JPS62174204A - Photosensitive composition - Google Patents
Photosensitive compositionInfo
- Publication number
- JPS62174204A JPS62174204A JP1542286A JP1542286A JPS62174204A JP S62174204 A JPS62174204 A JP S62174204A JP 1542286 A JP1542286 A JP 1542286A JP 1542286 A JP1542286 A JP 1542286A JP S62174204 A JPS62174204 A JP S62174204A
- Authority
- JP
- Japan
- Prior art keywords
- photoinitiator
- group
- photosensitive composition
- dimer
- chlorophenyl
- 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 abstract description 49
- 239000000539 dimer Substances 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- -1 2-(2-chlorophenyl)-4, 5-bis(3,5-dimethoxyphenyl)-imidazolyl Chemical class 0.000 abstract description 31
- 230000035945 sensitivity Effects 0.000 abstract description 13
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 abstract description 6
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 abstract description 5
- SIVZFLKJXSKCGT-UHFFFAOYSA-N 2-(naphthalen-1-ylamino)acetic acid Chemical compound C1=CC=C2C(NCC(=O)O)=CC=CC2=C1 SIVZFLKJXSKCGT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003617 indole-3-acetic acid Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 229920001169 thermoplastic Polymers 0.000 description 9
- 239000004416 thermosoftening plastic Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000007348 radical reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 3
- 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 3
- 238000009825 accumulation Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 3
- 238000007644 letterpress printing Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 210000003739 neck Anatomy 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OAZWDJGLIYNYMU-UHFFFAOYSA-N Leucocrystal Violet Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 OAZWDJGLIYNYMU-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 231100000704 bioconcentration Toxicity 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 1
- AKEXCWHQCBKPQG-UHFFFAOYSA-N 2-(5-chloro-1h-indol-2-yl)acetic acid Chemical compound ClC1=CC=C2NC(CC(=O)O)=CC2=C1 AKEXCWHQCBKPQG-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 1
- GZEYLLPOQRZUDF-UHFFFAOYSA-N 7-(dimethylamino)-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(N(C)C)=CC=C21 GZEYLLPOQRZUDF-UHFFFAOYSA-N 0.000 description 1
- OTNIKUTWXUODJZ-UHFFFAOYSA-N 7-(ethylamino)-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(NCC)=CC=C21 OTNIKUTWXUODJZ-UHFFFAOYSA-N 0.000 description 1
- XJGFWWJLMVZSIG-UHFFFAOYSA-N 9-aminoacridine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=NC2=C1 XJGFWWJLMVZSIG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical class OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960001441 aminoacridine Drugs 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical class C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- IWVKTOUOPHGZRX-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(=O)C(C)=C IWVKTOUOPHGZRX-UHFFFAOYSA-N 0.000 description 1
- NRZLHHHHUNKJOP-UHFFFAOYSA-N methyl 4-(diethylamino)benzoate Chemical compound CCN(CC)C1=CC=C(C(=O)OC)C=C1 NRZLHHHHUNKJOP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002979 perylenes Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高感度で熱安定性に優れた感光性組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photosensitive composition with high sensitivity and excellent thermal stability.
（従来の技術）
凸版印刷用版材、リスフィルム、プリント配線基板用フ
ォトレジストなどに使用されうる感光性組成物には多種
の組成物があり、なかでも光照射により重合可能なエチ
レン系不飽和単量体を主成分とする組成物が好適に利用
されている。このような組成物には、上記エチレン系不
飽和単量体のほかに、この単量体の重合反応を引き起こ
すためにラジカル発生剤および光開始剤が通常含有され
る。例えば、特公昭４５−３７３７７号公報には光開始
剤としてヘキサアリールビイミダゾール化合物を用いた
感光性組成物（写真画像形成性組成物）が開示されてい
る。これらの化合物のうち２位のフェニル基のオルソ位
にクロル基が置換した２・２′−ビス（０−クロルフェ
ニル）−４・４゛ ・５・５゛ −テトラキスフェニル
ビイミダゾール〔２−（２−クロルフェニル）−４・５
−ジフェニルイミダゾリル二量体：Ｃ１−ＨＡＢＩ）は
、熱安定性に優れるため、好適であるとされている。(Prior art) There are many types of photosensitive compositions that can be used for letterpress printing plates, lithium films, photoresists for printed wiring boards, etc. Among them, ethylenically unsaturated compositions that can be polymerized by light irradiation Compositions containing monomers as main components are preferably used. In addition to the ethylenically unsaturated monomer, such compositions usually contain a radical generator and a photoinitiator to induce a polymerization reaction of this monomer. For example, Japanese Patent Publication No. 45-37377 discloses a photosensitive composition (photographic image-forming composition) using a hexaarylbiimidazole compound as a photoinitiator. Among these compounds, 2-( 2-chlorophenyl)-4・5
-diphenylimidazolyl dimer: C1-HABI) is said to be suitable because it has excellent thermal stability.
しかし、上記化合物は、いずれも１通常の露光に使用さ
れる３００〜４００ｎｍの波長域の光の吸収性が低いた
め、感度が高いとはいえない。上記感光性組成物をリス
フィルムなどに利用すると、リスフィルムには９通常、
多量のカーボンブラックや顔料が配合されるため、露光
時に光が遮断されて単量体が充分に重合しないという問
題がある。さらに、上記光開始剤は、いずれも、特にＣ
Ｉ −ＨＡＢＩは、生体での蓄積性が大きいという欠点
を有する。However, all of the above compounds have low absorption of light in the wavelength range of 300 to 400 nm, which is used for normal exposure, and therefore cannot be said to have high sensitivity. When the above-mentioned photosensitive composition is used for a lithographic film, etc., the lithographic film usually has 9
Since large amounts of carbon black and pigments are blended, there is a problem in that light is blocked during exposure and the monomers are not sufficiently polymerized. Furthermore, all of the photoinitiators mentioned above are particularly suitable for C
I-HABI has the disadvantage of being highly bioaccumulative.
水系へ流出した化学物質は水生生物の体内に入って濃縮
され１食物連鎖を通して最終的には人体へ移動する可能
性がある。そのため１通産省では新規化学物質に関して
は、化学物質審査規制法で魚類の体内への該化学物質の
濃縮性試験を義務づけている。上記光開始剤は、いずれ
も、この規制基準を大きく越えるため、実質的に使用す
ることができない。Chemicals that leak into water systems can enter the bodies of aquatic organisms, become concentrated, and eventually be transferred to humans through the food chain. For this reason, the Ministry of International Trade and Industry (MITI) requires tests on the concentration of new chemical substances in fish bodies under the Chemical Substances Examination and Regulation Act. All of the above-mentioned photoinitiators greatly exceed this regulatory standard, so they cannot be practically used.
（発明が解決しようとする問題点） 本発明は上記従来の欠点を解決するものであり。(Problem to be solved by the invention) The present invention solves the above-mentioned conventional drawbacks.
その目的とするところは、高感度で、熱安定性に優れ、
かつ生体に対する蓄積性の少ない光開始剤を含有し、優
れた解像力を有する感光性組成物を提供することにある
。Its purpose is to provide high sensitivity, excellent thermal stability, and
Another object of the present invention is to provide a photosensitive composition that contains a photoinitiator that is less likely to accumulate in living organisms and has excellent resolution.
