JPH04106548A - Photopolymerizable composition - Google Patents
Photopolymerizable compositionInfo
- Publication number
- JPH04106548A JPH04106548A JP22475190A JP22475190A JPH04106548A JP H04106548 A JPH04106548 A JP H04106548A JP 22475190 A JP22475190 A JP 22475190A JP 22475190 A JP22475190 A JP 22475190A JP H04106548 A JPH04106548 A JP H04106548A
- Authority
- JP
- Japan
- Prior art keywords
- ring
- photopolymn
- polymn
- initiator system
- triazine
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 29
- -1 triazine compound Chemical class 0.000 claims description 16
- 230000000977 initiatory effect Effects 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 238000012644 addition polymerization Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 24
- 239000003999 initiator Substances 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 6
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000975 dye Substances 0.000 description 17
- 230000003595 spectral effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 150000001735 carboxylic acids Chemical class 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- 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 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- RCUOAHPSDFRHOR-UHFFFAOYSA-N 2-phenylsulfanyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(SC=2C=CC=CC=2)=N1 RCUOAHPSDFRHOR-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000010147 laser engraving Methods 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- JMMVHMOAIMOMOF-UHFFFAOYSA-N (4-prop-2-enoyloxyphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=C(OC(=O)C=C)C=C1 JMMVHMOAIMOMOF-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MPNIGZBDAMWHSX-UHFFFAOYSA-N 2-(4-methylphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(C)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MPNIGZBDAMWHSX-UHFFFAOYSA-N 0.000 description 1
- YIXVNSVLWYQVSM-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl octanoate Chemical compound CCCCCCCC(=O)OCCOCCOCCO YIXVNSVLWYQVSM-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- QAGHEHQMRFEQMB-UHFFFAOYSA-N 2-ethylidenepropanedioic acid Chemical compound CC=C(C(O)=O)C(O)=O QAGHEHQMRFEQMB-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DOSGQNSHFPTAOA-UHFFFAOYSA-N 2-propyl-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CCCC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DOSGQNSHFPTAOA-UHFFFAOYSA-N 0.000 description 1
- VRBUPQGTJAXZAE-UHFFFAOYSA-N 2-propylidenebutanedioic acid Chemical compound CCC=C(C(O)=O)CC(O)=O VRBUPQGTJAXZAE-UHFFFAOYSA-N 0.000 description 1
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical class O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 206010034960 Photophobia Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 241000190020 Zelkova serrata Species 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- HSZUHSXXAOWGQY-UHFFFAOYSA-N [2-methyl-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(C)(COC(=O)C=C)COC(=O)C=C HSZUHSXXAOWGQY-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- MDMKOESKPAVFJF-UHFFFAOYSA-N [4-(2-methylprop-2-enoyloxy)phenyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(OC(=O)C(C)=C)C=C1 MDMKOESKPAVFJF-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AMEDKBHURXXSQO-UHFFFAOYSA-N azonous acid Chemical group ONO AMEDKBHURXXSQO-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- PIPBVABVQJZSAB-UHFFFAOYSA-N bis(ethenyl) benzene-1,2-dicarboxylate Chemical compound C=COC(=O)C1=CC=CC=C1C(=O)OC=C PIPBVABVQJZSAB-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- IQIJRJNHZYUQSD-UHFFFAOYSA-N ethenyl(phenyl)diazene Chemical compound C=CN=NC1=CC=CC=C1 IQIJRJNHZYUQSD-UHFFFAOYSA-N 0.000 description 1
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 235000015073 liquid stocks Nutrition 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
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229940035339 tri-chlor Drugs 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は光重合性組成物に関するものである。[Detailed description of the invention] [Industrial application field] The present invention relates to photopolymerizable compositions.
特に、長波長領域の光線に対し高感度を示す改良された
光重合性組成物に関するものである。In particular, it relates to improved photopolymerizable compositions that exhibit high sensitivity to light in the long wavelength region.
従来、光重合系を利用した画像形成法は多数知られてい
る。例えば、付加重合可能なエチレン性二重結合を含む
化合物と光重合開始剤、さらに所望により用いられる有
機高分子結合剤等からなる光重合性組成物を調製し、こ
の光重合性組成物を支持体上に塗布して光重合性組成物
の層を設けた感光材料を作成し、所望画像を像露光して
露光部分を重合硬化させ、未露光部分を溶解除去するこ
とにより硬化レリーフ画像を形成する方法、光による接
着強度の変化を惹起させた後、支持体を剥離することに
より画像を形成する方法、その他光重合性組成物層の光
によるトナー耐着性の変化を利用した画像作成方法等が
ある。これらの方法に応用される光重合性組成物の光重
合開始剤とじては従来、ベンゾイン、ベンゾインアルキ
ルエーテル、ベンジルケタール、ベンゾフェノン、アン
トラキノン、ベンジル、あるいはミヒラーケトンなどが
用いられてきた。Conventionally, many image forming methods using photopolymerization systems are known. For example, a photopolymerizable composition consisting of a compound containing an ethylenic double bond capable of addition polymerization, a photopolymerization initiator, and an organic polymer binder used if desired is prepared, and this photopolymerizable composition is supported. A photosensitive material is prepared by applying a layer of a photopolymerizable composition onto the body, image-wise exposing the desired image, polymerizing and curing the exposed areas, and dissolving and removing the unexposed areas to form a cured relief image. A method of forming an image by inducing a change in adhesive strength due to light and then peeling off the support, and other methods of creating an image using a change in toner adhesion resistance of a photopolymerizable composition layer due to light. etc. Conventionally, benzoin, benzoin alkyl ether, benzyl ketal, benzophenone, anthraquinone, benzyl, Michler's ketone, and the like have been used as photopolymerization initiators for photopolymerizable compositions applied to these methods.
これらの光重合開始剤は400nm以下の紫外線領域を
中心とした短波長の光線に対し感応し得る機能を有して
いた。These photopolymerization initiators had a function of being sensitive to short wavelength light mainly in the ultraviolet region of 400 nm or less.
