WO1993011468A1 - A method for increasing the hydrophobicity of a silver image - Google Patents
A method for increasing the hydrophobicity of a silver image Download PDFInfo
- Publication number
- WO1993011468A1 WO1993011468A1 PCT/EP1992/002590 EP9202590W WO9311468A1 WO 1993011468 A1 WO1993011468 A1 WO 1993011468A1 EP 9202590 W EP9202590 W EP 9202590W WO 9311468 A1 WO9311468 A1 WO 9311468A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrophobic polymer
- mercapto groups
- mercapto
- silver halide
- imaging element
- Prior art date
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 53
- 239000004332 silver Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 38
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- -1 silver halide Chemical class 0.000 claims abstract description 41
- 238000007639 printing Methods 0.000 claims abstract description 31
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000000839 emulsion Substances 0.000 claims abstract description 27
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 21
- 238000003384 imaging method Methods 0.000 claims abstract description 21
- 238000011161 development Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 27
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 description 32
- 239000010410 layer Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000000975 dye Substances 0.000 description 18
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 18
- 238000012545 processing Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004133 Sodium thiosulphate Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 1
- LLCOQBODWBFTDD-UHFFFAOYSA-N 1h-triazol-1-ium-4-thiolate Chemical group SC1=CNN=N1 LLCOQBODWBFTDD-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-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
- CBHTTYDJRXOHHL-UHFFFAOYSA-N 2h-triazolo[4,5-c]pyridazine Chemical class N1=NC=CC2=C1N=NN2 CBHTTYDJRXOHHL-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 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 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004285 Potassium sulphite Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229920001079 Thiokol (polymer) Polymers 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical class NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003897 fog Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004849 latent hardener Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- XCGQJCSSCTYHDV-UHFFFAOYSA-N mercury(1+);sulfane Chemical compound S.[Hg+] XCGQJCSSCTYHDV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000007981 phosphate-citrate buffer Substances 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/06—Silver salts
- G03F7/063—Additives or means to improve the lithographic properties; Processing solutions characterised by such additives; Treatment after development or transfer, e.g. finishing, washing; Correction or deletion fluids
- G03F7/066—Organic derivatives of bivalent sulfur, e.g. onium derivatives
Definitions
- the present invention relates to a method for hydrophobizing a silver image obtained according to the silver salt diffusion transfer process so that said silver image can be used in a lithographic printing process.
- DTR-process The principles of the silver complex diffusion transfer reversal process, hereinafter called DTR-process, have been described e.g. in TJS-P 2,352,014 and in the book "Photographic Silver Halide Diffusion Processes" by Andre Rott and Edith eyde - The Focal Press - London and New York, (1972) .
- non-developed silver halide of an information-wise exposed photographic silver halide emulsion layer material is transformed with a so-called silver halide solvent into soluble silver complex compounds which are allowed to diffuse into an image-receiving element and are reduced therein with a developing agent, generally in the presence of physical development nuclei, to form a silver image having reversed image density values ("DTR-image") with respect to the black silver image obtained in the exposed areas of the photographic material.
- DTR-image reversed image density values
- a DTR-image bearing material can be used as a planographic printing plate wherein the DTR-silver image areas form the water-repellant ink-receptive areas on a water-receptive ink-repellant background.
- the DTR-image can be formed in the image-receiving layer of a sheet or web material which is a separate element with respect to the photographic silver halide emulsion material (a so-called two-sheet DTR element) or in the image-receiving layer of a so-called single-support-element, also called mono-sheet element, which contains at least one photographic silver halide emulsion layer integral with an image-receiving layer in water permeable relationship therewith. It is the latter mono-sheet version which is preferred for the preparation of offset printing plates by the DTR method.
- hydrophobizing agents are used. These agents are commonly added to a processing liquid used during processing of an information-wise exposed DTR-imaging element e.g. to the developing liquid, the neutralization liquid etc.. Alternatively they may also be applied after development of the plate using a so-called finishing liquid or starter solution.
