JPH0583562B2 - - Google Patents
Info
- Publication number
- JPH0583562B2 JPH0583562B2 JP60220179A JP22017985A JPH0583562B2 JP H0583562 B2 JPH0583562 B2 JP H0583562B2 JP 60220179 A JP60220179 A JP 60220179A JP 22017985 A JP22017985 A JP 22017985A JP H0583562 B2 JPH0583562 B2 JP H0583562B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- formula
- dyes
- benzophenone
- 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 - Lifetime
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 239000000975 dye Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 13
- 239000012965 benzophenone Substances 0.000 claims description 8
- 230000002165 photosensitisation Effects 0.000 claims description 8
- 239000003504 photosensitizing agent Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 6
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 claims description 6
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical class C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 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 claims description 5
- 239000001017 thiazole dye Substances 0.000 claims description 5
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000001018 xanthene dye Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- -1 benzoylperoxy compound Chemical class 0.000 description 25
- 125000003118 aryl group Chemical group 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Chemical group 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MOGPYMSSJLWALN-UHFFFAOYSA-N 2-(dimethylamino)-1,3-diphenylprop-2-en-1-one Chemical compound C=1C=CC=CC=1C(=O)C(N(C)C)=CC1=CC=CC=C1 MOGPYMSSJLWALN-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- YUFZFDCSLAUIPS-UHFFFAOYSA-N 2-nitro-1,3-diphenylprop-2-en-1-one Chemical compound C=1C=CC=CC=1C(=O)C([N+](=O)[O-])=CC1=CC=CC=C1 YUFZFDCSLAUIPS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZRJVUBAAWZFJRV-UHFFFAOYSA-M [4-[2,6-bis(4-ethylphenyl)thiopyran-4-ylidene]cyclohexa-2,5-dien-1-ylidene]-pentyloxidanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(=[O+]CCCCC)C=CC1=C1C=C(C=2C=CC(CC)=CC=2)SC(C=2C=CC(CC)=CC=2)=C1 ZRJVUBAAWZFJRV-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N chalcone Chemical class C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GBUFRJCGZJNUSB-UHFFFAOYSA-N 1,4-diphenylbut-3-en-1-one Chemical compound C=1C=CC=CC=1C(=O)CC=CC1=CC=CC=C1 GBUFRJCGZJNUSB-UHFFFAOYSA-N 0.000 description 1
- DVWQSKNALFXODO-UHFFFAOYSA-M 2,4,6-triphenylpyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=[O+]C(C=2C=CC=CC=2)=C1 DVWQSKNALFXODO-UHFFFAOYSA-M 0.000 description 1
- UAMORFUEIWNPCP-UHFFFAOYSA-M 2,4,6-triphenylthiopyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=[S+]C(C=2C=CC=CC=2)=C1 UAMORFUEIWNPCP-UHFFFAOYSA-M 0.000 description 1
- NILKBBWMPNIUNJ-UHFFFAOYSA-L 2,4,6-triphenylthiopyrylium;sulfate Chemical compound [O-]S([O-])(=O)=O.C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=[S+]C(C=2C=CC=CC=2)=C1.C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=[S+]C(C=2C=CC=CC=2)=C1 NILKBBWMPNIUNJ-UHFFFAOYSA-L 0.000 description 1
- WPFBPHJBJLQPBB-UHFFFAOYSA-M 2,6-bis(4-ethylphenyl)-4-(4-pentoxyphenyl)pyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OCCCCC)=CC=C1C1=CC(C=2C=CC(CC)=CC=2)=[O+]C(C=2C=CC(CC)=CC=2)=C1 WPFBPHJBJLQPBB-UHFFFAOYSA-M 0.000 description 1
- BXUXWKVZQIPOBA-UHFFFAOYSA-M 2,6-bis(4-methoxyphenyl)-4-phenylpyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OC)=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC(OC)=CC=2)=[O+]1 BXUXWKVZQIPOBA-UHFFFAOYSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GODBBAPLWRHHEO-UHFFFAOYSA-M 2-(3,4-dichlorophenyl)-4-(4-methoxyphenyl)-6-phenylpyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OC)=CC=C1C1=CC(C=2C=CC=CC=2)=[O+]C(C=2C=C(Cl)C(Cl)=CC=2)=C1 GODBBAPLWRHHEO-UHFFFAOYSA-M 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WNIWWVYQLROYBA-UHFFFAOYSA-N 2-(diethylamino)-1,3-diphenylprop-2-en-1-one Chemical compound C=1C=CC=CC=1C(=O)C(N(CC)CC)=CC1=CC=CC=C1 WNIWWVYQLROYBA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DGXKARFROUZPQX-UHFFFAOYSA-N 2-methyl-1,4-diphenylbut-3-en-1-one Chemical compound CC(C(=O)C1=CC=CC=C1)C=CC1=CC=CC=C1 DGXKARFROUZPQX-UHFFFAOYSA-N 0.000 description 1
