WO2019244898A1 - 感光性樹脂組成物およびレジストパターンの形成方法 - Google Patents
感光性樹脂組成物およびレジストパターンの形成方法 Download PDFInfo
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- WO2019244898A1 WO2019244898A1 PCT/JP2019/024154 JP2019024154W WO2019244898A1 WO 2019244898 A1 WO2019244898 A1 WO 2019244898A1 JP 2019024154 W JP2019024154 W JP 2019024154W WO 2019244898 A1 WO2019244898 A1 WO 2019244898A1
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- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 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 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- DWCZIOOZPIDHAB-UHFFFAOYSA-L methyl green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)[N+](C)(C)C)=C1C=CC(=[N+](C)C)C=C1 DWCZIOOZPIDHAB-UHFFFAOYSA-L 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 125000006611 nonyloxy group Chemical group 0.000 description 1
- 125000005295 norbornyloxy group Chemical group C12(CCC(CC1)C2)O* 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical group C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000005440 p-toluyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C(*)=O)C([H])([H])[H] 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
-
- 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
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—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
Definitions
- the present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and the like.
- a photosensitive resin laminate obtained by laminating a photosensitive resin layer on a support film, and further laminating a protective film as necessary on the photosensitive resin layer, A so-called dry film photoresist (hereinafter sometimes referred to as DF) is used.
- DF dry film photoresist
- the photosensitive resin layer is generally of an alkali developing type using a weak alkaline aqueous solution as a developing solution.
- the following steps are performed.
- the protective film is first peeled off.
- DF is laminated on a substrate for permanent circuit such as a copper-clad laminate or a flexible substrate using a laminator or the like, and is exposed through a wiring pattern mask film or the like.
- the support film is peeled off, and the photosensitive resin layer of an uncured portion (for example, an unexposed portion in a negative type) is dissolved or dispersed and removed with a developer, and a cured resist pattern (hereinafter, simply referred to as (Sometimes called a resist pattern).
- the first method is a method in which a substrate surface not covered with a resist pattern (eg, a copper surface of a copper-clad laminate) is removed by etching, and then the resist pattern portion is removed with an alkaline aqueous solution stronger than a developing solution (etching method). It is.
- a second method after performing a plating treatment on the substrate surface with copper, solder, nickel, tin, or the like, the resist pattern portion is removed in the same manner as in the first method, and further, a substrate surface (for example, This is a method (plating method) of etching the copper surface of the copper-clad laminate.
- a substrate surface for example, This is a method (plating method) of etching the copper surface of the copper-clad laminate.
- cupric chloride, ferric chloride, a copper-ammonia complex solution or the like is used for the etching.
- Patent Document 1 describes a photosensitive resin composition in which the resolution is enhanced by a specific thermoplastic resin, a monomer, and a photopolymerizable initiator. .
- a heating step may be performed on the photosensitive resin layer, followed by development, if necessary.
- This heating step high resolution and high adhesion can be further improved.
- a post-exposure baking step is added, there is a problem that the conventional photosensitive resin composition does not sufficiently improve the adhesiveness, or that if the elapsed time after the exposure is long, good adhesiveness cannot be obtained.
- the present invention has been proposed in view of such a conventional situation.
- the present inventors have conducted intensive studies and found that the above object can be achieved by using a specific amount of a monomer component having a specific structural unit in an alkali-soluble polymer constituting a photosensitive resin composition. Having arrived at what can be done, the present invention has been completed. In addition, the present inventors have conducted intensive studies and, as a result, have found that the above object can be achieved by using a specific photopolymerization initiator in an alkali-soluble polymer constituting the photosensitive resin composition, The present invention has been completed. That is, the present invention is as follows.
- a photosensitive resin composition for obtaining a cured resin by heating and then developing, wherein the photosensitive resin composition, based on the total solid content of the photosensitive resin composition, the following: component: (A) alkali-soluble polymer: 10% to 90% by mass; (B) a compound having an ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) a photopolymerization initiator: 0.01% by mass to 20% by mass; Including (A) The photosensitive resin composition, wherein the constituent unit of styrene and / or a styrene derivative in the whole alkali-soluble polymer is 15% by mass or more.
- the content of the compound (B-1) in which the concentration of the bisphenol A skeleton is 0.18 mol / 100 g or more as the compound (B) having an ethylenically unsaturated double bond is the solid content of the photosensitive resin composition.
- the photosensitive resin composition according to [6], wherein the compound (B) having an ethylenically unsaturated double bond includes a (meth) acrylate compound having six or more ethylenically unsaturated double bonds.
- the anthracene derivative may have an optionally substituted alkoxy group having 1 to 40 carbon atoms and / or an optionally substituted aryl group having 6 to 40 carbon atoms at the 9-position and / or 10-position.
- the anthracene derivative has an optionally substituted alkoxy group having 1 to 40 carbon atoms and / or an optionally substituted aryl group having 6 to 40 carbon atoms at the 9,10 positions. , [18] or [19].
- the photosensitive resin composition according to [20] wherein the photopolymerization initiator (C) includes 9,10-diphenylanthracene.
- photopolymerization initiator comprises a compound in which the 9- and / or 10-position alkoxy group of 9,10-dialkoxyanthracene is modified with one or more halogen atoms.
- Photosensitive resin composition [26] The photosensitive resin composition according to any one of [18] to [25], wherein the photopolymerization initiator (C) includes a compound having a halogen atom directly bonded to an anthracene skeleton.
- [41] A method for manufacturing a circuit board, comprising forming a circuit board by etching or plating a substrate having a resist pattern manufactured by the method according to any one of [34] to [40].
- the photosensitive resin composition according to any one of the above.
- the adhesiveness at the time of developing after heating after exposure can be improved remarkably, and especially the photosensitive resin which realizes favorable adhesiveness even when the elapsed time after exposure becomes long A composition can be provided.
- the photosensitive resin composition of the present invention after exposure, is a photosensitive resin composition for obtaining a cured resin by heating and then developing, wherein the photosensitive resin composition is the photosensitive resin composition.
- the photosensitive resin composition Based on the total solid content, the following components: (A) alkali-soluble polymer: 10% to 90% by mass; (B) compound having an ethylenically unsaturated double bond: 5% to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass.
- the photosensitive resin composition of the present embodiment particularly contains (A) styrene and / or a styrene derivative in the entire alkali-soluble polymer.
- the structural unit is 15% by mass or more.
- the dry film resist obtained from the photosensitive resin composition generally does not have the effect of improving the adhesiveness unless heated immediately after exposure, but the dry film resist obtained from the photosensitive resin composition of the present invention has Good adhesion (that is, a thin resist) can be exhibited even when the elapsed time afterward becomes long.
- the photosensitive resin composition of the present invention has a composition suitable for this property.
- the alkali-soluble polymer contains a plurality of types of alkali-soluble polymers
- (A) the structural unit of styrene and / or styrene derivative in the whole alkali-soluble polymer Is 15% by mass or more
- the adhesiveness when heated and developed after exposure can be remarkably improved, and in particular, good adhesiveness can be obtained even when the elapsed time after exposure is long.
- each component will be described in order.
- the alkali-soluble polymer includes a polymer that is easily soluble in an alkaline substance. More specifically, (A) the amount of the carboxyl group contained in the alkali-soluble polymer is from 100 to 600, preferably from 250 to 450, in terms of acid equivalent.
- the acid equivalent refers to the mass (unit: gram) of a polymer having one equivalent of a carboxyl group in the molecule.
- the carboxyl group in the alkali-soluble polymer is necessary for giving the photosensitive resin layer developability and peelability to an aqueous alkali solution.
- the acid equivalent is a value measured by a potentiometric titration method using a potentiometric titrator and titrating with a 0.1 mol / L NaOH aqueous solution.
- the weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. It is preferred that the weight average molecular weight be 500,000 or less from the viewpoint of improving resolution and developability.
- the weight average molecular weight is more preferably 100,000 or less, further preferably 70,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.
- setting the weight-average molecular weight to 5,000 or more is necessary to control the properties of the developed aggregates and the properties of the unexposed film such as edge fuse properties and cut chip properties in the case of a photosensitive resin laminate. Is preferred.
- the weight average molecular weight is more preferably 10,000 or more, and even more preferably 20,000 or more.
- the edge fusing property refers to the degree of the ease with which a photosensitive resin layer (that is, a layer made of a photosensitive resin composition) protrudes from an end face of a roll when the photosensitive resin laminate is wound into a roll.
- the cut chip property refers to the degree of chip flying when an unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate or the like, it is transferred to a mask in a later exposure step or the like, which causes a defective product.
- the degree of dispersion of the alkali-soluble polymer is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, and preferably from 1.0 to 4.0. More preferably, it is more preferably from 1.0 to 3.0.
- the photosensitive resin composition can significantly improve the adhesiveness when heated and developed after exposure, and particularly when the elapsed time after exposure is long, the adhesiveness is good.
- the (A) alkali-soluble polymer contains a monomer component having an aromatic hydrocarbon group.
- examples of such an aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
- the content ratio of the monomer component having an aromatic hydrocarbon group in the alkali-soluble polymer (A) is preferably 20% by mass or more, and more preferably 40% by mass, based on the total mass of all the monomer components.
- the upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 80% by mass or less.
- the content ratio of the monomer component having an aromatic hydrocarbon group in the case of containing a plurality of (A) alkali-soluble polymers was determined as a weight average value.
- Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative. Among them, a monomer having an aralkyl group or styrene is preferable.
- Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group.
- a substituted or unsubstituted benzyl group is preferable.
- Examples of the comonomer having a phenylalkyl group include phenylethyl (meth) acrylate.
- Examples of the comonomer having a benzyl group include (meth) acrylates having a benzyl group, such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; vinyl monomers having a benzyl group, such as vinyl benzyl chloride and vinyl benzyl alcohol Is mentioned. Among them, benzyl (meth) acrylate is preferred.
- the alkali-soluble polymer (A) containing a monomer component having an aromatic hydrocarbon group is a monomer having an aromatic hydrocarbon group and at least one of a first monomer described below and / or It is preferably obtained by polymerizing at least one of the second monomers described below.
- the (A) alkali-soluble polymer that does not contain a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described below, More preferably, it is obtained by copolymerizing at least one kind of a monomer and at least one kind of a second monomer described below.
- the first monomer is a monomer having a carboxyl group in the molecule.
- the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester.
- (meth) acrylic acid is preferred.
- (meth) acrylic acid means acrylic acid or methacrylic acid
- (meth) acryloyl group means acryloyl group or methacryloyl group
- the copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. Making the copolymerization ratio 10% by mass or more is preferable from the viewpoint of developing good developability and controlling the edge fusing property, and more preferably 15% by mass or more, and further preferably 20% by mass or more. . It is preferred that the copolymerization ratio be 50% by mass or less from the viewpoint of high resolution and sushi shape of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, and from these viewpoints, 35% by mass. The content is more preferably at most 32% by mass, particularly preferably at most 30% by mass.
- the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
- the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate (Meth) acrylates such as tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; vinyl acetate And the like, and esters of vinyl alcohol such as (meth) acrylonitrile.
- methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferable.
- Having a monomer having an aralkyl group and / or styrene as a monomer can significantly improve the adhesiveness when heated and developed after exposure, and particularly the elapsed time after exposure. It is preferable from the viewpoint of exhibiting good adhesion even when the length becomes long.
- a copolymer containing methacrylic acid, benzyl methacrylate, and styrene and a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are preferable.
- the alkali-soluble polymer can be used singly or as a mixture of two or more.
- two kinds of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group may be used in combination, or a monomer component having an aromatic hydrocarbon group may be used.
- an alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more based on the total amount of (A) the alkali-soluble polymer. It is more preferably at least 80 mass%, more preferably at least 80 mass%, more preferably at least 90 mass%, most preferably at least 95 mass%.
- the (A) alkali-soluble polymer of the present embodiment contains, in the photosensitive resin composition, an alkali-soluble polymer (A-1) containing 52% by mass or more of a structural unit of styrene and / or a styrene derivative as a monomer component. Is preferably 3% by mass or more based on the solid content of This makes it possible to remarkably improve the adhesiveness when heated and developed after the exposure, and it is possible to obtain good adhesiveness even when the elapsed time after the exposure becomes long.
- the alkali-soluble polymer (A) more preferably contains the alkali-soluble polymer (A-1) in an amount of 10% by mass or more, and more preferably 15% by mass, based on the solid content in the photosensitive resin composition. More preferably, the content is 20% by mass or more, particularly preferably 30% by mass or more.
- the styrene derivative include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer and the like.
- the alkali-soluble polymer when (A) the alkali-soluble polymer is composed of a plurality of kinds of alkali-soluble polymers, the structural unit of styrene and / or styrene derivative in (A) the entire alkali-soluble polymer is 15% by mass. That is all.
- the constituent unit of styrene and / or a styrene derivative in the alkali-soluble polymer is preferably 25% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more. It is particularly preferably at least 40% by mass.
- the upper limit of the constituent unit of styrene and / or styrene derivative in the alkali-soluble polymer is preferably 90% by mass or less, more preferably 80% by mass or less, and more preferably 75% by mass or less. More preferably, it is particularly preferably at most 70% by mass.
- the content of the styrene skeleton is not less than 15% by mass in the whole alkali-soluble polymer (A). Even in a large amount system, the mobility of the resin is improved by heating, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly compatible, and as a result, the adhesion is significantly improved. I think it was possible. Then, it is considered that since the adhesion was remarkably improved, good adhesion could be obtained even when the elapsed time after exposure was long.
- (A-1) preferably contains 25% by mass or more of (meth) acrylic acid as a monomer component, more preferably 26% by mass or more, even more preferably 27% by mass or more. It is particularly preferable that the content be 28% by mass or more, and most preferable that the content be 29% by mass or more. From the same viewpoint, the content is preferably 35% by mass or less, more preferably 32% by mass or less, and even more preferably 30% by mass or less.
- the synthesis of the alkali-soluble polymer is performed by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and adding benzoyl peroxide, azoisobutyronitrile, or the like to the solution. It is preferable that the polymerization is performed by adding an appropriate amount of a radical polymerization initiator and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After the reaction, the solvent may be further added to adjust the concentration to a desired concentration. As a synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
- the weight average value Tg total of the glass transition temperature Tg of the alkali-soluble polymer is 30 ° C or more and 150 ° C or less. Tg total is calculated by a method described in Examples described later.
- the Tg total of the alkali-soluble polymer (A) is preferably 135 ° C or lower, more preferably 130 ° C or lower, further preferably 125 ° C or lower, and more preferably 120 ° C or lower. More preferably, it is particularly preferably 110 ° C. or lower. It is preferable to use (A) an alkali-soluble polymer having a Tg total of 30 ° C. or more from the viewpoint of improving edge fuse resistance. In this respect, the Tg total of (A) the alkali-soluble polymer is more preferably 40 ° C or higher, further preferably 50 ° C or higher, and particularly preferably 60 ° C or higher.
