more. In the case, a plurality of R 3 may be the same or different.
In addition, carbon number of an alkyl ester group means carbon number of an alkyl part.
また、a、b、及びcは、それぞれ独立に、0~5の整数を示し、0~3の整数が好ましく、0~2の整数がより好ましい。 From the viewpoint of further improving sensitivity, R 1 , R 2 , and R 3 in formula (1) are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 carbon atom. It may be an alkyl ester group having 6 to 6, an amino group, or an alkylamino group having 1 to 20 carbon atoms.
A, b and c each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2.
上記感光性樹脂組成物は、(E)成分として、アミン化合物の少なくとも1種を含有していてもよい。アミン化合物としては、ビス[4-(ジメチルアミノ)フェニル]メタン、ビス[4-(ジエチルアミノ)フェニル]メタン、ロイコクリスタルバイオレット等が挙げられる。これらのアミン化合物は、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。 (E) component: amine compound The said photosensitive resin composition may contain at least 1 sort (s) of an amine compound as (E) component. Examples of the amine compound include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leuco crystal violet. These amine compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
上記感光性樹脂組成物は、必要に応じて、分子内に少なくとも1つのカチオン重合可能な環状エーテル基を有する光重合性化合物(オキセタン化合物等)、カチオン重合開始剤、(D)成分以外の他の増感色素、マラカイトグリーン、ビクトリアピュアブルー、ブリリアントグリーン、メチルバイオレット等の染料、トリブロモフェニルスルホン、ジフェニルアミン、ベンジルアミン、トリフェニルアミン、ジエチルアニリン、2-クロロアニリン等の光発色剤、熱発色防止剤、4-トルエンスルホンアミド等の可塑剤、顔料、充填剤、消泡剤、難燃剤、安定剤、密着性付与剤、レベリング剤、剥離促進剤、酸化防止剤、香料、イメージング剤、熱架橋剤などの他の成分を含有していてもよい。これらの他の成分は、それぞれの成分について、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。 (Other ingredients)
The photosensitive resin composition may be used in addition to a photopolymerizable compound (oxetane compound, etc.) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, and a component (D) as necessary. Sensitizing dyes, dyes such as malachite green, Victoria pure blue, brilliant green and methyl violet, photochromic agents such as tribromophenylsulfone, diphenylamine, benzylamine, triphenylamine, diethylaniline and 2-chloroaniline, thermal coloring Inhibitors, plasticizers such as 4-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, perfumes, imaging agents, heat Other components such as a crosslinking agent may be contained. These other components may be used alone or in combination of two or more for each component.
上記感光性樹脂組成物は、有機溶剤の少なくとも1種を更に含有していてもよい。有機溶剤としては、メタノール、エタノール等のアルコール溶剤;アセトン、メチルエチルケトン等のケトン溶剤;メチルセロソルブ、エチルセロソルブ、プロピレングリコールモノメチルエーテル等のグリコールエーテル溶剤;トルエン等の芳香族炭化水素溶剤;N,N-ジメチルホルムアミド等の非プロトン性極性溶剤などが挙げられる。これらの有機溶剤は、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。上記感光性樹脂組成物に含まれる有機溶剤の含有量は目的等に応じて適宜選択することができる。例えば、感光性樹脂組成物に有機溶剤を含有させて固形分が30~60質量%程度の溶液として用いることができる。以下、有機溶剤を含有する感光性樹脂組成物を「塗布液」ともいう。 [Solution of photosensitive resin composition]
The photosensitive resin composition may further contain at least one organic solvent. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N— And aprotic polar solvents such as dimethylformamide. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type. Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, it can be used as a solution having a solid content of about 30 to 60 mass% by adding an organic solvent to the photosensitive resin composition. Hereinafter, the photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”.
また、上記感光性樹脂組成物は、後述するレジストパターン付き基板の製造方法に使用できる。すなわち、本開示の別の実施形態は、(A)成分:(メタ)アクリル酸に由来する構造単位を有するバインダーポリマーと、(B)成分:EO基の構造単位数が6未満であるビスフェノールA型ジ(メタ)アクリレートを含む光重合性化合物と、(C)成分:光重合開始剤と、(D)成分:式(1)で示されるスチリルピリジン化合物と、を含有する感光性樹脂組成物のレジストパターン付き基板の製造方法への応用である。 The said photosensitive resin composition can be applied to formation of the photosensitive layer of the photosensitive element mentioned later. That is, another embodiment of the present disclosure relates to (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: bisphenol A in which the number of structural units of the EO group is less than 6. Photosensitive resin composition comprising a photopolymerizable compound containing a di (meth) acrylate, a component (C): a photopolymerization initiator, and a component (D): a styrylpyridine compound represented by formula (1) Application to photosensitive elements.