- Known hydrophobizing agents are e.g. those described in US-P 3,776,728, and TJS-P 4,563,410. Specific examples are 5-n-heptyl-2-mercapto-l,3,4,-oxadiazol and 3-mercapto-4-acetamido-5-n.heptyl-l,2,4-triazole.
- the printing properties of a lithographic printing plate obtained according to the DTR-process can be improved using the above mentioned hydrophobizing agents some of these printing properties still need to be improved.
- the first copies obtained are generally of low quality and have to be disposed.
- some printing jobs require a high printing endurance i.e. the quality of the copies needs to be constant over a large number of copies.
- a method for obtaining a lithographic printing plate comprising the steps of developing an information-wise exposed imaging element according to the DTR-process and treating said information-wise exposed imaging element during or after said development with a liquid containing a hydrophobic polymer comprising mercapto-groups.
- the printing properties of a lithographic printing plate obtained according to the DTR-process can be improved by adding a hydrophobic polymer containing mercapto-groups to one or more liquids used for processing an information-wise exposed imaging element to a lithographic printing plate or by treating a lithographic printing plate obtained according to the DTR-process with a finishing liquid or starter solution comprising a polymer containing mercapto-groups so that the hydrophobicity of the obtained silver image is improved.
- Hydrophobic polymers for use in accordance with the method of the present invention may be polymers that contain mercapto-groups in the side chain or polymers that are mercapto terminated.
- Specific examples are mercapto terminated polymers and copolymers of vinyl monomers e.g. acrylate, methacrylate, vinyl chloride, vinylidene chloride, styrenes etc., mercapto terminated epoxy resins, mercapto terminated polysulphides, polysiloxanes having mercapto groups in the side chain etc..
- Preferably used are mercapto terminated polysulphides or polysiloxanes having a mercapto group in the side chain.
- the mercapto containing polymers used in accordance with the present invention may be prepared using the well known polymerization methods e.g. radical polymerization or polycondensation. Alternatively they may be prepared by polymer modification reactions.
- hydrophobic polymer In order to improve the hydrophobicity of the silver image it is essential that the polymers are hydrophobic.
- hydrophobic polymer is meant that said polymers do not dissolve in water i.e. their solubility is lower than 0.05% by weight and preferably lower than 0.01% by weight.
- the polymers containing mercapto-groups used in accordance with the present invention are preferably used in the form of a dispersion or emulsion e.g. in an aqueous processing liquid or in an aqueous finishing liquid.
- Surfactants used for making said dispersion may be ionic or non-ionic surfactants e.g. a block copolymer of ethylene oxide and propylene oxide, alkylsulphonates, alkylarylsulphonates, alkylaryl substituted ethylene oxides, polyethylenoxides containing an acetylenic group such as surfynol 104, surfynol 465, surfynol 440 etc. all available from Air Reduction Chemical Company New York..
- the polymers containing mercapto-groups used in accordance with the present invention are preferably of low molecular weight.
- the weight average molecular weight of the preferably used mercapto terminated polysulphide is preferably between 1000 and 30000 most preferably between 1000 and 10000.
- the dispersion of the mercapto-containing polymers according to the present invention may be mixed with dispersion of hydrophobic polymers not containing a mercapto-group. It has indeed been found that the concentration of said polymers containing mercapto groups can be lowered by the addition of a dispersion of another hydrophobic polymer not containing mercapto groups while still maintaining good printing properties. Such o fers an ecological advantage.
- Suitable hydrophobic polymers not containing mercapto groups are e.g. polystyrene, poly(meth) crylates, polyethylene etc..
- the concentration of the mercapto containing polymers used in accordance with the present invention is preferably between 0.05% by weight and 40% by weight most preferably between 0.1% and 30% by weight.
- the mercapto containing polymers according to the present invention may be used in combination with low molecular weight hydrophobizing agents e.g. those described in US-P 3,776,728, and US-P 4,563,410.
- Said low molecular weight hydrophobizing agents may be present in the same liquid that contains the mercapto containing polymers or may be present in another liquid used for obtaining a lithographic printing plate according to the DTR-process.
