JP3784931B2 - Development method of photosensitive lithographic printing plate and developer used therefor - Google Patents
Development method of photosensitive lithographic printing plate and developer used therefor Download PDFInfo
- Publication number
- JP3784931B2 JP3784931B2 JP21854197A JP21854197A JP3784931B2 JP 3784931 B2 JP3784931 B2 JP 3784931B2 JP 21854197 A JP21854197 A JP 21854197A JP 21854197 A JP21854197 A JP 21854197A JP 3784931 B2 JP3784931 B2 JP 3784931B2
- Authority
- JP
- Japan
- Prior art keywords
- lithographic printing
- printing plate
- developer
- meth
- developing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 24
- 238000011161 development Methods 0.000 title claims description 13
- -1 methacryloyl group Chemical group 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 239000011342 resin composition Substances 0.000 claims description 20
- 229920005596 polymer binder Polymers 0.000 claims description 17
- 239000002491 polymer binding agent Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 8
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 230000018109 developmental process Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- 229940001593 sodium carbonate Drugs 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 238000000866 electrolytic etching Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- GTVSVCVFJRRHBM-UHFFFAOYSA-N 1-phenylbuta-1,3-dien-1-amine Chemical class C=CC=C(N)C1=CC=CC=C1 GTVSVCVFJRRHBM-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- NJJQKUCTKNDSPO-UHFFFAOYSA-N 2,4-diamino-1,5-diphenylpenta-1,4-dien-3-one Chemical compound C=1C=CC=CC=1C=C(N)C(=O)C(N)=CC1=CC=CC=C1 NJJQKUCTKNDSPO-UHFFFAOYSA-N 0.000 description 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical class NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- DQYSALLXMHVJAV-UHFFFAOYSA-M 3-heptyl-2-[(3-heptyl-4-methyl-1,3-thiazol-3-ium-2-yl)methylidene]-4-methyl-1,3-thiazole;iodide Chemical compound [I-].CCCCCCCN1C(C)=CS\C1=C\C1=[N+](CCCCCCC)C(C)=CS1 DQYSALLXMHVJAV-UHFFFAOYSA-M 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
- CDSULTPOCMWJCM-UHFFFAOYSA-N 4h-chromene-2,3-dione Chemical class C1=CC=C2OC(=O)C(=O)CC2=C1 CDSULTPOCMWJCM-UHFFFAOYSA-N 0.000 description 1
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- YKXVZTWMMZZVRA-UHFFFAOYSA-N CC1(C=CC=C1)[Ti]C1(C=CC=C1)C Chemical compound CC1(C=CC=C1)[Ti]C1(C=CC=C1)C YKXVZTWMMZZVRA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 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 1
- WZKXBGJNNCGHIC-UHFFFAOYSA-N Leucomalachite green Chemical compound C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=CC=C1 WZKXBGJNNCGHIC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005277 alkyl imino group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GSEZYWGNEACOIW-UHFFFAOYSA-N bis(2-aminophenyl)methanone Chemical class NC1=CC=CC=C1C(=O)C1=CC=CC=C1N GSEZYWGNEACOIW-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- PIPBVABVQJZSAB-UHFFFAOYSA-N bis(ethenyl) benzene-1,2-dicarboxylate Chemical compound C=COC(=O)C1=CC=CC=C1C(=O)OC=C PIPBVABVQJZSAB-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- UIZLQMLDSWKZGC-UHFFFAOYSA-N cadmium helium Chemical compound [He].[Cd] UIZLQMLDSWKZGC-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 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
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- 229940011411 erythrosine Drugs 0.000 description 1
- 239000004174 erythrosine Substances 0.000 description 1
- 235000012732 erythrosine Nutrition 0.000 description 1
- IYNRVIKPUTZSOR-HWKANZROSA-N ethenyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC=C IYNRVIKPUTZSOR-HWKANZROSA-N 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical class C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013020 steam cleaning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、アルミニウム板支持体表面に光重合型感光性樹脂組成物の感光層が形成された感光性平版印刷版の現像方法、およびそれに用いる現像液に関し、さらに詳しくは、経時や繰り返しの使用による現像性能の低下が抑えられると共に、非画像部の汚れもなく、良好な現像性と強固な画像強度が得られる感光性平版印刷版の現像方法、およびそれに用いる現像液に関する。
【０００２】
【従来の技術】
従来より広く使用されているネガ型感光性平版印刷版は、アルミニウム板支持体表面に設けられた感光層がジアゾ樹脂からなるために、現像液には有機溶媒を使用せざるを得ず、現像廃液の処理やその環境への影響が懸念されている。
また、ポジ型感光性平版印刷版の感光層には、ｏ−キノンジアジド化合物がノボラック樹脂を結合材として用いられているため、現像液にはノボラック樹脂を溶解可能なアルカリ性の珪酸塩水溶液を用いることができる。しかし、ノボラック樹脂を溶解可能なアルカリ現像液のｐＨは１３程度で、このような高ｐＨ現像液は、皮膚や粘膜に付着した場合の刺激性が強く、取扱いには十分な注意を必要とした。また、珪酸塩はアルカリ性領域では安定であるが、中性ではゲル化、不溶化し、また蒸発乾固するとフッ化水素酸のような強烈な酸にしか溶けなくなる欠点を持っており、実際、自動現像機の現像槽周辺の液はねによる固化物の汚れや、現像廃液を廃棄する際の中和による不溶化物の析出等がその実害として挙げられる。
【０００３】
一方、従来より、アルミニウム板支持体表面に光重合型感光性樹脂組成物の感光層を有する感光性平版印刷版は、画像露光した後、支持体上に画像を形成するための現像液として、アルカリ金属の珪酸塩、燐酸塩、炭酸塩、水酸化物等、および有機アミン化合物等の水溶液が用いられている。
しかし、これら従来の現像液は、経時的におよび繰り返しの使用により、現像性能が低下し易く、また、非画像部での感光層の抜け性も不十分であり、結果として、現像性および画像強度が必ずしも市場の要求を満たすものではない。
【０００４】
これに対して、この経時および繰り返しの使用による現像性能の低下を抑えるべく、特開平５−８８３７７号公報には、ガラス基板表面に形成した感光性樹脂組成物層を、例えば、ｐＨ１０前後の炭酸ナトリウムと炭酸水素ナトリウムの混合水溶液で現像することが提案されている。