（問題点を解決するための手段および作用）本発明の感
光性組成物は光開始剤、ラジカル発生剤およびエチレン
系不飽和単量体を含有し、該光開始剤が下記式（Ｉ）で
示される２・４・５−トリアリールイミダゾリル二量体
であり、そのことにより上記目的が達成される。(Means and effects for solving the problems) The photosensitive composition of the present invention contains a photoinitiator, a radical generator, and an ethylenically unsaturated monomer, and the photoinitiator is represented by the following formula (I). The 2,4,5-triarylimidazolyl dimer shown above achieves the above object.
（以下余白）
（ここで、Ｘはハロゲン基、シアノ基、炭素原子数１〜
４のアルキル基またはアリール基；Ｙ１〜Ｙ、はそれぞ
れ炭素原子数１〜４のアルコキシルＪＡｓＺ＋〜Ｚ、。(Left below) (Here, X is a halogen group, a cyano group, or a carbon atom number of 1 to
4 alkyl group or aryl group; Y1 to Y are alkoxyl JAsZ+ to Z, each having 1 to 4 carbon atoms;
はそれぞれ水素または炭素原子数１〜４のアルコキシル
基を示す。ただしｒ Ｙｌ〜Ｙ４およびＺ、〜Ｚ、。each represents hydrogen or an alkoxyl group having 1 to 4 carbon atoms. However, r Yl~Y4 and Z, ~Z,.
はそれぞれ同一の置換基でなくてもよい。）本発明の感
光性組成物に含有される光開始剤は上記化学構造（Ｉ）
を有する２・４・５−トリアリールイミダゾリル二量体
である。このような光開始剤には９例えば、２−（２−
クロルフェニル）−４・５−ビス（３・５−ジメトキシ
フェニル）イミダゾリル二量体、２−（２−クロルフェ
ニル）−４−（３・５−ジメトキシフェニル）−５−（
３・４・５−トリメトキシフェニル）イミダゾリルニｌ
ｔ体、２− （２−クロルフェニル）−４・５−ビス（
３・４・５−トリメトキシフェニル）イミダゾリル二量
体、２− （２−クロルフェニル）−４−（２・３・５
−トリメトキシフェニル）−５−（３・４・５−トリメ
トキシフェニル）イミタソリルニＩＬ ２−（２−ク
ロルフェニル）−４・５−ビス（３・４・５−トリメト
キシフェニル）イミダゾリル二量体、２−（２−クロル
−５−メトキシフェニル）−４・５−ビス（３・５−ジ
メトキシフェニル）イミダゾリル二量体がある。may not be the same substituent. ) The photoinitiator contained in the photosensitive composition of the present invention has the above chemical structure (I).
It is a 2,4,5-triarylimidazolyl dimer having the following. Such photoinitiators include 9 e.g. 2-(2-
Chlorphenyl)-4,5-bis(3,5-dimethoxyphenyl)imidazolyl dimer, 2-(2-chlorphenyl)-4-(3,5-dimethoxyphenyl)-5-(
3,4,5-trimethoxyphenyl)imidazolyl
t-form, 2-(2-chlorophenyl)-4,5-bis(
3,4,5-trimethoxyphenyl)imidazolyl dimer, 2-(2-chlorophenyl)-4-(2,3,5
-trimethoxyphenyl)-5-(3,4,5-trimethoxyphenyl)imidazolyl 2-(2-chlorophenyl)-4,5-bis(3,4,5-trimethoxyphenyl)imidazolyl dimer , 2-(2-chloro-5-methoxyphenyl)-4,5-bis(3,5-dimethoxyphenyl)imidazolyl dimer.
このほか、クロル基の代わりに（上記構造式のＸとして
）ブロム基、フルオロ基、ヨード基などの他のハロゲン
基；シアノ基；メチル基、エチル基。In addition, other halogen groups such as a bromine group, a fluoro group, and an iodo group (as X in the above structural formula) in place of a chloro group; a cyano group; a methyl group and an ethyl group.
プロピル基、ブチル基などのアルキル基；フェニル基な
どのアリール基が置換した化合物やメトキシ基の代わり
に（上記構造式のＹ、〜Ｙａ、 Ｚ＋”Ｚ＋。Alkyl groups such as propyl and butyl groups; instead of compounds substituted with aryl groups such as phenyl groups and methoxy groups (Y, ~Ya, Z+"Z+ in the above structural formula).
として）エトキシ基、プロポキシ基、ブトキシ基など他
のアルコキシル基の置換した化合物も挙げられる。これ
らの化合物は、Ｙｌ〜Ｙ４がアルコキシル基であること
に特徴がある。この位置にアルコキシル基が置換してい
るため、３００〜４００ ｎｍの領域での光吸収性が高
くなる。つまり、光開始剤の感度が上がり、その結果、
感光性組成物の感度も高くなる。そのため１例えば、多
量にカーボンブラックを配合したリスフィルムとして利
用しても充分な感度が得られる。Examples include compounds substituted with other alkoxyl groups such as ethoxy, propoxy, and butoxy groups. These compounds are characterized in that Yl to Y4 are alkoxyl groups. Since the alkoxyl group is substituted at this position, the light absorption in the 300-400 nm region becomes high. This means that the sensitivity of the photoinitiator increases, and as a result,
The sensitivity of the photosensitive composition also increases. Therefore, for example, sufficient sensitivity can be obtained even when used as a lith film containing a large amount of carbon black.
上記光開始剤は感光性組成物（溶媒を除く；以下、含有
量を示すときには溶媒を除いた値を基準とする）中に０
．３〜１５．０重量％の割合で含有される。過少である
と光照射によるラジカル反応が充分に起こらないため、
後述の単量体の重合反応が不充分となり感度が悪くなる
。過剰であってもそれ以上の効果は得られない。The above photoinitiator is present in the photosensitive composition (excluding the solvent; hereinafter, when indicating the content, the value excluding the solvent is used as a reference).
．． It is contained in a proportion of 3 to 15.0% by weight. If the amount is too low, radical reactions due to light irradiation will not occur sufficiently.
The polymerization reaction of the monomers described below becomes insufficient, resulting in poor sensitivity. Even if it is excessive, no further effect can be obtained.
本発明の組成物に含有されるラジカル発生剤としては２
通常のラジカル反応に用いられるラジカル発生剤が使用
されうる。そのような化合物としては、アミン類、ロイ
コ染料、ハロゲン化炭化水素、チオ尿素酸、インドール
誘導体、ベンジル誘導体などがあり１例えば、Ｎ−フェ
ニルグリシン。As the radical generator contained in the composition of the present invention, 2
Radical generators used in common radical reactions can be used. Such compounds include amines, leuco dyes, halogenated hydrocarbons, thioureaic acids, indole derivatives, benzyl derivatives, etc.1, for example, N-phenylglycine.
ミヒラーケトン、ミヒラーチオケトン、ジメドン。Michler Ketone, Michler Thioketone, Dimedone.