- RFKUPJUWGRZWAV-UHFFFAOYSA-M 4-(2,4-dichlorophenyl)-2,6-diphenylpyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.ClC1=CC(Cl)=CC=C1C1=CC(C=2C=CC=CC=2)=[O+]C(C=2C=CC=CC=2)=C1 RFKUPJUWGRZWAV-UHFFFAOYSA-M 0.000 description 1
- NXVYMWMERRXANY-UHFFFAOYSA-M 4-(2,4-dichlorophenyl)-2,6-diphenylthiopyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.ClC1=CC(Cl)=CC=C1C1=CC(C=2C=CC=CC=2)=[S+]C(C=2C=CC=CC=2)=C1 NXVYMWMERRXANY-UHFFFAOYSA-M 0.000 description 1
- SZAUSSVBAVVLHB-UHFFFAOYSA-M 4-(4-butoxyphenyl)-2,6-diphenylpyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OCCCC)=CC=C1C1=CC(C=2C=CC=CC=2)=[O+]C(C=2C=CC=CC=2)=C1 SZAUSSVBAVVLHB-UHFFFAOYSA-M 0.000 description 1
- VFTZYHHPMYCBEY-UHFFFAOYSA-M 4-(4-methoxyphenyl)-2,6-diphenylpyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OC)=CC=C1C1=CC(C=2C=CC=CC=2)=[O+]C(C=2C=CC=CC=2)=C1 VFTZYHHPMYCBEY-UHFFFAOYSA-M 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- OIEKYRGRMKNGHK-UHFFFAOYSA-M [4-(2,6-diphenylpyran-4-ylidene)cyclohexa-2,5-dien-1-ylidene]-dimethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(N(C)C)=CC=C1C1=CC(C=2C=CC=CC=2)=[O+]C(C=2C=CC=CC=2)=C1 OIEKYRGRMKNGHK-UHFFFAOYSA-M 0.000 description 1
- CJCZCZXMNXAQLJ-UHFFFAOYSA-M [4-(2,6-diphenylthiopyran-4-ylidene)cyclohexa-2,5-dien-1-ylidene]-methyloxidanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OC)=CC=C1C1=CC(C=2C=CC=CC=2)=[S+]C(C=2C=CC=CC=2)=C1 CJCZCZXMNXAQLJ-UHFFFAOYSA-M 0.000 description 1
- XGSJBCZLRKWXIO-UHFFFAOYSA-M [4-(4,6-diphenylthiopyran-2-ylidene)cyclohexa-2,5-dien-1-ylidene]-ethyloxidanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(=[O+]CC)C=CC1=C1C=C(C=2C=CC=CC=2)C=C(C=2C=CC=CC=2)S1 XGSJBCZLRKWXIO-UHFFFAOYSA-M 0.000 description 1
- VWDNDYBQHSLMFE-UHFFFAOYSA-M [4-[2,6-bis(4-ethylphenyl)thiopyran-4-ylidene]cyclohexa-2,5-dien-1-ylidene]-methyloxidanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(CC)=CC=C1C1=CC(C=2C=CC(OC)=CC=2)=CC(C=2C=CC(CC)=CC=2)=[S+]1 VWDNDYBQHSLMFE-UHFFFAOYSA-M 0.000 description 1
- JPWVNNRSLGQPQG-UHFFFAOYSA-M [4-[2,6-bis(4-pentoxyphenyl)thiopyran-4-ylidene]cyclohexa-2,5-dien-1-ylidene]-methyloxidanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OCCCCC)=CC=C1C1=CC(C=2C=CC(OC)=CC=2)=CC(C=2C=CC(OCCCCC)=CC=2)=[S+]1 JPWVNNRSLGQPQG-UHFFFAOYSA-M 0.000 description 1
- JLZZNONDICSXSG-UHFFFAOYSA-M [4-[4,6-bis(4-methoxyphenyl)thiopyran-2-ylidene]cyclohexa-2,5-dien-1-ylidene]-methyloxidanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OC)=CC=C1C1=CC(C=2C=CC(OC)=CC=2)=[S+]C(C=2C=CC(OC)=CC=2)=C1 JLZZNONDICSXSG-UHFFFAOYSA-M 0.000 description 1
- ZNYAUMLKZPZAKF-UHFFFAOYSA-M [4-[6-(4-methoxyphenyl)-4-phenylthiopyran-2-ylidene]cyclohexa-2,5-dien-1-ylidene]-methyloxidanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC(OC)=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC(OC)=CC=2)=[S+]1 ZNYAUMLKZPZAKF-UHFFFAOYSA-M 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- NENAMKMSJOINIR-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl) 4-[3,4-bis(2,4,4-trimethylpentan-2-ylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)CC(C)(C)C)C(C(=O)OOC(C)(C)CC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)CC(C)(C)C)C(C(=O)OOC(C)(C)CC(C)(C)C)=C1 NENAMKMSJOINIR-UHFFFAOYSA-N 0.000 description 1
- ITXCLKMRLHBUEP-UHFFFAOYSA-N bis(2-methylbutan-2-yl) 4-[3,4-bis(2-methylbutan-2-ylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)CC)C(C(=O)OOC(C)(C)CC)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)CC)C(C(=O)OOC(C)(C)CC)=C1 ITXCLKMRLHBUEP-UHFFFAOYSA-N 0.000 description 1
- YGWAFVKXCAQAGJ-UHFFFAOYSA-N bis(2-methylpentan-2-yl) 4-[3,4-bis(2-methylpentan-2-ylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)CCC)C(C(=O)OOC(C)(C)CCC)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)CCC)C(C(=O)OOC(C)(C)CCC)=C1 YGWAFVKXCAQAGJ-UHFFFAOYSA-N 0.000 description 1