しかしながら、本発明者は、この現像液を、アルミニウム板支持体表面に光重合型感光性樹脂組成物の感光層を有する感光性平版印刷版に適用したところ、非画像部での感光層の抜け性が必ずしも十分とは言えず、良好な現像性および強固な画像強度は得られなかった。
【０００５】
【発明が解決しようとする課題】
本発明は前述の従来技術に鑑みてなされたものであって、従って、本発明は、アルミニウム板支持体表面に光重合型感光性樹脂組成物の感光層が形成された感光性平版印刷版を現像するにおいて、経時や繰り返しの使用による現像性能の低下が抑えられると共に、非画像部の汚れもなく、良好な現像性と強固な画像強度が得られる感光性平版印刷版の現像方法、およびそれに用いる現像液を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者は、前記課題を解決すべく鋭意検討した結果、感光層を構成する光重合型感光性樹脂組成物として特定のものを用い、かつ、ｐＨを特定の範囲に規定すると共に導電率を特定の範囲に規定した、アルカリ金属の炭酸塩と炭酸水素塩の混合物の水溶液を用いて現像することにより目的を達成し得ることを見出し、本発明を完成したものである。
即ち、本発明は、アルミニウム板支持体表面にエチレン性不飽和結合含有単量体、光重合開始剤、および高分子結合材からなる光重合型感光性樹脂組成物の感光層が形成された平版印刷版を、画像露光した後、アルカリ金属の炭酸塩と炭酸水素塩の水溶液であって、ｐＨ８．５〜１１．５、導電率３〜３０ｍＳ／ｃｍの現像液で現像する感光性平版印刷版の現像方法、およびそれに用いる現像液を要旨とする。
【０００７】
【発明の実施の形態】
本発明において、アルミニウム板支持体としてのアルミニウムとは、アルミニウムまたはその合金を意味し、その厚さは、通常、０．０５〜１ｍｍ程度である。
これらのアルミニウム板支持体は、その表面への感光層の形成に先立ち、通常、脱脂処理、粗面化処理（砂目立て処理）、陽極酸化処理、および水洗浄処理等の表面処理が施される。
【０００８】
脱脂処理は、溶剤を用いて拭き取り、浸漬、蒸気洗浄する方法、アルカリ水溶液を用いて浸漬、噴霧した後、酸水溶液で中和する方法、界面活性剤を用いて浸漬、噴霧する方法等の常法に従い、通常、室温〜８０℃程度の温度で、１秒〜１分程度の時間でなされる。
【０００９】
次いで施される粗面化処理（砂目立て処理）は、ブラシ研磨法、ボール研磨法、ブラスト研磨法、バフ研磨法等の機械的処理方法、電解エッチング法、化学エッチング法、液体ホーニング法等の常法に従い、通常、表面平均粗さ０．１〜１．５μｍ程度に粗面化がなされる。中で、塩酸または硝酸電解液中で交流または直流により電解を行う電解エッチング法が好適である。
【００１０】
次いで、必要に応じて酸又はアルカリ水溶液でデスマット処理が施された後、施される陽極酸化処理は、硫酸、修酸、燐酸、クロム酸、マロン酸等の１種または２種以上を含む水溶液を電解液とし、アルミニウム板を陽極として電解を行うことによりなされ、これにより形成される酸化皮膜量は、通常、１〜５０ｍｇ／ｄｍ2 である。中で、硫酸を含む水溶液を電解液とする方法が好適であり、具体的には、例えば、特開昭５８−２１３８９４号公報に記載されるように、硫酸５〜５０重量％、温度５〜５０℃、電流密度１〜６０Ａ／ｄｍ2 で５〜６０秒間程度行われる。
【００１１】
その後施される水洗浄処理は、水道水、地下水等をそのまま、または軟化して用い、通常、室温〜４０℃程度の温度で、１秒〜５分程度の時間、シャワー、スプレー、浸漬、塗布等することによりなされる。
【００１２】
本発明において、表面処理された前記アルミニウム板支持体表面に形成された感光層を構成する光重合型感光性樹脂組成物の一成分としてのエチレン性不飽和結合含有単量体とは、光重合型感光性樹脂組成物が活性光線の照射を受けたとき、他の一成分としての光重合開始剤の作用により付加重合し、場合により架橋、硬化するようなエチレン性不飽和結合を含有する化合物を言い、従って、ここで言う単量体の意味するところは、いわゆる重合体に相対する概念であって、狭義の単量体以外にも、二量体、三量体やオリゴマーをも包含するものである。
【００１３】
本発明におけるこのエチレン性不飽和結合含有単量体としては、具体的には、例えば、(1) アクリル酸およびメタクリル酸（なお、以降、両者を纏めて「（メタ）アクリル酸」と言うことがある。）等の不飽和カルボン酸、(2) これらのアルキルエステル、（メタ）アクリロニトリル、スチレン等の外、(3) エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、および同様のイタコネート、クロトネート、マレエート等の脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル、(4) ヒドロキノンジ（メタ）アクリレート、レゾルシンジ（メタ）アクリレート、ピロガロールトリ（メタ）アクリレート等の芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル、(5) エチレングリコールと（メタ）アクリル酸とフタル酸との縮合物、ペンタエリスリトールと（メタ）アクリル酸とテレフタル酸との縮合物、ブタンジオールとグリセリンと（メタ）アクリル酸とアジピン酸との縮合物等のポリヒドロキシ化合物と不飽和カルボン酸と多価カルボン酸との縮合物、(6) トリレンジイソシアネート等のポリイソシアネート化合物とヒドロキシエチル（メタ）アクリレート等の水酸基含有（メタ）アクリレートとの付加反応物のようなウレタン（メタ）アクリレート、(7) 多価エポキシ化合物とヒドロキシエチル（メタ）アクリレート等の水酸基含有（メタ）アクリレートとの付加反応物のようなエポキシ（メタ）アクリレート、(8) エチレンビス（メタ）アクリルアミド等のアクリルアミド、(9) フタル酸ジアリル等のアリルエステル、(10)ジビニルフタレート等のビニル基含有化合物、等が挙げられる。
【００１４】
さらに、本発明において好適なエチレン性不飽和結合含有単量体として、前記エチレン性不飽和基含有単量体と（メタ）アクリロイル基含有燐酸エステルとの単量体混合物が挙げられ、その（メタ）アクリロイル基含有燐酸エステルとして、特に、下記式（１）で表されるものが好適である。
【００１５】
【化１】
【００１６】
前記式（１）で表されるものの中で、本発明に用いられるものは単体でも混合体であってもよいが、ｎが１〜１０であるものが耐刷性および非画像部の抜け性の面で特に好ましく、具体的には、メタアクリロイルオキシエチルホスフェート、ビス（メタアクリロイルオキシエチル）ホスフェート等が挙げられる。
本発明において、エチレン性不飽和単量体全体に占めるこの（メタ）アクリロイル基含有燐酸エステルの含有量は、１〜６０重量％、特には２〜４０重量％であるのが好ましい。この範囲においては、感光層としての露光感度、耐刷性が向上すると共に、現像性が改善される。
【００１７】
また、本発明において、感光層を構成する光重合型感光性樹脂組成物の一成分としての光重合開始剤としては、具体的には、例えば、ジシクロペンタジエニルチタニウムジクロライド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，４−ジフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，６−ジフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，４，６−トリフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６−テトラフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６−ペンタフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６−ジフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６−ペンタフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，６−ジフルオロ−３−（１−ピロリル）フェニル）等のチタノセン化合物、および、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−クロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ，ｐ−ジクロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−フルオロフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジブロモフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｏ，ｐ−ジクロロフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｐ−ヨードフェニル）ビイミダゾール、２，２’−ビス（ｏ−ブロモフェニル）−４，４’，５，５’−テトラ（ｏ−クロロ−ｐ−メトキシフェニル）ビイミダゾール、２，２’−ビス（ｏ−クロロフェニル）−４，４’，５，５’−テトラ（ｐ−クロロナフチル）ビイミダゾール等のハロゲン置換芳香族環を有するヘキサアリールビイミダゾール化合物が、感光層としての支持体への密着性、露光感度、および保存性の面から好適に用いられるが、その他に、ハロゲン化炭化水素誘導体、ジアリールヨードニウム塩、有機過酸化物等が挙げられる。
【００１８】
また、本発明において、感光層を構成する光重合型感光性樹脂組成物の一成分としての高分子結合材としては、具体的には、例えば、（メタ）アクリル酸、（メタ）アクリル酸エステル、（メタ）アクリロニトリル、（メタ）アクリルアミド、マレイン酸、スチレン、酢酸ビニル、塩化ビニリデン、マレイミド等の単独または共重合体、ならびに、ポリアミド、ポリエステル、ポリエーテル、ポリウレタン、ポリビニルブチラール、ポリビニルピロリドン、ポリエチレンオキシド、アセチルセルロース等が挙げられる。中で、カルボキシル基含有重合体が好適であり、具体的には、（メタ）アクリル酸と（メタ）アクリル酸エステルとの共重合体が好ましく、このカルボキシル基含有重合体の酸価は１０〜２５０、重量平均分子量は０．５〜１００万であるのが好ましい。
【００１９】
さらに、本発明における高分子結合材は、側鎖にエチレン性不飽和結合を有するものであるのが好適であり、そのエチレン性不飽和結合として、特に、下記式（２）、（３）、および（４）で表されるものが好適である。
【００２０】
【化２】
（式中、Ｒ2 は水素原子またはメチル基を示し、Ｒ3 〜Ｒ7 は各々独立して、水素原子、ハロゲン原子、アミノ基、ジアルキルアミノ基、カルボキシル基、アルコキシカルボニル基、スルホ基、ニトロ基、シアノ基、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアルキルアミノ基、置換基を有していてもよいアリールアミノ基、置換基を有していてもよいアルキルスルホニル基、または、置換基を有していてもよいアリールスルホニル基を示し、Ｚは酸素原子、硫黄原子、イミノ基、または、アルキルイミノ基を示す。）