- the ratio of the alkali-soluble polymer to the total solid content of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, More preferably, it is 40% by mass to 60% by mass. It is preferable that the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition be 90% by mass or less from the viewpoint of controlling the development time. On the other hand, it is preferable that the ratio of the alkali-soluble polymer (A) to the photosensitive resin composition be 10% by mass or more from the viewpoint of improving edge fuse resistance.
- the compound (B) having an ethylenically unsaturated double bond preferably contains a compound having a (meth) acryloyl group in the molecule from the viewpoint of curability and compatibility with (A) an alkali-soluble polymer.
- the number of (meth) acryloyl groups in the compound (B) may be one or more.
- the compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure.
- the ethylenically unsaturated bond is more preferably derived from a methacryloyl group.
- the compound (B) having an ethylenically unsaturated bond preferably has an alkylene oxide structure having 3 or more carbon atoms.
- the alkylene oxide structure preferably has 3 to 6 carbon atoms, and more preferably 3 to 4 carbon atoms.
- the (B) compound having one (meth) acryloyl group for example, a compound obtained by adding (meth) acrylic acid to one end of a polyalkylene oxide or a (meth) acrylic compound at one end of a polyalkylene oxide
- a compound obtained by adding (meth) acrylic acid to one end of a polyalkylene oxide or a (meth) acrylic compound at one end of a polyalkylene oxide examples thereof include compounds in which an acid is added and the other end is alkyl-etherified or allyl-etherified, phthalic acid compounds, and the like, which are preferable from the viewpoint of releasability and cured film flexibility.
- Examples of such a compound include phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group, polypropylene glycol to which an average of 2 mol of propylene oxide is added, Mole of ethylene glycol added to nonylphenol and 4- (normal) nonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate, which is a (meth) acrylate of compound added to nonylphenol, polypropylene to which an average of 1 mole of propylene oxide is added (Meth) acrylate, which is a compound obtained by adding glycol and polyethylene glycol having an average of 5 moles of ethylene oxide added to nonylphenol.
- Examples of the compound having two (meth) acryloyl groups in the molecule include a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain, or an alkylene in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in a block.
- Compounds having (meth) acryloyl groups at both ends of the oxide chain can be exemplified.
- Examples of such a compound include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (Polethylene glycol (meth) acrylates such as (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of a 12 mol ethylene oxide chain And polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and the like.
- polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound for example, an average of 3 mol of ethylene oxide is further added to both ends of polypropylene glycol having an average of 12 mol of propylene oxide.
- Dimethacrylate of glycol, and dimethacrylate of glycol having an average of 15 moles of ethylene oxide further added to both ends of polypropylene glycol having an average of 18 moles of propylene oxide added thereto, FA-023M, FA-024M, FA-027M (product name) And Hitachi Chemical Co., Ltd.). These are preferred from the viewpoint of flexibility, resolution, adhesion and the like.
- a compound having (meth) acryloyl groups at both ends by alkylene oxide modification of bisphenol A is known as a compound having resolution and adhesion. It is preferable from the viewpoint of.
- R 1 and R 2 each independently represent a hydrogen atom or a methyl group
- A is C 2 H 4
- B is C 3 H 6
- n 1 and n 3 are each independently 1 to 39
- N1 + n3 is an integer of 2 to 40
- n2 and n4 are each independently an integer of 0 to 29, and n2 + n4 is an integer of 0 to 30
- the arrangement of (BO)-repeating units may be random or block. In the case of a block, one of-(A-O)-and-(BO)-may be on the bisphenyl group side.
- the compound represented by ⁇ can be used.
- dimethacrylate of polyethylene glycol having an average of 5 moles of ethylene oxide added to both ends of bisphenol A and polyethylene glycol having an average of 2 moles of ethylene oxide added to both ends of bisphenol A
- Polymethacrylate dimethacrylate in which 1 mole of ethylene oxide is added to both ends of dimethacrylate and bisphenol A on the average, respectively, is preferable in terms of resolution and adhesion.
- a compound in which the aromatic ring in the general formula (I) has a hetero atom and / or a substituent may be used.
- hetero atom examples include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group.
- substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom.
- the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.
- the compound having three or more (meth) acryloyl groups in the molecule the compound having three or more moles of a group capable of adding an alkylene oxide group in the molecule as a central skeleton, and further having an ethyleneoxy group, a propyleneoxy group, It can be obtained by converting an alcohol obtained by adding an alkyleneoxy group such as a butyleneoxy group to a (meth) acrylate.
- examples of the compound capable of forming the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and an isocyanurate ring.
- These compounds include tri (meth) acrylates, for example, ethoxylated glycerine tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate (eg, Trimethacrylate in which an average of 21 moles of ethylene oxide is added to trimethylolpropane, and trimethacrylate in which an average of 30 moles of ethylene oxide is added to trimethylolpropane are preferable from the viewpoint of flexibility, adhesion, and bleed-out suppression); (Meth) acrylates, for example, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate ; Penta (meth) acrylate,
- Compounds having three or more (meth) acryloyl groups can significantly improve the adhesiveness when heated and developed after exposure, and particularly when the elapsed time after exposure is long, the adhesiveness is good. Is preferred from the viewpoint of exhibiting the following, and more preferably a compound having three or more methacryl groups.
- Pentaerythritol tetra (meth) acrylate is preferable.
- Pentaerythritol tetra (meth) acrylate may be tetra (meth) acrylate in which a total of 1 to 40 moles of alkylene oxide is added to four terminals of pentaerythritol.
- hexa (meth) acrylate hexa (meth) acrylate in which 1 to 40 moles of ethylene oxide is added to 6 terminals of dipentaerythritol, and 1 to 20 moles of ⁇ at 6 terminals of dipentaerythritol in total.
- Hexa (meth) acrylate with caprolactone added is preferred.
- the (B) compound having an ethylenically unsaturated double bond which contains a (meth) acrylate compound having three or more ethylenically unsaturated double bonds, has an adhesive property when heated and developed after exposure. Is remarkably improved, and is particularly preferable from the viewpoint that good adhesion can be obtained even when the elapsed time after exposure is long. From the same viewpoint, it is more preferable to include a (meth) acrylate compound having four or more ethylenically unsaturated double bonds, and to include a (meth) acrylate compound having five or more ethylenically unsaturated double bonds. More preferably, a (meth) acrylate compound having at least 6 ethylenically unsaturated double bonds is contained. From the same viewpoint, these are preferably methacrylate compounds.
- Compounds having three or more, four or more, five or more, and six or more ethylenically unsaturated double bonds are considered to have an effect of increasing the crosslink density at the time of polymerization by exposure. In many cases, a desired crosslinking density cannot be obtained due to the influence of steric hindrance due to the large number.
- a compound having three or more ethylenically unsaturated double bonds is preferable, a compound having four or more ethylenically unsaturated double bonds is more preferable, and a compound having five or more ethylenically unsaturated double bonds is more preferable.
- Compounds having at least six ethylenically unsaturated double bonds are also subjected to heat treatment after exposure to improve the mobility in the system, so that the effects of steric hindrance even when the number of functional groups is large. , And high adhesion can be obtained.
- a compound having three or more ethylenically unsaturated double bonds more preferably a compound having four or more ethylenically unsaturated double bonds, even more preferably a compound having five or more ethylenically unsaturated double bonds,
- the content of the compound having 6 or more ethylenically unsaturated double bonds is preferably 3% by mass or more, more preferably 5% by mass or more based on the solid content of the photosensitive resin composition. More preferably, it is still more preferably 7% by mass or more, particularly preferably 10% by mass or more.
- the upper limit of the content is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and preferably 15% by mass or less, from the viewpoint of exhibiting the effect of the heat treatment after exposure. Is particularly preferred.
- Examples of the (meth) acrylate compound having three or more ethylenically unsaturated bonds include: Tri (meth) acrylates, such as ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane tri (meth) acrylate (eg, flexible, As a preferred example from the viewpoint of adhesion and bleed-out suppression, tri (meth) acrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane, and trimethyl acrylate obtained by adding an average of 30 moles of ethylene oxide to trimethylolpropane (Meth) acrylate) and the like; Tetra (meth) acrylate, for example, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tetra
- the (meth) acrylate compound having three or more ethylenically unsaturated bonds preferably has a weight average molecular weight of 500 or more, more preferably 700 or more, and still more preferably 900 or more, from the viewpoint of suppressing bleed-out. .
- pentaerythritol tetra (meth) acrylate is preferable.
- pentaerythritol tetra (meth) acrylate tetra (meth) acrylate in which a total of 1 to 40 mol of alkylene oxide is added to four terminals of pentaerythritol is preferable.
- Tetra (meth) acrylate has the following general formula (II):
- R 3 to R 6 each independently represent an alkyl group having 1 to 4 carbon atoms
- X represents an alkylene group having 2 to 6 carbon atoms
- m 1 , m 2 , m 3 and m 4 is each independently an integer of 0 to 40
- m 1 + m 2 + m 3 + m 4 is 1 to 40
- a plurality of X is more preferably a tetramethacrylate compound represented by ⁇ , which may be the same as or different from each other.
- the use of the photosensitive resin composition containing the tetramethacrylate compound represented by the general formula (II) can significantly improve the adhesiveness when heated and developed after exposure, and particularly after exposure. It is preferable from the viewpoint of realizing good adhesion even when the elapsed time becomes long.
- At least one of the groups R 3 to R 6 is preferably a methyl group, and more preferably all of the groups R 3 to R 6 are a methyl group.
- X is preferably —CH 2 —CH 2 — from the viewpoint of obtaining a desired resolution, a swelling shape, and a remaining film ratio of the resist pattern.
- m 1 , m 2 , m 3, and m 4 are each independently an integer of 1 to 20 from the viewpoint of obtaining desired resolution, swell shape, and residual film ratio of the resist pattern. And more preferably an integer of 2 to 10. Further, in the general formula (II), m 1 + m 2 + m 3 + m 4 is preferably from 1 to 36 or from 4 to 36.
- Examples of the compound represented by the general formula (II) include pentaerythritol (poly) alkoxytetramethacrylate and the like.
- Examples of the compound represented by the general formula (II) include compounds listed in JP-A-2013-156369, for example, pentaerythritol (poly) alkoxytetramethacrylate and the like.
- hexa (meth) acrylate compound hexa (meth) acrylate in which 1 to 24 mol of ethylene oxide is added to 6 terminals of dipentaerythritol in total, and 1 to 10 mol in total of 6 terminals of dipentaerythritol are added.
- Hexa (meth) acrylate to which ⁇ -caprolactone is added is preferred.
- the photosensitive material according to the present embodiment can significantly improve the adhesiveness when heated and developed after exposure, and in particular, from the viewpoint of achieving good adhesiveness even when the elapsed time after exposure is long.
- the conductive resin composition contains, as the compound (B) having an ethylenically unsaturated bond, a (meth) acrylate compound having four or more ethylenically unsaturated bonds and having an alkylene oxide chain.
- the ethylenically unsaturated bond is more preferably derived from a methacryloyl group
- the alkylene oxide chain is more preferably an ethylene oxide chain.
- the conductive resin composition preferably contains (B) a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton as a compound having an ethylenically unsaturated bond.
- alkylene oxide chain include an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentylene oxide chain, a hexylene oxide chain, and the like.
- the photosensitive resin composition contains a plurality of alkylene oxide chains, they may be the same or different.
- an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain are more preferable, an ethylene oxide chain and a propylene oxide chain are more preferable, and an ethylene oxide chain is particularly preferable.
- the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is an ester of a dipentaerythritol compound in which at least one of a plurality of hydroxyl groups is modified with an alkyleneoxy group, and (meth) acrylic acid.
- Six hydroxyl groups of the dipentaerythritol skeleton may be modified with an alkyleneoxy group.
- the number of ester bonds in one ester molecule may be from 1 to 6, and is preferably 6.
- Examples of the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include, for example, a hexamer obtained by adding an alkylene oxide to dipentaerythritol in an average of 4 to 30 mol, an average of 6 to 24 mol, or an average of 10 to 14 mol.
- (Meth) acrylates are examples of the (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton.
- a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton it is possible to significantly improve the adhesiveness when heated and then developed after exposure, and particularly, the elapsed time after the exposure.
- R is preferable that the average value of all n is 4 or more, or that n is 1 or more.
- R is preferably a methyl group.
- the content of the (meth) acrylate compound having the alkylene oxide chain and the dipentaerythritol skeleton based on the total solid content in the photosensitive resin composition is preferably 1% by mass to 50% by mass, more preferably 5% by mass. It is in the range of from 40% by mass to 40% by mass, more preferably from 7% by mass to 30% by mass.
- the content of the (meth) acrylate compound having three or more ethylenically unsaturated bonds is more than 0% by mass and 40% by mass or less based on the total solid content of the photosensitive resin composition. Is preferred. When the content exceeds 0% by mass, the adhesion after heating and development after exposure can be remarkably improved, and particularly, even when the elapsed time after exposure is long, good adhesion can be obtained. When the content is 40% by mass or less, the flexibility of the cured resist is improved, and the peeling time tends to be shortened.
- the content is more preferably 2% by mass or more and 30% by mass or less, and further preferably 4% by mass or more and 25% by mass or less.
- the photosensitive resin composition contains (B2) a butylene oxide chain or a propylene oxide chain as a compound having an ethylenically unsaturated bond, and It is preferable to include a compound having two (meth) acryloyl groups.
- the compound having a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups is preferably 500 or more, more preferably 700 or more, and further preferably, from the viewpoint of suppressing bleed-out. Has a molecular weight of 1000 or more.
- (B2) As a compound having a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups, polypropylene glycol (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol ( (Meth) acrylate, polytetramethylene glycol di (meth) acrylate, and the like.
- the compound having a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups may contain an ethylene oxide chain in addition to the butylene oxide chain or the propylene oxide chain.
- the compound (b2) having a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups is preferably 1 to 20, more preferably 4 to 15, and Preferred are (meth) acrylates or di (meth) acrylates having 6 to 12 C 4 H 8 O or C 3 H 6 O.
- the content of the compound having (b2) a butylene oxide chain or a propylene oxide chain and one or two (meth) acryloyl groups is more than 0% by mass based on the total solid content of the photosensitive resin composition. And 20% by mass or less.
- (B) in order to suppress the bleed-out of the components of the dry film resist and improve the storage stability, (B) preferably 70 mass% based on the total solid content of the compound having an ethylenically unsaturated bond. % Or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 100% by weight, is a compound having a weight average molecular weight of 500 or more. From the viewpoint of suppressing bleed-out and the chemical resistance of the resist pattern, the weight average molecular weight of the compound (B) having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, still more preferably 830 or more, particularly preferably 830 or more.