- VRZQMDDQCTXMKG-UHFFFAOYSA-N bis(2-phenylpropan-2-yl) 4-[3,4-bis(2-phenylpropan-2-ylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C=1C=CC=CC=1C(C)(C)OOC(=O)C1=CC=C(C(=O)C=2C=C(C(C(=O)OOC(C)(C)C=3C=CC=CC=3)=CC=2)C(=O)OOC(C)(C)C=2C=CC=CC=2)C=C1C(=O)OOC(C)(C)C1=CC=CC=C1 VRZQMDDQCTXMKG-UHFFFAOYSA-N 0.000 description 1
- ARSWOISMYKDULL-UHFFFAOYSA-N bis[4-(2,2-dihydroxyethylamino)phenyl]methanone Chemical compound C1=CC(NCC(O)O)=CC=C1C(=O)C1=CC=C(NCC(O)O)C=C1 ARSWOISMYKDULL-UHFFFAOYSA-N 0.000 description 1
- FGURETDKISOZJH-UHFFFAOYSA-N bis[4-(dicyclohexylamino)phenyl]methanone Chemical compound C=1C=C(N(C2CCCCC2)C2CCCCC2)C=CC=1C(=O)C(C=C1)=CC=C1N(C1CCCCC1)C1CCCCC1 FGURETDKISOZJH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003973 paint Substances 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
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- NTQLADLBRQMNQJ-UHFFFAOYSA-M pyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC=[O+]C=C1 NTQLADLBRQMNQJ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- 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
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
Description
〔産業上の利用分野〕
本発明は、不飽和化合物重合用の光重合開始剤
組成物に関するものである。不飽和結合を分子中
に含むモノマー、オリゴマー及びポリマーは光重
合開始剤の存在下で光重合することは良く知られ
ており、印刷版やプリント基板、IC等を作成す
る際に用いられるフオトポリマーやフオトレジス
トとして広く利用されている。
〔従来の技術〕
フオトポリマー及びフオトレジストに用いられ
る高感度の光重合開始剤としては、例えば特開昭
59−20304号におけるベンゾイルペルオキシ化合
物とキサントンに代表される芳香族カルボニル化
合物との組み合せから成る光重合開始剤、及び特
開昭59−45303号公報や特開昭60−76503号公報に
おける有機過酸化物とピリリウム塩やチオピリリ
ウム塩との組み合わせから成る光重合開始剤等が
ある。また、特開昭60−35725号公報には４，
4′−ビス（ジアルキルアミノ）ベンゾフエノンと
芳香族ケトン化合物と有機過酸化物とを組み合わ
せた光重合性組成物が記載されている。
〔発明が解決しようとする問題点〕
印刷版材への実用化に関しては、より多くの部
数を印刷する為の強靭な膜が要求され、またフオ
トレジスト材料への実用化に関しては、耐酸性が
必須であり、その為にも膜の強度は重要である。
このように、光重合開始剤には、市場からのニー
ズとして高感度化と膜強度とが挙げられる。しか
るに上記、有機過酸化物と可視光吸収化合物との
組合せから成る光重合開始剤においては、高感度
な画像を得ることが出来るが実用性を考慮した場
合、画像が形成された皮膜の強度が十分ではな
い。本発明は、高感度でかつ十分な光硬化膜強度
を得ることのできる光重合開始剤組成物を提供す
ることを目的としている。
〔問題を解決するための手段〕
本発明は、下記一般式（Ｉ）で示されるベンゾ
フエノン基含有多価ペルオキシエステル、一般式
（）で示される４，4′−ビス（ジアルキルアミ
ノ）ベンゾフエノン及び下記に示す光増感色素か
らなる不飽和単量体重合用光重合開始剤組成物を
提供するものである。
[Industrial Field of Application] The present invention relates to a photopolymerization initiator composition for polymerizing unsaturated compounds. It is well known that monomers, oligomers, and polymers containing unsaturated bonds in their molecules are photopolymerized in the presence of a photoinitiator, and photopolymers are used to create printing plates, printed circuit boards, ICs, etc. It is widely used as a photoresist. [Prior Art] As a highly sensitive photopolymerization initiator used in photopolymers and photoresists, for example,
A photopolymerization initiator consisting of a combination of a benzoylperoxy compound and an aromatic carbonyl compound represented by xanthone in No. 59-20304, and an organic peroxide in JP-A-59-45303 and JP-A-60-76503. There are photopolymerization initiators made of a combination of pyrylium salts and pyrylium salts or thiopyrylium salts. In addition, 4,
A photopolymerizable composition is described that combines 4'-bis(dialkylamino)benzophenone, an aromatic ketone compound, and an organic peroxide. [Problems to be solved by the invention] For practical use in printing plate materials, a strong film is required to print a larger number of copies, and for practical use in photoresist materials, acid resistance is required. This is essential, and for that reason, the strength of the membrane is also important.
As described above, the market needs for photopolymerization initiators include higher sensitivity and higher film strength. However, with the above-mentioned photopolymerization initiator consisting of a combination of an organic peroxide and a visible light absorbing compound, it is possible to obtain a highly sensitive image, but when considering practicality, the strength of the film on which the image is formed is limited. Not enough. An object of the present invention is to provide a photopolymerization initiator composition that is highly sensitive and can provide sufficient photocured film strength. [Means for solving the problem] The present invention provides benzophenone group-containing polyhydric peroxyester represented by the following general formula (I), 4,4'-bis(dialkylamino)benzophenone represented by the general formula (), and the following The present invention provides a photopolymerization initiator composition for polymerizing unsaturated monomers comprising the photosensitizing dye shown in the following.