【００２２】
前記式（２）で表されるエチレン性不飽和結合を側鎖に有する高分子結合材は、カルボキシル基含有重合体に、アリルグリシジルエーテル、グリシジル（メタ）アクリレート、α−エチルグリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、グリシジルクロトネート、グリシジルイソクロトネート、クロトニルグリシジルエーテル、イタコン酸モノアルキルモノグリシジルエステル、フマール酸モノアルキルモノグリシジルエステル、マレイン酸モノアルキルモノグリシジルエステル等の脂肪族エポキシ基含有不飽和化合物、および、特開平１−２８９８２０号公報に開示されるような脂環式エポキシ基含有不飽和化合物等を、８０〜１２０℃程度の温度、１〜５０時間程度の時間で、カルボキシル基含有重合体の有するカルボキシル基の５〜９０モル％、好ましくは３０〜７０モル％程度を反応させることにより製造される。
【００２３】
また、前記式（３）で表されるエチレン性不飽和結合を側鎖に有する高分子結合材は、アリル（メタ）アクリレート、３−アリルオキシ−２−ヒドロキシプロピル（メタ）アクリレート、シンナミル（メタ）アクリレート、クロトニル（メタ）アクリレート、メタリル（メタ）アクリレート、Ｎ，Ｎ−ジアリル（メタ）アクリルアミド等の２種以上の不飽和基を有する化合物と、また、前記式（４）で表されるエチレン性不飽和結合を側鎖に有する高分子結合材は、ビニル（メタ）アクリレート、１−クロロビニル（メタ）アクリレート、２−フェニルビニル（メタ）アクリレート、１−プロペニル（メタ）アクリレート、ビニルクロトネート、ビニル（メタ）アクリルアミド等の２種以上の不飽和基を有する化合物と、それぞれ、（メタ）アクリル酸等の不飽和カルボン酸、またはさらに不飽和カルボン酸エステルとを、前者の不飽和基を有する化合物の全体に占める割合を１０〜９０モル％、好ましくは３０〜８０モル％程度となるように共重合させることにより製造される。
【００２４】
本発明において、感光層を構成する光重合型感光性樹脂組成物としての前記エチレン性不飽和結合含有単量体、前記光重合開始剤、および前記高分子結合材の使用割合は、エチレン性不飽和結合含有単量体１００重量部に対して、光重合開始剤は０．１〜８０重量部、特には０．５〜６０重量部であるのが好ましく、高分子結合材は１０〜４００重量部、特には２０〜２００重量部であるのが好ましい。
【００２５】
なお、本発明において、光重合型感光性樹脂組成物としては、前記エチレン性不飽和結合含有単量体、前記光重合開始剤、および前記高分子結合材の外に、活性光線の照射時に光重合開始剤を活性化して効果的に活性ラジカルを発生させるために、例えば、米国特許第３４７９１８５号明細書に開示されるロイコクリスタルバイオレットやロイコマラカイトグリーン等のトリフェニルメタン系ロイコ色素、エリスロシンやエオシンＹ等の光還元性染料、米国特許第３５４９３６７号、同第３６５２２７５号各明細書に開示されるミヒラーズケトンやアミノスチリルケトン等のアミノフェニルケトン類、米国特許第３８４４７９０号明細書に開示されるβ−ジケトン類、米国特許第４１６２１６２号明細書に開示されるインダノン類、特開昭５２−１１２６８１号公報に開示されるケトクマリン類、特開昭５９−５６４０３号公報に開示されるアミノスチレン誘導体やアミノフェニルブタジエン誘導体、米国特許第４５９４３１０号明細書に開示されるアミノフェニル複素環類、米国特許第４９６６８３０号明細書に開示されるジュロリジン複素環類、特開平５−２４１３３８号公報に開示されるピロメテン系色素等の増感剤を、前記エチレン性不飽和結合含有単量体１００重量部に対して０．０１〜２０重量部、特には０．０５〜１０重量部使用するのが好ましく、さらに同様の目的で、例えば、２−メルカプトベンゾチアゾール、２−メルカプトベンズイミダゾール、２−メルカプトベンズオキサゾール、３−メルカプト−１，２，４−トリアゾール、Ｎ−フェニルグリシン、Ｎ，Ｎ−ジアルキルアミノ安息香酸アルキルエステル等の水素供与性化合物を、０．０１〜３０重量部、特には０．０５〜２０重量部使用するのが好ましい。
【００２６】
さらに、光重合型感光性樹脂組成物としては、必要に応じて、各種添加剤、例えば、ヒドロキノン、ｐ−メトキシフェノール、２，６−ジ−ｔ−ブチル−ｐ−クレゾール等の熱重合防止剤を２重量部以下、有機または無機の染顔料からなる着色剤を２０重量部以下、ジオクチルフタレート、ジドデシルフタレート、トリクレジルホスフェート等の可塑剤を４０重量部以下、三級アミンやチオール等の感度特性改善剤、その他色素前駆体等を３０重量部以下、添加してもよい。
【００２７】
本発明における光重合型感光性樹脂組成物は、以上の前記エチレン性不飽和結合含有単量体、前記光重合開始剤、および前記高分子結合材、ならびに、前記増感剤、前記水素供与性化合物、前記添加剤等を、例えば、シクロヘキサノン、プロピレングリコールモノメチルエーテルアセテート、エタノール等の溶媒の溶液として、例えば、ディップコート、コーティングロッド、スピナーコート、スプレーコート、ロールコート等の従来公知の方法により、前記アルミニウム板支持体表面に、乾燥膜厚が０．１〜１０ｇ／ｍ2 程度となるように塗布し乾燥することにより、感光性平版印刷版の感光層とされる。
【００２８】
なお、この際、感光層を保護するために、塗布後の版の搬送ロール等の感光層と接触する部材としてテフロン等の材質のものが好適に用いられる。
また、通常、前記感光層の上には、酸素による重合禁止作用を防止するために、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンオキシド、セルロース等の酸素遮蔽層が設けられる。
【００２９】
本発明における前記光重合型感光性樹脂組成物の感光層を、例えば、カーボンアーク、高圧水銀灯、キセノンランプ、メタルハライドランプ、蛍光ランプ、タングステンランプ、ハロゲンランプ、ヘリウムカドミウムレーザー、アルゴンイオンレーザー、ＹＡＧレーザー、ヘリウムネオンレーザー等の従来公知の活性光源で画像露光した後、現像処理することにより、アルミニウム板支持体表面に画像を形成することができる。
【００３０】
本発明において現像に用いる現像液は、アルカリ金属の炭酸塩と炭酸水素塩の水溶液であって、ｐＨ８．５〜１１．５、導電率３〜３０ｍＳ／ｃｍのものである。
ここで、アルカリ金属としては、リチウム、ナトリウム、カリウム等が挙げられ、中で、ナトリウムが好ましい。
また、ｐＨは、８．５〜１１．５であることが必須であり、９．０〜１１．０であるのが好ましく、９．０〜１０．５であるのがさらに好ましい。
また、導電率は、３〜３０ｍＳ／ｃｍであることが必須であり、５〜２５ｍＳ／ｃｍであるのが好ましく、８〜２０ｍＳ／ｃｍであることがさらに好ましく、１０〜１７ｍＳ／ｃｍであることが特に好ましい。
【００３１】
現像液が炭酸塩と炭酸水素塩の混合物以外のアルカリ金属塩からなる場合は、前記範囲のｐＨおよび導電率であっても、経時および繰り返しの使用による現像性能の低下が生じる。また、炭酸塩と炭酸水素塩の混合物からなる場合であっても、ｐＨが前記範囲を下回ると、画像形成ができなくなり、前記範囲を上回ると、空気中の炭酸ガスによる劣化等により現像性能の低下が生じる。また、導電率が前記範囲を下回ると、アルミニウム板支持体表面の感光性樹脂組成物の溶出が困難となって画像形成ができず、前記範囲を上回ると、非画像部に残膜を生じることとなり、いずれも現像性能が低下する。
【００３２】
前記現像液は、アルカリ金属の炭酸塩と炭酸水素塩の両者を同一水中に添加、溶解して作製したものであっても、両者のそれぞれの水溶液を混合して作製したものであってもよい。
【００３３】
また、前記現像液には、画質向上、現像時間の短縮等を目的として、必要に応じて、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、モノグリセリドアルキルエステル類等のノニオン系、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類等のアニオン系、アルキルベタイン類、アミノ酸類等の両性の界面活性剤、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコール等の水溶性有機溶剤、水酸基またはカルボキシル基を有する低分子化合物、消泡剤、硬水軟化剤等を添加することができる。
【００３４】
本発明における感光性平版印刷版の前記現像液による現像は、常法に従って、０〜６０℃、好ましくは１５〜４５℃程度の温度で、例えば、露光処理した平版印刷版を現像液に浸漬することにより行う。
この際、現像液中のアルカリ金属の炭酸塩の濃度をＡ（モル／リットル）、アルカリ金属の炭酸水素塩の濃度をＢ（モル／リットル）、液温をＴ（℃）として、下記の三つの式を同時に満足した条件で現像することにより、繰り返し使用による現像液の現像性能の低下を抑えることができる。
０．０００１≦Ａ≦１
０≦Ｔ≦６０
（１００−Ｔ）Ａ0.6 ／２≦７５Ｂ≦（１００−Ｔ）Ａ0.6
【００３５】
即ち、アルカリ金属の炭酸塩（Ｍ2 ＣＯ3 ）水溶液とアルカリ金属の炭酸水素塩（ＭＨＣＯ3 ）水溶液との混合液においては、両者共に完全にイオンに解離し、Ｍ+ 、ＣＯ3 2- 、ＨＣＯ3 - といったイオン種を生じる。そして、ＨＣＯ3 - ＋Ｈ+ →（←）Ｈ2 ＣＯ3 の平衡反応により混合水溶液中にはＭ+ 、ＣＯ3 2- 、ＨＣＯ3 - の三者の平衡が存在する。従って、Ｍ2 ＣＯ3 水溶液とＭＨＣＯ3 水溶液との比率を適宜選択して混合水溶液のｐＨを所定の範囲に調整するならば、Ｈ2 ＣＯ3 の濃度を空気中のＣＯ2 の分圧とバランスさせてＣＯ2 の吸収および放出を十分抑えることができ、上記の三つの式を同時に満足したときにこれが可能となる。ここで、各成分が水中に溶解した状態で存在すればよく、解離しない状態で存在することを必須としない。
【００３６】
現像液で現像処理した感光性平版印刷版は、通常、水洗水、界面活性剤等を含有するリンス液、アラビアガムや澱粉誘導体等を主成分とするフィニッシャーや保護ガム液で後処理する。
【００３７】
【実施例】
以下、本発明を実施例によりさらに具体的に説明するが、本発明はその要旨を越えない限り以下の実施例に限定されるものではない。
なお、使用したアルミニウム板支持体、エチレン性不飽和結合含有単量体、光重合開始剤、および高分子結合材、ならびに現像液は、以下の通りである。
【００３８】
アルミニウム板支持体
支持体▲１▼
アルミニウム板を３重量％水酸化ナトリウムで脱脂し、１１．５ｇ／リットル塩酸浴中で、２５℃、８０Ａ／ｄｍ2 の電流密度で１１秒間、電解エッチングし、水洗後、３０重量％硫酸浴中で、３０℃、１１．５ｇ／ｄｍ2 の電流密度で１５秒間、陽極酸化処理し、水洗、乾燥した支持体。
支持体▲２▼
支持体▲１▼を、さらに１重量％メタ珪酸ナトリウム水溶液で、８５℃で３０秒間、親水化処理し、水洗、乾燥した支持体。
【００３９】
エチレン性不飽和結合含有単量体
単量体▲１▼
下記の化合物。
【００４０】
【化３】