インドール酢酸、Ｎ−ナフチルグリシン、５−ｎ−ブチ
ルチオグリコール酸、４・４”−ビス（ジメチルアミノ
）ベンジル、ｐ−ジアルキルアミノ安息香酸エステル、
ロイコクリスタルバイオレットインドキシル酸、１−ク
ロロインドキシル酸、２−クロロインドキシル酸、４・
４°−ビス（ジエチルアミノ）ベンジル、ｐ−ジエチル
アミノ安息香酸メチル、トリ （ｐ−ジエチルアミノ−
０−トリル）メタン、トリ （ｐ−ジメチルアミノ−０
−トリル）メタン、５−クロロインドール酢酸などが挙
げられる。これらの化合物のうちで特に本発明で使用さ
れる光開始剤と組み合わせて好適であるのは。Indole acetic acid, N-naphthylglycine, 5-n-butylthioglycolic acid, 4,4"-bis(dimethylamino)benzyl, p-dialkylaminobenzoic acid ester,
Leuco crystal violet indoxylic acid, 1-chloroindoxylic acid, 2-chloroindoxylic acid, 4.
4°-Bis(diethylamino)benzyl, methyl p-diethylaminobenzoate, tri(p-diethylamino-
0-tolyl)methane, tri(p-dimethylamino-0
-tolyl)methane, 5-chloroindoleacetic acid, and the like. Among these compounds, those which are particularly suitable in combination with the photoinitiator used in the present invention are:
ジメドン、インドール酢酸、Ｎ−ナフチルグリシン、５
−ｎ−ブチルチオグリコール酸、４・４′−ビス（ジメ
チルアミノ）ベンジル、ｐ−ジアルキルアミノ安息香酸
エステル、ロイコクリスタルバイオレット、インドキシ
ル酸およびこれら化合物の誘導体である。Dimedone, indoleacetic acid, N-naphthylglycine, 5
-n-butylthioglycolic acid, 4,4'-bis(dimethylamino)benzyl, p-dialkylaminobenzoic acid ester, leuco crystal violet, indoxylic acid and derivatives of these compounds.
ラジカル発生剤は組成物中に０．３〜１５．０重量％の
割合で含有される。過少であると光照射によるラジカル
反応が充分に起こらないため、後述の単量体の重合反応
が不充分となり感度が悪くなる。The radical generator is contained in the composition in a proportion of 0.3 to 15.0% by weight. If the amount is too small, radical reactions due to light irradiation will not occur sufficiently, resulting in insufficient polymerization reactions of monomers, which will be described later, resulting in poor sensitivity.
過剰であってもそれ以上の効果は得られない。Even if it is excessive, no further effect can be obtained.
エチレン系不飽和単量体は不飽和基を有し、ラジカル発
生剤により開始されるラジカル反応により付加重合し高
分子を形成しうる化合物である。The ethylenically unsaturated monomer is a compound that has an unsaturated group and can undergo addition polymerization to form a polymer through a radical reaction initiated by a radical generator.
このような化合物としては、アクリル酸もしくはメタク
リル酸の誘導体〔（メタ）アクリル酸誘導体〕が好適に
利用される。そのような化合物としては、シクロへキシ
ルアクリレート、デシルアクリレート、ラウリルアクリ
レートなどのアルキル（メタ）アクリレート頚；２−ヒ
ドロキシエチルアクリレートなどのヒドロキシアルキル
（メタ）アクリレート［；Ｎ−Ｎ−ジメチルアミノエチ
ルアクリレートなどのアミノアルキル（メタ）アクリレ
ート類；２−メトキシエチルアクリレートなどのエーテ
ルアルキル（メタ）アクリレート類；グリシジルアクリ
レート類；ハロゲン化アルキルアクリレート類；トリメ
チロールプロパントリアクリレート、トリメチロールプ
ロパントリメタクリレート トリエチレングリコールジ
メタクリレートなどの多官能（メタ）アクリレート類が
挙げられる。As such a compound, a derivative of acrylic acid or methacrylic acid [(meth)acrylic acid derivative] is suitably used. Such compounds include alkyl (meth)acrylate necks such as cyclohexyl acrylate, decyl acrylate, and lauryl acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl acrylate; N-N-dimethylaminoethyl acrylate, etc. aminoalkyl (meth)acrylates; etheralkyl (meth)acrylates such as 2-methoxyethyl acrylate; glycidyl acrylates; halogenated alkyl acrylates; trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triethylene glycol dimethacrylate Examples include polyfunctional (meth)acrylates such as.
上記化合物のほか、エチレン性不飽和基を側鎖に有する
重合体１例えば、下記の熱可塑性樹脂もエチレン性不飽
和単量体として使用することかできる。In addition to the above compounds, polymers 1 having ethylenically unsaturated groups in their side chains, such as the following thermoplastic resins, can also be used as ethylenically unsaturated monomers.
Ｃ１０゜
このようなエチレン系不飽和単量体は組成物中に２５〜
８０重量％の割合で含有される。過少であると膜性能が
低下する。過剰であると他の添加剤の配合量が少なくな
り、感度や膜性能が低下する。C10゜Such ethylenically unsaturated monomers are present in the composition from 25 to
It is contained in a proportion of 80% by weight. If it is too small, the membrane performance will deteriorate. If it is excessive, the amount of other additives to be blended will be reduced, resulting in a decrease in sensitivity and film performance.
感光性組成物には、必要に応じて、熱可塑性結合剤が含
有される。熱可塑性結合剤としては、酸。The photosensitive composition contains a thermoplastic binder, if necessary. As a thermoplastic binder, acid.
アルカリ、または有機溶剤に可溶な熱可塑性樹脂が用い
られる。このような熱可塑性結合剤としては、ポリアミ
ド、ポリアクリル酸エステル、アクリル酸−アクリル酸
アルキルエステル共重合体。A thermoplastic resin soluble in alkali or organic solvents is used. Examples of such thermoplastic binders include polyamides, polyacrylic esters, and acrylic acid-acrylic acid alkyl ester copolymers.
メタクリル酸−メタクリル酸アルキルエステル共重合体
、ポリビニルフェノール、ポリビニルエステル、ポリア
クリルアミド、ポリビニルアルコール、ポリエチレンオ
キシド、ゼラチン、セルロースエステル、セルロースエ
ーテルなどが用いられる。Methacrylic acid-methacrylic acid alkyl ester copolymer, polyvinylphenol, polyvinyl ester, polyacrylamide, polyvinyl alcohol, polyethylene oxide, gelatin, cellulose ester, cellulose ether, etc. are used.
このような熱可塑性結合剤は２組成物に露光を行いエチ
レン系不飽和単量体が重合反応を起こすと、生じた重合
体の分子間に組み込まれて該重合体とともにマトリック
スを形成する。その結果。When the two compositions are exposed to light and the ethylenically unsaturated monomer undergoes a polymerization reaction, such a thermoplastic binder is incorporated between the molecules of the resulting polymer and forms a matrix together with the polymer. the result.
