JP3971046B2 - Positive photosensitive resin composition and use thereof - Google Patents
Positive photosensitive resin composition and use thereof Download PDFInfo
- Publication number
- JP3971046B2 JP3971046B2 JP37254498A JP37254498A JP3971046B2 JP 3971046 B2 JP3971046 B2 JP 3971046B2 JP 37254498 A JP37254498 A JP 37254498A JP 37254498 A JP37254498 A JP 37254498A JP 3971046 B2 JP3971046 B2 JP 3971046B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- photosensitive resin
- positive photosensitive
- resin
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011342 resin composition Substances 0.000 title claims description 31
- 239000011347 resin Substances 0.000 claims description 60
- 229920005989 resin Polymers 0.000 claims description 60
- -1 ruthenocene compound Chemical class 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000003504 photosensitizing agent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 47
- 150000001875 compounds Chemical class 0.000 description 27
- 239000002253 acid Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 238000004070 electrodeposition Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 239000000975 dye Substances 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
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- 238000007639 printing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 230000002165 photosensitisation Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- KWCQJEWFGWPEPS-UHFFFAOYSA-N 10,10,16,16-tetramethyl-5-(1,3-thiazol-2-yl)-3-oxa-13-azatetracyclo[7.7.1.02,7.013,17]heptadeca-1,5,7,9(17)-tetraen-4-one Chemical compound CC1(C)CCN2CCC(C)(C)C(C=3OC4=O)=C2C1=CC=3C=C4C1=NC=CS1 KWCQJEWFGWPEPS-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- 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 2
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MLRCQIICAYVJHD-UHFFFAOYSA-N 1-but-1-enoxybut-1-ene Chemical group CCC=COC=CCC MLRCQIICAYVJHD-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- ZKJNETINGMOHJG-UHFFFAOYSA-N 1-prop-1-enoxyprop-1-ene Chemical group CC=COC=CC ZKJNETINGMOHJG-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- KGWYICAEPBCRBL-UHFFFAOYSA-N 1h-indene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C=CC2=C1 KGWYICAEPBCRBL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
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Landscapes
- Materials For Photolithography (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、特異な構造を有するルテノセン化合物又はその錯体を光酸発生剤として現像処理による溶解安定性や高い感度を示す、特に電子デバイスの回路形成、印刷用材料等に有用なパターンを形成するポジ型感光性樹脂組成物及びその用途に係わる。
【０００２】
【従来の技術及びその課題】
現在、電子デバイス等の回路パターンの形成にはポジ型フオトレジストが広く使用されている。これらの用途に使用されるポジ型レジスト組成物としては、多くの場合、アルカリ可溶性ノボラツク樹脂と感光剤としてキノンジアジド化合物を組み合わせたものが使用されている。
【０００３】
この組成物は紫外線の照射によりキノンジアジド基が光分解しケテンを経由してインデンカルボン酸を形成する反応を利用している。
【０００４】
しかし、このキノンジアジド化合物を使用したレジストは、可視光反応性が弱く、非常に細密なパターンを形成する必要がある場合、解像度が不足するなどの問題がある。
【０００５】
近年、これに代わるポジ型感光性組成物として、カルボキシル基を含む重合体、多ビニルエーテル化合物、及び活性エネルギー線照射により分解して酸を発生する化合物からなる可視光にも感光する組成物が実用化されている。この組成物は、それから形成された塗膜を加熱すると、カルボキシル基とビニルエーテル基との付加反応により架橋して、溶剤やアルカリ水溶液に対して不溶性となり、さらに、活性エネルギー線を照射し且つ照射後加熱すると、発生した酸の触媒作用で架橋構造が切断されて照射部分が溶剤やアルカリ水溶液に対して再び可溶性になるというメカニズムで機能する感光性組成物である。
【０００６】
この組成物は、キノンジアジドを感光剤とするレジストのように吸光係数の高い官能基を多量に使用する必要がないので、活性エネルギー線に対する透明性を高くすることができ、また、照射部に発生する酸は加熱時に触媒として作用し、架橋構造を連鎖的に切断するために、ポジ型に作用する感光性組成物としての感度を高くすることができる等の利点を有する。
【０００７】
しかし、この感光性組成物を基盤に塗布して加熱架橋させる際、生産性の面から、加熱時間の短縮が求められている。そのため１００℃以上の高温加熱による時間短縮を試みると、該感光性組成物中に存在する光酸発生化合物が可視光線を照射する前に酸を発生してしまい現像するときに形成した膜全体が溶解するという問題がある。このため当該技術分野では該感光性組成物の溶解安定性の改良が強く望まれている。
【０００８】
本発明者らは、前述の感光性組成物が有する問題を解決する方法について鋭意検討を重ねた結果、今回可視光線の照射により分解して酸を発生する化合物として、特定のルテノセン化合物又はその錯体を用い、必要に応じて増感色素と組合せて用いることにより解決できることを見い出し、本発明を完成するに至った。 即ち、本発明は、ポジ型感光性樹脂及び下記一般式（１）で表されるルテノセン化合物又はその錯体（以下、単に「ルテノセン（錯）化合物」と呼ぶことがある。）を光酸発生剤として含有することを特徴とするポジ型感光性樹脂組成物。
【０００９】
一般式（１）
【００１０】
【化３】
（ただし、上記式（１）において、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5はそれぞれ独立に、水素原子、直鎖状又は分枝を有するアルキル基又は一般式（２）に示される置換基を表し、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5のうち少なくとも一つは下記一般式（２）に示される置換基または共役二重結合の末端炭素原子にテトラヒドロキノリル基を有する。Ｒ6は置換基を有しても良いシクロペンタジエニル、またはπ−アレーンを表し、ｎは１又は２の整数を表し、Ｒ7、Ｒ8、Ｒ9、Ｒ10はそれぞれ独立に、水素原子、またはメチル基を表し、Ｒ11は、水素原子、メチル基、または水酸基を表す。）
一般式（２）
【００１２】
【化４】
【発明の実施の形態】
本発明のポジ型感光性樹脂組成物は、前記ルテノセン（錯）化合物を含有するものである。
【００１４】
本発明で使用する一般式（Ｉ）で表されるルテノセン（錯）化合物は特に可視光線の波長に極めて大きな吸収を有しており、かつ、それらの光に非常に高感度でありポジ型感光性樹脂組成物に適用可能な有用な材料である。
【００１５】
なお、本発明で言う「ポジ型感光性樹脂組成物」とは、例えば塗料、インキ、接着剤、刷版材、レジスト材及びこれらのものから形成される未感光被膜等を意味する。
【００１６】