【化】
〔式中、R1およびR′1はそれぞれ炭素数４から８
の第３アルキル基または炭素数９から12の第３ア
ラルキル基、R2およびR′2はそれぞれ水素原子ま
たは炭素数４から８の第３アルコキシ基または炭
素数９から12の第３アラルキルオキシ基を表わ
す。〕[In the formula, R 1 and R′ 1 each have 4 to 8 carbon atoms]
A tertiary alkyl group or a tertiary aralkyl group having 9 to 12 carbon atoms, R 2 and R' 2 are each a hydrogen atom, a tertiary alkoxy group having 4 to 8 carbon atoms, or a tertiary aralkyloxy group having 9 to 12 carbon atoms represents. ]
光増感色素
〔ベンザルアセトフエノン類、ピリリウム塩類、
チオピリリウム塩類、シアニン系染料、メロシア
ニン系染料、キサンテン系染料、チアゾール系染
料から選ばれる１種以上のもの〕
本発明に用いる一般式（Ｉ）で表わされるベン
ゾフエノン基含有多価ペルオキシエステルの例と
しては、例えば３，3′，４，4′−テトラ−（ｔ−
ブチルペルオキシカルボニル）ベンゾフエノン、
３，3′，４，4′−テトラ−（ｔ−アミルペルオキ
シカルボニル）ベンゾフエノン、３，3′，４，
4′−テトラ（ｔ−ヘキシルペルオキシカルボニ
ル）ベンゾフエノン、３，3′，４，4′−テトラ
（ｔ−オクチルペルオキシカルボニル）ベンゾフ
エノン、３，3′，４，4′−テトラ（クミルペルオ
キシカルボニル）ベンゾフエノン、３，3′，４，
4′−テトラ（ｐ−イソプロピルクミルペルオキシ
カルボニル）ベンゾフエノン等があり、これらを
１種または２種以上混合して使用できる。
本発明に用いる一般式（）で示される４，
4′−ビス（ジアルキルアミノ）ベンゾフエノンの
例としては、例えば４，4′−ビス（ジメチルアミ
ノ）ベンゾフエノン、４，4′−ビス（ジエチルア
ミノ）ベンゾフエノン、４，4′−ビス（ジシクロ
ヘキシルアミノ）ベンゾフエノン、４，4′−ビス
（ジヒドロキシエチルアミノ）ベンゾフエノン等
がある。これらのうちで４，4′−ビス（ジメチル
アミノ）ベンゾフエノンと４，4′−ビス（ジエチ
ルアミノ）ベンゾフエノンが特に好ましい。
本発明に用いる光増感色素として、ベンザルア
セトフエノン類、ピリリウム塩類、チオピリリウ
ム塩類、シアニン系染料、メロシアニン系染料、
キサンテン系染料、チアゾール系染料等の可視光
線を吸収する化合物である。
上記ベンザルアセトフエノン類の例としては、
ベンザルアセトフエノン、ベンザルメチルアセト
フエノン、メチルベンザルメチルアセトフエノ
ン、メチルベンザルエチルアセトフエノン、メチ
ルベンザルメトキシアセトフエノン、エチルベン
ザルブトキシアセトフエノン、メトキシベンザル
メトキシアセトフエノン、メトキシベンザルエチ
ルアセトフエノン、エチルベンザルフエノキシア
セトフエノン、ブチルベンザルメトキシアセトフ
エノン、ベンザルジメチルアミノアセトフエノ
ン、ジメチルアミノベンザルジメチルアミノアセ
トフエノン、メトキシベンザルジメチルアミノア
セトフエノン、アミノベンザルアミノアセトフエ
ノン、ジメチルアミノベンザルメトキシアセトフ
エノン、ベンザルジエチルアミノアセトフエノ
ン、ジメチルアミノベンザルアセトフエノン、ブ
トキシベンザルジメチルアミノアセトフエノン、
クロルベンザルメチルアセトフエノン、メチルベ
ンザルニトロアセトフエノン、ベンザルニトロア
セトフエノン、ニトロベンザルアセトフエノン等
がある。
ピリリウム塩類及びチオピリリウム塩類の例と
しては、２，４，６−トリフエニルピリリウムパ
ークロレート、４−（４−メトキシフエニル）−
２，６−ジフエニルピリリウムパークロレート、
２，６−ビス（４−メトキシフエニル）−４−フ
エニルピリリウムパークロレート、４−（４−ブ
トキシフエニル）−２，６−ジフエニルピリリウ
ムパークロレート、４−（４−アミロキシフエニ
ル）−２，６−ビス（４−エチルフエニル）ピリ
リウムパークロレート、２，４，６−トリフエニ
ルピリリウムフルオロボレート、２，４，６−ト
リフエニルチアピリリウムパークロレート、２，
６−ビス（４−エチルフエニル）−４−（４−アミ
ルオキシフエニル）チオピリリウムパークロレー
ト、４−（４−メトキシフエニル）−２，６−ジフ
エニルチオピリリウムパークロレート、６−（４
−エトキシフエニル）−２，４−ジフエニルチオ
ピリリウムパークロレート、２，４，６−トリ
（４−メトキシフエニル）チオピリリウムパーク
ロレート、４−（４−アミロキシフエニル）−２，
６−ビス（４−エチルフエニル）チオピリリウム
パークロレート、２，４，６−トリフエニルチオ
ピリリウムフルオロボレート、２，４，６−トリ
フエニルチオピリリウムサルフエート、４−（４
−メトキシフエニル）−２，６−ジフエニルチオ
ピリリウムフルオロボレート、２−（４−アミロ
キシフエニル）−４，６−ジフエニルチオピリリ
ウムフルオロボレート、４−（４−アミロキシフ
エニル）−２，６−ビス（４−メトキシフエニル）
チオピリリウムパークロレート、４−（４−メト
キシフエニル）−２，６−ビス（４−エチルフエ
ニル）チオピリリウムパークロレート、４−（２，
４−ジクロロフエニル）−２，６−ジフエニルピ
リリウムパークロレート、２−（３，４−ジクロ
ロフエニル）−４−（４−メトキシフエニル）−６
−フエニルピリリウムパークロレート、４−（４
−アミロキシフエニル）−２，６−ビス（４−エ
チルフエニル）ピリリウムパークロレート、２，
６−ビス（４−エチルフエニル）−４−（４−メト
キシフエニル）ピリリウムフルオロボレート、４
−（４−ジメチルアミノフエニル）−２，６−ジフ
エニルピリリウムパークロレート、２，６−ビス
（４−エチルフエニル）−４−メトキシフエニルチ
オピリリウムフルオロボレート、４−（４−ブト
キシフエニル）−２，６−ビス（４−ジメトキシ
フエニル）チオピリリウムフルオロボレート、
２，６−ビス（４−メトキシフエニル）−４−フ
エニルチオピリリウムパークロレート、４−（２，
４−ジクロロフエニル）−２，６−ジフエニルチ
オピリリウムパークロレート、２，６−ビス（４
−アミロキシフエニル）−４−（４−メトキシフエ
ニル）チオピリリウムパークロレート等がある。
また、シアニン系染料、メロシアニン系染料、
キサンテン系染料およびチアゾール系染料の例と
しては下記のものが該当する。
Ａ：シアニン系染料
Photosensitizing dyes [benzalacetophenones, pyrylium salts,
One or more selected from thiopyrylium salts, cyanine dyes, merocyanine dyes, xanthene dyes, and thiazole dyes] Examples of the benzophenone group-containing polyhydric peroxyester represented by the general formula (I) used in the present invention are: , for example, 3,3',4,4'-tetra-(t-
butylperoxycarbonyl)benzophenone,
3,3',4,4'-tetra-(t-amylperoxycarbonyl)benzophenone, 3,3',4,
4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-octylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(cumylperoxycarbonyl) benzophenone, 3,3',4,