露光を受けた部分は全体として酸、アルカリまたは有機
溶剤でなる現像剤に不溶となる。側鎖に重合性の基を有
する熱可塑性結合剤（例えば、ポリビニルフェノール）
は、エチレン系不飽和単量体とともに重合反応に関与し
２重合体を形成する場合もある。上記熱可塑性結合剤の
うちカルボキシル基、ヒドロキシフェニル基、スルホン
酸基、酸により４級化されうる窒素原子を含有するポリ
マーが好適に利用される。カルボキシル基、ヒドロキシ
フェニル基、スルホン酸基を有するポリマーは水系アル
カリ溶媒に可溶であり、酸により４級化されうる窒素原
子を含有するポリマーは水系酸溶媒に可溶である。その
ため、これら溶媒を用いて簡単に現像を行い、水洗によ
り現像を停止することも容易である。例えば、カルボキ
シル基を有するポリマーには（メタ）アクリル系ポリマ
ーが。The exposed area becomes insoluble as a whole in a developer made of an acid, alkali or organic solvent. Thermoplastic binders with polymerizable groups in their side chains (e.g. polyvinylphenol)
may participate in a polymerization reaction together with an ethylenically unsaturated monomer to form a dipolymer. Among the above thermoplastic binders, polymers containing a carboxyl group, a hydroxyphenyl group, a sulfonic acid group, and a nitrogen atom that can be quaternized with an acid are preferably used. Polymers having carboxyl groups, hydroxyphenyl groups, and sulfonic acid groups are soluble in aqueous alkaline solvents, and polymers containing nitrogen atoms that can be quaternized with acids are soluble in aqueous acidic solvents. Therefore, it is easy to carry out development using these solvents and to stop the development by washing with water. For example, (meth)acrylic polymers are polymers with carboxyl groups.
ヒドロキシフェニル基を有するポリマーにはポリビニル
フェノールが、スルホン酸基を有するポリマーにはポリ
スチレンスルホン酸が、そして酸により４級化されうる
窒素原子を含有するポリマーにはポリアクリルアミドが
ある。Polyvinylphenol is an example of a polymer having hydroxyphenyl groups, polystyrene sulfonic acid is an example of a polymer having a sulfonic acid group, and polyacrylamide is an example of a polymer containing a nitrogen atom that can be quaternized by an acid.
上記熱可塑性結合剤は組成物中に６０．０重量％以下の
割合で含有される。過剰であると、エチレン系不飽和単
量体の量が過少になるため、露光による重合反応が不充
分となり解像力に劣る。The thermoplastic binder is contained in the composition in an amount of 60.0% by weight or less. If it is in excess, the amount of the ethylenically unsaturated monomer becomes too small, resulting in insufficient polymerization reaction upon exposure and poor resolution.
本発明の組成物には、さらに、必要に応じて。The composition of the present invention further includes, if necessary.
増感剤、活性光線吸収剤、エネルギー移送性染料。Sensitizers, actinic light absorbers, energy transfer dyes.
酸素除去剤、連鎖移動促進剤、熱重合禁止剤などの添加
剤が含有される。上記添加剤のうち、増悪剤としては、
フルオレセイン、エオシンなどのヒドロキシフタレイン
染料；３・６−ビス（アルキルアミノ）アクリジン類な
どのアミノアクリジン染料；３・３” −ジエチルオキ
サカルボシアニンヨーダイドなどのカルボシアン染料；
７−シメチルアミノー４−メチルクマリン、７−シエチ
ルアミノー４−メチルクマリンなどのクマリン頚；ｐ−
アミノフェニルケトン類；フラン頚；オキサゾール類；
オキサジアゾール類；芳香族炭化水素；ペリレン類；ピ
レン類；ビス（ｐ−アミノフェニル）−α、β−不飽和
ケトン類などがある。活性光線吸収剤としては、カーボ
ンブラック、酸化チタン、金属や金属酸化物粉末、顔料
、染料などが用いられる。It contains additives such as oxygen scavengers, chain transfer promoters, and thermal polymerization inhibitors. Among the above additives, aggravating agents include:
Hydroxyphthalein dyes such as fluorescein and eosin; Aminoacridine dyes such as 3,6-bis(alkylamino)acridines; Carbocyan dyes such as 3,3''-diethyloxacarbocyanine iodide;
Coumarin neck such as 7-dimethylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin; p-
Aminophenyl ketones; Furan neck; Oxazoles;
Oxadiazoles; aromatic hydrocarbons; perylenes; pyrenes; bis(p-aminophenyl)-α,β-unsaturated ketones and the like. As the actinic ray absorber, carbon black, titanium oxide, metal or metal oxide powder, pigment, dye, etc. are used.
上記添加剤は組成物中に３重量％以下の割合で含有され
る。ただし、顔料を多重に使用するＵＶ硬化塗料、フォ
トレジスト用インク、非銀系リスフィルムなどの用途に
利用するときには、添加剤は、その合計量で組成物に５
〜７５重量％の割合で含有されていてもよい。The above additives are contained in the composition in a proportion of 3% by weight or less. However, when used in applications such as UV-curable paints, photoresist inks, and non-silver lithium-ion films that use multiple pigments, the total amount of additives added to the composition may
It may be contained in a proportion of up to 75% by weight.
上記光開始剤、ラジカル発生剤、エチレン系不飽和単量
体、さらに必要に応じて、熱可塑性結合剤、各種添加剤
などを含有する組成物は、凸版。The composition containing the above-mentioned photoinitiator, radical generator, ethylenically unsaturated monomer, and if necessary, a thermoplastic binder, various additives, etc. can be prepared by letterpress printing.
石版印刷版、非銀系リスフィルム、色校正版など印刷関
連材料として、あるいはフォトレジストソルダーマスク
、など電子関連材料として使用されうる。組成物は目的
に応じて液状で、あるいはフィルム形状などの固形状で
利用されうる。It can be used as printing-related materials such as lithographic printing plates, non-silver lithographic films, and color proofing plates, or as electronic-related materials such as photoresist solder masks. The composition can be used in a liquid form or in a solid form such as a film, depending on the purpose.
例えば１本発明の感光性組成物を用いてリスフィルムを
調製するにはカーボンブラックが５〜７５重景％重量合
で含有された上記組成物に適当な溶媒を加えて希釈し、
ポリエチレンテレフタレートなどの透明プラスチックシ
ート上にコーターを用いて均一に塗布・乾燥する。乾燥
後の厚みは１０μｍ以下、好ましくは１〜５μｍである
。このようにして得られたリスフィルムの感光層上に所
望の原図（パターンマスク）を重ねて露光を行う。これ
を例えば水系酸溶媒または水系アルカリ溶媒で現像する
と、未露光部分は溶解して除去され、露光部分は不溶性
となるため残存する。その結果、微細な凹凸のレリーフ
が得られる。不溶部分にはカーボンブラックが配合され
ているため、露光部分は黒く、未露光部分は透明なフィ
ルムが得られる。For example, in order to prepare a lithographic film using the photosensitive composition of the present invention, the above composition containing carbon black in an amount of 5 to 75% by weight is diluted by adding an appropriate solvent.
Use a coater to evenly coat and dry onto a transparent plastic sheet such as polyethylene terephthalate. The thickness after drying is 10 μm or less, preferably 1 to 5 μm. A desired original pattern (pattern mask) is superimposed on the photosensitive layer of the lithographic film thus obtained and exposed. When this is developed with, for example, an aqueous acid solvent or an aqueous alkaline solvent, the unexposed portions are dissolved and removed, and the exposed portions remain because they become insoluble. As a result, a relief of fine irregularities is obtained. Since carbon black is blended into the insoluble portion, a film is obtained in which the exposed portion is black and the unexposed portion is transparent.
このように、特定の構造を有する光開始剤を用い、高感
度の感光性組成物が得られる。本発明の組成物に用いら
れる光開始剤は、従来の光開始剤と異なり、非ハロゲン
系溶剤２例えば、アルコール系溶剤にも可溶である。そ
のため、塗工ドープ溶剤として、クロロホルム、ジクロ
ルメタンなどのハロゲン系溶剤を使用する必要がない。In this way, a highly sensitive photosensitive composition can be obtained using a photoinitiator having a specific structure. The photoinitiator used in the composition of the present invention, unlike conventional photoinitiators, is also soluble in non-halogenated solvents 2, such as alcoholic solvents. Therefore, there is no need to use a halogen solvent such as chloroform or dichloromethane as a coating dope solvent.
従って。Therefore.
ハロゲン系溶剤によりコーターなどの塗工装置が腐食さ
れるおそれがなく、かつ発ガン性の疑いがあると言われ
るハロゲン系溶剤を作業時に吸入するおそれもない。光
開始剤は、生物に対する蓄積性（生物濃縮性）も極小で
あるため、生体に対しても安全である。さらに、優れた
熱安定性を有するため、感光性組成物を長時間１例えば
、室温に１年以上、保存しても組成物の解像力にはほと
んど変化が認められない。There is no risk of coating equipment such as a coater being corroded by halogenated solvents, and there is no risk of inhaling halogenated solvents, which are suspected of being carcinogenic, during work. Photoinitiators also have minimal accumulation (bioconcentration) in living organisms, so they are safe for living organisms. Further, since it has excellent thermal stability, almost no change in the resolution of the photosensitive composition is observed even when the photosensitive composition is stored at room temperature for a long time, for example, one year or more.
−１および １
以下に本発明組成物に使用する光開始剤の諸性質を示す
実験例と１本発明組成物の実施例とを示す。-1 and 1 Below, experimental examples showing various properties of the photoinitiator used in the composition of the present invention and an example of the composition of the present invention are shown.
次ＩＬＬ
本発明に用いられる光開始剤および従来の光開始剤のを
機溶媒（メタノール、酢酸エチル、クロロホルム）に対
する溶解性をそれぞれ調べた（実験例１−１〜１−５お
よび比較実験例１−１〜１−２）。その結果を表１に示
す。Next ILL The solubility of the photoinitiator used in the present invention and the conventional photoinitiator in organic solvents (methanol, ethyl acetate, chloroform) was investigated (Experimental Examples 1-1 to 1-5 and Comparative Experimental Example 1). -1 to 1-2). The results are shown in Table 1.
（以下余白）
表１から９本発明に用いられる光開始剤はいずれもアル
コール系溶剤、酢酸エステル系溶剤などのハロゲン系溶
剤以外の溶剤に比較的良好な溶解性を示すことが明らか
である。(The following is a blank space) Tables 1 to 9 It is clear that all of the photoinitiators used in the present invention exhibit relatively good solubility in solvents other than halogen-based solvents, such as alcohol-based solvents and acetate-based solvents.
スミｆ辻Ａ二」−
光開始剤として２−（２−クロルフェニル）−４・５−
ビス（３・４・５−トリメトキシフェニル）イミダゾリ
ル二量体を０．００８０ｇ 、 ラジカル発生剤として
ジメドンを０．００３０ｇ 、エチレン系不飽和単量体
としてトリメチロールプロパントリアクリレートを０．
０３２ｇ、熱可塑性結合剤としてメタクリル酸メチル−
メタクリル酸共重合体（モル比７０： ３０） ０．１
０ｇ 、そして溶媒として塩化メチレン−メタノール混
液（重量比３：１）を１０．００ｇの割合で含有する組
成物を、４０℃で暗所に２日間保存した。保存後の光開
始剤の残存率を測定した。その結果を表２に示す。実験
例２−２〜２−３および比較実験例２−１〜２−６の結
果もあわせて表２に示す。Sumi f Tsuji A2' - 2-(2-chlorophenyl)-4,5- as a photoinitiator
0.0080 g of bis(3,4,5-trimethoxyphenyl)imidazolyl dimer, 0.0030 g of dimedone as a radical generator, and 0.0 g of trimethylolpropane triacrylate as an ethylenically unsaturated monomer.
032g, methyl methacrylate as thermoplastic binder
Methacrylic acid copolymer (molar ratio 70:30) 0.1
A composition containing 10.00 g of methylene chloride-methanol mixture (weight ratio 3:1) as a solvent was stored at 40° C. in the dark for 2 days. The residual rate of the photoinitiator after storage was measured. The results are shown in Table 2. The results of Experimental Examples 2-2 to 2-3 and Comparative Experimental Examples 2-1 to 2-6 are also shown in Table 2.
入Ｂ二」−
光開始剤として２−（２−クロルフェニル）−４・５−
ビス（３・５−ジメトキシフェニル）イミダゾリル二量
体を使用したこと以外は実験例２−１と同様である。2-(2-chlorophenyl)-4.5- as a photoinitiator
The procedure was the same as in Experimental Example 2-1 except that bis(3,5-dimethoxyphenyl)imidazolyl dimer was used.
（以下余白）
１ｍｍ二
元開始剤として２−（２−クロルフェニル）−４−（３
・４・５−トリメトキシフェニル）−５−（３・５−ジ
メトキシフェニル）イミダゾリル二量体を使用したこと
以外は実験例２−１と同様である。(Left below) As a 1mm binary initiator, 2-(2-chlorophenyl)-4-(3
- Same as Experimental Example 2-1 except that 4,5-trimethoxyphenyl)-5-(3,5-dimethoxyphenyl)imidazolyl dimer was used.
此木ブＩＪ引り１工
光開始剤として２−（２−クロルフェニル）−４・５−
ジフェニルイミダゾリル二量体を使用したこと以外は実
験例２−１と同様である。2-(2-chlorophenyl)-4,5- as a photoinitiator for IJ pulling
It is the same as Experimental Example 2-1 except that diphenylimidazolyl dimer was used.
ル較実並■に叉
光開始剤として２−（２−メトキシフェニル）−４・５
−ビス（３−メトキシフェニル）イミダゾリル二量体を
使用したこと以外は実験例２−１と同様である。2-(2-methoxyphenyl)-4・5 as a photoinitiator
The procedure was the same as in Experimental Example 2-1 except that -bis(3-methoxyphenyl)imidazolyl dimer was used.
几蔦ノ」１１Ｌ二ｌ
光開始剤として２−（２−クロルフェニル）−４・５−
ビス（４−メトキシフェニル）イミダゾリル二量体を使
用したこと以外は実験例２−１と同様である。2-(2-chlorophenyl)-4・5- as a photoinitiator
It is the same as Experimental Example 2-1 except that bis(4-methoxyphenyl)imidazolyl dimer was used.