本発明で使用するルテノセン（錯）化合物は上記一般式（１）及びその錯体の光酸発生剤である。該ルテノセン化合物は、ルテノセニル基に共役二重結合を介して２−ユロリジル基またはテトラヒドロキノリル基が結合した一群の化合物である。一般式（１）において、Ｒ1〜Ｒ5の少なくとも一つは一般式（２）に示す構造、または共役二重結合の末端炭素原子にテトラヒドロキノリル基が結合した構造が望ましく、その余はそれぞれ独立に水素原子又は、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、１−メチルプロピル基、ペンチル基、ヘキシル基などの直鎖状若しくは分枝を有するアルキル基を表すものとする。なお、一般式（２）において、ｎは１又は２の整数を表し、Ｒ7〜Ｒ10はそれぞれ独立に水素原子又はメチル基を、また、Ｒ11は水素原子、メチル基又は水酸基をそれぞれ表す。
【００１７】
また、一般式（１）において、Ｒ6は置換基を有しても良いシクロペンタジエニル−またはπ−アレーンを表し、シクロペンタジエニル−は、直鎖状又は分枝を有するアルキル基、又は一般式（２）に示す構造を有する置換基により一置換または多置換されていても良い。直鎖状又は分枝を有するアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、１−メチルプロピル基、ペンチル基、ヘキシル基などのアルキル基が挙げられる。また、π−アレーンは特に炭素原子数６個ないし２４個を有する芳香族基を表すか、または、炭素原子数３個ないし３０個及びヘテロ原子１個または２個を有するヘテロ芳香族基を表し、これらの基は、同一または異なる一価の基、例えば、ハロゲン原子、または、炭素原子数１ないし８のアルキル基、炭素原子数１ないし８のアルコキシ基により一置換または多置換されていても良い。前記π−アレーンは単環状、縮合環状であってよい。π−アレーンとしては、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン、クメン、メトキシベンゼン、エトキシベンゼン、ジメトキシベンゼン、ｐ−クロロトルエン、ｍ−クロロトルエン、クロロベンゼン、ブロモベンゼン、ジクロロベンゼン、ジイソプロピルベンゼン、トリメチルベンゼン、ナフタレン、メチルナフタレン、スチルベン、インデン、フルオレン、フェナントレン、アントラセン、ピレン、ペリレンなどが挙げられる。
【００１８】
本発明で使用するルテノセン化合物は、例えばルテノセン誘導体とユロリジルアルデヒドとのＷｉｔｔｉｇ反応により製造することができる。このようなルテノセン化合物は、優れた電子供与性を有している。電子供与性は、当該化合物の酸化電位を、例えば、銀−塩化銀電極を参照電極として測定することができる。該ルテノセン化合物の酸化電位は、通常０．５Ｖ以下である。
【００１９】
また、ルテノセン化合物の錯体は、下記一般式（３）
【００２０】
【化５】
（ただし、式（３）においてＸ−はＢＦ4−、ＰＦ6−、ＡｓＦ6−又はＳｂＦ6−を表す。）で表される。
【００２２】
本発明で使用する光酸発生剤の使用量は、ルテノセン（錯）化合物の種類や量、相互作用すべき樹脂成分の種類により異なるが、通常、樹脂成分１００重量部当たり、ルテノセン（錯）化合物の使用量が０．１〜１０重量部、好ましくは０．３〜５重量部の範囲内が適当である。ルテノセン（錯）化合物の使用量が０．１重量部より少なすぎると、形成される被膜の感光性が低下する傾向があり、１０重量部より多くなると、溶解性の点から、組成物を均一な状態に保つことが困難になる傾向が見られる。
【００２３】
本発明で使用するルテノセン（錯）化合物の光酸発生剤は、従来から公知のその他の光酸発生剤と併用して使用することができる。その他の光酸発生剤としては、例えばスルホニウム塩、アンモニウム塩、ホスホニウム塩、ヨードニウム塩、セレニウム塩等のオニウム塩類、鉄−アレン錯体類、シラノ−ル−金属キレート錯体類、トリアジン化合物類、ジアジドナフトキノン化合物類、スルホン酸エステル類、スルホン酸イミドエステル類、ハロゲン系化合物類等を使用することができる。また、上記した以外に特開平7-146552号公報、特願平9-289218号に記載の光酸発生剤も使用することができる。この光酸発生剤成分は、上記した樹脂との混合物であっても樹脂に結合したものであっても構わない。その他の光酸発生剤の配合割合は、樹脂１００重量部に対して約０．１〜４０重量部、特に約０．２〜２０重量部の範囲で含有することが好ましい。
【００２４】
本発明のポジ型感光性樹脂組成物は、露光により化合物が分解し現像液に溶解性を示すような、従来から公知のポジ型感光性樹脂組成物（例えば、塗料、インキ、接着剤、刷板材、プリント配線板用レジスト材で使用されているもの）にルテニウム（錯）化合物の光酸発生剤を必須成分として含有するものである。
【００２５】
上記した従来から公知のポジ型感光性樹脂組成物について、代表的なものについて以下に述べる。
【００２６】
該樹脂組成物は、光酸発生剤により発生した酸成分により、樹脂が切断されて低分子量となったり、樹脂に酸基が付与されたり、溶解性物質（例えば、（ポリ）Ｐ−ヒドロキシスチレン）に変化し、これにより有機溶剤や水性現像液に分散性もしくは溶解性を示すものとなったりするもの等が挙げられる。
【００２７】
これらのものとしては、例えば、▲１▼照射光によって酸基を発生する光酸発生剤を触媒として基体樹脂（ポリマー）に脱離反応を連鎖的に生じさせて照射部と未照射部との溶解性の変化を利用した化学増幅系感光材料（特開平4-226461号公報、米国特許第4,491,628号、特開昭59-45439号、特開昭63-250642号公報、Polymers in Electronics”Davidson T.編集.ACS Symposium Series 242,American Chemical Society,Washington D.C,,1984の11頁.Hayashi,T.Ueno,M.Toriumi,etc,ACSPolym.materialsSci.Eng.,61,417(1989)、H.Ito,C.G.Wilson,ACS Symp.Ser.,242,11(1984)等参照）；▲２▼加熱により溶剤やアルカリ水溶液に対して不溶性の架橋被膜を形成し、更に光線照射により酸基を発生する光酸発生剤により架橋構造が切断されて照射部が溶剤やアルカリ水溶液に対して可溶性となるメカニズムを利用したポジ型感光性組成物（特開平6-295064号公報、特開平6-308733号公報、特開平6-313134号公報、特開平6-313135号公報、特開平6-313136号公報、特開平7-146552号公報等参照）等が代表的なものとして挙げられる。
【００２８】
上記▲１▼のものは、樹脂中で現像液に対する溶解性を支配している官能基（水酸基、カルボキシル基等）をブロック（酸不安定基）して不溶性とし、光酸発生剤によりブロックを解離し、ポリマーの溶解性を復元するものである。該水酸基（−ＯＨ基）をブロックした酸不安定基（−ＯＲのＲ基）としては、例えば、ｔ−ブトキシカルボニル基（ｔ−ＢＯＣ基）、ｔ−ブトキシ基、ｔ−ブトキシカルボニルメチル基、テトラヒドロピラニル基、トリメチルシリル基、ｉｓｏ−プロポキシカルボニル基等が包含される。水酸基を有する樹脂としては、上記した効果を発揮するものであれば特に制限されないが、通常、フェノール性水酸基である。該酸不安定基としては、特に、ｔ−ＢＯＣ基、ｔ−ブトキシ基が好ましくこのものとしては、例えば、ポリ（ｔ−ブトキシカルボニルオキシスチレン）、ポリ（ｔ−ブトキシカルボニルオキシ−α−スチレン）、ポリ（ｔ−ブトキシスチレン）及びこれらのモノマーとその他の重合性モノマー（例えば、メチル（メタ）アクリル酸のＣ１〜２４個のアルキル又はシクロアルキルエステル類、マレイミド、スルフォン等）との共重合体等が挙げられる。該ｔ−ＢＯＣ基を含有するポリ（ｔ−ブトキシカルボニルオキシスチレン）の組成物について説明すると、例えば、光酸発生剤によって発生した酸によりｔ−ＢＯＣ基が分解してイソブテンと炭酸ガスが蒸発してポリスチレンとなり、ｔ−ＢＯＣ基が水酸基に変化することにより樹脂の極性が変化（高くなる）することにより現像液（アルカリ水溶液）に対する溶解性が向上する性質を利用したものである。また、カルボキシル基（−ＣＯＯＨ基）をブロックした酸不安定基（−ＣＯＯＲ´のＲ´基）としては、ｔ−ブチル基を有するカルボン酸エステル誘導体等が挙げられる。
【００２９】
また、このものの成分としては酸不安定基を持つ樹脂及び光酸発生剤の２成分系として、また、酸不安定基を持つ樹脂、光酸発生剤、その他の樹脂の３成分系として使用することができる。該その他の樹脂は、このものを使用することにより、例えば、組成物の塗装作業性を向上させたり現像液に対する溶解性を変化させたりすることができる。
【００３０】
上記▲２▼のものは、カルボキシル基及び／又はヒドロキシフェニル基を含有する樹脂（ａ）、エーテル結合含有オレフィン性不飽和化合物（ｂ）、光線照射により酸基を発生する光酸発生剤を含有してなる液状もしくは固体状樹脂組成物である。
【００３１】
樹脂（ａ）において、カルボキシル基及びヒドロキシフェニル基の両方の基を有する場合は、これらの基が同一分子中に有する樹脂であっても、これらの基が異なって含有する樹脂の混合樹脂であってもどちらでも構わない。
【００３２】
カルボキシル基含有樹脂（ａー１）としては、例えば、アクリル系樹脂、ポリエステル系樹脂等が挙げられる。
【００３３】
上記した樹脂（ａー１）は一般に約５００〜約１０００００、特に約１５００〜３００００の数平均分子量を有していることが好ましく、また、カルボキシル基は樹脂１Ｋｇ当たり約０．５〜１０モル、特に約０．７〜５モルのものが好ましい。
【００３４】
ヒドロキシフェニル基含有樹脂（ａ−２）としては、例えば、１官能又は多官能フェノール化合物、アルキルフェノール化合物、又はそれらの混合物とホルムアルデヒド、アセトン等のカルボニル化合物との縮合物；Ｐ−ヒドロキシスチレン等のヒドロキシフェニル基含有不飽和単量体と必要に応じて上記したその他の重合性不飽和単量体との共重合体等が挙げられる。
【００３５】
上記した樹脂（ａー２）は一般に約５００〜約１０００００、特に約１５００〜３００００の数平均分子量を有していることが好ましく、また、ヒドロキシフェニル基は樹脂１Ｋｇ当たり約１．０モル以上、特に約２〜８モルが好ましい。
【００３６】
また、樹脂（ａー１）と樹脂（ａ−２）とを混合して使用する場合には、その混合割合は９０／１０〜１０／９０重量比で配合することが好ましい。
【００３７】