- the weight average molecular weight of the compound (B) having an ethylenically unsaturated bond can be determined as the molecular weight calculated from the molecular structure of the compound (B) having an ethylenically unsaturated bond.
- the molecular weight can be determined by weighting the molecular weight of each compound by the content.
- the concentration of the methacryloyl group in the compound (B) having an ethylenically unsaturated bond is preferably 0.20 mol / 100 g or more. , More preferably at least 0.30 mol / 100 g, even more preferably at least 0.35 mol / 100 g.
- the upper limit of the concentration of the methacryloyl group is not limited as long as the polymerizability and the alkali developability are ensured, but may be, for example, 0.90 mol / 100 g or less or 0.80 mol / 100 g or less.
- the value of (methacryloyl group concentration / (methacryloyl group concentration + acryloyl group concentration)) in the compound (B) having an ethylenically unsaturated bond is preferably 0.50 or more, more preferably 0. .60 or more, more preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.
- the (meth) acrylate compounds described above can be used independently or in combination.
- the photosensitive resin composition may also contain other compounds as the compound (B) having an ethylenically unsaturated bond.
- Other compounds include a (meth) acrylate having a urethane bond, a compound obtained by reacting an ⁇ , ⁇ -unsaturated carboxylic acid with a polyhydric alcohol, and a reaction of an ⁇ , ⁇ -unsaturated carboxylic acid with a glycidyl group-containing compound.
- 1,6-hexanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate.
- the ratio of the compound having an ethylenically unsaturated double bond to the total solid content of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable to set this ratio to 5% by mass or more from the viewpoints of sensitivity, resolution and adhesion. This ratio is more preferably set to 20% by mass or more, and further preferably 30% by mass or more. On the other hand, it is preferable to set the ratio to 70% by mass or less from the viewpoint of suppressing edge fuses and peeling delay of the cured resist. It is more preferable that this ratio be 50% by mass or less.
- the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol / 100 g or more is defined as the solid content of the photosensitive resin composition.
- the content is preferably 0 to 18% by mass.
- the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol / 100 g or more as the compound (B) having an ethylenically unsaturated double bond is as follows.
- the solid content of the photosensitive resin composition is preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and 6% by mass or less. More preferably, it is more preferably 3% by mass or less, most preferably 1% by mass or less.
- the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.20 mol / 100 g or more as the compound (B) having an ethylenically unsaturated double bond is the same as that of the photosensitive resin composition. It is preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, even more preferably 6% by mass or less, based on the solid content of the product. It is particularly preferably at most 3% by mass, most preferably at most 1% by mass.
- the value of [(A) content of alkali-soluble polymer] / [(B) content of compound having an ethylenically unsaturated double bond] is preferably 0.94 or more.
- [(A) the content of the alkali-soluble polymer] / [(B) the content of the compound having an ethylenically unsaturated double bond] is more preferably 1.04 or more, It is more preferably 1.11 or more, particularly preferably 1.21 or more, more preferably 1.30 or more, and most preferably 1.35 or more.
- Increasing the value of [(A) content of alkali-soluble polymer] / [(B) content of compound having an ethylenically unsaturated double bond] is generally alkali-soluble, that is, hydrophilic.
- the Tg in the system increases and the mobility decreases, so that the double bond reaction rate decreases, and as a result, the adhesion decreases.
- the value of [(A) content of alkali-soluble polymer] / [(B) content of compound having an ethylenically unsaturated double bond] is large, and heat treatment is also performed after exposure. Therefore, even if the value of [(A) content of alkali-soluble polymer] / [(B) content of compound having an ethylenically unsaturated double bond] is large, mobility in the system is improved and double bond is obtained. It is considered that the effect of the present invention was able to be realized by improving the reaction rate and further improving the adhesion by the interaction of the carboxyl group of the alkali-soluble polymer with copper.
- the value of [(A) content of alkali-soluble polymer] / [(B) content of compound having an ethylenically unsaturated double bond] is preferably 5 or less, more preferably 4 or less. , More preferably 3 or less, particularly preferably 2 or less, and most preferably 1.5 or less.
- the photopolymerization initiator is a compound that polymerizes a monomer by light.
- the photosensitive resin composition of the present embodiment comprises a compound generally known in the art as (C-1) a photopolymerization initiator ((C) a photopolymerization initiator). Including.
- the total content of the photopolymerization initiator (C-1) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 10% by mass. It is in the range of 1% to 7% by weight, particularly preferably 0.1% to 6% by weight.
- the total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity. From the viewpoint of obtaining image properties, the content is preferably 20% by mass or less.
- photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic esters, oximes Esters and acridines (eg, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, and 9- (m-methylphenyl) acridine are preferred in terms of sensitivity, resolution, and adhesion.
- acridines eg, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, and 9- (m-methylphenyl) acridine are preferred in terms of sensitivity, resolution, and adhesion.
- hexaarylbiimidazole, pyrazoline compounds, and anthracene compounds eg, 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, and 9,10-diethoxyanthracene.
- Coumarin compound) Eg, 7-diethylamino-4-methylcoumarin is preferred in terms of sensitivity, resolution, and adhesion
- N-arylamino acid or its ester compound eg, N-phenylglycine is preferred in terms of sensitivity, resolution, and adhesion
- a halogen compound eg, tribromomethylphenylsulfone
- 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6-trimethylbenzo Irdiphenyl-phosphine oxide and triphenylphosphine oxide may be used.
- aromatic ketones examples include benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Can be. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion.
- the content of the aromatic ketone in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by mass. % By mass.
- hexaarylbiimidazole examples include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5'-Tetrakis- (3-methoxyphenyl) -biimidazo
- the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer. %, More preferably from 0.1% to 6% by mass, and still more preferably from 1% to 5% by mass.
- the photosensitive resin composition contains a pyrazoline compound and an anthracene compound (eg, 9,10-diphenylanthracene, 9,10 -Dibutoxyanthracene and 9,10-diethoxyanthracene are preferred in terms of sensitivity, resolution and adhesion).
- anthracene compound eg, 9,10-diphenylanthracene, 9,10 -Dibutoxyanthracene and 9,10-diethoxyanthracene are preferred in terms of sensitivity, resolution and adhesion).
- Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazolin, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazolin, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazolin, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl Phenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl)
- the content of the photosensitizer in the photosensitive resin composition is preferably set to 0.1 from the viewpoint of transmittance and from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer.
- the photosensitive resin composition contains anthracene and / or an anthracene derivative as (C-2) a photopolymerization initiator ((C) a photopolymerization initiator). Can be used.
- anthracene and / or an anthracene derivative as a photopolymerization initiator can significantly improve the adhesiveness when heated and developed after exposure, and particularly, the elapsed time after exposure. This is advantageous from the viewpoint that good adhesion can be obtained even when the length is longer.
- the anthracene and / or anthracene derivative can function as a polymerization initiator by absorbing the first active light having a central wavelength of less than 390 nm and the second active light having a central wavelength of 390 nm or more.
- the activation light is, for example, laser light.
- the photosensitive resin composition can have sensitivity to the first active light and the second active light, and can be used for two-wavelength exposure.
- the anthracene and / or anthracene derivative can also be selected to have a plurality of absorption maxima in the wavelength range of the first active light and the second active light.
- the central wavelength of the first active light is preferably 350 to 380 nm, more preferably 355 to 375 nm, and particularly preferably 375 nm.
- the central wavelength of the second active light is preferably 400 to 410 nm, more preferably 402 to 408 nm, and particularly preferably 405 nm (h-line).
- the total content of the photopolymerization initiator (C-2) in the photosensitive resin composition is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 10% by mass. It is in the range of 1% to 7% by weight, particularly preferably 0.1% to 6% by weight.
- the total content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining a sufficient sensitivity, and sufficiently transmits light to the bottom of the resist to obtain a good high solution. From the viewpoint of obtaining image properties, the content is preferably 20% by mass or less.
- anthracene and anthracene derivatives can significantly improve the adhesion when heated and developed after exposure, and are particularly advantageous in that they achieve good adhesion even when the elapsed time after exposure is long. It is. From the same viewpoint, the anthracene derivative is preferably an alkoxy group having 1 to 40 carbon atoms and / or a substituent at a 9-position and / or a 10-position, more preferably a 9,10-position. Having an aryl group having 6 to 40 carbon atoms.
- the anthracene derivative can significantly improve the adhesiveness when heated and developed after exposure, and particularly, a viewpoint of achieving good adhesiveness even when the elapsed time after exposure is long. It is preferable that at least one of the 9th and 10th positions has an optionally substituted alkoxy group having 1 to 40 carbon atoms, and at least one of the 9th and 10th positions has a substituent. It is more preferred to have an optionally substituted alkoxy group having 1 to 30 carbon atoms. From the viewpoint of obtaining good adhesiveness and resolution, it is preferable to have an optionally substituted alkoxy group having 1 to 40 carbon atoms at the 9 and 10 positions, and to have a substituent at the 9 and 10 positions.
- an optionally substituted alkoxy group having 1 to 30 carbon atoms It is more preferred to have an optionally substituted alkoxy group having 1 to 30 carbon atoms.
- the carbon numbers of the 9-position and 10-position groups may be the same or different.
- the optionally substituted alkoxy group include: Methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, 2-methylpropoxy, 1-methylpropoxy, n-pentyloxy, isoamyloxy, n- Hexyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tetradecyloxy group, hexadecyloxy group, eicosyloxy group, cyclohexyloxy group, norbornyloxy group, A tricyclodecanyloxy group, a tetracyclododecy
- the anthracene derivative can significantly improve the adhesiveness when heated and developed after exposure, and particularly, a viewpoint of achieving good adhesiveness even when the elapsed time after exposure is long. It is preferable that at least one of the 9-position and the 10-position has an optionally substituted aryl group having 6 to 40 carbon atoms, and at least one of the 9-position and the 10-position has a substituent. It is more preferred to have an optionally substituted aryl group having 6 to 30 carbon atoms.
- Adhesion when heated and developed after exposure can be significantly improved, and in particular, from the viewpoint of achieving good adhesion even when the elapsed time after exposure is long, to the ninth and tenth positions, It is preferable to have an aryl group having 6 to 40 carbon atoms which may have a substituent, and to have an aryl group having 6 to 30 carbon atoms which may have a substituent at positions 9 and 10. More preferred.
- the carbon numbers of the 9-position and 10-position groups may be the same or different. Further, the groups at the 9-position and the 10-position may be the same group or different groups.
- the group at the 9-position is an alkoxy group having 1 to 40 carbon atoms which may have a substituent
- the group at the 10-position is an aryl group having 6 to 40 carbon atoms which may have a substituent. There may be.
- Examples of the optionally substituted aryl group having 6 to 40 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group and an anthracenyl group; an aryl group to which an alkoxy group is added, such as a methoxyphenyl group and an ethoxyphenyl group; An aryl group to which an alkyl group is added, such as a tolyl group, a xylyl group, a mesityl group, or a nonylphenyl group; an aryl group to which a halogen is added, such as a chlorophenyl group; an aryl group to which a hydroxyl group is added, such as a hydroxyphenyl group. Can be Of these, a phenyl group is more preferred.
- the anthracene derivative is preferably represented by the following general formula (IV).
- R 1 is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, Represents an unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or an N (R ′) 2 group, and two or more R 1 may be bonded to each other to form a cyclic structure, wherein the cyclic structure is a heteroatom May be included.
- X independently represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a —N (R ′) — group, a —CO—O— group, a —CO—S— group, a —SO 2 —O— group , —SO 2 —S—, —SO 2 —N (R ′) —, —O—CO—, —S—CO—, —O—SO 2 — or S—SO 2 — Show.
- X excludes a single bond and R 1 excludes a combination of hydrogen atoms (that is, unsubstituted anthracene).
- R ′ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, Represents up to 40 substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups, and R's may be mutually bonded to form a cyclic structure, and the cyclic structure may include a heteroatom .
- P is an integer of 1 to 10, preferably 2 to 4.
- Examples of the substituted or unsubstituted alkyl group having 1 to 40 carbon atoms in R 1 and R ′ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-pentyl group, -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-eicosyl group, i -Propyl group, i-butyl group, sec-butyl group and t-butyl group.
- R 1 and R ′ Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in R 1 and R ′ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a bridged group having 6 to 20 carbon atoms.
- Alicyclic hydrocarbon group for example, norbornyl group, tricyclodecanyl group, tetracyclododecyl group, adamantyl group, methyladamantyl group, ethyladamantyl group, butyladamantyl group and the like);
- alkenyl group having 2 to 4 carbon atoms in R 1 and R ′ include vinyl and propenyl groups.
- substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R 1 and R ′ include phenyl, biphenyl, naphthyl, anthracenyl, methoxyphenyl, ethoxyphenyl, tolyl, and xylyl.
- Examples of the substituted or unsubstituted heteroaryl group in R 1 and R ′ include a group containing one or more hetero atoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in a substituted or unsubstituted aryl group, for example, a pyridyl group. , Imidazolyl group, morpholinyl group, piperidyl group, pyrrolidyl group and the like.
- each hydrocarbon group of R 1 and R ′ may be substituted by a substituent.
- substituents include a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 4 carbon atoms (eg, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, A hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, etc., an alkoxyl group having 1 to 4 carbon atoms (eg, a methoxy group, Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc.), cyano group, cyanoalkyl group having 2 to 5 carbon atoms ( For example,
- each of the hydrocarbon groups of R 1 and R ′ is substituted with a halogen atom.
- the anthracene derivative preferably has an alkoxy group substituted by a halogen atom at the 9-position and / or the 10-position.
- R 1 and R ′ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl Groups, n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, camphoroyl group, norbornyl group, p-toluyl group, benzyl group, methylbenzyl group, phenyl group and 1-naphthyl group.
- X examples include a single bond, an oxygen atom, a sulfur atom, a —N (R ′) — group, a —O—CO— group, and an O—SO 2 — group.
- R ′ is hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, cyclopentyl group, cyclohexyl.
- Groups, camphoroyl groups, norbornyl groups or benzyl groups are preferred.
- Examples of the compound represented by the general formula (IV) include, for example, 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-t-butylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 9-vinylanthracene, 9-phenylanthracene, 9,10-diphenylanthracene, 2-bromo-9,10-diphenylanthracene, 9- (4-bromophenyl) -10-phenylanthracene, 9- (1-naphthyl) anthracene , 9- (2-naphthyl) anthracene, 2-bromo-9,10-bis (2-naphthyl) anthracene, 2,6-dibromo-9,10-bis (2-naphthyl) anthracene, 9,10-diethoxy Anthracene, 9,10-di
- 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di (2 -Ethylhexyloxy) anthracene and 9,10-bis- (3-chloropropoxy) anthracene are preferred, and the adhesion after heating and development after exposure can be remarkably improved.
- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene, 9,10-bis- (3-chloro) Propoxy) anthracene is more preferred, and 9,10-dibutoxyanthracene and , 10-diphenyl anthracene, 9,10-bis - (3-chloropropoxy) anthracene is particularly preferable.
- the compound represented by the general formula (IV) may be used alone or in combination of two or more.
- the photoinitiator preferably comprises (1) 9,10-diphenylanthracene; (2) comprises 9,10-dialkoxyanthracene; (3) comprises an anthracene derivative having a halogen atom; (4) (5) Includes compounds in which the 9- and / or 10-position alkoxy group of 9,10-dialkoxyanthracene is modified with one or more halogen atoms. And / or (6) a compound having a halogen atom directly bonded to the anthracene skeleton.
- the compound represented by the general formula (IV) can remarkably improve the adhesiveness when heated and developed after exposure, and especially when the elapsed time after exposure is long, the adhesiveness is excellent. And is used for two-wavelength exposure using a first active light having a central wavelength of less than 390 nm and a second active light having a central wavelength of 390 nm or more. It is also advantageous in that a photosensitive resin composition exhibiting excellent sensitivity, adhesion and resolution can be provided.
- the (C-2) photopolymerization initiator preferably contains an anthracene derivative having a halogen atom.
- a preferred example of the anthracene derivative having a halogen atom is a halogen-substituted 9,10-dialkoxyanthracene.
- a preferred example of the halogen substituent is a compound in which the 9- and / or 10-position alkoxy group of 9,10-dialkoxyanthracene is modified with one or more halogens.
- Preferred alkoxy groups include those exemplified above as alkoxy groups having 1 to 40 carbon atoms.
- anthracene derivative a compound having a halogen atom directly bonded to the anthracene skeleton is also preferable.
- anthracene compounds include 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10- (2-naphthyl) anthracene, and 9-bromo-10- (1-naphthyl) Anthracene, 9- (2-biphenylyl) -10-bromoanthracene, 9- (4-biphenylyl) -10-bromoanthracene, 9-bromo-10- (9-phenanthryl) anthracene, 2-bromoanthracene, 9-bromoanthracene , 2-chloroanthracene and 9,10-dibromoanthracene.
- the total amount of the anthracene and the anthracene derivative, or in a preferred embodiment, the amount of the compound represented by the general formula (IV) is preferably 0.05 to 5% by mass relative to the total solid content of the photosensitive resin composition, It is more preferably in the range of 0.1 to 3% by mass, and particularly preferably in the range of 0.1 to 1.0% by mass.
- the photopolymerization initiator may further contain a compound other than anthracene and an anthracene derivative, and examples of such a compound include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin and Benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic esters, oxime esters, acridines (eg, 9-phenylacridine, bisacridinylheptane, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine is preferred in terms of sensitivity, resolution, and adhesion), hexaarylbiimidazole, pyrazoline compounds, and coumarin compounds (for example, 7-diethylamino-4-methylcoumarin is preferred for sensitivity, resolution, and (Preferable in terms of adhesion) N- arylamino
- aromatic ketones examples include benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Can be. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. Further, from the viewpoint of transmittance, the content of the aromatic ketone in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by mass. % By mass.
- hexaarylbiimidazole examples include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5'-Tetrakis- (3-methoxyphenyl) -biimidazo
- the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably from 0.05% by mass to 8% by mass, more preferably from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer. It is in the range of 0.1% by mass to 7% by mass, more preferably 1% by mass to 6% by mass.
- the photosensitive resin composition contains one or more pyrazoline compounds as a photopolymerization initiator (C-2). Is preferred.
- Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazolin, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazolin, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazolin, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropyl Phenyl) -pyrazolin, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl
- the photosensitive resin composition further contains (D) an inhibitor from the viewpoint that the shortest developing time of the unexposed portion is not extended even if heating after exposure is performed.
- the inhibitor (D) is preferably a radical polymerization inhibitor or a phenol derivative, and more preferably a phenol derivative.
- the inhibitor may be originally contained in the raw material components to be used, or may be added at the time of preparing the photosensitive resin composition preparation liquid. When the raw material components used are originally contained, the content of the inhibitor can be quantified by GC-MS analysis or the like after preparing the photosensitive resin laminate.
- radical polymerization inhibitor examples include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenylhydroxyamine aluminum salt is preferred.
- phenol derivative examples include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) ), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5- Di-tert-butylhydroquinone, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-tert-butyl-5-ethylphenyl) methane, triethylene glycol-bis [ 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) pro Onate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl)
- the ratio of the (D) inhibitor to the total solid content of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. This ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, from the viewpoint that the shortest developing time of the unexposed portion is not extended even if heating after exposure is performed.
- the content is more preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more.
- this ratio is preferably 10% by mass or less, more preferably 2% by mass or less, and more preferably 1% by mass or less, from the viewpoint of little decrease in sensitivity and improvement in resolution. Is more preferably 0.5% by mass or less, most preferably 0.3% by mass or less.
- Benzotriazole derivative it is preferable to include (E) a benzotriazole derivative from the viewpoint that no discoloration is observed on the copper surface after development and removal of the photosensitive resin composition layer even when heating after exposure is performed.
- the benzotriazole derivative preferably contains at least one compound selected from the group consisting of benzotriazoles and carboxybenzotriazoles.
- benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.
- carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylene Carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like can be mentioned. Of these, carboxybenzotriazoles are particularly preferred.
- the content of the benzotriazole derivative is preferably 0.001% by mass to 3% by mass when the total solid content of the photosensitive resin composition is 100% by mass.
- the content of 0.001% by mass or more is preferred from the viewpoint that no discoloration is observed on the copper surface after development and removal of the photosensitive resin composition layer even when heating after exposure is performed. It is more preferably at least 02% by mass, even more preferably at least 0.05% by mass.
- setting the content to 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye, more preferably 2% by mass or less, still more preferably 1% by mass or less, and 0.5% by mass. % Or less, particularly preferably 0.3% by mass or less.
- the decolorization of the dye can be measured by the transmittance at a wavelength of 630 nm.
- a high transmittance at a wavelength of 630 nm indicates that the dye has been decolorized.
- the transmittance of the laminate of the support film and the photosensitive resin composition layer at a wavelength of 630 nm is preferably 80% or less, more preferably 78% or less, preferably 75% or less, and more preferably 72% or less. Is preferably 70% or less, more preferably 68% or less, preferably 65% or less, preferably 62% or less, and preferably 60% or less, It is preferably at most 58%, more preferably at most 55%, preferably at most 52%, more preferably at most 50%.
- This transmittance is the transmittance of the laminate of the support film and the photosensitive resin composition layer, and does not include the protective layer.
- the photosensitive resin composition may optionally contain additives such as a dye, a plasticizer, an antioxidant, and a stabilizer.
- additives such as a dye, a plasticizer, an antioxidant, and a stabilizer.
- the additives listed in JP-A-2013-156369 may be used.
- the photosensitive resin composition may further contain at least one selected from the group consisting of a dye (for example, a leuco dye, a fluoran dye or the like) and a coloring substance, if desired.
- the coloring substance examples include fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, and Malachite Green (for example, Eizen (registered trademark) MALACHITE @ GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20 and Diamond Green (for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.).
- the content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total solid content of the photosensitive resin composition is 100% by mass. Making the content 0.001% by mass or more is preferable from the viewpoint of improving the handleability of the photosensitive resin composition. On the other hand, setting the content to 1% by mass or less is preferable from the viewpoint of maintaining the storage stability of the photosensitive resin composition.
- the photosensitive resin composition is preferable from the viewpoint of visibility because the exposed portion develops a color by containing a dye, and when an inspection machine or the like reads an alignment marker for exposure, an exposed portion and an unexposed portion are used. Is more advantageous because it is easier to recognize.
- Preferred dyes in this respect include leuco dyes and fluoran dyes.
- the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green] and the like.
- leuco crystal violet bis (4-dimethylaminophenyl) phenylmethane
- the content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass based on the total solid content of the photosensitive resin composition. Making the content 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed portion and the unexposed portion. This content is more preferably at least 0.2% by mass, particularly preferably at least 0.4% by mass. On the other hand, it is preferable to set the content to 10% by mass or less from the viewpoint of maintaining storage stability. This content is more preferably 5% by mass or less, particularly preferably 2% by mass or less.
- the leuco dye in the photosensitive resin composition in combination with the halogen compound described above in the photopolymerization initiator (C) from the viewpoint of optimizing the adhesion and the contrast.
- the content of the halogen compound in the photosensitive resin composition is 0.01% by mass when the total solid content of the photosensitive resin composition is 100% by mass. % To 3% by mass is preferable from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.
- the photosensitive resin composition may further contain an epoxy compound of bisphenol A.
- bisphenol A epoxy compounds include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminal.
- the photosensitive resin composition may further contain a plasticizer.
- the plasticizer include phthalic esters (eg, diethyl phthalate), o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and acetyl tricitrate.
- ADEKANOL SDX-1569, ADEKANOL SDX-1570, ADEKANOL SDX-1571, ADEKANOL SDX-479 (all manufactured by Asahi Denka Co., Ltd.), Newpole BP-23P, Newpole BP-3P, Newpole BP-5P, New Pole BPE-20T, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Uniall DB-400, Uniall DAB-800, Uniall DA-350F, Uniall DA- Compounds having a bisphenol skeleton such as 400, UNIOL DA-700 (all manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U
- the content of the plasticizer in the photosensitive resin composition is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 30% by mass, based on the total solid mass of the photosensitive resin composition. It is. It is preferable to set the content to 1% by mass or more from the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film. On the other hand, it is preferable to set the content to 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow. When the amount of water in the photosensitive resin composition is large, local plasticization of the photosensitive resin composition is rapidly promoted, and an edge fuse is generated.
- the water content in the photosensitive resin composition is 0.7% or less based on the photosensitive resin composition after coating and drying the photosensitive resin composition preparation liquid on the support film.
- the water content in the photosensitive resin composition is preferably 0.65% or less, more preferably 0.6% or less, preferably 0.55% or less, and is 0.5% or less.
- the photosensitive resin composition can be used in the production of a photosensitive resin laminate in the form of a photosensitive resin composition prepared by dissolving it in a solvent.
- the solvent include ketones and alcohols.
- the ketones are represented by methyl ethyl ketone (MEK) and acetone.
- the alcohols are represented by methanol, ethanol, and isopropanol.
- the solvent is used in an amount such that the viscosity at 25 ° C. of the photosensitive resin composition preparation liquid to be applied on the support layer in the production of the photosensitive resin laminate is from 500 mPa ⁇ s to 4,000 mPa ⁇ s. It is preferably added to the resin composition.
- a transparent support film that transmits light emitted from an exposure light source is preferable.
- a support film for example, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be stretched as required.
- the support film has a haze of preferably 5% or less, more preferably 2% or less, still more preferably 1.5% or less, particularly preferably 1.0% or less, from the viewpoint of suppressing light scattering during exposure.
- the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less. The thinner the film is, the more advantageous it is for improving the image formability and economy.
- a film having a thickness of 10 ⁇ m to 30 ⁇ m is preferably used.
- the size of the fine particles such as a lubricant contained in the support film is preferably less than 5 ⁇ m.
- the support film may have a single-layer structure or a multilayer structure in which resin layers formed from a plurality of compositions are laminated.
- a multilayer structure there may be an antistatic layer.
- a resin layer containing fine particles is formed on one surface A, and fine particles are formed on the other surface B in the same manner as (1) Surface A. , (2) a smaller amount of fine particles than the surface A, (3) finer particles than the surface A, and (4) no fine particles.
- the size of the fine particles at this time is preferably less than 1.5 ⁇ m from the viewpoint of the effect of the present invention.
- the protective layer used in the photosensitive resin laminate is that the adhesion to the photosensitive resin layer is sufficiently smaller than that of the support layer, and the protective layer can be easily peeled off.
- a polyethylene film or a polypropylene film can be preferably used as the protective layer.
- a film having excellent releasability as disclosed in JP-A-59-202457 can be used.
- the thickness of the protective layer is preferably from 10 ⁇ m to 100 ⁇ m, more preferably from 10 ⁇ m to 50 ⁇ m.
- a gel called fisheye may be present on the polyethylene film surface.
- the fish eyes may be transferred to the photosensitive resin layer.
- the material of the protective layer is preferably stretched polypropylene.
- a specific example is Oji Paper Co., Ltd.'s Alphan E-200A.
- the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 1 ⁇ m to 300 ⁇ m, more preferably 3 ⁇ m to 100 ⁇ m, particularly preferably 5 ⁇ m to 60 ⁇ m, and most preferably 10 ⁇ m to 30 ⁇ m. As the thickness of the photosensitive resin layer decreases, the resolution improves, and as the thickness increases, the film strength improves.
- a method for manufacturing the photosensitive resin laminate will be described.
- a method for producing a photosensitive resin laminate by sequentially laminating a support layer, a photosensitive resin layer, and, if necessary, a protective layer a known method can be employed.
- the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent for dissolving the same to form a uniform solution, first coated on a support layer using a bar coater or a roll coater, and then dried to dry the solvent. By removing, a photosensitive resin layer composed of a photosensitive resin composition can be laminated on the support layer.
- a protective layer is laminated on the photosensitive resin layer to produce a photosensitive resin laminate.
- the method can include an exposure step of exposing the photosensitive resin composition, a heating step of heating the exposed photosensitive resin composition, and a development step of developing the photosensitive resin composition.
- the resist pattern include a printed wiring board, a semiconductor element, a printing plate, a liquid crystal display panel, a touch panel, a flexible substrate, a lead frame substrate, a COF (chip-on-film) substrate, a semiconductor package substrate, a liquid crystal transparent electrode, and a liquid crystal.
- Pattern for TFT wiring, PDP (plasma display panel) electrode, and the like will be described below.
- the printed wiring board is manufactured through the following steps.
- the heating temperature during lamination is generally 40 ° C to 160 ° C.
- thermocompression bonding at the time of lamination at least twice, the adhesion of the obtained resist pattern to the substrate can be improved.
- a two-stage laminator provided with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly pressed several times to pass through the rolls.
- the exposure step is preferably performed by an exposure method by direct drawing of a drawing pattern, or by an exposure method of projecting an image of a photomask through a lens, and more preferably by an exposure method by direct drawing of a drawing pattern.
- the advantage of the photosensitive resin composition according to the present embodiment is more remarkable in the exposure method by direct drawing of a drawing pattern or the exposure method of projecting an image of a photomask through a lens, and the exposure by direct drawing of a drawing pattern This is particularly noticeable in the method.