Moreover, the said photosensitive resin composition can be used for the manufacturing method of the board | substrate with a resist pattern mentioned later. That is, another embodiment of the present disclosure relates to (A) component: a binder polymer having a structural unit derived from (meth) acrylic acid, and (B) component: bisphenol A in which the number of structural units of the EO group is less than 6. Photosensitive resin composition comprising a photopolymerizable compound containing a di (meth) acrylate, a component (C): a photopolymerization initiator, and a component (D): a styrylpyridine compound represented by formula (1) This is an application to a method for manufacturing a substrate with a resist pattern.
本実施形態の感光性エレメントは、支持体と、該支持体上に設けられた上記感光性樹脂組成物を用いてなる感光層と、を備える。なお、感光層は、上記感光性樹脂組成物を用いて形成される塗膜であって、上記感光性樹脂組成物が未硬化状態のものである。感光性エレメントは、必要に応じて保護層等のその他の層を有していてもよい。 <Photosensitive element>
The photosensitive element of this embodiment is equipped with a support body and the photosensitive layer which uses the said photosensitive resin composition provided on this support body. In addition, a photosensitive layer is a coating film formed using the said photosensitive resin composition, Comprising: The said photosensitive resin composition is a thing of an unhardened state. The photosensitive element may have other layers, such as a protective layer, as needed.
上記感光性樹脂組成物を用いて、レジストパターン付き基板を製造することができる。本実施形態のレジストパターン付き基板の製造方法は、(i)基板上に、上記感光性樹脂組成物を用いてなる感光層を形成する工程(感光層形成工程)と、(ii)上記感光層の少なくとも一部の領域に活性光線を照射して、上記領域を光硬化させて硬化物領域を形成する工程(露光工程)と、(iii)上記感光層の上記硬化物領域以外の少なくとも一部を上記基板上から除去して、上記基板上にレジストパターンを形成する工程(現像工程)と、を有する。上記レジストパターン付き基板の製造方法は、必要に応じて更にその他の工程を有していてもよい。 <Method for manufacturing substrate with resist pattern>
A substrate with a resist pattern can be produced using the photosensitive resin composition. The method for manufacturing a substrate with a resist pattern according to this embodiment includes (i) a step of forming a photosensitive layer using the photosensitive resin composition on the substrate (photosensitive layer forming step), and (ii) the photosensitive layer. Irradiating at least a part of the actinic ray to photocuring the region to form a cured product region (exposure step); and (iii) at least a part of the photosensitive layer other than the cured product region. Is removed from the substrate and a resist pattern is formed on the substrate (development step). The manufacturing method of the said board | substrate with a resist pattern may have another process further as needed.
まず、上記感光性樹脂組成物を用いて感光層3を基板上に形成する。基板としては、例えば、絶縁層と該絶縁層上に形成された導体層とを備える基板(回路形成用基板)を用いることができる。絶縁層としては、例えば、ガラスエポキシ材が挙げられる。導体層としては、例えば、銅箔が挙げられる。 (I) Photosensitive layer formation process First, the photosensitive layer 3 is formed on a board | substrate using the said photosensitive resin composition. As the substrate, for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used. As an insulating layer, a glass epoxy material is mentioned, for example. An example of the conductor layer is copper foil.
露光工程では、上記のようにして基板上に形成された感光層3の少なくとも一部の領域に活性光線を照射することで、活性光線が照射された露光部が光硬化して、潜像が形成される。この際、感光層3上に存在する支持体2が活性光線に対して透明である場合には、支持体2を通して活性光線を照射することができる。一方、支持体2が活性光線に対して遮光性を示す場合には、支持体2を除去した後で感光層3に活性光線を照射する。 (Ii) Exposure Step In the exposure step, the exposed portion irradiated with the actinic ray is photocured by irradiating at least a part of the photosensitive layer 3 formed on the substrate as described above with the actinic ray. Thus, a latent image is formed. At this time, when the support 2 existing on the photosensitive layer 3 is transparent to the active light, the active light can be irradiated through the support 2. On the other hand, when the support 2 shows a light-shielding property against actinic rays, the photosensitive layer 3 is irradiated with actinic rays after the support 2 is removed.
