JP7327485B2 - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board - Google Patents
Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board Download PDFInfo
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- JP7327485B2 JP7327485B2 JP2021539767A JP2021539767A JP7327485B2 JP 7327485 B2 JP7327485 B2 JP 7327485B2 JP 2021539767 A JP2021539767 A JP 2021539767A JP 2021539767 A JP2021539767 A JP 2021539767A JP 7327485 B2 JP7327485 B2 JP 7327485B2
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- meth
- photosensitive
- resin composition
- resist pattern
- mass
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- 238000000034 method Methods 0.000 title claims description 49
- 239000011342 resin composition Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000005530 etching Methods 0.000 claims description 18
- 239000004020 conductor Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 14
- 150000003440 styrenes Chemical class 0.000 claims description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
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- 239000010410 layer Substances 0.000 description 63
- -1 phthalic acid compound Chemical class 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
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- 238000011161 development Methods 0.000 description 18
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 230000036211 photosensitivity Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000003673 urethanes Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZGUNAGUHMKGQNY-ZETCQYMHSA-N L-alpha-phenylglycine zwitterion Chemical compound OC(=O)[C@@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-ZETCQYMHSA-N 0.000 description 3
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- SCEFCWXRXJZWHE-UHFFFAOYSA-N 1,2,3-tribromo-4-(2,3,4-tribromophenyl)sulfonylbenzene Chemical compound BrC1=C(Br)C(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C(Br)=C1Br SCEFCWXRXJZWHE-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NREFJJBCYMZUEK-UHFFFAOYSA-N 2-[2-[4-[2-[4-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]phenyl]propan-2-yl]phenoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOCCOC(=O)C(C)=C)C=C1 NREFJJBCYMZUEK-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 2
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 239000002518 antifoaming agent Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- TVIPVNDJQQUGOQ-UHFFFAOYSA-N 2-(2-fluorophenyl)-2-[2-(2-fluorophenyl)-4,5-bis(3-methoxyphenyl)imidazol-2-yl]-4,5-bis(3-methoxyphenyl)imidazole Chemical compound COC1=CC=CC(C=2C(=NC(N=2)(C=2C(=CC=CC=2)F)C2(N=C(C(=N2)C=2C=C(OC)C=CC=2)C=2C=C(OC)C=CC=2)C=2C(=CC=CC=2)F)C=2C=C(OC)C=CC=2)=C1 TVIPVNDJQQUGOQ-UHFFFAOYSA-N 0.000 description 1
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- GMDJMLOOHULQEV-UHFFFAOYSA-N 2-(n-ethylanilino)acetic acid Chemical compound OC(=O)CN(CC)C1=CC=CC=C1 GMDJMLOOHULQEV-UHFFFAOYSA-N 0.000 description 1
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- 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
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Description
本開示は、感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法に関する。 TECHNICAL FIELD The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.
プリント配線板の製造分野においては、エッチング処理又はめっき処理等に用いられるレジスト材料として、感光性樹脂組成物、及び、支持フィルム上に感光性樹脂組成物を用いて形成された層(以下、「感光層」ともいう)を備える感光性エレメントが広く用いられている。 In the field of manufacturing printed wiring boards, a photosensitive resin composition is used as a resist material for etching or plating, and a layer formed using a photosensitive resin composition on a support film (hereinafter referred to as " Photosensitive elements with a "photosensitive layer") are widely used.
プリント配線板は、上記感光性エレメントを用いて、例えば、以下の手順で製造されている。すなわち、まず、感光性エレメントの感光層を銅張積層板等の回路形成用基板上にラミネートする。次に、マスクフィルム等を介して感光層を露光し、光硬化部を形成する。このとき、露光前又は露光後に支持フィルムを剥離する。その後、感光層の光硬化部以外の領域を現像液で除去し、レジストパターンを形成する。次に、レジストパターンをレジストとして、エッチング処理又はめっき処理を施して導体パターンを形成させ、最終的に感光層の光硬化部(レジストパターン)を剥離(除去)する。 A printed wiring board is manufactured using the above-described photosensitive element, for example, according to the following procedure. That is, first, the photosensitive layer of the photosensitive element is laminated on a circuit-forming substrate such as a copper-clad laminate. Next, the photosensitive layer is exposed through a mask film or the like to form a photocured portion. At this time, the support film is peeled off before or after the exposure. After that, the area of the photosensitive layer other than the photocured portion is removed with a developer to form a resist pattern. Next, using the resist pattern as a resist, an etching process or a plating process is performed to form a conductor pattern, and finally the photocured portion (resist pattern) of the photosensitive layer is stripped (removed).
近年、プリント配線板の高密度化に伴い、導体パターンの微細化が進むにつれて、回路形成用基板とレジストである感光層との接触面積が小さくなっている。そのため、感光層には、エッチング処理又はめっき処理における優れた特性が要求されると共に、回路形成用基板との優れた密着性、及び、レジストパターンの形成における優れた解像度が要求されている。 In recent years, as the density of printed wiring boards has increased, the contact area between the circuit-forming substrate and the photosensitive layer, which is a resist, has become smaller as conductor patterns have become finer. Therefore, the photosensitive layer is required to have excellent properties in etching treatment or plating treatment, as well as excellent adhesion to circuit forming substrates and excellent resolution in forming a resist pattern.
例えば、特許文献1には、特定の増感色素を用いることで、感度及び解像度に優れた感光性樹脂組成物が開示されている。また、特許文献2には、特定のアルカリ可溶性高分子及びエチレン性二重結合を有する化合物を用いることで、感度及び解像度に優れた感光性樹脂組成物が開示されている。
For example,
生産効率の向上のために、各プロセスの短縮、短時間化が要求されている。例えば剥離時間の短縮が、解像度等の要求と同時に要求されている。感光性樹脂組成物には、未露光部の現像性が高く、優れた解像度を有するレジストパターンを形成することが求められるだけでなく、レジストパターンを剥離除去するために、光硬化部の剥離特性に優れることが求められる。 In order to improve production efficiency, each process is required to be shortened and shortened. For example, shortening of peeling time is demanded at the same time as resolution and the like are demanded. The photosensitive resin composition is required to form a resist pattern with high developability in the unexposed area and excellent resolution. It is required to be excellent in
本開示は、現像性、解像度及び剥離特性のバランスに優れる感光性樹脂組成物、該感光性樹脂組成物を用いた感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法を提供することを目的とする。 The present disclosure provides a photosensitive resin composition having an excellent balance of developability, resolution and release properties, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for producing a printed wiring board. for the purpose.
本開示に係る感光性樹脂組成物は、スチレン又はスチレン誘導体に由来する構造単位を有するバインダーポリマーと、光重合性化合物と、光重合開始剤と、を含有し、上記バインダーポリマーの酸価が、165~195mgKOH/gであり、上記光重合性化合物が、フタル酸骨格を有する(メタ)アクリレートを含む。 The photosensitive resin composition according to the present disclosure contains a binder polymer having a structural unit derived from styrene or a styrene derivative, a photopolymerizable compound, and a photopolymerization initiator, and the acid value of the binder polymer is 165 to 195 mgKOH/g, and the photopolymerizable compound contains a (meth)acrylate having a phthalic acid skeleton.
上記バインダーポリマーは、スチレン又はスチレン誘導体に由来する構造単位を41~64質量%有してよい。上記バインダーポリマーの重量平均分子量は、5000~37000であってよい。 The binder polymer may have 41 to 64% by mass of structural units derived from styrene or styrene derivatives. The weight average molecular weight of the binder polymer may range from 5,000 to 37,000.
上記フタル酸骨格を有する(メタ)アクリレートの含有量は、バインダーポリマー及び光重合性化合物の総量100質量部に対して、1~30質量部であってよい。また、上記光重合開始剤は、アクリジン系光重合開始剤を含んでよい。 The content of the (meth)acrylate having a phthalic acid skeleton may be 1 to 30 parts by mass with respect to 100 parts by mass as the total amount of the binder polymer and the photopolymerizable compound. Moreover, the photopolymerization initiator may include an acridine-based photopolymerization initiator.
本開示に係る感光性エレメントは、支持体と、該支持体上に形成された感光層とを備え、感光層が上述の感光性樹脂組成物を含む。 A photosensitive element according to the present disclosure comprises a support and a photosensitive layer formed on the support, wherein the photosensitive layer contains the photosensitive resin composition described above.
本開示に係るレジストパターンの形成方法は、基板上に、上述の感光性樹脂組成物又は感光性エレメントを用いて、感光層を形成する工程と、感光層の所定部分に活性光線を照射して、光硬化部を形成する工程と、上記基板から、感光層の光硬化部以外の少なくとも一部を除去する工程と、を備える。 The method for forming a resist pattern according to the present disclosure includes the steps of forming a photosensitive layer on a substrate using the above-described photosensitive resin composition or photosensitive element, and irradiating a predetermined portion of the photosensitive layer with an actinic ray. forming a photo-cured portion; and removing at least a portion of the photosensitive layer other than the photo-cured portion from the substrate.
本開示に係るプリント配線板の製造方法は、上記レジストパターンの形成方法によりレジストパターンが形成された基板を、エッチング処理又はめっき処理して導体パターンを形成する工程を備える。上記プリント配線板の製造方法は、エッチング処理又はめっき処理の後に、上記光硬化部を除去する工程を更に備えてよい。 A printed wiring board manufacturing method according to the present disclosure includes a step of etching or plating a substrate on which a resist pattern has been formed by the resist pattern forming method to form a conductor pattern. The printed wiring board manufacturing method may further include a step of removing the photocured portion after the etching treatment or the plating treatment.
本開示によれば、現像性、解像度及び剥離特性のバランスに優れる感光性樹脂組成物、該感光性樹脂組成物を用いた感光性エレメント、レジストパターンの形成方法、及びプリント配線板の製造方法を提供することができる。 According to the present disclosure, a photosensitive resin composition having an excellent balance of developability, resolution and peeling properties, a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for producing a printed wiring board are provided. can provide.
以下、本開示について、詳細に説明する。本明細書において、「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。また、本明細書中に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。 The present disclosure will be described in detail below. In this specification, a numerical range indicated using "to" indicates a range including the numerical values before and after "to" as the minimum and maximum values, respectively. In addition, in the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range at one stage may be replaced with the upper limit or lower limit of the numerical range at another stage. In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
本明細書において、「(メタ)アクリル酸」とは、「アクリル酸」及びそれに対応する「メタクリル酸」の少なくとも一方を意味し、(メタ)アクリレート等の他の類似表現についても同様である。 As used herein, "(meth)acrylic acid" means at least one of "acrylic acid" and "methacrylic acid" corresponding thereto, and the same applies to other similar expressions such as (meth)acrylate.
本明細書において、「固形分」とは、感光性樹脂組成物に含まれる水、溶媒等の揮発する物質を除いた不揮発分のことであり、該樹脂組成物を乾燥させた際に、揮発せずに残る成分を示し、また25℃付近の室温で液状、水飴状、及びワックス状のものも含む。 As used herein, the term “solid content” refers to non-volatile content excluding volatile substances such as water and solvents contained in the photosensitive resin composition, and when the resin composition is dried, It also includes those that are liquid, syrup-like, and wax-like at room temperature around 25°C.
[感光性樹脂組成物]
本実施形態に係る感光性樹脂組成物は、スチレン又はスチレン誘導体に由来する構造単位を有するバインダーポリマーと、光重合性化合物と、光重合開始剤と、を含有する。上記バインダーポリマーの酸価は、165~195mgKOH/gであり、上記光重合性化合物は、フタル酸系化合物を含む。以下、本実施形態における感光性樹脂組成物で用いられる各成分について詳細に説明する。[Photosensitive resin composition]
The photosensitive resin composition according to this embodiment contains a binder polymer having a structural unit derived from styrene or a styrene derivative, a photopolymerizable compound, and a photopolymerization initiator. The binder polymer has an acid value of 165 to 195 mgKOH/g, and the photopolymerizable compound includes a phthalic acid compound. Each component used in the photosensitive resin composition of the present embodiment will be described in detail below.
((A)バインダーポリマー)
(A)バインダーポリマー(以下、「(A)成分」ともいう)は、スチレン又はスチレン誘導体に由来する構造単位を有することで、感光性樹脂組成物から形成される感光層の剥離特性を向上することができる。(A)成分は、例えば、スチレン又はスチレン誘導体を含む重合性単量体をラジカル重合させることにより製造することができる。((A) binder polymer)
(A) The binder polymer (hereinafter also referred to as "(A) component") has a structural unit derived from styrene or a styrene derivative, thereby improving the release properties of the photosensitive layer formed from the photosensitive resin composition. be able to. Component (A) can be produced, for example, by radically polymerizing a polymerizable monomer containing styrene or a styrene derivative.
スチレン誘導体は、ビニルトルエン、α-メチルスチレン等のスチレンのα位又は芳香環における水素原子が置換された重合可能な化合物である。(A)成分におけるスチレン又はスチレン誘導体に由来する構造単位の含有量は、(A)成分の全体量を基準として、41~64質量%、41~60質量%、42~55質量%、又は43~50質量%であってもよい。この含有量が41質量%以上では、解像度がより向上する傾向があり、64質量%以下では、現像時に剥離片が大きくなることを抑制でき、剥離に要する時間の長時間化が抑えられる傾向がある。 Styrene derivatives are polymerizable compounds such as vinyltoluene, α-methylstyrene, etc., in which the hydrogen atom at the α-position or aromatic ring of styrene is substituted. The content of structural units derived from styrene or styrene derivatives in component (A) is 41 to 64% by mass, 41 to 60% by mass, 42 to 55% by mass, or 43% by mass, based on the total amount of component (A). It may be up to 50% by mass. When this content is 41% by mass or more, the resolution tends to be further improved, and when it is 64% by mass or less, it is possible to suppress the increase in peeled pieces during development, and the tendency is to suppress the lengthening of the time required for peeling. be.
(A)成分は、アルカリ現像性の見地から、カルボキシ基を有してもよい。カルボキシ基を有する(A)成分は、例えば、カルボキシ基を有する重合性単量体と、スチレン又はスチレン誘導体を含む重合性単量体とをラジカル重合させることにより製造することができる。 The component (A) may have a carboxy group from the standpoint of alkali developability. The component (A) having a carboxy group can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxy group and a polymerizable monomer containing styrene or a styrene derivative.
カルボキシ基を有する重合性単量体としては、例えば、(メタ)アクリル酸、α-ブロモアクリル酸、α-クロルアクリル酸、β-フリル(メタ)アクリル酸、β-スチリル(メタ)アクリル酸、マレイン酸、マレイン酸無水物、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピル等のマレイン酸モノエステル、フマール酸、ケイ皮酸、α-シアノケイ皮酸、イタコン酸、クロトン酸、及びプロピオール酸が挙げられる。アルカリ現像性をより向上する点から、カルボキシ基を有する重合性単量体は、(メタ)アクリル酸であってもよく、メタクリル酸であってもよい。 Examples of polymerizable monomers having a carboxy group include (meth)acrylic acid, α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, Maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and other maleic acid monoesters, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. mentioned. From the viewpoint of further improving alkali developability, the polymerizable monomer having a carboxy group may be (meth)acrylic acid or methacrylic acid.
アルカリ現像性とアルカリ耐性とをバランスよく向上させる点から、カルボキシ基を有する重合性単量体に由来する構造単位の含有量は、(A)成分の全体量を基準として、10~50質量%、15~40質量%、又は20~35質量%であってもよい。この含有量が10質量%以上ではアルカリ現像性が向上する傾向があり、50質量%以下ではアルカリ耐性に優れる傾向がある。 From the viewpoint of improving alkali developability and alkali resistance in a well-balanced manner, the content of structural units derived from a polymerizable monomer having a carboxy group is 10 to 50% by mass based on the total amount of component (A). , 15 to 40% by weight, or 20 to 35% by weight. When the content is 10% by mass or more, the alkali developability tends to be improved, and when the content is 50% by mass or less, the alkali resistance tends to be excellent.
(A)成分は、スチレン又はスチレン誘導体及びカルボキシ基を有する重合性単量体以外の重合性単量体(以下、「(他の重合性単量体」ともいう)に由来する構造単位を更に有してもよい。他の重合性単量体としては、例えば、ジアセトンアクリルアミド等のアクリルアミド、アクリロニトリル、ビニル-n-ブチルエーテル等のビニルアルコールのエーテル類、(メタ)アクリル酸アルキルエステル、(メタ)アクリル酸ベンジルエステル、(メタ)アクリル酸テトラヒドロフルフリルエステル、(メタ)アクリル酸ジメチルアミノエチルエステル、(メタ)アクリル酸ジエチルアミノエチルエステル、(メタ)アクリル酸グリシジルエステル、2,2,2-トリフルオロエチル(メタ)アクリレート、2,2,3,3-テトラフルオロプロピル(メタ)アクリレート、が挙げられる。他の重合性単量体は、1種を単独で又は2種以上を組み合わせて用いることができる。 Component (A) further includes a structural unit derived from a polymerizable monomer other than styrene or a styrene derivative and a polymerizable monomer having a carboxy group (hereinafter also referred to as "(other polymerizable monomer")). Other polymerizable monomers include, for example, acrylamides such as diacetone acrylamide, acrylonitrile, vinyl alcohol ethers such as vinyl-n-butyl ether, (meth)acrylic acid alkyl esters, (meth) ) benzyl acrylate, (meth)acrylate tetrahydrofurfuryl ester, (meth)acrylate dimethylaminoethyl ester, (meth)acrylate diethylaminoethyl ester, (meth)acrylate glycidyl ester, 2,2,2-tri fluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, etc. Other polymerizable monomers may be used alone or in combination of two or more. can be done.
(A)成分は、可塑性を向上する点から、(メタ)アクリル酸アルキルエステルに由来する構造単位を有してもよい。(メタ)アクリル酸アルキルエステルとしては、例えば、(メタ)アクリル酸メチルエステル、(メタ)アクリル酸エチルエステル、(メタ)アクリル酸プロピルエステル、(メタ)アクリル酸ブチルエステル、(メタ)アクリル酸ペンチルエステル、(メタ)アクリル酸ヘキシルエステル、(メタ)アクリル酸ヘプチルエステル、(メタ)アクリル酸オクチルエステル、(メタ)アクリル酸2-エチルヘキシルエステル、(メタ)アクリル酸ノニルエステル、(メタ)アクリル酸デシルエステル、(メタ)アクリル酸ウンデシルエステル、及び(メタ)アクリル酸ドデシルエステルが挙げられる。 The component (A) may have a structural unit derived from a (meth)acrylic acid alkyl ester from the viewpoint of improving plasticity. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate. Ester, (meth)acrylic acid hexyl ester, (meth)acrylic acid heptyl ester, (meth)acrylic acid octyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid nonyl ester, (meth)acrylic acid decyl ester esters, undecyl (meth)acrylate, and dodecyl (meth)acrylate.
(A)成分の酸価は、165~195mgKOH/gであり、現像性、解像度及び剥離特性のバランスをより向上する点から、170~195mgKOH/g、175~193mgKOH/g、又は180~190mgKOH/gであってもよい。 The acid value of component (A) is 165 to 195 mgKOH/g, and from the viewpoint of further improving the balance between developability, resolution and peeling properties, it is 170 to 195 mgKOH/g, 175 to 193 mgKOH/g, or 180 to 190 mgKOH/g. g.
(A)成分の重量平均分子量(Mw)は、5000~37000、8000~36000、10000~35000、又は15000~33000であってもよい。(A)成分のMwが5000以上では、光硬化部の耐現像液性が優れる傾向にあり、37000以下では、未露光部の現像時間が長くなるのを抑えられる傾向にある。(A)成分は、分散度(重量平均分子量/数平均分子量)が1.0~3.0、又は1.0~2.0であってもよい。分散度が小さくなると解像度が向上する傾向にある。 The weight average molecular weight (Mw) of component (A) may be 5,000 to 37,000, 8,000 to 36,000, 10,000 to 35,000, or 15,000 to 33,000. When the Mw of the component (A) is 5,000 or more, the developer resistance of the photocured portion tends to be excellent. Component (A) may have a degree of dispersion (weight average molecular weight/number average molecular weight) of 1.0 to 3.0, or 1.0 to 2.0. Resolution tends to improve as the degree of dispersion decreases.
本明細書における重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定され、標準ポリスチレンを標準試料として換算した値である。 The weight-average molecular weight and number-average molecular weight in this specification are values measured by gel permeation chromatography (GPC) and converted using standard polystyrene as a standard sample.
(A)成分は、1種を単独で又は2種以上を組み合わせて用いることができる。2種以上を組み合わせて使用する場合の(A)成分としては、例えば、異なる重合性単量体からなる2種以上のバインダーポリマー、異なるMwの2種以上のバインダーポリマー、及び、異なる分散度の2種以上のバインダーポリマーが挙げられる。 (A) Component can be used individually by 1 type or in combination of 2 or more types. As the component (A) when two or more are used in combination, for example, two or more binder polymers composed of different polymerizable monomers, two or more binder polymers having different Mw, and different dispersion degrees Two or more binder polymers are included.
(A)成分の含有量は、(A)成分及び後述する(B)成分の総量100質量部に対して、30~80質量部、40~75質量部、50~70質量部、又は50~60質量部であってもよい。(A)成分の含有量がこの範囲内であると、感光層の光硬化部の強度がより良好となる。 The content of component (A) is 30 to 80 parts by mass, 40 to 75 parts by mass, 50 to 70 parts by mass, or 50 to It may be 60 parts by mass. If the content of component (A) is within this range, the strength of the photocured portion of the photosensitive layer will be better.
((B)光重合性化合物)
(B)光重合性化合物(以下、「(B)成分」ともいう)は、フタル酸骨格を有する(メタ)アクリレートを含むことで、レジストパターンの解像度及び硬化後の剥離特性をバランスよく向上させることができる。((B) photopolymerizable compound)
(B) The photopolymerizable compound (hereinafter also referred to as "(B) component") contains a (meth)acrylate having a phthalic acid skeleton, thereby improving the resolution of the resist pattern and the release properties after curing in a well-balanced manner. be able to.
フタル酸骨格を有する(メタ)アクリレートとしては、例えば、γ-クロロ-β-ヒドロキシプロピル-β’-(メタ)アクリロイルオキシエチル-o-フタレート、β-ヒドロキシエチル-β’-(メタ)アクリロイルオキシエチル-o-フタレート、及びβ-ヒドロキシプロピル-β’-(メタ)アクリロイルオキシエチル-o-フタレートが挙げられる。γ-クロロ-β-ヒドロキシプロピル-β’-メタクリロイルオキシエチル-o-フタレートは、FA-MECH(日立化成株式会社)として商業的に入手可能である。 (Meth)acrylates having a phthalic acid skeleton include, for example, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxy Ethyl-o-phthalate, and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate. γ-Chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (Hitachi Chemical Co., Ltd.).
フタル酸骨格を有する(メタ)アクリレートの含有量は、(A)成分及び(B)成分の総量100質量部に対して、1~30質量部、2~25質量部、5~20質量部、又は8~15質量部であってもよい。フタル酸骨格を有する(メタ)アクリレートの含有量がこの範囲内であると、剥離特性がより良好となる。 The content of the (meth)acrylate having a phthalic acid skeleton is 1 to 30 parts by mass, 2 to 25 parts by mass, 5 to 20 parts by mass, based on 100 parts by mass of the total amount of components (A) and (B). Alternatively, it may be 8 to 15 parts by mass. If the content of the (meth)acrylate having a phthalic acid skeleton is within this range, the peeling properties will be better.
(B)成分は、フタル酸骨格を有する(メタ)アクリレート以外の光重合性化合物(以下、「他の光重合性化合物」ともいう)を更に含んでよい。他の光重合性化合物としては、エチレン性不飽和結合を有する化合物を用いることができる。他の光重合性化合物は、1種を単独で又は2種以上を組み合わせて用いてもよい。 The component (B) may further contain a photopolymerizable compound other than the (meth)acrylate having a phthalic acid skeleton (hereinafter also referred to as “another photopolymerizable compound”). As another photopolymerizable compound, a compound having an ethylenically unsaturated bond can be used. Other photopolymerizable compounds may be used singly or in combination of two or more.
エチレン性不飽和結合は、光重合が可能であれば特に限定されない。エチレン性不飽和結合としては、例えば、(メタ)アクリロイル基等のα,β-不飽和カルボニル基が挙げられる。α,β-不飽和カルボニル基を有する光重合性化合物としては、例えば、多価アルコールのα,β-不飽和カルボン酸エステル、ビスフェノール型(メタ)アクリレート、グリシジル基含有化合物のα,β-不飽和カルボン酸付加物、ウレタン結合を有する(メタ)アクリレート、ノニルフェノキシポリエチレンオキシアクリレート、及び(メタ)アクリル酸アルキルエステルが挙げられる。 The ethylenically unsaturated bond is not particularly limited as long as photopolymerization is possible. Examples of ethylenically unsaturated bonds include α,β-unsaturated carbonyl groups such as (meth)acryloyl groups. Examples of the photopolymerizable compound having an α,β-unsaturated carbonyl group include α,β-unsaturated carboxylic acid esters of polyhydric alcohols, bisphenol-type (meth)acrylates, and α,β-unsaturated glycidyl group-containing compounds. Saturated carboxylic acid adducts, (meth)acrylates having urethane bonds, nonylphenoxypolyethyleneoxyacrylates, and (meth)acrylic acid alkyl esters can be mentioned.
多価アルコールのα,β-不飽和カルボン酸エステルとしては、例えば、エチレン基の数が2~14であるポリエチレングリコールジ(メタ)アクリレート、プロピレン基の数が2~14であるポリプロピレングリコールジ(メタ)アクリレート、エチレン基の数が2~14でありプロピレン基の数が2~14であるポリエチレン・ポリプロピレングリコールジ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、EO変性トリメチロールプロパントリ(メタ)アクリレート、PO変性トリメチロールプロパントリ(メタ)アクリレート、EO,PO変性トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、及びジペンタエリスリトール又はペンタエリスリトール由来の骨格を有する(メタ)アクリレート化合物が挙げられる。「EO変性」とはエチレンオキサイド(EO)基のブロック構造を有するものであることを意味し、「PO変性」とはプロピレンオキサイド(PO)基のブロック構造を有するものであることを意味する。 Examples of α,β-unsaturated carboxylic acid esters of polyhydric alcohols include polyethylene glycol di(meth)acrylate having 2 to 14 ethylene groups and polypropylene glycol di(meth)acrylate having 2 to 14 propylene groups. meth)acrylate, polyethylene-polypropylene glycol di(meth)acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth) Acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO, PO-modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra (Meth)acrylates and (meth)acrylate compounds having a skeleton derived from dipentaerythritol or pentaerythritol. "EO-modified" means having a block structure of ethylene oxide (EO) groups, and "PO-modified" means having a block structure of propylene oxide (PO) groups.
(B)成分は、レジストパターンの柔軟性を向上する観点から、ポリアルキレングリコールジ(メタ)アクリレートを含んでもよい。ポリアルキレングリコールジ(メタ)アクリレートは、EO基及びPO基の少なくとも一方を有してもよく、EO基及びPO基の双方を有してもよい。EO基及びPO基の双方を有するポリアルキレングリコールジ(メタ)アクリレートにおいて、EO基及びPO基は、それぞれ連続してブロック的に存在しても、ランダムに存在してもよい。また、PO基は、オキシ-n-プロピレン基又はオキシイソプロピレン基のいずれであってもよい。なお、(ポリ)オキシイソプロピレン基において、プロピレン基の2級炭素が酸素原子に結合していてもよく、1級炭素が酸素原子に結合していてもよい。 The component (B) may contain polyalkylene glycol di(meth)acrylate from the viewpoint of improving the flexibility of the resist pattern. The polyalkylene glycol di(meth)acrylate may have at least one of EO and PO groups, or both EO and PO groups. In the polyalkylene glycol di(meth)acrylate having both EO groups and PO groups, the EO groups and PO groups may be present continuously in blocks or randomly. Also, the PO group may be either an oxy-n-propylene group or an oxyisopropylene group. In addition, in the (poly)oxyisopropylene group, the secondary carbon of the propylene group may be bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.
ポリアルキレングリコールジ(メタ)アクリレートの市販品としては、例えば、FA-023M(日立化成株式会社製)、FA-024M(日立化成株式会社製)、及びNKエステルHEMA-9P(新中村化学工業株式会社製)が挙げられる。 Examples of commercially available polyalkylene glycol di(meth)acrylates include FA-023M (manufactured by Hitachi Chemical Co., Ltd.), FA-024M (manufactured by Hitachi Chemical Co., Ltd.), and NK Ester HEMA-9P (Shin-Nakamura Chemical Co., Ltd. manufactured by the company).
(B)成分は、レジストパターンの柔軟性を向上する観点から、ウレタン結合を有する(メタ)アクリレートを含んでもよい。ウレタン結合を有する(メタ)アクリレートとしては、例えば、β位にOH基を有する(メタ)アクリルモノマーとジイソシアネート(イソホロンジイソシアネート、2,6-トルエンジイソシアネート、2,4-トルエンジイソシアネート、1,6-ヘキサメチレンジイソシアネート等)との付加反応物、トリス((メタ)アクリロキシテトラエチレングリコールイソシアネート)ヘキサメチレンイソシアヌレート、EO変性ウレタンジ(メタ)アクリレート、及びEO,PO変性ウレタンジ(メタ)アクリレートが挙げられる。 The component (B) may contain a (meth)acrylate having a urethane bond from the viewpoint of improving the flexibility of the resist pattern. The (meth)acrylate having a urethane bond includes, for example, a (meth)acrylic monomer having an OH group at the β-position and a diisocyanate (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexa methylene diisocyanate, etc.), tris((meth)acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di(meth)acrylate, and EO, PO-modified urethane di(meth)acrylate.
EO変性ウレタンジ(メタ)アクリレートの市販品としては、例えば、「UA-11」及び「UA-21EB」(新中村化学工業株式会社製)が挙げられる。EO,PO変性ウレタンジ(メタ)アクリレートの市販品としては、例えば、「UA-13」(新中村化学工業株式会社製)が挙げられる。 Commercially available EO-modified urethane di(meth)acrylates include, for example, “UA-11” and “UA-21EB” (manufactured by Shin-Nakamura Chemical Co., Ltd.). Commercially available EO, PO-modified urethane di(meth)acrylates include, for example, "UA-13" (manufactured by Shin-Nakamura Chemical Co., Ltd.).
(B)成分は、厚膜のレジストパターンが形成し易く、解像度及び密着性をバランスよく向上させる観点から、ジペンタエリスリトール又はペンタエリスリトール由来の骨格を有する(メタ)アクリレート化合物を含んでもよい。ジペンタエリスリトール又はペンタエリスリトール由来の骨格を有する(メタ)アクリレート化合物は、(メタ)アクリロイル基を4つ以上有することが好ましく、ジペンタエリスリトールペンタ(メタ)アクリレート、又はジペンタエリスリトールヘキサ(メタ)アクリレートであってもよい。 The component (B) may contain a (meth)acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol from the viewpoint of facilitating the formation of a thick resist pattern and improving resolution and adhesion in a well-balanced manner. The (meth)acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol preferably has four or more (meth)acryloyl groups, and is dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate. may be
解像度及び硬化後の剥離特性をより向上させる観点から、(B)成分は、ビスフェノール型(メタ)アクリレートを含んでもよく、ビスフェノール型(メタ)アクリレートの中でもビスフェノールA型(メタ)アクリレートを含んでもよい。ビスフェノールA型(メタ)アクリレートとしては、例えば、2,2-ビス(4-((メタ)アクリロキシポリエトキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシポリプロポキシ)フェニル)プロパン、2,2-ビス(4-((メタ)アクリロキシポリブトキシ)フェニル)プロパン、及び2,2-ビス(4-((メタ)アクリロキシポリエトキシポリプロポキシ)フェニル)プロパンが挙げられる。中でも、解像度及びパター形成性を更に向上させる観点から、2,2-ビス(4-((メタ)アクリロキシポリエトキシ)フェニル)プロパンが好ましい。 From the viewpoint of further improving resolution and release properties after curing, the component (B) may contain a bisphenol type (meth)acrylate, and among the bisphenol type (meth)acrylates, it may contain a bisphenol A type (meth)acrylate. . Bisphenol A type (meth)acrylates include, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolypropoxy) phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane. be done. Among them, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane is preferable from the viewpoint of further improving the resolution and puttability.
商業的に入手可能なものとしては、例えば、2,2-ビス(4-((メタ)アクリロキシジプロポキシ)フェニル)プロパンは、BPE-200(新中村化学工業株式会社)、2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパンは、BPE-500(新中村化学工業株式会社)、FA-321M(日立化成株式会社)等が挙げられる。 Commercially available ones include, for example, 2,2-bis(4-((meth)acryloxydipropoxy)phenyl)propane, BPE-200 (Shin-Nakamura Chemical Co., Ltd.), 2,2- Bis(4-(methacryloxypentaethoxy)phenyl)propane includes BPE-500 (Shin-Nakamura Chemical Co., Ltd.) and FA-321M (Hitachi Chemical Co., Ltd.).
ノニルフェノキシポリエチレンオキシアクリレートとしては、例えば、ノニルフェノキシテトラエチレンオキシアクリレート、ノニルフェノキシペンタエチレンオキシアクリレート、ノニルフェノキシヘキサエチレンオキシアクリレート、ノニルフェノキシヘプタエチレンオキシアクリレート、ノニルフェノキシオクタエチレンオキシアクリレート、ノニルフェノキシノナエチレンオキシアクリレート、ノニルフェノキシデカエチレンオキシアクリレート、及びノニルフェノキシウンデカエチレンオキシアクリレートが挙げられる。 Examples of nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxy acrylates, nonylphenoxydecaethyleneoxy acrylate, and nonylphenoxyundecaethyleneoxy acrylate.
((C)光重合開始剤)
(C)光重合開始剤(以下、「(C)成分」ともいう)としては、(B)成分を重合させることができるものであれば、特に制限は無く、通常用いられる光重合開始剤から適宜選択することができる。パターン形成性を向上させる観点から、活性光線により遊離ラジカルを生成するもの、例えば、アシルホスフィンオキサイド系、オキシムエステル系、芳香族ケトン系、キノン系、アルキルフェノン系、イミダゾール系、アクリジン系、フェニルグリシン系、クマリン系等の光重合開始剤が挙げられる。((C) photoinitiator)
(C) The photopolymerization initiator (hereinafter also referred to as "component (C)") is not particularly limited as long as it can polymerize the component (B). It can be selected as appropriate. From the viewpoint of improving pattern formability, substances that generate free radicals by actinic rays, such as acylphosphine oxides, oxime esters, aromatic ketones, quinones, alkylphenones, imidazoles, acridines, and phenylglycine and coumarin-based photopolymerization initiators.
(C)成分は、感度及び解像度をバランスよく向上する点で、アクリジン系光重合開始剤、フェニルグリシン系光重合開始剤、又は、イミダゾール系光重合開始剤を含んでもよい。(C)成分は、1種を単独で又は2種以上を組み合わせて用いることができる。 The component (C) may contain an acridine-based photopolymerization initiator, a phenylglycine-based photopolymerization initiator, or an imidazole-based photopolymerization initiator in order to improve sensitivity and resolution in a well-balanced manner. (C) Component can be used individually by 1 type or in combination of 2 or more types.
アクリジン系光重合開始剤としては、例えば、9-フェニルアクリジン、9-(p-メチルフェニル)アクリジン、9-(m-メチルフェニル)アクリジン、9-(p-クロロフェニル)アクリジン、9-(m-クロロフェニル)アクリジン、9-アミノアクリジン、9-ジメチルアミノアクリジン、9-ジエチルアミノアクリジン、9-ペンチルアミノアクリジン、1,2-ビス(9-アクリジニル)エタン、1,4-ビス(9-アクリジニル)ブタン、1,6-ビス(9-アクリジニル)ヘキサン、1,8-ビス(9-アクリジニル)オクタン、1,10-ビス(9-アクリジニル)デカン、1,12-ビス(9-アクリジニル)ドデカン、1,14-ビス(9-アクリジニル)テトラデカン、1,16-ビス(9-アクリジニル)ヘキサデカン、1,18-ビス(9-アクリジニル)オクタデカン、1,20-ビス(9-アクリジニル)エイコサン等のビス(9-アクリジニル)アルカン、1,3-ビス(9-アクリジニル)-2-オキサプロパン、1,3-ビス(9-アクリジニル)-2-チアプロパン、及び1,5-ビス(9-アクリジニル)-3-チアペンタンが挙げられる。 Examples of acridine photopolymerization initiators include 9-phenylacridine, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine, 9-(p-chlorophenyl)acridine, 9-(m- chlorophenyl)acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine, 9-pentylaminoacridine, 1,2-bis(9-acridinyl)ethane, 1,4-bis(9-acridinyl)butane, 1,6-bis(9-acridinyl)hexane, 1,8-bis(9-acridinyl)octane, 1,10-bis(9-acridinyl)decane, 1,12-bis(9-acridinyl)dodecane, 1, Bis(9) such as 14-bis(9-acridinyl)tetradecane, 1,16-bis(9-acridinyl)hexadecane, 1,18-bis(9-acridinyl)octadecane, 1,20-bis(9-acridinyl)eicosane -acridinyl)alkanes, 1,3-bis(9-acridinyl)-2-oxapropane, 1,3-bis(9-acridinyl)-2-thiapropane, and 1,5-bis(9-acridinyl)-3- Thiapentane is mentioned.
フェニルグリシン系光重合開始剤としては、例えば、N-フェニルグリシン、N-メチル-N-フェニルグリシン、及びN-エチル-N-フェニルグリシンが挙げられる。 Phenylglycine-based photopolymerization initiators include, for example, N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
イミダゾール系光重合開始剤としては、例えば、2-(o-クロロフェニル)-4,5-ジフェニルビイミダゾール、2,2’,5-トリス-(o-クロロフェニル)-4-(3,4-ジメトキシフェニル)-4’,5’-ジフェニルビイミダゾール、2,4-ビス-(o-クロロフェニル)-5-(3,4-ジメトキシフェニル)-ジフェニルビイミダゾール、2,4,5-トリス-(o-クロロフェニル)-ジフェニルビイミダゾール、2-(o-クロロフェニル)-ビス-4,5-(3,4-ジメトキシフェニル)-ビイミダゾール、2,2’-ビス-(2-フルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,3-ジフルオロメチルフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、2,2’-ビス-(2,4-ジフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾール、及び2,2’-ビス-(2,5-ジフルオロフェニル)-4,4’,5,5’-テトラキス-(3-メトキシフェニル)-ビイミダゾールが挙げられる。 Examples of imidazole-based photopolymerization initiators include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2′,5-tris-(o-chlorophenyl)-4-(3,4-dimethoxy Phenyl)-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, 2,2′-bis-(2,3-difluoromethylphenyl)-4,4′,5,5′-tetrakis-( 3-methoxyphenyl)-biimidazole, 2,2′-bis-(2,4-difluorophenyl)-4,4′,5,5′-tetrakis-(3-methoxyphenyl)-biimidazole, and 2, 2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.
(C)成分の含有量は、(A)成分及び(B)成分の総量100質量部に対して、0.1~10質量部、0.2~5質量部、0.4~3質量部、又は0.5~2質量部であってもよい。(C)成分の含有量が0.1質量部以上では、光感度、解像度及び密着性が向上する傾向があり、10質量部以下では、レジストパターン形成性により優れる傾向がある。 The content of component (C) is 0.1 to 10 parts by mass, 0.2 to 5 parts by mass, and 0.4 to 3 parts by mass based on 100 parts by mass of the total amount of components (A) and (B). , or 0.5 to 2 parts by mass. When the content of component (C) is 0.1 parts by mass or more, photosensitivity, resolution and adhesion tend to be improved, and when it is 10 parts by mass or less, resist pattern formability tends to be more excellent.
(その他の成分)
本実施形態に係る感光性樹脂組成物には、必要に応じて、染料、光発色剤、熱発色防止剤、可塑剤、顔料、充填剤、消泡剤、難燃剤、密着性付与剤、レベリング剤、剥離促進剤、酸化防止剤、香料、イメージング剤、熱架橋剤、重合禁止剤等の添加剤を更に含有してもよい。これらの添加剤は、1種を単独で又は2種以上を組み合わせて用いることができる。(other ingredients)
The photosensitive resin composition according to the present embodiment may optionally contain a dye, a photocoloring agent, a thermal coloring inhibitor, a plasticizer, a pigment, a filler, an antifoaming agent, a flame retardant, an adhesion imparting agent, and a leveling agent. Additives such as agents, release accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents, and polymerization inhibitors may be further contained. These additives can be used singly or in combination of two or more.
染料としては、例えば、マラカイトグリーン、ビクトリアピュアブルー、ブリリアントグリーン、及びメチルバイオレットが挙げられる。光発色剤としては、例えば、トリブロモフェニルスルホン、ロイコクリスタルバイオレット、ジフェニルアミン、ベンジルアミン、トリフェニルアミン、ジエチルアニリン、及びo-クロロアニリンが挙げられる。可塑剤としては、例えば、p-トルエンスルホンアミドが挙げられる。 Dyes include, for example, malachite green, victoria pure blue, brilliant green, and methyl violet. Photochromic agents include, for example, tribromophenylsulfone, leucocrystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline. Plasticizers include, for example, p-toluenesulfonamide.
添加剤の含有量は、(A)成分及び(B)成分の総量100質量部に対してそれぞれ0.01~10質量部、0.05~5質量部、又は0.1~3質量部であってもよい。 The content of the additive is 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass based on 100 parts by mass of the total amount of components (A) and (B). There may be.
感光性樹脂組成物は、必要に応じて、メタノール、エタノール、アセトン、メチルエチルケトン、メチルセロソルブ、エチルセロソルブ、トルエン、N,N-ジメチルホルムアミド、プロピレングリコールモノメチルエーテル等の溶剤又はこれらの混合溶剤に溶解して、固形分が30~60質量%程度の溶液として調製することができる。 The photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof, if necessary. can be prepared as a solution with a solid content of about 30 to 60% by mass.
[感光性エレメント]
本実施形態の感光性エレメントは、支持体と、該支持体上に形成されたと感光層とを備え、感光層は上述の感光性樹脂組成物を含む。本実施形態の感光性エレメントを用いる場合には、感光層を基板上にラミネートした後、支持体(支持フィルム)を剥離することなく露光してもよい。本実施形態に係る感光性エレメント1は、図1にその一例の模式断面図を示すように、支持体2と、支持体2上に形成された上記感光性樹脂組成物に由来する感光層3とを備え、必要に応じて設けられる保護層4等のその他の層を備えて構成される。[Photosensitive element]
The photosensitive element of this embodiment comprises a support and a photosensitive layer formed on the support, and the photosensitive layer contains the photosensitive resin composition described above. When the photosensitive element of this embodiment is used, after the photosensitive layer is laminated on the substrate, exposure may be performed without peeling off the support (support film). A
(支持体)
支持体しては、例えば、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)、ポリエチレン-2,6-ナフタレート(PEN)等のポリエステルフィルム、及びポリプロピレン、ポリエチレン等のポリオレフィンフィルムが挙げられる。中でも、入手し易く、且つ、製造工程におけるハンドリング性(特に、耐熱性、熱収縮率、破断強度)に優れる点で、PETフィルムであってもよい。(support)
Examples of the support include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene-2,6-naphthalate (PEN), and polyolefin films such as polypropylene and polyethylene. Among them, a PET film may be used because it is easily available and has excellent handleability (in particular, heat resistance, heat shrinkage, and breaking strength) in the manufacturing process.
支持体のヘーズは、0.01~1.0%又は0.01~0.5%であってもよい。ヘーズが0.01%以上であると、支持体自体を製造し易くなる傾向があり、1.0%以下であると、レジストパターンに発生し得る微小欠損を低減する傾向がある。「ヘーズ」とは、曇り度を意味する。本開示におけるヘーズは、JIS K 7105に規定される方法に準拠して、市販の曇り度計(濁度計)を用いて測定された値をいう。ヘーズは、例えば、NDH-5000(日本電色工業(株)製)等の市販の濁度計で測定が可能である。 The haze of the support may be 0.01-1.0% or 0.01-0.5%. A haze of 0.01% or more tends to facilitate the production of the support itself, and a haze of 1.0% or less tends to reduce minute defects that may occur in the resist pattern. "Haze" means cloudiness. Haze in the present disclosure refers to a value measured using a commercially available cloudiness meter (turbidity meter) in accordance with the method specified in JIS K 7105. Haze can be measured with a commercially available turbidity meter such as NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
支持体の厚みは、1~100μm、5~60μm、10~50μm、10~40μm、10~30μm、又は10~25μmであってもよい。支持体の厚みが1μm以上であることで、支持体を剥離する際に支持体が破れることを抑制できる傾向がある。また、支持体の厚みが100μm以下であることで、支持体を通して露光する場合に解像性が低下することを抑制することができる。 The thickness of the support may be 1-100 μm, 5-60 μm, 10-50 μm, 10-40 μm, 10-30 μm, or 10-25 μm. When the thickness of the support is 1 μm or more, it tends to be possible to suppress tearing of the support when the support is peeled off. Further, when the thickness of the support is 100 μm or less, it is possible to suppress deterioration in resolution when exposure is performed through the support.
(保護層)
感光性エレメントは、必要に応じて保護層を更に備えてもよい。保護層としては、感光層と支持体との間の接着力よりも、感光層と保護層との間の接着力が小さくなるようなフィルムを用いてもよく、また、低フィッシュアイのフィルムを用いてもよい。具体的には、例えば、上述する支持体として用いることができるものが挙げられる。感光層からの剥離性の見地から、ポリエチレンフィルムであってもよい。保護層の厚さは、用途により異なるが、1~100μm程度であってもよい。(protective layer)
The photosensitive element may further comprise a protective layer if desired. As the protective layer, a film in which the adhesive strength between the photosensitive layer and the protective layer is smaller than the adhesive strength between the photosensitive layer and the support may be used. may be used. Specific examples include those that can be used as the support described above. From the standpoint of releasability from the photosensitive layer, it may be a polyethylene film. The thickness of the protective layer may be about 1 to 100 μm, depending on the application.
感光性エレメントは、例えば、以下のようにして製造することができる。すなわち、支持体上に、感光性樹脂組成物の溶液(塗布液)を塗布して塗布層を形成し、これを乾燥することで感光層を形成する。次いで、感光層の支持体とは反対側の面を保護層で被覆することにより、支持体と、該支持体上に形成された感光層と、該感光層上に積層された保護層とを備える、感光性エレメントが得られる。 A photosensitive element can be manufactured, for example, as follows. That is, a solution (coating liquid) of a photosensitive resin composition is applied onto a support to form a coating layer, which is then dried to form a photosensitive layer. Then, the surface of the photosensitive layer opposite to the support is covered with a protective layer, thereby separating the support, the photosensitive layer formed on the support, and the protective layer laminated on the photosensitive layer. A photosensitive element is obtained comprising:
塗布液の支持体上への塗布は、例えば、ロールコート、コンマコート、グラビアコート、エアーナイフコート、ダイコート、バーコート等の公知の方法により行うことができる。 Application of the coating solution onto the support can be carried out by known methods such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating and the like.
塗布層の乾燥は、塗布層から有機溶剤の少なくとも一部を除去することができれば特に制限はない。例えば、70~150℃にて、5~30分間程度行ってもよい。乾燥後、感光層中の残存溶剤量は、後の工程での溶剤の拡散を防止する観点から、2質量%以下であってもよい。 There are no particular restrictions on the drying of the coating layer as long as at least part of the organic solvent can be removed from the coating layer. For example, it may be carried out at 70 to 150° C. for about 5 to 30 minutes. After drying, the amount of solvent remaining in the photosensitive layer may be 2% by mass or less from the viewpoint of preventing diffusion of the solvent in subsequent steps.
感光性エレメントにおける感光層の厚みは、用途により適宜選択することができるが、乾燥後の厚みで1~100μm、1~50μm、又は、5~40μmであってもよい。厚さが1μm以上であることで、工業的な塗工が容易になり、生産性が向上する。また、100μm以下であることで、密着性及び解像度が向上する。 The thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on the application, and the thickness after drying may be 1 to 100 μm, 1 to 50 μm, or 5 to 40 μm. When the thickness is 1 µm or more, industrial coating is facilitated and productivity is improved. Further, when the thickness is 100 μm or less, adhesion and resolution are improved.
感光性エレメントの形態は特に制限されない。例えば、シート状であってもよく、巻芯にロール状に巻き取った形状であってもよい。ロール状に巻き取る場合、支持フィルムが外側になるように巻き取ってもよい。巻芯としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂又はABS樹脂(アクリロニトリル-ブタジエン-スチレン共重合体)等のプラスチックが挙げられる。 The form of the photosensitive element is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core. When wound into a roll, the film may be wound with the support film on the outside. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
ロール状の感光性エレメントの端面には、端面保護の点から端面セパレータを設置してもよく、耐エッジフュージョンの点から防湿端面セパレータを設置してもよい。感光性エレメントは、透湿性の小さいブラックシートに包んで包装してもよい。 An end face separator may be provided on the end face of the roll-shaped photosensitive element for protection of the end face, or a moisture-proof end face separator may be provided for edge fusion resistance. The photosensitive element may be packaged by wrapping it in a black sheet with low moisture permeability.
感光性エレメントは、例えば、後述するレジストパターンの形成方法に好適に用いることができる。中でも、解像性の観点で、めっき処理によって導体パターンを形成する製造方法への応用に適している。 The photosensitive element can be suitably used, for example, in the method of forming a resist pattern, which will be described later. Above all, from the viewpoint of resolution, it is suitable for application to a manufacturing method in which a conductive pattern is formed by plating.
[レジストパターンの形成方法]
本実施形態のレジストパターンの形成方法は、(i)基板上に、上記感光性樹脂組成物、又は、上記感光性エレメントを用いて、感光層を形成する工程(感光層形成工程)と、(ii)上記感光層の少なくとも一部(所定部分)に活性光線を照射して、光硬化部を形成する工程(露光工程)と、(iii)上記基板上から上記光硬化部以外の少なくとも一部を除去する工程(現像工程)と、を備え、必要に応じてその他の工程を含んで構成されてもよい。レジストパターンとは、感光性樹脂組成物の光硬化物パターンともいえ、レリーフパターンともいえる。レジストパターンの形成方法は、レジストパターン付き基板の製造方法ともいえる。[Method of forming a resist pattern]
The method for forming a resist pattern of the present embodiment includes (i) a step of forming a photosensitive layer on a substrate using the photosensitive resin composition or the photosensitive element (photosensitive layer forming step); ii) a step of irradiating at least a portion (predetermined portion) of the photosensitive layer with actinic rays to form a photocured portion (exposure step); and (iii) at least a portion other than the photocured portion from the substrate. and a step of removing the (development step), and may include other steps as necessary. A resist pattern can be said to be a pattern of a photocured product of a photosensitive resin composition, or a relief pattern. The method of forming a resist pattern can also be said to be a method of manufacturing a substrate with a resist pattern.
((i)感光層形成工程)
基板上に感光層を形成する方法としては、例えば、上記感光性樹脂組成物を塗布及び乾燥してもよく、又は、上記感光性エレメントから保護層を除去した後、感光性エレメントの感光層を加熱しながら上記基板に圧着してもよい。感光性エレメントを用いた場合、基板と感光層と支持体とからなり、これらが順に積層された積層体が得られる。上記基板としては特に制限されないが、通常、絶縁層と絶縁層上に形成された導体層とを備えた回路形成用基板、又は合金基材等のダイパッド(リードフレーム用基材)が用いられる。((i) Photosensitive layer forming step)
As a method for forming a photosensitive layer on a substrate, for example, the photosensitive resin composition may be applied and dried, or after removing the protective layer from the photosensitive element, the photosensitive layer of the photosensitive element may be formed. It may be pressure-bonded to the substrate while being heated. When a photosensitive element is used, a laminate comprising a substrate, a photosensitive layer and a support, which are laminated in order, is obtained. Although the substrate is not particularly limited, a circuit forming substrate comprising an insulating layer and a conductor layer formed on the insulating layer, or a die pad (lead frame substrate) such as an alloy substrate is usually used.
感光性エレメントを用いた場合、感光層形成工程は、密着性及び追従性の見地から、減圧下で行うことが好ましい。圧着の際の感光層及び/又は基板の加熱は、70~130℃の温度で行ってもよい。圧着は、0.1~1.0MPa程度(1~10kgf/cm2程度)の圧力で行ってもよいが、これらの条件は必要に応じて適宜選択される。なお、感光層を70~130℃に加熱すれば、予め基板を予熱処理することは必要ではないが、密着性及び追従性を更に向上させるために、基板の予熱処理を行うこともできる。When a photosensitive element is used, the photosensitive layer forming step is preferably carried out under reduced pressure from the viewpoint of adhesion and followability. Heating of the photosensitive layer and/or the substrate during compression may be performed at a temperature of 70 to 130.degree. Crimping may be performed at a pressure of approximately 0.1 to 1.0 MPa (approximately 1 to 10 kgf/cm 2 ), but these conditions are appropriately selected as necessary. If the photosensitive layer is heated to 70 to 130° C., it is not necessary to preheat the substrate, but the substrate may be preheated in order to further improve adhesion and followability.
((ii)露光工程)
露光工程においては、基板上に形成された感光層の少なくとも一部に活性光線を照射することで、活性光線が照射された部分が光硬化して、潜像が形成される。この際、感光層上に支持体が存在する場合、その支持体が活性光線に対して透過性であれば、支持体を通して活性光線を照射することができるが、支持体が遮光性の場合には、支持体を除去した後に感光層に活性光線を照射する。((ii) exposure step)
In the exposure step, at least a portion of the photosensitive layer formed on the substrate is irradiated with actinic rays, and the portion irradiated with actinic rays is photocured to form a latent image. In this case, when a support is present on the photosensitive layer, actinic rays can be irradiated through the support if the support is transparent to actinic rays. irradiates the photosensitive layer with an actinic ray after removing the support.
露光方法としては、アートワークと呼ばれるネガ又はポジマスクパターンを介して活性光線を画像状に照射する方法(マスク露光法)が挙げられる。また、投影露光法により活性光線を画像状に照射する方法を採用してもよい。また、LDI(Laser Direct Imaging)露光法、DLP(Digital Light Processing)露光法等の直接描画露光法により活性光線を画像状に照射する方法を採用してもよい。 Examples of the exposure method include a method of irradiating actinic rays imagewise through a negative or positive mask pattern called artwork (mask exposure method). Alternatively, a method of irradiating an actinic ray imagewise by a projection exposure method may be employed. Moreover, you may employ|adopt the method of irradiating an actinic ray imagewise by direct drawing exposure methods, such as LDI (Laser Direct Imaging) exposure method and DLP (Digital Light Processing) exposure method.
活性光線の光源としては、公知の光源を用いることができ、例えば、カーボンアーク灯、水銀蒸気アーク灯、高圧水銀灯、キセノンランプ、アルゴンレーザ等のガスレーザ、YAGレーザ等の固体レーザ、半導体レーザ等の紫外線、可視光を有効に放射するものが用いられる。 As a light source for actinic rays, known light sources can be used. A material that effectively emits ultraviolet rays and visible light is used.
((iii)現像工程)
現像工程においては、上記感光層の光硬化部以外の少なくとも一部が基板上から除去されることで、レジストパターンが基板上に形成される。((iii) development step)
In the developing step, at least a portion of the photosensitive layer other than the photocured portion is removed from the substrate, thereby forming a resist pattern on the substrate.
感光層上に支持体が存在している場合には、支持体を除去してから、上記光硬化部以外の領域(未露光部分ともいえる)の除去(現像)を行う。現像方法には、ウェット現像とドライ現像とがあるが、ウェット現像が広く用いられている。 When a support is present on the photosensitive layer, after removing the support, areas other than the photocured areas (which can be called unexposed areas) are removed (developed). Developing methods include wet development and dry development, and wet development is widely used.
ウェット現像による場合、感光性樹脂組成物に対応した現像液を用いて、公知の現像方法により現像する。現像方法としては、ディップ方式、パドル方式、スプレー方式、ブラッシング、スラッピング、スクラッビング、揺動浸漬等を用いた方法が挙げられ、解像性向上の観点からは、高圧スプレー方式を用いてもよい。これら2種以上の方法を組み合わせて現像を行ってもよい。 In the case of wet development, development is performed by a known developing method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include methods using a dip method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, etc. From the viewpoint of improving resolution, a high-pressure spray method may be used. . Development may be performed by combining two or more of these methods.
現像液の構成は上記感光性樹脂組成物の構成に応じて適宜選択される。現像液としては、例えば、アルカリ性水溶液及び有機溶剤現像液が挙げられる。 The composition of the developer is appropriately selected according to the composition of the photosensitive resin composition. The developer includes, for example, an alkaline aqueous solution and an organic solvent developer.
安全且つ安定であり、操作性が良好である見地から、現像液として、アルカリ性水溶液を用いてもよい。アルカリ性水溶液の塩基としては、リチウム、ナトリウム又はカリウムの水酸化物等の水酸化アルカリ;リチウム、ナトリウム、カリウム又はアンモニウムの炭酸塩又は重炭酸塩等の炭酸アルカリ;リン酸カリウム、リン酸ナトリウム等のアルカリ金属リン酸塩;ピロリン酸ナトリウム、ピロリン酸カリウム等のアルカリ金属ピロリン酸塩;ホウ砂、メタケイ酸ナトリウム、水酸化テトラメチルアンモニウム、エタノールアミン、エチレンジアミン、ジエチレントリアミン、2-アミノ-2-ヒドロキシメチル-1,3-プロパンジオール、1,3-ジアミノプロパノール-2、モルホリンなどが用いられる。 From the standpoint of safety, stability, and good operability, an alkaline aqueous solution may be used as the developer. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates; potassium phosphate, sodium phosphate and the like. alkali metal phosphate; alkali metal pyrophosphate such as sodium pyrophosphate and potassium pyrophosphate; borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl- 1,3-propanediol, 1,3-diaminopropanol-2, morpholine and the like are used.
現像に用いるアルカリ性水溶液としては、0.1~5質量%炭酸ナトリウムの希薄溶液、0.1~5質量%炭酸カリウムの希薄溶液、0.1~5質量%水酸化ナトリウムの希薄溶液、0.1~5質量%四ホウ酸ナトリウムの希薄溶液等を用いることができる。アルカリ性水溶液のpHは、9~11の範囲としてもよく、その温度は、感光層のアルカリ現像性に合わせて調節できる。アルカリ性水溶液中には、例えば、表面活性剤、消泡剤、現像を促進させるための少量の有機溶剤等を混入させてもよい。 Alkaline aqueous solutions used for development include dilute solutions of 0.1 to 5% by mass sodium carbonate, dilute solutions of 0.1 to 5% by mass potassium carbonate, dilute solutions of 0.1 to 5% by mass sodium hydroxide, and 0.1% to 5% by mass. A dilute solution of 1 to 5 mass % sodium tetraborate or the like can be used. The pH of the alkaline aqueous solution may be in the range of 9 to 11, and the temperature can be adjusted according to the alkaline developability of the photosensitive layer. The alkaline aqueous solution may contain, for example, a surfactant, an antifoaming agent, a small amount of organic solvent for promoting development, and the like.
アルカリ性水溶液に用いられる有機溶剤としては、例えば、アセトン、酢酸エチル、炭素数1~4のアルコキシ基をもつアルコキシエタノール、エチルアルコール、イソプロピルアルコール、ブチルアルコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、及びジエチレングリコールモノブチルエーテルが挙げられる。 Organic solvents used in the alkaline aqueous solution include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. Monobutyl ether may be mentioned.
有機溶剤現像液に用いられる有機溶剤としては、例えば、1,1,1-トリクロロエタン、N-メチルピロリドン、N,N-ジメチルホルムアミド、シクロヘキサノン、メチルイソブチルケトン及びγ-ブチロラクトン等が挙げられる。これらの有機溶剤には、引火防止のため、1~20質量%の範囲となるように水を添加して有機溶剤現像液としてもよい。 Examples of organic solvents used in organic solvent developers include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methylisobutylketone and γ-butyrolactone. In order to prevent ignition, water may be added to these organic solvents in a range of 1 to 20% by mass to prepare an organic solvent developer.
本実施形態におけるレジストパターンの形成方法においては、現像工程において未硬化部分を除去した後、必要に応じて60~250℃程度での加熱又は0.2~10J/cm2程度の露光を行うことにより、レジストパターンを更に硬化する工程を含んでもよい。In the method of forming a resist pattern in the present embodiment, after removing the uncured portion in the development step, heating at about 60 to 250° C. or exposure at about 0.2 to 10 J/cm 2 is performed as necessary. may include a step of further hardening the resist pattern.
[プリント配線板の製造方法]
本実施形態のプリント配線板の製造方法は、上記レジストパターンの形成方法によって、レジストパターンが形成された基板をエッチング処理又はめっき処理して導体パターンを形成する工程を含み、必要に応じて、レジストパターン除去工程等のその他の工程を含んで構成されてもよい。[Method for manufacturing printed wiring board]
The method for manufacturing a printed wiring board of the present embodiment includes a step of etching or plating a substrate on which a resist pattern is formed by the above method of forming a resist pattern to form a conductor pattern. It may be configured to include other processes such as a pattern removing process.
めっき処理では、基板上に形成されたレジストパターンをマスクとして、基板上に設けられた導体層にめっき処理が行われる。めっき処理の後、後述するレジストパターンの除去によりレジストを除去し、更にこのレジストによって被覆されていた導体層をエッチングして、導体パターンを形成してもよい。めっき処理の方法としては、電解めっき処理であっても、無電解めっき処理であってもよいが、無電解めっき処理であってもよい。 In plating, a conductor layer provided on a substrate is plated using a resist pattern formed on the substrate as a mask. After plating, the resist may be removed by removing the resist pattern, which will be described later, and the conductor layer covered with the resist may be etched to form the conductor pattern. The method of plating treatment may be electrolytic plating treatment, electroless plating treatment, or electroless plating treatment.
一方、エッチング処理では、基板上に形成されたレジストパターンをマスクとして、基板上に設けられた導体層をエッチング除去し、導体パターンを形成する。エッチング処理の方法は、除去すべき導体層に応じて適宜選択される。エッチング液としては、例えば、塩化第二銅溶液、塩化第二鉄溶液、アルカリエッチング溶液、過酸化水素系エッチング液等が挙げられる。 On the other hand, in the etching process, a conductor layer provided on the substrate is removed by etching using a resist pattern formed on the substrate as a mask to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide-based etching solution, and the like.
エッチング処理又はめっき処理の後、基板上のレジストパターンは除去してもよい。レジストパターンの除去は、例えば、上記現像工程に用いたアルカリ性水溶液よりも更に強アルカリ性の水溶液により剥離することができる。この強アルカリ性の水溶液としては、例えば、1~10質量%水酸化ナトリウム水溶液、1~10質量%水酸化カリウム水溶液等が用いられる。 After etching or plating, the resist pattern on the substrate may be removed. The resist pattern can be removed, for example, with a stronger alkaline aqueous solution than the alkaline aqueous solution used in the developing step. As the strong alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution, or the like is used.
めっき処理を施してからレジストパターンを除去した場合、更にエッチング処理によってレジストで被覆されていた導体層をエッチングし、導体パターンを形成することで所望のプリント配線板を製造することができる。この際のエッチング処理の方法は、除去すべき導体層に応じて適宜選択される。例えば、上述のエッチング液を適用することができる。 When the resist pattern is removed after the plating treatment, the desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by etching treatment to form the conductor pattern. The etching method at this time is appropriately selected according to the conductor layer to be removed. For example, the etchant described above can be applied.
本実施形態に係るプリント配線板の製造方法は、単層プリント配線板のみならず、多層プリント配線板の製造にも適用可能であり、また小径スルーホールを有するプリント配線板等の製造にも適用可能である。 The printed wiring board manufacturing method according to the present embodiment can be applied not only to manufacturing single-layer printed wiring boards, but also to manufacturing multilayer printed wiring boards, and also to manufacturing printed wiring boards having small-diameter through-holes. It is possible.
以下、実施例及び比較例に基づいて本実施態様の目的及び利点をより具体的に説明するが、本実施態様は以下の実施例に限定されるものではない。 EXAMPLES The purpose and advantages of the present embodiment will be described in more detail below based on examples and comparative examples, but the present embodiment is not limited to the following examples.
(バインダーポリマー(A-1))
メタクリル酸24g、メタクリル酸メチル26g、スチレン35g、4-メトキシフェノール0.02g、及びアゾビスイソブチロニトリル0.7gを混合して、溶液aを調製した。また、プロピレングリコールモノメチルエーテル9g、トルエン7.6g、及びアゾビスイソブチロニトリル0.14gを混合して、溶液bを調製した。さらに、プロピレングリコールモノメチルエーテル4.5g、トルエン7.6g、及びアゾビスイソブチロニトリル0.5gを混合して、溶液cを調製した。(Binder polymer (A-1))
A solution a was prepared by mixing 24 g of methacrylic acid, 26 g of methyl methacrylate, 35 g of styrene, 0.02 g of 4-methoxyphenol, and 0.7 g of azobisisobutyronitrile. Also, 9 g of propylene glycol monomethyl ether, 7.6 g of toluene, and 0.14 g of azobisisobutyronitrile were mixed to prepare solution b. Furthermore, 4.5 g of propylene glycol monomethyl ether, 7.6 g of toluene, and 0.5 g of azobisisobutyronitrile were mixed to prepare solution c.
撹拌機、還流冷却器、温度計、滴下ロート及び窒素ガス導入管を備えたフラスコに、プロピレングリコールモノメチルエーテル48g、トルエン40g、メタクリル酸5g、及びスチレン10gを投入し、フラスコ内に窒素ガスを吹き込みながら80℃で30分間撹拌して混合液を得た。 48 g of propylene glycol monomethyl ether, 40 g of toluene, 5 g of methacrylic acid, and 10 g of styrene were charged into a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas introduction tube, and nitrogen gas was blown into the flask. While stirring at 80° C. for 30 minutes, a mixed solution was obtained.
フラスコ内の混合液に上記溶液aを4時間かけて滴下した後、80℃で2時間撹拌した。次いで、フラスコ内の溶液に上記溶液bを滴下し、80℃で2時間撹拌した。更に、撹拌を続けたまま、フラスコ内の溶液を1時間かけて95℃まで昇温させた後、上記溶液cを10分間かけて滴下して95℃で2時間撹拌して反応を行った。反応液を50℃まで冷却した後、メタノールを添加してバインダーポリマー(A-1)の溶液を得た。バインダーポリマー(A-1)の不揮発分(固形分)は47.7質量%であった。 After the above solution a was added dropwise to the mixed liquid in the flask over 4 hours, the mixture was stirred at 80° C. for 2 hours. Next, the above solution b was added dropwise to the solution in the flask, and the mixture was stirred at 80°C for 2 hours. Further, the solution in the flask was heated to 95° C. over 1 hour while stirring was continued, and then the above solution c was added dropwise over 10 minutes, followed by stirring at 95° C. for 2 hours for reaction. After cooling the reaction solution to 50° C., methanol was added to obtain a solution of binder polymer (A-1). The non-volatile content (solid content) of the binder polymer (A-1) was 47.7% by mass.
(バインダーポリマー(A-2)及び(A-3))
重合性単量体を表1に示す材料を同表に示す質量比で用いた以外は、バインダーポリマー(A-1)の溶液を得るのと同様にして、バインダーポリマー(A-2)及び(A-3)の溶液を得た。(Binder Polymers (A-2) and (A-3))
Binder polymer (A-2) and (A-2) and ( A-3) solution was obtained.
(重量平均分子量)
バインダーポリマー溶液を120mg採取し、5mLのTHFに溶解して、Mw測定用の試料を調製した。Mwは、ゲルパーミエーションクロマトグラフィー法(GPC)によって測定し、標準ポリスチレンの検量線を用いて換算することにより導出した。GPCの条件を以下に示す。(Weight average molecular weight)
120 mg of the binder polymer solution was collected and dissolved in 5 mL of THF to prepare a sample for Mw measurement. Mw was derived by measuring by gel permeation chromatography (GPC) and converting using a standard polystyrene calibration curve. The conditions of GPC are shown below.
(GPC条件)
ポンプ:日立 L-6000型(株式会社日立製作所製)
カラム:Gelpack GL-R420、Gelpack GL-R430及びGelpack GL-R440(日立化成株式会社製、カラム仕様:10.7mmφ×300mm)
溶離液:テトラヒドロフラン(以下、「THF」ともいう)
測定温度:40℃
注入量:200μL
圧力:49Kgf/cm2(4.8MPa)
流量:2.05mL/分
検出器:日立 L-3300型RI(株式会社日立製作所製)(GPC conditions)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420, Gelpack GL-R430 and Gelpack GL-R440 (manufactured by Hitachi Chemical Co., Ltd., column specifications: 10.7 mmφ × 300 mm)
Eluent: Tetrahydrofuran (hereinafter also referred to as "THF")
Measurement temperature: 40°C
Injection volume: 200 μL
Pressure: 49 kgf/cm 2 (4.8 MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)
(酸価)
バインダーポリマー約1gに混合溶剤(質量比:トルエン/メタノール=70/30)を加えて溶解した溶液に、指示薬としてフェノールフタレイン溶液を適量添加し、0.1Nの水酸化カリウム水溶液で滴定を行うことで、バインダーポリマーの酸価を測定した。(acid number)
A suitable amount of a phenolphthalein solution is added as an indicator to a solution prepared by adding a mixed solvent (mass ratio: toluene/methanol = 70/30) to about 1 g of the binder polymer, and titration is performed with a 0.1N potassium hydroxide aqueous solution. Thus, the acid value of the binder polymer was measured.
[感光性樹脂組成物]
表2に示す配合量(質量部)の各成分と、溶剤(メタノール、トルエン、アセトン)とを混合することにより、実施例及び比較例の感光性樹脂組成物をそれぞれ調製した。表2に示すバインダーポリマーの配合量は、不揮発分の質量(固形分量)である。[Photosensitive resin composition]
The photosensitive resin compositions of Examples and Comparative Examples were prepared by mixing each component in the amounts (parts by mass) shown in Table 2 and solvents (methanol, toluene, acetone). The blending amount of the binder polymer shown in Table 2 is the mass of non-volatile matter (solid content).
表2に示す各成分の詳細は、以下のとおりである。
((B)光重合性化合物)
FA-321M:2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパン(日立化成株式会社)
M2200:エトキシ化ビスフェノールAジメタクリレート(EO平均20mol変性)(Miwon社製)
BPE-200:エトキシ化ビスフェノールAジメタクリレート(EO平均4mol変性)(新中村化学工業株式会社)
FA-MECH:γ-クロロ-β-ヒドロキシプロピル-β’-メタクリロイルオキシエチル-o-フタレート(日立化成株式会社)
((C)光重合開始剤)
9-PA:9-フェニルアクリジン(常州強力電子新材料株式会社)
N-PG:N-フェニルグリシン(常州強力電子新材料株式会社)
(光発色剤)
LCV:ロイコクリスタルバイオレット(山田化学工業株式会社)
TPS:トリブロモフェニルスルホン(常州強力電子新材料株式会社)
(密着付与剤)
SF-808H:カルボキシベンゾトリアゾール、5-アミノ-1H-テトラゾール及びメトキシプロパノールの混合物(サンワ化成株式会社)
(染料)
MKG:マラカイトグリーン(大阪有機化学工業株式会社)Details of each component shown in Table 2 are as follows.
((B) photopolymerizable compound)
FA-321M: 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (Hitachi Chemical Co., Ltd.)
M2200: Ethoxylated bisphenol A dimethacrylate (modified with EO average of 20 mol) (manufactured by Miwon)
BPE-200: Ethoxylated bisphenol A dimethacrylate (modified with
FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (Hitachi Chemical Co., Ltd.)
((C) photoinitiator)
9-PA: 9-phenylacridine (Changzhou Power Electronics New Materials Co., Ltd.)
N-PG: N-phenylglycine (Changzhou Power Electronics New Materials Co., Ltd.)
(Photochromic agent)
LCV: Leuco Crystal Violet (Yamada Chemical Industry Co., Ltd.)
TPS: Tribromophenyl sulfone (Changzhou Power Electronics New Materials Co., Ltd.)
(Adherence imparting agent)
SF-808H: a mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol (Sanwa Kasei Co., Ltd.)
(dye)
MKG: Malachite Green (Osaka Organic Chemical Industry Co., Ltd.)
[感光性エレメント]
感光性樹脂組成物の溶液を、厚み16μmのポリエチレンテレフタレート(PET)フィルム(帝人フィルムソリューション株式会社、商品名「G2J」)(支持体)上に塗布し、75℃及び125℃の熱風対流式乾燥器で順次乾燥して、乾燥後の厚みが25μmの感光層を形成した。この感光層上にポリプロピレンフィルム(タマポリ株式会社、製品名「NF-13」)(保護層)を貼り合わせ、支持体と、感光層と、保護層とがこの順に積層された感光性エレメントをそれぞれ得た。[Photosensitive element]
The solution of the photosensitive resin composition is applied onto a polyethylene terephthalate (PET) film (Teijin Film Solution Co., Ltd., trade name "G2J") (support) with a thickness of 16 µm, and dried by hot air convection at 75°C and 125°C. They were dried in order in a vessel to form a photosensitive layer having a thickness of 25 μm after drying. A polypropylene film (manufactured by Tamapoly Co., Ltd., product name "NF-13") (protective layer) is laminated on the photosensitive layer, and a photosensitive element in which a support, a photosensitive layer, and a protective layer are laminated in this order is prepared. Obtained.
(積層体)
銅箔(厚み:35μm)をガラス繊維強化エポキシ樹脂層の両面に積層した銅張積層板(日立化成株式会社製、商品名「MCL-E-67」)を水洗、酸洗及び水洗後、空気流で乾燥した。次いで、銅張積層板を80℃に加温し、感光性エレメントを銅張積層板の銅表面に積層した。積層は、110℃のヒートロールを用いて、保護層を除去しながら、基板の0.4MPaの圧着圧力、1.0m/分のロール速度で行った。こうして、銅張積層板と感光層と支持体とがこの順に積層された積層体を得た。(Laminate)
A copper clad laminate (manufactured by Hitachi Chemical Co., Ltd., product name "MCL-E-67") in which copper foil (thickness: 35 μm) is laminated on both sides of a glass fiber reinforced epoxy resin layer is washed with water, acid washed, and washed with water. Dried in stream. The copper clad laminate was then heated to 80° C. to laminate the photosensitive element on the copper surface of the copper clad laminate. The lamination was carried out using a heat roll at 110° C. while removing the protective layer at a pressing pressure of 0.4 MPa on the substrate and a roll speed of 1.0 m/min. Thus, a laminate was obtained in which the copper-clad laminate, the photosensitive layer, and the support were laminated in this order.
(光感度)
積層体の支持体上に、ネガマスクとして濃度領域0.00~2.00、濃度ステップ0.05、タブレットの大きさ20mm×187mm、各ステップの大きさが3mm×12mmである日立41段ステップタブレット(日立化成株式会社製)を載置した。次いで、半導体レーザを光源とした波長405nmのDLP露光機(日立ビアメカニクス株式会社製、商品名「DE-1UH」)を用いて、所定のエネルギー量で感光層を露光した。(light sensitivity)
On the support of the laminate, a Hitachi 41-step tablet as a negative mask having a density range of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm x 187 mm, and each step size of 3 mm x 12 mm. (manufactured by Hitachi Chemical Co., Ltd.) was placed. Then, the photosensitive layer was exposed with a predetermined amount of energy using a DLP exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., product name "DE-1UH") with a wavelength of 405 nm using a semiconductor laser as a light source.
露光後、支持体を剥離し、30℃の1質量%炭酸ナトリウム水溶液を最短現像時間(未露光部分が除去される最短時間)の2倍の時間でスプレーし、未露光部分を除去した(現像処理)。現像処理後、基板上に形成された光硬化膜のステップタブレットの段数が15.0段となるエネルギー量(mJ/cm2)を求め、感光性樹脂組成物の光感度を評価した。この数値が小さいほど、光感度が高いことを示す。After exposure, the support was peeled off, and a 1% by weight sodium carbonate aqueous solution at 30° C. was sprayed for twice the shortest development time (shortest time for removing the unexposed portion) to remove the unexposed portion (development process). After the development treatment, the amount of energy (mJ/cm 2 ) at which the step tablet of the photocured film formed on the substrate becomes 15.0 steps was determined, and the photosensitivity of the photosensitive resin composition was evaluated. A smaller value indicates a higher photosensitivity.
(解像度)
積層体の支持体上に、解像度評価用ネガとしてガラスクロムタイプのフォトツール(解像度ネガ:ライン幅/スペース幅がx/x(x:1~30、単位:μm)の配線パターンを有するもの)を使用し、日立41段ステップタブレットの現像後の残存ステップ段数が17.0となるエネルギー量で露光を行った。露光後、光感度の評価と同様に、感光層の現像処理を行った。(resolution)
On the support of the laminate, a glass chrome type photo tool as a negative for resolution evaluation (resolution negative: having a wiring pattern with a line width/space width of x/x (x: 1 to 30, unit: μm)) was used, and the amount of energy was such that the number of steps remaining after development of the Hitachi 41-step tablet was 17.0. After exposure, the photosensitive layer was developed in the same manner as in the photosensitivity evaluation.
現像処理後、スペース部分(未露光部分)がきれいに除去され、かつライン部分(露光部分)が蛇行又は欠けを生じることなく形成されたレジストパターンのうち、最も小さいスペース幅の値により、解像度を評価した。この数値が小さいほど、解像度及び密着性が良好であることを意味する。 Evaluate the resolution from the smallest space width value of the resist pattern formed after the development processing, in which the space portion (unexposed portion) is cleanly removed and the line portion (exposed portion) is formed without meandering or chipping. did. A smaller numerical value means better resolution and adhesion.
(剥離特性)
40mm×50mmの硬化膜を形成する描画パターンを用いて、積層体の感光層に対して露光を行った。露光後、支持体を剥離し、光感度の評価と同様の現像処理を行うことにより、基板上に40mm×50mmの硬化膜が形成された試験片を作製した。(Peeling property)
The photosensitive layer of the laminate was exposed using a drawing pattern that forms a cured film of 40 mm×50 mm. After the exposure, the support was peeled off, and a test piece having a cured film of 40 mm×50 mm formed on the substrate was prepared by performing the same development treatment as in the photosensitivity evaluation.
試験片を室温で一昼夜放置した後、50℃の3.0質量%水酸化ナトリウム水溶液に試験片を浸漬し、硬化膜が基板から完全に剥離するまでの時間(秒)を計測した。また、剥離片のサイズを目視で観察した。剥離時間が短く、剥離片サイズが小さいほど剥離特性が良好であることを意味する。 After leaving the test piece at room temperature for a whole day and night, the test piece was immersed in a 3.0% by mass sodium hydroxide aqueous solution at 50° C., and the time (seconds) until the cured film was completely peeled off from the substrate was measured. Also, the size of the peeled pieces was visually observed. A shorter peeling time and a smaller peeled piece size indicate better peeling properties.
1…感光性エレメント、2…支持体、3…感光層、4…保護層。
DESCRIPTION OF
Claims (7)
前記バインダーポリマーが、前記スチレン又はスチレン誘導体に由来する構造単位を41~64質量%有し、
前記バインダーポリマーの酸価が、180~195mgKOH/gであり、
前記バインダーポリマーの重量平均分子量が、5000~36000であり、
前記光重合性化合物が、フタル酸骨格を有する(メタ)アクリレートを含む、感光性樹脂組成物。 Containing a binder polymer having a structural unit derived from styrene or a styrene derivative, a photopolymerizable compound, and a photopolymerization initiator,
The binder polymer has 41 to 64% by mass of structural units derived from the styrene or styrene derivative,
The acid value of the binder polymer is 180 to 195 mgKOH/g,
The binder polymer has a weight average molecular weight of 5000 to 36000,
A photosensitive resin composition, wherein the photopolymerizable compound contains a (meth)acrylate having a phthalic acid skeleton.
前記感光層が、請求項1~3のいずれか一項に記載の感光性樹脂組成物を含む、感光性エレメント。 comprising a support and a photosensitive layer formed on the support;
A photosensitive element, wherein the photosensitive layer comprises the photosensitive resin composition according to any one of claims 1 to 3 .
前記感光層の所定部分に活性光線を照射して、光硬化部を形成する工程と、
前記基板から、前記感光層の前記光硬化部以外の少なくとも一部を除去する工程と、
を備える、レジストパターンの形成方法。 forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 3 or the photosensitive element according to claim 4 ;
a step of irradiating a predetermined portion of the photosensitive layer with an actinic ray to form a photocured portion;
removing at least a portion of the photosensitive layer other than the photocured portion from the substrate;
A method of forming a resist pattern, comprising:
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