カルボキシル基及びヒドロキシフェニル基を有する樹脂（ａー３）としては、例えばカルボキシル基含有重合性不飽和単量体（（メタ）アクリル酸等）とヒドロキシフェニル基含有重合性不飽和単量体（ヒドロキシスチレン等）及び必要に応じてその他の重合性不飽和単量体（メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２ーエチルヘキシル（メタ）アクリレート等のアクリル酸の炭素数１〜１２のアルキルエステル、スチレン等の芳香族化合物、（メタ）アクリロニトリル等の含窒素不飽和単量体等）との共重合体；ヒドロキシ安息香酸類、没食子酸、レゾルシン酸等と、又はそれらとフェノール、ナフトール類、レゾルシン、カテコール等との混合物をホルムアルデヒドと反応して得られるフェノール樹脂等が挙げられる。
【００３８】
上記した樹脂（ａー３）は一般に約５００〜約１０００００、特に約１５００〜３００００の数平均分子量を有していることが好ましく、また、カルボキシル基は樹脂１Ｋｇ当たり約０．５〜１０モル、特に約０．７〜５モルのものが好ましい。ヒドロキシフェニル基は樹脂１Ｋｇ当たり約１．０モル以上、特に約２〜８モルが好ましい。
【００３９】
エーテル結合含有オレフィン性不飽和化合物（ｂ）としては、例えば、分子末端にビニルエーテル基、１ープロペニルエーテル基、１ーブテニルエーテル基等の不飽和エーテル基を約１〜４個含有するものが挙げられる。該化合物（ｂ）は、１分子中に、式 −Ｒ″−Ｏ−Ａ［ここで、Ａはビニル基、１ープロペニル基又は１ーブテニルのオレフィン性不飽和基を示し、Ｒ″はエチレン、プロピレン、ブチレンなどの炭素数１〜６の直鎖状もしくは分岐鎖状のアルキレン基を表わす］で示される不飽和エーテル基を少なくとも１個、好ましくは２〜４個含有する低分子量又は高分子量の化合物であり、例えば、ビスフエノールＡ、ビスフエノールＦ、ビスフエノールＳ、フエノール樹脂などのポリフエノール化合物や、エチレングリコール、プロピレングリコール、トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトールなどのポリオール類とクロロエチルビニルエーテルなどのハロゲン化アルキル不飽和エーテルとの縮合物；トリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネートなどのポリイソシアネート化合物とヒドロキシエチルビニルエーテルのようなヒドロキシアルキル不飽和エーテルとの反応物等が挙げられる。特に、上記ポリフエノール化合物とハロゲン化アルキル不飽和エーテルとの縮合物及び芳香環をもつポリイソシアネート化合物とヒドロキシアルキル不飽和エーテルとの反応物が、エツチング耐性、形成されるパターンの精度等の観点から好適である。該化合物（ｂ）は、樹脂（ａ）１００重量部に対して、通常約５〜１５０重量部、好ましくは約１０〜１００重量部の範囲である。
【００４０】
（ａ）及び（ｂ）成分を含有する組成物は、それから形成された被膜は加熱により、カルボキシル基及び／又はヒドロキシフェニル基と不飽和エーテル基との付加反応により架橋して、溶剤やアルカリ水溶液に対して不溶性となり、次いで活性エネルギー線照射し、更に照射後加熱すると、発生した酸の触媒作用で架橋構造が切断されて照射部が溶剤やアルカリ水溶液に対して再び可溶性となるポジ型感光性樹脂組成物である。
【００４１】
該組成物においては、形成される膜を露光する際に発生する酸によって酸加水分解反応が露光部分で生じるが、この酸加水分解反応をスムーズに進行させるには水分が存在することが望ましい。このため本発明の組成物中に、ポリエチレングリコール、ポリプロピレングリコール、メチルセルロース、エチルセルロース等の親水性樹脂を含有させておくことによって、形成される塗膜中に上記反応に必要な水分を容易に取り込ませるようにすることができる。かかる親水性樹脂の添加量は、通常、樹脂成分１００重量部に対して一般に２０重量部以下、好ましくは０.１〜１０重量部の範囲内とすることができる。
【００４２】
また、上記▲１▼、▲２▼に記載の光酸発生剤は、本発明で使用するルテニウム（錯）化合物を必須成分とするものである。
【００４３】
また、本発明においては、必要に応じて従来から公知の光増感剤を使用することができる。具体的には、例えば４００〜７００ｎｍの波長領域の光（可視光）を吸収することにより励起され、前記した樹脂や光酸発生剤と相互作用性を有する化合物であり、シアニン系色素、メロシアニン系色素、クマリン系色素、ホウ素系色素等を挙げることができる。ここでいう「相互作用」には励起された光増感剤から他の成分へのエネルギー移動や電子移動などが包含される。上記シアニン系色素及びメロシアニン系色素としては特開昭６１−２１３８３８号公報に記載されているもの、クマリン系色素としては特開昭６１−９７６５０号公報、特開平３−２２３７５９号公報に記載されているもの、ホウ素系色素としては、例えば特開平５−２４１３３８号公報、特開平７−５６７８５号公報、特開平７−２２５４７４号公報、特開平８−６２４５号公報等が挙げられる。
【００４４】
本発明の組成物においては、上記した樹脂以外に有機溶剤や水性現像液での溶解性を良くしたり、また、逆に悪くしたりすることができる、水もしくは有機溶剤に不溶性もしくは溶解（又は分散）を示す上記したその他の樹脂を必要に応じて配合することができる。具体的には、例えば、フェノール系樹脂、ポリエステル系樹脂、アクリル系樹脂、ビニル系樹脂、酢酸ビニル樹脂、エポキシ系樹脂、シリコン系樹脂、フッ素系樹脂及びこれらの２種以上の混合物もしくは変性物等が挙げられる。
【００４５】
また、本発明の組成物を用いて形成される膜に適当な可撓性、非粘着性等を付与するために、本発明の組成物には、フタル酸エステル等の可塑剤、ポリエステル樹脂、アクリル樹脂等を添加することができる。
【００４６】
さらに、本発明の組成物には、必要に応じて、流動性調節剤、可塑剤、染料、顔料等の着色剤等を添加してもよい。
【００４７】
本発明の樹脂組成物は、一般に用いられている公知の感光性材料、例えば、塗料、インキ、接着剤、レジスト材、刷版材（平板や凸版用製版材、オフセット印刷用ＰＳ板等）、情報記録材料、レリーフ像作製材料等幅広い用途への使用が可能である。
【００４８】
次に、本発明の感光性樹脂組成物の代表的なレジスト材（例えば、一般的なポジ型感光性レジスト材料及び電着塗装用ポジ型レジスト材料）について説明する。
【００４９】
一般的なポジ型感光性レジスト材料としては、例えば、本発明のポジ型感光性樹脂組成物を溶剤（水も含む）に分散もしくは溶解（着色剤に顔料を用いた場合は顔料を微分散）させて、感光液を調製し、これを支持体上に、例えば、ローラー、ロールコーター、スピンコーター等のごとき塗布装置を用いて塗布し、乾燥する方法により、これをポジ型レジスト材料として用いることができる。
【００５０】
ポジ型感光性樹脂組成物を溶解もしくは分散するために使用する溶剤としては、例えば、ケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン等）、エステル類（酢酸エチル、酢酸ブチル、安息香酸メチル、プロピオン酸メチル等）、エーテル類（テトラヒドロフラン、ジオキサン、ジメトキシエタン等）、セロソルブ類（メチルセロソルブ、エチルセロソルブ、ジエチレングリコールモノメチルエーテル等）、芳香族炭化水素（ベンゼン、トルエン、キシレン、エチルベンゼン等）、ハロゲン化炭化水素（クロロホルム、トリクロロエチレン、ジクロロメタン等）、アルコール（エチルアルコール、ベンジルアルコール等）、その他（ジメチルホルムアミド、ジメチルスルホキシド等）、水等が挙げられる。
【００５１】
また、支持体としては、例えば、アルミニウム、マグネシウム、銅、亜鉛、クロム、ニッケル、鉄等の金属またはそれらを成分とした合金のシートまたはこれらの金属で表面を処理したプリント基板、プラスチック、ガラスまたはシリコーンウエハー、カーボン等が挙げられる。
【００５２】
また、電着塗装用ポジ型レジスト材料として用いる場合には、最初に本発明のポジ型感光性樹脂組成物を水分散化物とするか、または水溶液化物とする。
【００５３】
ポジ型感光性樹脂組成物の水分散化または水溶化は、▲１▼樹脂中にカルボキシル基等のアニオン性基が導入されている場合にはアルカリ（中和剤）で中和するか、または▲２▼アミノ基等のカチオン性基が導入されている場合には、酸（中和剤）で中和することによって行われる。その際に使用されるアルカリ中和剤としては、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類；トリエチルアミン、ジエチルアミン、モノエチルアミン、ジイソプロピルアミン、トリメチルアミン、ジイソブチルアミン等のアルキルアミン類；ジメチルアミノエタノール等のアルキルアルカノールアミン類；シクロヘキシルアミン等の脂環族アミン類；カセイソーダ、カセイカリ等のアルカリ金属水酸化物；アンモニア等が挙げられる。また、酸中和剤としては、例えば、ギ酸、酢酸、乳酸、酪酸等のモノカルボン酸が挙げられる。これらの中和剤は単独でまたは混合して使用できる。中和剤の使用量は感光性樹脂組成物中に含まれるイオン性基１当量当たり、一般に０．２〜１．０当量、特に０．３〜０．８当量の範囲が望ましい。
【００５４】
水溶化または水分散化した樹脂成分の流動性をさらに向上させるために、必要により、上記ポジ型感光性樹脂組成物に親水性溶剤、例えば、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、ｔ−ブタノール、メトキシエタノール、エトキシエタノール、ブトキシエタノール、ジエチレングリコールモノメチルエーテル、ジオキサン、テトラヒドロフラン等を加えることができる。かかる親水性溶剤の使用量は、一般には、樹脂固形成分１００重量部当たり、３００重量部まで、好ましくは１００重量部までとすることができる。
【００５５】
また、被塗装物への塗着量を多くするため、上記ポジ型感光性樹脂組成物に対し、疎水性溶剤、例えば、トルエン、キシレン等の石油系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン類；酢酸エチル、酢酸ブチル等のエステル類；２−エチルヘキシルアルコール、ベンジルアルコール等のアルコール類等も加えることができる。これらの疎水性溶剤の配合量は、樹脂固形成分１００重量部当たり、通常、２００重量部まで、好ましくは、１００重量部以下とすることができる。
【００５６】