- the exposure step is an exposure method using direct writing
- the laser light has a center wavelength of 350 nm or more and 380 nm or less, or has a center wavelength of 400 nm or more and 410 nm or less.
- the exposure is preferably performed by a method of exposing with a first laser light having a center wavelength of less than 390 nm and a second laser light having a center wavelength of 390 nm or more. More preferably, the center wavelength of the first laser light is 350 nm or more and 380 nm or less, and the center wavelength of the second laser light is 400 nm or more and 410 nm or less.
- the exposed photosensitive resin composition is preferably subjected to a heating step at about 30 ° C. to about 200 ° C., more preferably at 30 ° C. to 150 ° C. More preferably, the temperature is in the range of 60 to 120 ° C.
- a heating furnace, a thermostat, a hot plate, a hot-air dryer, an infrared dryer, a hot roll, or the like of a hot air, infrared or far-infrared method can be used. It is preferable that the heating method is a hot roll in that processing can be performed in a short time, and it is more preferable that the number of hot rolls is two or more.
- the resin can be heated even if the system contains 15% by mass or more of styrene and / or a styrene derivative structural unit and is heated and then developed after exposure, even if the system has a high styrene skeleton content, the resin can be heated.
- the mobility is improved, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can both be highly compatible.
- (C-2) at least anthracene and / or an anthracene derivative are used as the photopolymerization initiator ((C) photopolymerization initiator), and the photopolymerization initiator is heated and then developed after being exposed to light.
- the mobility of the resin is improved, and for example, even in a system having a relatively high content of a styrene skeleton, the hydrophobicity of the styrene skeleton and the reactivity of a carbon-carbon double bond can be highly compatible.
- the adhesion can be significantly improved. And, since the adhesiveness is remarkably improved, good adhesiveness can be obtained even when the elapsed time after exposure is long.
- the support layer on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution, so that the resist pattern is formed on the substrate.
- a developing solution of an alkaline aqueous solution As the alkaline aqueous solution, an aqueous solution of Na 2 CO 3 or K 2 CO 3 is used.
- the alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but is preferably a Na 2 CO 3 aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and about 20 ° C. to about 40 ° C.
- a circuit board is formed by etching or plating a substrate having a resist pattern manufactured by the above method.
- Etching step or plating step The substrate surface exposed by development (for example, the copper surface of the copper clad laminate) is etched or plated to produce a conductor pattern.
- Stripping Step Thereafter, the resist pattern is stripped from the substrate using an appropriate stripping solution.
- the stripping solution used here include an alkaline aqueous solution and an amine-based stripping solution.
- a resist pattern formed from the photosensitive resin composition of the present invention through post-exposure baking exhibits good releasability with respect to an amine-based release liquid, and a release piece is not excessively miniaturized. It has the following features. Therefore, it is preferable to use an amine-based stripping solution as the stripping solution, since the advantageous effects of the present invention are maximized.
- the amine contained in the amine-based stripping solution may be an inorganic amine or an organic amine.
- examples of the inorganic amine include ammonia, hydroxylamine, hydrazine and the like.
- Examples of the organic amine include ethanolamine, propanolamine, alkylamine, cyclic amine, and quaternary ammonium salt. Specific examples of these include: Examples of the ethanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, aminoethoxyethanol and the like; As propanolamine, for example, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and the like; Examples of the alkylamine include monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, tetraethylenepentamine and the like; Cyclic amines such as choline, morpholine and the like; Examples of quatern
- the amine-based release agent used in the present invention may be an aqueous solution containing one or more of the amines exemplified above.
- concentration of the amine in the aqueous solution may be appropriately set depending on the purpose, the composition of the photosensitive resin layer, the development conditions, and the like.
- the amine-based release agent used in the present invention may further contain additives usually used for the release agent, such as a surfactant, an antifoaming agent, a pH adjuster, a preservative, and an anti-redeposition agent. Good.
- the peeling step is performed at a temperature of, for example, 0 ° C. or more and 100 ° C. or less, preferably room temperature (23 ° C.) or more and 50 ° C. or less, for example, for 1 second to 1 hour, preferably 10 seconds to 10 minutes.
- the substrate from which the resist pattern has been removed may be washed with pure water or the like, if desired.
- the photosensitive resin laminate of this embodiment includes a printed wiring board, a flexible substrate, a lead frame substrate, a touch panel substrate, a COF substrate, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, a PDP electrode, and the like.
- This is a photosensitive resin laminate suitable for the production of a conductive pattern.
- the weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK) KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (using a calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) It was determined in terms of polystyrene. Further, the degree of dispersion of the polymer was calculated as a ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
- a photosensitive resin composition layer was formed.
- the dry thickness of the photosensitive resin composition layer was 25 ⁇ m.
- a 19 ⁇ m-thick polyethylene film (manufactured by Tamapoly Corporation, GF-818) is laminated as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film is not laminated. A laminate was obtained.
- ⁇ Board leveling> As a substrate for evaluation of image quality, a 0.4 mm thick copper-clad laminate obtained by laminating 35 ⁇ m rolled copper foil was jetted with a spraying agent (# 400, manufactured by Uji Denka Kogyo KK) at a spray pressure of 0.2 MPa. After scrub polishing, the substrate surface was washed with a 10% by mass H 2 SO 4 aqueous solution.
- ⁇ Laminate> While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was applied to a copper-clad laminate preheated to 50 ° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). Lamination was performed at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
- the evaluation substrate 7 minutes after the exposure was heated by a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation).
- the roll temperature was 105 ° C.
- the air pressure was 0.30 MPa
- the laminating speed was 0.5 m / min. Note that if the elapsed time after the exposure is lengthened, the effect of the heating is lost, so that the heating is usually performed for about one minute after the exposure. For this reason, heating after 7 minutes of exposure in this embodiment is a very severe condition.
- ⁇ Development> After peeling off the polyethylene terephthalate film (support layer), a 1% by mass aqueous solution of Na 2 CO 3 at 30 ° C. is sprayed for a predetermined period of time using an alkali developing machine (developing machine for dry film manufactured by Fuji Kiko Co., Ltd.) for development. Was done.
- the time of the development spray was twice the minimum development time, and the time of the water spray after development was four times the minimum development time. At this time, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was taken as the shortest development time.
- A Normal Shortest Development Time After laminating the photosensitive resin laminate on the substrate and peeling the support film, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was measured.
- B Shortest development time after heating After laminating the photosensitive resin laminate on the substrate, it was heated by a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). The roll temperature was 105 ° C., the air pressure was 0.30 MPa, and the laminating speed was 0.1 m / min.
- ⁇ The shortest developing times of (B) and (A) are the same (no delay)
- ⁇ The shortest developing time of (B) is 1 to 3 seconds longer than the shortest developing time of (A) (with a delay)
- Table 1-1 The above evaluation results are shown in Table 1-1 together with the components of the photosensitive resin compositions of Examples and Comparative Examples.
- Table 1-2 shows the names of the components represented by abbreviations in Table 1-1.
- the heating conditions after the exposure in this example are very strict conditions because the heating is performed 7 minutes after the exposure.
- the adhesion was 12.0 ⁇ m. That is, in the composition of Comparative Example 1, no effect was observed by heating after 7 minutes of exposure, but in Example 1, the adhesion could be improved even under very severe conditions. Further, under the condition of heating after one minute of exposure, 10.0 ⁇ m adhesion was obtained in each of the compositions of Example 1 and Comparative Example 1.
- Second embodiment evaluation was performed on a photosensitive resin composition in which (B) the compound having an ethylenically unsaturated double bond includes a (meth) acrylate compound having three or more ethylenically unsaturated double bonds.
- Evaluation samples were prepared in the same manner as in the above-described first example using the components shown in Table 2-1 below.
- ⁇ Exposure> Two hours after the lamination, the evaluation substrate was exposed with a direct drawing exposure machine (Nuvogo 1000, manufactured by Orbotech Co., Ltd., light source: 375 nm (30%) + 405 nm (70%)) using a 41-step Stoffer tablet. . The exposure was performed with an exposure amount such that the maximum number of remaining film steps was 19 when exposed and developed using the 41-step stofer step tablet as a mask.
- ⁇ Development> After peeling off the polyethylene terephthalate film (support layer), a 1% by mass aqueous solution of Na 2 CO 3 at 30 ° C. is sprayed for a predetermined period of time using an alkali developing machine (developing machine for dry film manufactured by Fuji Kiko Co., Ltd.) for development. Was done.
- the time of the developing spray was twice the shortest developing time, and the time of the water spray after the developing was three times the shortest developing time. At this time, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was taken as the shortest development time.
- Evaluation was performed in the same manner as in the first example except that the steps of exposure to development were performed as described above.
- the above evaluation results are shown in Table 2-1 together with the components of the photosensitive resin compositions of Examples and Comparative Examples.
- Table 2-2 shows the names of the components represented by abbreviations in Table 2-1.
- the heating conditions after the exposure in this example are very strict conditions because the heating is performed 7 minutes after the exposure.
- the adhesiveness when the compositions of Example 1 and Comparative Example 1 were developed without heating after exposure was 11.8 ⁇ m. That is, in the composition of Comparative Example 1, no effect was observed by heating after 7 minutes of exposure, but in Example 1, the adhesion could be improved even under very severe conditions. Further, under the condition of heating after one minute of exposure, in each of the compositions of Example 1 and Comparative Example 1, adhesion of 9.6 ⁇ m was obtained.
- the adhesion is good under the general heating conditions after exposure, the adhesion is improved under the severe condition of heating 7 minutes after exposure in this example. Absent.
- the present invention was able to improve the adhesion even under such severe post-exposure heating conditions. Thereby, when manufacturing a circuit board, good adhesion can be obtained even if the elapsed time after exposure becomes long, so that a high-definition circuit pattern can be stably formed.
- (C-2) a photosensitive resin composition in which the photopolymerization initiator contains anthracene and / or an anthracene derivative was evaluated. Evaluation samples were prepared in the same manner as in the first example described above, using the components shown in Table 3-1 below. ⁇ Exposure> Two hours after the lamination, the evaluation substrate was exposed with a direct drawing exposure machine (Nuvogo 1000, manufactured by Orbotech Co., Ltd., light source: 375 nm (30%) + 405 nm (70%)) using a 41-step Stoffer tablet. . The exposure was performed with an exposure amount such that the maximum number of remaining film steps was 21 when exposed and developed using the 41-step stofer step tablet as a mask.
- a direct drawing exposure machine Nuvogo 1000, manufactured by Orbotech Co., Ltd., light source: 375 nm (30%) + 405 nm (70%)
- ⁇ Development> After peeling off the polyethylene terephthalate film (support layer), a 1% by mass aqueous solution of Na 2 CO 3 at 30 ° C. is sprayed for a predetermined period of time using an alkali developing machine (developing machine for dry film manufactured by Fuji Kikko Co., Ltd.) for development. Was done.
- the time of the developing spray was twice the shortest developing time, and the time of the water spray after the developing was three times the shortest developing time. At this time, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was taken as the shortest development time.
- the adhesion is good under the general heating conditions after exposure, the adhesion is not improved under the severe condition of heating 7 minutes after exposure.
- the adhesion can be improved even under such severe post-exposure heating conditions. That is, according to the composition of the present invention, when manufacturing a circuit board, it is possible to obtain good adhesion even if the elapsed time after exposure becomes longer, so that a high-definition circuit pattern can be stabilized. And can be formed.
- the photosensitive resin composition according to the present invention it is possible to remarkably improve the adhesiveness when heated and developed after exposure, and in particular, even when the elapsed time after exposure is long, good adhesion is obtained. And can be widely used as a photosensitive resin composition.