近年、画像形成技術の発展に伴い可視領域の光線に対し
高度な感応性を有するフォトポリマーが強く要請される
欅になってきた0例えば、アルゴンイオンレーザ−の4
88nmの発振ビームを用いたレーザー製版方式は将来
有望視される技法の一つと考えられており、これに対応
して500nm前後迄感度域を拡張した光重合開始系が
多数提案されている。更に、最近に至っては、600n
■を超える長波長光線に対応した光開始系の研究が活発
化してきた。それらの応用技術の一つは、He−Neレ
ーザーや半導体レーザーを用いたレーザー製版であり、
他の一つは光重合系を用いたフルカラー画像の複製技術
である。In recent years, with the development of image forming technology, there has been a strong demand for photopolymers that are highly sensitive to light in the visible region.For example, argon ion laser 4
A laser engraving method using an 88 nm oscillation beam is considered to be one of the promising techniques in the future, and in response to this, many photopolymerization initiation systems with a sensitivity range extended to around 500 nm have been proposed. Furthermore, recently, 600n
Research on photoinitiation systems that are compatible with long-wavelength light exceeding (2) has become active. One of these applied technologies is laser plate making using He-Ne laser or semiconductor laser.
The other is a full-color image reproduction technology using a photopolymerization system.
後者に関しては、古くは特公昭46−41346号明細
書に記載されており、同明細書によれば、青、緑、赤色
光に対応した各光重合開始剤とカラーカプラーを含有す
る小滴状光重合性組成物をゼラチン膜中に各々分散した
ものを三層塗布し、感光層を形成する。次いでカラー画
像光線を照射して発色現像液で処理すれば未硬化部分が
発色しフルカラー画像が得られるという技術を開示して
いる。また、この思想をマイクロカプセルを用いた感圧
発色の手法と組合せた応用技術も提案されている0例え
ば、特開昭62−143044号明細書にその記載が見
られる。同明細書によれば、各三色光線に感応する光重
合開始剤と各ロイコ色素を含む光重合性組成物をマイク
ロカプセルに充填しシート上に塗布する。これをカラー
画像光線に露出した後、未硬化部分のカプセルを発色シ
ート上に加圧破壊、転写して各黄、マゼンタ、シアンの
発色をうながし、フルカラー画像を得ている。Regarding the latter, it was previously described in the specification of Japanese Patent Publication No. 46-41346, and according to the specification, a droplet-shaped product containing each photopolymerization initiator and color coupler corresponding to blue, green, and red light. Three layers of photopolymerizable compositions each dispersed in a gelatin film are applied to form a photosensitive layer. The patent discloses a technique in which the uncured portions are then irradiated with color image light and treated with a color developing solution to develop color and a full color image is obtained. Further, an applied technique combining this idea with a pressure-sensitive coloring method using microcapsules has been proposed. For example, the description can be found in Japanese Patent Application Laid-open No. 143044/1983. According to the specification, a photopolymerizable composition containing a photopolymerization initiator sensitive to each of the three color rays and each leuco dye is filled into microcapsules and applied onto a sheet. After exposing this to color image light, the uncured portions of the capsules are pressure-broken and transferred onto a color-forming sheet to promote the development of yellow, magenta, and cyan colors to obtain a full-color image.
以上述べたレーザー製版やフルカラー画像の複製技法に
おいて要請される課題の一つは長波長、特に600n−
を超えた領域の光線に対する感材感度の向上であるが、
更に、光開始系の感材中における溶解安定性や特にフル
カラー複製技術においては適切な分光感度が要求される
。我々は、先に、スクアリリウム色素と特定なトリアジ
ン化合物との組合せからなる光開始系を提案したがそれ
の溶解安定性や分光感度特性は必ずしも充分では無かっ
た0本発明は、これらの問題点を改善すべ(検討を重ね
た結果なされたものである。従って、本発明の目的は、
長波長、特に600〜700n−の領域の光線に対し高
感応であり、溶解安定性に秀れ、かつ良好な分光感度特
性を具備した光開始系を提供することにある。One of the challenges required in the laser engraving and full-color image reproduction techniques described above is the long wavelength, especially 600n-
This is an improvement in the sensitivity of the sensitive material to light rays in the region exceeding
Furthermore, dissolution stability in photo-initiated sensitive materials and appropriate spectral sensitivity are required, especially in full-color reproduction technology. We previously proposed a photoinitiation system consisting of a combination of squarylium dye and a specific triazine compound, but its solubility stability and spectral sensitivity characteristics were not necessarily sufficient.The present invention solves these problems. Improvements to be made (This was made as a result of repeated studies. Therefore, the purpose of the present invention is to
The object of the present invention is to provide a photoinitiation system that is highly sensitive to long wavelength light, particularly in the 600 to 700 n- region, has excellent dissolution stability, and has good spectral sensitivity characteristics.
哉々は、これらの諸問題が特定な構造のスクアリリウム
色素とs−)リアジン化合物とを組合せた系により解決
できることを見い出した。The inventors have discovered that these problems can be solved by a system that combines a squarylium dye with a specific structure and an s-) lyazine compound.
すなわち、本発明の要旨とする所は、付加重合可能なエ
チレン性不飽和化合物と光重合開始系とから成る光重合
性組成物において、該光重合開始系が、
(a) 下記一般式〔I〕で表わされるスクアリリウ
ム色素、
〔式中、RI、Rtは各々置換基があっても良いアルキ
ル基またはアリール基、環A、環Bは置換基があっても
良いベンゼン環またはナフタリン環を示す、〕および、
(ハ)少なくとも1個のハロゲン化メチル基を有するs
−)リアジン化合物から成ることを特徴とする光重合性
組成物に存する。That is, the gist of the present invention is to provide a photopolymerizable composition comprising an ethylenically unsaturated compound capable of addition polymerization and a photopolymerization initiation system, wherein (a) the photopolymerization initiation system has the following general formula [I ] A squarylium dye represented by [wherein RI and Rt each represent an optionally substituent alkyl group or aryl group, and Ring A and Ring B represent a benzene ring or naphthalene ring that optionally have a substituent, ] and (c) s having at least one halogenated methyl group
-) A photopolymerizable composition comprising a riazine compound.