電着塗料としてポジ型感光性樹脂組成物の調製は、従来から公知の方法で行うことができる。例えば、前記の中和により水溶化された樹脂、光酸発生剤、光増感剤、さらに必要に応じ、溶剤およびその他の成分をよく混合し、水を加えることにより調製することができる。
【００５７】
このようにして調製された組成物は、通常の方法で、さらに水で希釈し、例えば、pHが４〜９の範囲内、浴濃度（固形分濃度）３〜２５重量％、好ましくは５〜１５重量％の範囲内の電着塗料（または電着浴）とすることができる。
【００５８】
上記のようにして調製された電着塗料は、次のようにして被塗物である導体表面に塗装することができる。すなわち、まず、浴のpHおよび浴濃度を上記の範囲に調整し、浴温度を１５〜４０℃、好ましくは１５〜３０℃に管理する。次いで、このように管理された電着塗装浴に、塗装されるべき導体を電着塗料がアニオン型の場合には陽極として、また、カチオン型の場合には陰極として、浸漬、５〜２００Ｖの直流電流を通電する。通電時間は１０秒〜５分が適当である。
【００５９】
得られる膜厚は乾燥膜厚で、一般に０．５〜５０μm 、好適には、１〜２０μm である。電着塗装後、電着浴から被塗物を引き上げ水洗いした後、電着塗膜中に含まれる水分等を熱風等で乾燥、除去する（組成物として、（ａ）及び（ｂ）を使用した場合には、塗布された基板を、カルボキシル基及び／又はヒドロキシフェニル基含有重合体とビニルエーテル基含有化合物との間で架橋反応が実質的に起る温度及び時間条件下、例えば、約６０〜約１５０℃の温度で約１分〜約３０分間加熱して、塗膜を架橋硬化させる）。
【００６０】
導体としては、金属、カーボン、酸化錫等の導電性材料またはこれらを積層、メッキ等によりプラスチック、ガラス表面に固着させたものが使用できる。
【００６１】
上記のようにして導体表面に形成されるレジスト材料、および、電着塗装によって得られるレジスト電着塗膜は、画像に応じて、露光し、分解させ、露光部を現像処理によって除去することにより、画像を形成することができる。
【００６２】
露光のための光源としては、超高圧、高圧、中圧、低圧の水銀灯、ケミカルランプ、カーボンアーク灯、キセノン灯、メタルハライド灯、蛍光灯、タングステン灯、太陽光等の各光源により得られる光源や紫外カットフィルターによりカットした可視領域の光線や、可視領域に発振線を持つ各種レーザー等が使用できる。高出力で安定なレーザー光源として、アルゴンレーザー、あるいはＹＡＧレーザーの第二高調波（５３２ｎｍ）が好ましい。
【００６３】
現像処理は、露光部膜がアニオン性の場合にはアルカリ水溶液を用いて、また、カチオン性の場合にはpH５以下の酸水溶液を用いて洗い流すことにより行われる。アルカリ水溶液は通常、カセイソーダ、炭酸ソーダ、カセイカリ、アンモニア水等塗膜中に有する遊離のカルボン酸と中和して水溶性を与えることのできるものが、また、酸水溶液は酢酸、ギ酸、乳酸等が使用可能である。
【００６４】
また、イオン性基を持たない感光性樹脂の場合の現像処理は、１，１，１−トリクロロエタン、トリクレン、メチルエチルケトン、塩化メチレン等の溶剤を使って露光部を溶解することによって行う。現像した後の塗膜は、水洗後、熱風等により乾燥され、導体上に目的とする画像が形成される。また、必要に応じて、エッチングを施し、露出した導体部を除去した後、レジスト膜を除去し、プリント回路板の製造を行うこともできる。
【００６５】
組成物として、（ａ）及び（ｂ）を使用した場合には、光線が照射された基板を該照射により発生した酸の存在下で前記硬化塗膜の架橋構造の切断が生ずるような温度及び時間条件下、例えば、約６０〜約１５０℃の温度で約１〜約３０分間加熱し、照射部分の塗膜の架橋構造を実質的に切断する。その際好適には、光線が照射された基板を予め水と接触させる。水との接触によって酸が発生しやすくなり、次の架橋構造の切断反応が容易になる。水との接触は基板を常温水又は温水中に浸漬するか、水蒸気を吹付けることにより行うことができる。
【００６６】
本発明のポジ型感光性樹脂組成物は、上記した以外に、例えば、カバーフィルム層となるポリエチレンテレフタレート等のポリエステル樹脂、アクリル樹脂、ポリエチレン、ポリ塩化ビニル樹脂等の透明樹脂フィルム上に、本発明の組成物をロールコ−タ、ブレ−ドコ−タ、カーテンフロ−コータ等を使用して塗布し、乾燥してレジスト被膜（乾燥膜厚約０．５〜５μｍ）を形成した後、該被膜表面に保護フィルムを貼り付けたドライフィルムレジストとして使用することができる。
【００６７】
このようなドライフィルムレジストは、保護フィルムを剥離した後、レジスト被膜が面接するように支持体に熱圧着させる等の方法で接着してレジスト被膜を形成することができる。該レジスト被膜は上記した電着塗膜と同様の方法で、画像に応じて、露光し、現像処理することにより画像を形成することができる。
【００６８】
【実施例】
本発明について実施例を掲げて詳細に説明する。尚、実施例及び比較例の「部」は「重量部」を示す。
【００６９】
実施例１
テトラヒドロフラン２００部、Ｐーヒドロキシスチレン６５部、ｎ−ブチルアクリレート２８部、アクリル酸１１部及びアゾビスイソブチロニトリル３部の混合物を１００℃で２時間反応させて得られた反応物を１５００ｃｃのトルエン溶剤中に注ぎ込み、反応物を沈殿、分離した後、沈殿物を６０℃で乾燥して分子量約５２００、ヒドロキシフェニル基含有量４．６モル／Ｋｇの感光性樹脂を得た。次いでこのもの１００部にジビニルエーテル化合物（ビスフェノール化合物１モルと２ークロロエチルビニルエーテル２モルとの縮合物）６０部、下記式のルテノセン化合物１０部及び光増感色素（ＮＫＸ−１５９５、（株）日本感光色素研究所社製、商品名）１．５部の配合物をジエチレングリコールジメチルエーテルに溶解して固形分２０％に調整して感光液を得た。
【００７０】
次いで、この感光液を乾燥膜厚が５μｍになるように、銅張積層板上に、スピンコーターを用いて塗布した後、１２０℃で８分間加熱させてレジスト被膜を形成した。この基板にポジ型パターンマスクを介して１５ｍＪ／ｃｍ2強度のアルゴンレーザーを、上記の感光層に光照射し、１２０℃で１０分間加熱した後、１％炭酸ナトリウム水溶液を用いて現像した。可視光線照射量に対する現像後の膜の残存を調べた結果、コントラストに優れた被膜を形成し、未露光部分の膜の減少、膨潤は全く見られなかつた。
【００７１】
また、感光層を室温で６ヶ月間放置した後に、同様の評価を行ったところ、前記の感光感度に変化は認められなかった。
【００７２】
【化６】
実施例２
実施例１で得られた感光液１００部（固形分）にカルボキシル基に対してトリエチルアミン０．８当量を混合攪拌した後、脱イオン水中に分散して水分散樹脂溶液（固形分１５％）を得た。
【００７４】
得られた水分散樹脂溶液を電着塗装浴として、積層銅板を陽極とし、乾燥膜厚が５μｍとなるようにアニオン電着塗装を行った後、水洗し、１２０℃で８分間加熱し、得られた基板にポジ型パターンマスクを介して１５ｍＪ／ｃｍ2強度のアルゴンレーザーを、上記の感光層に光照射し、１２０℃で１０分間加熱した後、１％炭酸ナトリウム水溶液を用いて現像した。可視光線照射量に対する現像後の膜の残存を調べた結果、コントラストに優れた被膜を形成し、未露光部分の膜の減少、膨潤は全く見られなかつた。
【００７５】
また、感光層を室温で６ヶ月間放置した後に、同様の評価を行ったところ、前記の感光感度に変化は認められなかった。
【００７６】
実施例３
実施例１において光増感色素（ＮＫＸ−１５９５、（株）日本感光色素研究所社製、商品名）に代えて下記のものを使用した以外は実施例１と同様にして感光液を得た。
【００７７】
次いで、この感光液を乾燥膜厚が５μｍになるように、銅張積層板上に、スピンコーターを用いて塗布した後、１２０℃で８分間加熱させてレジスト被膜を形成した。この基板にＹＡＧレーザーの第２高調波（５３２ｎｍ）を直接照射上記の感光層に光照射し、１２０℃で１０分間加熱した後、１％炭酸ナトリウム水溶液を用いて現像した。可視光線照射量に対する現像後の膜の残存を調べた結果、コントラストに優れた被膜を形成し、未露光部分の膜の減少、膨潤は全く見られなかつた。
【００７８】
また、感光層を室温で６ヶ月間放置した後に、同様の評価を行ったところ、前記の感光感度に変化は認められなかった。
【００７９】
比較例１
実施例１において、光酸発生剤としてフェロセン５部を使用した以外は実施例１と同様にして感光液を調整した。これを用いて、実施例１と同様に感光層を形成し、１２０℃で８分間加熱し、得られた基板にポジ型パターンマスクを介して５ｍＪ／ｃｍ2強度のアルゴンレーザーを、上記の感光層に光照射し、１２０℃で１０分間加熱した後、１％炭酸ナトリウム水溶液を用いて現像した。可視光線照射量に対する現像後の膜の残存を調べた結果、被膜が溶解せずに悪かった。
【００８０】
【発明の効果】
本発明において、特定の化合物を光酸発生剤として含有するポジ型可視光感光性樹脂組成物は実用上極めて有用性の高い組成物である。従来、光分解反応を用いた情報記録の分野で、コンピューターによって電子編集された原稿を、そのまま直接レーザーを用いて出力し記録する方式では、感光層の経時安定性が低く、また、感度が低く、溶解性、保存安定性等の問題があった。
【００８１】
しかし、本発明のポジ型可視光感光性樹脂組成物は、樹脂と光酸発生剤の相溶性が極めてよく、かつ、汎用の塗布溶液に溶解し、支持体上で均一、かつ、経時保存安定性に優れた塗面を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention forms a pattern useful for circuit formation of electronic devices, printing materials, etc., which exhibits dissolution stability and high sensitivity by development processing using a ruthenocene compound having a unique structure or a complex thereof as a photoacid generator. The present invention relates to a positive photosensitive resin composition and its use.
[0002]
[Prior art and problems]
Currently, positive photoresists are widely used for forming circuit patterns of electronic devices and the like. In many cases, a positive resist composition used in these applications is a combination of an alkali-soluble novolac resin and a quinonediazide compound as a photosensitizer.
[0003]
This composition utilizes a reaction in which a quinonediazide group is photodegraded by irradiation with ultraviolet rays to form indenecarboxylic acid via ketene.
[0004]
However, the resist using the quinonediazide compound has a problem that the visible light reactivity is weak and the resolution is insufficient when a very fine pattern needs to be formed.
[0005]
In recent years, as a positive type photosensitive composition that replaces this, a composition sensitive to visible light comprising a polymer containing a carboxyl group, a polyvinyl ether compound, and a compound that decomposes upon irradiation with active energy rays to generate an acid is put into practical use. It has become. When the coating film formed from the composition is heated, the composition is crosslinked by an addition reaction between a carboxyl group and a vinyl ether group, becomes insoluble in a solvent or an aqueous alkali solution, and is irradiated with active energy rays and after irradiation. It is a photosensitive composition that functions by a mechanism in which when heated, the crosslinked structure is cut by the catalytic action of the generated acid, and the irradiated portion becomes soluble again in a solvent or an aqueous alkali solution.
[0006]
This composition does not require the use of a large amount of functional groups with a high extinction coefficient unlike resists that use quinonediazide as a photosensitizer, so it can be highly transparent to active energy rays and is also generated in the irradiated area. The acid that acts as a catalyst during heating has the advantage that the sensitivity as a photosensitive composition acting positively can be increased because the cross-linked structure is cut in a chain.
[0007]
However, when this photosensitive composition is applied to a substrate and heat-crosslinked, shortening of the heating time is required from the viewpoint of productivity. Therefore, when trying to shorten the time by heating at a high temperature of 100 ° C. or higher, the photoacid generator compound present in the photosensitive composition generates an acid before being irradiated with visible light, and the entire film formed when developing is formed. There is a problem of dissolution. For this reason, improvement in the dissolution stability of the photosensitive composition is strongly desired in the art.
[0008]
As a result of intensive studies on a method for solving the problems of the photosensitive composition described above, the present inventors have identified a specific ruthenocene compound or a complex thereof as a compound that decomposes upon irradiation with visible light to generate an acid. It was found that this can be solved by using in combination with a sensitizing dye as required, and the present invention has been completed. That is, in the present invention, a positive photosensitive resin and a ruthenocene compound represented by the following general formula (1) or a complex thereof (hereinafter sometimes simply referred to as “ruthenocene (complex) compound”) are photoacid generators. A positive photosensitive resin composition characterized by comprising:
[0009]
General formula (1)
[0010]
[Chemical 3]
(However, in the above formula (1), R 1 , R 2 , R Three , R Four , R Five Each independently represents a hydrogen atom, a linear or branched alkyl group or a substituent represented by the general formula (2); 1 , R 2 , R Three , R Four , R Five At least one of them has a tetrahydroquinolyl group at the terminal carbon atom of the substituent or conjugated double bond represented by the following general formula (2). R 6 Represents an optionally substituted cyclopentadienyl or π-arene, n represents an integer of 1 or 2, R 7 , R 8 , R 9 , R Ten Each independently represents a hydrogen atom or a methyl group; 11 Represents a hydrogen atom, a methyl group, or a hydroxyl group. )
General formula (2)
[0012]
[Formula 4]
DETAILED DESCRIPTION OF THE INVENTION
The positive photosensitive resin composition of the present invention contains the ruthenocene (complex) compound.
[0014]
The ruthenocene (complex) compound represented by the general formula (I) used in the present invention has extremely large absorption particularly in the wavelength of visible light, and is very sensitive to such light, and is positive type photosensitive. It is a useful material applicable to the conductive resin composition.
[0015]
The “positive type photosensitive resin composition” in the present invention means, for example, paints, inks, adhesives, printing plate materials, resist materials, and non-photosensitive coatings formed from these.
[0016]
The ruthenocene (complex) compound used in the present invention is a photoacid generator of the above general formula (1) and its complex. The ruthenocene compound is a group of compounds in which a 2-urolidyl group or a tetrahydroquinolyl group is bonded to a ruthenocenyl group via a conjugated double bond. In the general formula (1), R 1 ~ R Five Is preferably a structure represented by the general formula (2), or a structure in which a tetrahydroquinolyl group is bonded to the terminal carbon atom of the conjugated double bond, and the remainder is independently a hydrogen atom or, for example, a methyl group, It represents a linear or branched alkyl group such as an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 1-methylpropyl group, a pentyl group, or a hexyl group. In general formula (2), n represents an integer of 1 or 2, and R 7 ~ R Ten Each independently represents a hydrogen atom or a methyl group, and R 11 Represents a hydrogen atom, a methyl group or a hydroxyl group.
[0017]
In the general formula (1), R 6 Represents cyclopentadienyl- or π-arene which may have a substituent, and cyclopentadienyl- has a linear or branched alkyl group or a structure represented by the general formula (2) It may be mono- or polysubstituted by a substituent. Examples of the linear or branched alkyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 1-methylpropyl group, a pentyl group, and a hexyl group. It is done. In addition, π-arene particularly represents an aromatic group having 6 to 24 carbon atoms, or represents a heteroaromatic group having 3 to 30 carbon atoms and one or two heteroatoms. These groups may be mono- or poly-substituted by the same or different monovalent group, for example, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. good. The π-arene may be monocyclic or condensed cyclic. Examples of π-arene include benzene, toluene, xylene, ethylbenzene, cumene, methoxybenzene, ethoxybenzene, dimethoxybenzene, p-chlorotoluene, m-chlorotoluene, chlorobenzene, bromobenzene, dichlorobenzene, diisopropylbenzene, and trimethylbenzene. , Naphthalene, methylnaphthalene, stilbene, indene, fluorene, phenanthrene, anthracene, pyrene, perylene and the like.
[0018]
The ruthenocene compound used in the present invention can be produced, for example, by a Wittig reaction between a ruthenocene derivative and urolidyl aldehyde. Such ruthenocene compounds have excellent electron donating properties. The electron donating property can be determined by measuring the oxidation potential of the compound, for example, using a silver-silver chloride electrode as a reference electrode. The oxidation potential of the ruthenocene compound is usually 0.5 V or less.
[0019]
The complex of ruthenocene compound is represented by the following general formula (3)
[0020]
[Chemical formula 5]
(However, in Formula (3), X- is BF. Four -, PF 6 -, AsF 6 -Or SbF 6 -Represents. ).
[0022]
The amount of the photoacid generator used in the present invention varies depending on the type and amount of the ruthenocene (complex) compound and the type of the resin component to be interacted, but usually the ruthenocene (complex) compound per 100 parts by weight of the resin component. The amount used is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight. If the amount of the ruthenocene (complex) compound used is less than 0.1 parts by weight, the photosensitivity of the formed film tends to decrease. If the amount used exceeds 10 parts by weight, the composition becomes homogeneous from the viewpoint of solubility. There is a tendency that it is difficult to maintain a stable state.
[0023]
The ruthecene (complex) compound photoacid generator used in the present invention can be used in combination with other conventionally known photoacid generators. Examples of other photoacid generators include onium salts such as sulfonium salts, ammonium salts, phosphonium salts, iodonium salts, selenium salts, iron-allene complexes, silanol-metal chelate complexes, triazine compounds, diazides. Naphthoquinone compounds, sulfonic acid esters, sulfonic acid imide esters, halogen compounds, and the like can be used. In addition to the above, photoacid generators described in JP-A-7-65552 and Japanese Patent Application No. 9-289218 can also be used. This photoacid generator component may be a mixture with the above-described resin or a resin bonded to the resin. The mixing ratio of the other photoacid generator is preferably about 0.1 to 40 parts by weight, particularly about 0.2 to 20 parts by weight, based on 100 parts by weight of the resin.
[0024]
The positive photosensitive resin composition of the present invention is a conventionally known positive photosensitive resin composition (for example, paint, ink, adhesive, printing, etc.) in which the compound decomposes upon exposure and exhibits solubility in a developer. A plate material and a resist material for printed wiring boards) containing a photoacid generator of a ruthenium (complex) compound as an essential component.
[0025]
Representative examples of the above-described conventionally known positive photosensitive resin compositions will be described below.
[0026]
The resin composition has a low molecular weight by being cleaved by an acid component generated by a photoacid generator, an acid group is imparted to the resin, or a soluble substance (for example, (poly) P-hydroxystyrene). And the like, and the like may exhibit dispersibility or solubility in an organic solvent or an aqueous developer.
[0027]
As these, for example, (1) a photoacid generator that generates an acid group by irradiated light is used as a catalyst to cause a base resin (polymer) to undergo a elimination reaction in a chain, so that an irradiated portion and an unirradiated portion Chemical amplification type photosensitive material utilizing change in solubility (Japanese Patent Laid-Open No. 4-264461, US Pat. No. 4,491,628, Japanese Patent Laid-Open No. 59-45439, Japanese Patent Laid-Open No. 63-250642, Polymers in Electronics ”Davidson T Edited by ACS Symposium Series 242, American Chemical Society, Washington DC, 1984, page 11 Hayashi, T. Ueno, M. Toriumi, etc, ACS Polym.materials Sci. Eng., 61, 417 (1989), H. Ito, CGWilson , ACS Symp.Ser., 242, 11 (1984), etc.); (2) Photoacid generator that forms an insoluble cross-linked film in solvents and aqueous alkali solutions by heating and generates acid groups by light irradiation. A positive photosensitive composition utilizing a mechanism in which the cross-linked structure is cut by the above and the irradiated part becomes soluble in a solvent or an aqueous alkali solution ( No. 6-95064, JP-A-6-308733, JP-A-6-313134, JP-A-6-313135, JP-A-6-313136, JP-A-7-65552, etc.) Is a typical example.
[0028]
In the above (1), functional groups (hydroxyl groups, carboxyl groups, etc.) that control the solubility in the developer in the resin are blocked (acid labile groups) to make them insoluble, and the photoacid generator blocks the functional group. It dissociates and restores the solubility of the polymer. Examples of the acid labile group (R group of —OR) in which the hydroxyl group (—OH group) is blocked include, for example, t-butoxycarbonyl group (t-BOC group), t-butoxy group, t-butoxycarbonylmethyl group, Tetrahydropyranyl group, trimethylsilyl group, iso-propoxycarbonyl group and the like are included. The resin having a hydroxyl group is not particularly limited as long as it exhibits the above-described effects, but is usually a phenolic hydroxyl group. The acid labile group is particularly preferably a t-BOC group or a t-butoxy group. Examples of the acid labile group include poly (t-butoxycarbonyloxystyrene) and poly (t-butoxycarbonyloxy-α-styrene). , Poly (t-butoxystyrene) and copolymers of these monomers with other polymerizable monomers (for example, C1-24 alkyl or cycloalkyl esters of methyl (meth) acrylic acid, maleimide, sulfone, etc.) Etc. The composition of poly (t-butoxycarbonyloxystyrene) containing the t-BOC group will be described. For example, the t-BOC group is decomposed by the acid generated by the photoacid generator, and isobutene and carbon dioxide gas are evaporated. Thus, the property that the solubility in the developer (alkaline aqueous solution) is improved by changing (increasing) the polarity of the resin by changing the t-BOC group to a hydroxyl group. Examples of the acid labile group (R ′ group of —COOR ′) that blocks the carboxyl group (—COOH group) include carboxylic acid ester derivatives having a t-butyl group.
[0029]
In addition, as a component of this, it is used as a two-component system of a resin having an acid labile group and a photoacid generator, and as a three-component system of a resin having an acid labile group, a photoacid generator, and other resins. be able to. By using this other resin, for example, the coating workability of the composition can be improved or the solubility in a developer can be changed.
[0030]
The above (2) includes a resin (a) containing a carboxyl group and / or a hydroxyphenyl group, an ether bond-containing olefinically unsaturated compound (b), and a photoacid generator that generates an acid group upon irradiation with light. A liquid or solid resin composition.
[0031]
In the case where the resin (a) has both a carboxyl group and a hydroxyphenyl group, even if these groups are in the same molecule, the resin is a mixed resin containing these groups differently. But either is fine.
[0032]
Examples of the carboxyl group-containing resin (a-1) include acrylic resins and polyester resins.
[0033]
The above resin (a-1) generally has a number average molecular weight of about 500 to about 100,000, particularly about 1500 to 30000, and the carboxyl group is about 0.5 to 10 mol per kg of resin, Especially about 0.7-5 mol is preferable.
[0034]
Examples of the hydroxyphenyl group-containing resin (a-2) include condensates of monofunctional or polyfunctional phenolic compounds, alkylphenolic compounds, or mixtures thereof with carbonyl compounds such as formaldehyde and acetone; hydroxy such as P-hydroxystyrene Examples thereof include a copolymer of a phenyl group-containing unsaturated monomer and other polymerizable unsaturated monomers as described above.
[0035]
The above resin (a-2) generally has a number average molecular weight of about 500 to about 100,000, particularly about 1500 to 30000, and the hydroxyphenyl group is about 1.0 mol or more per 1 kg of the resin, About 2 to 8 mol is particularly preferable.
[0036]
Moreover, when mixing and using resin (a-1) and resin (a-2), it is preferable to mix | blend the mixing ratio by 90/10-10/90 weight ratio.
[0037]
Examples of the resin (a-3) having a carboxyl group and a hydroxyphenyl group include a carboxyl group-containing polymerizable unsaturated monomer ((meth) acrylic acid and the like) and a hydroxyphenyl group-containing polymerizable unsaturated monomer (hydroxy Styrene etc.) and other polymerizable unsaturated monomers as required (methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.) Copolymers of acrylic acid with 1 to 12 carbon alkyl esters, aromatic compounds such as styrene, nitrogen-containing unsaturated monomers such as (meth) acrylonitrile, etc .; hydroxybenzoic acids, gallic acid, resorcinic acid Or mixtures thereof with phenol, naphthols, resorcin, catechol, etc. Phenolic resins obtained by the reaction with formaldehyde.
[0038]
The above-mentioned resin (a-3) generally has a number average molecular weight of about 500 to about 100,000, particularly about 1500 to 30000, and the carboxyl group is about 0.5 to 10 mol per 1 kg of resin, Especially about 0.7-5 mol is preferable. The hydroxyphenyl group is preferably about 1.0 mol or more, particularly about 2 to 8 mol, per 1 kg of resin.