現像工程では、上記感光層3の未硬化部分が基板上から現像処理により除去されることで、感光層3が光硬化した硬化物であるレジストパターンが基板上に形成される。感光層3上に支持体2が存在している場合には、支持体2を除去してから、未露光部分の除去(現像)を行う。現像処理には、ウェット現像とドライ現像とがあるが、ウェット現像が広く用いられている。 (Iii) Development Step In the development step, the uncured portion of the photosensitive layer 3 is removed from the substrate by development processing, whereby a resist pattern, which is a cured product obtained by photocuring the photosensitive layer 3, is formed on the substrate. . When the support 2 is present on the photosensitive layer 3, the support 2 is removed, and then the unexposed portion is removed (developed). Development processing includes wet development and dry development, and wet development is widely used.
本実施形態のプリント配線板の製造方法は、上記レジストパターン付き基板の製造方法によりレジストパターンが形成された基板に対してエッチング処理及びめっき処理の少なくとも一方の処理を行う工程を有する。
つまり、第1実施形態のプリント配線板の製造方法は、上記レジストパターン付き基板の製造方法によりレジストパターンが形成された基板に対してエッチング処理を行う工程を有する。
また、第2実施形態のプリント配線板の製造方法は、上記レジストパターン付き基板の製造方法によりレジストパターンが形成された基板に対してめっき処理を行う工程を有する。
基板としては、例えば、絶縁層と該絶縁層上に形成された導体層とを備える基板(回路形成用基板)を用いることが好ましい。上記プリント配線板の製造方法は、必要に応じてレジスト除去工程等のその他の工程を有していてもよい。基板のエッチング処理及びめっき処理は、形成されたレジストパターンをマスクとして、基板の導体層等に対して行われる。 <Method for manufacturing printed wiring board>
The method for manufacturing a printed wiring board according to the present embodiment includes a step of performing at least one of an etching process and a plating process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern.
That is, the method for manufacturing a printed wiring board according to the first embodiment includes a step of performing an etching process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern.
Moreover, the method for manufacturing a printed wiring board according to the second embodiment includes a step of performing a plating process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern.
As the substrate, for example, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer is preferably used. The method for manufacturing a printed wiring board may have other steps such as a resist removal step as necessary. The etching process and the plating process of the substrate are performed on the conductor layer of the substrate using the formed resist pattern as a mask.
また、より好適な実施形態は、上記感光性樹脂組成物の高密度パッケージ基板の製造への応用であり、上記感光性樹脂組成物のセミアディティブ工法への応用である。以下に、セミアディティブ工法による配線板の製造工程の一例について、図2を参照しながら説明する。図2における部材の大きさは概念的なものであり、部材間の大きさの相対的な関係はこれに限定されない。 The said photosensitive resin composition can be used conveniently for manufacture of a printed wiring board. That is, in one preferred embodiment, component (A): a binder polymer having a structural unit derived from (meth) acrylic acid, and component (B): bisphenol A having an EO group having less than 6 structural units Photosensitive resin composition comprising a photopolymerizable compound containing a di (meth) acrylate, a component (C): a photopolymerization initiator, and a component (D): a styrylpyridine compound represented by formula (1) Application to the production of printed wiring boards.
A more preferred embodiment is application of the photosensitive resin composition to the production of a high-density package substrate, and application of the photosensitive resin composition to a semi-additive construction method. Below, an example of the manufacturing process of the wiring board by a semi-additive construction method is demonstrated, referring FIG. The size of the members in FIG. 2 is conceptual, and the relative relationship between the sizes of the members is not limited to this.