以下本発明について詳細に説明する。The present invention will be explained in detail below.
本発明の光重合性組成物において第一の必須成分として
含まれるエチレン性不飽和二重結合を少な(とも1個有
する付加重合可能な化合物(以下、「エチレン性化合物
」と略す)とは、光重合性組酸物が活性光線の照射を受
けた場合、第二の必須成分である光重合開始系の作用に
より付加重合し、硬化するようなエチレン性不飽和二重
結合を有する化合物であって、例えば前記の二重結合を
有する単量体、または、側鎖もしくは主鎖にエチレン性
不飽和二重結合を有する重合体である。なお、本発明に
おける単量体の意味するところは、所謂高分子物質に相
対する概念であって、従って、狭義の単量体以外に二量
体、三量体、オリゴマーをも包含するものである。The addition-polymerizable compound (hereinafter abbreviated as "ethylenic compound") having at least one ethylenically unsaturated double bond contained as the first essential component in the photopolymerizable composition of the present invention means: It is a compound having ethylenically unsaturated double bonds that undergoes addition polymerization and hardening due to the action of the photopolymerization initiation system, which is the second essential component, when the photopolymerizable composite acid is irradiated with actinic rays. For example, it is a monomer having the above-mentioned double bond, or a polymer having an ethylenically unsaturated double bond in the side chain or main chain.In addition, the monomer in the present invention means: It is a concept that is opposed to so-called polymeric substances, and therefore includes dimers, trimers, and oligomers in addition to monomers in the narrow sense.
エチレン性不飽和結合を存する単量体としては例えば不
飽和カルボン酸、それとモノヒドロキシ化合物とのエス
テル、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸
とのエステル、芳香族ポリヒドロキシ化合物と不飽和カ
ルボン酸とのエステル、不飽和カルボン酸と多価カルボ
ン酸および前述の脂肪族ポリヒドロキシ化合物、芳香族
ポリヒドロキシ化合物等の多価ヒドロキシ化合物とのエ
ステル化反応により得られるエステル等が挙げられる。Examples of monomers containing ethylenically unsaturated bonds include unsaturated carboxylic acids, esters of these with monohydroxy compounds, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids, and aromatic polyhydroxy compounds with unsaturated carboxylic acids. and esters obtained by esterification reactions between unsaturated carboxylic acids, polyhydric carboxylic acids, and polyhydric hydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds.
前記脂肪族ポリヒドロキシ化合物と不飽和カルボン酸と
のエステルは限定はされないが、具体例としては、エチ
レングリコールジアクリレート、トリエチレングリコー
ルジアクリレート、トリメチロールプロパントリアクリ
レート、トリメチロールエタントリアクリレート、ペン
タエリスリトールジアクリレート、ペンタエリスリトー
ルトリアクリレート、ペンタエリスリトールテトラアク
リレート、ジペンタエリスリトールテトラアクリレート
、ジペンタエリスリトールペンタアクリレート、ジペン
タエリスリトールへキサアクリレート、グリセロールア
クリレート等のアクリル酸エステル、これら例示化合物
のアクリレートをメタクリレートに代えたメタクリル酸
エステル、同様にイタコネートに代えたイタコン酸エス
テル、クロトネートに代えたクロトン酸エステルもしく
はマレエートに代えたマレイン酸エステル等がある。The ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid is not limited, but specific examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and pentaerythritol. Acrylic acid esters such as diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and methacrylates are substituted for the acrylates of these exemplary compounds. Examples include methacrylic esters, itaconic esters in place of itaconate, crotonic esters in place of crotonate, and maleic esters in place of maleate.
芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエ
ステルとしては、ハイドロキノンジアクリレート、ハイ
ドロキノンジメタクリレート、レゾルシンジアクリレー
ト、レゾルシンジメタクリレート、ピロガロールトリア
クリレート等が挙ケられる。Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
不飽和カルボン酸と多価カルボン酸及び多価ヒドロキシ
化合物とのエステル化反応により得られるエステルとし
ては必ずしも単一物では無いが代表的な具体例を挙げれ
ば、アクリル酸、フタル酸およびエチレングリコールの
縮合物、アクリル酸、マレイン酸およびジエチレングリ
コールの縮合物、メタクリル酸、テレフタル酸およびペ
ンタエリスリトールの縮合物、アクリル酸、アジピン酸
、ブタンジオールおよびグリセリンの縮合物等がある。Esters obtained by the esterification reaction of unsaturated carboxylic acids with polyhydric carboxylic acids and polyhydric hydroxy compounds are not necessarily single, but typical examples include acrylic acid, phthalic acid, and ethylene glycol. Condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin, and the like.
その信奉発明に用いられるエチレン性化合物の例として
はエチレンビスアクリルアミド等のアクリルアミド類;
フタル酸ジアリル等のアリルエステル類;ジビニルフタ
レート等のビニル基含有化合物などが有用である。Examples of ethylenic compounds used in the invention include acrylamides such as ethylenebisacrylamide;
Allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.
前記した主鎖にエチレン性不飽和結合を有する重合体は
、例えば、不飽和二価カルボン酸とジヒドロキシ化合物
との重縮合反応により得られるポリエステル、不飽和二
価カルボン酸とジアミンとの重縮合反応により得られる
ポリアミド等がある。The aforementioned polymers having an ethylenically unsaturated bond in the main chain include, for example, polyesters obtained by a polycondensation reaction between an unsaturated dicarboxylic acid and a dihydroxy compound, and polycondensation reactions between an unsaturated dicarboxylic acid and a diamine. There are polyamides obtained by.
側鎖にエチレン性不飽和結合を有する重合体は側鎖に不
飽和結合をもつ二価カルボン酸例えばイタコン酸、プロ
ピリデンコハク酸、エチリデンマロン酸等とジヒドロキ
シまたはジアミン化合物との縮合重合体がある。また側
鎖にヒドロキシ基やハロゲン化メチル基の如き反応活性
を有する官能基をもつ重合体、例えばポリビニルアルコ
ール、ポリ(2−ヒドロキシエチルメタクリレート)、
ポリエピクロルヒドリン等とアクリル酸、メタクリル酸
、クロトン酸等の不飽和カルボン酸との高分子反応によ
り得られるポリマーも好適に使用し得る。Polymers having ethylenically unsaturated bonds in their side chains include condensation polymers of dicarboxylic acids having unsaturated bonds in their side chains, such as itaconic acid, propylidene succinic acid, ethylidene malonic acid, etc., and dihydroxy or diamine compounds. . In addition, polymers having reactive functional groups such as hydroxy groups or halogenated methyl groups in their side chains, such as polyvinyl alcohol, poly(2-hydroxyethyl methacrylate),
Polymers obtained by polymer reaction of polyepichlorohydrin or the like with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, or crotonic acid may also be suitably used.
以上記載したエチレン性化合物の内、アクリル酸エステ
ルまたはメタクリル酸エステルの単量体が特に好適に使
用できる。Among the ethylenic compounds described above, acrylic ester or methacrylic ester monomers can be particularly preferably used.
次に、本発明の光重合性組成物の第2の必須成分である
光重合開始系について説明する0本発明の光重合開始系
は2種成分の組合せから構成されており、その第1の成
分は(a)は、下記一般式〔■]で表わされるスクアリ
リウム色素である。Next, the photopolymerization initiation system, which is the second essential component of the photopolymerizable composition of the present invention, will be explained. The photopolymerization initiation system of the present invention is composed of a combination of two components, and the first Component (a) is a squarylium dye represented by the following general formula [■].
〔式中、Rr、Rzは置換基があっても良いアルキル基
またはアリール基、環A1環Bは各々置換基があっても
良いベンゼン環またはナフタリン環を示す。〕
従来、スクアリリウム色素は感光層中において充分な溶
解性を有するものが少なく、析出し易い傾向を有してお
り、その結果、安定した感光特性が得にくい欠点を有し
ていた。また、スクアリリウム色素の多くは600nn
+〜700nmの光線、即ち、赤色光に対応した増感剤
となり得る為、フルカラー画像複製の為の赤感感材に利
用できるが、分光感度特性は必ずしも充分でなかった。[In the formula, Rr and Rz are an alkyl group or an aryl group which may have a substituent, and Ring A1 and Ring B each represent a benzene ring or a naphthalene ring which may have a substituent. ] Conventionally, few squarylium dyes have sufficient solubility in the photosensitive layer and tend to precipitate easily, resulting in the disadvantage that stable photosensitive characteristics are difficult to obtain. In addition, many squarylium pigments are 600nn
Since it can be used as a sensitizer for light rays of + to 700 nm, that is, red light, it can be used as a red-sensitive material for full-color image reproduction, but its spectral sensitivity characteristics have not always been sufficient.
その傾向は長波長対応である赤感感材において特に顕著
であるが、その原因は所望しない短波長側へ太きくスソ
引きしている為である。例えば、赤感感材の場合、50
0〜600nmの領域において望ましくない感光を生じ
、結果的に色再現性を悪化させる。この分光感度特性を
評価する為のパラメーターとしては、赤感感材の場合は
、650nm対応感度の550nn+対応感度δこ対す
る比率の大きさにより評価し得る。つまり、この比率の
値が大きい程分光感度特性ひいては色再現性が良好であ
ることを意味する。以後、この値を分光感度値と略記す
る。This tendency is particularly noticeable in red-sensitive materials that are compatible with long wavelengths, and the reason for this is that they are thickly streaked toward the undesired short wavelength side. For example, in the case of red-sensitive material, 50
Undesirable light sensitivity occurs in the 0-600 nm region, resulting in poor color reproducibility. As a parameter for evaluating this spectral sensitivity characteristic, in the case of a red-sensitive material, it can be evaluated by the ratio of 550 nn of the corresponding sensitivity to 650 nm + the corresponding sensitivity δ. That is, it means that the larger the value of this ratio, the better the spectral sensitivity characteristics and the better the color reproducibility. Hereinafter, this value will be abbreviated as a spectral sensitivity value.
従来のスクアリリウム色素において、前記の溶解安定性
と分光感度特性との両者を満足させることは困難であっ
たが、我々は前記の一般式(1)の色素が良好な特性を
有することを見い出した。Although it has been difficult for conventional squarylium dyes to satisfy both the above-mentioned dissolution stability and spectral sensitivity characteristics, we have found that the dye of general formula (1) above has good characteristics. .
前記一般式のR1、R2は、好ましくはアルキル基とし
ては、メチル基、エチル基、n−プロピル基、n−ブチ
ル基、n−ヘキシル基、n−オクチル基であり、アリー
ル基であればフェニル基、ナフチル基である。これらは
更に置換基を有していてもよく、用いられる置換基とし
ては、フェニル基、フェノキシ基、メトキシ基、エトキ
シ基が好ましい。R1 and R2 in the above general formula are preferably a methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group as an alkyl group, and phenyl group as an aryl group. group, naphthyl group. These may further have a substituent, and the substituent used is preferably a phenyl group, a phenoxy group, a methoxy group, or an ethoxy group.
環A1環Bは置換基があってもよいベンゼン環、ナフタ
リン環であり、好ましい置換基としては、メチル基、エ
チル基の様なアルキル基;メトキシ、エトキシ基の様な
アルコキシ基;塩素、臭素の様なハロゲン原子が好まし
い。Ring A1 Ring B is a benzene ring or a naphthalene ring which may have a substituent, and preferred substituents include an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy or ethoxy group; chlorine or bromine. A halogen atom such as is preferred.
このような条件を満たすスクアリリウムとして好適なも
のを例示すると、次のような化合物が挙げられる。〔〕
内は化合物の略号である。Suitable examples of squarylium satisfying such conditions include the following compounds. []
The symbol inside is the abbreviation of the compound.
0−C2H5
以上、例示した本発明に用いられるスクアリリウム色素
は、常法に従い、例えば、H3E、Sprenger著
Angew、Chem、 1nternat E
dit 6 553 (1967)に記載の方法によ
り調製することができる。0-C2H5 The above-exemplified squarylium dyes used in the present invention can be prepared according to conventional methods, for example, H3E, Sprenger, Angew, Chem, 1nternat E.
dit 6 553 (1967).
次に、本発明の光重合開始系を構成する第2の成分0)
)について述べる。Next, the second component 0) constituting the photopolymerization initiation system of the present invention
).
成分(b)は少なくとも1つのモノ、ジ、トリハロゲン
置換メチル基がs−1リアジン環に結合したS−トリア
ジン誘導体である。これらは、例えば、若林ら著、Bu
ll、Chem、Soc、Japan、42.2924
(1969)、米国特許3゜987.037号明細書
、F、C15chaefer et al、J、O
rg、Chem、。Component (b) is an S-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-1 riazine ring. These are, for example, written by Wakabayashi et al., Bu
ll, Chem, Soc, Japan, 42.2924
(1969), U.S. Pat. No. 3,987.037, F. Chaefer et al., J. O.
rg,Chem,.
29.1527 (1964)記載の化合物が挙げられ
る。以下、これらの化合物を具体的に例示するが〔〕内
の文字は、以後用いる化合物の略号である。それらは、
例えば、2,4.6−1−リス(トリクロルメチル)−
s−)リアジン(b−1)、2−メチル−4,6−ビス
(トリクロルメチル)s−)リアジンl’b−2)、2
−フェニル−4゜6−ビス(トリクロルメチル)−S−
)リアジン、2−(p−クロルフェニル)−4,6−ビ
ス(トリクロルメチル)−S−)リアジン、2−フェニ
ルチオ−4,6−ビス゛(トリクロルメチル) −S−
トリアジン(b−3L 2−ベンジルチオ−4゜6−ビ
ス(トリクロルメチル)−s−1リアジン、2−(p−
トリル)−4,6−ビス(トリクロルメチル)−S−ト
リアジン、2−(p−メトキシフェニル)−4,6−ビ
ス(トリクロルメチル)−8−トリアジン、2−n−プ
ロピル−4,6−ビス(トリクロルメチル)−S−トリ
アジン、2−(α、α、β−トリクロルエチル)−4,
6ビス(トリクロルメチル)−S−トリアジン、2−ス
チリル−4,6−ビス(トリクロルメチル)−8−トリ
アジン、2,4.6−)リス(ジクロルメチル)−s−
トリアジン、2.4.6−)リス(トリブロムメチル)
−S−トリアジン(b−4〕、2−メチル−4,6−
ビス(トリブロムメチル)−s−)リアジン、2,4.
6−1−リス(ジブロメチル)−S−トリアジン等であ
る。これらの内、特に好適なものは、例えば、2.4゜
6−トリス(トリクロルメチル)−S−)リアジン、2
−フェニル−4,6−ビス(トリクロルメチル)−s−
)リアジン、2−メチル−4,6−ビス(トリクロルメ
チル)−S−)リアジン、2−フェニルチオ−4,6−
ビス(トリクロルメチル)−s−トリアジン、2,4.
6−)リス(トリブロムメチル)−S−)リアジン等ト
リクロルまたはトリブロムメチル基が2個以上含まれる
Sトリアジン類があげられる。これらS−トリアジン類
は、上記文献に従って、対応するニトリル化合物を臭化
アルミニウムと塩化水素の存在下で反応させるか、対応
するイミデートを経由して合成することができる。29.1527 (1964). Specific examples of these compounds will be given below, and the characters in [ ] are abbreviations of the compounds used hereinafter. They are,
For example, 2,4.6-1-lis(trichloromethyl)-
s-) riazine (b-1), 2-methyl-4,6-bis(trichloromethyl) s-) riazine l'b-2), 2
-Phenyl-4゜6-bis(trichloromethyl)-S-
)Ryazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-S-)Ryazine, 2-phenylthio-4,6-bis(trichloromethyl)-S-
Triazine (b-3L 2-benzylthio-4゜6-bis(trichloromethyl)-s-1 riazine, 2-(p-
tolyl)-4,6-bis(trichloromethyl)-S-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-8-triazine, 2-n-propyl-4,6- Bis(trichloromethyl)-S-triazine, 2-(α,α,β-trichloroethyl)-4,
6bis(trichloromethyl)-S-triazine, 2-styryl-4,6-bis(trichloromethyl)-8-triazine, 2,4.6-)lis(dichloromethyl)-s-
triazine, 2.4.6-)lis(tribromomethyl)
-S-triazine (b-4), 2-methyl-4,6-
Bis(tribromomethyl)-s-)riazine, 2,4.
6-1-lis(dibromethyl)-S-triazine and the like. Among these, particularly preferred are, for example, 2.4°6-tris(trichloromethyl)-S-) riazine, 2
-phenyl-4,6-bis(trichloromethyl)-s-
) riazine, 2-methyl-4,6-bis(trichloromethyl)-S-) riazine, 2-phenylthio-4,6-
Bis(trichloromethyl)-s-triazine, 2,4.
Examples include S triazines containing two or more trichlor or tribromomethyl groups, such as 6-)lis(tribromomethyl)-S-)riazine. These S-triazines can be synthesized by reacting the corresponding nitrile compound with aluminum bromide in the presence of hydrogen chloride, or via the corresponding imidate, according to the above-mentioned literature.
本発明の光重合開始系は前述の(a)、(b)二成分の
組合せによりはじめて顕著な効果を発揮し得るが、その
使用割合は(a) : (b)の重量比で、好ましくは
、1:30ないし10:1の範囲、特に好ましくは、1
:15ないし4:1までの範囲である。また本発明の光
重合性組成物に含まれる光重合開始系、即ち(a)成分
、(b)成分の合計量は、前記エチレン性化合物に対し
て重量比率で好ましくは0.1%ないし30%であり、
特に好ましくは0,5%ないし20%の範囲である。The photopolymerization initiation system of the present invention can only exhibit remarkable effects by combining the two components (a) and (b) described above, and the ratio of their use is preferably a weight ratio of (a):(b). , in the range from 1:30 to 10:1, particularly preferably 1
:15 to 4:1. Further, the total amount of the photopolymerization initiation system, that is, the components (a) and (b) contained in the photopolymerizable composition of the present invention is preferably 0.1% to 30% by weight relative to the ethylenic compound. %,
Particularly preferred is a range of 0.5% to 20%.
本発明の光重合性組成物は前記の各構成成分の他に、そ
れの使用目的に応じて、更に、他の物質を添加混合する
ことができる。In addition to the above-mentioned components, the photopolymerizable composition of the present invention may further contain other substances depending on the intended use thereof.
例えば、皮膜形成能や粘度調節能を必要とする場合は有
機高分子物質を結合剤として添加すれば良い。その具体
例としては、例えば、(メタ)アクリル酸、それらのエ
ステル化物、マレイン酸、アクリロニトリル、スチレン
、酢酸ビニル、塩化ビニリデン等の単独もしくは共重合
体、その他、ポリエチレンオキサイド、ポリビニルピロ
リドン、ポリアミド、ポリウレタン、ポリエチレンテレ
フタレートイソフタレート、アセチルセルロースまたは
ポリビニルブチラール等が挙げられる。これらの結合剤
は前記エチレン性化合物に対し重量比率で好ましくは5
00%以下、特に好ましくは200%以下の範囲で添加
混合することができる。For example, when film-forming ability or viscosity control ability is required, an organic polymer substance may be added as a binder. Specific examples include (meth)acrylic acid, esterified products thereof, maleic acid, acrylonitrile, styrene, vinyl acetate, vinylidene chloride, etc. alone or copolymers, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane. , polyethylene terephthalate isophthalate, acetyl cellulose or polyvinyl butyral. These binders are preferably used in a weight ratio of 5 to the ethylenic compound.
It can be added and mixed in a range of 00% or less, particularly preferably 200% or less.
その他、ハイドロキノン、P−メトキシフェノール、2
,6−ジーt−ブチル−P−クレゾールなどの熱重合防
止剤;有機または無機の染顔料から成る着色剤;ジオク
チルフタレート、ジドデシルフタレート、トリクレジル
ホスフェート、ジオクチルアジペート、トリエチレング
リコールシカプリレート等の可塑剤、その他、三級アミ
ンやチオールの様な感度改善剤などの添加剤も加えるこ
とができる。Others: hydroquinone, P-methoxyphenol, 2
, 6-di-t-butyl-P-cresol; colorants consisting of organic or inorganic dyes and pigments; dioctyl phthalate, didodecyl phthalate, tricresyl phosphate, dioctyl adipate, triethylene glycol caprylate Additives such as plasticizers such as tertiary amines and sensitivity improvers such as thiols can also be added.
本組成物をカラー画像の複製技法に応用する場合は、色
素前駆体、例えば、特公昭46−41346号明細書に
記載されている様な常用カラー写真フィルムに用いられ
ている様な発色材料や感圧色素の技術分野などで良く知
られている色素ロイコ体を添加することができる。色素
ロイコ体としては、例えば、トリアリールメタン、ビス
アリールメタン、キサンチン化合物、フルオラン、チア
ジン化合物やその部分骨格としてラクトン、ラクタム、
スルトン、スピロピラン構造を形成させた化合物などが
包含される。When the present composition is applied to color image reproduction techniques, dye precursors, such as color forming materials such as those used in conventional color photographic films as described in Japanese Patent Publication No. 46-41346, or A leuco dye well known in the technical field of pressure-sensitive dyes can be added. Examples of leuco pigments include triarylmethane, bisarylmethane, xanthine compounds, fluoran, thiazine compounds, and their partial skeletons such as lactones, lactams,
Compounds having a sultone, spiropyran structure, etc. are included.
以上述べた各種添加剤の好ましい添加量は、光重合性組
成物の固形分に対する重量比率で熱重合防止剤2%以下
、着色剤20%以下、可塑剤40%以下、色素前駆体4
0%以下の範囲である。Preferred addition amounts of the various additives mentioned above are, in terms of weight ratio to the solid content of the photopolymerizable composition, thermal polymerization inhibitor 2% or less, colorant 20% or less, plasticizer 40% or less, and dye precursor 4%.
It is in the range of 0% or less.
本組成物を用いて作製される感光材料の形態は使用目的
に応じて適宜選択することができる。The form of the photosensitive material produced using the present composition can be appropriately selected depending on the purpose of use.
例えば、無溶媒または適当な溶剤で希釈してシート、例
えばポリマーシート、紙、金属シート上に塗布、乾燥し
、必要に応じて酸素遮断の為のオーバーコート層を更に
上層に設けた形態、異相媒質中に小滴分散した複数種の
感材を多層塗布した形態、該組成物をマイクロカプセル
中に内包させシート上に塗布した形態など種々の選択が
可能である。For example, it can be applied without a solvent or diluted with an appropriate solvent to a sheet, such as a polymer sheet, paper, or metal sheet, dried, and if necessary, an overcoat layer for oxygen blocking is further provided on the upper layer. Various options are possible, such as a multilayer coating of a plurality of types of sensitive materials dispersed in small droplets in a medium, and a coating of the composition encapsulated in microcapsules on a sheet.
本発明の組成物に適用し得る露光光源としては特に限定
されないが、例えば、カーボンアーク、高圧水銀燈、キ
セノンランプ、メタルハライドランプ、蛍光ランプ、タ
ングステンランプ、ハロゲンランプ、ヘリウムネオンレ
ーザ−1半導体レーザー等600nm以上の可視光線を
含む光源が特に好適に使用し得る。Exposure light sources applicable to the composition of the present invention are not particularly limited, but include, for example, carbon arc, high-pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, helium neon laser-1 semiconductor laser, etc. A light source containing the above visible light rays can be particularly preferably used.
以下、本発明を実施例および比較例により更に具体的に
説明するが、本発明は、その要旨を越えない限りこれら
の実施例に限定されるものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.
なお、実施例、比較例中で用いているスクアリリウム色
素およびS−)リアジンの略号は明細書中に例示したも
のならびに下記の化合物に対応している。The abbreviations of squarylium dye and S-) liazine used in Examples and Comparative Examples correspond to those exemplified in the specification and the compounds below.
R8
R1
実施例1〜8および比較例1〜4
評価項目の溶解安定性と分光感度値は各々下記の方法に
従って得た評価結果を表わしたものである。R8 R1 Examples 1 to 8 and Comparative Examples 1 to 4 The evaluation items of dissolution stability and spectral sensitivity values each represent the evaluation results obtained according to the following methods.
溶解安定性
この項目は安定的な溶解性の度合いを評価したものであ
る。ペンタエリスリトールトリアクリレート中にスクア
リリウム色素1重量%、S−)リアジン化合物を5重量
%添加し、加温溶解後室層にて放置する。−ケ月間放置
後、前記添加物の析出が認められない場合を「良好」、
わずかに析出した場合を 「や−良好」、結晶析出が顕
著な場合を「不良」とした。Dissolution stability This item evaluates the degree of stable solubility. 1% by weight of squarylium dye and 5% by weight of S-) riazine compound were added to pentaerythritol triacrylate, and after dissolving with heating, the mixture was allowed to stand in a room. - If no precipitation of the additive is observed after being left for several months, it is considered "good".
A case in which a slight amount of crystallization was observed was rated as "fairly good", and a case in which significant crystallization was rated as "poor".
分光感度値
この項目は赤色光分光感度特性を評価、測定したもので
ある。メタクリル酸メチル/メタクリル酸共重合体(重
量平均分子量45,000、共重合比85/12)2g
、ペンタエリスリトールトリアクリレート8gをメチル
エチルケトン120g中に溶解し、感光液原液を調製し
た。この原液を分は取り、表−1に記載したスクアリリ
ウム色素1重量%(対固形分)およびs−)リアジン5
重量%(対固形分)を添加して試料感光液を調整した。Spectral sensitivity value This item evaluates and measures red light spectral sensitivity characteristics. Methyl methacrylate/methacrylic acid copolymer (weight average molecular weight 45,000, copolymerization ratio 85/12) 2 g
, 8 g of pentaerythritol triacrylate was dissolved in 120 g of methyl ethyl ketone to prepare a photosensitive liquid stock solution. A portion of this stock solution was taken, and the squarylium dye 1% by weight (based on solid content) listed in Table 1 and s-) riazine 5 were added.
A sample photosensitive solution was prepared by adding % by weight (based on solid content).
得られた各感光液を砂目室てかつ陽極酸化を施したアル
ミニウムシート上にホワラーを用い、乾燥膜厚1.6μ
mとなる欅に塗布し、次いで70°C13分間乾燥した
。Each photosensitive solution obtained was placed on a grained and anodized aluminum sheet using a whirler to form a dry film with a dry film thickness of 1.6 μm.
The mixture was applied to a piece of Japanese zelkova, and then dried at 70°C for 13 minutes.
その表面に更にポリビニルアルコール水溶液を塗布し、
乾燥膜厚3μmのオーバーコート層を設け、感光材試料
を作成した。次に、これらの試料に対し分光照射装置(
“’RM−23−1”、ナルミ社製)を用いて一定時間
露光した後、現像液(ブチルセロソルブ9重量%、ケイ
酸ソーダ1重量%を含む水溶液)により現像を行ない各
波長に対する光硬化速度を求めた。ここにおける分光感
度値は赤色光対応のそれを示しており、即ち、650n
sの光線に対応する光硬化速度の550n園対応のそれ
に対する比率として求めた値である。この値は、赤色光
対応の感度をそれより短波長側ヘスソ引きしている感度
に比較した場合の大きさを示しており、この値が大きい
程、良好な分光感度を有していることを示している。表
−1で明らかな様に本願発明の光開始系は良好な溶解性
と分光感度特性との両者を具備していることが分かる。Further apply a polyvinyl alcohol aqueous solution to the surface,
A photosensitive material sample was prepared by providing an overcoat layer with a dry thickness of 3 μm. Next, these samples were exposed to a spectroscopic irradiation device (
After exposure for a certain period of time using "'RM-23-1" (manufactured by Narumi Co., Ltd.), development was performed with a developer (an aqueous solution containing 9% by weight of butyl cellosolve and 1% by weight of sodium silicate), and the photocuring rate for each wavelength was I asked for The spectral sensitivity values here are for red light, i.e. 650n
This value is calculated as the ratio of the photocuring speed corresponding to the 550n beam to that corresponding to the 550n beam. This value indicates the magnitude when comparing the sensitivity for red light with the sensitivity that is lower on the shorter wavelength side, and the larger this value is, the better the spectral sensitivity is. It shows. As is clear from Table 1, the photoinitiation system of the present invention has both good solubility and spectral sensitivity characteristics.
表−1
〔発明の効果〕
本発明により600〜700nmの波長の光に対し、特
に優れた感度を示すと同時ムこ保存安定性にも優れた光
重合性組成物を得られる。Table 1 [Effects of the Invention] According to the present invention, a photopolymerizable composition can be obtained which exhibits particularly excellent sensitivity to light having a wavelength of 600 to 700 nm and also has excellent storage stability.