単量体▲２▼
下記の化合物。
【００４１】
【化４】
単量体▲３▼
下記の化合物。
【００４２】
【化５】
下記の化合物。
【００４３】
【化６】
【００４４】
光重合開始剤
下記の化合物
【００４５】
【化７】
高分子結合材
高分子結合材▲１▼
メチルメタクリレート（３５モル％）／イソブチルメタクリレート（２０モル％）／イソブチルアクリレート（１０モル％）／メタクリル酸（３５モル％）共重合体（重量平均分子量７万）。
高分子結合材▲２▼
前記高分子結合材▲１▼に、３，４−エポキシシクロヘキシルメチルアクリレートを反応させて得られた反応生成物（酸化６０、メタクリル酸成分のカルボキシル基の６０モル％が反応）。
【００４７】
高分子結合材▲３▼
ビニルメタクリレート（６０モル％）／メチルメタクリレート（２０モル％）／メタクリル酸（２０モル％）共重合体（重量平均分子量１４万）。
【００４８】
現像液
現像液▲１▼
炭酸ナトリウム０．００３モルと炭酸水素ナトリウム０．０１モルを１リットルの水に溶かし、界面活性剤（竹本油脂社製、「パイオニンＡ−４１Ｂ」）２０ｇを加えた水溶液（ｐＨ９．３、導電率２．６ｍＳ／ｃｍ）。
現像液▲２▼
現像液▲１▼に、塩化ナトリウム５ｇを加えた水溶液（ｐＨ９．３、導電率１１ｍＳ／ｃｍ）。
現像液▲３▼
炭酸ナトリウム０．０３モルと炭酸水素ナトリウム０．１０モルを１リットルの水に溶かし、界面活性剤（花王社製、「ペレックスＮＢＬ」）８０ミリリットルを加えた水溶液（ｐＨ９．３、導電率１２ｍＳ／ｃｍ）。
現像液▲４▼
炭酸ナトリウム０．０４モルと炭酸水素ナトリウム０．２４モルを１リットルの水に溶かし、界面活性剤（花王社製、「ペレックスＮＢＬ」）５０ミリリットルを加えた水溶液（ｐＨ９．３、導電率２２ｍＳ／ｃｍ）。
現像液▲５▼
炭酸ナトリウム０．１８モルと炭酸水素ナトリウム０．６０モルを１リットルの水に溶かし、界面活性剤（花王社製、「ペレックスＮＢＬ」）８０ミリリットルを加えた水溶液（ｐＨ９．３、導電率６０ｍＳ／ｃｍ）。
現像液▲６▼
炭酸ナトリウム０．０７モルと炭酸水素ナトリウム０．０８モルを１リットルの水に溶かし、界面活性剤（花王社製、「ペレックスＮＢＬ」）８０ミリリットルを加えた水溶液（ｐＨ１０．３、導電率１５ｍＳ／ｃｍ）。
現像液▲７▼
炭酸ナトリウム５ｇを１リットルの水に溶かし、界面活性剤（花王社製、「ペレックスＮＢＬ」）５０ミリリットルを加えた水溶液（ｐＨ１１．５、導電率１０ｍＳ／ｃｍ）。
現像液▲８▼
水酸化カリウム（８５％グレーン）５．３２ｇ、Ａ珪酸カリウム１４．９９ｇ、界面活性剤（花王社製、「ペレックスＮＢＬ」）１５．２１ｇ、およびｐ−ｔ−ブチル安息香酸３ｇを水２６０ｇに溶かした水溶液（ｐＨ１３．８、導電率４５ｍＳ／ｃｍ）。
【００４９】
実施例１〜５、比較例１〜３
表１に示すように、エチレン性不飽和結合含有単量体の混合物を用い、該単量体１００重量部に対して、光重合開始剤１８．２重量部、高分子結合材８１．８重量部、さらに、下記式で示される増感剤５．５重量部、
【００５０】
【化８】
２−メルカプトベンゾチアゾール９．１重量部、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル１８．２重量部、銅フタロシアニン顔料５．５重量部、および、シクロヘキサノン１９８２重量部を加えた光重合型感光性樹脂組成物塗布液を、それぞれ表１に示す支持体にバーコーターを用いて乾燥膜厚が２ｇ／ｍ2 となるように塗布、乾燥し、さらにその上に、ポリビニルアルコール水溶液をバーコーターを用いて乾燥膜厚が３ｇ／ｍ2 となるように塗布、乾燥することにより、感光性平版印刷版を作製した。
【００５２】
得られたそれぞれの感光性平版印刷版について、回折分光照射装置（ナルミ社製、「ＲＭ−２３」）を用いて露光した後、表１に示す現像液を用い２５℃で現像し、得られた重合、硬化画像の高さより、波長４８８ｎｍの光線による光重合、硬化に要する光エネルギー量を求め、露光感度を評価した。
また、得られたそれぞれの感光性平版印刷版について、未露光のまま、表１に示す現像液を用い２５℃で３０秒間浸漬してからスポンジで５回擦ることにより現像を行った後、メチルセロソルブ一滴を落として乾燥させ、現像インク（コニカ社製、「ＳＰＯ−１」）でインク盛りをすることにより、非画像部のインク着肉性を観察し、現像性を評価した。全くインクがのらないレベルを○、メチルセロソルブ滴下跡にフリンジが発生するレベルを△、全体にインクが着肉するレベルを×とした。
【００５３】
さらに、得られたそれぞれの感光性平版印刷版を空冷アルゴンレーザー（大日本スクリーン社製、「ＰＩ−Ｒ」）で１００μｊ／ｃｍ2 の露光量で走査露光した後、表１に示す現像液を用い２５℃で現像処理し、１％小点の再現性を評価した。完全に再現しているレベルを○、小点を完全に再現しているものの一部の小点がやや細りぎみであるレベルを△、小点の一部が再現していないレベルを×とした。
引き続いて、得られた平版印刷版を印刷機（三菱重工社製、「ＤＡＩＹＡ−１Ｆ−２型」）を用いて印刷し、画線部（１２０線、４％の小点）が跳ぶまでの印刷枚数で耐刷性を評価した。
以上の露光感度、現像性、小点再現性、および耐刷性の評価結果を表１に示した。
【００５４】
【表１】
実施例６〜７、比較例４〜５
ポリビニルアルコール層を設けなかった外は前記実施例２におけると同様にして作製した感光性平版印刷版について、表２に示すそれぞれの現像液を用い２５℃で現像し、現像液の繰り返し使用による現像性の低下の度合いを、現像時間と、ｐＨ、ΔＯＨ量を測定することにより評価した。なお、併せて、それぞれの現像液の一晩放置後のｐＨも測定した。
得られた結果を表２に示した。
【００５６】
【表２】
実施例８〜９、比較例６〜７
前記現像液▲３▼を用い、ポリビニルアルコール層を設けなかった外は前記実施例２におけると同様にして作製した感光性平版印刷版（実施例８）、ポリビニルアルコール層を設けなかったことと支持体▲２▼を用いたことの外は前記実施例２と同様にして作製した感光性平版印刷版（実施例９）、および、ノボラック系ポジ型感光性平版印刷版（三菱化学社製、「ＰＭ−１」）（比較例６）、ジアゾ系ネガ型感光性平版印刷版（三菱化学社製、「ＮＷ−１」）（比較例７）のそれぞれについて、前記実施例におけると同様にして現像性を評価した。
その結果、実施例８および実施例９では○、比較例６では現像不可、比較例７では×であった。
【００５８】
【発明の効果】
本発明によれば、アルミニウム板支持体表面に光重合型感光性樹脂組成物の感光層が形成された感光性平版印刷版を現像するにおいて、経時や繰り返しの使用による現像性能の低下が抑えられると共に、非画像部の汚れもなく、良好な現像性と強固な画像強度が得られる感光性平版印刷版の現像方法、およびそれに用いる現像液を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for developing a photosensitive lithographic printing plate in which a photosensitive layer of a photopolymerizable photosensitive resin composition is formed on the surface of an aluminum plate support, and a developer used therefor. The present invention relates to a developing method of a photosensitive lithographic printing plate that can suppress deterioration in developing performance due to the above, and can provide good developability and strong image strength without contamination of non-image areas, and a developer used therefor.
[0002]
[Prior art]
The negative photosensitive lithographic printing plate that has been widely used in the past has to use an organic solvent as a developer because the photosensitive layer provided on the surface of the aluminum plate support is made of a diazo resin. There are concerns about the treatment of waste liquid and its impact on the environment.
In addition, since an o-quinonediazide compound is used as a binder for the photosensitive layer of the positive photosensitive lithographic printing plate, an alkaline silicate aqueous solution capable of dissolving the novolak resin should be used as the developer. Can do. However, the pH of an alkaline developer capable of dissolving the novolak resin is about 13, and such a high pH developer is highly irritating when attached to the skin or mucous membrane, and requires careful handling. . Silicates are stable in the alkaline region, but are neutralized and gelled and insolubilized, and when evaporated to dryness, they have the disadvantage of being soluble only in strong acids such as hydrofluoric acid. Examples of the actual damage include contamination of the solidified product due to splashing around the developing tank of the developing machine and precipitation of insolubilized product due to neutralization when the developing waste solution is discarded.