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Abstract
Description
第二の方法は、上記基板面に、銅、半田、ニッケル、スズ等のメッキ処理を行った後、第一の方法と同様にしてレジストパターン部分を除去し、更に、現れた基板面(例えば銅張積層板の銅面)をエッチングする方法(メッキ法)である。エッチングには塩化第二銅、塩化第二鉄、銅アンモニア錯体溶液等が用いられる。
露光後に加熱してから現像したときの密着性を著しく向上させることができ、特には露光後の経過時間が長くなったときにおいても良好な密着性を実現する感光性樹脂組成物を提供することにある。
また、本発明者らは鋭意検討を続けた結果、感光性樹脂組成物を構成するアルカリ可溶性高分子において、特定の光重合開始剤を用いることにより上記目的を達成することができることに想到し、本発明を完成させるに至った。
すなわち、本発明は以下のとおりである。
[1]
露光後、加熱してから現像して樹脂硬化物を得るための感光性樹脂組成物であって、前記感光性樹脂組成物が、該感光性樹脂組成物の全固形分質量基準で、以下の成分:
(A)アルカリ可溶性高分子:10質量%~90質量%;
(B)エチレン性不飽和二重結合を有する化合物:5質量%~70質量%;及び
(C)光重合開始剤:0.01質量%~20質量%;
を含み、
前記(A)アルカリ可溶性高分子全体におけるスチレン及び/又はスチレン誘導体の構成単位が15質量%以上であることを特徴とする感光性樹脂組成物。
[2]
前記(B)エチレン性不飽和二重結合を有する化合物として、ビスフェノールA骨格の濃度が0.18mol/100g以上である化合物(B-1)の含有量が、前記感光性樹脂組成物の固形分に対して0以上18質量%以下である、[1]に記載の感光性樹脂組成物。
[3]
更に(D)禁止剤を含む、[1]または[2]に記載の感光性樹脂組成物。
[4]
更に(E)ベンゾトリアゾール誘導体を含む、[1]~[3]のいずれかに記載の感光性樹脂組成物。
[5]
前記(B)エチレン性不飽和二重結合を有する化合物は、エチレン性不飽和二重結合を3個以上有する(メタ)アクリレート化合物を含む、[1]~[4]のいずれかに記載の感光性樹脂組成物。
[6]
前記(B)エチレン性不飽和二重結合を有する化合物は、エチレン性不飽和二重結合を4個以上有する(メタ)アクリレート化合物を含む、[5]に記載の感光性樹脂組成物。
[7]
前記(B)エチレン性不飽和二重結合を有する化合物は、エチレン性不飽和二重結合を6個以上有する(メタ)アクリレート化合物を含む、[6]に記載の感光性樹脂組成物。
[8]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が0.94以上である、[1]~[7]のいずれかに記載の感光性樹脂組成物。
[9]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.04以上である、[8]に記載の感光性樹脂組成物。
[10]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.11以上である、[9]に記載の感光性樹脂組成物。
[11]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.21以上である、[10]に記載の感光性樹脂組成物。
[12]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.30以上である、[11]に記載の感光性樹脂組成物。
[13]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が5以下である、[1]~[12]のいずれかに記載の感光性樹脂組成物。
[14]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が4以下である、[13]に記載の感光性樹脂組成物。
[15]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が3以下である、[14]に記載の感光性樹脂組成物。
[16]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が2以下である、[15]に記載の感光性樹脂組成物。
[17]
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.5以下である、[16]に記載の感光性樹脂組成物。
[18]
露光後、加熱してから現像して樹脂硬化物を得るための感光性樹脂組成物であって、前記感光性樹脂組成物が、前記感光性樹脂組成物の全固形分質量基準で、以下の成分:
(A)アルカリ可溶性高分子:10質量%~90質量%;
(B)エチレン性不飽和二重結合を有する化合物:5質量%~70質量%;及び
(C)光重合開始剤:0.01質量%~20質量%;
を含み、
前記(C)光重合開始剤がアントラセン及び/又はアントラセン誘導体を含むことを特徴とする感光性樹脂組成物。
[19]
前記アントラセン誘導体は、9位及び/又は10位に、置換基を有していてもよい炭素数1~40のアルコキシ基及び/又は置換基を有していてもよい炭素数6~40のアリール基を有する、[18]に記載の感光性樹脂組成物。
[20]
前記アントラセン誘導体は、9,10位に、置換基を有していてもよい炭素数1~40のアルコキシ基及び/又は置換基を有していてもよい炭素数6~40のアリール基を有する、[18]又は[19]に記載の感光性樹脂組成物。
[21]
前記(C)光重合開始剤は、9,10-ジフェニルアントラセンを含む、[20]に記載の感光性樹脂組成物。
[22]
前記(C)光重合開始剤は、9,10-ジアルコキシアントラセンを含む、[20]に記載の感光性樹脂組成物。
[23]
前記(C)光重合開始剤は、ハロゲン原子を有するアントラセン誘導体を含む、[18]~[22]のいずれかに記載の感光性樹脂組成物。
[24]
前記(C)光重合開始剤は、9,10-ジアルコキシアントラセンのハロゲン置換体を含む、[23]に記載の感光性樹脂組成物。
[25]
前記(C)光重合開始剤は、9,10-ジアルコキシアントラセンの9位及び/又は10位のアルコキシ基が1つ以上のハロゲン原子で修飾されている化合物を含む、[24]に記載の感光性樹脂組成物。
[26]
前記(C)光重合開始剤は、アントラセン骨格に直接結合したハロゲン原子を有する化合物を含む、[18]~[25]のいずれかに記載の感光性樹脂組成物。
[27]
前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が15質量%以上である、[18]~[26]のいずれかに記載の感光性樹脂組成物。
[28]
前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が25質量%以上である、[1]~[27]のいずれかに記載の感光性樹脂組成物。
[29]
前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が30質量%以上である、[28]に記載の感光性樹脂組成物。
[30]
前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が35質量%以上である、[29]に記載の感光性樹脂組成物。
[31]
前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が40質量%以上である、[30]に記載の感光性樹脂組成物。
[32]
前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が90質量%以下である、[1]~[31]のいずれかに記載の感光性樹脂組成物。
[33]
前記(A)アルカリ可溶性高分子が、単量体成分としてベンジル(メタ)アクリレートを更に含む、[1]~[32]のいずれかに記載の感光性樹脂組成物。
[34]
[1]~[33]のいずれかに記載の感光性樹脂組成物を露光する工程と、露光された前記感光性樹脂組成物を加熱する加熱工程と、加熱された前記感光性樹脂組成物を現像する現像工程と、を含むレジストパターンの形成方法。
[35]
前記加熱工程における加熱温度が30℃~150℃の範囲である、[34]に記載のレジストパターンの形成方法。
[36]
前記露光工程を、描画パターンの直接描画による露光方法、又はフォトマスクの像を、レンズを通して投影させる露光方法により行う、[34]又は[35]に記載のレジストパターンの形成方法。
[37]
前記露光工程を、描画パターンの直接描画による露光方法により行う、[34]又は[35]に記載のレジストパターンの形成方法。
[38]
前記加熱工程を、露光から15分以内に行う、[34]~[37]のいずれかに記載のレジストパターンの形成方法。
[39]
前記露光工程を、中心波長390nm未満の第1のレーザー光と、中心波長390nm以上の第2のレーザー光とで露光する方法により行う、[34]~[38]のいずれかに記載のレジストパターンの形成方法。
[40]
前記第1のレーザー光の中心波長が350nm以上380nm以下であり、前記第2のレーザー光の中心波長が400nm以上410nm以下である、[39]に記載のレジストパターンの形成方法。
[41]
[34]~[40]のいずれかに記載の方法により製造されたレジストパターンを有する基板に対してエッチング又はめっきを施すことにより回路基板を形成する、回路基板の製造方法。
[42]
中心波長390nm未満の第1のレーザー光と、中心波長390nm以上の第2のレーザー光とで露光して樹脂硬化物を得るための感光性樹脂組成物である、[1]~[33]のいずれかに記載の感光性樹脂組成物。
[43]
前記第1のレーザー光の中心波長が350nm以上380nm以下であり、前記第2のレーザー光の中心波長が400nm以上410nm以下である、[42]に記載の感光性樹脂組成物。
本発明の感光性樹脂組成物は、露光後、加熱してから現像して樹脂硬化物を得るための感光性樹脂組成物であって、感光性樹脂組成物が、該感光性樹脂組成物の全固形分質量基準で、以下の成分:(A)アルカリ可溶性高分子:10質量%~90質量%;(B)エチレン性不飽和二重結合を有する化合物:5質量%~70質量%;及び(C)光重合開始剤:0.01質量%~20質量%;を含む。
そして特に本実施形態の感光性樹脂組成物は、(A)アルカリ可溶性高分子が複数種類のアルカリ可溶性高分子からなる場合には、(A)アルカリ可溶性高分子全体におけるスチレン及び/又はスチレン誘導体の構成単位が15質量%以上であることを特徴とする。
以下、各成分を順に説明する。
本開示で、(A)アルカリ可溶性高分子は、アルカリ物質に溶け易い高分子を包含する。より具体的には、(A)アルカリ可溶性高分子に含まれるカルボキシル基の量は、酸当量で100~600であり、好ましくは250~450である。酸当量とは、その分子中に1当量のカルボキシル基を有する重合体の質量(単位:グラム)を言う。(A)アルカリ可溶性高分子中のカルボキシル基は、感光性樹脂層に、アルカリ水溶液に対する現像性及び剥離性を与えるために必要である。酸当量を100以上にすることは、現像耐性、解像性、及び密着性を向上させる観点から好ましい。そして酸当量を250以上にすることがより好ましい。一方で、酸当量を600以下にすることは、現像性及び剥離性を向上させる観点から好ましい。そして酸当量を450以下にすることがより好ましい。本開示で、酸当量は、電位差滴定装置を用い、0.1mol/LのNaOH水溶液で滴定する電位差滴定法により測定される値である。
フェニルアルキル基を有するコモノマーとしては、フェニルエチル(メタ)アクリレート等が挙げられる。
ベンジル基を有するコモノマーとしては、ベンジル基を有する(メタ)アクリレート、例えば、ベンジル(メタ)アクリレート、クロロベンジル(メタ)アクリレート等;ベンジル基を有するビニルモノマー、例えば、ビニルベンジルクロライド、ビニルベンジルアルコール等が挙げられる。中でもベンジル(メタ)アクリレートが好ましい。
芳香族炭化水素基を有する単量体成分を含有しない(A)アルカリ可溶性高分子は、後述する第一の単量体の少なくとも1種を重合することにより得られることが好ましく、第一の単量体の少なくとも1種と後述する第二の単量体の少なくとも1種とを共重合することにより得られることがより好ましい。
なお、本明細書において「(メタ)アクリル酸」とは、アクリル酸又はメタクリル酸を意味し、「(メタ)アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味し、かつ「(メタ)アクリレート」とは、「アクリレート」又は「メタクリレート」を意味する。
アラルキル基を有する単量体、及び/又はスチレンを単量体として含有することが、露光後に加熱してから現像したときの密着性を著しく向上させることができ、特には露光後の経過時間が長くなったときにおいても良好な密着性を発現する観点から好ましい。例えば、メタクリル酸とベンジルメタクリレートとスチレンを含む共重合体、メタクリル酸とメチルメタクリレートとベンジルメタクリレートとスチレンを含む共重合体等が好ましい。
スチレン誘導体としては、例えば、メチルスチレン、ビニルトルエン、tert-ブトキシスチレン、アセトキシスチレン、4-ビニル安息香酸、スチレンダイマー、スチレントリマー等が挙げられる。
(B)エチレン性不飽和二重結合を有する化合物は、硬化性及び(A)アルカリ可溶性高分子との相溶性の観点から、分子内に(メタ)アクリロイル基を有する化合物を含むことが好ましい。(B)化合物中の(メタ)アクリロイル基の数は、1個以上であればよい。
また、γ-クロロ-β-ヒドロキシプロピル-β'-メタクリロイルオキシエチル-о-フタレートを含むと、上記観点に加えて、感度、解像性、密着性の観点でも好ましい。
具体的には下記一般式(I):
例えば、ビスフェノ-ルAの両端にそれぞれ平均5モルずつのエチレンオキサイドを付加したポリエチレングリコ-ルのジメタクリレ-ト、ビスフェノ-ルAの両端にそれぞれ平均2モルずつのエチレンオキサイドを付加したポリエチレングリコ-ルのジメタクリレ-ト、ビスフェノ-ルAの両端にそれぞれ平均1モルずつのエチレンオキサイドを付加したポリエチレングリコ-ルのジメタクリレ-トが、解像性、密着性の点で好ましい。
また、上記一般式(I)中の芳香環が、ヘテロ原子及び/又は置換基を有する化合物を用いてもよい。
ヘキサ(メタ)アクリレートとしては、ジペンタエリスリトールの6つの末端に合計1~40モルのエチレンオキサイドが付加されているヘキサ(メタ)アクリレート、ジペンタエリスリトールの6つの末端に合計1~20モルのε-カプロラクトンが付加されているヘキサ(メタ)アクリレートが好ましい。
トリ(メタ)アクリレート、例えば、エトキシ化グリセリントリ(メタ)アクリレート、エトキシ化イソシアヌル酸トリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、及びトリメチロールプロパントリ(メタ)アクリレート(例えば、柔軟性、密着性、及びブリードアウト抑制の観点での好適例として、トリメチロールプロパンに平均21モルのエチレンオキサイドを付加したトリ(メタ)アクリレート、及び、トリメチロールプロパンに平均30モルのエチレンオキサイドを付加したトリ(メタ)アクリレート)等;
テトラ(メタ)アクリレート、例えば、ジトリメチロールプロパンテトラ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート等;
ペンタ(メタ)アクリレート、例えば、ジペンタエリスリトールペンタ(メタ)アクリレート等;
ヘキサ(メタ)アクリレート、例えば、ジペンタエリスリトールヘキサ(メタ)アクリレート、等が挙げられる。
これらの中でも、テトラ、ペンタ又はヘキサ(メタ)アクリレートが好ましい。
(b2)ブチレンオキサイド鎖又はプロピレンオキサイド鎖と、1個又は2個の(メタ)アクリロイル基とを有する化合物は、ブリードアウトの抑制の観点から、好ましくは500以上、より好ましくは700以上、更に好ましくは1000以上の分子量を有する。
[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値を大きくすることは、一般的にはアルカリ可溶性、つまりは親水性の成分が多くなり、かつ系内のTgも上がりモビリティが低下することにより二重結合反応率が低下し、結果として密着性が低下することが一般的である。しかし本発明においては、[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が大きく、かつ露光後に加熱処理も行うことにより、[(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が大きくても系内のモビリティが向上して二重結合反応率も向上し、更にはアルカリ可溶性高分子が有するカルボキシル基の銅との相互作用による密着性向上の効果も加わり、本発明の効果を実現できたと考える。
(C)光重合開始剤は、光によりモノマーを重合させる化合物である。
(C-1)光重合開始剤
本実施形態の感光性樹脂組成物は、(C-1)光重合開始剤((C)光重合開始剤)として本技術分野において一般に知られている化合物を含む。
ピラゾリン化合物としては、例えば、1-フェニル-3-(4-tert-ブチル-スチリル)-5-(4-tert-ブチル-フェニル)-ピラゾリン、1-(4-(ベンゾオキサゾール-2-イル)フェニル)-3-(4-tert-ブチル-スチリル)-5-(4-tert-ブチル-フェニル)-ピラゾリン、1-フェニル-3-(4-ビフェニル)-5-(4-tert-ブチル-フェニル)-ピラゾリン、1-フェニル-3-(4-ビフェニル)-5-(4-tert-オクチル-フェニル)-ピラゾリン、1-フェニル-3-(4-イソプロピルスチリル)-5-(4-イソプロピルフェニル)-ピラゾリン、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、1-フェニル-3-(3,5-ジメトキシスチリル)-5-(3,5-ジメトキシフェニル)-ピラゾリン、1-フェニル-3-(3,4-ジメトキシスチリル)-5-(3,4-ジメトキシフェニル)-ピラゾリン、1-フェニル-3-(2,6-ジメトキシスチリル)-5-(2,6-ジメトキシフェニル)-ピラゾリン、1-フェニル-3-(2,5-ジメトキシスチリル)-5-(2,5-ジメトキシフェニル)-ピラゾリン、1-フェニル-3-(2,3-ジメトキシスチリル)-5-(2,3-ジメトキシフェニル)-ピラゾリン、1-フェニル-3-(2,4-ジメトキシスチリル)-5-(2,4-ジメトキシフェニル)-ピラゾリン等が上記の観点から好ましく、挙げられる。これらの中でも、1-フェニル-3-(4-ビフェニル)-5-(4-tert-ブチル-フェニル)-ピラゾリンがより好ましい。
また、本実施形態において、感光性樹脂組成物は、(C-2)光重合開始剤((C)光重合開始剤)として、アントラセン及び/又はアントラセン誘導体を含むものを用いることができる。
置換基を有していてもよいアルコキシ基としては:
メトキシ基、エトキシ基、n-プロポキシ基、i-プロポキシ基、n-ブトキシ基、t-ブトキシ基、2-メチルプロポキシ基、1-メチルプロポキシ基、n-ペンチルオキシ基、イソアミルオキシ基、n-ヘキシルオキシ基、2-エチルヘキシルオキシ基、ノニルオキシ基、デシルオキシ基、ウンデシルオキシ基、ドデシルオキシ基、テトラデシルオキシ基、ヘキサデシルオキシ基、エイコシルオキシ基、シクロヘキシルオキシ基、ノルボルニルオキシ基、トリシクロデカニルオキシ基、テトラシクロドデシルオキシ基、アダマンチルオキシ基、メチルアダマンチルオキシ基、エチルアダマンチルオキシ基、及びブチルアダマンチルオキシ基;
ハロゲンで修飾されたアルコキシ基、例えば、クロロブトキシ基、クロロプロポキシ基;
ヒドロキシル基が付加したアルコキシ基、例えば、ヒドロキシブチルオキシ基;
シアノ基が付加したアルコキシ基、例えば、シアノブトキシ基;
アルキレンオキサイド基が付加したアルコキシ基、例えば、メトキシブトキシ基;
アリール基が付加したアルコキシ基、例えば、フェノキシブトキシ基、
等が挙げられる。この中でn-ブトキシ基がより好ましい。
本実施の形態では、感光性樹脂組成物は、更に(D)禁止剤を含むことが、露光後の加熱を行っても、未露光部分の最短現像時間が延長しない観点から好ましい。同様の観点から、(D)禁止剤としては、ラジカル重合禁止剤、またはフェノール誘導体であることが好ましく、フェノール誘導体であることがより好ましい。(D)禁止剤は、使用する原料成分に元から含まれていてもよく、感光性樹脂組成物調合液の調合時に添加してもよい。使用する原料成分に元から含まれている場合は、感光性樹脂積層体を作成後に、GC-MS分析等により禁止剤含有量を定量することができる。
更に(E)ベンゾトリアゾール誘導体を含むことが、露光後の加熱を行っても、感光性樹脂組成物層を現像除去した後の銅表面に変色が見られない観点から好ましい。(E)ベンゾトリアゾール誘導体としては、ベンゾトリアゾール類、及びカルボキシベンゾトリアゾール類から成る群より選ばれる少なくとも1種の化合物を含有することが好ましい。
ベンゾトリアゾール類としては、例えば、1,2,3-ベンゾトリアゾール、1-クロロ-1,2,3-ベンゾトリアゾール、ビス(N-2-エチルヘキシル)アミノメチレン-1,2,3-ベンゾトリアゾール、ビス(N-2-エチルヘキシル)アミノメチレン-1,2,3-トリルトリアゾール、ビス(N-2-ヒドロキシエチル)アミノメチレン-1,2,3-ベンゾトリアゾール等が挙げられる。
カルボキシベンゾトリアゾール類としては、例えば、4-カルボキシ-1,2,3-ベンゾトリアゾール、5-カルボキシ-1,2,3-ベンゾトリアゾール、N-(N,N-ジ-2-エチルヘキシル)アミノメチレンカルボキシベンゾトリアゾール、N-(N,N-ジ-2-ヒドロキシエチル)アミノメチレンカルボキシベンゾトリアゾール、N-(N,N-ジ-2-エチルヘキシル)アミノエチレンカルボキシベンゾトリアゾール等が挙げられる。
これらの中ではカルボキシベンゾトリアゾール類が特に好ましい。
感光性樹脂組成物は、所望により、染料、可塑剤、酸化防止剤、安定化剤等の添加剤を含んでよい。例えば、特開2013-156369号公報に列挙されている添加剤を使用してよい。
(染料及び着色物質)
本実施の形態では、感光性樹脂組成物は、所望により、染料(例えばロイコ染料、フルオラン染料等)及び着色物質から成る群より選ばれる少なくとも1種を更に含有してもよい。
ロイコ染料としては、トリス(4-ジメ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]、ビス(4-ジメチルアミノフェニル)フェニルメタン[ロイコマラカイトグリーン]等が挙げられる。とりわけ、コントラストが良好となる観点から、ロイコ染料としては、ロイコクリスタルバイオレットを用いることが好ましい。感光性樹脂組成物中のロイコ染料の含有量は、感光性樹脂組成物の全固形分質量に対して0.1質量%~10質量%であることが好ましい。この含有量を0.1質量%以上にすることは、露光部分と未露光部分とのコントラストを良好にする観点から好ましい。この含有量は、0.2質量%以上にすることがより好ましく、0.4質量%以上にすることが特に好ましい。一方で、この含有量を10質量%以下にすることが保存安定性を維持するという観点から好ましい。この含有量は、5質量%以下にすることがより好ましく、2質量%以下にすることが特に好ましい。
本実施の形態では、感光性樹脂組成物は、ビスフェノールAのエポキシ化合物類を更に含有してもよい。ビスフェノールAのエポキシ化合物類としては、例えば、ビスフェノールAをポリプロピレングリコールで修飾し末端をエポキシ化した化合物等が挙げられる。
本実施の形態では、感光性樹脂組成物は、可塑剤を更に含有してもよい。可塑剤としては、例えば、フタル酸エステル類(例えば、ジエチルフレート等)、o-トルエンスルホン酸アミド、p-トルエンスルホン酸アミド、クエン酸トリブチル、クエン酸トリエチル、アセチルクエン酸トリエチル、アセチルクエン酸トリ-n-プロピル、アセチルクエン酸トリ-n-ブチル、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレングリコールアルキルエ-テル、ポリプロプレンレングリコールアルキルエーテル等が挙げられる。また、アデカノールSDX-1569、アデカノールSDX-1570、アデカノールSDX-1571、アデカノールSDX-479(以上旭電化(株)製)、ニューポールBP-23P、ニューポールBP-3P、ニューポールBP-5P、ニューポールBPE-20T、ニューポールBPE-60、ニューポールBPE-100、ニューポールBPE-180(以上三洋化成(株)製)、ユニオールDB-400、ユニオールDAB-800、ユニオールDA-350F、ユニオールDA-400、ユニオールDA-700 (以上日本油脂(株)製)、BA-P4Uグリコール、BA-P8グリコール(以上日本乳化剤(株)製)等のビスフェノール骨格を有する化合物も挙げられる。
感光性樹脂組成物中の水分量が多いと、感光性樹脂組成物の局所的な可塑化が急激に促進され、エッジフューズが発生する。エッジフューズを抑制する観点から感光性樹脂組成物調合液を支持フィルムに塗布、乾燥後の感光性樹脂組成物を基準として、感光性樹脂組成物中の水分量は0.7%以下であることが好ましい。感光性樹脂組成物中の水分量は0.65%以下であることが好ましく、0.6%以下であることが好ましく、0.55%以下であることが好ましく、0.5%以下であることが好ましく、0.45%以下であることが好ましく、0.4%以下であることが好ましく、0.35%以下であることが好ましく、0.3%以下であることが好ましく、0.25%以下であることが好ましく、0.2%以下であることが好ましい。
感光性樹脂組成物は、溶剤に溶解させて感光性樹脂組成物調合液の形態で、感光性樹脂積層体の製造に使用できる。溶剤としては、ケトン類、アルコール類等が挙げられる。前記ケトン類は、メチルエチルケトン(MEK)、アセトンに代表される。前記アルコール類は、メタノール、エタノール、及びイソプロパノールに代表される。溶剤は、感光性樹脂積層体の製造に際して、支持層上に塗布する感光性樹脂組成物調合液の25℃における粘度が、500mPa・s~4,000mPa・sとなるような量で、感光性樹脂組成物に添加されることが好ましい。
支持フィルムとしては、露光光源から放射される光を透過する透明な支持フィルムが好ましい。このような支持フィルムとしては、例えば、ポリエチレンテレフタレートフィルム、ポリビニルアルコールフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリ塩化ビニリデンフィルム、塩化ビニリデン共重合フィルム、ポリメタクリル酸メチル共重合体フィルム、ポリスチレンフィルム、ポリアクリロニトリルフィルム、スチレン共重合体フィルム、ポリアミドフィルム、セルロース誘導体フィルム等が挙げられる。これらのフィルムは、必要に応じて延伸されたものも使用可能である。
支持フィルムとしては、露光時の光散乱を抑制する観点からヘイズ5%以下のものであることが好ましく、2%以下がより好ましく、1.5%以下が更に好ましく、1.0%以下が特に好ましい。同様の観点から、感光層と接する面の表面粗さRaは30nm以下が好ましく、20nm以下がより好ましく、10nm以下が特に好ましい。フィルムの厚みは、薄いほど画像形成性及び経済性を向上させるため有利であるが、感光性樹脂積層体の強度を維持するために、10μm~30μmのものが好ましく用いられる。支持フィルムが含有する滑剤等の微粒子の大きさとしては5μm未満であることが好ましい。
支持層及び感光性樹脂層、並びに必要により保護層を順次積層して感光性樹脂積層体を作製する方法としては、既知の方法を採用することができる。例えば、感光性樹脂層に用いる感光性樹脂組成物を、これを溶解する溶剤と混ぜ合わせ均一な溶液にし、まず支持層上にバーコーター又はロールコーターを用いて塗布し、次いで乾燥して前記溶剤を除去することにより、支持層上に感光性樹脂組成物から成る感光性樹脂層を積層することができる。次いで必要により、感光性樹脂層上に保護層をラミネートすることにより、感光性樹脂積層体を作製することができる。
次に、本実施の形態の感光性樹脂積層体を用いてレジストパターンを製造する方法の一例を説明する。該方法は、感光性樹脂組成物を露光する露光工程、露光された感光性樹脂組成物を加熱する加熱工程、及び該感光性樹脂組成物を現像する現像工程を含むことができる。
レジストパターンとしては、例えば、プリント配線板、半導体素子、印刷版、液晶ディスプレイパネル、タッチパネル、フレキシブル基板、リードフレーム基板、COF(チップオンフィルム)用基板、半導体パッケージ用基板、液晶用透明電極、液晶用TFT用配線、PDP(プラズマディスプレイパネル)用電極等のパターンが挙げられる。一例として、プリント配線板の製造方法を、下記の通り説明する。
(1)ラミネート工程
先ず、ラミネート工程において、ラミネーターを用いて基板上に感光性樹脂層を形成する。具体的には、感光性樹脂積層体が保護層を有する場合には保護層を剥離した後、ラミネーターで感光性樹脂層を基板表面に加熱圧着しラミネートする。基板の材料としては、例えば、銅、ステンレス鋼(SUS)、ガラス、酸化インジウムスズ(ITO)等が挙げられる。
本実施形態では、感光性樹脂層は基板表面の片面だけにラミネートするか、又は必要に応じて両面にラミネートしてもよい。ラミネート時の加熱温度は一般的に40℃~160℃である。また、ラミネート時の加熱圧着を2回以上行うことにより、得られるレジストパターンの基板に対する密着性を向上させることができる。加熱圧着時には、二連のロールを備えた二段式ラミネーターを使用するか、又は基板と感光性樹脂層との積層物を数回繰り返してロールに通すことにより圧着してもよい。
本工程では、所望の配線パターンを有するマスクフィルムを支持層上に密着させて活性光源を用いて行う露光方法、所望の配線パターンである描画パターンの直接描画による露光方法、又はフォトマスクの像を、レンズを通して投影させることによる露光方法によって、感光性樹脂層を露光する。
本工程では、露光された感光性樹脂組成物に対し、約30℃~約200℃の加熱工程を行うことが好ましく、30℃~150℃の範囲であることがより好ましく、60℃~120℃の範囲であることが更に好ましい。この加熱工程を実施することにより、解像性、密着性の向上が可能となる。加熱には、熱風、赤外線、又は遠赤外線の方式の加熱炉、恒温槽、ホットプレート、熱風乾燥機、赤外線乾燥機、ホットロールなどを用いることができる。加熱方法がホットロールであると短時間処理が可能な点で好ましく、ホットロールが2連以上であるとより好ましい。
本工程では、露光後、感光性樹脂層上の支持層を剥離し、続いてアルカリ水溶液の現像液を用いて未露光部を現像除去することにより、レジストパターンを基板上に形成する。
アルカリ水溶液としては、Na2CO3又はK2CO3の水溶液を用いる。アルカリ水溶液は、感光性樹脂層の特性に合わせて適宜選択されるが、約0.2質量%~約2質量%の濃度、かつ約20℃~約40℃のNa2CO3水溶液が好ましい。
上記の(1)~(4)の各工程を経てレジストパターンを得ることができる。
現像により露出した基板表面(例えば銅張積層板の銅面)をエッチング又はめっきし、導体パターンを製造する。
(6)剥離工程
その後、レジストパターンを、適当な剥離液を用いて基板から剥離する。
ここで使用される剥離液としては、例えば、アルカリ水溶液、アミン系剥離液等を挙げることができる。しかしながら、本発明の感光性樹脂組成物から露光後加熱を経て形成されたレジストパターンは、アミン系剥離液に対して良好な剥離性を示すとともに、剥離片が過度に微細化されることがないとの特徴を有する。したがって、剥離液としてアミン系剥離液を用いると、本発明の有利な効果が最大限に発揮されて好ましい。
無機アミンとしては、例えば、アンモニア、ヒドロキシルアミン、ヒドラジン等が挙げられる。
エタノールアミンとして、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、N-メチルエタノールアミン、N-エチルエタノールアミン、N、N-ジメチルエタノールアミン、N、N-ジエチルエタノールアミン、アミノエトキシエタノール等を;
プロパノールアミンとして、例えば、1-アミノ-2-プロパノール、2-アミノ-2-メチル-1-プロパノール、2-アミノ-2-メチル-1,3-プロパンジオール等を;
アルキルアミンとして、例えば、モノメチルアミン、ジメチルアミン、トリメチルアミン、エチレンアミン、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ヘキサメチレンテトラミン、テトラエチレンペンタミン等を;
環状アミンとして、例えば、コリン、モルホリン等を;
第4級アンモニウム塩として、例えば、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、N、N、N-トリエチル-N-(2-ヒドロキシエチル)アンモニウムヒドロキシド、N、N-ジエチル-N、N-ジ(2-ヒドロキシエチル)アンモニウムヒドロキシド等を;
それぞれ例示できる。
本発明で用いられるアミン系剥離剤は、剥離剤に通常用いられる添加剤、例えば、界面活性剤、消泡剤、pH調整剤、防腐剤、再付着防止剤等を、更に含有していてもよい。
剥離工程は、例えば0℃以上100℃以下、好ましくは室温(23℃)以上50℃以下の温度において、例えば、1秒以上1時間以下、好ましくは10秒以上10分以下の時間、行われる。
なお、上述した各種パラメータについては、特に断りのない限り、後述の実施例における測定方法又はこれと同等であることが当業者に理解される方法に準じて測定される。