此煎Ｊｌｕ［と１土
光開始剤として２−ナフチル−４・５−ジフェニルイミ
ダゾリル二量体を使用したこと以外は実験例２−１と同
様である。The procedure was the same as in Experimental Example 2-1 except that 2-naphthyl-4,5-diphenylimidazolyl dimer was used as the initiator.
１較大鼓開主ニエ
光開始剤として２・４・５−トリフェニルイミダゾリル
二量体を使用したこと以外は実験例２−１と同様である
。1. Experimental Example 2-1 was the same as in Experimental Example 2-1 except that 2,4,5-triphenylimidazolyl dimer was used as the photoinitiator.
ル較尖肱拠１ニエ
光開始剤として２−（２−メトキシフェニル）４・５−
ジフェニルイミダゾリル二量体を使用したこと以外は実
験例２−１と同様である。2-(2-methoxyphenyl)4,5- as a photoinitiator
It is the same as Experimental Example 2-1 except that diphenylimidazolyl dimer was used.
（以下余白）
表２
表２より本発明で用いられる光開始剤は溶液中での熱安
定性に優れていることがわかる。従来の光開始剤である
２−（２−クロルフェニル）−４・５−ジフェニルイミ
ダゾリル二量体も熱安定性は高いが、この化合物は生体
に対する蓄積性が高いため好ましくない。(The following is a blank space) Table 2 Table 2 shows that the photoinitiator used in the present invention has excellent thermal stability in a solution. 2-(2-chlorophenyl)-4,5-diphenylimidazolyl dimer, which is a conventional photoinitiator, also has high thermal stability, but this compound is not preferred because it has a high tendency to accumulate in living organisms.
大腋炭主二上
光開始剤の生体に対する蓄積性の目安としてｎ−オクチ
ルアルコール−水系での分配係数を測定した。The partition coefficient in the n-octyl alcohol-water system was measured as a measure of the bioaccumulability of the axillary charcoal-based photoinitiator in living organisms.
ｎ−オクチルアルコール約１０１１１１および水約１０
ｍ１を分液ロートに入れ、さらに光開始剤として２−（
２−クロルフェニル）−４・５−ビス（３・４・５−ト
リメトキシフェニル）イミダゾリル二量体１．０ｇを加
えて数回振盪した後、静置した。n-octyl alcohol about 101111 and water about 10
m1 was placed in a separatory funnel, and 2-(
After adding 1.0 g of 2-chlorophenyl)-4,5-bis(3,4,5-trimethoxyphenyl)imidazolyl dimer and shaking several times, the mixture was allowed to stand still.
ｎ−オクチルアルコールおよび水に溶解した光開始剤の
量をそれぞれ測定し１分配係数を算出した：分配係数（
ρ） ＝ｌｏｇ （０／ｗ）ここで、０はｎ−オクチ
ルアルコールに溶解した光開始剤の量、そしてＷは水に
溶解した光開始剤の量を示す。The amount of photoinitiator dissolved in n-octyl alcohol and water was measured and the distribution coefficient was calculated: Partition coefficient (
ρ) = log (0/w) where 0 indicates the amount of photoinitiator dissolved in n-octyl alcohol and W indicates the amount of photoinitiator dissolved in water.
その結果を表３に示す。実験例３−２〜３−３および比
較実験例３−１〜３−２の結果もあわせて表３に示す。The results are shown in Table 3. The results of Experimental Examples 3-2 to 3-3 and Comparative Experimental Examples 3-1 to 3-2 are also shown in Table 3.
尖腋舅にＩ
光開始剤として２−（２−クロルフェニル）−４・５−
ビス（３・５−ジメトキシフェニル）イミダゾリル二量
体を使用したこと以外は実験例３−１と同様である。2-(2-chlorophenyl)-4,5- as a photoinitiator
The procedure was the same as in Experimental Example 3-1 except that bis(3,5-dimethoxyphenyl)imidazolyl dimer was used.
ス１」しし二ｌ
光開始剤として２−（２−クロルフェニル）−４−（３
・４・５−トリメトキシフェニル）−５−（３・５−ジ
メトキシフェニル）イミダゾリル二量体を使用したこと
以外は実験例３−１と同様である。2-(2-chlorophenyl)-4-(3
- Same as Experimental Example 3-1 except that 4,5-trimethoxyphenyl)-5-(3,5-dimethoxyphenyl)imidazolyl dimer was used.
北本】Ｊｕ１Ｌ二上
光開始剤として２−（２−クロルナフチル）−４・５−
ジフェニルイミダゾリル二量体を使用したこと以外は実
験例３−１と同様である。Kitamoto] 2-(2-chlornaphthyl)-4,5- as a photoinitiator for Ju1L Nijo
It is the same as Experimental Example 3-1 except that diphenylimidazolyl dimer was used.
ル較１貌■ユニ又
光開始剤として２−（２−クロルフェニル）−４・５−
ジフェニルイミダゾリル二量体を使用したこと以外は実
験例３−１と同様である。Comparison ■ 2-(2-chlorophenyl)-4,5- as a photoinitiator
It is the same as Experimental Example 3-1 except that diphenylimidazolyl dimer was used.
ｎ−オクチルアルコール−水系での分配係数が大きいほ
ど生体への濃縮・蓄積性が大きく９通常。The larger the partition coefficient in the n-octyl alcohol-water system, the greater the concentration and accumulation in living organisms9.
分配係数が３以下であれば安全な化合物であるとされて
いる。表３から０本発明に用いられる光開始剤の分配係
数はいずれも３以下であり、安全な化合物であるとみな
される。It is said that a compound is safe if its partition coefficient is 3 or less. From Table 3, all of the photoinitiators used in the present invention have partition coefficients of 3 or less and are considered to be safe compounds.
去肱桝土二土
光開始Ｍ２− （２−クロルフェニル）−４・５−ビス
（３・４・５−トリメトキシフェニル）イミダゾリル二
量体を１０ｐｐｍのクロロホルム溶液とし１石英セル（
厚さ１．０ａａ）を使用して３６５ ｎｍでの吸光度を
測定した。その結果を表４に示す。実験例４−２〜４−
３および比較実験例４−１〜４−３の結果もあわせて表
４に示す。M2- (2-chlorophenyl)-4,5-bis(3,4,5-trimethoxyphenyl)imidazolyl dimer was dissolved in chloroform at 10 ppm, and one quartz cell (
Absorbance was measured at 365 nm using a 1.0 aa thick film. The results are shown in Table 4. Experimental examples 4-2 to 4-
Table 4 also shows the results of Example No. 3 and Comparative Experimental Examples 4-1 to 4-3.
叉肱炎土二１
光開始剤として２−（２−クロルフェニル）−４・５−
ビス（３・５ジメトキシフエニル）イミダゾリル二量体
を使用したこと以外は実験例４−１と同様である。2-(2-chlorophenyl)-4,5- as a photoinitiator
The procedure was the same as in Experimental Example 4-1 except that bis(3.5 dimethoxyphenyl) imidazolyl dimer was used.