[0003]
On the other hand, a photosensitive lithographic printing plate having a photosensitive layer of a photopolymerizable photosensitive resin composition on the surface of an aluminum plate support is conventionally used as a developer for forming an image on a support after image exposure. Aqueous solutions of alkali metal silicates, phosphates, carbonates, hydroxides, and organic amine compounds are used.
However, these conventional developers are liable to deteriorate in developing performance with time and repeated use, and the photosensitive layer is insufficiently removed in non-image areas. Strength does not always meet market demands.
[0004]
On the other hand, in order to suppress the deterioration of the development performance due to the aging and repeated use, JP-A-5-88377 discloses a photosensitive resin composition layer formed on the surface of a glass substrate, for example, a carbonic acid having a pH of about 10. It has been proposed to develop with a mixed aqueous solution of sodium and sodium bicarbonate.
However, the present inventor applied this developer to a photosensitive lithographic printing plate having a photosensitive layer of a photopolymerizable photosensitive resin composition on the surface of an aluminum plate support. Therefore, good developability and strong image strength could not be obtained.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described prior art. Accordingly, the present invention provides a photosensitive lithographic printing plate in which a photosensitive layer of a photopolymerizable photosensitive resin composition is formed on the surface of an aluminum plate support. In development, a method for developing a photosensitive lithographic printing plate that can suppress deterioration in development performance due to aging and repeated use, and that can provide good developability and strong image strength without contamination of non-image areas, and to it It aims at providing the developing solution to be used.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor used a specific photopolymerization type photosensitive resin composition constituting the photosensitive layer, specified the pH within a specific range, and increased the conductivity. The inventors have found that the object can be achieved by developing with an aqueous solution of a mixture of an alkali metal carbonate and bicarbonate specified in a specific range, and completed the present invention.
That is, the present invention provides a lithographic plate in which a photosensitive layer of a photopolymerizable photosensitive resin composition comprising an ethylenically unsaturated bond-containing monomer, a photopolymerization initiator, and a polymer binder is formed on the surface of an aluminum plate support. Photosensitive lithographic printing plate which is an aqueous solution of alkali metal carbonate and hydrogen carbonate, and is developed with a developer having a pH of 8.5 to 11.5 and a conductivity of 3 to 30 mS / cm after image exposure of the printing plate The developing method and the developer used therefor are summarized as follows.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, aluminum as an aluminum plate support means aluminum or an alloy thereof, and the thickness is usually about 0.05 to 1 mm.
These aluminum plate supports are usually subjected to surface treatment such as degreasing treatment, roughening treatment (graining treatment), anodizing treatment, and water washing treatment prior to the formation of the photosensitive layer on the surface. .
[0008]
The degreasing treatment is usually performed by wiping with a solvent, immersing or steam cleaning, immersing or spraying with an alkaline aqueous solution, neutralizing with an acid aqueous solution, or immersing or spraying with a surfactant. According to the method, it is usually performed at a temperature of room temperature to about 80 ° C. for a time of about 1 second to 1 minute.
[0009]
Next, the roughening treatment (graining treatment) applied is a mechanical treatment method such as a brush polishing method, a ball polishing method, a blast polishing method, a buff polishing method, an electrolytic etching method, a chemical etching method, a liquid honing method, or the like. According to a conventional method, the surface is usually roughened to an average surface roughness of about 0.1 to 1.5 μm. Among them, an electrolytic etching method in which electrolysis is performed by alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution is preferable.
[0010]
Subsequently, after desmutting with an acid or alkaline aqueous solution as necessary, the applied anodizing treatment is an aqueous solution containing one or more of sulfuric acid, oxalic acid, phosphoric acid, chromic acid, malonic acid and the like. Is an electrolytic solution and an aluminum plate is used as an anode, and the amount of the oxide film formed is usually 1 to 50 mg / dm.2It is. Among them, a method in which an aqueous solution containing sulfuric acid is used as the electrolytic solution is preferable. Specifically, as described in, for example, JP-A No. 58-213894, sulfuric acid is 5 to 50% by weight, and temperature is 5 to 5. 50 ° C., current density 1-60 A / dm2For about 5 to 60 seconds.
[0011]
The subsequent water washing treatment uses tap water, groundwater or the like as it is or is softened, usually at a temperature of room temperature to about 40 ° C. for a time of about 1 second to about 5 minutes, shower, spraying, dipping, coating. It is made by doing.
[0012]
In the present invention, the ethylenically unsaturated bond-containing monomer as one component of the photopolymerization type photosensitive resin composition constituting the photosensitive layer formed on the surface of the surface-treated aluminum plate support is a photopolymerization. Compound containing an ethylenically unsaturated bond that undergoes addition polymerization by the action of a photopolymerization initiator as another component when the photosensitive resin composition is irradiated with actinic rays, and in some cases is crosslinked or cured Therefore, the term "monomer" as used herein is a concept opposite to a so-called polymer and includes dimers, trimers and oligomers in addition to monomers in a narrow sense. Is.
[0013]
Specifically, as the ethylenically unsaturated bond-containing monomer in the present invention, for example, (1) acrylic acid and methacrylic acid (hereinafter, both are collectively referred to as “(meth) acrylic acid”) (2) In addition to these alkyl esters, (meth) acrylonitrile, styrene, etc. (3) Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol tetra ( ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, and similar itaconate, crotonate, maleate and other aliphatic polyhydroxys Ester of compound and unsaturated carboxylic acid, (4) ester of aromatic polyhydroxy compound such as hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate and unsaturated carboxylic acid, (5 ) Condensate of ethylene glycol, (meth) acrylic acid and phthalic acid, condensate of pentaerythritol, (meth) acrylic acid and terephthalic acid, butanediol, glycerin, (meth) acrylic acid and adipic acid Condensates of polyhydroxy compounds such as condensates and unsaturated carboxylic acids and polyvalent carboxylic acids, (6) Polyisocyanate compounds such as tolylene diisocyanate and hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate Urethane (meth) acrylates such as addition reaction products, (7) Epoxy (meth) acrylates such as addition reaction products of polyhydric epoxy compounds and hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, (8 ) Such as ethylenebis (meth) acrylamide; (9) allyl esters such as diallyl phthalate; and (10) vinyl group-containing compounds such as divinyl phthalate.
[0014]
Furthermore, examples of the ethylenically unsaturated bond-containing monomer suitable for the present invention include a monomer mixture of the ethylenically unsaturated group-containing monomer and the (meth) acryloyl group-containing phosphate ester. ) As the acryloyl group-containing phosphate ester, one represented by the following formula (1) is particularly preferable.
[0015]
[Chemical 1]
[0016]
Among those represented by the above formula (1), those used in the present invention may be a single substance or a mixture, but those having n of 1 to 10 have printing durability and non-image area slippage. In particular, methacryloyloxyethyl phosphate, bis (methacryloyloxyethyl) phosphate and the like are specifically mentioned.
In the present invention, the content of the (meth) acryloyl group-containing phosphate ester in the entire ethylenically unsaturated monomer is preferably 1 to 60% by weight, particularly 2 to 40% by weight. In this range, the exposure sensitivity and printing durability as the photosensitive layer are improved, and the developability is improved.
[0017]
In the present invention, specific examples of the photopolymerization initiator as a component of the photopolymerization type photosensitive resin composition constituting the photosensitive layer include, for example, dicyclopentadienyltitanium dichloride, dicyclopentadichloride. Enyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,4-difluorophenyl), dicyclopentadienyl titanium bis (2,6-difluorophenyl), dicyclopentadienyl titanium bis (2,4,6 -Trifluorophenyl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl), Di (methylcyclopentadienyl) titanium bis (2,6-difluorophenyl), di Titanocene such as methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), dicyclopentadienyltitanium bis (2,6-difluoro-3- (1-pyrrolyl) phenyl) Compounds and 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) Biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-fluorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) Nyl) -4,4 ′, 5,5′-tetra (o, p-dibromophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra ( o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) biimidazole, 2,2′-bis (o -Bromophenyl) -4,4 ', 5,5'-tetra (o-chloro-p-methoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5 ' -A hexaarylbiimidazole compound having a halogen-substituted aromatic ring such as tetra (p-chloronaphthyl) biimidazole is preferably used in terms of adhesion to a support as a photosensitive layer, exposure sensitivity, and storage stability. But in addition, Halogenated hydrocarbon derivatives, diaryliodonium salts, organic peroxides and the like can be mentioned.
[0018]
In the present invention, as the polymer binder as one component of the photopolymerization type photosensitive resin composition constituting the photosensitive layer, specifically, for example, (meth) acrylic acid, (meth) acrylic acid ester , (Meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate, vinylidene chloride, maleimide, and the like, as well as polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl pyrrolidone, polyethylene oxide And acetyl cellulose. Among them, a carboxyl group-containing polymer is suitable, specifically, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable, and the acid value of this carboxyl group-containing polymer is 10 to 10. 250, and the weight average molecular weight is preferably 0.5 to 1,000,000.
