JPH04240855A - Negative type photosensitive resin composition - Google Patents
Negative type photosensitive resin compositionInfo
- Publication number
- JPH04240855A JPH04240855A JP8567791A JP8567791A JPH04240855A JP H04240855 A JPH04240855 A JP H04240855A JP 8567791 A JP8567791 A JP 8567791A JP 8567791 A JP8567791 A JP 8567791A JP H04240855 A JPH04240855 A JP H04240855A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- alkylol
- photosensitive resin
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 16
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims abstract description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 35
- 238000007639 printing Methods 0.000 abstract description 11
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007644 letterpress printing Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 150000003672 ureas Chemical class 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 12
- 239000000976 ink Substances 0.000 description 12
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- -1 ethylene, propylene, maleic anhydride Chemical class 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 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 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- XKALZGSIEJZJCZ-UHFFFAOYSA-N 1,3-bis(methoxymethyl)urea Chemical compound COCNC(=O)NCOC XKALZGSIEJZJCZ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical class C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical class CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical class CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical class CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical class FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- WRVILNMDVRHVGJ-UHFFFAOYSA-N 4-hydroxy-3-(hydroxymethyl)but-2-enamide Chemical compound C(O)C(=CC(=O)N)CO WRVILNMDVRHVGJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical class C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical class CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229960002130 benzoin Drugs 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
- 150000008366 benzophenones Chemical class 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
- 238000003490 calendering Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical class CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical class CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- FAIDIRVMPHBRLT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OCC(O)CO FAIDIRVMPHBRLT-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、新規なネガ型感光性樹
脂組成物、さらに詳しくは、現像液として水を用いるこ
とができ、かつ水性インキに対して優れた抵抗性を有す
る凸版印刷版を与えうるネガ型感光性樹脂組成物に関す
るものである。[Industrial Application Field] The present invention relates to a novel negative photosensitive resin composition, and more specifically, a letterpress printing plate that can use water as a developer and has excellent resistance to water-based inks. This invention relates to a negative photosensitive resin composition that can provide the following properties.
【0002】0002
【従来の技術】従来、凸版印刷版においては油性インキ
が使用されてきたが、この油性インキはミストが人体に
対して悪影響を及ぼす上、それを用いた印刷物は乾燥に
長時間を要するとともに、手を汚したりするなどの欠点
を有することから、最近水性インキが注目されるように
なり、そのため、該油性インキに代わる水性インキに適
応するネガ型感光性樹脂組成物の出現が特に望まれてい
る。[Prior Art] Conventionally, oil-based ink has been used in letterpress printing plates, but the mist of this oil-based ink has a negative effect on the human body, and printed matter made with it takes a long time to dry. Recently, water-based inks have attracted attention because they have drawbacks such as staining hands, and therefore, the emergence of a negative photosensitive resin composition suitable for water-based inks as an alternative to oil-based inks is particularly desired. There is.
【0003】一方、従来より知られているネガ型感光性
樹脂組成物は、その現像液として、アルコール類や、ハ
ロゲン系などの有機溶剤を用いて現像されるもの(例え
ば米国特許第3,024,180号明細書、特公昭51
−43374号公報、米国特許第3,801,328号
明細書など)とアルカリ水現像型や水現像型のもの(例
えば特公昭54−3790号公報、特公昭53−208
2号公報など)があるが、現在は、安全性、労働環境、
現像液調製のミス防止などの面から、水現像型のネガ型
感光性樹脂組成物の使用が強く望まれている。On the other hand, conventionally known negative photosensitive resin compositions are developed using organic solvents such as alcohols and halogens as developing solutions (for example, as disclosed in US Pat. No. 3,024). , Specification No. 180, Special Publication No. 1973
-43374, U.S. Patent No. 3,801,328, etc.) and alkaline water developable type or water developable type (for example, Japanese Patent Publication No. 54-3790, Japanese Patent Publication No. 53-208).
Publication No. 2, etc.), but currently there are issues such as safety, working environment,
From the viewpoint of preventing errors in preparing a developer, it is strongly desired to use a water-developable negative photosensitive resin composition.
【0004】しかしながら、従来の水現像型のものは耐
水性が劣るため、水性インキを使用して印刷できないと
いう問題があった。したがって、このような問題を解決
するために、これまで種々のネガ型感光性樹脂組成物が
提案されている(特開昭61−22339号公報、特開
昭61−246742号公報、特開平1−306836
号公報、特開平2−4255号公報)。However, conventional water-developable inks have a problem in that they cannot be printed using water-based inks because they have poor water resistance. Therefore, in order to solve such problems, various negative photosensitive resin compositions have been proposed (Japanese Unexamined Patent Publications No. 61-22339, No. 61-246742, No. 1999). -306836
(Japanese Patent Application Laid-open No. 2-4255).
【0005】しかしながら、これらの組成物は水現像性
を有し、かつ水性インキによる印刷が可能であるものの
、完全な水現像型でないため、現像液が濁ったり、界面
活性剤を加えたりしなければならない上、得られる印刷
版はレリーフ部の耐水性が十分ではなく、耐刷性に劣る
などの欠点を有している。[0005] However, although these compositions have water-developability and can be printed with water-based ink, they are not completely water-developable, resulting in cloudy developing solutions and the need to add surfactants. In addition, the resulting printing plate has drawbacks such as insufficient water resistance in the relief portion and poor printing durability.