ス潰け１Ｌ二１
光開始剤として２−（２−クロルフェニル）−４−（３
・４・５−トリメトキシフェニル）−５−（３・５−ジ
メトキシフェニル）イミダゾリル二量体を使用したこと
以外は実験例４−１と同様である。Crushed 1L21 2-(2-chlorophenyl)-4-(3
- Same as Experimental Example 4-1 except that 4,5-trimethoxyphenyl)-5-(3,5-dimethoxyphenyl)imidazolyl dimer was used.
几鴬ＩＬｆＬ虹二上
光開始剤として２−（２−クロルナフチル）−４・５−
ジフェニルイミダゾリル二量体を使用したこと以外は実
験例４−１と同様である。2-(2-chlornaphthyl)-4.5- as a photoinitiator for ILfL Nijijo
It is the same as Experimental Example 4-1 except that diphenylimidazolyl dimer was used.
止較ｌ狭炭土二１
光開始剤として２−（２−クロルフェニル）４・５−ビ
ス（３−メトキシフェニル）イミダゾリル二量体を使用
したこと以外は実験例４−１と同様である。Comparison l Narrow Soil 21 Same as Experimental Example 4-1 except that 2-(2-chlorophenyl)4,5-bis(3-methoxyphenyl)imidazolyl dimer was used as the photoinitiator. .
凡漫】ｌ■（（二１
光開始剤として２−（２−クロルフェニル）−４・５−
ジフェニルイミダゾリル二量体を使用したこと以外は実
験例４−１と同様である。General】l■((21 As a photoinitiator, 2-(2-chlorophenyl)-4・5-
It is the same as Experimental Example 4-1 except that diphenylimidazolyl dimer was used.
表４
表４から本発明の光開始剤は１通常、露光の行われる３
００〜４００ ｎｍにおける吸光度が高いため。Table 4 From Table 4, the photoinitiators of the present invention are 1. Usually exposed to light 3.
Because the absorbance is high in the wavelength range of 00 to 400 nm.
感度の良好なことが明らかである。It is clear that the sensitivity is good.
去立鮮土
メタクリル酸メチル−メタクリル酸共重合体（モル比７
０ ： ３０） ４３．４重量部、カーボンブラ・ツク
（紫外線遮断剤） １０．６重量部、トリメチロールプ
ロパントリアクリレート３６．０重量部、２−（２−ク
ロルフェニル）−４・５−ビス（３・４・５−トリメト
キシフェニル）イミダゾリル二量体（光開始剤）および
ジメドン（ラジカル発生剤）の１：１のモル比の混合物
を１０．０重量部、ハイドロキノンモノメチルエーテル
０．０３重量部そしてメタノール３１７．０重量部を混
合して感光性組成物を調製した。下引き層を有する厚さ
１００μｍの透明二軸延伸ポリエチレンテレフタレート
製フィルム上に。Methyl methacrylate-methacrylic acid copolymer (molar ratio 7)
0: 30) 43.4 parts by weight, 10.6 parts by weight of carbon black (ultraviolet blocker), 36.0 parts by weight of trimethylolpropane triacrylate, 2-(2-chlorophenyl)-4,5-bis 10.0 parts by weight of a mixture of (3,4,5-trimethoxyphenyl)imidazolyl dimer (photoinitiator) and dimedone (radical generator) in a molar ratio of 1:1, and 0.03 parts by weight of hydroquinone monomethyl ether. 1 part and 317.0 parts by weight of methanol were mixed to prepare a photosensitive composition. On a 100 μm thick transparent biaxially oriented polyethylene terephthalate film with a subbing layer.
上記組成物を、乾燥後の厚さが４μｍとなるように、リ
バースコーターを用いて塗布した。形成された感光層の
光学濃度は、３５０〜４００ｎｍの範囲で平均２．６で
あった。感光層の表面にさらに１０％ポリビニルアルコ
ール（ケン化度９８〜９９モル％９重合度５００）水溶
液を塗布・乾燥し、厚さ２μｍの保護層を形成した。The above composition was applied using a reverse coater so that the thickness after drying was 4 μm. The optical density of the formed photosensitive layer was 2.6 on average in the range of 350 to 400 nm. A 10% aqueous solution of polyvinyl alcohol (saponification degree: 98-99 mol %, polymerization degree: 500) was further coated on the surface of the photosensitive layer and dried to form a protective layer with a thickness of 2 μm.
得られたリスフィルムの保護層表面に２１Ｊ″Ｔステツ
プタブレツト（コダソク社製）を重ねて超高圧水銀灯（
オーク製作所製；ポリマープリンター３０００ ； １
４０ Ｗ／ｍ２）を用いて露光を行なった。A 21J″T step tablet (manufactured by Kodasoku Co., Ltd.) was layered on the surface of the protective layer of the obtained lith film, and an ultra-high pressure mercury lamp (
Made by Oak Seisakusho; Polymer Printer 3000; 1
40 W/m2).
水洗して保護層を除去した後、２％炭酸ナトリウム水溶
液中に２５°Ｃで６秒間浸漬し、さらに水に浸漬してス
ポンジでこすって現像を行なった。このようにして露光
時間を種々にかえて行い、ステップタブレットの６段を
硬化するのに最適な露光時間を求めた。別に、未露光の
リスフィルムを２５°Ｃで２％炭酸ナトリウム水溶液に
漫清し、感光層が完全に溶解するのに要する時間を測定
した。After washing with water to remove the protective layer, the film was immersed in a 2% aqueous sodium carbonate solution at 25°C for 6 seconds, further immersed in water, and rubbed with a sponge for development. In this way, the exposure time was varied and the optimum exposure time for curing the 6 stages of the step tablet was determined. Separately, an unexposed lithium film was washed with a 2% aqueous sodium carbonate solution at 25°C, and the time required for the photosensitive layer to completely dissolve was measured.
次に未露光のリスフィルムを４０℃の暗所で所定時間（
１ケ月問および２ケ月間）保存した後、上記最適露光時
間を求める実験と未露光の感光層が完全に溶解するのに
要する時間を測定する実験とをそれぞれ行なった。Next, place the unexposed lithium film in a dark place at 40°C for a predetermined period of time (
After storage for 1 month and 2 months, experiments were conducted to determine the optimum exposure time and to measure the time required for the unexposed photosensitive layer to completely dissolve.
これらの結果を表５に示す。実施例２〜５および比較例
１〜４の結果もあわせて表５に示す。These results are shown in Table 5. The results of Examples 2 to 5 and Comparative Examples 1 to 4 are also shown in Table 5.
尖立（社）主
光開始剤として２−（２−クロルフェニル）−４・５−
ビス（３・５−ジメトキシフェニル）イミダゾリル二量
体を用いたこと以外は実施例１と同様である。Chitatsu Co., Ltd. 2-(2-chlorophenyl)-4,5- as the main photoinitiator
The same as Example 1 except that bis(3,5-dimethoxyphenyl)imidazolyl dimer was used.