[0019]
Furthermore, the polymer binder in the present invention preferably has an ethylenically unsaturated bond in the side chain, and as the ethylenically unsaturated bond, in particular, the following formulas (2), (3), And those represented by (4) are preferred.
[0020]
[Chemical formula 2]
(Wherein R2Represents a hydrogen atom or a methyl group, RThree~ R7Each independently represents a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an optionally substituted alkyl group, or a substituent. An aryl group which may have, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent An optionally substituted arylamino group, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group, Z represents an oxygen atom, a sulfur atom, an imino group; Or an alkylimino group. )
[0022]
The polymer binder having an ethylenically unsaturated bond represented by the above formula (2) in the side chain includes a carboxyl group-containing polymer, allyl glycidyl ether, glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate. 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumaric acid monoalkyl monoglycidyl ester, maleic acid monoalkyl monoglycidyl ester Such as aliphatic epoxy group-containing unsaturated compounds, and alicyclic epoxy group-containing unsaturated compounds as disclosed in JP-A-1-289820, at a temperature of about 80 to 120 ° C. for 1 to 50 hours. In about the time, Calboki 5-90 mol% of the carboxyl groups of the Le group-containing polymer, are preferably prepared by reacting about 30 to 70 mol%.
[0023]
The polymer binder having an ethylenically unsaturated bond represented by the formula (3) in the side chain is allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth). A compound having two or more unsaturated groups such as acrylate, crotonyl (meth) acrylate, methallyl (meth) acrylate, N, N-diallyl (meth) acrylamide, and ethylenic compound represented by the formula (4) The polymer binder having an unsaturated bond in the side chain is vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, A compound having two or more unsaturated groups, such as vinyl (meth) acrylamide, and (meth) The proportion of unsaturated carboxylic acid such as crylic acid or further unsaturated carboxylic acid ester to the whole compound having an unsaturated group is 10 to 90 mol%, preferably about 30 to 80 mol%. Produced by copolymerization.
[0024]
In the present invention, the ethylenically unsaturated bond-containing monomer, the photopolymerization initiator, and the polymer binder used as the photopolymerization type photosensitive resin composition constituting the photosensitive layer are used in an ethylenically unsaturated manner. The photopolymerization initiator is preferably 0.1 to 80 parts by weight, particularly 0.5 to 60 parts by weight, and the polymer binder is 10 to 400 parts by weight with respect to 100 parts by weight of the saturated bond-containing monomer. Parts, particularly 20 to 200 parts by weight.
[0025]
In the present invention, the photopolymerizable photosensitive resin composition includes, in addition to the ethylenically unsaturated bond-containing monomer, the photopolymerization initiator, and the polymer binder, light upon irradiation with actinic rays. In order to activate the polymerization initiator and generate active radicals effectively, for example, triphenylmethane leuco dyes such as leuco crystal violet and leucomalachite green disclosed in US Pat. No. 3,479,185, erythrosine and eosin Photoreducible dyes such as Y, aminophenyl ketones such as Michler's ketone and aminostyryl ketone disclosed in US Pat. Nos. 3,549,367 and 3,652,275, and β--disclosed in US Pat. No. 3,844,790. Diketones, indanones disclosed in US Pat. No. 4,162,162, -112681, ketocoumarins disclosed in JP-A-59-56403, aminostyrene derivatives and aminophenylbutadiene derivatives disclosed in US Pat. No. 4,594,310, aminophenyl heterocycles disclosed in US Pat. No. 4,594,310, Sensitizers such as julolidine heterocycles disclosed in Japanese Patent No. 4966830 and pyromethene dyes disclosed in JP-A-5-241338 are added to 100 parts by weight of the ethylenically unsaturated bond-containing monomer. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole are preferably used for 0.01 to 20 parts by weight, particularly 0.05 to 10 parts by weight. , 3-mercapto-1,2,4-triazole, N-phenylglycine, N, It is preferable to use a hydrogen donating compound such as an N-dialkylaminobenzoic acid alkyl ester in an amount of 0.01 to 30 parts by weight, particularly 0.05 to 20 parts by weight.
[0026]
Furthermore, as the photopolymerization type photosensitive resin composition, various additives, for example, thermal polymerization inhibitors such as hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-p-cresol, and the like, as necessary. 2 parts by weight or less, a colorant comprising an organic or inorganic dye / pigment 20 parts by weight or less, a plasticizer such as dioctyl phthalate, didodecyl phthalate, or tricresyl phosphate 40 parts by weight or less, a tertiary amine, thiol or the like A sensitivity property improver, other dye precursors, and the like may be added in an amount of 30 parts by weight or less.
[0027]
The photopolymerizable photosensitive resin composition according to the present invention includes the above-described monomer containing an ethylenically unsaturated bond, the photopolymerization initiator, the polymer binder, the sensitizer, and the hydrogen donating property. The compound, the additive, etc., for example, as a solution in a solvent such as cyclohexanone, propylene glycol monomethyl ether acetate, ethanol, etc., for example, by a conventionally known method such as dip coating, coating rod, spinner coating, spray coating, roll coating, On the surface of the aluminum plate support, the dry film thickness is 0.1 to 10 g / m.2By applying and drying to a degree, a photosensitive layer of the photosensitive lithographic printing plate is obtained.
[0028]
In this case, in order to protect the photosensitive layer, a member made of a material such as Teflon is preferably used as a member that comes into contact with the photosensitive layer such as a transport roll of the coated plate.
In general, an oxygen shielding layer such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, cellulose or the like is provided on the photosensitive layer in order to prevent a polymerization inhibiting action due to oxygen.
[0029]
The photosensitive layer of the photopolymerizable photosensitive resin composition in the present invention may be, for example, a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium cadmium laser, an argon ion laser, or a YAG laser. An image can be formed on the surface of the aluminum plate support by exposing the image with a conventionally known active light source such as a helium neon laser and then developing the image.
[0030]
The developer used for development in the present invention is an aqueous solution of alkali metal carbonate and bicarbonate, and has a pH of 8.5 to 11.5 and a conductivity of 3 to 30 mS / cm.
Here, as an alkali metal, lithium, sodium, potassium, etc. are mentioned, and sodium is preferable in it.
Moreover, it is essential that pH is 8.5-11.5, it is preferable that it is 9.0-11.0, and it is further more preferable that it is 9.0-10.5.
Further, the conductivity is essential to be 3 to 30 mS / cm, preferably 5 to 25 mS / cm, more preferably 8 to 20 mS / cm, and 10 to 17 mS / cm. Is particularly preferred.
[0031]
When the developer is made of an alkali metal salt other than a mixture of carbonate and hydrogen carbonate, the development performance deteriorates with time and repeated use even if the pH and conductivity are in the above ranges. Further, even in the case of a mixture of carbonate and bicarbonate, if the pH falls below the above range, image formation becomes impossible, and if it exceeds the above range, the development performance is deteriorated due to deterioration due to carbon dioxide gas in the air. A decrease occurs. Further, if the conductivity is lower than the above range, elution of the photosensitive resin composition on the surface of the aluminum plate support becomes difficult and image formation cannot be performed, and if it exceeds the above range, a remaining film is generated in the non-image area. In both cases, the development performance deteriorates.
[0032]
The developer may be prepared by adding and dissolving both alkali metal carbonate and hydrogen carbonate in the same water, or may be prepared by mixing respective aqueous solutions of both. .
[0033]
In addition, for the purpose of improving the image quality, shortening the development time, and the like, the developer includes, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan, if necessary. Nonionics such as alkyl esters, monoglyceride alkyl esters, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters, and the like, alkyl betaines, amino acids, etc. Amphoteric surfactants, water-soluble organic solvents such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, hydroxyl groups or carbohydrates Low molecular compounds having a sill group, can be added a defoaming agent, a hard water softening agent or the like.
[0034]
The development of the photosensitive lithographic printing plate in the present invention with the developer is performed by immersing the exposed lithographic printing plate in the developer at a temperature of about 0 to 60 ° C., preferably about 15 to 45 ° C., according to a conventional method. By doing.
At this time, the alkali metal carbonate concentration in the developer is A (mol / liter), the alkali metal bicarbonate concentration is B (mol / liter), and the solution temperature is T (° C.). By developing under the conditions satisfying the two equations at the same time, it is possible to suppress a decrease in the developing performance of the developer due to repeated use.
0.0001 ≦ A ≦ 1
0 ≦ T ≦ 60
(100-T) A0.6/ 2≤75B≤ (100-T) A0.6
[0035]
That is, alkali metal carbonate (M2COThree) Aqueous solution and alkali metal bicarbonate (MHCO)Three) In the mixed solution with the aqueous solution, both are completely dissociated into ions, and M+, COThree 2-, HCOThree -This produces ionic species. And HCOThree -+ H+→ (←) H2COThreeIn the mixed aqueous solution due to the equilibrium reaction of+, COThree 2-, HCOThree -There is a three-way equilibrium. Therefore, M2COThreeAqueous solution and MHCOThreeIf the pH of the mixed aqueous solution is adjusted to a predetermined range by appropriately selecting the ratio with the aqueous solution,2COThreeConcentration of CO in air2Balance with the partial pressure of CO2Absorption and release can be sufficiently suppressed, and this is possible when the above three expressions are satisfied at the same time. Here, it is sufficient that each component exists in a dissolved state in water, and it is not essential that each component exist in a non-dissociated state.