【0006】また、ポリビニルアルコールやビニルアル
コール共重合体をN−メチロールアクリルアミド又はN
−メチロールメタクリルアミドと反応させて、水酸基の
1〜40モル%をアクリルアミドメチルエーテル化又は
メタクリルアミドメチルエーテル化させた不飽和ポリビ
ニルアルコールを感光成分とする水現像型のネガ型感光
性樹脂組成物が開示されている(特公昭49−5923
号公報)。しかしながら、この組成物は、感度が低い上
、硬化物の耐水性が不十分であるなどの欠点を有してい
る。[0006] Polyvinyl alcohol or vinyl alcohol copolymers can also be converted into N-methylol acrylamide or N-methylol acrylamide.
- A water-developable negative photosensitive resin composition containing as a photosensitive component unsaturated polyvinyl alcohol in which 1 to 40 mol% of the hydroxyl groups are converted to acrylamide methyl ether or methacrylamide methyl ether by reacting with methylol methacrylamide. Disclosed (Special Publication No. 49-5923
Publication No.). However, this composition has drawbacks such as low sensitivity and insufficient water resistance of the cured product.
【0007】このように、従来のネガ型感光性樹脂組成
物は、いずれも得られる印刷版が耐水性に劣り、水性イ
ンキに対する印刷適性が不十分である上、完全な水現像
型ではないなどの欠点を有し、その改良が強く望まれて
いた。[0007] As described above, all conventional negative-working photosensitive resin compositions have poor water resistance, insufficient printability with water-based inks, and are not completely water-developable. However, there has been a strong desire for improvement.
【0008】[0008]
【発明が解決しようとする課題】本発明は、このような
要望にこたえ、耐水性が良好で、水性インキに対する印
刷適性に優れた凸版印刷版を与えうる水現像型のネガ型
感光性樹脂組成物を提供することを目的としてなされた
ものである。SUMMARY OF THE INVENTION In response to these demands, the present invention provides a water-developable negative photosensitive resin composition that can provide a letterpress printing plate with good water resistance and excellent printability with water-based inks. It was done for the purpose of providing something.
【0009】[0009]
【課題を解決するための手段】本発明者らは、前記の好
ましい性質を有するネガ型感光性樹脂組成物を開発すべ
く鋭意研究を重ねた結果、特定のビニルアルコール系重
合体、尿素誘導体、不飽和アクリルウレタン系オリゴマ
ー及び光重合開始剤を含有して成る樹脂組成物により、
その目的を達成しうることを見い出し、この知見に基づ
いて本発明を完成するに至った。[Means for Solving the Problems] As a result of intensive research to develop a negative photosensitive resin composition having the above-mentioned preferable properties, the present inventors have found that specific vinyl alcohol polymers, urea derivatives, With a resin composition containing an unsaturated acrylic urethane oligomer and a photopolymerization initiator,
The inventors have discovered that the object can be achieved, and have completed the present invention based on this knowledge.
【0010】すなわち、本発明は、(A)低級アルキロ
ールアクリルアミド又は低級アルキロールメタクリルア
ミドでエーテル化されたビニルアルコール系重合体、(
B)尿素、チオ尿素又はこれらの低級アルキル化、低級
アルキロール化若しくは低級アルキル低級アルキロール
化誘導体と低級アルキロールアクリルアミド又は低級ア
ルキロールメタクリルアミドとの縮合物、(C)不飽和
アクリルウレタン系オリゴマー及び(D)光重合開始剤
を含有して成るネガ型感光性樹脂組成物を提供するもの
である。Specifically, the present invention provides (A) a vinyl alcohol polymer etherified with lower alkylol acrylamide or lower alkylol methacrylamide;
B) Condensate of urea, thiourea or lower alkylated, lower alkylolated or lower alkyl lower alkylolated derivatives thereof and lower alkylol acrylamide or lower alkylol methacrylamide, (C) Unsaturated acrylic urethane oligomer and (D) a negative photosensitive resin composition comprising a photopolymerization initiator.
【0011】本発明組成物においては、(A)成分とし
て低級アルキロールアクリルアミド又は低級アルキロー
ルメタクリルアミドでエーテル化されたビニルアルコー
ル系重合体が用いられる。このビニルアルコール系重合
体における低級アルキロールアクリルアミド又は低級ア
ルキロールメタクリルアミドの低級アルキロールとして
は、例えばメチロール、エチロール、プロピロール、ブ
チロールなどを挙げることができる。また、ビニルアル
コール系重合体としては、ポリビニルアセテートを完全
ケン化したポリビニルアルコールであってもよいし、部
分ケン化物の形、すなわちビニルアルコール単位を有す
るビニルアルコール共重合体であってもよい。共重合体
を用いる場合には、ビニルアルコール単位60モル%以
上を含有するものが望ましい。この共重合体の共重合成
分としては、例えば酢酸ビニル、アクリル酸、メタクリ
ル酸、アクリルアミド、メタクリルアミド、N−メチロ
ールアクリルアミド、N−メチロールメタクリルアミド
、スチレン、エチレン、プロピレン、無水マレイン酸、
アクリロニトリル、メタクリロニトリル、アクリル酸エ
ステル、メタクリル酸エステルなどが挙げられる。In the composition of the present invention, a vinyl alcohol polymer etherified with lower alkylol acrylamide or lower alkylol methacrylamide is used as component (A). Examples of the lower alkylol of the lower alkylol acrylamide or lower alkylol methacrylamide in this vinyl alcohol polymer include methylol, ethylol, propyrrole, and butyrol. Further, the vinyl alcohol polymer may be polyvinyl alcohol obtained by completely saponifying polyvinyl acetate, or may be in the form of a partially saponified product, that is, a vinyl alcohol copolymer having vinyl alcohol units. When using a copolymer, one containing 60 mol% or more of vinyl alcohol units is desirable. Copolymerization components of this copolymer include, for example, vinyl acetate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, styrene, ethylene, propylene, maleic anhydride,
Examples include acrylonitrile, methacrylonitrile, acrylic esters, and methacrylic esters.