なお、図2ではマスク20を用いてレジストパターン30を形成する方法について説明したが、マスク20を用いずに直接描画露光法によりレジストパターン30を形成してもよい。 In FIG. 2A, a substrate (circuit forming substrate) in which the
Although the method for forming the resist
<感光性樹脂組成物の溶液の調製>
表2及び表3に示す各成分を同表に示す配合量(単位:g)で、アセトン9g、トルエン5g、及びメタノール5gと混合することにより、実施例1~6及び比較例1~4の感光性樹脂組成物の溶液をそれぞれ調製した。表2及び表3に示す(A)成分の配合量は不揮発分の質量(固形分量)である。表2及び表3に示す各成分の詳細については、以下のとおりである。なお、「-」は未配合を意味する。 (Examples 1 to 6 and Comparative Examples 1 to 4)
<Preparation of solution of photosensitive resin composition>
Each component shown in Table 2 and Table 3 was mixed with 9 g of acetone, 5 g of toluene, and 5 g of methanol in the blending amount (unit: g) shown in the same table, whereby Examples 1 to 6 and Comparative Examples 1 to 4 were mixed. Each solution of the photosensitive resin composition was prepared. The blending amount of the component (A) shown in Tables 2 and 3 is the mass (solid content) of the nonvolatile content. Details of each component shown in Tables 2 and 3 are as follows. “-” Means not blended.
[バインダーポリマー(A-1)の合成]
重合性単量体(モノマー)であるメタクリル酸81g、スチレン135g、メタクリル酸ベンジル69g、及びメタクリル酸メチル15g(質量比:27/45/23/5)と、アゾビスイソブチロニトリル1.5gとを混合して得た溶液を「溶液a」とした。 (A) Binder polymer [synthesis of binder polymer (A-1)]
A polymerizable monomer (monomer) 81 g of methacrylic acid, 135 g of styrene, 69 g of benzyl methacrylate, and 15 g of methyl methacrylate (mass ratio: 27/45/23/5) and 1.5 g of azobisisobutyronitrile A solution obtained by mixing the above was designated as “Solution a”.
バインダーポリマー(A-1)の不揮発分(固形分)は41.5質量%であり、重量平均分子量は44000であり、酸価は176mgKOH/gであり、分散度は2.2であった。 The solution a was added dropwise to the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring. Next, the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a solution of binder polymer (A-1).
The non-volatile content (solid content) of the binder polymer (A-1) was 41.5% by mass, the weight average molecular weight was 44000, the acid value was 176 mgKOH / g, and the degree of dispersion was 2.2.
ポンプ:日立 L-6000型(株式会社日立製作所製)
カラム:以下の計3本、カラム仕様:10.7mmφ×300mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M(以上、日立化成株式会社製)
溶離液:テトラヒドロフラン(THF)
試料濃度:固形分が40質量%の樹脂溶液を120mg採取し、5mLのTHFに溶解して試料を調製した。
測定温度:40℃
注入量:200μL
圧力:49kgf/cm2(4.8MPa)
流量:2.05mL/分
検出器:日立 L-3300型RI(株式会社日立製作所製) GPC condition Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran (THF)
Sample concentration: 120 mg of a resin solution having a solid content of 40% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49 kgf / cm 2 (4.8 MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)
重合性単量体(モノマー)であるメタクリル酸81g、メタクリル酸2-ヒドロキシエチル9g、スチレン141g、及びメタクリル酸ベンジル69g(質量比:27/3/47/23)と、アゾビスイソブチロニトリル2.4gとを混合して得た溶液を「溶液c」とし、溶液aの代わりに溶液cを用いたほかは、バインダーポリマー(A-1)の溶液を得るのと同様にして、バインダーポリマー(A-2)の溶液を得た。
バインダーポリマー(A-2)の不揮発分(固形分)は41.7質量%であり、重量平均分子量は38000であり、酸価は176mgKOH/gであり、分散度は1.8であった。 [Synthesis of Binder Polymer (A-2)]
A polymerizable monomer (monomer) 81 g of methacrylic acid, 9 g of 2-hydroxyethyl methacrylate, 141 g of styrene, 69 g of benzyl methacrylate (mass ratio: 27/3/47/23), and azobisisobutyronitrile The solution obtained by mixing 2.4 g was designated as “solution c”, and the binder polymer (A-1) was obtained in the same manner as in the case of obtaining the solution of the binder polymer (A-1) except that the solution c was used instead of the solution a. A solution of (A-2) was obtained.