[0036]
The photosensitive lithographic printing plate developed with a developer is usually post-treated with a washing water, a rinse solution containing a surfactant, a finisher or a protective gum solution mainly composed of gum arabic or starch derivatives.
[0037]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
The aluminum plate support, the ethylenically unsaturated bond-containing monomer, the photopolymerization initiator, the polymer binder, and the developer used are as follows.
[0038]
Aluminum plate support
Support ▲ 1 ▼
The aluminum plate was degreased with 3% by weight sodium hydroxide and 11.5 g / liter hydrochloric acid bath at 25 ° C. and 80 A / dm.2Electrolytically etched at a current density of 11 seconds, washed with water, 30% sulfuric acid bath at 30 ° C., 11.5 g / dm2The support was anodized at a current density of 15 seconds, washed with water and dried.
Support body ▲ 2 ▼
A support obtained by hydrophilizing the support (1) with a 1% by weight aqueous sodium metasilicate solution at 85 ° C. for 30 seconds, washing with water and drying.
[0039]
Monomers containing ethylenically unsaturated bonds
Monomer (1)
The following compounds.
[0040]
[Chemical Formula 3]
Monomer (2)
The following compounds.
[0041]
[Formula 4]
Monomer (3)
The following compounds.
[0042]
[Chemical formula 5]
The following compounds.
[0043]
[Chemical 6]
[0044]
Photopolymerization initiator
The following compounds
[0045]
[Chemical 7]
Polymer binder
Polymer binding material (1)
Methyl methacrylate (35 mol%) / isobutyl methacrylate (20 mol%) / isobutyl acrylate (10 mol%) / methacrylic acid (35 mol%) copolymer (weight average molecular weight 70,000).
Polymer binder (2)
A reaction product obtained by reacting 3,4-epoxycyclohexylmethyl acrylate with the polymer binder (1) (oxidation 60, 60 mol% of carboxyl groups of methacrylic acid component react).
[0047]
Polymer binding material (3)
Vinyl methacrylate (60 mol%) / methyl methacrylate (20 mol%) / methacrylic acid (20 mol%) copolymer (weight average molecular weight 140,000).
[0048]
Developer
Developer (1)
An aqueous solution (pH 9.3, conductivity) obtained by dissolving 0.003 mol of sodium carbonate and 0.01 mol of sodium hydrogen carbonate in 1 liter of water and adding 20 g of a surfactant (“Pionin A-41B” manufactured by Takemoto Yushi Co., Ltd.) 2.6 mS / cm).
Developer (2)
An aqueous solution obtained by adding 5 g of sodium chloride to the developer (1) (pH 9.3, conductivity 11 mS / cm).
Developer (3)
Aqueous solution (pH 9.3, conductivity 12 mS /) by dissolving 0.03 mol of sodium carbonate and 0.10 mol of sodium hydrogen carbonate in 1 liter of water and adding 80 ml of a surfactant (“PEX NBL” manufactured by Kao Corporation) cm).
Developer (4)
An aqueous solution (pH 9.3, conductivity 22 mS /) of 0.04 mol of sodium carbonate and 0.24 mol of sodium hydrogencarbonate dissolved in 1 liter of water and added with 50 ml of a surfactant (“PEX NBL” manufactured by Kao Corporation) cm).
Developer (5)
An aqueous solution (pH 9.3, conductivity 60 mS /) of 0.18 mol of sodium carbonate and 0.60 mol of sodium hydrogen carbonate dissolved in 1 liter of water and added with 80 ml of a surfactant (“PEX NBL” manufactured by Kao Corporation) cm).
Developer (6)
An aqueous solution (pH of 10.3, conductivity of 15 mS / s) obtained by dissolving 0.07 mol of sodium carbonate and 0.08 mol of sodium hydrogen carbonate in 1 liter of water and adding 80 ml of a surfactant (“PEX NBL” manufactured by Kao Corporation) cm).
Developer ▲ 7 ▼
An aqueous solution (pH 11.5, conductivity 10 mS / cm) in which 5 g of sodium carbonate was dissolved in 1 liter of water and 50 ml of a surfactant (manufactured by Kao Corporation, “Perex NBL”) was added.
Developer (8)
Dissolve 5.32 g of potassium hydroxide (85% grain), 14.99 g of potassium A silicate, 15.21 g of a surfactant (manufactured by Kao Corporation, “Perex NBL”), and 3 g of pt-butylbenzoic acid in 260 g of water. Aqueous solution (pH 13.8, conductivity 45 mS / cm).
[0049]
Examples 1-5, Comparative Examples 1-3
As shown in Table 1, using a mixture of ethylenically unsaturated bond-containing monomers, the photopolymerization initiator 18.2 parts by weight and the polymer binder 81.8 parts by weight with respect to 100 parts by weight of the monomers. Further, 5.5 parts by weight of a sensitizer represented by the following formula:
[0050]
[Chemical 8]
Photopolymerization type photosensitivity in which 9.1 parts by weight of 2-mercaptobenzothiazole, 18.2 parts by weight of N, N-dimethylaminobenzoic acid ethyl ester, 5.5 parts by weight of copper phthalocyanine pigment, and 1982 parts by weight of cyclohexanone are added. The resin composition coating solution was dried at a film thickness of 2 g / m using a bar coater on each support shown in Table 1.2Then, a polyvinyl alcohol aqueous solution is further dried using a bar coater to a dry film thickness of 3 g / m.2A photosensitive lithographic printing plate was prepared by coating and drying so that
[0052]
Each of the obtained photosensitive lithographic printing plates was exposed using a diffraction spectroscopic irradiation apparatus (“RM-23” manufactured by Narumi Co., Ltd.) and then developed at 25 ° C. using the developer shown in Table 1. The amount of light energy required for photopolymerization and curing with light having a wavelength of 488 nm was determined from the height of the polymerized and cured images, and the exposure sensitivity was evaluated.
Further, each of the obtained photosensitive lithographic printing plates was unexposed and developed by immersing it at 25 ° C. for 30 seconds using a developer shown in Table 1, followed by rubbing with a sponge 5 times, One drop of cellosolve was dropped and dried, and the ink was deposited with a developing ink (manufactured by Konica, “SPO-1”), thereby observing the ink deposition property of the non-image area and evaluating the developability. The level at which no ink was applied was indicated by ◯, the level at which fringe was generated on the methyl cellosolve dripping trace was indicated by Δ, and the level at which ink was completely deposited was indicated by ×.
[0053]
Further, each of the obtained photosensitive lithographic printing plates was air-cooled with an argon laser (Dainippon Screen, “PI-R”) at 100 μj / cm.2After scanning exposure with the exposure amount of 1, development processing was performed at 25 ° C. using the developer shown in Table 1, and the reproducibility of 1% small point was evaluated. The level that is completely reproduced is indicated by ○, the level that completely reproduces the small dots, but the level that some of the small dots are slightly narrowed is △, and the level that does not reproduce part of the small points is ×. .
Subsequently, the obtained lithographic printing plate was printed using a printing machine (Mitsubishi Heavy Industries, “DAIYA-1F-2”) until the image line part (120 lines, 4% dot) jumped. Printing durability was evaluated by the number of printed sheets.
The evaluation results of the above exposure sensitivity, developability, small dot reproducibility, and printing durability are shown in Table 1.
[0054]
[Table 1]
Examples 6-7, Comparative Examples 4-5
The photosensitive lithographic printing plate produced in the same manner as in Example 2 except that the polyvinyl alcohol layer was not provided was developed at 25 ° C. using each developer shown in Table 2, and developed by repeated use of the developer. The degree of deterioration was evaluated by measuring the development time, pH, and ΔOH amount. In addition, the pH of each developer after standing overnight was also measured.
The obtained results are shown in Table 2.
[0056]
[Table 2]
Examples 8-9, Comparative Examples 6-7
A photosensitive lithographic printing plate (Example 8) prepared in the same manner as in Example 2 except that the developer (3) was not used and a polyvinyl alcohol layer was not provided. A photosensitive lithographic printing plate (Example 9) prepared in the same manner as in Example 2 except that the body (2) was used, and a novolak positive photosensitive lithographic printing plate (manufactured by Mitsubishi Chemical Corporation, “ PM-1 ") (Comparative Example 6) and a diazo negative photosensitive lithographic printing plate (" NW-1 "manufactured by Mitsubishi Chemical Corporation) (Comparative Example 7) were each developed in the same manner as in the above Examples. Sex was evaluated.
As a result, Example 8 and Example 9 were o, Comparative Example 6 was not developable, and Comparative Example 7 was x.
[0058]
【The invention's effect】
According to the present invention, in developing a photosensitive lithographic printing plate in which a photosensitive layer of a photopolymerizable photosensitive resin composition is formed on the surface of an aluminum plate support, it is possible to suppress deterioration in developing performance due to aging or repeated use. At the same time, it is possible to provide a developing method for a photosensitive lithographic printing plate in which good developability and strong image strength can be obtained without contamination of non-image areas, and a developer used therefor.