Examples include 4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone, and these may be used alone or in combination of two or more. 4 represented by the general formula () used in the present invention,
Examples of 4'-bis(dialkylamino)benzophenone include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, Examples include 4,4'-bis(dihydroxyethylamino)benzophenone. Among these, 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone are particularly preferred. Photosensitizing dyes used in the present invention include benzalacetophenones, pyrylium salts, thiopyrylium salts, cyanine dyes, merocyanine dyes,
Compounds that absorb visible light, such as xanthene dyes and thiazole dyes. Examples of the above benzalacetophenones include:
Benzalacetophenone, benzalmethylacetophenone, methylbenzalmethylacetophenone, methylbenzalethylacetophenone, methylbenzalmethoxyacetophenone, ethylbenzalbutoxyacetophenone, methoxybenzalmethoxyaceto Phenone, methoxybenzalethyl acetophenone, ethylbenzalphenoxyacetophenone, butylbenzalmethoxyacetophenone, benzaldimethylaminoacetophenone, dimethylaminobenzaldimethylaminoacetophenone, methoxybenzaldimethylamino Acetophenone, aminobenzalaminoacetophenone, dimethylaminobenzalmethoxyacetophenone, benzaldiethylaminoacetophenone, dimethylaminobenzalacetophenone, butoxybenzaldimethylaminoacetophenone,
Examples include chlorobenzalmethylacetophenone, methylbenzalnitroacetophenone, benzalnitroacetophenone, and nitrobenzalacetophenone. Examples of pyrylium salts and thiopyrylium salts include 2,4,6-triphenylpyrylium perchlorate, 4-(4-methoxyphenyl)-
2,6-diphenylpyrylium perchlorate,
2,6-bis(4-methoxyphenyl)-4-phenylpyrylium perchlorate, 4-(4-butoxyphenyl)-2,6-diphenylpyrylium perchlorate, 4-(4-amyloxyphenyl) )-2,6-bis(4-ethylphenyl)pyrylium perchlorate, 2,4,6-triphenylpyrylium fluoroborate, 2,4,6-triphenylthiapyrylium perchlorate, 2,
6-bis(4-ethylphenyl)-4-(4-amyloxyphenyl)thiopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-diphenylthiopyrylium perchlorate, 6-( 4
-ethoxyphenyl)-2,4-diphenylthiopyrylium perchlorate, 2,4,6-tri(4-methoxyphenyl)thiopyrylium perchlorate, 4-(4-amyloxyphenyl)-2 ，
6-bis(4-ethylphenyl)thiopyrylium perchlorate, 2,4,6-triphenylthiopyrylium fluoroborate, 2,4,6-triphenylthiopyrylium sulfate, 4-(4
-methoxyphenyl)-2,6-diphenylthiopyrylium fluoroborate, 2-(4-amyloxyphenyl)-4,6-diphenylthiopyrylium fluoroborate, 4-(4-amyloxyphenyl) )-2,6-bis(4-methoxyphenyl)
Thiopyrylium perchlorate, 4-(4-methoxyphenyl)-2,6-bis(4-ethylphenyl)thiopyrylium perchlorate, 4-(2,
4-dichlorophenyl)-2,6-diphenylpyrylium perchlorate, 2-(3,4-dichlorophenyl)-4-(4-methoxyphenyl)-6
-Phenylpyrylium perchlorate, 4-(4
-amyloxyphenyl)-2,6-bis(4-ethylphenyl)pyrylium perchlorate, 2,
6-bis(4-ethylphenyl)-4-(4-methoxyphenyl)pyrylium fluoroborate, 4
-(4-dimethylaminophenyl)-2,6-diphenylpyrylium perchlorate, 2,6-bis(4-ethylphenyl)-4-methoxyphenylthiopyrylium fluoroborate, 4-(4-butoxyphenyl) -2,6-bis(4-dimethoxyphenyl)thiopyrylium fluoroborate,
2,6-bis(4-methoxyphenyl)-4-phenylthiopyrylium perchlorate, 4-(2,
4-dichlorophenyl)-2,6-diphenylthiopyrylium perchlorate, 2,6-bis(4
-amyloxyphenyl)-4-(4-methoxyphenyl)thiopyrylium perchlorate and the like. In addition, cyanine dyes, merocyanine dyes,
Examples of xanthene dyes and thiazole dyes include the following. A: Cyanine dye
【化】
〔R1は水素原子、炭素数１〜６のアルキル基、
アリール基、アルコキシ基またはジアルキルアミ
ノ基を表わし、R2は水素原子、炭素数１〜10の
アルキル基またはアリール基を表わし、Ｘはハロ
ゲン原子を表わし、ｎは１〜３までの整数を表わ
す。Ｙは[R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
It represents an aryl group, an alkoxy group or a dialkylamino group, R2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, X represents a halogen atom, and n represents an integer from 1 to 3. Y is
【式】【formula】
【式】または[expression] or
【式】を表わす。〕Represents [formula]. ]
【化】
〔R1，R2は水素原子、炭素数１〜10のアルキル
基またはアリール基を表わし、Ｘはハロゲン原子
を表わし、[R 1 and R 2 represent a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, X represents a halogen atom,
【式】は【ceremony
【式】【formula】
【式】 または【formula】 or
【式】を表わす。Represents [formula].