The binder polymer (A-2) had a nonvolatile content (solid content) of 41.7% by mass, a weight average molecular weight of 38000, an acid value of 176 mgKOH / g, and a dispersity of 1.8.
・BPE-100(新中村化学工業株式会社製):2,2-ビス(4-(メタクリロキシエトキシ)フェニル)プロパン(EO基:2.6mol(平均値))
・BPE-80N(新中村化学工業株式会社製):2,2-ビス(4-(メタクリロキシエトキシ)フェニル)プロパン(EO基:2.3mol(平均値))
・FA-324ME(日立化成株式会社製):2,2-ビス(4-(メタクリロキシジエトキシ)フェニル)プロパン(EO基:4mol(平均値))
・ABE-300(新中村化学工業株式会社製):2,2-ビス(4-(アクリロキシポリエトキシ)フェニル)プロパン(EO基:3mol(平均値))
・FA-321M(日立化成株式会社製):2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパン(EO基:10mol(平均値))
・FA-3200MY(日立化成株式会社製):2,2-ビス(4-(メタクリロキシエトキシプロポキシ)フェニル)プロパン(EO基:12mol(平均値)、PO基:4mol(平均値))
・FA-024M(日立化成株式会社製):(PO)(EO)(PO)変性ポリプロピレングリコール#700ジメタクリレート
なお、EO基及びPO基についてのmol数は、各EO基又はPO基の構造単位数を意味する。 (B) Photopolymerizable compound BPE-100 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis (4- (methacryloxyethoxy) phenyl) propane (EO group: 2.6 mol (average value))
BPE-80N (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis (4- (methacryloxyethoxy) phenyl) propane (EO group: 2.3 mol (average value))
FA-324ME (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (EO group: 4 mol (average value))
ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.): 2,2-bis (4- (acryloxypolyethoxy) phenyl) propane (EO group: 3 mol (average value))
FA-321M (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (EO group: 10 mol (average value))
FA-3200MY (manufactured by Hitachi Chemical Co., Ltd.): 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (EO group: 12 mol (average value), PO group: 4 mol (average value))
FA-024M (manufactured by Hitachi Chemical Co., Ltd.): (PO) (EO) (PO) modified polypropylene glycol # 700 dimethacrylate The number of moles for the EO group and the PO group is the structural unit of each EO group or PO group Means number.
・B-CIM(Hampford社製):2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビスイミダゾール[2-(2-クロロフェニル)-4,5-ジフェニルイミダゾール二量体] (C) Photopolymerization initiator B-CIM (manufactured by Hampford): 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole [2- (2-chlorophenyl ) -4,5-diphenylimidazole dimer]
・2,4-DMOP-DSP:3,5-ビス(2,4-ジメトキシベンジリデンジシクロペンタノ[b,e])-4-(2,4-ジメトキシフェニル)ピリジン (D) A styrylpyridine compound represented by the formula (1): 2,4-DMOP-DSP: 3,5-bis (2,4-dimethoxybenzylidenedicyclopentano [b, e])-4- (2, 4-Dimethoxyphenyl) pyridine
・PYR-1(株式会社日本化学工業所製):1-フェニル-3-(4-メトキシスチリル)-5-(4-メトキシフェニル)ピラゾリン
・EAB(保土谷化学工業株式会社製):4,4’-ジエチルアミノベンゾフェノン
・H-MOP-DSP:4,6-ビス(4-メトキシベンジリデンジシクロヘキサノ[b,e])-5-(4-メトキシフェニル)ピリジン Sensitizing dye other than component (D) PYR-1 (manufactured by Nippon Chemical Industry Co., Ltd.): 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline EAB ( Hodogaya Chemical Co., Ltd.): 4,4'-diethylaminobenzophenone H-MOP-DSP: 4,6-bis (4-methoxybenzylidenedicyclohexano [b, e])-5- (4-methoxyphenyl) ) Pyridine
・LCV(山田化学工業株式会社製):ロイコクリスタルバイオレット (E) Amine compound LCV (manufactured by Yamada Chemical Co., Ltd.): Leuco Crystal Violet
・MKG(大阪有機化学工業株式会社製):マラカイトグリーン Dye ・ MKG (Osaka Organic Chemical Co., Ltd.): Malachite Green
上記で得られた感光性樹脂組成物の溶液を、それぞれ厚さ16μmのポリエチレンテレフタレートフィルム(東レ株式会社製、「FB-40」)(支持体)上に塗布し、70℃及び110℃の熱風対流式乾燥器で順次乾燥処理して、乾燥後の膜厚が25μmである感光層を形成した。この感光層上にポリエチレンフィルム(王子製紙株式会社製、「E-200K」)(保護層)を貼り合わせ、支持体と感光層と保護層とが順に積層された感光性エレメントをそれぞれ得た。 <Production of photosensitive element>
The photosensitive resin composition solution obtained above was applied onto a 16 μm thick polyethylene terephthalate film (“FB-40”, manufactured by Toray Industries, Inc.) (support), and hot air at 70 ° C. and 110 ° C. A drying process was sequentially performed with a convection dryer to form a photosensitive layer having a dried film thickness of 25 μm. A polyethylene film (“E-200K” manufactured by Oji Paper Co., Ltd.) (protective layer) was bonded onto the photosensitive layer to obtain a photosensitive element in which a support, a photosensitive layer, and a protective layer were sequentially laminated.