【0012】このビニルアルコール系重合体の重合度に
ついては、該重合体が水溶性であればよく特に制限はな
いが、平均重合度が200〜2000、好ましくは30
0〜1000のものが好適である。The degree of polymerization of this vinyl alcohol polymer is not particularly limited as long as the polymer is water-soluble, but the average degree of polymerization is 200 to 2000, preferably 30.
A value of 0 to 1000 is preferable.
【0013】本発明において(A)成分として用いられ
るエーテル化されたビニルアルコール系重合体は、例え
ば無機酸、スルホン酸誘導体、ハロゲン化アンモニウム
などの酸性触媒の存在下に、前記ビニルアルコール系重
合体を低級アルキロールアクリルアミド又は低級アルキ
ロールメタクリルアミドと反応させることにより、製造
することができる。The etherified vinyl alcohol polymer used as component (A) in the present invention is prepared by treating the vinyl alcohol polymer in the presence of an acidic catalyst such as an inorganic acid, a sulfonic acid derivative, or an ammonium halide. It can be produced by reacting with lower alkylol acrylamide or lower alkylol methacrylamide.
【0014】このようにして得られたエーテル化ビニル
アルコール系重合体は、ビニルアルコール単位50モル
%以上を含有するものが好ましく、このものを用いるこ
とによって得られる感光性樹脂組成物は十分な感度を有
するとともに、満足しうる柔軟性、耐水性及び印刷適性
を有する印刷版を与えることができる。The etherified vinyl alcohol polymer thus obtained preferably contains 50 mol% or more of vinyl alcohol units, and the photosensitive resin composition obtained using this polymer has sufficient sensitivity. It is possible to provide a printing plate that has not only the above properties but also satisfactory flexibility, water resistance, and printability.
【0015】本発明組成物においては、(B)成分とし
て尿素、チオ尿素又はこれらの低級アルキル化、低級ア
ルキロール化若しくは低級アルキル低級アルキロール化
誘導体と低級アルキロールアクリルアミド又は低級アル
キロールメタクリルアミドとの縮合物が用いられる。In the composition of the present invention, urea, thiourea or lower alkylated, lower alkylolated or lower alkyl lower alkylolated derivatives thereof, lower alkylolacrylamide or lower alkylolmethacrylamide are used as component (B). A condensate of is used.
【0016】この縮合物としては、例えば尿素又はチオ
尿素のアルキロール誘導体やアルキル化アルキロール誘
導体と、N−アルキロールアクリルアミド又はN−アル
キロールメタクリルアミドとを酸又はアンモニウム塩の
存在下で重縮合させるか、あるいは尿素又はチオ尿素と
ホルムアルデヒドとを反応させて線状縮重合体を形成さ
せ、次いでこれにN−アルキロールアクリルアミド又は
N−アルキロールメタクリルアミドを酸又はアンモニウ
ム塩の存在下でグラフト化反応させることにより得られ
るもの(特公昭54−3790号公報)、あるいは尿素
、チオ尿素又はそれらのアルキル誘導体とN−アルキロ
ールアクリルアミド、N−アルキロールメタクリルアミ
ドを水又は親水性有機溶媒中で酸又はアルカリ触媒を用
いて、熱重合禁止剤の存在下、60〜95℃の温度範囲
で1〜5時間かきまぜながら反応させることにより得ら
れたもの(特公平1−48528号公報)などを挙げる
ことができる。ここで、低級アルキル化、低級アルキロ
ール化若しくは低級アルキル低級アルキロール化誘導体
における低級アルキルとしては、メチル、エチル、プロ
ピル、ブチルなどを、低級アルキロールとしてはメチロ
ール、エチロール、プロピロール、ブチロールなどを、
低級アルキロールアクリルアミド又は低級アルキロール
メタクリルアミドの低級アルキロールとしてはメチロー
ル、エチロール、プロピロール、ブチロールなどを挙げ
ることができる。[0016] This condensate is obtained by polycondensing, for example, an alkylol derivative or alkylated alkylol derivative of urea or thiourea and N-alkylol acrylamide or N-alkylol methacrylamide in the presence of an acid or an ammonium salt. or reacting urea or thiourea with formaldehyde to form a linear condensation polymer, which is then grafted with N-alkylol acrylamide or N-alkylol methacrylamide in the presence of an acid or ammonium salt. (Japanese Patent Publication No. 54-3790), or by reacting urea, thiourea or their alkyl derivatives with N-alkylol acrylamide or N-alkylol methacrylamide in water or a hydrophilic organic solvent with an acid. Or those obtained by reacting using an alkali catalyst with stirring in the temperature range of 60 to 95°C for 1 to 5 hours in the presence of a thermal polymerization inhibitor (Japanese Patent Publication No. 1-48528). Can be done. Here, the lower alkyl in the lower alkylated, lower alkylolated, or lower alkyl lower alkylolated derivative includes methyl, ethyl, propyl, butyl, etc., and the lower alkylol includes methylol, ethylol, propyrrol, butyrol, etc. ,
Examples of the lower alkylol in lower alkylol acrylamide or lower alkylol methacrylamide include methylol, ethylol, propyrrole, and butyrol.