Claims (1)
開始系とから成る光重合性組成物において、該光重合開
始系が、 (a)下記一般式〔 I 〕で表わされるスクアリリウム
色素、 ▲数式、化学式、表等があります▼〔 I 〕 〔式中、R_1、R_2は各々置換基があっても良いア
ルキル基またはアリール基、環A、環Bは各々置換基が
あっても良いベンゼン環またはナフタリン環を示す。〕
および、 (b)少なくとも1個のハロゲン化メチル基を有するs
−トリアジン化合物 から成ることを特徴とする光重合性組成物。(1) A photopolymerizable composition comprising an ethylenically unsaturated compound capable of addition polymerization and a photopolymerization initiation system, in which the photopolymerization initiation system comprises (a) a squarylium dye represented by the following general formula [I], ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, R_1 and R_2 are each an alkyl group or an aryl group that may have a substituent, and Ring A and Ring B are each a benzene ring that may have a substituent. Or indicates a naphthalene ring. ]
and (b) s having at least one halogenated methyl group
- A photopolymerizable composition comprising a triazine compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22475190A JP2897375B2 (en) | 1990-08-27 | 1990-08-27 | Photopolymerizable composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22475190A JP2897375B2 (en) | 1990-08-27 | 1990-08-27 | Photopolymerizable composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04106548A true JPH04106548A (en) | 1992-04-08 |
JP2897375B2 JP2897375B2 (en) | 1999-05-31 |
Family
ID=16818670
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22475190A Expired - Lifetime JP2897375B2 (en) | 1990-08-27 | 1990-08-27 | Photopolymerizable composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2897375B2 (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0568993A2 (en) * | 1992-05-06 | 1993-11-10 | Kyowa Hakko Kogyo Co., Ltd. | Chemical amplification resist composition |
WO1994001806A1 (en) * | 1992-07-13 | 1994-01-20 | Kyowa Hakko Kogyo Co., Ltd. | Photopolymerizable composition |
US6232038B1 (en) | 1998-10-07 | 2001-05-15 | Mitsubishi Chemical Corporation | Photosensitive composition, image-forming material and image-forming method employing it |
GB2373509A (en) * | 2001-03-21 | 2002-09-25 | Kalibrant Ltd | Long wavelength 4-[1-(naphtho[1,2-d]thiazol-1-ium-2-yl)methylidene]-3-oxo-2-[(2,3-dihydro-1H-indol-2-yliden)methyl]cyclobuten-1-olate based fluorescent dyes |
US7052822B2 (en) | 2002-09-30 | 2006-05-30 | Fuji Photo Film Co., Ltd. | Photosensitive composition |
EP1862301A1 (en) | 2006-06-02 | 2007-12-05 | FUJIFILM Corporation | Image recording material, planographic printing plate precursor, and planographic printing method using the same |
US7338748B2 (en) | 2002-09-30 | 2008-03-04 | Fujifilm Corporation | Polymerizable composition and planographic printing plate precursor |
EP1901124A1 (en) | 2006-08-29 | 2008-03-19 | FUJIFILM Corporation | Image recording material |
EP1930770A2 (en) | 2006-12-07 | 2008-06-11 | FUJIFILM Corporation | Imaging recording material and novel compound |
US7425400B2 (en) | 2003-02-20 | 2008-09-16 | Fujifilm Corporation | Planographic printing plate precursor |
US7820357B2 (en) | 2005-12-26 | 2010-10-26 | Fujifilm Corporation | Polymerizable composition and planographic printing plate precursor using the same |
-
1990
- 1990-08-27 JP JP22475190A patent/JP2897375B2/en not_active Expired - Lifetime
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0568993A2 (en) * | 1992-05-06 | 1993-11-10 | Kyowa Hakko Kogyo Co., Ltd. | Chemical amplification resist composition |
EP0568993A3 (en) * | 1992-05-06 | 1994-12-14 | Kyowa Hakko Kogyo Kk | Chemical amplification resist composition. |
US5527659A (en) * | 1992-05-06 | 1996-06-18 | Kyowa Hakko Kogyo Co., Ltd. | Chemical amplification resist composition containing photochemical acid generator, binder and squarylium compound |
WO1994001806A1 (en) * | 1992-07-13 | 1994-01-20 | Kyowa Hakko Kogyo Co., Ltd. | Photopolymerizable composition |
US6232038B1 (en) | 1998-10-07 | 2001-05-15 | Mitsubishi Chemical Corporation | Photosensitive composition, image-forming material and image-forming method employing it |
GB2373509A (en) * | 2001-03-21 | 2002-09-25 | Kalibrant Ltd | Long wavelength 4-[1-(naphtho[1,2-d]thiazol-1-ium-2-yl)methylidene]-3-oxo-2-[(2,3-dihydro-1H-indol-2-yliden)methyl]cyclobuten-1-olate based fluorescent dyes |
US7052822B2 (en) | 2002-09-30 | 2006-05-30 | Fuji Photo Film Co., Ltd. | Photosensitive composition |
US7338748B2 (en) | 2002-09-30 | 2008-03-04 | Fujifilm Corporation | Polymerizable composition and planographic printing plate precursor |
US7425400B2 (en) | 2003-02-20 | 2008-09-16 | Fujifilm Corporation | Planographic printing plate precursor |
US7820357B2 (en) | 2005-12-26 | 2010-10-26 | Fujifilm Corporation | Polymerizable composition and planographic printing plate precursor using the same |
EP1862301A1 (en) | 2006-06-02 | 2007-12-05 | FUJIFILM Corporation | Image recording material, planographic printing plate precursor, and planographic printing method using the same |
EP1901124A1 (en) | 2006-08-29 | 2008-03-19 | FUJIFILM Corporation | Image recording material |
US7445882B2 (en) | 2006-08-29 | 2008-11-04 | Fujifilm Corportation | Image recording material |
EP1930770A2 (en) | 2006-12-07 | 2008-06-11 | FUJIFILM Corporation | Imaging recording material and novel compound |
US7723011B2 (en) | 2006-12-07 | 2010-05-25 | Fujifilm Corporation | Image recording material and novel compound |
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