Claims (6)
０．０００１≦Ａ≦１
０≦Ｔ≦６０
（１００−Ｔ）Ａ0.6 ／２≦７５Ｂ≦（１００−Ｔ）Ａ0.6 Assuming that the developer has an alkali metal carbonate concentration of A (mol / liter), an alkali metal bicarbonate concentration of B (mol / liter), and a liquid temperature of T (° C.), the following three formulas are obtained. 5. The method for developing a photosensitive lithographic printing plate according to claim 1, which is simultaneously satisfied.
0.0001 ≦ A ≦ 1
0 ≦ T ≦ 60
(100-T) A 0.6 / 2 ≦ 75B ≦ (100-T) A 0.6
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21854197A JP3784931B2 (en) | 1997-08-13 | 1997-08-13 | Development method of photosensitive lithographic printing plate and developer used therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21854197A JP3784931B2 (en) | 1997-08-13 | 1997-08-13 | Development method of photosensitive lithographic printing plate and developer used therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1165126A JPH1165126A (en) | 1999-03-05 |
| JP3784931B2 true JP3784931B2 (en) | 2006-06-14 |
Family
ID=16721554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21854197A Expired - Fee Related JP3784931B2 (en) | 1997-08-13 | 1997-08-13 | Development method of photosensitive lithographic printing plate and developer used therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3784931B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2157478A2 (en) | 2008-08-22 | 2010-02-24 | Fujifilm Corporation | Method of producing lithographic printing plate |
| EP2159640A1 (en) | 2008-08-29 | 2010-03-03 | Fujifilm Corporation | Method of preparing lithographic printing plate |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001316416A (en) * | 2000-05-10 | 2001-11-13 | Nippon Paint Co Ltd | Photopolymerizable composition and photopolymerizable putty composition |
| EP1199606A1 (en) * | 2000-10-16 | 2002-04-24 | Fuji Photo Film Co., Ltd. | Plate-making method of lithographic printing plate |
| EP1502941B1 (en) | 2003-07-30 | 2015-12-23 | FUJIFILM Corporation | Image-forming method and developer |
| JP2005049542A (en) | 2003-07-31 | 2005-02-24 | Fuji Photo Film Co Ltd | Picture forming method and developer |
| US7115352B2 (en) | 2003-10-30 | 2006-10-03 | Fuji Photo Film Co., Ltd. | Method for forming images |
| US7125648B2 (en) | 2003-12-19 | 2006-10-24 | Fuji Photo Film Co., Ltd. | Method for forming images |
| JP4900913B2 (en) | 2006-02-01 | 2012-03-21 | 富士フイルム株式会社 | Planographic printing plate making method |
| WO2008020558A1 (en) * | 2006-08-18 | 2008-02-21 | Konica Minolta Medical & Graphic, Inc. | Method of processing material for photosensitive lithographic printing plate |
| US7326521B1 (en) * | 2006-08-31 | 2008-02-05 | Eastman Kodak Company | Method of imaging and developing negative-working elements |
| US8198011B2 (en) * | 2008-02-04 | 2012-06-12 | Eastman Kodak Company | Method of imaging and developing positive-working imageable elements |
| JP5020871B2 (en) * | 2008-03-25 | 2012-09-05 | 富士フイルム株式会社 | Planographic printing plate manufacturing method |
| JP5422134B2 (en) * | 2008-03-25 | 2014-02-19 | 富士フイルム株式会社 | Automatic development method for immersion lithographic printing plates |
| JP5264427B2 (en) * | 2008-03-25 | 2013-08-14 | 富士フイルム株式会社 | Preparation method of lithographic printing plate |
| JP4914864B2 (en) | 2008-03-31 | 2012-04-11 | 富士フイルム株式会社 | Preparation method of lithographic printing plate |
| JP5248203B2 (en) | 2008-05-29 | 2013-07-31 | 富士フイルム株式会社 | Lithographic printing plate developing treatment solution and method for preparing a lithographic printing plate |
| JP5228631B2 (en) | 2008-05-29 | 2013-07-03 | 富士フイルム株式会社 | Lithographic printing plate developing treatment solution and method for preparing a lithographic printing plate |
| CN102132218A (en) | 2008-08-22 | 2011-07-20 | 富士胶片株式会社 | Process for producing lithographic printing plate |
| US20110168044A1 (en) | 2008-09-24 | 2011-07-14 | Fujifilm Corporation | Method of preparing lithographic printing plate |
| JP2010102330A (en) | 2008-09-24 | 2010-05-06 | Fujifilm Corp | Method of preparing lithographic printing plate |
| JP5433351B2 (en) | 2008-09-25 | 2014-03-05 | 富士フイルム株式会社 | Planographic printing plate precursor and lithographic printing plate manufacturing method |
| JP2010079083A (en) | 2008-09-26 | 2010-04-08 | Fujifilm Corp | Plate making method of lithographic printing plate |
| BRPI0921394A8 (en) | 2008-11-26 | 2019-01-15 | Fujifilm Corp | lithographic printing plate manufacturing process, lithographic printing plate precursor developer and lithographic printing plate precursor developer |
| JP2010197620A (en) | 2009-02-24 | 2010-09-09 | Fujifilm Corp | Automatic developing apparatus and processing method for lithographic printing plate precursor |
| JP5449866B2 (en) * | 2009-05-29 | 2014-03-19 | 富士フイルム株式会社 | Planographic printing plate precursor and lithographic printing plate preparation method |
| JP2011090295A (en) | 2009-09-24 | 2011-05-06 | Fujifilm Corp | Method of preparing lithographic printing plate |
| JP2011090294A (en) | 2009-09-24 | 2011-05-06 | Fujifilm Corp | Method of preparing lithographic printing plate |
| JP5541913B2 (en) * | 2009-12-25 | 2014-07-09 | 富士フイルム株式会社 | Preparation method of lithographic printing plate |
| JP5588887B2 (en) | 2010-01-29 | 2014-09-10 | 富士フイルム株式会社 | Preparation method of lithographic printing plate |
| JP5525873B2 (en) | 2010-03-15 | 2014-06-18 | 富士フイルム株式会社 | Preparation method of lithographic printing plate |
| JP2011221522A (en) | 2010-03-26 | 2011-11-04 | Fujifilm Corp | Method for manufacturing lithograph printing plate |
| CN102834779B (en) | 2010-03-31 | 2015-07-08 | 富士胶片株式会社 | Developer for processing planographic printing plate precursor, method for preparing planographic printing plate using the developer, and method for printing |
| EP2869122A4 (en) * | 2012-06-29 | 2016-03-02 | Fujifilm Corp | Method for concentrating processing waste liquid and method for recycling processing waste liquid |
-
1997
- 1997-08-13 JP JP21854197A patent/JP3784931B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2157478A2 (en) | 2008-08-22 | 2010-02-24 | Fujifilm Corporation | Method of producing lithographic printing plate |
| EP2159640A1 (en) | 2008-08-29 | 2010-03-03 | Fujifilm Corporation | Method of preparing lithographic printing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1165126A (en) | 1999-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3784931B2 (en) | Development method of photosensitive lithographic printing plate and developer used therefor | |
| JP4512281B2 (en) | Negative type planographic printing plate precursor | |
| JP2003098674A (en) | Photopolymerizable planographic printing plate | |
| JP2002091016A (en) | Method for producing planographic printing plate | |
| JP4317330B2 (en) | Method for making a photosensitive lithographic printing plate | |
| JP4503199B2 (en) | Photosensitive composition for photosensitive lithographic printing plate | |
| JP3275809B2 (en) | Photosensitive lithographic printing plate | |
| JP3784933B2 (en) | Development method for photosensitive lithographic printing plate | |
| JP3263172B2 (en) | Photopolymerizable composition | |
| JP4138990B2 (en) | Photosensitive planographic printing plate | |
| JP3376912B2 (en) | Processing method of photosensitive lithographic printing plate | |
| JP2002091015A (en) | Method for producing planographic printing plate | |
| JP3881130B2 (en) | Photopolymerizable image forming material | |
| JP2007025220A (en) | Photosensitive lithographic printing plate | |
| JP2002091014A (en) | Method for producing planographic printing plate | |
| JP4579427B2 (en) | Photosensitive planographic printing plate and image forming method | |
| JP3746624B2 (en) | Photopolymerizable composition, image forming material, and photosensitive lithographic printing plate | |
| JP2003098673A (en) | Photosensitive planographic printing plate and method for making planographic printing plate | |
| JP2003114537A (en) | Developing solution for photosensitive planographic printing plate and method for making planographic printing plate | |
| JP2681414B2 (en) | Method for producing lithographic printing plate support | |
| JPH09319096A (en) | Processing method of photosensitive lithographic printing plate | |
| JP2003043701A (en) | Method for processing planographic printing plate and developing solution for photosensitive planographic printing plate | |
| JP2002251019A (en) | Photopolymerizable planographic printing plate | |
| JP2002091017A (en) | Method for producing planographic printing plate | |
| JP2681412B2 (en) | Method for producing a lithographic printing plate support |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20040510 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040906 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050524 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050720 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20050907 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20051109 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20051115 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051215 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20060123 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060214 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060316 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090324 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090324 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100324 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100324 Year of fee payment: 4 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100324 Year of fee payment: 4 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100324 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110324 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120324 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120324 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130324 Year of fee payment: 7 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130324 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130324 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140324 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |