JP4985768B2 - 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 - Google Patents
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 Download PDFInfo
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- JP4985768B2 JP4985768B2 JP2009514138A JP2009514138A JP4985768B2 JP 4985768 B2 JP4985768 B2 JP 4985768B2 JP 2009514138 A JP2009514138 A JP 2009514138A JP 2009514138 A JP2009514138 A JP 2009514138A JP 4985768 B2 JP4985768 B2 JP 4985768B2
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- FRCAGVUKJQCWBD-UHFFFAOYSA-L iodine green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)[N+](C)(C)C)=C/1C=C(C)C(=[N+](C)C)C=C\1 FRCAGVUKJQCWBD-UHFFFAOYSA-L 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- GLVAUDGFNGKCSF-UHFFFAOYSA-N mercaptopurine Chemical compound S=C1NC=NC2=C1NC=N2 GLVAUDGFNGKCSF-UHFFFAOYSA-N 0.000 description 1
- 229960001428 mercaptopurine Drugs 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 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
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SEXOVMIIVBKGGM-UHFFFAOYSA-N naphthalene-1-thiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1 SEXOVMIIVBKGGM-UHFFFAOYSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000000206 photolithography Methods 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
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 238000003077 quantum chemistry computational method Methods 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-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
- 150000003852 triazoles Chemical class 0.000 description 1
- QEXITCCVENILJI-UHFFFAOYSA-M tributyl(phenyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)C1=CC=CC=C1 QEXITCCVENILJI-UHFFFAOYSA-M 0.000 description 1
- GLSQMJPVEVGXMZ-UHFFFAOYSA-N tributyl-(2,5-dihydroxyphenyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)C1=CC(O)=CC=C1O GLSQMJPVEVGXMZ-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- OFZAYFUSFITYES-UHFFFAOYSA-M trimethyl(2-phenylethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC1=CC=CC=C1 OFZAYFUSFITYES-UHFFFAOYSA-M 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials For Photolithography (AREA)
- Epoxy Resins (AREA)
- Polymerisation Methods In General (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
ΔG=Eox−Ered−hν (eV) (A−1)
[Eox:電子供与体の酸化電位(V vs.Ag/AgCl)、Ered:電子受容体の還元電位(V vs.Ag/AgCl)、hν:光による励起エネルギー(eV)。]
ΔG=−εHOMO+εLUMO−hν (eV) (A−2)
[εHOMO:電子供与体(Sens)のHOMO準位(eV)=−4.695(eV)、εLUMO:電子受容体(OXE−01)のLUMO準位(eV)=−2.090(eV)、hν:光による励起エネルギー(eV)=405nmでは3.062(eV)。]
YDF2001(東都化成(株)製、ビスフェノールF型エポキシ樹脂、一般式(5)において、Y2=グリシジル基、R12=水素原子である化合物)475質量部、アクリル酸72質量部、ハイドロキノン0.5質量部、カルビトールアセテート120質量部を仕込み、90℃で加熱撹拌して反応混合物を溶解した。次に、得られた溶液を60℃に冷却し、そこに塩化ベンジルトリメチルアンモニウム2質量部を加え、100℃に加熱して、固形分酸価が1mgKOH/gになるまで反応させた。更に、無水マレイン酸98質量部とカルビトールアセテート85質量部とを加え、80℃に加熱して、約6時間反応させた。その後、室温まで冷却し、固形分濃度が60質量%になるようにカルビトールアセテートで希釈して、(A)成分としてのカルボン酸変性ビスフェノールF型エポキシアクリレート(以下、「エポキシ樹脂A1」という)を得た。
YDCN704(東都化成(株)製、クレゾールノボラック型エポキシ樹脂、一般式(4)において、Y1=グリシジル基、R11=メチル基である化合物)220質量部、アクリル酸72質量部、ハイドロキノン1.0質量部、カルビトールアセテート180質量部を仕込み、90℃で加熱撹拌して反応混合物を溶解した。次に、得られた溶液を60℃に冷却し、そこに塩化ベンジルトリメチルアンモニウム1質量部を加え、100℃に加熱して、固形分酸価が1mgKOH/gになるまで反応させた。更に、テトラヒドロ無水フタル酸152質量部とカルビトールアセテート100質量部とを加え、80℃に加熱して、約6時間反応させた。その後、室温まで冷却し、固形分濃度が60質量%になるようにカルビトールアセテートで希釈して、(A)成分としてのカルボン酸変性クレゾールノボラック型エポキシアクリレート(以下、「エポキシ樹脂A2」という)を得た。
下記表2に示す配合組成(単位:質量部)に従って組成物を配合した後、3本ロールミルで混練し、固形分濃度が70質量%になるようにカルビトールアセテートを加えて、感光性樹脂組成物を得た。なお、下記表2中の各成分の配合量は、固形分の配合量を示す。
ビスフェノールF型エポキシ樹脂(商品名:YSLV−80XY−F、東都化成社製、)、
DPHA(商品名:カヤラッドDPHA、日本化薬社製、ジペンタエリスリトールヘキサアクリレート)、
OXE−01(商品名、チバスペシャルティーケミカルズ社製、上記式(8)で示される1,2−オクタンジオン−1−[4−(フェニルチオ)フェニル]−2−(O−ベンゾイルオキシム)、
IC907(商品名:イルガキュア907、チバスペシャルティーケミカルズ社製、下記式(17)で表される化合物)、
NF−EO(商品名、日本化学工業所社製、上記式(13)で表される1−フェニル−3−(4−tert−ブチル−スチリル)−5−(4−tert−ブチル−フェニル)−ピラゾリン、最大吸収波長:387.2nm)、
クマリン(C−314T)(商品名:C−314T、アクロス社製、下記式(18)で表される化合物、最大吸収波長:435nm)、
MBO(上記式(9)で示されるメルカプトベンゾオキサゾール)、
MBT(上記式(10)で示されるメルカプトベンゾチアゾール)、
MBI(上記式(11)で示されるメルカプトベンゾイミダゾール)、
NPG(和光純薬工業社製、N−フェニルグリシン)、
EAB(商品名、保土谷化学社製、ジエチルアミノベンゾフェノン、最大吸収波長:365nm)。
実施例1〜4及び比較例1〜6の感光性樹脂組成物をスクリーン印刷法により、120メッシュのテトロンスクリーンを用いて、乾燥後の厚さが約20μmとなるように、銅張り積層板に塗布し、熱風循環式乾燥機により80℃で30分間乾燥させた。これにより、銅張り積層板上に感光性樹脂組成物からなる感光性樹脂組成物層が積層された評価基板を得た。得られた評価基板を用い、以下に示した方法により各特性の評価を行った。その結果をまとめて表3に示す。
評価基板の感光性樹脂組成物層上にネガマスク(ストーファー41段ステッタブレットプ)を載せ、さらにその上に、波長405±30nmの光を分光するバンドパスフィルターである朝日分光株式会社製分光フィルタ(商品名:HG0405)を載せ、この状態で、5kWショートアークランプを光源とする平行光露光機(商品名:EXM−1201、オーク製作所社製)を用いて、露光量100mJ/cm2の紫外線を照射した。なお、バンドパスフィルターを透過した光の照度を、紫外線積算光量計(商品名:UIT−150−A、ウシオ電機株式会社製、照度計としても使用可能)及び受光器である「UVD−S405」(商品名、感度波長域:320nm〜470nm、絶対校正波長:405nm)を用いて測定し、照度×露光時間を露光量とした。その後、1質量%の炭酸ナトリウム水溶液(30℃)で60秒間、1.8kgf/cm2の圧力でスプレー現像し、未露光部を溶解除去した。未露光部分を除去した後、銅張り積層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を測定することにより、感光性樹脂組成物の光感度を評価した。光感度は、ステップタブレットの段数で示され、このステップタブレットの段数が高いほど光感度が高いことを意味する。
評価基板の感光性樹脂組成物層上に、ビアマスク開口寸法が100μmのマスクを置き、さらにその上に、波長405±30nmの光を分光するバンドパスフィルターである朝日分光株式会社製分光フィルタ(商品名:HG0405)を載せ、この状態で、5kWショートアークランプを光源とする平行光露光機(商品名:EXM−1201、オーク製作所社製)を用いて、露光量100mJ/cm2の紫外線を照射した。なお、バンドパスフィルターを透過した光の照度を、紫外線積算光量計(商品名:UIT−150−A、ウシオ電機株式会社製、照度計としても使用可能)及び受光器である「UVD−S405」(商品名、感度波長域:320nm〜470nm、絶対校正波長:405nm)を用いて測定し、照度×露光時間を露光量とした。その後、1%の炭酸ナトリウム水溶液(30℃)で60秒間、0.18MPaの圧力でスプレー現像を行った。その後、形成されたビア開口部を目視観察し、以下の基準に従って現像性の評価を行った。
A:開口寸法が80μm以上のビア開口部が得られた場合、
B:開口寸法が60μm以上80μm未満のビア開口部が得られた場合、
C:ビア開口部の開口寸法が60μm未満であった場合。
評価基板の感光性樹脂組成物層上に、波長405±30nmの光を分光するバンドパスフィルターである朝日分光株式会社製分光フィルタ(商品名:HG0405)を載せ、この状態で、5kWショートアークランプを光源とする平行光露光機(商品名:EXM−1201、オーク製作所社製)を用いて、露光量100mJ/cm2の紫外線を照射した。なお、バンドパスフィルターを透過した光の照度を、紫外線積算光量計(商品名:UIT−150−A、ウシオ電機株式会社製、照度計としても使用可能)及び受光器である「UVD−S405」(商品名、感度波長域:320nm〜470nm、絶対校正波長:405nm)を用いて測定し、照度×露光時間を露光量とした。その後、1質量%の炭酸ナトリウム水溶液(30℃)で60秒間、1.8kgf/cm2の圧力でスプレー現像し、未露光部を溶解除去した。次に、150℃で1時間加熱し、感光性樹脂組成物層の硬化膜を有する試験板を作製した。得られた試験板を用い、以下に示した方法により各特性の評価を行った。その結果をまとめて表3に示す。
試験板に対し、JIS K5400に準じた方法により、剥離試験を行った。すなわち、試験板の硬化膜に1mmの碁盤目を100個作製して、碁盤目にセロハンテープを貼り付けた後に引き剥がした。引き剥がし後の碁盤目の剥離状態を観察し、以下の基準に従って密着性の評価を行った。
A:碁盤目の90/100以上が剥離なし、
B:碁盤目の50/100以上90/100未満が剥離なし、
C:碁盤目の50/100未満が剥離なし。
試験板をイソプロピルアルコールに室温で30分間浸漬した後、硬化膜の外観に異常がないかを目視にて確認した。その後、セロハンテープを硬化膜に貼り付けて引き上げる剥離試験を行い、硬化膜が銅張り積層板から剥離するかどうかを確認した。それらの結果から、以下の基準に従って耐溶剤性の評価を行った。
A:硬化膜の外観に異常がなく、且つ、剥離試験において剥離のないもの、
B:硬化膜の外観に異常があるか、又は、剥離試験において剥離するもの。
試験板の硬化膜表面にロジン系フラックスを塗布した後、260℃のはんだ槽に10秒間浸漬した。これを1サイクルとして、6サイクル繰り返した後、硬化膜の外観を目視観察し、以下の基準に従ってはんだ耐熱性の評価を行った。
A:硬化膜の外観に異常(剥離、フクレ)がなく、はんだのもぐりがないもの、
B:硬化膜の外観に異常(剥離、フクレ)があるか、又は、はんだのもぐりがあるもの。
表2に示した組成において、硬化剤であるビスフェノールF型エポキシ樹脂、並びに、光重合性化合物であるエポキシ樹脂A1及びA2を除き、カルビトールアセテートを加えて粘度を50Pa・sに調整し、経日安定性評価用溶液を得た。得られた溶液を室温(25℃)にて放置し、溶液が流動しなくなるか又はゲル化が起こるまでの時間を測定した。その結果を表3に示す。
Claims (8)
- 前記オキシムエステル結合を有する化合物が、下記一般式(1)又は(2)で表される化合物の少なくとも1種を含むものである、請求項1に記載の感光性樹脂組成物。
- 前記(A)酸変性ビニル基含有エポキシ樹脂が、下記一般式(4)で表されるノボラック型エポキシ樹脂、下記一般式(5)で表されるビスフェノール型エポキシ樹脂、及び、下記一般式(6)で表されるサリチルアルデヒド型エポキシ樹脂からなる群より選択される少なくとも1種のエポキシ樹脂(a)と、ビニル基含有モノカルボン酸(b)と、を反応させて得られる樹脂である、請求項1〜3のいずれか一項に記載の感光性樹脂組成物。
- 支持体と、該支持体上に形成された請求項1〜4のいずれか1項に記載の感光性樹脂組成物からなる感光性樹脂組成物層と、を備える感光性エレメント。
- 請求項1〜4のいずれか一項に記載の感光性樹脂組成物からなる感光性樹脂組成物層を基板上に積層する積層工程と、
前記感光性樹脂組成物層に活性光線を画像状に照射して露光部を光硬化せしめる露光工程と、
前記感光性樹脂組成物層の未露光部を現像により除去する現像工程と、
を含むレジストパターンの形成方法。 - 前記露光工程は、波長405nmのレーザ光により前記感光性樹脂組成物層を直接描画露光して露光部を光硬化せしめる工程である、請求項6に記載のレジストパターンの形成方法。
- 請求項6又は7に記載のレジストパターンの形成方法によりレジストパターンの形成された回路形成用基板を、エッチング又はめっきする、プリント配線板の製造方法。
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