WO2018181556A1 - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- WO2018181556A1 WO2018181556A1 PCT/JP2018/012941 JP2018012941W WO2018181556A1 WO 2018181556 A1 WO2018181556 A1 WO 2018181556A1 JP 2018012941 W JP2018012941 W JP 2018012941W WO 2018181556 A1 WO2018181556 A1 WO 2018181556A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photosensitive resin
- resin composition
- resist pattern
- photosensitizer
- mass
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 98
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 62
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 17
- NGQSLSMAEVWNPU-YTEMWHBBSA-N 1,2-bis[(e)-2-phenylethenyl]benzene Chemical class C=1C=CC=CC=1/C=C/C1=CC=CC=C1\C=C\C1=CC=CC=C1 NGQSLSMAEVWNPU-YTEMWHBBSA-N 0.000 claims abstract description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 81
- 239000011347 resin Substances 0.000 claims description 81
- 238000000034 method Methods 0.000 claims description 67
- 239000000758 substrate Substances 0.000 claims description 37
- 238000007747 plating Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 239000004065 semiconductor Substances 0.000 claims description 22
- 238000010494 dissociation reaction Methods 0.000 claims description 21
- 230000005593 dissociations Effects 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 230000008033 biological extinction Effects 0.000 claims description 13
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- KIAAMJMIIHTGBH-KQQUZDAGSA-N 4-[(e)-2-[4-[(e)-2-(4-cyanophenyl)ethenyl]phenyl]ethenyl]benzonitrile Chemical compound C1=CC(C#N)=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=C(C#N)C=C1 KIAAMJMIIHTGBH-KQQUZDAGSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- JRVKAPLKKVWGKU-SQIWNDBBSA-N 2-[(e)-2-[4-[(e)-2-(3-cyanophenyl)ethenyl]phenyl]ethenyl]benzonitrile Chemical compound N#CC1=CC=CC(\C=C\C=2C=CC(\C=C\C=3C(=CC=CC=3)C#N)=CC=2)=C1 JRVKAPLKKVWGKU-SQIWNDBBSA-N 0.000 claims description 6
- RBABXJPJIHMBBP-UHFFFAOYSA-N 2-[2-[4-[2-(2-cyanophenyl)ethenyl]phenyl]ethenyl]benzonitrile Chemical compound N#CC1=CC=CC=C1C=CC(C=C1)=CC=C1C=CC1=CC=CC=C1C#N RBABXJPJIHMBBP-UHFFFAOYSA-N 0.000 claims description 6
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- VZTHUHAJEZPWNC-UHFFFAOYSA-N 4-[5-(4-chlorophenyl)-3,4-dihydropyrazol-2-yl]benzenesulfonamide Chemical group C1=CC(S(=O)(=O)N)=CC=C1N1N=C(C=2C=CC(Cl)=CC=2)CC1 VZTHUHAJEZPWNC-UHFFFAOYSA-N 0.000 claims description 4
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- OQVQNTRMZCGXIB-ICYHVJMASA-N 2-[(e)-2-[4-[(e)-2-(4-cyanophenyl)ethenyl]phenyl]ethenyl]benzonitrile Chemical compound C1=CC(C#N)=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=CC=C1C#N OQVQNTRMZCGXIB-ICYHVJMASA-N 0.000 claims description 2
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- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- JYAUISNYDRMEMW-UHFFFAOYSA-N hexyl 2-anilinoacetate Chemical compound CCCCCCOC(=O)CNC1=CC=CC=C1 JYAUISNYDRMEMW-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940086559 methyl benzoin Drugs 0.000 description 1
- 150000004702 methyl esters Chemical class 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
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- SHXOKQKTZJXHHR-UHFFFAOYSA-N n,n-diethyl-5-iminobenzo[a]phenoxazin-9-amine;hydrochloride Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=[NH2+])C2=C1 SHXOKQKTZJXHHR-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 230000036211 photosensitivity Effects 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 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
- 230000002265 prevention Effects 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- MYBNTSLQHDGJFY-UHFFFAOYSA-N tert-butyl 2-anilinoacetate Chemical compound CC(C)(C)OC(=O)CNC1=CC=CC=C1 MYBNTSLQHDGJFY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 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
- 150000003918 triazines Chemical class 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
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- 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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- 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
- G03F7/20—Exposure; 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
-
- 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
- H05K3/0002—Apparatus or processes for manufacturing printed circuits for manufacturing artworks for printed circuits
Definitions
- the present invention relates to a photosensitive resin composition and the like.
- a photosensitive resin laminate in which a photosensitive resin layer is laminated on a support film, and a protective film is laminated on the photosensitive resin layer as necessary, A so-called dry film resist (hereinafter sometimes referred to as DF) is used.
- DF dry film resist
- an alkali developing type using a weak alkaline aqueous solution as a developing solution is generally used.
- a protective film first peel off the protective film and then use a laminator or the like on a permanent circuit production board such as a copper-clad laminate or a flexible board.
- Laminate DF and expose through a wiring pattern mask film.
- the support film is peeled off, and the photosensitive resin layer of the unexposed part (in the case of negative type) is dissolved or dispersed and removed by a developer, and a cured resist pattern (hereinafter simply referred to as a resist pattern) is formed on the substrate. (Sometimes called).
- the process of forming a circuit after forming a resist pattern is roughly divided into two methods.
- the first method is a method in which a substrate surface not covered with a resist pattern (for example, 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 developer (etching method). It is.
- the second method after plating the surface of the substrate with copper, solder, nickel, tin or the like, the resist pattern portion is similarly removed, and the substrate surface that appears again (for example, the copper surface of a copper-clad laminate)
- This is a method of etching (plating method).
- etching a solution of cupric chloride, ferric chloride, a copper ammonia complex or the like is used.
- Patent Document 1 describes a blue-violet laser photosensitive composition.
- This photosensitive composition is highly sensitive to laser light in the blue-violet region and is excellent in safe light under a yellow light, particularly as a dry film resist material and for direct drawing with blue-violet laser light. It can be used suitably.
- the photosensitive resin composition described in Patent Document 1 does not satisfy the sensitivity (productivity), resolution, adhesion, and the like at the same time, and still has room for improvement.
- an object of the present invention is to provide a photosensitive resin composition that is superior in sensitivity (productivity), resolution, and adhesion to conventional laser direct imaging type exposure systems.
- the present inventor has found that the above problems can be solved by containing a specific component as (D) a photosensitizer. That is, the present invention is as follows. [1] The following ingredients: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a photosensitizer, Including The photosensitive resin composition in which the said (D) photosensitizer contains the distyrylbenzene derivative represented by following General formula (2).
- R 3 , R 4 and R 5 each represent a cyano group, c and e each independently represent an integer of 1 to 5, and d represents an integer of 0 to 4.
- the photosensitizer (D) is 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, 4 ′-(2-cyanostyryl).
- the photosensitive resin composition according to [1] comprising at least one compound selected from -4-stilbenecarbonitrile and 1,4-bis (4-cyanostyryl) benzene.
- the (D) photosensitizer includes 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, according to [2].
- Photosensitive resin composition [4] The photosensitive resin composition according to [2], wherein the (D) photosensitizer includes 4 ′-(2-cyanostyryl) -4-stilbenecarbonitrile.
- the (C) photopolymerization initiator includes a hexaarylbiimidazole compound.
- a transmittance of light having a wavelength of 405 nm at a film thickness of 25 ⁇ m of the photosensitive resin composition is greater than 10%.
- a photosensitive resin laminate comprising: a support; and a photosensitive resin layer comprising the photosensitive resin composition according to any one of 1 to 9 provided on the support.
- the resist pattern forming method according to [11] wherein the exposure is performed by direct drawing of a drawing pattern.
- the following ingredients (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a photosensitizer, Including
- the acid dissociation constant pKa of the (D) photosensitizer is greater than 9 and less than 12, and the molar extinction coefficient at a wavelength of 405 nm is 100 ⁇ -1 cm -1 or more (where ⁇ is a unit of molar concentration)
- the molar extinction coefficient is a value when acetone is used as a solvent.
- the acid dissociation constant pKa of the (D) photosensitizer is greater than 9.5 and less than 11.
- a photosensitive resin laminate comprising: a support; and a photosensitive resin layer including the photosensitive resin composition according to any one of [15] to [23] provided on the support.
- the present invention provides a photosensitive resin composition excellent in sensitivity (productivity), resolution, and adhesion.
- the photosensitive resin composition comprises the following components (A) to (E): (A) an alkali-soluble polymer (also referred to as component (A) in the present disclosure), (B) A compound having a saturated double bond (also referred to as component (B) in the present disclosure), (C) a photopolymerization initiator (also referred to as component (C) in the present disclosure), (D) a photosensitizer (in the present disclosure ( D) component)). (E) An additive (also referred to as component (E) in the present disclosure) may be included.
- each component will be described in order.
- Alkali-soluble polymer is a polymer that is easily soluble in an alkali substance. Specifically, a functional group that contributes to alkali solubility (for example, a carboxyl group) is dissolved in a desired alkali substance. It is a polymer that has a sufficient amount to do. Also, typically, the amount of carboxyl groups contained in (A) the alkali-soluble polymer is from 100 to 600, preferably from 250 to 450, in terms of acid equivalent. The acid equivalent means the mass (unit: gram) of a linear polymer having 1 equivalent of a carboxyl group in the molecule.
- the carboxyl group in the alkali-soluble polymer is necessary for providing the photosensitive resin layer with developability and peelability with respect to an aqueous alkali solution.
- Setting the acid equivalent to 100 or more is preferable from the viewpoint of improving development resistance, resolution, and adhesion, and it is preferable to set the acid equivalent to 250 or more.
- the acid equivalent is preferably 600 or less from the viewpoint of improving developability and peelability, and the acid equivalent is preferably 450 or less.
- the weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. Setting the weight average molecular weight to 500,000 or less is preferable from the viewpoint of improving resolution and developability, more preferably setting the weight average molecular weight to 300,000 or less, and further to 200,000 or less. preferable. On the other hand, setting the weight average molecular weight to 5,000 or more is preferable from the viewpoint of controlling the properties of the development aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property of the photosensitive resin laminate, The weight average molecular weight is more preferably 10,000 or more, and further preferably 20,000 or more.
- the edge fuse property refers to a phenomenon in which the photosensitive resin layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll.
- the cut chip property refers to a phenomenon in which a chip flies when an unexposed film is cut with a cutter. If the chip adheres to the upper surface of the photosensitive resin laminate, the chip is transferred to a mask in a later exposure process or the like, resulting in a defective product.
- the degree of dispersion of the alkali-soluble polymer may be about 1 to 6, preferably 1 to 4.
- a weight average molecular weight and a number average molecular weight are the values measured by polystyrene conversion using gel permeation chromatography.
- the alkali-soluble polymer is preferably a copolymer obtained from at least one first monomer described later and at least one second monomer described later.
- the first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule.
- the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. Particularly preferred is (meth) acrylic acid.
- (meth) acryl indicates acrylic and / or methacrylic. The same applies hereinafter.
- the second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule.
- Examples of 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.
- the copolymerization ratio of the first monomer and the second monomer is such that (A) the first monomer is 10 to 60% by mass from the viewpoint of adjusting the alkali solubility of the alkali-soluble polymer.
- the second monomer is preferably 40 to 90% by mass, more preferably 15 to 35% by mass of the first monomer and 65 to 85% by mass of the second monomer. %.
- the synthesis of the alkali-soluble polymer is carried out by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out by adding an appropriate amount of a radical polymerization initiator such as butyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
- a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out by adding an appropriate amount of a radical polymerization initiator such as butyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into
- an alkali-soluble polymer (a mixture of a plurality of types of alkali-soluble polymers) is used as (A) component, (B) component, (C) component, (D) component, and
- the proportion of the component (E) in the total amount (hereinafter sometimes referred to as the total amount of the components (A) to (E)) is preferably in the range of 10 to 90% by mass, more preferably 30 to 70%. % By mass, more preferably 40 to 60% by mass.
- the ratio of the component (A) to the total amount of the components (A) to (E) is preferably 90% by mass or less from the viewpoint of controlling the development time, while the total amount of the components (A) to (E). Setting the ratio of the component (A) to 10% by mass or more is preferable from the viewpoint of improving the edge fuse property.
- the ratio of the alkali-soluble polymer to the total solid mass of the photosensitive resin composition may be 10% by mass or more, 20% by mass or more, and 25% by mass or more. May be 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, and 50% by mass or more. May be 55 mass% or more, and may be 60 mass% or more. Further, it may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less. Good. The range is preferably 10% to 90% by weight, more preferably 30% to 70% by weight, and still more preferably 40% to 60% by weight.
- the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition is preferable from the viewpoint of controlling the development time.
- the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition be 10% by mass or more.
- the photosensitive resin composition has, as the component (A), one or more components selected from the group consisting of the following (a-1) and (a-2): (A-1) Derived from a polymerization component comprising 15 to 60% by mass of styrene and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester.
- Acrylic copolymer (A-2) 20 to 85% by mass of benzyl methacrylate and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester other than benzyl methacrylate
- the proportion of the total amount of the component (a-1) and the component (a-2) in the total amount of the components (A) to (E) is 10 to 60% by mass in order to express high resolution. Is preferable.
- the above ratio is preferably 20% by mass or more, more preferably 30% by mass or more from the viewpoint of resolution, and preferably 55% by mass or less, more preferably 50% by mass or less from the viewpoint of cut-tip properties.
- the polymerization component in (a-1) may be composed of only styrene and the above acrylic monomer, or may further contain other monomers. Further, the polymerization component in (a-2) may be composed only of benzyl methacrylate and the above acrylic monomer, or may further contain other monomers.
- styrene is 15 to 60% by mass
- methacrylic acid is 20 to 35% by mass
- the remainder is methyl methacrylate
- styrene is 30 to 50% by mass with methacrylic acid.
- 2-ethylhexyl acrylate is 10 to 20% by mass
- the remainder is a combination of 2-hydroxyethyl methacrylate
- benzyl methacrylate is 20 to 60% by mass
- styrene is 10 to 30% by mass
- the rest is methacrylic
- Examples include a combination of acids, 60 to 85% by mass of benzyl methacrylate, 0 to 15% by mass of 2-ethylhexyl acrylate, and the remainder of methacrylic acid. Containing a monomer having an aralkyl group and / or styrene as a monomer is preferable from the viewpoint of chemical resistance, adhesion, high resolution, or sword shape of a resist pattern.
- (B) Compound having ethylenically unsaturated double bond is an acryloyl group in the molecule from the viewpoint of curability and compatibility with (A) alkali-soluble polymer. It is preferable that the compound which has this is included.
- the compound having an acryloyl group in the molecule include a compound in which (meth) acrylic acid is added to one end of polyalkylene oxide, or (meth) acrylic acid is added to one end and the other end is alkyl. Examples include etherified or allyl etherified compounds.
- phenoxyhexaethylene glycol mono (meth) acrylate which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, or an average of 2 moles of propylene oxide (hereinafter sometimes abbreviated as PO).
- 4-methylnonylphenoxyheptaethyleneglycol diglycol which is a (meth) acrylate of a compound in which polyethylene glycol added with an average of 7 moles of ethylene oxide (hereinafter sometimes abbreviated as EO) is added to nonylphenol.
- Propylene glycol (meth) acrylate, polypropylene glycol with an average of 1 mol of propylene oxide and polyethylene glycol with an average of 5 mol of ethylene oxide are attached to nonylphenol.
- the compound (meth) acrylate 4-n-nonylphenoxy pentaethylene glycol monopropylene glycol (meth) acrylate.
- Examples also include 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate (for example, M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol having an average of 8 mol of ethylene oxide added to nonylphenol.
- a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain or a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks. be able to.
- Examples of such compounds 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 (meth).
- Polyethylene glycol (meth) acrylate such as acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, a compound having a (meth) acryloyl group at both ends of 12 moles of ethylene oxide chain, Examples thereof include polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate.
- Examples of the polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound include, for example, a glycol obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol added with an average of 12 moles of propylene oxide. And diglycolate of glycol obtained by adding an average of 15 moles of ethylene oxide to both ends of polypropylene glycol having an average of 18 moles of propylene oxide added thereto.
- polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate having both ethylene oxide and polypropylene oxide for example, “FA-023M, FA-024M, FA-027M, product name, Hitachi, Ltd.) "Made by Kasei Kogyo" is preferred from the viewpoints of flexibility, resolution, adhesion and the like.
- a compound in which bisphenol A is modified with alkylene oxide and has (meth) acryloyl groups at both ends is preferable from the viewpoint of resolution and adhesion.
- alkylene oxide modification include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification.
- a compound in which bisphenol A is modified with ethylene oxide and has (meth) acryloyl groups at both ends is particularly preferable.
- Examples of such compounds include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane (for example, NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) (Acryloxypentaethoxy) phenyl) propane (for example, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl Propane, 2,2-bis (4-((me
- B carboxymethyl polyethoxy) phenyl) propane.
- di (meth) acrylate of polyalkylene glycol obtained by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol A, or an average of 2 moles of propylene oxide and an average of 15 moles to both ends of bisphenol A, respectively.
- ethylene oxide-modified and propylene oxide-modified compounds such as poly (alkylene glycol) di (meth) acrylates to which ethylene oxide is added are also preferred.
- the number of moles of ethylene oxide relative to 1 mole of bisphenol A in a compound having a (meth) acryloyl group at both ends modified with alkylene oxide from bisphenol A is from the viewpoint of improving resolution, adhesion and flexibility. 10 mol or more and 30 mol or less are preferable.
- the compound having an ethylenically unsaturated double bond includes a compound having more than two (meth) acryloyl groups in one molecule, and exhibits high resolution.
- the number of (meth) acryloyl groups in one molecule is more preferably 3 or more.
- the number of (meth) acryloyl groups in one molecule is preferably 6 or less, more preferably 4 or less, from the viewpoint of peelability.
- a compound having more than two (meth) acryloyl groups in one molecule has 3 moles or more of groups that can add an alkylene oxide group in the molecule as a central skeleton (that is, 3 or more per central skeleton).
- a (meth) acrylate from an alcohol to which an alkylene oxide group such as an ethylene oxide group, a propylene oxide group or a butylene oxide group is added, and (meth) acrylic acid.
- an alkylene oxide group such as an ethylene oxide group, a propylene oxide group or a butylene oxide group is added
- acrylic acid If the central skeleton is alcohol, it can also be obtained by directly forming (meth) acrylic acid and (meth) acrylate.
- the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.
- Such compounds include trimethylolpropane EO3 mol modified triacrylate, trimethylolpropane EO6 mol modified triacrylate, trimethylolpropane EO9 mol modified triacrylate, trimethylolpropane EO12 mol modified triacrylate, glycerol EO3.
- Mole-modified triacrylate for example, A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.
- EO9 mol-modified triacrylate of glycerol for example, A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.
- EO6 mol PO6 of glycerol Mole-modified triacrylate A-GLY-0606PE
- glycerin EO9 mol PO9 mol-modified triacrylate A-GLY-0909PE
- pentaerythritol 4EO-modified tetraacrylate eg Sert Over Japan Co., Ltd.
- SR-494 35EO modified tetraacrylate pentaerythritol (e.g. Shin Nakamura Kagaku Kogyo Co., Ltd. NK Ester ATM-35E), dipentaerythritol tetraacrylate, and the like.
- the compound having at least three methacryloyl groups include trimethacrylate, for example, ethoxylated glycerin trimethacrylate, ethoxylated isocyanuric acid trimethacrylate, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate (for example, an average of 21 moles in trimethylolpropane).
- Trimethacrylate with an ethylene oxide added, and trimethacrylate with an average of 30 moles of ethylene oxide added to trimethylolpropane are preferred from the viewpoints of flexibility, adhesion, and suppression of bleedout), etc .
- tetramethacrylate for example, ditrimethylolpropane Tetramethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, etc .
- Rate for example, dipentaerythritol penta methacrylate
- hexamethylene dimethacrylate for example, dipentaerythritol hexa methacrylate.
- tetra, penta or hexamethacrylate is preferable.
- preferred examples of the compound (B) having an ethylenically unsaturated double bond are those having a melting point lower than room temperature and not easily solidified at the time of storage, particularly from the viewpoint of handleability, and particularly EO3 molar modification of trimethylolpropane. 4EO-modified tetraacrylate of triacrylate and pentaerythritol is preferable.
- the content of the compound having more than two (meth) acryloyl groups in one molecule is preferably 50 to 100% by mass of the compound (B) having an ethylenically unsaturated double bond.
- the content is preferably 50% by mass or more, more preferably 60% by mass or more from the viewpoint of resolution.
- the content may be 100% by mass, but is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of peelability.
- the component (B) can appropriately contain, for example, the following compounds.
- urethane compounds are also mentioned.
- hexamethylene diisocyanate, tolylene diisocyanate or a diisocyanate compound for example, 2,2,4-trimethylhexamethylene diisocyanate
- a compound having a hydroxyl group and a (meth) acryl group in one molecule for example, 2-hydroxypropyl
- examples thereof include urethane compounds with acrylates and oligopropylene glycol monomethacrylates.
- there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate for example, Bremer PP1000 manufactured by NOF Corporation.
- di- or tri (meth) acrylates of isocyanuric acid esters modified with polypropylene glycol or polycaprolactone are also included.
- the urethane oligomer obtained by making the terminal of the urethane compound obtained as a polyadduct of diisocyanate and a polyol react with the compound which has an ethylenically unsaturated double bond and a hydroxyl group etc. can be mentioned, for example.
- (B) As compounds having an ethylenically unsaturated bond, 4-normalnonylphenoxyoctaethylene glycol acrylate, 4-normalnonylphenoxytetraethylene glycol acrylate, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl
- a compound having one ethylenically unsaturated bond such as - Why-phthalate may be included. It is preferable from the viewpoints of releasability and cured film flexibility, and it is also preferable from the viewpoint of sensitivity, resolution, and adhesion when ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ ′-methacryloyloxyethyl- GmbH-phthalate is included.
- the compound (B) having an ethylenically unsaturated double bond preferably contains a hydroxyl group in the molecule. As a result, the sensitivity (productivity), resolution, and adhesion are particularly excellent.
- the ratio of the compound having an ethylenically unsaturated double bond to the total amount of the components (A) to (E) is preferably 5 to 70% by mass. Setting this ratio to 5% by mass or more is preferable from the viewpoint of sensitivity, resolution, and adhesion, and this ratio is more preferably 10% by mass or more, and further preferably 20% by mass or more. On the other hand, setting this ratio to 70% by mass or less is preferable from the viewpoint of suppressing the peeling delay of the edge fuse and the cured resist, and this ratio is more preferably 60% by mass or less, and further preferably 50% by mass or less. .
- the ratio with respect to the total solid mass of the photosensitive resin composition of the compound having an ethylenically unsaturated double bond may be 5% by mass or more, 10% by mass or more, and 20% by mass. % Or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, 40 mass% or more, 45 mass% % Or more, or 50 mass% or more. Moreover, 70 mass% or less may be sufficient, 60 mass% or less may be sufficient, and 50 mass% or less may be sufficient. The amount is preferably 5% by mass to 70% by mass. Setting this ratio to 5% by mass or more is preferable from the viewpoints of sensitivity, resolution, and adhesion.
- This ratio is more preferably 20% by mass or more, and further preferably 30% by mass or more. On the other hand, setting this ratio to 70% by mass or less is preferable from the viewpoint of suppressing the delay of peeling of the edge fuse and the cured resist. More preferably, this ratio is 50% by mass or less.
- substances other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond contained in the solid content in the photosensitive resin composition are other than (A) and (B).
- the value of [mass of components other than (A) and (B)] / [mass of compound (B) having an ethylenically unsaturated bond] is preferably 0.190 or less.
- this value is 0.190 or less, the content of components that are not incorporated into the crosslinked structure can be reduced with respect to the content of the compound (B) having an ethylenically unsaturated bond that forms the crosslinked structure.
- the value of [(A) content of alkali-soluble polymer] / [(B) content of compound having an ethylenically unsaturated bond] contained in the solid content in the photosensitive resin composition is preferably 5.00 or less. 5.00 or less is preferable from the viewpoint of the cured film flexibility, more preferably 3.00 or less from the same viewpoint, further preferably 2.00 or less, and 1.800 or less. Particularly preferred is 1.600 or less.
- the lower limit is not particularly limited, but this value may be 0.200 or more, 0.300 or more, or 0.500 or more.
- Photopolymerization initiator (C) The photopolymerization initiator preferably contains a hexaarylbiimidazole compound from the viewpoint of obtaining sensitivity and resolution.
- Hexaarylbiimidazole compounds 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) -biimidazole, 2,
- N-aryl- ⁇ -amino acid compounds examples include benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoates, oxime esters, acridines, N-aryl amino acid ester compounds, and halogen compounds.
- N-aryl- ⁇ -amino acid compounds examples include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like.
- N-phenylglycine is preferable because of its high sensitizing effect.
- quinones examples include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2 , 3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone and the like.
- aromatic ketones examples include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, and 4-methoxy-4′-dimethylaminobenzophenone. be able to.
- acetophenones examples include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl- Mention may be made of 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1.
- examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.
- acylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. 4,4-trimethyl-pentylphosphine oxide and the like.
- Commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.
- benzoin or benzoin ethers examples include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.
- dialkyl ketals examples include benzyl dimethyl ketal and benzyl diethyl ketal.
- thioxanthones examples include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.
- dialkylaminobenzoic acid esters examples include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate, and the like.
- oxime esters examples include 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime.
- Commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals.
- acridines examples include 1,7-bis (9,9′-acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9- Ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- ( 4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-
- ester compounds of N-aryl amino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, N-phenylglycine 1-butyl ester, N-phenylglycine 2-butyl ester, N-phenylglycine tert-butyl ester, N-phenylglycine pentyl ester, N-phenylglycine hexyl ester, N-phenylglycine pentyl ester, N -Octyl ester of phenylglycine and the like.
- halogen compound examples include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, diallyl iodonium compounds, etc.
- the content of the halogen compound in the photosensitive resin composition is preferably 0.01 to 3% by mass with respect to the total amount of the components (A) to (E) from the viewpoint of sensitivity.
- photopolymerization initiators may be used alone or in combination of two or more.
- the ratio of the photopolymerization initiator to the total amount of the components (A) to (E) is preferably 0.1 to 20% by mass. This ratio is preferably 0.1% by mass or more from the viewpoint of obtaining sufficient sensitivity, this ratio is more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more. . On the other hand, setting this ratio to 20% by mass or less is preferable from the viewpoint of obtaining high resolution and suppressing aggregation in the developer, and it is more preferable to set this ratio to 10% by mass or less. .
- the blending amount of the (C) hexaarylbiimidazole compound as the photopolymerization initiator is 0.01 to 10% by mass with respect to the total amount of the components (A) to (E). It is necessary from the viewpoint of obtaining sufficient sensitivity that the blending amount be 0.01% by mass or more.
- the blending amount is preferably 1% by mass or more, more preferably 3% by mass or more. preferable.
- the (D) photosensitizer contains a distyrylbenzene derivative represented by the following general formula (2).
- distyrylbenzene itself is not included.
- R 3 , R 4 and R 5 each represent a cyano group
- c and e each independently represent an integer of 1 to 5
- d represents an integer of 0 to 4.
- the photosensitive resin composition of the present embodiment can be used in a laser direct imaging type exposure method, as compared with the conventional case. Excellent sensitivity (productivity), resolution, and adhesion.
- a cyano group is an electron-withdrawing group unlike a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, for example, and has an effect of lowering the energy level of the photosensitizer. It is presumed that this has the effect of facilitating the transfer of energy with a photoinitiator typified by lophine, and is effective in increasing the sensitivity.
- Examples of the distyrylbenzene derivative represented by the general formula (2) include 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, It includes at least one compound selected from '-(2-cyanostyryl) -4-stilbenecarbonitrile and 1,4-bis (4-cyanostyryl) benzene.
- 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, and 1,4-bis (4-cyanostyryl) benzene are particularly preferable. .
- the photosensitive resin composition of the present embodiment is particularly excellent in sensitivity (productivity), resolution, and adhesion.
- 1,4-bis (4-cyanostyryl) benzene is particularly preferable from the viewpoints of sensitivity (productivity), resolution, and adhesion.
- the reason why 1,4-bis (4-cyanostyryl) benzene is particularly preferred is presumed that both CN groups are in the para position, and that the excitation energy gap is increased by extending the conjugated system.
- the acid dissociation constant pKa of (D) the photosensitizer is greater than 9 and less than 12.
- the pKa is greater than 9.5 and less than 11.
- the photosensitive resin composition of the present embodiment has a sensitivity (productivity), a solution higher than that in the conventional laser direct imaging type exposure method. It is excellent in image quality and adhesion.
- the value of pKa uses a value calculated by Advanced Chemistry Development (AD / Labs) Software V11.02 (1994-2018 ACD / Labs).
- the molar extinction coefficient of the photosensitizer at a wavelength of 405 nm is 100 ⁇ ⁇ 1 cm ⁇ 1 or more.
- ⁇ is a unit of molar concentration
- the molar extinction coefficient is a value when acetone is used as a solvent.
- Examples of such (D) photosensitizer include 4- [3- (4-chlorophenyl) -4,5-dihydro-1H-pyrazol-1-yl] benzenesulfonamide.
- the sensitivity (productivity), resolution, and adhesion are particularly excellent.
- pKa is a pH value at which the dissociation rate of the ionic compound is 50%.
- the dissociation rate decreases at a pH of pKa or lower, and the dissociation rate increases at a pH of pKa or higher.
- sodium carbonate which is a developer used in a dry film, has a weak alkalinity of about 10, and a pH of a stripping solution such as sodium hydroxide or an amine stripping solution is 14 or more.
- the dissociation ratio of the ionic compound in the stripping solution is small, and a large improvement in stripping property cannot be expected.
- pKa is less than the same value as the pH of the developer, the dissociation rate of the ionic compound in the developer is large, and pattern swelling occurs during development. Therefore, by using a photosensitizer having an acid dissociation constant pKa larger than 9 and smaller than 12, both suppression of swelling during development and improvement of peelability can be achieved.
- the molar extinction coefficient at a wavelength of 405 nm is 100 ⁇ ⁇ 1 cm ⁇ 1 or more, the resist can efficiently absorb laser light, and sensitivity (productivity) is improved.
- the acid dissociation constant pKa is larger than 9 and smaller than 12, it is difficult to obtain a desired effect by using a sensitizer that does not satisfy the molar extinction coefficient and a photosensitizer that satisfies the molar extinction coefficient. It is thought that this is because a sensitizer compound satisfying pKa undergoes an addition reaction with the monomer, so that the conjugate structure of the compound is broken and stable dissociation cannot be performed in the stripping solution.
- the photosensitizer satisfying both pKa and molar extinction coefficient as in the present application transfers the light energy absorbed after photoexcitation to the hexaarylbiimidazole compound, which is the initiator, and returns to the original ground state.
- the molecular structure of the compound is not broken, stable dissociation is possible even in a stripping solution, and strippability can be improved.
- the acid dissociation constant pKa of the photosensitizer is more preferably 9.1 or more and 11.9 or less from the viewpoints of sensitivity (productivity), resolution, and adhesion.
- the acid dissociation constant pKa of the photosensitizer may be 9.2 or more, 9.5 or more, 9.8 or more, or 10.0 or more. May be 10.2 or more, 10.5 or more, 10.8 or more, 11.0 or more, or 11.2 or more. 11.5 or more may be sufficient and 11.8 or more may be sufficient. Further, the acid dissociation constant pKa may be 11.8 or less, 11.6 or less, 11.4 or less, 11.2 or less, or 11.0. Or 10.6 or less, 10.6 or less, 10.4 or less, 10.2 or less, or 10.0. Or 9.8 or less, 9.6 or less, 9.4 or less, or 9.2 or less.
- the molar extinction coefficient at a wavelength of 405 nm of the photosensitizer is more preferably 200 ⁇ ⁇ 1 cm ⁇ 1 or more and 1.0 ⁇ 10 10 ⁇ ⁇ from the viewpoint of sensitivity (productivity), resolution, and adhesion. 1 cm ⁇ 1 or less.
- a molar extinction coefficient of wavelength 405nm of the photosensitizer may also be 500 ⁇ -1 cm -1 or more, it may also be 1.0 ⁇ 10 3 ⁇ -1 cm -1 or more, 2.
- the upper limit is not particularly limited, but may be 1.0 ⁇ 10 5 ⁇ ⁇ 1 cm ⁇ 1 or less, 5.0 ⁇ 10 4 ⁇ ⁇ 1 cm ⁇ 1 or less, and 1.0 ⁇ It may be 10 4 ⁇ ⁇ 1 cm ⁇ 1 or less, or 5.0 ⁇ 10 3 ⁇ ⁇ 1 cm ⁇ 1 or less.
- a photosensitizer satisfies either of the following (1) or (2).
- (1) The relative fluorescence intensity for 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is greater than 100%.
- (2) The relative fluorescence intensity with respect to 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is 5% or more, and the intersection wavelength between the absorption spectrum and the fluorescence spectrum is It is less than 400 nm.
- the photosensitive resin composition of this embodiment becomes the thing excellent in the sensitivity, resolution, and adhesiveness.
- the initiation mechanism in the sensitizer and lophine (2,4,5-triphenylimidazole) system can be explained by the energy transfer from the photoexcited sensitizer to lofine and the subsequent cleavage of lophine.
- the photoexcited sensitizer returns to the ground state by emitting fluorescence, phosphorescence, or heat through an excited singlet state or an excited triplet state. This process takes time from nanoseconds to microseconds, and when the excitation light is still irradiated after returning to the ground state, the sensitizer repeats the photoexcitation-decay cycle again. As the number of cycles increases within the irradiation time of the excitation light, the existence probability of the photoexcited state increases, and therefore sensitization reaction to lophine is likely to occur.
- the singlet sensitizer has a short lifetime, that is, it is considered that the sensitivity increases as the fluorescence of the sensitizer increases (the fluorescence quantum yield increases).
- triplet sensitizers have a long lifetime in the triplet state with low excitation energy, so the time to return to the ground state and photoexcitation again increases, and the number of excitation cycles per hour is singlet sensitized. Therefore, the efficiency of sensitization to lophine is low. This situation is a particularly remarkable phenomenon in laser direct imaging type exposure that is high illumination and short time exposure.
- the free energy change in photoelectron transfer is expressed by the Rehm-Weller equation, and it is considered that the initiation reaction is more likely to occur as the excitation energy increases. From the above, it can be considered that the sensitivity improves as the fluorescence quantum yield of the photosensitizer and the minimum excitation energy E increase.
- the adhesion of the resist is improved when the exposure amount is increased.
- increasing the exposure dose tends to increase the line width of the resist top, it is important to compare the adhesion with the same line width.
- an increase in the transmittance decreases the absolute value of the absorbed exposure amount itself, so that the sensitivity becomes a problem.
- a high-sensitivity photosensitizer is effective for adhesion, and a photosensitizer that satisfies the following requirements is particularly effective. That is, in the photosensitive resin composition of this embodiment, it is preferable that (D) the photosensitizer satisfies either of the following (1) or (2). In the photosensitive resin composition of this embodiment, since (D) the component which has a specific physical property as a photosensitizer is contained, it was able to make resolution and adhesiveness compatible, without reducing a sensitivity. Become.
- the relative fluorescence intensity for 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is greater than 100%.
- the relative fluorescence intensity indicates how the excitation energy is used. Excitation energy is converted into heat and light. High relative fluorescence intensity means that much of the excitation energy is converted into light and emitted. The higher the relative fluorescence intensity, the better.
- the relative fluorescence intensity is preferably 110% or more, more preferably 120% or more, still more preferably 130% or more, still more preferably 140% or more, still more preferably 150% or more, and further preferably 160. % Or more, more preferably 170% or more, and particularly preferably 180% or more.
- the relative fluorescence intensity with respect to 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is 5% or more, and the intersection wavelength between the absorption spectrum and the fluorescence spectrum is It is less than 400 nm.
- the intersection wavelength represents the magnitude of the excitation energy. That is, the smaller the wavelength, the greater the excitation energy.
- the lowest excitation energy of a photosensitizer is the difference between the lowest energy of the ground state and the excited singlet state. From the Franck-Condon principle, the energy at the intersection wavelength of the absorption spectrum and the fluorescence spectrum is the lowest. Corresponds to excitation energy.
- the relative fluorescence intensity is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, still more preferably 40% or more, still more preferably 50% or more, and further preferably 60%. % Or more, more preferably 70% or more, and particularly preferably 80% or more.
- Such (D) photosensitizer is, for example, a fluorescent dye having a maximum absorption peak at 330 nm to 450 nm.
- fluorescent dyes include pyrazoline compounds, anthracene compounds, coumarin compounds, distyrylbenzene compounds, pyrene compounds, perylene compounds, benzoxazole compounds, etc., which satisfy the above conditions (1) and (2). It is limited to a specific structure.
- the photosensitizer may contain a diphenylpyrazoline derivative represented by the following general formula (1).
- diphenylpyrazoline itself is not included.
- R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, an amino group, or a carbon number 1 to 20 alkylamino group, fluoro group, chloro group, bromo group, carboxyl group, cyano group, nitro group, acetyl group, sulfonyl group, sulfonamide group, a and b are each independently an integer of 0 to 5 Indicates.
- a is 2 or more, a plurality of R1s may be the same or different, and when b is 2 or more, a plurality of R2s may be the same or different.
- Examples of the diphenylpyrazoline derivative represented by the general formula (1) include 4- [3- (4-chlorophenyl) -4,5-dihydro-1H-pyrazol-1-yl] benzenesulfonamide.
- the ratio of the photosensitizer to the total amount of the components (A) to (E) is preferably 0.01 to 1% by mass. Setting this ratio to 0.01% by mass or more is preferable from the viewpoint of obtaining sufficient sensitivity, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. . On the other hand, setting this ratio to 1% by mass or less is preferable from the viewpoint of obtaining high resolution, and it is more preferable to set this ratio to 0.8% by mass or less, and to 0.5% by mass or less. Further preferred.
- the total amount of the diphenylpyrazoline derivative or the distyrylbenzene derivative is 0.01 to 1% by mass with respect to the total amount of the components (A) to (E). It is necessary to make this blending amount 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and it is preferable that this blending amount be 0.05% by mass or more, and 0.1% by mass or more. More preferably. On the other hand, it is necessary to make this blending amount 1% by mass or less from the viewpoint of obtaining high resolution, and this blending amount is preferably 0.8% by mass or less, and 0.5% by mass or less. More preferably.
- the “(E) additive” is a component blended to give a desired function to the photosensitive resin composition, and the above-described (A) component, (B) component, Includes components other than the component (C) and the component (D).
- the additive contains carboxyl benzotriazoles from the viewpoint of preventing the blush of the substrate.
- Carboxybenzotriazoles are contained in an amount of 0.01 to 5% by mass based on the total amount of the components (A) to (E).
- the blending amount is preferably 0.03% by mass or more, and more preferably 0.05% by mass or more.
- the blending amount is preferably 3% by mass or less, and preferably 1% by mass or less. Further preferred.
- carboxyl benzotriazoles examples include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and an aminomethyl group that may be substituted 1 -[N, N-bis (2-ethylhexyl) aminomethyl] -5-carboxylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -4-carboxylbenzotriazole, 1- [N, N-bis (isopropyl) aminomethyl] -5-carboxylbenzotriazole, 1- [N-hydro-N-3- (2-ethylhexyloxy) -1-propylaminomethyl] -5-carboxylbenzotriazole, 1- [N, N-bis (1-octyl) aminomethyl] -5-carboxylbenzotriazol 1- [N, N-bis (2-hydroxypropyl) aminomethyl] -5-carboxylbenzotriazo
- 1- [N, N-bis (1-butyl) aminomethyl] -5-carboxylbenzotriazole is preferable from the viewpoint of blush prevention performance.
- the substitution position of the carboxyl group the 5-position and the 6-position may be mixed in the synthesis process, both of which are preferable, for example, 0.5: 1.5 to 1.5:
- a 0.5 (mass ratio) mixture, in particular a 1: 1 (mass ratio) mixture, can be used. It may be simply described as “1-N-dibutylaminomethylcarboxylbenzotriazole” to indicate a mixture of a 5-position substituent and a 6-position substituent.
- carboxyl benzotriazole for example, compounds described in JP-A-2008-175957 can also be used.
- 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1, 2,4-triazole, 3-mercapto-1,2,4-triazole, 3-mercaptotriazole, 4,5-diphenyl-1,3-diazol-2-yl, 5-amino-1H-tetrazole, etc. can also be used. .
- additives that may be added as component (E) to the photosensitive resin composition described above include colorants, radical polymerization inhibitors, benzotriazoles other than carboxyl benzotriazoles, bisphenol A epoxy compounds, And plasticizers.
- colorant examples include fuchsin, phthalocyanine green, auramin base, paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue. 20.
- Diamond green for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.
- 1,4-bis (4-methylphenylamino) -9,10-anthraquinone for example, manufactured by Orient Chemical Industry Co., Ltd.) OPLAS GREEN533
- 1,4-bis (butylamino) anthraquinone for example, OIL BLUE 2N, manufactured by Orient Chemical Industry Co., Ltd.
- 1,4-bis (isopropylamino) 9,10-anthraquinone e.g. Orient Chemical Industries Co., OIL BLUE 630
- the like for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.
- 1,4-bis (4-methylphenylamino) -9,10-anthraquinone for example, manufactured by Orient Chemical Industry Co., Ltd.
- the ratio of the colorant to the total amount of the components (A) to (E) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.5 to 2%. % By mass, particularly preferably 0.5 to 1% by mass.
- the colorant for example, a leuco dye or a fluoran dye may be contained.
- the exposed portion of the photosensitive resin layer is colored, which is preferable from the viewpoint of visibility, and when an inspection machine or the like reads the alignment marker for exposure, the contrast between the exposed portion and the unexposed portion is high. Since the larger one becomes easier to recognize, it is advantageous.
- the leuco dye examples include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], and the like.
- leuco crystal violet as the leuco dye.
- the content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass based on the total amount of the components (A) to (E). Setting the content to 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed part and the unexposed part, more preferably setting the content to 0.2% by mass or more.
- the content be 4% by mass or more.
- the content is preferably 10% by mass or less from the viewpoint of maintaining storage stability, the content is more preferably 2% by mass or less, and particularly preferably 1% by mass or less. preferable.
- a combination of a leuco dye and a halogen compound in the photosensitive resin composition from the viewpoint of optimizing adhesion and contrast.
- the halogen compound can be derived from the organic halogen compound described above as the component (C), and tribromomethylphenylsulfone is particularly preferable.
- radical polymerization inhibitor examples include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, a nitrosophenylhydroxyamine aluminum salt is preferred.
- benzotriazoles other than carboxyl benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and 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, etc. .
- Examples of epoxy compounds of bisphenol A include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the ends.
- the total content of radical polymerization inhibitors, benzotriazoles other than carboxyl benzotriazoles, carboxyl benzotriazoles, and epoxy compounds of bisphenol A is based on the total amount of components (A) to (E).
- the content is preferably 0.001 to 3% by mass, and more preferably 0.01 to 1% by mass. Setting the content to 0.001% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition, while setting the content to 3% by mass or less is photosensitive. This is preferable from the viewpoint of maintaining the sensitivity of the resin composition and suppressing decolorization and color development of the dye.
- plasticizer examples include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and tri-n-acetyl citrate.
- phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and tri-n-acetyl citrate.
- Adecanol SDX-1569, Adecanol SDX-1570, Adecanol SDX-1571, Adecanol SDX-479 (manufactured by Asahi Denka Co., Ltd.), New Pole BP-23P, New Pole BP-3P, New Pole BP-5P, New Pole Pole BPE-20T, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Unior DB-400, Unior DAB-800, Unior DA-350F, Unior DA- Examples include compounds having a bisphenol skeleton such as 400, Uniol DA-700 (manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.).
- the content of the plasticizer with respect to the total amount of the components (A) to (E) is preferably 1 to 50% by mass, more preferably 1 to 30% by mass. Setting the content to 1% by mass or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while making the content 50% by mass or less, This is preferable from the viewpoint of suppressing insufficient curing and cold flow.
- the photosensitive resin composition of the present embodiment preferably has a light transmittance of 405 nm at a film thickness of 25 ⁇ m that is greater than 10%. Since the transmittance is high, the adhesion is high, and the sensitivity is also high, so that the productivity is excellent.
- the photosensitive resin laminated body of this embodiment is equipped with a support body and the photosensitive resin layer containing the photosensitive resin composition provided on the support body.
- Another embodiment provides a photosensitive resin laminate in which a photosensitive resin layer composed of the photosensitive resin composition as described above is laminated on a support. If necessary, the photosensitive resin laminate may have a protective layer on the surface opposite to the support side of the photosensitive resin layer.
- the support is usually a support film.
- the support film is preferably a transparent film that transmits light emitted from the exposure light source.
- support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films can be stretched if necessary, and preferably have a haze of 5 or less. The thinner the film is, the more advantageous it is for improving the image forming property and the economical efficiency, but a film having a thickness of 10 to 30 ⁇ m is preferably used in order to maintain the strength of the photosensitive resin laminate.
- the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support in terms of adhesion to the photosensitive resin layer and can be easily peeled off.
- a polyethylene film or a polypropylene film can be preferably used as the protective layer.
- a film having excellent peelability disclosed in JP-A-59-202457 can be used.
- the thickness of the protective layer is preferably 10 to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
- the protective layer When polyethylene is used for the protective layer, there is a gel called fish eye on the surface of the polyethylene film, which may be transferred to the photosensitive resin layer. When the fish eye is transferred to the photosensitive resin layer, air may be entrained during the lamination, resulting in voids, leading to a defect in the resist pattern.
- the protective layer is preferably made of stretched polypropylene. Specific examples include Alfane E-200A manufactured by Oji Paper Co., Ltd.
- the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, it is preferably 5 ⁇ m to 100 ⁇ m, more preferably 7 ⁇ m to 60 ⁇ m. The thinner the thickness, the higher the resolution, and the thicker the film strength. .
- a method for producing the photosensitive resin laminate will be described.
- a method for producing a photosensitive resin laminate by sequentially laminating a support, 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 that dissolves the photosensitive resin composition into a uniform solution, first applied onto the support film using a bar coater or roll coater, and then dried to form the support film.
- a photosensitive resin layer made of a photosensitive resin composition is laminated thereon.
- a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
- examples of the solvent include ketones typified by methyl ethyl ketone (MEK), alcohols typified by methanol, ethanol, and isopropanol.
- MEK methyl ethyl ketone
- the solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support film is 500 to 4000 mPa ⁇ s at 25 ° C.
- Resist pattern formation method includes the steps of laminating the above-described photosensitive resin laminate on a substrate, exposing and developing.
- Resist patterns include circuit boards (printed wiring boards), flexible boards, lead frame boards, COF (chip on film) boards, semiconductor package boards, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, and organic EL displays. Examples thereof include resist patterns formed on wirings, PDP (plasma display panel) electrodes, and the like.
- the resist pattern can be formed through the following steps.
- the resist pattern forming method of the present embodiment includes a step of laminating a photosensitive resin laminate on a substrate, a step of exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer.
- the laminating conditions may be appropriately set under conventionally known conditions.
- Exposure process A mask film having a desired pattern (for example, a wiring pattern) is brought into close contact with the support of the photosensitive resin laminate and exposed using an active light source, or a drawing pattern corresponding to the desired pattern is formed. Exposure by direct drawing. The exposure is preferably performed by direct drawing of a drawing pattern. As the exposure wavelength, i-line, h-line, g-line, a mixture thereof and the like can be used as appropriate. This is advantageous in that sensitivity and high resolution can be realized. Thereby, the photosensitive resin composition of this Embodiment is useful especially in direct drawing.
- the exposure conditions may be appropriately set under conventionally known conditions.
- the support on the photosensitive resin layer is peeled off, and subsequently, the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to form a resist pattern on the substrate.
- an 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 an aqueous Na 2 CO 3 solution having a concentration of about 0.2 to 2% by mass and about 20 to 40 ° C. is generally used.
- a resist pattern can be obtained through each of the above steps, but in some cases, a heating step of about 100 to 300 ° C. can be further performed. By carrying out this heating step, chemical resistance can be further improved.
- a heating step of about 100 to 300 ° C.
- chemical resistance can be further improved.
- a hot air, infrared, or far infrared heating furnace can be used.
- the method for forming a metal wiring of the present embodiment includes a step of forming a resist pattern by the above method, a step of forming a metal wiring (conductor pattern) using the resist pattern, and a step of peeling the resist pattern.
- Another aspect includes a process for producing a circuit board, comprising the steps of laminating, exposing, developing, and plating the above-described photosensitive resin laminate to a substrate, and the above-mentioned photosensitive resin laminate to the substrate.
- a method of manufacturing a circuit board which includes steps of laminating, exposing, developing, and etching.
- the circuit board can be manufactured by further etching or plating the base material on which the resist pattern is formed by the procedure described above for the resist pattern forming method.
- Etching and plating can be performed as follows.
- Etching process or plating process The surface of the base material exposed by the above development (for example, a copper surface in the case of a copper clad laminate) is etched or plated to form a conductor pattern.
- etching and plating methods conventionally known methods can be appropriately used.
- the resist pattern is stripped from the substrate with an aqueous solution having alkalinity stronger than the developer.
- the alkaline aqueous solution for peeling is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ° C. is generally used.
- a small amount of a water-soluble solvent can also be added to the stripping solution.
- the use of a diphenylpyrazoline derivative as the (D) photosensitizer has particularly excellent post-plating peelability.
- the circuit board can be manufactured by the procedure as described above.
- the semiconductor package manufacturing method of the present embodiment includes a step of forming a resist pattern on a semiconductor package substrate as a base material by the above-described resist pattern forming method, and a semiconductor package substrate on which the resist pattern is formed.
- a method for manufacturing a semiconductor package which includes a step of etching or plating.
- the configuration of the semiconductor package substrate and the semiconductor package any conventionally known one can be adopted as appropriate. Further, the formation of the resist pattern and the etching or plating can be performed by the procedure as described above.
- the photosensitive resin laminate of the present embodiment includes a circuit board (printed wiring board), a flexible board, a lead frame board, a COF (chip on film) board, a semiconductor package board, a transparent electrode for a liquid crystal panel, and a liquid crystal panel.
- This is a photosensitive resin laminate suitable for the production of conductor patterns such as TFT wiring, organic EL display wiring, and PDP (plasma display panel) electrodes.
- a photosensitive resin composition excellent in sensitivity (productivity), resolution, and adhesion, a photosensitive resin laminate, and the photosensitive resin laminate are provided. It is possible to provide a method for forming a resist pattern and a method for forming a conductor pattern using the.
- ⁇ 405 nm transmittance of photosensitive resin layer The polyethylene film of the photosensitive resin laminate was peeled off, and the absorption spectrum was measured with a spectrophotometer (Hitachi U-3010). Absorbance at 405 nm was converted to transmittance to obtain a measured value.
- the addition amount of the photosensitizer was set so that the transmittance at 405 nm was about 40%, so that the performance of the resist when the photosensitizer absorbed the same amount of light could be compared.
- a 1 mass% Na 2 CO 3 aqueous solution at 30 ° C. was sprayed for a predetermined time using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine).
- the exposed portion was dissolved and removed in a time twice as long as the minimum development time.
- the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time.
- the actual development time was twice as long as the minimum development time to obtain a cured resist pattern.
- the exposure amount at which the top line width of the resist of the mask pattern having a line / space of 20 ⁇ m / 20 ⁇ m was 20 ⁇ m as the mask value was defined as sensitivity.
- ⁇ Resolution evaluation> Similar to the sensitivity evaluation procedure, substrate leveling and lamination are performed, and a line pattern with a ratio of 1: 1 between the exposed area and the unexposed area is the exposure amount obtained by the sensitivity evaluation using the drawing data. Exposed. Thereafter, development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which the cured resist line was normally formed was defined as the resolution value.
- ⁇ Adhesion evaluation> Similar to the sensitivity evaluation procedure, the substrate is flattened and laminated, and the line pattern having a ratio of 1: 200 between the exposed area and the unexposed area is the exposure amount obtained by the sensitivity evaluation using the drawing data. Exposed. Thereafter, development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which the cured resist line was normally formed was defined as the adhesion value.
- Copper sulfate conch (Meltex Co., Ltd.) was diluted 3.6 times with 19 wt% sulfuric acid, and 200 ppm of concentrated hydrochloric acid was added. Subsequently, capalacid HL and caparacid GS were added as brighteners at 0.4 ml / l and 20 ml / l, respectively.
- the plating current evaluation substrate (6 cm ⁇ 12.5 cm) after the pre-plating treatment was subjected to an applied current of 0 with a Haring cell uniform plating apparatus (manufactured by Yamamoto Kakin Tester Co., Ltd.) using the prepared copper sulfate plating solution. Plated at 4A for 65 minutes.
- the thickness of the copper plating film at this time was 20 ⁇ m.
- substrate which gave the plating process was put into 50 degreeC and 1.5 wt% caustic soda aqueous solution, and it immersed for 4 minutes, without stirring, and the resist film was peeled and removed. At this time, the minimum mask width at which the cured resist line between the plating patterns was completely peeled was defined as the post-plating peelability value.
- Examples 1 to 3 and Comparative Examples 1 to 7 The photosensitive resin composition and the solvent having the composition shown in Table 1 (where the numbers of the respective components indicate the blending amount (parts by mass) as the solid content) are sufficiently stirred and mixed to obtain a photosensitivity having a solid content of 60% by mass.
- the resin composition preparation liquid was obtained.
- a 16 ⁇ m thick polyethylene terephthalate film (FB40 manufactured by Toray Industries Inc., haze value 0.6) is prepared as a support, and the photosensitive resin composition preparation liquid is uniformly applied to the surface of the film using a bar coater.
- the photosensitive resin layer was formed by drying in a dryer at 95 ° C. for 2 minutes and 30 seconds.
- the thickness of the photosensitive resin layer was 25 ⁇ m.
- Example 1 or 2 in which the acid dissociation constant pKa of the photosensitizer is larger than 9 and smaller than 12 is different from Comparative Examples 1 to 6 in which pKa is 9 or less or 12 or more in h-line exposure. It can be seen that high sensitivity and high resolution characteristics can be expressed. It can also be seen that (D) Example 1 using a diphenylpyrazoline derivative as a photosensitizer exhibits particularly excellent post-plating peelability.
- the photosensitive resin composition of the present invention has high sensitivity and high resolution
- a circuit board printed wiring board
- a flexible board a lead frame board
- a COF (chip on film) board a semiconductor package board
- a liquid crystal It can be suitably used for the production of conductor patterns in panel transparent electrodes, liquid crystal panel TFT wiring, organic EL display wiring, PDP (plasma display panel) electrodes, and the like.
Abstract
Description
すなわち、本発明は以下の通りのものである。
[1]
以下の成分:
(A)アルカリ可溶性高分子、
(B)エチレン性不飽和二重結合を有する化合物、
(C)光重合開始剤、および
(D)光増感剤、
を含み、
前記(D)光増感剤が、下記一般式(2)で表されるジスチリルベンゼン誘導体を含む、感光性樹脂組成物。
[2]
前記(D)光増感剤は、4’-(2-シアノスチリル)-2-スチルベンカルボニトリル、4’-(2-シアノスチリル)-3-スチルベンカルボニトリル、4’-(2-シアノスチリル)-4-スチルベンカルボニトリル、1,4-ビス(4-シアノスチリル)ベンゼンから選ばれる少なくとも1つの化合物を含む、[1]に記載の感光性樹脂組成物。
[3]
前記(D)光増感剤は、4’-(2-シアノスチリル)-2-スチルベンカルボニトリル、4’-(2-シアノスチリル)-3-スチルベンカルボニトリルを含む、[2]に記載の感光性樹脂組成物。
[4]
前記(D)光増感剤は、4’-(2-シアノスチリル)-4-スチルベンカルボニトリルを含む、[2]に記載の感光性樹脂組成物。
[5]
前記(D)光増感剤は、1,4-ビス(4-シアノスチリル)ベンゼンを含む、[2]に記載の感光性樹脂組成物。
[6]
前記(D)光増感剤は、最大吸収ピークを330nm-450nmに有する蛍光色素である、[1]から[5]のいずれかに記載の感光性樹脂組成物。
[7]
前記(C)光重合開始剤は、ヘキサアリールビイミダゾール化合物を含む、[1]~[6]のいずれかに記載の感光性樹脂組成物。
[8]
前記感光性樹脂組成物の膜厚25μmにおける波長405nmの光の透過率が10%よりも大きい、[1]~[7]のいずれかに記載の感光性樹脂組成物。
[9]
前記感光性樹脂組成物は金属配線形成用の感光性樹脂組成物である、[1]~[8]のいずれかに記載の感光性樹脂組成物。
[10]
支持体と、前記支持体上に設けられた1~9のいずれかに記載の感光性樹脂組成物を含む感光性樹脂層と、を備える、感光性樹脂積層体。
[11]
[10]に記載の感光性樹脂積層体を基材にラミネートする工程と、
前記感光性樹脂層を露光する工程と、
前記露光後の感光性樹脂層を現像する工程と、
を含む、レジストパターン形成方法。
[12]
前記露光を、描画パターンの直接描画により行う、[11]に記載のレジストパターン形成方法。
[13]
[11]または[12]に記載の方法によりレジストパターンを形成する工程と、
前記レジストパターンを用いて金属配線を形成する工程と、
前記レジストパターンを剥離する工程と、
を含む、金属配線の形成方法。
[14]
[11]または[12]に記載のレジストパターン形成方法によって、基材としての半導体パッケージ用基板上にレジストパターンを形成する工程、及び前記レジストパターンが形成された半導体パッケージ用基板をエッチングするかまたはめっきする工程を含む、半導体パッケージの製造方法。
[15]
以下の成分:
(A)アルカリ可溶性高分子、
(B)エチレン性不飽和二重結合を有する化合物、
(C)光重合開始剤、および
(D)光増感剤、
を含み、
前記(D)光増感剤の酸解離定数pKaが9より大きく12より小さく、且つ、波長405nmのモル吸光係数が100М-1cm-1以上である(ただし、Мはモル濃度の単位であり、前記モル吸光係数はアセトンを溶媒に用いた場合の値である。)感光性樹脂組成物。
[16]
前記(D)光増感剤は、4-[3-(4-クロロフェニル)-4,5-ジヒドロ-1H-ピラゾール-1-イル]ベンゼンスルフォンアミドである、[15]に記載の感光性樹脂組成物。
[17]
前記(B)エチレン性不飽和二重結合を有する化合物は、分子内にヒドロキシル基を含む、[16]に記載の感光性樹脂組成物。
[18]
前記(D)光増感剤は、最大吸収ピークを330nm-450nmに有する蛍光色素である、[15]~[17]のいずれかに記載の感光性樹脂組成物。
[19]
前記(C)光重合開始剤は、ヘキサアリールビイミダゾール化合物を含む、[15]~[18]のいずれかに記載の感光性樹脂組成物。
[20]
前記感光性樹脂組成物の膜厚25μmにおける波長405nmの光の透過率が10%よりも大きい、[15]~[19]のいずれかに記載の感光性樹脂組成物。
[21]
前記(D)光増感剤の酸解離定数pKaが9.5より大きく11より小さい、[15]~[20]のいずれかに記載の感光性樹脂組成物。
[22]
前記(B)エチレン性不飽和二重結合を有する化合物は、分子内にヒドロキシル基を含む、[15]~[21]のいずれかに記載の感光性樹脂組成物。
[23]
前記感光性樹脂組成物は金属配線形成用の感光性樹脂組成物である、[15]~[22]のいずれかに記載の感光性樹脂組成物。
[24]
支持体と、前記支持体上に設けられた[15]~[23]のいずれかに記載の感光性樹脂組成物を含む感光性樹脂層と、を備える、感光性樹脂積層体。
[25]
[24]に記載の感光性樹脂積層体を基材にラミネートする工程と、
前記感光性樹脂層を露光する工程と、
前記露光後の感光性樹脂層を現像する工程と、
を含む、レジストパターン形成方法。
[26]
前記露光を、描画パターンの直接描画により行う、[25]に記載のレジストパターン形成方法。
[27]
[25]または[26]に記載の方法によりレジストパターンを形成する工程と、
前記レジストパターンを用いて金属配線を形成する工程と、
前記レジストパターンを剥離する工程と、
を含む、金属配線の形成方法。
[28]
[25]または[26]に記載のレジストパターン形成方法によって、基材としての半導体パッケージ用基板上にレジストパターンを形成する工程、及び前記レジストパターンが形成された半導体パッケージ用基板をエッチングするかまたはめっきする工程を含む、半導体パッケージの製造方法。 As a result of intensive studies and experiments to solve the above problems, the present inventor has found that the above problems can be solved by containing a specific component as (D) a photosensitizer.
That is, the present invention is as follows.
[1]
The following ingredients:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated double bond,
(C) a photopolymerization initiator, and (D) a photosensitizer,
Including
The photosensitive resin composition in which the said (D) photosensitizer contains the distyrylbenzene derivative represented by following General formula (2).
[2]
The photosensitizer (D) is 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, 4 ′-(2-cyanostyryl). ) The photosensitive resin composition according to [1], comprising at least one compound selected from -4-stilbenecarbonitrile and 1,4-bis (4-cyanostyryl) benzene.
[3]
The (D) photosensitizer includes 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, according to [2]. Photosensitive resin composition.
[4]
The photosensitive resin composition according to [2], wherein the (D) photosensitizer includes 4 ′-(2-cyanostyryl) -4-stilbenecarbonitrile.
[5]
The photosensitive resin composition according to [2], wherein the (D) photosensitizer includes 1,4-bis (4-cyanostyryl) benzene.
[6]
The photosensitive resin composition according to any one of [1] to [5], wherein the (D) photosensitizer is a fluorescent dye having a maximum absorption peak at 330 nm to 450 nm.
[7]
The photosensitive resin composition according to any one of [1] to [6], wherein the (C) photopolymerization initiator includes a hexaarylbiimidazole compound.
[8]
The photosensitive resin composition according to any one of [1] to [7], wherein a transmittance of light having a wavelength of 405 nm at a film thickness of 25 μm of the photosensitive resin composition is greater than 10%.
[9]
The photosensitive resin composition according to any one of [1] to [8], wherein the photosensitive resin composition is a photosensitive resin composition for forming a metal wiring.
[10]
A photosensitive resin laminate comprising: a support; and a photosensitive resin layer comprising the photosensitive resin composition according to any one of 1 to 9 provided on the support.
[11]
A step of laminating the photosensitive resin laminate according to [10] on a substrate;
Exposing the photosensitive resin layer;
Developing the photosensitive resin layer after the exposure;
A resist pattern forming method.
[12]
The resist pattern forming method according to [11], wherein the exposure is performed by direct drawing of a drawing pattern.
[13]
Forming a resist pattern by the method according to [11] or [12];
Forming a metal wiring using the resist pattern;
Removing the resist pattern;
A method for forming a metal wiring including:
[14]
The method of forming a resist pattern on a semiconductor package substrate as a base material by the resist pattern forming method according to [11] or [12], and etching the semiconductor package substrate on which the resist pattern is formed, or A method for manufacturing a semiconductor package, including a step of plating.
[15]
The following ingredients:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated double bond,
(C) a photopolymerization initiator, and (D) a photosensitizer,
Including
The acid dissociation constant pKa of the (D) photosensitizer is greater than 9 and less than 12, and the molar extinction coefficient at a wavelength of 405 nm is 100 М -1 cm -1 or more (where М is a unit of molar concentration) The molar extinction coefficient is a value when acetone is used as a solvent.) Photosensitive resin composition.
[16]
The photosensitive resin according to [15], wherein the (D) photosensitizer is 4- [3- (4-chlorophenyl) -4,5-dihydro-1H-pyrazol-1-yl] benzenesulfonamide. Composition.
[17]
(B) The photosensitive resin composition according to [16], wherein the compound having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule.
[18]
The photosensitive resin composition according to any one of [15] to [17], wherein the (D) photosensitizer is a fluorescent dye having a maximum absorption peak at 330 nm to 450 nm.
[19]
The photosensitive resin composition according to any one of [15] to [18], wherein the (C) photopolymerization initiator includes a hexaarylbiimidazole compound.
[20]
The photosensitive resin composition according to any one of [15] to [19], wherein a transmittance of light having a wavelength of 405 nm at a film thickness of 25 μm of the photosensitive resin composition is greater than 10%.
[21]
The photosensitive resin composition according to any one of [15] to [20], wherein the acid dissociation constant pKa of the (D) photosensitizer is greater than 9.5 and less than 11.
[22]
The photosensitive resin composition according to any one of [15] to [21], wherein the compound (B) having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule.
[23]
The photosensitive resin composition according to any one of [15] to [22], wherein the photosensitive resin composition is a photosensitive resin composition for forming a metal wiring.
[24]
A photosensitive resin laminate comprising: a support; and a photosensitive resin layer including the photosensitive resin composition according to any one of [15] to [23] provided on the support.
[25]
A step of laminating the photosensitive resin laminate according to [24] on a substrate;
Exposing the photosensitive resin layer;
Developing the photosensitive resin layer after the exposure;
A resist pattern forming method.
[26]
The resist pattern forming method according to [25], wherein the exposure is performed by direct drawing of a drawing pattern.
[27]
Forming a resist pattern by the method according to [25] or [26];
Forming a metal wiring using the resist pattern;
Removing the resist pattern;
A method for forming a metal wiring including:
[28]
The step of forming a resist pattern on a semiconductor package substrate as a base material by the resist pattern forming method described in [25] or [26], and the semiconductor package substrate on which the resist pattern is formed are etched or A method for manufacturing a semiconductor package, including a step of plating.
実施の形態では、感光性樹脂組成物は、以下の(A)~(E)の各成分:(A)アルカリ可溶性高分子(本開示で(A)成分ともいう)、(B)エチレン性不飽和二重結合を有する化合物(本開示で(B)成分ともいう)、(C)光重合開始剤(本開示で(C)成分ともいう)、(D)光増感剤(本開示で(D)成分ともいう)からなる。(E)添加剤(本開示で(E)成分ともいう)を含んでいてもよい。以下、各成分を順に説明する。 <Photosensitive resin composition>
In the embodiment, the photosensitive resin composition comprises the following components (A) to (E): (A) an alkali-soluble polymer (also referred to as component (A) in the present disclosure), (B) A compound having a saturated double bond (also referred to as component (B) in the present disclosure), (C) a photopolymerization initiator (also referred to as component (C) in the present disclosure), (D) a photosensitizer (in the present disclosure ( D) component)). (E) An additive (also referred to as component (E) in the present disclosure) may be included. Hereinafter, each component will be described in order.
(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であり、具体的には、アルカリ可溶性に寄与する官能基(例えばカルボキシル基)を、所望のアルカリ物質に溶解するのに十分な量で有する高分子である。また、典型的には、(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線状重合体の質量(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好ましく、そして酸当量を250以上にすることが好ましい。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く、そして酸当量を450以下にすることが好ましい。 (A) Alkali-soluble polymer (A) An alkali-soluble polymer is a polymer that is easily soluble in an alkali substance. Specifically, a functional group that contributes to alkali solubility (for example, a carboxyl group) is dissolved in a desired alkali substance. It is a polymer that has a sufficient amount to do. Also, typically, the amount of carboxyl groups contained in (A) the alkali-soluble polymer is from 100 to 600, preferably from 250 to 450, in terms of acid equivalent. The acid equivalent means the mass (unit: gram) of a linear polymer having 1 equivalent of a carboxyl group in the molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary for providing the photosensitive resin layer with developability and peelability with respect to an aqueous alkali solution. Setting the acid equivalent to 100 or more is preferable from the viewpoint of improving development resistance, resolution, and adhesion, and it is preferable to set the acid equivalent to 250 or more. On the other hand, the acid equivalent is preferably 600 or less from the viewpoint of improving developability and peelability, and the acid equivalent is preferably 450 or less.
(a-1)スチレン15~60質量%と、アクリル酸、メタクリル酸、アクリル酸エステル、及びメタクリル酸エステルからなる群から選択される1種以上のアクリル単量体とを含む重合成分に由来するアクリル共重合体;
(a-2)ベンジルメタクリレート20~85質量%と、アクリル酸、メタクリル酸、アクリル酸エステル、及びベンジルメタクリレート以外のメタクリル酸エステルからなる群から選択される1種以上のアクリル単量体とを含む重合成分に由来するアクリル共重合体;
を含むことが、高解像性を発現する上で好ましい。(a-1)成分及び(a-2)成分の総量の、(A)成分~(E)成分の総量中に占める割合としては、10~60質量%が、高解像性を発現する上で好ましい。上記割合は解像性の観点から好ましくは20質量%以上、より好ましくは30質量%以上であり、カットチップ性の観点から好ましくは55質量%以下、より好ましくは50質量%以下である。 In particular, the photosensitive resin composition has, as the component (A), one or more components selected from the group consisting of the following (a-1) and (a-2):
(A-1) Derived from a polymerization component comprising 15 to 60% by mass of styrene and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester. Acrylic copolymer;
(A-2) 20 to 85% by mass of benzyl methacrylate and one or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester other than benzyl methacrylate An acrylic copolymer derived from a polymerization component;
It is preferable that high resolution is exhibited. The proportion of the total amount of the component (a-1) and the component (a-2) in the total amount of the components (A) to (E) is 10 to 60% by mass in order to express high resolution. Is preferable. The above ratio is preferably 20% by mass or more, more preferably 30% by mass or more from the viewpoint of resolution, and preferably 55% by mass or less, more preferably 50% by mass or less from the viewpoint of cut-tip properties.
(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アクリロイル基を有する化合物を含むことが好ましい。分子内にアクリロイル基を有する化合物としては、例えば、ポリアルキレンオキシドの片方の末端に(メタ)アクリル酸を付加した化合物又は、片方の末端に(メタ)アクリル酸を付加し、他方の末端をアルキルエーテル化又はアリルエーテル化したもの等を挙げることができる。 (B) Compound having ethylenically unsaturated double bond (B) Compound having ethylenically unsaturated double bond is an acryloyl group in the molecule from the viewpoint of curability and compatibility with (A) alkali-soluble polymer. It is preferable that the compound which has this is included. Examples of the compound having an acryloyl group in the molecule include a compound in which (meth) acrylic acid is added to one end of polyalkylene oxide, or (meth) acrylic acid is added to one end and the other end is alkyl. Examples include etherified or allyl etherified compounds.
前記(B)エチレン性不飽和二重結合を有する化合物は、分子内にヒドロキシル基を含むことが好ましい。これにより、特に感度(生産性)、解像性、密着性に優れものとなる。 (B) As compounds having an ethylenically unsaturated bond, 4-normalnonylphenoxyoctaethylene glycol acrylate, 4-normalnonylphenoxytetraethylene glycol acrylate, γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl A compound having one ethylenically unsaturated bond such as -о-phthalate may be included. It is preferable from the viewpoints of releasability and cured film flexibility, and it is also preferable from the viewpoint of sensitivity, resolution, and adhesion when γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-о-phthalate is included.
The compound (B) having an ethylenically unsaturated double bond preferably contains a hydroxyl group in the molecule. As a result, the sensitivity (productivity), resolution, and adhesion are particularly excellent.
また、下限値には限定は無いが、この値は0.005以上であってもよく、0.010以上であってもよく、0.030以上であってもよく、0.050以上であってもよい。 In the present embodiment, substances other than (A) the alkali-soluble polymer and (B) the compound having an ethylenically unsaturated bond contained in the solid content in the photosensitive resin composition are other than (A) and (B). When used as a component, the value of [mass of components other than (A) and (B)] / [mass of compound (B) having an ethylenically unsaturated bond] is preferably 0.190 or less. When this value is 0.190 or less, the content of components that are not incorporated into the crosslinked structure can be reduced with respect to the content of the compound (B) having an ethylenically unsaturated bond that forms the crosslinked structure. Therefore, it is preferable from the viewpoint of excellent adhesion and resolution even under extremely severe development conditions such as over-development and over-washing and the developer temperature is high. From the same viewpoint, it is more preferably 0.185 or less, further preferably 0.180 or less, particularly preferably 0.175 or less, and most preferably 0.170 or less. It may be 0.165 or less, or 0.160 or less.
The lower limit is not limited, but this value may be 0.005 or more, 0.010 or more, 0.030 or more, or 0.050 or more. May be.
(C)光重合開始剤は、感度と解像度を得る観点からヘキサアリールビイミダゾール化合物を含むことが好ましい。 (C) Photopolymerization initiator (C) The photopolymerization initiator preferably contains a hexaarylbiimidazole compound from the viewpoint of obtaining sensitivity and resolution.
下にすることがより好ましい。 (C) The ratio of the photopolymerization initiator to the total amount of the components (A) to (E) is preferably 0.1 to 20% by mass. This ratio is preferably 0.1% by mass or more from the viewpoint of obtaining sufficient sensitivity, this ratio is more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more. . On the other hand, setting this ratio to 20% by mass or less is preferable from the viewpoint of obtaining high resolution and suppressing aggregation in the developer, and it is more preferable to set this ratio to 10% by mass or less. .
本実施形態の感光性樹脂組成物において、前記(D)光増感剤が、下記一般式(2)で表されるジスチリルベンゼン誘導体を含む。なお、本実施形態では、ジスチリルベンゼンそのものは含まない。
(D)光増感剤として上記一般式(2)で表されるジスチリルベンゼン誘導体を含むことにより、本実施形態の感光性樹脂組成物は、レーザーダイレクトイメージング型露光方式において、従来よりも、感度(生産性)、解像性、密着性に優れたものとなる。
シアノ基は、例えば、水素原子、アルキル基、アルコキシ基、ハロゲン原子と異なり、電子吸引性基であり、光増感剤のエネルギー準位を下げる効果がある。これがロフィンに代表される光開始剤とのエネルギーの授受を行いやすい効果があり、高感度化に有効であると推測する。 (D) Photosensitizer In the photosensitive resin composition of the present embodiment, the (D) photosensitizer contains a distyrylbenzene derivative represented by the following general formula (2). In the present embodiment, distyrylbenzene itself is not included.
(D) By including the distyrylbenzene derivative represented by the above general formula (2) as a photosensitizer, the photosensitive resin composition of the present embodiment can be used in a laser direct imaging type exposure method, as compared with the conventional case. Excellent sensitivity (productivity), resolution, and adhesion.
A cyano group is an electron-withdrawing group unlike a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, for example, and has an effect of lowering the energy level of the photosensitizer. It is presumed that this has the effect of facilitating the transfer of energy with a photoinitiator typified by lophine, and is effective in increasing the sensitivity.
その中でも特に、4’-(2-シアノスチリル)-2-スチルベンカルボニトリル、4’-(2-シアノスチリル)-3-スチルベンカルボニトリル、1,4-ビス(4-シアノスチリル)ベンゼンが好ましい。これにより、本実施形態の感光性樹脂組成物は、特に、感度(生産性)、解像性、密着性に優れたものとなる。
特に、1,4-ビス(4-シアノスチリル)ベンゼンが感度(生産性)、解像性、密着性の観点から特に好ましい。1,4-ビス(4-シアノスチリル)ベンゼンが特に好ましい理由は、2つのCN基が両方ともパラ位にあり、共役系が伸びることで励起エネルギーギャップが大きくなるためと推測する。 Examples of the distyrylbenzene derivative represented by the general formula (2) include 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, It includes at least one compound selected from '-(2-cyanostyryl) -4-stilbenecarbonitrile and 1,4-bis (4-cyanostyryl) benzene.
Of these, 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, and 1,4-bis (4-cyanostyryl) benzene are particularly preferable. . Thereby, the photosensitive resin composition of the present embodiment is particularly excellent in sensitivity (productivity), resolution, and adhesion.
In particular, 1,4-bis (4-cyanostyryl) benzene is particularly preferable from the viewpoints of sensitivity (productivity), resolution, and adhesion. The reason why 1,4-bis (4-cyanostyryl) benzene is particularly preferred is presumed that both CN groups are in the para position, and that the excitation energy gap is increased by extending the conjugated system.
また、(D)光増感剤の波長405nmのモル吸光係数は100М-1cm-1以上である。ただし、Мはモル濃度の単位であり、前記モル吸光係数はアセトンを溶媒に用いた場合の値である。
このような(D)光増感剤としては、4-[3-(4-クロロフェニル)-4,5-ジヒドロ-1H-ピラゾール-1-イル]ベンゼンスルフォンアミドが挙げられる。これにより特に感度(生産性)、解像性、密着性に優れたものとなる。 In the photosensitive resin composition of this embodiment, the acid dissociation constant pKa of (D) the photosensitizer is greater than 9 and less than 12. Preferably, the pKa is greater than 9.5 and less than 11. (D) Since the acid dissociation constant pKa of the photosensitizer is in the above range, the photosensitive resin composition of the present embodiment has a sensitivity (productivity), a solution higher than that in the conventional laser direct imaging type exposure method. It is excellent in image quality and adhesion. The value of pKa uses a value calculated by Advanced Chemistry Development (AD / Labs) Software V11.02 (1994-2018 ACD / Labs).
Further, (D) the molar extinction coefficient of the photosensitizer at a wavelength of 405 nm is 100 М −1 cm −1 or more. However, М is a unit of molar concentration, and the molar extinction coefficient is a value when acetone is used as a solvent.
Examples of such (D) photosensitizer include 4- [3- (4-chlorophenyl) -4,5-dihydro-1H-pyrazol-1-yl] benzenesulfonamide. As a result, the sensitivity (productivity), resolution, and adhesion are particularly excellent.
硬化したレジストを剥離するためには、強アルカリ溶液に浸漬する必要がある。これは、レジスト中のカルボキシル基を酸解離させることでレジスト中のイオン濃度および浸透圧を上げ、剥離液によるレジストの膨潤を促進するためである。したがって、剥離性を向上させるためにはレジスト中にイオン化合物を添加すればよい。しかし、単純にイオン化合物を添加した場合には、現像時にレジストが膨潤し、正常なパターンを形成することができない。したがって現像後のパターンを維持して剥離性を向上させるためには、現像液中では解離しないが、剥離液中で解離する化合物が必要である。 (D) When the acid dissociation constant pKa of the photosensitizer is larger than 9 and smaller than 12, and the molar extinction coefficient at a wavelength of 405 nm is 100 М −1 cm −1 or more, sensitivity (productivity), resolution, adhesion The reason for its superiority is not clear, but is estimated as follows.
In order to peel the cured resist, it is necessary to immerse it in a strong alkaline solution. This is because the carboxyl group in the resist is acid-dissociated to increase the ion concentration and osmotic pressure in the resist and promote the swelling of the resist by the stripping solution. Therefore, an ionic compound may be added to the resist in order to improve the peelability. However, when an ionic compound is simply added, the resist swells during development and a normal pattern cannot be formed. Therefore, in order to maintain the pattern after development and improve the peelability, a compound that does not dissociate in the developer but dissociates in the remover is required.
(D)光増感剤の酸解離定数pKaは9.2以上であってもよく、9.5以上であってもよく、9.8以上であってもよく、10.0以上であってもよく、10.2以上であってもよく、10.5以上であってもよく、10.8以上であってもよく、11.0以上であってもよく、11.2以上であってもよく、11.5以上であってもよく、11.8以上であってもよい。また、酸解離定数pKaは11.8以下であってもよく、11.6以下であってもよく、11.4以下であってもよく、11.2以下であってもよく、11.0以下であってもよく、10.8以下であってもよく、10.6以下であってもよく、10.4以下であってもよく、10.2以下であってもよく、10.0以下であってもよく、9.8以下であってもよく、9.6以下であってもよく、9.4以下であってもよく、9.2以下であってもよい。 (D) The acid dissociation constant pKa of the photosensitizer is more preferably 9.1 or more and 11.9 or less from the viewpoints of sensitivity (productivity), resolution, and adhesion.
(D) The acid dissociation constant pKa of the photosensitizer may be 9.2 or more, 9.5 or more, 9.8 or more, or 10.0 or more. May be 10.2 or more, 10.5 or more, 10.8 or more, 11.0 or more, or 11.2 or more. 11.5 or more may be sufficient and 11.8 or more may be sufficient. Further, the acid dissociation constant pKa may be 11.8 or less, 11.6 or less, 11.4 or less, 11.2 or less, or 11.0. Or 10.6 or less, 10.6 or less, 10.4 or less, 10.2 or less, or 10.0. Or 9.8 or less, 9.6 or less, 9.4 or less, or 9.2 or less.
(D)光増感剤の波長405nmのモル吸光係数は、500М-1cm-1以上であってもよく、1.0×103М-1cm-1以上であってもよく、2.0×103М-1cm-1以上であってもよく、3.0×103М-1cm-1以上であってもよく、5.0×103М-1cm-1以上であってもよく、1.0×104М-1cm-1以上であってもよく、5.0×104М-1cm-1以上であってもよい。上限は特に限定は無いが、1.0×105М-1cm-1以下であってもよく、5.0×104М-1cm-1以下であってもよく、1.0×104М-1cm-1以下であってもよく、5.0×103М-1cm-1以下であってもよい。 (D) The molar extinction coefficient at a wavelength of 405 nm of the photosensitizer is more preferably 200 М −1 cm −1 or more and 1.0 × 10 10 М − from the viewpoint of sensitivity (productivity), resolution, and adhesion. 1 cm −1 or less.
(D) a molar extinction coefficient of wavelength 405nm of the photosensitizer may also be 500М -1 cm -1 or more, it may also be 1.0 × 10 3 М -1 cm -1 or more, 2. It may be 0 × 10 3 М −1 cm −1 or more, may be 3.0 × 10 3 М −1 cm −1 or more, and may be 5.0 × 10 3 М −1 cm −1 or more. It may be 1.0 × 10 4 М −1 cm −1 or more, or 5.0 × 10 4 М −1 cm −1 or more. The upper limit is not particularly limited, but may be 1.0 × 10 5 М −1 cm −1 or less, 5.0 × 10 4 М −1 cm −1 or less, and 1.0 × It may be 10 4 М −1 cm −1 or less, or 5.0 × 10 3 М −1 cm −1 or less.
(1)1-フェニル-3-(4-ビフェニル)-5-(4-tert-ブチル-フェニル)-ピラゾリンに対する相対蛍光強度が100%より大きい。
(2)1-フェニル-3-(4-ビフェニル)-5-(4-tert-ブチル-フェニル)-ピラゾリンに対する相対蛍光強度が5%以上であり、且つ、吸収スペクトルと蛍光スペクトルの交点波長が400nm未満である。
(D)光増感剤として特定の物性を有する成分を含有することで、本実施形態の感光性樹脂組成物は、感度、解像性、密着性に優れたものとなる。 Furthermore, in the photosensitive resin composition of this embodiment, it is preferable that (D) a photosensitizer satisfies either of the following (1) or (2).
(1) The relative fluorescence intensity for 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is greater than 100%.
(2) The relative fluorescence intensity with respect to 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is 5% or more, and the intersection wavelength between the absorption spectrum and the fluorescence spectrum is It is less than 400 nm.
(D) By containing the component which has a specific physical property as a photosensitizer, the photosensitive resin composition of this embodiment becomes the thing excellent in the sensitivity, resolution, and adhesiveness.
光励起された増感剤は、励起一重項状態や励起三重項状態を経て、蛍光や燐光、熱を放出することで基底状態に戻る。この過程はナノ秒からマイクロ秒の時間がかかり、基底状態に戻った後にまだ励起光が照射されている場合、増感剤は再び光励起-減衰のサイクルを繰り返す。励起光の照射時間内にこのサイクルが多いほど光励起状態の存在確率が大きくなり、したがってロフィンへの増感反応が起こりやすくなる。このサイクルを増加させるためには、寿命の短い一重項増感剤であることが重要で、つまり増感剤の蛍光性が大きい(蛍光量子収率が大きい)ほど感度が向上すると考えられる。逆に、三重項増感剤は励起エネルギーの低い三重項状態に存在する寿命が長いため、基底状態に戻り再び光励起されるまでの時間も長くなり、時間あたりの励起サイクル数が一重項増感剤と比較して少なくなるため、ロフィンへの増感効率は低くなる。
この状況は、高照度かつ短時間露光であるレーザーダイレクトイメージング型露光において特に顕著な現象である。
また、光電子移動における自由エネルギー変化は、レーンウェラー式(Rehm-Weller equation)によって表され、励起エネルギーが大きいほど開始反応が起こりやすくなると考えられる。
上記のことから、光増感剤の蛍光量子収率と、最低励起エネルギーEが大きいほど感度が向上すると考えることができる。 The initiation mechanism in the sensitizer and lophine (2,4,5-triphenylimidazole) system can be explained by the energy transfer from the photoexcited sensitizer to lofine and the subsequent cleavage of lophine.
The photoexcited sensitizer returns to the ground state by emitting fluorescence, phosphorescence, or heat through an excited singlet state or an excited triplet state. This process takes time from nanoseconds to microseconds, and when the excitation light is still irradiated after returning to the ground state, the sensitizer repeats the photoexcitation-decay cycle again. As the number of cycles increases within the irradiation time of the excitation light, the existence probability of the photoexcited state increases, and therefore sensitization reaction to lophine is likely to occur. In order to increase this cycle, it is important that the singlet sensitizer has a short lifetime, that is, it is considered that the sensitivity increases as the fluorescence of the sensitizer increases (the fluorescence quantum yield increases). Conversely, triplet sensitizers have a long lifetime in the triplet state with low excitation energy, so the time to return to the ground state and photoexcitation again increases, and the number of excitation cycles per hour is singlet sensitized. Therefore, the efficiency of sensitization to lophine is low.
This situation is a particularly remarkable phenomenon in laser direct imaging type exposure that is high illumination and short time exposure.
Moreover, the free energy change in photoelectron transfer is expressed by the Rehm-Weller equation, and it is considered that the initiation reaction is more likely to occur as the excitation energy increases.
From the above, it can be considered that the sensitivity improves as the fluorescence quantum yield of the photosensitizer and the minimum excitation energy E increase.
一般的に、レジストの密着性は露光量を増加させると向上する。しかし露光量を増加させるとレジストトップの線幅が太る傾向があるため、密着性は同一線幅で比較することが重要である。
同一線幅での密着向上には、光増感剤を減量し、レジスト透過率を増加することが有効である。これによって、レジストトップとボトムの吸収露光量の差が小さくなるためである。しかし、透過率の増加は吸収露光量の絶対値そのものを低下させるため、感度が低くなることが問題になる。 In addition, the point that the above mechanism is particularly effective for the adhesion of fine wires will be described.
In general, the adhesion of the resist is improved when the exposure amount is increased. However, since increasing the exposure dose tends to increase the line width of the resist top, it is important to compare the adhesion with the same line width.
In order to improve the adhesion with the same line width, it is effective to reduce the amount of the photosensitizer and increase the resist transmittance. This is because the difference in the amount of absorbed exposure between the resist top and the bottom is reduced. However, an increase in the transmittance decreases the absolute value of the absorbed exposure amount itself, so that the sensitivity becomes a problem.
すなわち、本実施形態の感光性樹脂組成物において、(D)光増感剤が、下記(1)又は(2)のいずれかを満たすことが好ましい。本実施形態の感光性樹脂組成物では、(D)光増感剤として特定の物性を有する成分を含有しているので、感度を低下させることなく、解像性、密着性を両立したものとなる。 Therefore, it is considered that a high-sensitivity photosensitizer is effective for adhesion, and a photosensitizer that satisfies the following requirements is particularly effective.
That is, in the photosensitive resin composition of this embodiment, it is preferable that (D) the photosensitizer satisfies either of the following (1) or (2). In the photosensitive resin composition of this embodiment, since (D) the component which has a specific physical property as a photosensitizer is contained, it was able to make resolution and adhesiveness compatible, without reducing a sensitivity. Become.
相対蛍光強度は、励起エネルギーの使われ方を示す。励起エネルギーは、熱と光に変換される。相対蛍光強度が大きいということは、励起エネルギーの多くが光に変換されて放出されることを意味する。
相対蛍光強度は大きいほど好ましい。相対蛍光強度は110%以上が好ましく、より好ましくは120%以上であり、更に好ましくは130%以上であり、更に好ましくは140%以上であり、更に好ましくは150%以上であり、更に好ましくは160%以上であり、更に好ましくは170%以上であり、特に好ましくは180%以上である。 (1) The relative fluorescence intensity for 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is greater than 100%.
The relative fluorescence intensity indicates how the excitation energy is used. Excitation energy is converted into heat and light. High relative fluorescence intensity means that much of the excitation energy is converted into light and emitted.
The higher the relative fluorescence intensity, the better. The relative fluorescence intensity is preferably 110% or more, more preferably 120% or more, still more preferably 130% or more, still more preferably 140% or more, still more preferably 150% or more, and further preferably 160. % Or more, more preferably 170% or more, and particularly preferably 180% or more.
交点波長は、励起エネルギーの大きさを表す。すなわち、波長が小さいほど、励起エネルギーは大きい。光増感剤の最低励起エネルギーは、基底状態と励起一重項状態の最低エネルギーの差であり、フランクコンドンの原理(Franck-Condon principle)から、吸収スペクトルと蛍光スペクトルの交点波長のエネルギーが、最低励起エネルギーに相当する。従って、交点波長が小さい場合は励起エネルギーが大きいので、相対蛍光強度は小さくてもよい。相対蛍光強度は大きいほど好ましい。相対蛍光強度は10%以上が好ましく、より好ましくは20%以上であり、更に好ましくは30%以上であり、更に好ましくは40%以上であり、更に好ましくは50%以上であり、更に好ましくは60%以上であり、更に好ましくは70%以上であり、特に好ましくは80%以上である。 (2) The relative fluorescence intensity with respect to 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is 5% or more, and the intersection wavelength between the absorption spectrum and the fluorescence spectrum is It is less than 400 nm.
The intersection wavelength represents the magnitude of the excitation energy. That is, the smaller the wavelength, the greater the excitation energy. The lowest excitation energy of a photosensitizer is the difference between the lowest energy of the ground state and the excited singlet state. From the Franck-Condon principle, the energy at the intersection wavelength of the absorption spectrum and the fluorescence spectrum is the lowest. Corresponds to excitation energy. Therefore, when the intersection wavelength is small, the excitation energy is large, so the relative fluorescence intensity may be small. The higher the relative fluorescence intensity, the better. The relative fluorescence intensity is preferably 10% or more, more preferably 20% or more, still more preferably 30% or more, still more preferably 40% or more, still more preferably 50% or more, and further preferably 60%. % Or more, more preferably 70% or more, and particularly preferably 80% or more.
式(1)中、R1、R2は、それぞれ独立に、炭素数1~20のアルキル基、炭素数1~6のアルコキシ基、炭素数1~6のアルキルエステル基、アミノ基、炭素数1~20のアルキルアミノ基、フルオロ基、クロル基、ブロモ基、カルボキシル基、シアノ基、ニトロ基、アセチル基、スルホニル基、スルホンアミド基を示し、a、bはそれぞれ独立に0~5の整数を示す。但し、aが2以上の場合、複数存在するR1はそれぞれ同一でも異なっていてもよく、bが2以上の場合、複数存在するR2はそれぞれ同一でも異なっていてもよい。
上記一般式(1)で表されるジフェニルピラゾリン誘導体としては、4-[3-(4-クロロフェニル)-4,5-ジヒドロ-1H-ピラゾール-1-イル]ベンゼンスルフォンアミドが挙げられる。 (D) The photosensitizer may contain a diphenylpyrazoline derivative represented by the following general formula (1). In the present embodiment, diphenylpyrazoline itself is not included.
In formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having 1 to 6 carbon atoms, an amino group, or a carbon number 1 to 20 alkylamino group, fluoro group, chloro group, bromo group, carboxyl group, cyano group, nitro group, acetyl group, sulfonyl group, sulfonamide group, a and b are each independently an integer of 0 to 5 Indicates. However, when a is 2 or more, a plurality of R1s may be the same or different, and when b is 2 or more, a plurality of R2s may be the same or different.
Examples of the diphenylpyrazoline derivative represented by the general formula (1) include 4- [3- (4-chlorophenyl) -4,5-dihydro-1H-pyrazol-1-yl] benzenesulfonamide.
本開示で「(E)添加剤」とは、感光性樹脂組成物に所望の機能を与えるために配合される成分であって上述の(A)成分、(B)成分、(C)成分及び(D)成分以外のものを包含する。 (E) Additive In the present disclosure, the “(E) additive” is a component blended to give a desired function to the photosensitive resin composition, and the above-described (A) component, (B) component, Includes components other than the component (C) and the component (D).
本実施形態の感光性樹脂積層体は、支持体と、支持体上に設けられた感光性樹脂組成物を含む感光性樹脂層と、を備える。
別の実施の形態は、上記のような感光性樹脂組成物から成る感光性樹脂層が支持体上に積層された感光性樹脂積層体を提供する。必要により、感光性樹脂積層体は、感光性樹脂層の支持体側とは反対側の表面に保護層を有してもよい。 <Photosensitive resin laminate>
The photosensitive resin laminated body of this embodiment is equipped with a support body and the photosensitive resin layer containing the photosensitive resin composition provided on the support body.
Another embodiment provides a photosensitive resin laminate in which a photosensitive resin layer composed of the photosensitive resin composition as described above is laminated on a support. If necessary, the photosensitive resin laminate may have a protective layer on the surface opposite to the support side of the photosensitive resin layer.
別の態様は、上述した感光性樹脂積層体を基材にラミネートし、露光し、現像する工程を含む、レジストパターン形成方法を提供する。以下に、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形成する方法の一例を説明する。レジストパターンとしては、回路基板(プリント配線板)、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、液晶パネル用透明電極、液晶パネル用TFT配線、有機ELディスプレイ用配線、PDP(プラズマディスプレイパネル)用電極等において形成されるレジストパターンが挙げられる。 <Resist pattern formation method>
Another aspect provides a resist pattern forming method including the steps of laminating the above-described photosensitive resin laminate on a substrate, exposing and developing. Below, an example of the method of forming a resist pattern using the photosensitive resin laminated body of this Embodiment is demonstrated. Resist patterns include circuit boards (printed wiring boards), flexible boards, lead frame boards, COF (chip on film) boards, semiconductor package boards, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, and organic EL displays. Examples thereof include resist patterns formed on wirings, PDP (plasma display panel) electrodes, and the like.
本実施形態のレジストパターン形成方法は、感光性樹脂積層体を基材にラミネートする工程と、感光性樹脂層を露光する工程と、露光後の感光性樹脂層を現像する工程と、を含む。
(1)ラミネート工程
感光性樹脂層の保護層を剥がしながら、銅張積層板、フレキシブル基板等の基板上にホットロールラミネーターを用いて感光性樹脂積層体を密着させる。ラミネート条件は従来公知の条件で適宜設定すればよい。 The resist pattern can be formed through the following steps.
The resist pattern forming method of the present embodiment includes a step of laminating a photosensitive resin laminate on a substrate, a step of exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer.
(1) Lamination process While peeling off the protective layer of the photosensitive resin layer, the photosensitive resin laminate is brought into close contact with a substrate such as a copper clad laminate or a flexible substrate using a hot roll laminator. The laminating conditions may be appropriately set under conventionally known conditions.
所望のパターン(例えば配線パターン)を有するマスクフィルムを感光性樹脂積層体の支持体上に密着させて活性光源を用いて露光するか、又は所望のパターンに対応する描画パターンを直接描画によって露光する。露光を、描画パターンの直接描画によって行うことが好ましい。露光波長としては、i線、h線、g線、これらの混合等を適宜使用できるが、本実施の形態の感光性樹脂組成物は、i線又はh線、特にh線での露光において高感度及び高解像度を実現できる点で有利である。またこれにより、本実施の形態の感光性樹脂組成物は、特に直接描画において有用である。露光条件は従来公知の条件で適宜設定すればよい。 (2) Exposure process A mask film having a desired pattern (for example, a wiring pattern) is brought into close contact with the support of the photosensitive resin laminate and exposed using an active light source, or a drawing pattern corresponding to the desired pattern is formed. Exposure by direct drawing. The exposure is preferably performed by direct drawing of a drawing pattern. As the exposure wavelength, i-line, h-line, g-line, a mixture thereof and the like can be used as appropriate. This is advantageous in that sensitivity and high resolution can be realized. Thereby, the photosensitive resin composition of this Embodiment is useful especially in direct drawing. The exposure conditions may be appropriately set under conventionally known conditions.
露光後、感光性樹脂層上の支持体を剥離し、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して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0.2~2質量%の濃度、かつ約20~40℃のNa2CO3水溶液が一般的である。 (3) Development Step After the exposure, the support on the photosensitive resin layer is peeled off, and subsequently, the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to form a resist pattern on the substrate. 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 an aqueous Na 2 CO 3 solution having a concentration of about 0.2 to 2% by mass and about 20 to 40 ° C. is generally used.
別の態様は、上述の感光性樹脂積層体を基材にラミネートし、露光し、現像し、めっきする工程を含む、回路基板の製造方法、及び、上述の感光性樹脂積層体を基材にラミネートし、露光し、現像し、エッチングする工程を含む、回路基板の製造方法を提供する。回路基板は、レジストパターン形成方法について上述したような手順でレジストパターンが形成された基材を、更にエッチング又はめっきすることにより製造できる。特に、回路基板の製造において露光を描画パターンの直接描画により行うことは、マスクの作製が不要であるため、生産性の観点から有利である。エッチング及びめっきは、それぞれ以下のように実施できる。 The method for forming a metal wiring of the present embodiment includes a step of forming a resist pattern by the above method, a step of forming a metal wiring (conductor pattern) using the resist pattern, and a step of peeling the resist pattern. .
Another aspect includes a process for producing a circuit board, comprising the steps of laminating, exposing, developing, and plating the above-described photosensitive resin laminate to a substrate, and the above-mentioned photosensitive resin laminate to the substrate. Provided is a method of manufacturing a circuit board, which includes steps of laminating, exposing, developing, and etching. The circuit board can be manufactured by further etching or plating the base material on which the resist pattern is formed by the procedure described above for the resist pattern forming method. In particular, it is advantageous from the viewpoint of productivity to perform exposure by direct drawing of a drawing pattern in the manufacture of a circuit board, because it is not necessary to produce a mask. Etching and plating can be performed as follows.
上述の現像により露出した基材の表面(例えば銅張積層板の場合の銅面)をエッチング又はめっきし、導体パターンを形成する。エッチング及びめっきの方法はそれぞれ従来公知の方法を適宜使用できる。 (4) Etching process or plating process The surface of the base material exposed by the above development (for example, a copper surface in the case of a copper clad laminate) is etched or plated to form a conductor pattern. As the etching and plating methods, conventionally known methods can be appropriately used.
その後、レジストパターンを現像液よりも強いアルカリ性を有する水溶液により基板から剥離する。剥離用のアルカリ水溶液についても特に制限はないが、濃度約2~5質量%、かつ約40~70℃の温度のNaOH又はKOHの水溶液が一般に用いられる。剥離液に、少量の水溶性溶媒を加えることもできる。
特に本実施形態では、(D)光増感剤としてジフェニルピラゾリン誘導体を用いることにより、特に優れためっき後剥離性を有する。
上記のような手順で、回路基板を製造できる。 (5) Stripping step Thereafter, the resist pattern is stripped from the substrate with an aqueous solution having alkalinity stronger than the developer. The alkaline aqueous solution for peeling is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.
In particular, in the present embodiment, the use of a diphenylpyrazoline derivative as the (D) photosensitizer has particularly excellent post-plating peelability.
The circuit board can be manufactured by the procedure as described above.
感光性樹脂積層体のポリエチレンフィルムを剥がし、分光光度計(日立U-3010)により、吸収スペクトルを測定した。405nmの吸光度を透過率に変換し、測定値とした。ここで、光増感剤の添加量は405nmの透過率が約40%となるようにし、光増感剤が同一の光量を吸収した場合のレジストの性能を比較できるようにした。 <405 nm transmittance of photosensitive resin layer>
The polyethylene film of the photosensitive resin laminate was peeled off, and the absorption spectrum was measured with a spectrophotometer (Hitachi U-3010). Absorbance at 405 nm was converted to transmittance to obtain a measured value. Here, the addition amount of the photosensitizer was set so that the transmittance at 405 nm was about 40%, so that the performance of the resist when the photosensitizer absorbed the same amount of light could be compared.
まず、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で研削材(日本カーリット(株)製、サクランダムR(登録商標#220))を用いてジェットスラブ研磨した。 <Sensitivity evaluation>
First, a 0.4 mm-thick copper clad laminate on which 35 μm rolled copper foil is laminated is jetted using a grinding material (Nippon Carlit Co., Ltd., Sacradund R (registered trademark # 220)) at a spray pressure of 0.2 MPa. Slab polished.
感度評価手順と同様に基板整面及びラミネートを行い、露光部と未露光部との幅が1:1の比率のラインパターンを、描画データを用いて線幅が感度評価で求めた露光量で露光した。その後、最小現像時間の2倍の現像時間で現像し、硬化レジストラインが正常に形成されている最小マスク幅を解像度の値とした。 <Resolution evaluation>
Similar to the sensitivity evaluation procedure, substrate leveling and lamination are performed, and a line pattern with a ratio of 1: 1 between the exposed area and the unexposed area is the exposure amount obtained by the sensitivity evaluation using the drawing data. Exposed. Thereafter, development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which the cured resist line was normally formed was defined as the resolution value.
感度評価手順と同様に基板整面及びラミネートを行い、露光部と未露光部との幅が1:200の比率のラインパターンを、描画データを用いて線幅が感度評価で求めた露光量で露光した。その後、最小現像時間の2倍の現像時間で現像し、硬化レジストラインが正常に形成されている最小マスク幅を密着性の値とした。 <Adhesion evaluation>
Similar to the sensitivity evaluation procedure, the substrate is flattened and laminated, and the line pattern having a ratio of 1: 200 between the exposed area and the unexposed area is the exposure amount obtained by the sensitivity evaluation using the drawing data. Exposed. Thereafter, development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which the cured resist line was normally formed was defined as the adhesion value.
感度評価手順と同様に基板整面及びラミネートを行い、露光部と未露光部との幅が1:1の比率のラインパターンを、描画データを用いて線幅が感度評価で求めた露光量で露光した。その後、最小現像時間の2倍の現像時間で現像した。現像後の基板を、酸性脱脂FRX(10%水溶液、アトテックジャパン(株)製)浴に、40℃で4分浸せきした。水洗した後10%硫酸水溶液に室温下2分浸せきした。
硫酸銅コンク(メルテックス(株)製)を19wt%硫酸で3.6倍に希釈し、濃塩酸を200ppm添加した。次いで光沢剤としてカパラシッドHLとカパラシッドGSをそれぞれ0.4ml/l、20ml/l添加した。めっき前処理後の耐めっき性評価基板(6cm×12.5cm)を、作製された硫酸銅めっき液を用いてハーリングセル均一めっき装置(株式会社 山本鍍金試験器社製)により、引加電流0.4Aで65分間めっきした。このときの銅めっき被膜の厚みは20μm厚であった。
めっき処理を施した評価基板を、50℃、1.5wt%の苛性ソーダ水溶液に入れ、撹拌せずに4分間浸漬して、レジスト膜を剥離除去した。このとき、めっきパターン間の硬化レジストラインが完全に剥離されている最小マスク幅をめっき後剥離性の値とした。 <Evaluation of peelability after plating>
Similar to the sensitivity evaluation procedure, substrate leveling and lamination are performed, and a line pattern with a ratio of 1: 1 between the exposed area and the unexposed area is the exposure amount obtained by the sensitivity evaluation using the drawing data. Exposed. Thereafter, development was performed with a development time twice the minimum development time. The substrate after development was immersed in an acidic degreased FRX (10% aqueous solution, manufactured by Atotech Japan KK) bath at 40 ° C. for 4 minutes. After washing with water, it was immersed in a 10% aqueous sulfuric acid solution at room temperature for 2 minutes.
Copper sulfate conch (Meltex Co., Ltd.) was diluted 3.6 times with 19 wt% sulfuric acid, and 200 ppm of concentrated hydrochloric acid was added. Subsequently, capalacid HL and caparacid GS were added as brighteners at 0.4 ml / l and 20 ml / l, respectively. The plating current evaluation substrate (6 cm × 12.5 cm) after the pre-plating treatment was subjected to an applied current of 0 with a Haring cell uniform plating apparatus (manufactured by Yamamoto Kakin Tester Co., Ltd.) using the prepared copper sulfate plating solution. Plated at 4A for 65 minutes. The thickness of the copper plating film at this time was 20 μm.
The evaluation board | substrate which gave the plating process was put into 50 degreeC and 1.5 wt% caustic soda aqueous solution, and it immersed for 4 minutes, without stirring, and the resist film was peeled and removed. At this time, the minimum mask width at which the cured resist line between the plating patterns was completely peeled was defined as the post-plating peelability value.
表1に示す組成(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。)の感光性樹脂組成物及び溶媒を十分に攪拌、混合して固形分量60質量%の感光性樹脂組成物調合液を得た。支持体として16μm厚のポリエチレンテレフタラートフィルム(東レ社製FB40、ヘーズ値0.6)を用意して、そのフィルムの表面に、バーコーターを用いて感光性樹脂組成物調合液を均一に塗布し、95℃の乾燥器中で2分30秒間乾燥して感光性樹脂層を形成した。感光性樹脂層の厚みは25μmであった。 [Examples 1 to 3 and Comparative Examples 1 to 7]
The photosensitive resin composition and the solvent having the composition shown in Table 1 (where the numbers of the respective components indicate the blending amount (parts by mass) as the solid content) are sufficiently stirred and mixed to obtain a photosensitivity having a solid content of 60% by mass. The resin composition preparation liquid was obtained. A 16 μm thick polyethylene terephthalate film (FB40 manufactured by Toray Industries Inc., haze value 0.6) is prepared as a support, and the photosensitive resin composition preparation liquid is uniformly applied to the surface of the film using a bar coater. The photosensitive resin layer was formed by drying in a dryer at 95 ° C. for 2 minutes and 30 seconds. The thickness of the photosensitive resin layer was 25 μm.
得られた感光性樹脂積層体につき、各種評価を行った。結果を表1に示す。また、各実施例および比較例で用いた各成分(A)~(E)を表2に示す。 Next, a 19 μm thick polyethylene film (GF-818 made by Tamapoly Co., Ltd.) was bonded as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate. .
Various evaluation was performed about the obtained photosensitive resin laminated body. The results are shown in Table 1. Table 2 shows the components (A) to (E) used in the examples and comparative examples.
まず、(D)光増感剤の酸解離定数pKaが9より大きく12より小さい実施例1または2は、pKaが9以下または12以上である比較例1~6に対して、h線露光において高感度・高解像度の特性を発現できることが分かる。また、(D)光増感剤としてジフェニルピラゾリン誘導体を用いた実施例1では、特に優れためっき後剥離性を示すことが分かる。
実施例1と2とを比較することにより、(B)エチレン性不飽和二重結合を有する化合物が、分子内にヒドロキシル基を含むことにより(実施例1)、特に感度(生産性)、解像性、密着性に優れることがわかる。 From the results in Table 1, the following contents can be read.
First, (D) Example 1 or 2 in which the acid dissociation constant pKa of the photosensitizer is larger than 9 and smaller than 12 is different from Comparative Examples 1 to 6 in which pKa is 9 or less or 12 or more in h-line exposure. It can be seen that high sensitivity and high resolution characteristics can be expressed. It can also be seen that (D) Example 1 using a diphenylpyrazoline derivative as a photosensitizer exhibits particularly excellent post-plating peelability.
By comparing Examples 1 and 2, it was found that (B) the compound having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule (Example 1), particularly sensitivity (productivity), It turns out that it is excellent in image property and adhesiveness.
Claims (28)
- 以下の成分:
(A)アルカリ可溶性高分子、
(B)エチレン性不飽和二重結合を有する化合物、
(C)光重合開始剤、および
(D)光増感剤、
を含み、
前記(D)光増感剤が、下記一般式(2)で表されるジスチリルベンゼン誘導体を含む、感光性樹脂組成物。
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated double bond,
(C) a photopolymerization initiator, and (D) a photosensitizer,
Including
The photosensitive resin composition in which the said (D) photosensitizer contains the distyrylbenzene derivative represented by following General formula (2).
- 前記(D)光増感剤は、4’-(2-シアノスチリル)-2-スチルベンカルボニトリル、4’-(2-シアノスチリル)-3-スチルベンカルボニトリル、4’-(2-シアノスチリル)-4-スチルベンカルボニトリル、1,4-ビス(4-シアノスチリル)ベンゼンから選ばれる少なくとも1つの化合物を含む、請求項1に記載の感光性樹脂組成物。 The photosensitizer (D) is 4 ′-(2-cyanostyryl) -2-stilbenecarbonitrile, 4 ′-(2-cyanostyryl) -3-stilbenecarbonitrile, 4 ′-(2-cyanostyryl). 2. The photosensitive resin composition according to claim 1, comprising at least one compound selected from:)-4-stilbenecarbonitrile and 1,4-bis (4-cyanostyryl) benzene.
- 前記(D)光増感剤は、4’-(2-シアノスチリル)-2-スチルベンカルボニトリル、4’-(2-シアノスチリル)-3-スチルベンカルボニトリルを含む、請求項2に記載の感光性樹脂組成物。 The photosensitizer (D) according to claim 2, comprising 4 '-(2-cyanostyryl) -2-stilbenecarbonitrile, 4'-(2-cyanostyryl) -3-stilbenecarbonitrile. Photosensitive resin composition.
- 前記(D)光増感剤は、4’-(2-シアノスチリル)-4-スチルベンカルボニトリルを含む、請求項2に記載の感光性樹脂組成物。 3. The photosensitive resin composition according to claim 2, wherein the (D) photosensitizer comprises 4 '-(2-cyanostyryl) -4-stilbenecarbonitrile.
- 前記(D)光増感剤は、1,4-ビス(4-シアノスチリル)ベンゼンを含む、請求項2に記載の感光性樹脂組成物。 3. The photosensitive resin composition according to claim 2, wherein the (D) photosensitizer includes 1,4-bis (4-cyanostyryl) benzene.
- 前記(D)光増感剤は、最大吸収ピークを330nm-450nmに有する蛍光色素である、請求項1~5のいずれか1項に記載の感光性樹脂組成物。 6. The photosensitive resin composition according to claim 1, wherein the (D) photosensitizer is a fluorescent dye having a maximum absorption peak at 330 nm to 450 nm.
- 前記(C)光重合開始剤は、ヘキサアリールビイミダゾール化合物を含む、請求項1~請求項6のいずれか1項に記載の感光性樹脂組成物。 7. The photosensitive resin composition according to claim 1, wherein the (C) photopolymerization initiator includes a hexaarylbiimidazole compound.
- 前記感光性樹脂組成物の膜厚25μmにおける波長405nmの光の透過率が10%よりも大きい、請求項1~7のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 7, wherein a transmittance of light having a wavelength of 405 nm at a film thickness of 25 µm of the photosensitive resin composition is larger than 10%.
- 前記感光性樹脂組成物は金属配線形成用の感光性樹脂組成物である、請求項1~8のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 8, wherein the photosensitive resin composition is a photosensitive resin composition for forming a metal wiring.
- 支持体と、前記支持体上に設けられた請求項1~9のいずれか1項に記載の感光性樹脂組成物を含む感光性樹脂層と、を備える、感光性樹脂積層体。 A photosensitive resin laminate comprising: a support; and a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 9 provided on the support.
- 請求項10に記載の感光性樹脂積層体を基材にラミネートする工程と、
前記感光性樹脂層を露光する工程と、
前記露光後の感光性樹脂層を現像する工程と、
を含む、レジストパターン形成方法。 Laminating the photosensitive resin laminate according to claim 10 on a substrate;
Exposing the photosensitive resin layer;
Developing the photosensitive resin layer after the exposure;
A resist pattern forming method. - 前記露光を、描画パターンの直接描画により行う、請求項11に記載のレジストパターン形成方法。 The resist pattern forming method according to claim 11, wherein the exposure is performed by direct drawing of a drawing pattern.
- 請求項11または12に記載の方法によりレジストパターンを形成する工程と、
前記レジストパターンを用いて金属配線を形成する工程と、
前記レジストパターンを剥離する工程と、
を含む、金属配線の形成方法。 Forming a resist pattern by the method according to claim 11 or 12, and
Forming a metal wiring using the resist pattern;
Removing the resist pattern;
A method for forming a metal wiring including: - 請求項11または12に記載のレジストパターン形成方法によって、基材としての半導体パッケージ用基板上にレジストパターンを形成する工程、及び前記レジストパターンが形成された半導体パッケージ用基板をエッチングするかまたはめっきする工程を含む、半導体パッケージの製造方法。 13. The method of forming a resist pattern on a semiconductor package substrate as a base material by the resist pattern forming method according to claim 11 or 12, and etching or plating the semiconductor package substrate on which the resist pattern is formed. A manufacturing method of a semiconductor package including a process.
- 以下の成分:
(A)アルカリ可溶性高分子、
(B)エチレン性不飽和二重結合を有する化合物、
(C)光重合開始剤、および
(D)光増感剤、
を含み、
前記(D)光増感剤の酸解離定数pKaが9より大きく12より小さく、且つ、波長405nmのモル吸光係数が100М-1cm-1以上である(ただし、Мはモル濃度の単位であり、前記モル吸光係数はアセトンを溶媒に用いた場合の値である。)感光性樹脂組成物。 The following ingredients:
(A) an alkali-soluble polymer,
(B) a compound having an ethylenically unsaturated double bond,
(C) a photopolymerization initiator, and (D) a photosensitizer,
Including
The acid dissociation constant pKa of the (D) photosensitizer is greater than 9 and less than 12, and the molar extinction coefficient at a wavelength of 405 nm is 100 М -1 cm -1 or more (where М is a unit of molar concentration) The molar extinction coefficient is a value when acetone is used as a solvent.) Photosensitive resin composition. - 前記(D)光増感剤は、4-[3-(4-クロロフェニル)-4,5-ジヒドロ-1H-ピラゾール-1-イル]ベンゼンスルフォンアミドである、請求項15に記載の感光性樹脂組成物。 The photosensitive resin according to claim 15, wherein the (D) photosensitizer is 4- [3- (4-chlorophenyl) -4,5-dihydro-1H-pyrazol-1-yl] benzenesulfonamide. Composition.
- 前記(B)エチレン性不飽和二重結合を有する化合物は、分子内にヒドロキシル基を含む、請求項16に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 16, wherein the compound (B) having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule.
- 前記(D)光増感剤は、最大吸収ピークを330nm-450nmに有する蛍光色素である、請求項15~17のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 15 to 17, wherein the (D) photosensitizer is a fluorescent dye having a maximum absorption peak at 330 nm to 450 nm.
- 前記(C)光重合開始剤は、ヘキサアリールビイミダゾール化合物を含む、請求項15~18のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 15 to 18, wherein the (C) photopolymerization initiator includes a hexaarylbiimidazole compound.
- 前記感光性樹脂組成物の膜厚25μmにおける波長405nmの光の透過率が10%よりも大きい、請求項15~19のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 15 to 19, wherein a transmittance of light having a wavelength of 405 nm at a film thickness of 25 µm of the photosensitive resin composition is greater than 10%.
- 前記(D)光増感剤の酸解離定数pKaが9.5より大きく11より小さい、請求項15~20のいずれか1項に記載の感光性樹脂組成物。 21. The photosensitive resin composition according to claim 15, wherein the acid dissociation constant pKa of the (D) photosensitizer is larger than 9.5 and smaller than 11.
- 前記(B)エチレン性不飽和二重結合を有する化合物は、分子内にヒドロキシル基を含む、請求項15~21のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 15 to 21, wherein the compound (B) having an ethylenically unsaturated double bond contains a hydroxyl group in the molecule.
- 前記感光性樹脂組成物は金属配線形成用の感光性樹脂組成物である、請求項15~22のいずれか1項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 15 to 22, wherein the photosensitive resin composition is a photosensitive resin composition for forming a metal wiring.
- 支持体と、前記支持体上に設けられた請求項15~23のいずれか1項に記載の感光性樹脂組成物を含む感光性樹脂層と、を備える、感光性樹脂積層体。 A photosensitive resin laminate comprising: a support; and a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 15 to 23 provided on the support.
- 請求項24に記載の感光性樹脂積層体を基材にラミネートする工程と、
前記感光性樹脂層を露光する工程と、
前記露光後の感光性樹脂層を現像する工程と、
を含む、レジストパターン形成方法。 Laminating the photosensitive resin laminate according to claim 24 on a substrate;
Exposing the photosensitive resin layer;
Developing the photosensitive resin layer after the exposure;
A resist pattern forming method. - 前記露光を、描画パターンの直接描画により行う、請求項25に記載のレジストパターン形成方法。 26. The resist pattern forming method according to claim 25, wherein the exposure is performed by direct drawing of a drawing pattern.
- 請求項25または26に記載の方法によりレジストパターンを形成する工程と、
前記レジストパターンを用いて金属配線を形成する工程と、
前記レジストパターンを剥離する工程と、
を含む、金属配線の形成方法。 Forming a resist pattern by the method according to claim 25 or 26;
Forming a metal wiring using the resist pattern;
Removing the resist pattern;
A method for forming a metal wiring including: - 請求項25または26に記載のレジストパターン形成方法によって、基材としての半導体パッケージ用基板上にレジストパターンを形成する工程、及び前記レジストパターンが形成された半導体パッケージ用基板をエッチングするかまたはめっきする工程を含む、半導体パッケージの製造方法。 27. A step of forming a resist pattern on a semiconductor package substrate as a base material by the resist pattern forming method according to claim 25 or 26, and etching or plating the semiconductor package substrate on which the resist pattern is formed. A manufacturing method of a semiconductor package including a process.
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CN110325913A (en) | 2019-10-11 |
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