【0017】本発明組成物においては、(C)成分とし
て不飽和アクリルウレタン系オリゴマーが用いられる。
このウレタン系オリゴマーは、前記(A)成分及び(B
)成分と相容性のあるものが望ましく、このようなもの
としては、例えばジエチレングリコール、1,6−ヘキ
サンジオール、1,3−ジメチロール−2−プロピオン
酸などのジオール化合物とアジピン酸などのジカルボン
酸とを反応させてポリエステルのオリゴマーをまず形成
させたのち、このポリエステルオリゴマーの末端にある
2個の水酸基に対し、キシリレンジイソシアネートなど
のジイソシアネート化合物を反応させ、次いでこの反応
生成物の末端にあるイソシアネート基に2−ヒドロキシ
エチルメタクリレートなどを反応させることにより得ら
れた不飽和アクリルウレタン系オリゴマーなどを挙げる
ことができる。In the composition of the present invention, an unsaturated acrylic urethane oligomer is used as component (C). This urethane oligomer contains the component (A) and (B).
) components are desirable, and examples of such compounds include diol compounds such as diethylene glycol, 1,6-hexanediol, and 1,3-dimethylol-2-propionic acid, and dicarboxylic acids such as adipic acid. First, a polyester oligomer is formed by reacting with the polyester oligomer, and then a diisocyanate compound such as xylylene diisocyanate is reacted with the two hydroxyl groups at the ends of this polyester oligomer, and then the isocyanate at the ends of this reaction product is reacted with a diisocyanate compound such as xylylene diisocyanate. Examples include unsaturated acrylic urethane oligomers obtained by reacting 2-hydroxyethyl methacrylate with 2-hydroxyethyl methacrylate.
【0018】本発明組成物において、(D)成分として
用いられる光重合開始剤については特に制限はなく、従
来光重合性樹脂組成物に慣用されているものの中から、
任意のものを選択して用いることができる。該光重合開
始剤としては、例えばベンゾフェノン、2,4−ジヒド
ロキシベンゾフェノン、2−ヒドロキシ−4−アルコキ
シベンゾフェノンなどのベンゾフェノン誘導体、ベンゾ
イン、ベンゾインイソプロピルエーテル、ベンゾインメ
チルエーテルなどのベンゾイン誘導体、アントラキノン
、2−メチルアントラキノン、2−エチルアントラキノ
ンなどのアントラキノン誘導体などを挙げることができ
る。これらの光重合開始剤は1種用いてもよいし、2種
以上を組み合わせて用いてもよい。There are no particular limitations on the photopolymerization initiator used as component (D) in the composition of the present invention, and from among those conventionally used in photopolymerizable resin compositions,
Any one can be selected and used. Examples of the photopolymerization initiator include benzophenone derivatives such as benzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-alkoxybenzophenone, benzoin derivatives such as benzoin, benzoin isopropyl ether, and benzoin methyl ether, anthraquinone, and 2-methyl. Examples include anthraquinone derivatives such as anthraquinone and 2-ethylanthraquinone. These photopolymerization initiators may be used alone or in combination of two or more.
【0019】本発明組成物における各成分の配合割合に
ついては、(A)成分100重量部に対し、(B)成分
を10〜200重量部、(C)成分を5〜200重量部
、(D)成分を0.1〜10重量部の割合で配合するこ
とが好ましい。該(B)成分の配合量が10重量部未満
では感度が低く、露光時間が長くかかる上、架橋密度が
低いために得られる印刷版の機械的強度及び耐水性が不
十分であるし、200重量部を超えると感光性樹脂層の
表面がべたついたりしてネガフイルムとの密着性が悪く
なり、得られるレリーフの再現性が低下する傾向がみら
れる。Regarding the blending ratio of each component in the composition of the present invention, for 100 parts by weight of component (A), 10 to 200 parts by weight of component (B), 5 to 200 parts by weight of component (C), and 100 to 200 parts by weight of component (D). ) is preferably blended in a proportion of 0.1 to 10 parts by weight. If the amount of component (B) is less than 10 parts by weight, the sensitivity will be low, the exposure time will be long, and the mechanical strength and water resistance of the resulting printing plate will be insufficient due to the low crosslinking density. If the amount exceeds 1 part by weight, the surface of the photosensitive resin layer becomes sticky, resulting in poor adhesion to the negative film, which tends to reduce the reproducibility of the resulting relief.
【0020】また、(C)成分の配合量が5重量部未満
では柔軟性に劣り、印刷中に版の欠けを生じるおそれが
あるし、200重量部を超えると(A)成分との相容性
が低下し、不溶性物が表面に析出する傾向がみられる。Furthermore, if the amount of component (C) is less than 5 parts by weight, the flexibility will be poor and there is a risk of chipping of the plate during printing, while if it exceeds 200 parts by weight, it will not be compatible with component (A). There is a tendency for insoluble substances to precipitate on the surface.
【0021】一方、(D)成分の配合量が0.1重量部
未満では感度が低く、露光に長時間を要するし、10重
量部を超えると量の割には感度の向上がみられず、経済
的に不利となる。On the other hand, if the amount of component (D) is less than 0.1 part by weight, the sensitivity will be low and exposure will take a long time, and if it exceeds 10 parts by weight, no improvement in sensitivity will be seen in relation to the amount. , it becomes economically disadvantageous.
【0022】これらの各成分の好ましい配合割合は、(
A)成分100重量部に対し、(B)成分は30〜10
0重量部、(C)成分は20〜100重量部、(D)成
分は1〜5重量部の範囲で選ばれる。The preferred blending ratio of each of these components is (
Component (B) is 30 to 10 parts by weight for 100 parts by weight of component A).
0 parts by weight, 20 to 100 parts by weight of component (C), and 1 to 5 parts by weight of component (D).
【0023】本発明の感光性樹脂組成物には、所望に応
じ光重合性単量体を添加することもできる。この光重合
性単量体は、エチレン性不飽和基を少なくとも1個有す
る付加重合可能な化合物であって、他の成分と相容性を
有するものが用いられる。A photopolymerizable monomer may be added to the photosensitive resin composition of the present invention, if desired. This photopolymerizable monomer is an addition polymerizable compound having at least one ethylenically unsaturated group and is compatible with other components.