夫施拠ユ
光開始剤として２−（２−クロルフェニル）−４−（３
・４・５−トリメトキシフェニル）−５−（３・５−ジ
メトキシフェニル）イミダゾリル二量体を用いたこと以
外は実施例１と同様である。2-(2-chlorophenyl)-4-(3
- Same as Example 1 except that 4,5-trimethoxyphenyl)-5-(3,5-dimethoxyphenyl)imidazolyl dimer was used.
比較±よ
゛光開始剤として２・４・５−トリフェニルイミダゾリ
ル二量体を用いたこと以外は実施例１と同様である。Comparative Example Same as Example 1 except that 2,4,5-triphenylimidazolyl dimer was used as the photoinitiator.
止較炭又
光開始剤として２−（２−メトキシフェニル）４・５−
ジフェニルイミダゾリル二量体を用いたこと以外は実施
例１と同様である。2-(2-methoxyphenyl)4.5- as a charcoal or photoinitiator
The same as Example 1 except that diphenylimidazolyl dimer was used.
此ＭＵ津１
光開始剤として２−（２−クロルフェニル）−４・５−
ジフェニルイミダゾリル二量体を用いたこと以外は実施
例１と同様である。This MU Tsu1 2-(2-chlorophenyl)-4・5- as a photoinitiator
The same as Example 1 except that diphenylimidazolyl dimer was used.
比較炭土
光開始剤として２−（２−クロルフェニル）−４・５−
ビス（３−メトキシフェニル）イミダゾリル二量体を用
いたこと以外は実施例１と同様である。2-(2-chlorophenyl)-4・5- as a comparative carbonaceous photoinitiator
The same as Example 1 except that bis(3-methoxyphenyl)imidazolyl dimer was used.
（以下余白）
表５から９本発明の感光性組成物は高感度であり、かつ
経時変化かほどんど認められないことが明らかである。(The following is a blank space) Tables 5 to 9 It is clear that the photosensitive compositions of the present invention have high sensitivity and hardly any change over time is observed.
（発明の効果）
本発明では、このように、特定の構造を有する高感度の
光開始剤を利用しており、その結果、高感度・高解像力
の感光性組成物が得られる。本発明の組成物に用いられ
る光開始剤は、従来の光開始剤と異なり、非ハロゲン系
溶剤２例えば、アルコール系溶剤にも可溶である。その
ため、塗工ドープ溶剤として、クロロホルム、ジクロル
メタンなどのハロゲン系溶剤を使用する必要がない。従
って、ハロゲン系溶剤によりコーターなどの塗工装置が
腐食されるおそれがなく、かつ発ガン性の疑いがあると
言われるハロゲン系溶剤を作業時に吸入するおそれもな
い。光開始剤は、生物に対する蓄積性（生物濃縮性）も
極小であるため、生体に対しても安全である。さらに、
優れた熱安定性を有するため、感光性組成物を長時間１
例えば。(Effects of the Invention) As described above, the present invention utilizes a highly sensitive photoinitiator having a specific structure, and as a result, a photosensitive composition with high sensitivity and high resolution can be obtained. The photoinitiator used in the composition of the present invention, unlike conventional photoinitiators, is also soluble in non-halogenated solvents 2, such as alcoholic solvents. Therefore, there is no need to use a halogen solvent such as chloroform or dichloromethane as a coating dope solvent. Therefore, there is no risk that coating equipment such as a coater will be corroded by the halogenated solvent, and there is no risk of inhaling the halogenated solvent, which is suspected of being carcinogenic, during work. Photoinitiators also have minimal accumulation (bioconcentration) in living organisms, so they are safe for living organisms. moreover,
Due to its excellent thermal stability, photosensitive compositions can be stored for long periods of time.
for example.
室温に１年以上、保存しても組成物の解像力にはほとん
ど変化が認められない。このような感光性組成物はリス
フィルム、凸版印刷用版材、プリント配線基板用フォト
レジストなどの数多くの技術分野への応用が可能である
。There is almost no change in the resolution of the composition even if it is stored at room temperature for one year or more. Such photosensitive compositions can be applied to many technical fields such as lithographic films, letterpress printing plates, and photoresists for printed wiring boards.
以上that's all
Claims (1)
単量体を含有する感光性組成物であって、該光開始剤が
下記式（ I ）で示される２・４・５−トリアリールイ
ミダゾリル二量体である、感光性組成物： ▲数式、化学式、表等があります▼ （ここで、Ｘはハロゲン基、シアノ基、 炭素原子数１〜４のアルキル基またはアリ ール基；Ｙ＿１〜Ｙ＿４はそれぞれ炭素原子数１〜４の
アルコキシル基；Ｚ＿１〜Ｚ＿１＿０はそれぞれ水素ま
たは炭素原子数１〜４のアルコキシ ル基を示す。ただし、Ｙ＿１〜Ｙ＿４およびＺ＿１〜Ｚ
＿１＿０はそれぞれ同一の置換基でなくてもよい。）[Claims] 1. A photosensitive composition containing a photoinitiator, a radical generator, and an ethylenically unsaturated monomer, wherein the photoinitiator is represented by the following formula (I) 2.4・Photosensitive composition that is a 5-triarylimidazolyl dimer: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, X is a halogen group, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an aryl group. Group; Y_1 to Y_4 each represents an alkoxyl group having 1 to 4 carbon atoms; Z_1 to Z_1_0 each represents hydrogen or an alkoxyl group having 1 to 4 carbon atoms. However, Y_1 to Y_4 and Z_1 to Z
_1_0 may not be the same substituent. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1542286A JPH0651737B2 (en) | 1986-01-27 | 1986-01-27 | Photosensitive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1542286A JPH0651737B2 (en) | 1986-01-27 | 1986-01-27 | Photosensitive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62174204A true JPS62174204A (en) | 1987-07-31 |
| JPH0651737B2 JPH0651737B2 (en) | 1994-07-06 |
Family
ID=11888327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1542286A Expired - Fee Related JPH0651737B2 (en) | 1986-01-27 | 1986-01-27 | Photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0651737B2 (en) |
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| JPS6463954A (en) * | 1987-09-03 | 1989-03-09 | Fuji Photo Film Co Ltd | Photosensitive composition |
| WO1999046644A1 (en) * | 1998-03-11 | 1999-09-16 | E.I. Du Pont De Nemours And Company | Process for the continuous liquid processing of photosensitive compositions having reduced levels of residues |
| JP2004264728A (en) * | 2003-03-04 | 2004-09-24 | Sumitomo Chem Co Ltd | Photosensitive resin composition |
| JP2008009323A (en) * | 2006-06-30 | 2008-01-17 | Fujifilm Corp | Curable composition for color filter, color filter and method for manufacturing the same |
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-
1986
- 1986-01-27 JP JP1542286A patent/JPH0651737B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
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| US6180319B1 (en) | 1998-03-11 | 2001-01-30 | E. I. Du Pont De Nemours And Company | Process for the continuous liquid processing of photosensitive compositions having reduced levels of residues |
| CN100350327C (en) * | 1998-03-11 | 2007-11-21 | 纳幕尔杜邦公司 | Process for continuous liquid processing of photosensitive compositions having reduced levels of residues |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0651737B2 (en) | 1994-07-06 |
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