[0039]
Examples of the ether bond-containing olefinically unsaturated compound (b) include those containing about 1 to 4 unsaturated ether groups such as vinyl ether group, 1-propenyl ether group, 1-butenyl ether group at the molecular end. Can be mentioned. The compound (b) is represented by the formula —R ″ —O—A [wherein A represents a vinyl group, 1-propenyl group or 1-butenyl olefinically unsaturated group, and R ″ represents ethylene, propylene in one molecule. Represents a linear or branched alkylene group having 1 to 6 carbon atoms such as butylene, etc.] and has a low or high molecular weight compound containing at least 1, preferably 2 to 4 unsaturated ether groups For example, polyphenol compounds such as bisphenol A, bisphenol F, bisphenol S, and phenol resin; polyols such as ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, and pentaerythritol; and chloroethyl vinyl ether. Condensates with halogenated alkyl unsaturated ethers such as tolylene diisocyanate Examples thereof include a reaction product of a polyisocyanate compound such as anate, xylylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate and a hydroxyalkyl unsaturated ether such as hydroxyethyl vinyl ether. In particular, the condensation product of the polyphenol compound and the halogenated alkyl unsaturated ether and the reaction product of the polyisocyanate compound having an aromatic ring and the hydroxyalkyl unsaturated ether are resistant to etching, the accuracy of the pattern to be formed, and the like. Is preferred. The compound (b) is usually in the range of about 5 to 150 parts by weight, preferably about 10 to 100 parts by weight with respect to 100 parts by weight of the resin (a).
[0040]
In the composition containing the components (a) and (b), the film formed therefrom is heated to crosslink by an addition reaction between a carboxyl group and / or a hydroxyphenyl group and an unsaturated ether group, and then a solvent or an alkaline aqueous solution. When exposed to active energy rays and then heated after irradiation, the cross-linked structure is cut by the catalytic action of the generated acid, and the irradiated part becomes soluble again in solvents and alkaline aqueous solutions. It is a resin composition.
[0041]
In the composition, an acid hydrolysis reaction occurs in the exposed portion due to the acid generated when the film to be formed is exposed, but it is desirable that moisture is present in order to allow the acid hydrolysis reaction to proceed smoothly. Therefore, by incorporating a hydrophilic resin such as polyethylene glycol, polypropylene glycol, methyl cellulose, ethyl cellulose or the like into the composition of the present invention, moisture necessary for the above reaction can be easily taken into the formed coating film. Can be. The amount of the hydrophilic resin added is generally 20 parts by weight or less, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin component.
[0042]
The photoacid generators described in (1) and (2) above contain the ruthenium (complex) compound used in the present invention as an essential component.
[0043]
Moreover, in this invention, a conventionally well-known photosensitizer can be used as needed. Specifically, it is a compound that is excited by absorbing light (visible light) in a wavelength region of 400 to 700 nm, for example, and has an interaction property with the above-described resin or photoacid generator. Examples thereof include dyes, coumarin dyes, and boron dyes. The “interaction” here includes energy transfer and electron transfer from the excited photosensitizer to other components. The cyanine dyes and merocyanine dyes are described in JP-A-61-213838, and the coumarin dyes are described in JP-A-61-97650 and JP-A-3-223759. Examples of the boron-based dye include JP-A-5-241338, JP-A-7-56785, JP-A-7-225474, and JP-A-8-6245.
[0044]
In the composition of the present invention, in addition to the above-described resins, the solubility in an organic solvent or an aqueous developer can be improved, and conversely, the water or the organic solvent can be insoluble or dissolved (or dissolved (or The above-mentioned other resins exhibiting (dispersion) can be blended as necessary. Specifically, for example, phenol resin, polyester resin, acrylic resin, vinyl resin, vinyl acetate resin, epoxy resin, silicon resin, fluorine resin, and a mixture or modified product of two or more thereof. Is mentioned.
[0045]
Further, in order to impart appropriate flexibility, non-tackiness, etc. to the film formed using the composition of the present invention, the composition of the present invention includes a plasticizer such as phthalate ester, a polyester resin, An acrylic resin etc. can be added.
[0046]
Furthermore, you may add coloring agents, such as a fluidity modifier, a plasticizer, a dye, and a pigment, to the composition of this invention as needed.
[0047]
The resin composition of the present invention is a known photosensitive material that is generally used, such as paints, inks, adhesives, resist materials, printing plate materials (plate plates, letterpress plate making materials, offset printing PS plates, etc.), It can be used for a wide range of applications such as information recording materials and relief image forming materials.
[0048]
Next, representative resist materials (for example, a general positive photosensitive resist material and a positive resist material for electrodeposition coating) of the photosensitive resin composition of the present invention will be described.
[0049]
As a general positive photosensitive resist material, for example, the positive photosensitive resin composition of the present invention is dispersed or dissolved in a solvent (including water) (when a pigment is used as a colorant, the pigment is finely dispersed). To prepare a photosensitive solution, which is applied on a support using a coating apparatus such as a roller, a roll coater, a spin coater, etc., and then dried as a positive resist material. Can do.
[0050]
Examples of the solvent used to dissolve or disperse the positive photosensitive resin composition include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, methyl benzoate, propionic acid). Methyl), ethers (tetrahydrofuran, dioxane, dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.), halogenated hydrocarbons (Chloroform, trichloroethylene, dichloromethane, etc.), alcohol (ethyl alcohol, benzyl alcohol, etc.), others (dimethylformamide, dimethyl sulfoxide, etc.), water and the like.
[0051]
In addition, as the support, for example, a metal such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or an alloy sheet containing them as a component, a printed circuit board whose surface is treated with these metals, plastic, glass or Examples include silicone wafers and carbon.
[0052]
When using as a positive resist material for electrodeposition coating, the positive photosensitive resin composition of the present invention is first made into an aqueous dispersion or an aqueous solution.
[0053]
The water dispersion or water-solubilization of the positive photosensitive resin composition can be achieved by (1) neutralizing with an alkali (neutralizing agent) when an anionic group such as a carboxyl group is introduced into the resin, or (2) When a cationic group such as an amino group is introduced, it is carried out by neutralizing with an acid (neutralizing agent). Examples of the alkali neutralizer used in this case include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine and diisobutylamine; Examples thereof include alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as caustic soda and caustic potash; ammonia and the like. Examples of the acid neutralizer include monocarboxylic acids such as formic acid, acetic acid, lactic acid, and butyric acid. These neutralizing agents can be used alone or in combination. The amount of neutralizing agent used is generally in the range of 0.2 to 1.0 equivalent, particularly 0.3 to 0.8 equivalent, per equivalent of ionic group contained in the photosensitive resin composition.
[0054]
In order to further improve the fluidity of the water-soluble or water-dispersed resin component, a hydrophilic solvent such as methanol, ethanol, isopropanol, n-butanol, t-butanol is added to the positive photosensitive resin composition as necessary. Methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, dioxane, tetrahydrofuran and the like can be added. The amount of the hydrophilic solvent used can generally be up to 300 parts by weight, preferably up to 100 parts by weight per 100 parts by weight of the resin solid component.
[0055]
In addition, in order to increase the amount of coating on the object to be coated, a hydrophobic solvent such as a petroleum solvent such as toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone are used for the positive photosensitive resin composition. Esters such as ethyl acetate and butyl acetate; alcohols such as 2-ethylhexyl alcohol and benzyl alcohol can also be added. The amount of these hydrophobic solvents is usually up to 200 parts by weight, preferably 100 parts by weight or less, per 100 parts by weight of the resin solid component.
[0056]
The positive photosensitive resin composition can be prepared as an electrodeposition coating by a conventionally known method. For example, it can be prepared by mixing the water-solubilized resin, photoacid generator, photosensitizer, and, if necessary, the solvent and other components well, and adding water.
[0057]
The composition thus prepared is further diluted with water in the usual manner. For example, the pH is in the range of 4 to 9, and the bath concentration (solid content concentration) is 3 to 25% by weight, preferably 5 to 5%. The electrodeposition paint (or electrodeposition bath) can be in the range of 15% by weight.
[0058]
The electrodeposition paint prepared as described above can be applied to the surface of a conductor to be coated as follows. That is, first, the pH and concentration of the bath are adjusted to the above ranges, and the bath temperature is controlled to 15 to 40 ° C, preferably 15 to 30 ° C. Next, the conductor to be coated is immersed in the electrodeposition coating bath thus controlled as an anode when the electrodeposition paint is an anionic type, and as a cathode when the electrodeposition type is a cationic type, and is 5 to 200 V. Apply DC current. The energization time is suitably 10 seconds to 5 minutes.
[0059]
The film thickness obtained is a dry film thickness, generally 0.5-50 μm, preferably 1-20 μm. After electrodeposition coating, the object to be coated is lifted from the electrodeposition bath, washed with water, and then the moisture contained in the electrodeposition coating film is dried and removed with hot air or the like (using (a) and (b) as the composition) In this case, the coated substrate is subjected to temperature and time conditions under which a crosslinking reaction substantially occurs between the carboxyl group and / or hydroxyphenyl group-containing polymer and the vinyl ether group-containing compound, for example, about 60 to The coating is crosslinked and cured by heating at a temperature of about 150 ° C. for about 1 minute to about 30 minutes).
[0060]
As the conductor, a conductive material such as metal, carbon, tin oxide or the like, or a material obtained by laminating, plating or the like, and fixing it to a plastic or glass surface can be used.
[0061]
The resist material formed on the conductor surface as described above and the resist electrodeposition coating film obtained by electrodeposition coating are exposed and decomposed according to the image, and the exposed portion is removed by development processing. An image can be formed.
[0062]
Light sources for exposure include light sources obtained from each light source such as ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, sunlight, etc. A visible light beam cut by an ultraviolet cut filter, various lasers having an oscillation line in the visible region, and the like can be used. As a high-power and stable laser light source, an argon laser or a second harmonic (532 nm) of a YAG laser is preferable.
[0063]
The development processing is performed by washing away using an alkaline aqueous solution when the exposed portion film is anionic, and using an aqueous acid solution having a pH of 5 or less when the exposed portion film is cationic. Alkaline aqueous solutions are usually caustic soda, sodium carbonate, caustic potash, ammonia water, etc. that can be neutralized with free carboxylic acid in the coating film to give water solubility, and acid aqueous solutions are acetic acid, formic acid, lactic acid, etc. Can be used.
[0064]
Further, the development processing in the case of a photosensitive resin having no ionic group is performed by dissolving the exposed portion using a solvent such as 1,1,1-trichloroethane, trichlene, methyl ethyl ketone, or methylene chloride. The developed coating film is washed with water and then dried with hot air or the like to form a desired image on the conductor. Further, if necessary, after etching and removing the exposed conductor portion, the resist film is removed, and a printed circuit board can be manufactured.
[0065]
When (a) and (b) are used as the composition, a temperature at which the cross-linked structure of the cured coating film is cut in the presence of an acid generated by irradiation of the substrate irradiated with the light beam, and Under time conditions, for example, by heating at a temperature of about 60 to about 150 ° C. for about 1 to about 30 minutes, the crosslinked structure of the coating in the irradiated portion is substantially cut. In this case, preferably, the substrate irradiated with the light is previously brought into contact with water. The acid is easily generated by contact with water, and the subsequent cross-linking structure cleavage reaction is facilitated. The contact with water can be performed by immersing the substrate in normal temperature water or warm water, or by spraying water vapor.
[0066]
In addition to the above, the positive photosensitive resin composition of the present invention is formed on a transparent resin film such as a polyester resin such as polyethylene terephthalate that becomes a cover film layer, an acrylic resin, polyethylene, or a polyvinyl chloride resin. The composition is applied using a roll coater, a blade coater, a curtain flow coater, etc., and dried to form a resist film (dry film thickness of about 0.5 to 5 μm), and then the surface of the film It can be used as a dry film resist having a protective film attached thereto.
[0067]
Such a dry film resist can be bonded by a method such as thermocompression bonding to a support so that the resist film is in contact with the resist film after the protective film is peeled off to form a resist film. The resist film can be formed in the same manner as the above-mentioned electrodeposition coating film by exposing and developing according to the image.
[0068]
【Example】
The present invention will be described in detail with reference to examples. In the examples and comparative examples, “parts” represents “parts by weight”.
[0069]
Example 1
A reaction product obtained by reacting a mixture of 200 parts of tetrahydrofuran, 65 parts of P-hydroxystyrene, 28 parts of n-butyl acrylate, 11 parts of acrylic acid and 3 parts of azobisisobutyronitrile at 100 ° C. for 2 hours was obtained in 1500 cc. After pouring into a toluene solvent to precipitate and separate the reaction product, the precipitate was dried at 60 ° C. to obtain a photosensitive resin having a molecular weight of about 5200 and a hydroxyphenyl group content of 4.6 mol / Kg. Next, 100 parts of this product was added with 60 parts of a divinyl ether compound (condensate of 1 mol of a bisphenol compound and 2 mol of 2-chloroethyl vinyl ether), 10 parts of a ruthenocene compound of the following formula and a photosensitizing dye (NKX-1595, Inc.). Nippon Photosensitivity Laboratories Co., Ltd., trade name) 1.5 parts of a blend was dissolved in diethylene glycol dimethyl ether and adjusted to a solid content of 20% to obtain a photosensitive solution.
[0070]
Next, this photosensitive solution was applied onto a copper clad laminate using a spin coater so that the dry film thickness was 5 μm, and then heated at 120 ° C. for 8 minutes to form a resist film. 15mJ / cm on this substrate through a positive pattern mask 2 The photosensitive layer was irradiated with an intense argon laser, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of investigating the remaining film after development with respect to the amount of visible light irradiation, a film having excellent contrast was formed, and no decrease or swelling of the film in the unexposed part was observed.
[0071]
Further, when the same evaluation was performed after the photosensitive layer was allowed to stand at room temperature for 6 months, no change was observed in the above-mentioned photosensitive sensitivity.
[0072]
[Chemical 6]
Example 2
To 100 parts (solid content) of the photosensitive solution obtained in Example 1, 0.8 equivalent of triethylamine with respect to the carboxyl group was mixed and stirred, and then dispersed in deionized water to obtain an aqueous dispersion resin solution (solid content 15%). Obtained.
[0074]
The obtained water-dispersed resin solution was used as an electrodeposition coating bath, the laminated copper plate was used as an anode, anion electrodeposition coating was performed so that the dry film thickness was 5 μm, then washed with water and heated at 120 ° C. for 8 minutes. 15 mJ / cm through the positive pattern mask on the resultant substrate 2 The photosensitive layer was irradiated with an intense argon laser, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of investigating the remaining film after development with respect to the amount of visible light irradiation, a film having excellent contrast was formed, and no decrease or swelling of the film in the unexposed part was observed.
[0075]
Further, when the same evaluation was performed after the photosensitive layer was allowed to stand at room temperature for 6 months, no change was observed in the above-mentioned photosensitive sensitivity.
[0076]
Example 3
A photosensitizing solution was obtained in the same manner as in Example 1 except that the following were used in place of the photosensitizing dye (NKX-1595, manufactured by Nippon Photosensitive Dye Research Co., Ltd., trade name) in Example 1. .
[0077]
Next, this photosensitive solution was applied onto a copper clad laminate using a spin coater so that the dry film thickness was 5 μm, and then heated at 120 ° C. for 8 minutes to form a resist film. This substrate was directly irradiated with the second harmonic of a YAG laser (532 nm). The photosensitive layer was irradiated with light, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of investigating the remaining film after development with respect to the amount of visible light irradiation, a film having excellent contrast was formed, and no decrease or swelling of the film in the unexposed part was observed.
[0078]
Further, when the same evaluation was performed after the photosensitive layer was allowed to stand at room temperature for 6 months, no change was observed in the above-mentioned photosensitive sensitivity.
[0079]
Comparative Example 1
In Example 1, a photosensitive solution was prepared in the same manner as in Example 1 except that 5 parts of ferrocene was used as a photoacid generator. Using this, a photosensitive layer was formed in the same manner as in Example 1, heated at 120 ° C. for 8 minutes, and 5 mJ / cm was passed through the positive pattern mask to the obtained substrate. 2 The photosensitive layer was irradiated with an intense argon laser, heated at 120 ° C. for 10 minutes, and then developed using a 1% aqueous sodium carbonate solution. As a result of examining the film remaining after development with respect to the amount of visible light irradiation, the film did not dissolve and was bad.
[0080]
【The invention's effect】
In the present invention, a positive visible light photosensitive resin composition containing a specific compound as a photoacid generator is a highly useful composition for practical use. Conventionally, in the field of information recording using photolysis reaction, a method in which a manuscript electronically edited by a computer is directly output and recorded directly using a laser has a low photosensitive layer temporal stability and low sensitivity. There were problems such as solubility and storage stability.
[0081]
However, the positive visible light photosensitive resin composition of the present invention has extremely good compatibility between the resin and the photoacid generator, is dissolved in a general-purpose coating solution, is uniform on the support, and is stable over time. A coated surface with excellent properties can be obtained.
Claims (4)
一般式（１）
一般式（２）
General formula (1)
General formula (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37254498A JP3971046B2 (en) | 1998-12-28 | 1998-12-28 | Positive photosensitive resin composition and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37254498A JP3971046B2 (en) | 1998-12-28 | 1998-12-28 | Positive photosensitive resin composition and use thereof |
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| JP2000194137A JP2000194137A (en) | 2000-07-14 |
| JP3971046B2 true JP3971046B2 (en) | 2007-09-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6340545B1 (en) * | 1999-03-08 | 2002-01-22 | Kyodo Printing Co., Ltd. | Photosensitive resin composition, method of forming patterns, photosensitive liquid for forming colored images, and color filter |
| JP5913077B2 (en) | 2012-12-18 | 2016-04-27 | 信越化学工業株式会社 | Positive resist material and pattern forming method using the same |
| JP6195552B2 (en) * | 2014-02-21 | 2017-09-13 | 富士フイルム株式会社 | Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and electronic device manufacturing method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS52117616A (en) * | 1976-03-29 | 1977-10-03 | Toshiba Corp | Radio-sensitive composition |
| US5652280A (en) * | 1991-11-12 | 1997-07-29 | University Of Georgia Research Foundation, Inc. | Anionic photoinitiation |
| JP3605939B2 (en) * | 1996-05-13 | 2004-12-22 | 東洋インキ製造株式会社 | Energy-sensitive positive type sensitive composition |
| US6127445A (en) * | 1998-11-03 | 2000-10-03 | The University Of Georgia Research Foundation, Inc. | Substituted benzoylferrocene anionic photoinitiators |
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