【化】
〔R1は水素原子、炭素数１〜６のアルキル基、
アリール基、またはアルコキシ基を表わし、R2
は水素原子、炭素数１〜10のアルキル基またはア
リール基を表わし、Ｘはハロゲン原子を表わし、
ｎは１〜３までの整数を表わす。〕
Ｙは[R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Represents an aryl group or an alkoxy group, R 2
represents a hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms, X represents a halogen atom,
n represents an integer from 1 to 3. ] Y is
【式】、【formula】,
【式】、【formula】,
【式】 または【formula】 or
【式】を表わす。 Ｂ：メロシアニン系染料Represents [formula]. B: Merocyanine dye
【化】
〔R1，R2，R3は水素原子、炭素数１〜６までの
アルキル基またはアリール基を表わす。〕[R 1 , R 2 and R 3 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group. ]
【化】
〔R1，R2は水素原子または炭素数１〜４のアル
キル基を表わし、ｎは１〜３の整数を表わし、Ｘ
は[Chemical formula] [R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents an integer of 1 to 3, and
teeth
【式】【formula】
【式】【formula】
【式】、【formula】,
【式】【formula】
【式】【formula】
【式】または[expression] or
【式】を表わす。〕Represents [formula]. ]
Ｃ：キサンテン系染料 C: Xanthene dye
【化】
〔Ｘは水素原子またはアルカリ金属、Ｙは水素原
子またはハロゲン原子を表わす。〕[X represents a hydrogen atom or an alkali metal; Y represents a hydrogen atom or a halogen atom. ]
【化】
〔R1，R2，R3，R4は水素原子、炭素数１〜６の
アルキル基またはアリール基を表わし、Ｘはハロ
ゲン原子を表わし、Ｙは水素原子またはアルカリ
金属を表わす。
Ｄ：チアゾール系染料[R 1 , R 2 , R 3 , R 4 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, X represents a halogen atom, and Y represents a hydrogen atom or an alkali metal. D: Thiazole dye
【化】
〔Ｒは水素原子、炭素数１〜６のアルキル基、ア
リール基、アルコキシ基、ニトロ基またはアミノ
基を表わし、Ｘはアミノ基またはフエニルアミノ
基を表わす。〕[R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group, a nitro group, or an amino group, and X represents an amino group or a phenylamino group. ]
本発明の光重合開始剤組成物は、前記の(A)ベン
ゾフエノン基含有多価ペルオキシエステルと(B)
４，4′−ビス（ジアルキルアミノ）ベンゾフエノ
ンと(C)光増感色素とからなるものであり、(A)と(B)
両者の配合割合は、重量比で(A)：(B)が１：100〜
100：１であり、さらに好ましくは１：10〜30：
１である。
また、(A)と(C)両者の配合割合は、重量比で１：
100〜100：１であり、さらに好ましくは１：30〜
20：１である。
この範囲外では優れた光重合開始性能が得られ
ない。
本発明の光重合開始剤組成物は殆ど全ての不飽
和化合物、特に不飽和単量体を光重合することが
できる。すなわち、不飽和化合物とは重合性のエ
チレン系不飽和結合を有するモノマー、オリゴマ
ーまたはポリマーであり、例えばアクリル酸、メ
タクリル酸、イタコン酸、マレイン酸及びその無
水物、フマル酸等の不飽和酸や（メタ）アクリル
酸メチル（メタ）アクリル酸エチル、（メタ）ア
クリル酸ブチル、（メタ）アクリル酸グリシジル、
（メタ）アクリル酸ヒドロキシエチル、マレイン
酸ジメチル、マレイン酸ジエチル、フマル酸ジメ
チル、ペンタエリスリトールトリ（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、エチレングリコールジ（メタ）アク
リレート、プロピレングリコールジ（メタ）アク
リレート等の不飽和酸エステル化合物、スチレ
ン、アクリルアミド、アクリロニトリル、Ｎ−ビ
ニルピロリドン、酢酸ビニル等の単量体、さらに
不飽和ポリエステル、不飽和ポリエーテル、不飽
和ポリウレタンやエポキシ（メタ）アクリレート
化合物等がある。
本発明の光重合開始剤組成物は、これらの不飽
和化合物の単独かもしくは二種以上の混合物に添
加し、必要に応じてバインダー樹脂や適当な希釈
溶媒を加えて、光重合性の感光液として使用す
る。
その際、光重合開始剤組成物の添加量は前記不
飽和化合物100重量部に対して0.1〜30重量部、好
ましくは0.5〜20重量部である。
バインダー樹脂は、刷版材やフオトレジストな
どの塗膜形成助剤として物性向上の目的で用いる
ものであり、不飽和化合物100重量部に対して通
常50〜500重量部程度使用するのが好ましい。バ
インダー樹脂として例えば、（メタ）アクリル酸
エステル系の樹脂、ビニルピロリドン系の樹脂、
ビニルアルコール系の樹脂等がある。
また適当な希釈溶媒とは本発明の光重合開始剤
組成物及び不飽和化合物を溶解するものならすべ
て使用でき、例えば、水、メタノール、エタノー
ル、イソプロパノール、ブタノール、アセトン、
メチルエチルケトン、メチルイソブチルケトン、
トルエン、キシレン、酢酸エチル、酢酸ブチル、
メチルセロソルブ、テトラヒドロフラン、ジオキ
サン、ジクロルメタン、クロロホルム、四塩化炭
素、トリクロルエチレン、ジメチルホルムアミ
ド、ジメチルスルホキシド等がある。
このようにして得られた光重合性の感光液は紫
外線、可視光線またはレーザー光線のごとき活性
光線を照射することにより光重合反応が達成され
る。
〔発明の効果〕
本発明の光重合開始剤組成物は、ベンゾフエノ
ン基含有多価ペルオキシエステル、４，4′−ビス
（ジアルキルアミノ）ベンゾフエノン及び光増感
色素の３成分を組み合せて用いているため、従来
の光重合開始剤よりも著しく高感度であり、ま
た、得られた画像膜も強靭であることから、可視
光線でも十分に感光しかつ実用性のある画像膜を
得ることができ、作業性及び経済性の点で優れて
いる。
本発明の光重合開始剤組成物は、通常の光重合
反応に使用できるほか、光硬化型の塗料、印刷イ
ンキ、接着剤、印刷版材、フオトレジスト等の多
方面に適用することが可能である。
〔実施例〕
以下実施例及び比較例によつて本発明をさらに
詳細に説明する。例中の部は重量部を示す。
実施例 １〜10
バインダー樹脂としてメタクリル酸メチルとメ
タクリル酸との共重合体（分子量80000、酸価65）
100部と不飽和化合物としてペンタエリスリトー
ルトリアクリレート（新中村化学(株)製：Ａ−
TMM−3L）100部に表−１に示す本発明の光重
合開始剤組成物を表−１の割合で添加し、さらに
これを1000部のメチルセロソルブ溶媒に均一に溶
解して感光液を得た。
これらの感光液を陽極酸化処理したアルミニウ
ム板上に乾燥塗膜厚が1μmとなるようにスピンナ
ーを用いて塗布し、乾燥させたものをそれぞれ感
光試験用試料とした。
（感光試験）
●Ａ法（紫外線による光硬化）
上記の試料を用いて、2KW−超高圧水銀灯
を用い真空下で65cmの距離から積算光量計（(株)
オーク製作所製：UV−330AP−１）にて
10mJ／cm2の露光量になるように照射を行なつ
た。
●Ｂ法（可視光線による光硬化）
前記の試料に色ガラスフイルター（東芝硝子
(株)製Ｙ−47：470nm以下の光をカツト）を重ね
たのち、Ａ法と同じ光源で露光量が10mJ／cm2
になるように照射した。
光硬化膜の評価は、下記に示すゲル分率及び耐
溶性試験によつて行なつた。
●ゲル分率は下記のようにして求めた。
ゲル分率（％）＝W2−W0／W1−W0×100
W0：試料中のアルミニウム板の重量
W1：試料の重量
W2：試料を露光し、現像後に乾燥した重量
なお現像は、富士写真フイルム(株)製の
DN−3Cと水との重量が１：１になるよ
う調製した現像液を用いて25℃で５分間
浸漬した後、水洗した。
ゲル分率の値が大きいものは、高感度であり光
重合反応により十分硬化していることを示す。
●耐溶剤性試験：２枚重ね合せたガーゼにキシロ
ールを十分含ませたもので、光硬化膜の上を10
回こすり、この膜に膨潤や溶解などの異常が生
じないかを観察した。
結果を表−１に示す。
比較例 １〜４
ベンゾフエノン基含有多価ペルオキシエステ
ル、４，4′−ビス（ジアルキルアミノ）ベンゾフ
エノン各々単独と光増感色素との組合せなど表−
１に示す光重合開始剤を用いて実施例と同様な方
法により試料を作成し、露光後、ゲル分率及び耐
溶剤性試験を行なつた。結果を表−１に示す。
比較例 ５〜６
表−２に示す光重合開始剤を用いて、実施例と
同様な方法により試料を作成し、同様に試験を行
なつた。結果を表−２に示す。
表−１及び表−２の結果から明らかなように、
本発明のものはいずれも比較例のものより、ゲル
分率が大きく、耐溶剤性も優れており、特に可視
光線を使用した場合も十分な感度と光硬化膜強度
を有していることが認められる。
The photopolymerization initiator composition of the present invention comprises the above-mentioned (A) benzophenone group-containing polyhydric peroxyester and (B)
It consists of 4,4'-bis(dialkylamino)benzophenone and (C) a photosensitizing dye, and (A) and (B)