ガラスエポキシ材と、その両面に形成された銅箔(厚さ16μm)とからなる銅張積層板(日立化成株式会社製、「MCL-E-679F」)(以下、「基板」という。)を加熱して80℃に昇温させた後、実施例1~6及び比較例1~4に係る感光性エレメントを、基板の銅表面にラミネート(積層)した。ラミネートは、保護層を除去しながら、各感光性エレメントの感光層が基板の銅表面に密着するようにして、温度110℃、ラミネート圧力4kgf/cm2(0.4MPa)の条件下で行った。このようにして、基板の銅表面上に感光層及び支持体が積層された積層基板を得た。得られた積層基板は23℃まで放冷した。 <Production of laminated substrate>
A copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., “MCL-E-679F”) (hereinafter referred to as “substrate”) composed of a glass epoxy material and copper foil (thickness 16 μm) formed on both sides thereof. After heating to 80 ° C., the photosensitive elements according to Examples 1 to 6 and Comparative Examples 1 to 4 were laminated (laminated) on the copper surface of the substrate. Laminate, while removing the protective layer, the photosensitive layer of the photosensitive element so as to close contact with the copper surface of the substrate, temperature of 110 ° C., was carried out under the conditions of lamination pressure 4kgf / cm 2 (0.4MPa) . In this way, a laminated substrate in which the photosensitive layer and the support were laminated on the copper surface of the substrate was obtained. The obtained laminated substrate was allowed to cool to 23 ° C.
上記積層基板の支持体上に、濃度領域0.00~2.00、濃度ステップ0.05、タブレットの大きさ20mm×187mm、各ステップの大きさが3mm×12mmである41段ステップタブレットを有するフォトツールを配置させた。波長405nmの青紫色レーザダイオードを光源とする直描露光機(ビアメカニクス株式会社製、「DE-1UH」)を使用して、所定のエネルギー量(露光量)でフォトツール及び支持体を介して感光層に対して露光した。なお、照度の測定には、405nm対応プローブを適用した紫外線照度計(ウシオ電機株式会社製、「UIT-150」)を用いた。 <Evaluation of sensitivity>
On the support of the laminated substrate, there is a 41 step tablet having a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and a size of each step of 3 mm × 12 mm. A photo tool was placed. Using a direct exposure machine ("DE-1UH" manufactured by Via Mechanics Co., Ltd.) using a blue-violet laser diode having a wavelength of 405 nm as a light source, with a predetermined energy amount (exposure amount) via a photo tool and a support The photosensitive layer was exposed. For measurement of illuminance, an ultraviolet illuminance meter (“UIT-150” manufactured by USHIO INC.) Using a 405 nm probe was used.
ライン幅(L)/スペース幅(S)(以下、「L/S」と記す。)が3/3~30/30(単位:μm)である描画パターンを用いて、41段ステップタブレットの残存段数が14段となるエネルギー量で上記積層基板の感光層に対して露光(描画)した。露光後、上記感度の評価と同様の現像処理を行った。 <Evaluation of resolution and adhesion>
The remaining 41 step tablet using a drawing pattern having a line width (L) / space width (S) (hereinafter referred to as “L / S”) of 3/3 to 30/30 (unit: μm) The photosensitive layer of the laminated substrate was exposed (drawn) with an energy amount of 14 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.
41段ステップタブレットの残存段数が14段となるエネルギー量で上記感光性エレメントの感光層に対して露光し、光硬化物を得た。露光前後に、フーリエ変換型赤外分光(FT-IR)装置(ブルカー・オプティクス株式会社製、「VERTEX70」)を用いて、感光層又はその光硬化物のFT-IR測定を行った。そして、1570cm-1における芳香族に由来するピークを内部標準とし、1637cm-1に観察されるビニル基に由来するピークから、以下の式に従って反応率(%)を算出した。結果を表4及び表5に示す。
反応率(%)=(1-I/I0)×100
I:露光後におけるピーク強度
I0:露光前におけるピーク強度 <Evaluation of reaction rate>
The photosensitive layer of the photosensitive element was exposed with an energy amount such that the remaining number of stages of the 41-step tablet was 14 to obtain a photocured product. Before and after exposure, FT-IR measurement of the photosensitive layer or its photocured product was performed using a Fourier transform infrared spectroscopic (FT-IR) apparatus (manufactured by Bruker Optics, “VERTEX70”). Then, the internal standard peak derived from aromatic in 1570 cm -1, from a peak derived from vinyl group observed in 1637 cm -1, was calculated reaction rate (%) according to the following equation. The results are shown in Tables 4 and 5.
Reaction rate (%) = (1−I / I 0 ) × 100
I: Peak intensity after exposure I 0 : Peak intensity before exposure
フレキシブルプリント配線板用銅張積層板(ニッカン工業株式会社製、「F30VC1」)を加熱して80℃に昇温させた後、実施例1~6及び比較例1~4に係る感光性エレメントを、基板の銅表面にラミネート(積層)した。ラミネートは、保護層を除去しながら、各感光性エレメントの感光層が基板の銅表面に密着するようにして、温度110℃、ラミネート圧力4kgf/cm2(0.4MPa)の条件下で行った。このようにして、基板の銅表面上に感光層及び支持体が積層された評価用積層体を得た。得られた評価用積層体は23℃まで放冷した。 <Evaluation of plating solution resistance (chemical solution resistance)>
The copper-clad laminate for flexible printed wiring boards (“F30VC1” manufactured by Nikkan Kogyo Co., Ltd.) was heated to 80 ° C., and then the photosensitive elements according to Examples 1 to 6 and Comparative Examples 1 to 4 were used. The laminate was laminated on the copper surface of the substrate. Laminate, while removing the protective layer, the photosensitive layer of the photosensitive element so as to close contact with the copper surface of the substrate, temperature of 110 ° C., was carried out under the conditions of lamination pressure 4kgf / cm 2 (0.4MPa) . In this way, an evaluation laminate in which the photosensitive layer and the support were laminated on the copper surface of the substrate was obtained. The obtained laminate for evaluation was allowed to cool to 23 ° C.
また、式(1)で示されるスチリルピリジン化合物を含有しない感光性樹脂組成物を用いた比較例2~4は、感光性樹脂組成物の感度及びレジストパターンの薬液耐性が実施例1~6よりも劣っており、特に比較例3~4は、レジストパターンの解像度及び密着性にも劣っていた。 On the other hand, Comparative Example 1 using a photosensitive resin composition containing no bisphenol A type di (meth) acrylate having less than 6 EO group structural units was excellent in the sensitivity of the photosensitive resin composition. The resolution, adhesion, and chemical resistance of the resist pattern were inferior to those of Examples 1-6.
In Comparative Examples 2 to 4 using the photosensitive resin composition not containing the styrylpyridine compound represented by the formula (1), the sensitivity of the photosensitive resin composition and the chemical resistance of the resist pattern are higher than those of Examples 1 to 6. In particular, Comparative Examples 3 to 4 were also inferior in the resolution and adhesion of the resist pattern.
また、本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2016-053771 filed on Mar. 17, 2016 is incorporated herein by reference in its entirety.
In addition, all documents, patent applications, and technical standards described in this specification are the same as when individual documents, patent applications, and technical standards are specifically and individually described to be incorporated by reference. Which is incorporated herein by reference.
Claims (7)
- (メタ)アクリル酸に由来する構造単位を有するバインダーポリマーと、
エチレンオキシ基の構造単位数が6未満であるビスフェノールA型ジ(メタ)アクリレートを含む光重合性化合物と、
光重合開始剤と、
下記式(1)で示されるスチリルピリジン化合物と、を含有する感光性樹脂組成物。
[式(1)中、R1、R2、及びR3は、それぞれ独立に、炭素数1~20のアルキル基、炭素数1~6のアルコキシ基、炭素数1~6のアルキルエステル基、アミノ基、炭素数1~20のアルキルアミノ基、カルボキシ基、シアノ基、ニトロ基、アセチル基、又は(メタ)アクリロイル基を示し、a、b、及びcは、それぞれ独立に、0~5の整数を示す。] A binder polymer having a structural unit derived from (meth) acrylic acid;
A photopolymerizable compound containing a bisphenol A-type di (meth) acrylate having an ethyleneoxy group having less than 6 structural units;
A photopolymerization initiator;
The photosensitive resin composition containing the styryl pyridine compound shown by following formula (1).
[In the formula (1), R 1 , R 2 , and R 3 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, An amino group, an alkylamino group having 1 to 20 carbon atoms, a carboxy group, a cyano group, a nitro group, an acetyl group, or a (meth) acryloyl group, and a, b, and c are each independently 0 to 5 Indicates an integer. ] - 前記光重合開始剤が、下記式(2)で示される2,4,5-トリアリールイミダゾール二量体を含む、請求項1に記載の感光性樹脂組成物。
[式(2)中、Ar1、Ar2、Ar3、及びAr4は、それぞれ独立に、アルキル基、アルケニル基、及びアルコキシ基からなる群より選択される少なくとも1種の置換基で置換されていてもよいアリール基を示し、X1及びX2は、それぞれ独立に、ハロゲン原子、アルキル基、アルケニル基、又はアルコキシ基を示し、p及びqは、それぞれ独立に、1~5の整数を示す。] The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator includes a 2,4,5-triarylimidazole dimer represented by the following formula (2).
[In Formula (2), Ar 1 , Ar 2 , Ar 3 , and Ar 4 are each independently substituted with at least one substituent selected from the group consisting of an alkyl group, an alkenyl group, and an alkoxy group. X 1 and X 2 each independently represents a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group, and p and q each independently represents an integer of 1 to 5 Show. ] - 支持体と、前記支持体上に設けられた請求項1又は請求項2に記載の感光性樹脂組成物を用いてなる感光層と、を備える感光性エレメント。 A photosensitive element comprising: a support; and a photosensitive layer using the photosensitive resin composition according to claim 1 or 2 provided on the support.
- 基板上に、請求項1又は請求項2に記載の感光性樹脂組成物を用いてなる感光層を形成する工程と、
前記感光層の少なくとも一部の領域に活性光線を照射して、前記領域を光硬化させて硬化物領域を形成する工程と、
前記感光層の前記硬化物領域以外の少なくとも一部を前記基板上から除去して、前記基板上にレジストパターンを形成する工程と、を有するレジストパターン付き基板の製造方法。 Forming a photosensitive layer using the photosensitive resin composition according to claim 1 or 2 on a substrate;
Irradiating at least a part of the photosensitive layer with actinic rays to photocuring the region to form a cured product region;
Removing at least a portion of the photosensitive layer other than the cured product region from the substrate, and forming a resist pattern on the substrate. - 前記活性光線の波長が340~430nmの範囲内である、請求項4に記載のレジストパターン付き基板の製造方法。 The method for producing a substrate with a resist pattern according to claim 4, wherein the wavelength of the actinic ray is in the range of 340 to 430 nm.
- 請求項4又は請求項5に記載のレジストパターン付き基板の製造方法によりレジストパターンが形成された基板に対してエッチング処理を行う工程を有するプリント配線板の製造方法。 A printed wiring board manufacturing method comprising a step of performing an etching process on a substrate on which a resist pattern is formed by the method for manufacturing a substrate with a resist pattern according to claim 4 or 5.
- 請求項4又は請求項5に記載のレジストパターン付き基板の製造方法によりレジストパターンが形成された基板に対してめっき処理を行う工程を有するプリント配線板の製造方法。 A method for producing a printed wiring board, comprising a step of performing a plating process on a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern according to claim 4 or 5.
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