【0024】このような光重合性単量体としては、例え
ば多価アルコールのアクリル酸エステル又はメタクリル
酸エステル、グリセリンジアクリレート又はジメタクリ
レート、ジエチレングリコールモノアクリレート又はモ
ノメタクリレート、ジエチレングリコールジアクリレー
ト又はジメタクリレート、トリエチレングリコールジア
クリレート又はジメタクリレート、ヘキサンジオールジ
アクリレート又はジメタクリレート、トリメチロールプ
ロパントリアクリレート又はトリメタクリレート、ペン
タエリスリトールトリアクリレート又はトリメタクリレ
ート、ペンタエリスリトールテトラアクリレート又はテ
トラメタクリレート、あるいはエポキシ化合物とアクリ
ル酸又はメタクリル酸の付加反応物、カルボキシル基を
有する化合物とアクリル酸グリシジルの付加反応物又は
メタクリル酸グリシジルの付加反応物、一級又は二級の
アミノ基を有する化合物とアクリル酸グリシジルの付加
反応物又はメタクリル酸グリシジルの付加反応物、アク
リルアミド、メタクリルアミド、メチレンビスアクリル
アミド、メチレンビスメタクリルアミド、ジアセトンア
クリルアミド、トリアクリルホルマールなどのアクリル
アミド系化合物、水酸基を有するエチレン性不飽和化合
物とイソシアナートとの付加反応により得られる不飽和
ウレタン化合物などが挙げられる。これらのエチレン性
不飽和化合物は単独で使用してもよいし、2種以上を混
合して使用してもよい。この光重合性単量体の添加割合
は(A)成分100重量部に対して100重量部を超え
ない範囲であることが好ましい。100重量部を超える
と本発明の効果が十分に達成されないことがあり、好ま
しくない。Examples of such photopolymerizable monomers include acrylic esters or methacrylic esters of polyhydric alcohols, glycerin diacrylate or dimethacrylate, diethylene glycol monoacrylate or monomethacrylate, diethylene glycol diacrylate or dimethacrylate, and diethylene glycol diacrylate or dimethacrylate. Ethylene glycol diacrylate or dimethacrylate, hexanediol diacrylate or dimethacrylate, trimethylolpropane triacrylate or trimethacrylate, pentaerythritol triacrylate or trimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate, or epoxy compounds and acrylic or methacrylic acid addition reaction product of a compound having a carboxyl group and glycidyl acrylate or addition reaction product of glycidyl methacrylate; addition reaction product of a compound having a primary or secondary amino group and glycidyl acrylate or glycidyl methacrylate. Addition reaction products, acrylamide compounds such as acrylamide, methacrylamide, methylenebisacrylamide, methylenebismethacrylamide, diacetone acrylamide, triacrylformal, unsaturated compounds obtained by addition reaction between ethylenically unsaturated compounds having a hydroxyl group and isocyanates. Examples include saturated urethane compounds. These ethylenically unsaturated compounds may be used alone or in combination of two or more. The addition ratio of the photopolymerizable monomer is preferably within a range of not exceeding 100 parts by weight per 100 parts by weight of component (A). If it exceeds 100 parts by weight, the effects of the present invention may not be fully achieved, which is not preferable.
【0025】さらに、本発明においては、従来光重合性
樹脂組成物において慣用されている熱重合禁止剤、染料
や顔料などの着色剤、可塑剤、界面活性剤などを支障の
ない範囲で適宜配合して使用することもできる。Furthermore, in the present invention, thermal polymerization inhibitors, colorants such as dyes and pigments, plasticizers, surfactants, etc., which are conventionally used in photopolymerizable resin compositions, may be appropriately blended within the range that does not cause any hindrance. It can also be used as
【0026】本発明の感光性樹脂組成物は、所要量の前
記(A)成分、(B)成分、(C)成分、(D)成分及
び所望に応じて用いられる各種添加成分を均質に混合す
ることにより調製することができる。このようにして調
製された本発明の感光性樹脂組成物を用いて印刷用版材
を作成するには、例えば支持体上にカレンダー加工、コ
ーチング加工、圧縮成形、押出成形などの公知の方法に
よって厚さの均一なシートに成形し、感光層を形成させ
ればよい。該支持体としては、一般的に寸法精度や機械
的強度を向上させるためにアルミニウム、鋼、ステンレ
ス鋼、亜鉛、マグネシウムなどの金属板、ポリエチレン
テレフタレート、ポリプロピレン、セルロース誘導体な
どの合成樹脂のシートを使用することが好ましい。この
ような支持体を使用する場合には感光性樹脂層と支持体
との間に必要により接着層、ハレーション防止層あるい
はハレーション防止層兼接着層を設けることができる。The photosensitive resin composition of the present invention is prepared by homogeneously mixing the required amounts of the above components (A), (B), (C), and (D), and various additive components used as desired. It can be prepared by In order to create a printing plate material using the photosensitive resin composition of the present invention prepared in this way, for example, a known method such as calendering, coating, compression molding, extrusion molding, etc. is applied to the support. What is necessary is to form the sheet into a sheet having a uniform thickness and form a photosensitive layer thereon. As the support, metal plates such as aluminum, steel, stainless steel, zinc, and magnesium, and sheets of synthetic resins such as polyethylene terephthalate, polypropylene, and cellulose derivatives are generally used to improve dimensional accuracy and mechanical strength. It is preferable to do so. When such a support is used, an adhesive layer, an antihalation layer, or an antihalation layer and adhesive layer may be provided between the photosensitive resin layer and the support, if necessary.
【0027】[0027]
【発明の効果】本発明のネガ型感光性樹脂組成物は、特
定のビニルアルコール系重合体、尿素誘導体、不飽和ア
クリルウレタン系オリゴマー及び光重合開始剤を用いる
ことで、完全な水現像型となり、かつ耐水性及び印刷適
性に優れた印刷版を与えることができ、特に凸版印刷用
のネガ型感光性樹脂組成物として好適に用いられる。Effects of the Invention The negative photosensitive resin composition of the present invention can be completely water-developable by using a specific vinyl alcohol polymer, urea derivative, unsaturated acrylic urethane oligomer, and photopolymerization initiator. , and can provide a printing plate with excellent water resistance and printability, and is particularly suitable for use as a negative photosensitive resin composition for letterpress printing.
【0028】[0028]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.
【0029】製造例1
N−メチロールアクリルアミドでエーテル化されたポリ
ビニルアルコールA−1の製造
重合度500、ケン化度80%のポリ酢酸ビニル100
重量部に水100重量部、メチルアルコール20重量部
を加えて、80℃に保持して溶解した。これにN−メチ
ロールアクリルアミド30重量部、メチルヒドロキノン
0.1重量部及び85重量%のリン酸1重量部を加え、
80℃で3時間反応したのち、アンモニアで中和し、反
応物をアセトン1000重量部中に激しくかきまぜなが
ら加え、析出した沈殿物をろ過、乾燥して、N−メチロ
ールアクリルアミドでエーテル化されたポリビニルアル
コールA−1を得た。Production Example 1 Production of polyvinyl alcohol A-1 etherified with N-methylolacrylamide Polyvinyl acetate 100 with a degree of polymerization of 500 and a degree of saponification of 80%
100 parts by weight of water and 20 parts by weight of methyl alcohol were added to the parts by weight, and the mixture was maintained at 80°C to dissolve. To this, 30 parts by weight of N-methylolacrylamide, 0.1 part by weight of methylhydroquinone and 1 part by weight of 85% by weight phosphoric acid were added,
After reacting at 80°C for 3 hours, the reaction product was neutralized with ammonia, added to 1000 parts by weight of acetone with vigorous stirring, and the deposited precipitate was filtered and dried to obtain polyvinyl etherified with N-methylolacrylamide. Alcohol A-1 was obtained.
【0030】製造例2
N−メチロールアクリルアミドでエーテル化されたポリ
ビニルアルコールA−2の製造
重合度500、ケン化度88%のポリ酢酸ビニル100
重量部に水100重量部、メチルアルコール20重量部
を加えて、80℃に保持して溶解した。これにN−メチ
ロールアクリルアミド35重量部、メチルヒドロキノン
0.1重量部及び85重量%のリン酸1重量部を加え、
80℃で3時間反応したのち、アンモニア水で中和し、
反応物をアセトン1000重量部中に激しくかきまぜな
がら加え、析出した沈殿物をろ過、乾燥して、N−メチ
ロールアクリルアミドでエーテル化されたポリビニルア
ルコールA−2を得た。Production Example 2 Production of polyvinyl alcohol A-2 etherified with N-methylolacrylamide Polyvinyl acetate 100 with a degree of polymerization of 500 and a degree of saponification of 88%
100 parts by weight of water and 20 parts by weight of methyl alcohol were added to the parts by weight, and the mixture was maintained at 80°C to dissolve. To this, 35 parts by weight of N-methylolacrylamide, 0.1 part by weight of methylhydroquinone and 1 part by weight of 85% by weight phosphoric acid were added,
After reacting at 80°C for 3 hours, it was neutralized with aqueous ammonia,
The reactant was added to 1000 parts by weight of acetone with vigorous stirring, and the precipitate was filtered and dried to obtain polyvinyl alcohol A-2 etherified with N-methylolacrylamide.
【0031】製造例3
ジメチロールアクリルアミドと尿素との縮合物B−1の
製造
水30重量部にメチルヒドロキノン0.07重量部、塩
化アンモニウム1.4重量部を溶解し、これに尿素60
重量部、N−メチロールアクリルアミド138重量部を
加え、80℃に保持しながら2時間反応させて、反応物
をアセトン1000重量部中に激しくかきまぜながら加
え、析出した沈殿物をろ過、乾燥して、目的の縮合物B
−1を得た。Production Example 3 Production of condensate B-1 of dimethylolacrylamide and urea 0.07 parts by weight of methylhydroquinone and 1.4 parts by weight of ammonium chloride were dissolved in 30 parts by weight of water, and 60 parts by weight of urea was dissolved in this.
138 parts by weight of N-methylol acrylamide were added, the reaction was carried out for 2 hours while maintaining the temperature at 80°C, the reactant was added to 1000 parts by weight of acetone with vigorous stirring, and the precipitate precipitated was filtered and dried. Target condensate B
-1 was obtained.
【0032】製造例4
ジメチロール尿素ジメチルエーテルとN−メチロールア
クリルアミドとの縮合物B−2の製造
水10重量部にメチルヒドロキノン0.025重量部を
溶解し、これにジメチロール尿素ジメチルエーテル74
重量部、N−メチロールアクリルアミド202重量部、
塩化アンモニウム2重量部を加え、80℃に保持し2時
間反応したのち、反応物をアセトン1000重量部中に
激しくかきまぜながら加え、析出した沈殿物をろ過、乾
燥して、目的物の縮合物B−2を得た。Production Example 4 Production of condensate B-2 of dimethylol urea dimethyl ether and N-methylol acrylamide 0.025 parts by weight of methylhydroquinone was dissolved in 10 parts by weight of water, and 74 parts by weight of dimethylol urea dimethyl ether was dissolved in 10 parts by weight of water.
parts by weight, 202 parts by weight of N-methylol acrylamide,
After adding 2 parts by weight of ammonium chloride and reacting at 80°C for 2 hours, the reactant was added to 1000 parts by weight of acetone with vigorous stirring, and the precipitate precipitated was filtered and dried to obtain the target condensate B. -2 was obtained.
【0033】製造例5
不飽和アクリルウレタン系オリゴマーC−1の製造ジエ
チレングリコール、1,6−ヘキサンジオール、ジメチ
ロールプロピオン酸及びアジピン酸をモル比2:5:3
:7の割合で用いて、まずポリエステルを生成させたの
ち、この1モルに対してキシリレンジイソシアネート2
モルを反応させ、次いでこれに2−ヒドロキシエチルメ
タクリレート2モルを付加させることにより、不飽和ア
クリルウレタン系オリゴマーC−1を得た。Production Example 5 Production of unsaturated acrylic urethane oligomer C-1 Diethylene glycol, 1,6-hexanediol, dimethylolpropionic acid and adipic acid were mixed in a molar ratio of 2:5:3.
:7 to form a polyester, and then xylylene diisocyanate 2 to 1 mole of the polyester.
An unsaturated acrylic urethane oligomer C-1 was obtained by reacting 2 moles of 2-hydroxyethyl methacrylate and then adding 2 moles of 2-hydroxyethyl methacrylate thereto.
【0034】実施例1
製造例1で得たA−1 100重量部、製造例4で得
たB−2 100重量部、製造例5で得たC−1
50重量部、ペンタエリスリトールトリアクリレート2
0重量部、ベンジルジメチルケタール3重量部、メチル
ヒドロキノン0.05重量部及び水150重量部を90
℃に保温したフラスコ中でかきまぜながら均一に溶解し
た溶液を、0.17mmの厚さの鉄製基板上に設けられ
たハレーション防止層の上に流延したのち、40℃で1
5時間乾燥させて乾燥時の膜厚が0.4mmのネガ型感
光性樹脂層を得た。この層の上にテスト用ネガフイルム
とNo.2のステップタブレット(コダック社製)を重
ねて真空密着させ、ケミカルランプ〔(株)東芝製のF
L40BL型〕を用いて2.4cmの距離から4分間露
光後、ブラシ式溶出機を用いて30℃の温水で1分30
秒かけて未露光部を洗い出した。次いで100℃で5分
間乾燥し、さらに前記ケミカルランプを用いて5分間後
露光した。Example 1 100 parts by weight of A-1 obtained in Production Example 1, 100 parts by weight of B-2 obtained in Production Example 4, C-1 obtained in Production Example 5
50 parts by weight, pentaerythritol triacrylate 2
0 parts by weight, 3 parts by weight of benzyl dimethyl ketal, 0.05 parts by weight of methylhydroquinone and 150 parts by weight of water.
The solution was uniformly dissolved while stirring in a flask kept at 40°C, and then cast onto an antihalation layer provided on a 0.17 mm thick iron substrate.
After drying for 5 hours, a negative photosensitive resin layer having a dry film thickness of 0.4 mm was obtained. On top of this layer is a test negative film and No. Step 2 Tablets (manufactured by Kodak Corporation) are stacked and vacuum-adhered, and a chemical lamp [F manufactured by Toshiba Corporation] is applied.
After exposure for 4 minutes from a distance of 2.4 cm using [Model L40BL], incubate with warm water at 30°C for 1 minute and 30 minutes using a brush eluator.
It took a few seconds to wash out the unexposed areas. The film was then dried at 100° C. for 5 minutes, and further exposed to light using the chemical lamp described above for 5 minutes.
【0035】その結果、No.2のステップタブレット
による不溶化段数は16段であった。また、画像再現性
は表1に示すとおりであった。またこの版を25℃の水
に2時間浸漬したところ、レリーフ表面が厚さで5%膨
潤するだけで、画像部はしっかりしており、耐水性が優
れていることが確認された。さらに、この版を180°
に折り曲げても版が割れることはなく、柔軟性に富んで
いた。一方、この版を水性エマルジョンインキを使用し
て新聞凸版輪転機により印刷したところ、毎時10万部
のスピードで印刷しても3時間以上、シャープな画像が
維持された。As a result, No. The number of insolubilization stages using step 2 tablets was 16. Further, the image reproducibility was as shown in Table 1. When this plate was immersed in water at 25° C. for 2 hours, it was confirmed that the relief surface swelled by only 5% in thickness, and the image area was solid and had excellent water resistance. Furthermore, this plate is rotated 180°
The plate did not break even when bent, and was highly flexible. On the other hand, when this plate was printed using a water-based emulsion ink on a newspaper letterpress rotary press, sharp images were maintained for more than 3 hours even when printing at a speed of 100,000 copies per hour.
【0036】比較例1〜5
表1に示す組成から成るネガ型感光性樹脂組成物を用い
、実施例1と同様にして印刷版を作製し、その性能を評
価した。結果を表1に示す。これらの結果から、(A)
成分、(B)成分、(C)成分のそれぞれが、耐水性、
柔軟性のある印刷版を作製する上において、重要である
ことが確認された。Comparative Examples 1 to 5 Printing plates were prepared in the same manner as in Example 1 using negative photosensitive resin compositions having the compositions shown in Table 1, and their performance was evaluated. The results are shown in Table 1. From these results, (A)
Each of the components, (B) component, and (C) component has water resistance,
It was confirmed that this is important in producing flexible printing plates.
【表1】
(注)
1) 25℃の水に2時間浸漬後に画像部の状態につ
いて、〇は全く変化がないもの、△は細線の一部が膨潤
してレリーフが崩れたもの、×はレリーフが全て膨潤し
てレリーフの原形を留めないものをそれぞれ表わす。
2) 180°に折り曲げてたときの割れぐあいを柔
軟性でもって示し、〇は割れない物、×は割れてしまう
ものをそれぞれ表わす。
3) コダック社のステップタブレットNo.2を使
用したときの不溶化段数を表わす。
4) 65線/インチの網点部密度が再現される限界
値を表わす。
5) 再現できる最小線幅(μm)を表わす。
6) 0.5mmの白抜き部の製版後の深度(μm)
を表わす。[Table 1] (Notes) 1) Regarding the condition of the image area after immersion in water at 25°C for 2 hours, 〇 indicates that there is no change at all, △ indicates that some of the fine lines have swelled and the relief has collapsed, and × indicates that the relief has collapsed. Each represents a situation in which the relief is completely swollen and does not retain its original shape. 2) Flexibility indicates the degree of cracking when bent at 180°, with 〇 representing items that do not break and × representing items that will break. 3) Kodak Step Tablet No. It represents the number of insolubilization stages when 2 is used. 4) Represents the limit value at which a halftone dot density of 65 lines/inch can be reproduced. 5) Represents the minimum reproducible line width (μm). 6) Depth of 0.5mm white area after plate making (μm)
represents.
【0037】実施例2
製造例2で得たA−2 100重量部、製造例3で得
たB−1 100重量部、製造例5で得たC−1
40重量部、ベンジルメチルケタール2重量部、メチル
ヒドロキノン0.05重量部及び水130重量部を90
℃に保温したフラスコ中でかきまぜながら均一に溶解し
た溶液を、鉄製基板上に設けられたハレーション防止層
の上に一定の厚さに流延したのち、40℃で15時間乾
燥させて乾燥時の膜厚が0.5mmのネガ型感光性樹脂
層を得た。この層の上にテスト用ネガフイルムとNo.
2のステップタブレット(コダック社製)を重ねて真空
蒸着させ、ケミカルランプ〔(株)東芝製のFL40B
L型〕を用いて2.4cmの距離から5分間露光後、ブ
ラシ式溶出機を用いて30℃の温水で2分間かけて未露
光部を洗い出した。次いで100℃で5分間乾燥し、さ
らに前記ケミカルランプを用いて10分間後露光した。Example 2 100 parts by weight of A-2 obtained in Production Example 2, 100 parts by weight of B-1 obtained in Production Example 3, C-1 obtained in Production Example 5
40 parts by weight, 2 parts by weight of benzyl methyl ketal, 0.05 parts by weight of methylhydroquinone and 130 parts by weight of water.
The solution was uniformly dissolved while stirring in a flask kept at 40°C, and then cast to a certain thickness onto the antihalation layer provided on the iron substrate, and then dried at 40°C for 15 hours. A negative photosensitive resin layer having a film thickness of 0.5 mm was obtained. On top of this layer is a test negative film and No.
Step 2 tablets (manufactured by Kodak Corporation) were stacked and vacuum evaporated, and a chemical lamp [FL40B manufactured by Toshiba Corporation] was applied.
After exposure for 5 minutes from a distance of 2.4 cm using [L-type], the unexposed areas were washed out with warm water at 30° C. for 2 minutes using a brush type eluator. The film was then dried at 100° C. for 5 minutes, and further exposed to light using the chemical lamp described above for 10 minutes.
【0038】その結果、No.2のステップタブレット
による不溶化段数は15段であった。また、30μmの
最小線幅、65線/インチの2%ハイライト部の網点が
残存していた。さらにこの版を25℃の水に2時間浸漬
したところ、画像部の状態は変化がなく180°に折り
曲げても版が割れることはなかった。また、0.5mm
の白抜き部の製版後の深度は250μmであった。As a result, No. The number of insolubilization stages using step 2 tablets was 15. Further, halftone dots in the 2% highlight portion with a minimum line width of 30 μm and 65 lines/inch remained. Furthermore, when this plate was immersed in water at 25° C. for 2 hours, the condition of the image area remained unchanged, and the plate did not crack even when bent 180°. Also, 0.5mm
The depth of the white part after plate making was 250 μm.
Claims (1)
ド又は低級アルキロールメタクリルアミドでエーテル化
されたビニルアルコール系重合体、(B)尿素、チオ尿
素又はこれらの低級アルキル化、低級アルキロール化若
しくは低級アルキル低級アルキロール化誘導体と低級ア
ルキロールアクリルアミド又は低級アルキロールメタク
リルアミドとの縮合物、(C)不飽和アクリルウレタン
系オリゴマー及び(D)光重合開始剤を含有して成るネ
ガ型感光性樹脂組成物。Claim 1: (A) a vinyl alcohol polymer etherified with lower alkylol acrylamide or lower alkylol methacrylamide; (B) urea, thiourea, or lower alkylated, lower alkylolated or lower alkyl thereof; A negative photosensitive resin composition comprising a condensate of a lower alkylol derivative and a lower alkylol acrylamide or a lower alkylol methacrylamide, (C) an unsaturated acrylic urethane oligomer, and (D) a photopolymerization initiator. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8567791A JP2967791B2 (en) | 1991-01-25 | 1991-01-25 | Negative photosensitive resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8567791A JP2967791B2 (en) | 1991-01-25 | 1991-01-25 | Negative photosensitive resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04240855A true JPH04240855A (en) | 1992-08-28 |
JP2967791B2 JP2967791B2 (en) | 1999-10-25 |
Family
ID=13865468
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8567791A Expired - Lifetime JP2967791B2 (en) | 1991-01-25 | 1991-01-25 | Negative photosensitive resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2967791B2 (en) |
-
1991
- 1991-01-25 JP JP8567791A patent/JP2967791B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2967791B2 (en) | 1999-10-25 |
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