The mixing ratio of both (A):(B) is 1:100 to 1:100 by weight.
100:1, more preferably 1:10-30:
It is 1. Also, the blending ratio of both (A) and (C) is 1:
100 to 100:1, more preferably 1:30 to
The ratio is 20:1. Outside this range, excellent photopolymerization initiation performance cannot be obtained. The photoinitiator composition of the present invention can photopolymerize almost all unsaturated compounds, especially unsaturated monomers. That is, unsaturated compounds are monomers, oligomers, or polymers having polymerizable ethylenically unsaturated bonds, such as unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and its anhydrides, and fumaric acid. Methyl (meth)acrylate (meth)ethyl acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate,
Hydroxyethyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate ) Unsaturated acid ester compounds such as acrylate, monomers such as styrene, acrylamide, acrylonitrile, N-vinylpyrrolidone, and vinyl acetate, as well as unsaturated polyesters, unsaturated polyethers, unsaturated polyurethanes, epoxy (meth)acrylate compounds, etc. There is. The photopolymerization initiator composition of the present invention is added to these unsaturated compounds alone or in a mixture of two or more, and if necessary, a binder resin or a suitable diluting solvent is added to prepare a photopolymerizable photosensitive liquid. Use as. At that time, the amount of the photopolymerization initiator composition added is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the unsaturated compound. The binder resin is used as a coating film forming aid for printing plate materials, photoresists, etc. for the purpose of improving physical properties, and is preferably used in an amount of usually about 50 to 500 parts by weight per 100 parts by weight of the unsaturated compound. Examples of the binder resin include (meth)acrylic acid ester resin, vinylpyrrolidone resin,
There are vinyl alcohol-based resins, etc. In addition, any appropriate diluting solvent can be used as long as it dissolves the photopolymerization initiator composition and unsaturated compound of the present invention, such as water, methanol, ethanol, isopropanol, butanol, acetone,
Methyl ethyl ketone, methyl isobutyl ketone,
Toluene, xylene, ethyl acetate, butyl acetate,
Examples include methyl cellosolve, tetrahydrofuran, dioxane, dichloromethane, chloroform, carbon tetrachloride, trichlorethylene, dimethylformamide, and dimethyl sulfoxide. The photopolymerizable photosensitive liquid thus obtained undergoes a photopolymerization reaction by irradiating it with actinic light such as ultraviolet rays, visible light, or laser light. [Effects of the Invention] The photopolymerization initiator composition of the present invention uses a combination of three components: a benzophenone group-containing polyvalent peroxyester, 4,4'-bis(dialkylamino)benzophenone, and a photosensitizing dye. , has significantly higher sensitivity than conventional photopolymerization initiators, and the resulting image film is also tough, making it possible to obtain a practical image film that is sufficiently sensitive to visible light, making it easy to work with. It is superior in terms of performance and economy. The photopolymerization initiator composition of the present invention can be used in ordinary photopolymerization reactions, and can also be applied to a variety of applications such as photocurable paints, printing inks, adhesives, printing plate materials, and photoresists. be. [Examples] The present invention will be explained in more detail below using Examples and Comparative Examples. Parts in the examples indicate parts by weight. Examples 1 to 10 Copolymer of methyl methacrylate and methacrylic acid as binder resin (molecular weight 80000, acid value 65)
100 parts and pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.: A-
The photopolymerization initiator composition of the present invention shown in Table 1 was added to 100 parts of TMM-3L) in the proportions shown in Table 1, and this was further uniformly dissolved in 1000 parts of methyl cellosolve solvent to obtain a photosensitive liquid. Ta. These photosensitive solutions were applied onto an anodized aluminum plate using a spinner so that the dry film thickness was 1 μm, and the dried products were used as samples for photosensitive testing. (Photosensitivity test) ●Method A (photocuring with ultraviolet rays) Using the above sample, use an integrated light meter (Co., Ltd.) from a distance of 65cm under vacuum using a 2KW ultra-high pressure mercury lamp.