高分子の物性値の測定、並びに実施例及び比較例の評価用サンプルの作製方法を説明する。また、得られたサンプルについての評価方法及びその評価結果を示す。
第1の実施例では、(A)アルカリ可溶性高分子全体におけるスチレン及び/又はスチレン誘導体の構成単位が15質量%以上である感光性樹脂組成物についての評価を行った。
<高分子の重量平均分子量又は数平均分子量の測定>
高分子の重量平均分子量又は数平均分子量は、日本分光(株)製ゲルパーミエーションクロマトグラフィー(GPC)(ポンプ:Gulliver、PU-1580型、カラム:昭和電工(株)製Shodex(登録商標)(KF-807、KF-806M、KF-806M、KF-802.5)4本直列、移動層溶媒:テトラヒドロフラン、ポリスチレン標準サンプル(昭和電工(株)製Shodex STANDARD SM-105)による検量線使用)によりポリスチレン換算として求めた。
さらに、高分子の分散度は、数平均分子量に対する重量平均分子量の比(重量平均分子量/数平均分子量)として算出された。
評価用サンプルは以下のように作製した。
<感光性樹脂積層体の作製>
後掲する表1-1(表2-1、表3-1)に示す成分(但し、各成分の数字は固形分としての配合量(質量部)を示す。)及び溶媒を十分に攪拌、混合して、感光性樹脂組成物調合液を得た。表1-1(表2-1、表3-1)中に略号で表した成分の名称を、下記表1-2(表2-2、表3-2)に示す。支持フィルムとして16μm厚のポリエチレンテレフタラートフィルム(東レ(株)製、FB-40)を用い、その表面にバーコーターを用いて、この調合液を均一に塗布し、95℃の乾燥機中で3分間乾燥して、感光性樹脂組成物層を形成した。感光性樹脂組成物層の乾燥厚みは25μmであった。
次いで、感光性樹脂組成物層のポリエチレンテレフタラートフィルムを積層していない側の表面上に、保護層として19μm厚のポリエチレンフィルム(タマポリ(株)製、GF-818)を貼り合わせて感光性樹脂積層体を得た。
画像性の評価基板として、35μm圧延銅箔を積層した0.4mm厚の銅張積層板を、スプレー圧0.2MPaで研削剤(宇治電化学工業(株)製、#400)を用いてジェットスクラブ研磨した後、10質量%H2SO4水溶液で基板表面を洗浄した。
<ラミネート>
感光性樹脂積層体のポリエチレンフィルム(保護層)を剥がしながら、50℃に予熱した銅張積層板に、ホットロールラミネーター(旭化成(株)社製、AL-700)により、感光性樹脂積層体をロール温度105℃でラミネートした。エアー圧は0.35MPaとし、ラミネート速度は1.5m/minとした。
ラミネート後2時間経過した評価用基板に、直接描画露光機IP-8 8000Hにより、ストーファー41段ステップタブレットを用いて露光した。露光は、前記ストーファー41段ステップタブレットをマスクとして露光、現像したときの最高残膜段数が15段となる露光量で行った。
ポリエチレンテレフタレートフィルム(支持層)を剥離した後、アルカリ現像機(フジ機工製、ドライフィルム用現像機)を用い、30℃の1質量%Na2CO3水溶液を所定時間に亘ってスプレーして現像を行った。現像スプレーの時間は最短現像時間の2倍の時間とし、現像後の水洗スプレーの時間は最短現像時間の4倍の時間とした。この際、未露光部分の感光性樹脂層が完全に溶解するのに要する最も短い時間を最短現像時間とした。
マスクパターンL/S=Xμm/200μmのパターンが正常に形成されている最小ライン幅を光学顕微鏡により測定した。この測定を8本のラインについて行い、その8つの線幅の平均値を密着性の値として求めた。
現像までは上記と同様の工程を実施し、感光性樹脂組成物層をラミネートした未露光部において、感光性樹脂組成物層を現像除去した後の銅表面を目視で観察した。
〇:変色無し
△:少し変色が見られる
最短現像時間を以下の2条件で測定した。
(A)通常の最短現像時間
基板に感光性樹脂積層体をラミネートし、支持フィルムを剥離後、未露光部分の感光性樹脂層が完全に溶解するのに要する最も短い時間を測定した。
(B)加熱後の最短現像時間
基板に感光性樹脂積層体をラミネート後、ホットロールラミネーター(旭化成(株)社製、AL-700)により加熱した。ロール温度は105℃、エアー圧は0.30MPa、ラミネート速度は0.1m/minとした。
〇:(B)と(A)の最短現像時間が同じ(遅延なし)
△:(B)の最短現像時間が(A)の最短現像時間よりも1~3秒長い(遅延あり)
第2の実施例では、(B)エチレン性不飽和二重結合を有する化合物が、エチレン性不飽和二重結合を3個以上有する(メタ)アクリレート化合物を含む、感光性樹脂組成物についての評価を行った。
後掲する表2-1に示す成分で、上述した第1の実施例と同様にして、評価用サンプルを作製した。
<露光>
ラミネート後2時間経過した評価用基板に、直接描画露光機(オルボテック(株)製、Nuvogo1000、光源:375nm(30%)+405nm(70%))により、ストーファー41段ステップタブレットを用いて露光した。露光は、前記ストーファー41段ステップタブレットをマスクとして露光、現像したときの最高残膜段数が19段となる露光量で行った。
露光後7分経過した評価用基板を、ホットロールラミネーター(旭化成(株)社製、AL-700)により加熱した。ロール温度は105℃、エアー圧は0.30MPa、ラミネート速度は1m/minとした。なお、露光後の経過時間を長くすると加熱の効果が無くなってくるため、通常は露光後1分程度に加熱する。そのため、本実施例の露光7分後の加熱は非常に厳しい条件である。
ポリエチレンテレフタレートフィルム(支持層)を剥離した後、アルカリ現像機(フジ機工製、ドライフィルム用現像機)を用い、30℃の1質量%Na2CO3水溶液を所定時間に亘ってスプレーして現像を行った。現像スプレーの時間は最短現像時間の2倍の時間とし、現像後の水洗スプレーの時間は最短現像時間の3倍の時間とした。この際、未露光部分の感光性樹脂層が完全に溶解するのに要する最も短い時間を最短現像時間とした。
以上の評価結果を、実施例および比較例の感光性樹脂組成物の成分と併せて表2-1に示す。また、表2-1中に略号で表した成分の名称を表2-2に示す。
第3の実施例では、(C-2)光重合開始剤がアントラセン及び/又はアントラセン誘導体を含む感光性樹脂組成物についての評価を行った。
後掲する表3-1に示す成分で、上述した第1の実施例と同様にして、評価用サンプルを作製した。
<露光>
ラミネート後2時間経過した評価用基板に、直接描画露光機(オルボテック(株)製、Nuvogo1000、光源:375nm(30%)+405nm(70%))により、ストーファー41段ステップタブレットを用いて露光した。露光は、前記ストーファー41段ステップタブレットをマスクとして露光、現像したときの最高残膜段数が21段となる露光量で行った。
露光後7分経過した評価用基板を、ホットロールラミネーター(旭化成(株)社製、AL-700)により加熱した。ロール温度は105℃、エアー圧は0.30MPa、ラミネート速度は1m/minとした。なお、露光後の経過時間を長くすると加熱の効果が無くなってくるため、通常は露光後1分程度に加熱する。そのため、本実施例の露光7分後の加熱は非常に厳しい条件である。
ポリエチレンテレフタレートフィルム(支持層)を剥離した後、アルカリ現像機(フジ機工製、ドライフィルム用現像機)を用い、30℃の1質量%Na2CO3水溶液を所定時間に亘ってスプレーして現像を行った。現像スプレーの時間は最短現像時間の2倍の時間とし、現像後の水洗スプレーの時間は最短現像時間の3倍の時間とした。この際、未露光部分の感光性樹脂層が完全に溶解するのに要する最も短い時間を最短現像時間とした。
以上の評価結果を、実施例および比較例の感光性樹脂組成物の成分と併せて表3-1に示す。また、表3-1中に略号で表した成分の名称を表3-2に示す。
Claims (43)
- 露光後、加熱してから現像して樹脂硬化物を得るための感光性樹脂組成物であって、前記感光性樹脂組成物が、該感光性樹脂組成物の全固形分質量基準で、以下の成分:
(A)アルカリ可溶性高分子:10質量%~90質量%;
(B)エチレン性不飽和二重結合を有する化合物:5質量%~70質量%;及び
(C)光重合開始剤:0.01質量%~20質量%;
を含み、
前記(A)アルカリ可溶性高分子全体におけるスチレン及び/又はスチレン誘導体の構成単位が15質量%以上であることを特徴とする感光性樹脂組成物。 - 前記(B)エチレン性不飽和二重結合を有する化合物として、ビスフェノールA骨格の濃度が0.18mol/100g以上である化合物(B-1)の含有量が、前記感光性樹脂組成物の固形分に対して0以上18質量%以下である、請求項1に記載の感光性樹脂組成物。
- 更に(D)禁止剤を含む、請求項1または2に記載の感光性樹脂組成物。
- 更に(E)ベンゾトリアゾール誘導体を含む、請求項1~3のいずれか一項に記載の感光性樹脂組成物。
- 前記(B)エチレン性不飽和二重結合を有する化合物は、エチレン性不飽和二重結合を3個以上有する(メタ)アクリレート化合物を含む、請求項1~4のいずれか一項に記載の感光性樹脂組成物。
- 前記(B)エチレン性不飽和二重結合を有する化合物は、エチレン性不飽和二重結合を4個以上有する(メタ)アクリレート化合物を含む、請求項5に記載の感光性樹脂組成物。
- 前記(B)エチレン性不飽和二重結合を有する化合物は、エチレン性不飽和二重結合を6個以上有する(メタ)アクリレート化合物を含む、請求項6に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が0.94以上である、請求項1~7のいずれか一項に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.04以上である、請求項8に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.11以上である、請求項9に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.21以上である、請求項10に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.30以上である、請求項11に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が5以下である、請求項1~12のいずれか一項に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が4以下である、請求項13に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が3以下である、請求項14に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が2以下である、請求項15に記載の感光性樹脂組成物。
- [(A)アルカリ可溶性高分子の含有量]/[(B)エチレン性不飽和二重結合を有する化合物の含有量]の値が1.5以下である、請求項16に記載の感光性樹脂組成物。
- 露光後、加熱してから現像して樹脂硬化物を得るための感光性樹脂組成物であって、前記感光性樹脂組成物が、前記感光性樹脂組成物の全固形分質量基準で、以下の成分:
(A)アルカリ可溶性高分子:10質量%~90質量%;
(B)エチレン性不飽和二重結合を有する化合物:5質量%~70質量%;及び
(C)光重合開始剤:0.01質量%~20質量%;
を含み、
前記(C)光重合開始剤がアントラセン及び/又はアントラセン誘導体を含むことを特徴とする感光性樹脂組成物。 - 前記アントラセン誘導体は、9位及び/又は10位に、置換基を有していてもよい炭素数1~40のアルコキシ基及び/又は置換基を有していてもよい炭素数6~40のアリール基を有する、請求項18に記載の感光性樹脂組成物。
- 前記アントラセン誘導体は、9,10位に、置換基を有していてもよい炭素数1~40のアルコキシ基及び/又は置換基を有していてもよい炭素数6~40のアリール基を有する、請求項18又は19に記載の感光性樹脂組成物。
- 前記(C)光重合開始剤は、9,10-ジフェニルアントラセンを含む、請求項20に記載の感光性樹脂組成物。
- 前記(C)光重合開始剤は、9,10-ジアルコキシアントラセンを含む、請求項20に記載の感光性樹脂組成物。
- 前記(C)光重合開始剤は、ハロゲン原子を有するアントラセン誘導体を含む、請求項18~22のいずれか一項に記載の感光性樹脂組成物。
- 前記(C)光重合開始剤は、9,10-ジアルコキシアントラセンのハロゲン置換体を含む、請求項23に記載の感光性樹脂組成物。
- 前記(C)光重合開始剤は、9,10-ジアルコキシアントラセンの9位及び/又は10位のアルコキシ基が1つ以上のハロゲン原子で修飾されている化合物を含む、請求項24に記載の感光性樹脂組成物。
- 前記(C)光重合開始剤は、アントラセン骨格に直接結合したハロゲン原子を有する化合物を含む、請求項18~25のいずれか一項に記載の感光性樹脂組成物。
- 前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が15質量%以上である、請求項18~26のいずれか一項に記載の感光性樹脂組成物。
- 前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が25質量%以上である、請求項1~27のいずれか一項に記載の感光性樹脂組成物。
- 前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が30質量%以上である、請求項28に記載の感光性樹脂組成物。
- 前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が35質量%以上である、請求項29に記載の感光性樹脂組成物。
- 前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が40質量%以上である、請求項30に記載の感光性樹脂組成物。
- 前記(A)アルカリ可溶性高分子中におけるスチレン及び/又はスチレン誘導体の構成単位が90質量%以下である、請求項1~31のいずれか一項に記載の感光性樹脂組成物。
- 前記(A)アルカリ可溶性高分子が、単量体成分としてベンジル(メタ)アクリレートを更に含む、請求項1~32のいずれか一項に記載の感光性樹脂組成物。
- 請求項1~33のいずれか一項に記載の感光性樹脂組成物を露光する工程と、露光された前記感光性樹脂組成物を加熱する加熱工程と、加熱された前記感光性樹脂組成物を現像する現像工程と、を含むレジストパターンの形成方法。
- 前記加熱工程における加熱温度が30℃~150℃の範囲である、請求項34に記載のレジストパターンの形成方法。
- 前記露光工程を、描画パターンの直接描画による露光方法、又はフォトマスクの像を、レンズを通して投影させる露光方法により行う、請求項34又は35に記載のレジストパターンの形成方法。
- 前記露光工程を、描画パターンの直接描画による露光方法により行う、請求項34又は35に記載のレジストパターンの形成方法。
- 前記加熱工程を、露光から15分以内に行う、請求項34~37のいずれか一項に記載のレジストパターンの形成方法。
- 前記露光工程を、中心波長390nm未満の第1のレーザー光と、中心波長390nm以上の第2のレーザー光とで露光する方法により行う、請求項34~38のいずれか一項に記載のレジストパターンの形成方法。
- 前記第1のレーザー光の中心波長が350nm以上380nm以下であり、前記第2のレーザー光の中心波長が400nm以上410nm以下である、請求項39に記載のレジストパターンの形成方法。
- 請求項34~40のいずれか一項に記載の方法により製造されたレジストパターンを有する基板に対してエッチング又はめっきを施すことにより回路基板を形成する、回路基板の製造方法。
- 中心波長390nm未満の第1のレーザー光と、中心波長390nm以上の第2のレーザー光とで露光して樹脂硬化物を得るための感光性樹脂組成物である、請求項1~33のいずれか一項に記載の感光性樹脂組成物。
- 前記第1のレーザー光の中心波長が350nm以上380nm以下であり、前記第2のレーザー光の中心波長が400nm以上410nm以下である、請求項42に記載の感光性樹脂組成物。
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WO2022131324A1 (ja) * | 2020-12-17 | 2022-06-23 | 富士フイルム株式会社 | 転写フィルム、積層体の製造方法、回路配線の製造方法 |
WO2022138154A1 (ja) * | 2020-12-25 | 2022-06-30 | 富士フイルム株式会社 | 積層体の製造方法、回路配線の製造方法、転写フィルム |
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