Manufactured by Oak Seisakusho: UV-330AP-1)
Irradiation was performed at an exposure dose of 10 mJ/cm 2 . ●Method B (photocuring using visible light) A colored glass filter (Toshiba Glass Co., Ltd.) was applied to the above sample.
Y-47 (manufactured by Co., Ltd.: cuts light of 470 nm or less), and then the exposure amount is 10 mJ/cm 2 using the same light source as method A.
It was irradiated so that The photocured film was evaluated by the gel fraction and solubility test shown below. ●The gel fraction was determined as follows. Gel fraction (%) = W 2 - W 0 / W 1 - W 0 × 100 W 0 : Weight of aluminum plate in the sample W 1 : Weight of the sample W 2 : Weight of the sample exposed and dried after development. The developing process is made by Fuji Photo Film Co., Ltd.
After being immersed for 5 minutes at 25° C. in a developer prepared so that the weight ratio of DN-3C and water was 1:1, the sample was washed with water. A high gel fraction value indicates high sensitivity and sufficient curing by photopolymerization reaction. ●Solvent resistance test: Two layers of gauze soaked in xylol are used to coat the top of the photocured film for 10 minutes.
The membrane was rubbed several times and observed whether any abnormalities such as swelling or dissolution occurred in the membrane. The results are shown in Table-1. Comparative Examples 1 to 4 Table of benzophenone group-containing polyhydric peroxyesters, 4,4'-bis(dialkylamino)benzophenones, each alone and combinations with photosensitizing dyes, etc.
Samples were prepared in the same manner as in Examples using the photopolymerization initiator shown in 1, and after exposure, gel fraction and solvent resistance tests were conducted. The results are shown in Table-1. Comparative Examples 5 and 6 Samples were prepared in the same manner as in the examples using the photopolymerization initiators shown in Table 2, and tested in the same manner. The results are shown in Table-2. As is clear from the results in Tables 1 and 2,
All of the products of the present invention have a higher gel fraction and better solvent resistance than those of the comparative examples, and in particular have sufficient sensitivity and photocured film strength even when using visible light. Is recognized.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
基含有多価ペルオキシエステル、一般式（）で
示される４，4′−ビス（ジアルキルアミノ）ベン
ゾフエノン及び下記に示す光増感色素からなる不
飽和単量体重合用光重合開始剤組成物。 【化】 〔式中、R1およびR1′はそれぞれ炭素数４から８
の第３アルキル基または炭素数９から12の第３ア
ラルキル基、R2およびR2′はそれぞれ水素原子ま
たは炭素数４から８の第３アルコキシ基または炭
素数９から12の第３アラルキルオキシ基を表わ
す。〕 【式】 〔式中Ｒは炭素数１から６のアルキル基、シクロ
アルキル基またはヒドロキシアルキル基を表わ
す。〕 光増感色素 〔ベンザルアセトフエノン類、ピリリウム塩類、
チオピリリウム塩類、シアニン系染料、メロシア
ニン系染料、キサンテン系染料、チアゾール系染
料から選ばれる１種以上のもの〕[Scope of Claims] 1. A benzophenone group-containing polyhydric peroxyester represented by the following general formula (I), a 4,4'-bis(dialkylamino)benzophenone represented by the general formula (), and a photosensitizing dye shown below. A photopolymerization initiator composition for polymerizing unsaturated monomers. [In the formula, R 1 and R 1 ' each have 4 to 8 carbon atoms]
a tertiary alkyl group or a tertiary aralkyl group having 9 to 12 carbon atoms; R 2 and R 2 ' are each a hydrogen atom, a tertiary alkoxy group having 4 to 8 carbon atoms, or a tertiary aralkyloxy group having 9 to 12 carbon atoms; represents. [Formula] [In the formula, R represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, or a hydroxyalkyl group. ] Photosensitizing dyes [benzalacetophenones, pyrylium salts,
One or more selected from thiopyrylium salts, cyanine dyes, merocyanine dyes, xanthene dyes, and thiazole dyes]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22017985A JPS6281403A (en) | 1985-10-04 | 1985-10-04 | Photopolymerization initiator composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22017985A JPS6281403A (en) | 1985-10-04 | 1985-10-04 | Photopolymerization initiator composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6281403A JPS6281403A (en) | 1987-04-14 |
| JPH0583562B2 true JPH0583562B2 (en) | 1993-11-26 |
Family
ID=16747119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22017985A Granted JPS6281403A (en) | 1985-10-04 | 1985-10-04 | Photopolymerization initiator composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6281403A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01303430A (en) * | 1988-05-31 | 1989-12-07 | Toyobo Co Ltd | Photopolymerizable composition |
| JPH022562A (en) * | 1988-06-13 | 1990-01-08 | Toyobo Co Ltd | Photopolymerizable composition |
| JPH087437B2 (en) * | 1988-08-19 | 1996-01-29 | 富士写真フイルム株式会社 | Photopolymerizable composition |
| JP2751453B2 (en) * | 1989-09-05 | 1998-05-18 | 日本油脂株式会社 | Photopolymerization initiator |
| AU6140798A (en) * | 1997-02-04 | 1998-08-25 | John Gabriel Santobianco | Aminobenzophenones and photopolymerizable compositions including same |
| US6479706B1 (en) | 1997-02-04 | 2002-11-12 | Albemarle Corporation | Aminobenzophenones and photopolymerizable compositions including the same |
| JP4874147B2 (en) * | 2007-03-29 | 2012-02-15 | Ｉｄｅｃ株式会社 | Electrical equipment mounting structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6035725A (en) * | 1983-08-09 | 1985-02-23 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| JPS6076503A (en) * | 1983-10-03 | 1985-05-01 | Nippon Oil & Fats Co Ltd | High-sensitivity photo-reaction initiator composition |
-
1985
- 1985-10-04 JP JP22017985A patent/JPS6281403A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6035725A (en) * | 1983-08-09 | 1985-02-23 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| JPS6076503A (en) * | 1983-10-03 | 1985-05-01 | Nippon Oil & Fats Co Ltd | High-sensitivity photo-reaction initiator composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6281403A (en) | 1987-04-14 |
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