- a DTR- imaging element comprising in the order given on an anodized and roughened aluminium support a layer containing physical development nuclei, an optional hydrophilic layer as disclosed in e.g. EP-A-483415 and EP-A-410500 and a silver halide emulsion is information-wise exposed and subsequently developed in the presence of developing agent (s) and silver halide solvent (s) .
- developing agent s
- silver halide solvent s
- the plate is rinsed with water to remove the silver halide emulsion layer and any other optional layers so that the silver image is exposed.
- the plate is then preferably treated with a finishing solution comprising a polymer containing mercapto- groups.
- the concentration of said polymer in said finishing solution is preferably between 0.05% by weight and 20% by weight.
- Silver halide developing agents for use in accordance with the present invention are preferably of the p-dihydroxybenzene type, e.g. hydroquinone, methylhydroquinone or chlorohydroquinone, preferably in combination with an auxiliary developing agent being a l-phenyl-3-pyrazolidinone-type developing agent and/or p-monomethylaminophenol.
- Particularly useful auxiliary developing agents are of the phenidone type e.g. l-phenyl-3-pyrazolidinone, l-phenyl-4-monomethyl-3-pyrazolidinone, and l-phenyl-4,4-dimethyl-3-pyrazolidinone.
- Said developing agents may be contained in an alkaline processing liquid but are preferably contained in one or more layers of the imaging element. In the latter case the alkaline processing liquid merely serves as an alkaline activating liquid.
- the pH of said alkaline processing liquid is preferably between 12 and 14 and may be established by an organic and/or inorganic alkali agent.
- suitable alkali agents are e.g. sodium hydroxide, carbonates, depoty and/or tertiary alkanolamines, amines etc. or mixtures thereof.
- the DTR-process is carried out in the presence of (a) silver halide solvent (s) .
- Said silver halide solvent(s) can be present in one or more layers comprised in the imaging element but are preferably comprised in the alkaline processing liquid.
- Suitable silver halide solvents for use in accordance with the present invention are e.g. thiosulphate or thiocyanate.
- silver halide complexing agents are cyclic imides, preferably combined with alkanolamines, as described in US-P 4,297,430 and US-P 4,355,090 and 2-merca ⁇ tobenzoic acid derivatives as described in US-P 4,297,429, preferably combined with alkanolamines or with cyclic imides and alkanolamines.
- the alkaline processing liquid preferably also contains a preserving agent having antioxidation activity, e.g. sulphite ions provided e.g. by sodium or potassium sulphite.
- a preserving agent having antioxidation activity e.g. sulphite ions provided e.g. by sodium or potassium sulphite.
- the aqueous alkaline solution comprises sodium sulphite in an amount ranging from 0.15 to 1.0 mol/1.
- a thickening agent e.g. hydroxyethylcellulose and carboxymethylcellulose
- fog inhibiting agents e.g. potassium bromide, potassium iodide and a benzotriazole which is known to improve the printing endurance
- calcium-sequestering compounds e.g. potassium bromide, potassium iodide and a benzotriazole which is known to improve the printing endurance
- calcium-sequestering compounds e.g. potassium bromide, potassium iodide and
- the mercapto containing polymers used in accordance with the present invention may also be added to the alkaline processing liquid in addition to one or more low molecular weight hydrophobizing agents, e.g. those described in US-P 3,776,728, and US-P 4,563,410, that may be present in said processing liquid.
- one or more low molecular weight hydrophobizing agents e.g. those described in US-P 3,776,728, and US-P 4,563,410, that may be present in said processing liquid.
- Development acceleration can be accomplished with the aid of various compounds to the alkaline processing liquid and/or one or more layers of the imaging element, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-P 3,038,805 - 4,038,075 - 4,292,400 - 4,975,354.
- an imaging element comprising on a support &.g. a paper or resin support in the order given a silver halide emulsion layer and a surface layer containing physical development nuclei is information- wise exposed and developed in the presence of developing agent(s) and silver halide solven (s) using an alkaline processing liquid as described above.
- Said development step is preferably followed by a neutralization step using a neutralization liquid to lower the plate surface after development.
- the mercapto containing polymers used in accordance with the present invention are preferably contained -in the neutralization liquid optionally in combination with low molecular weight hydrophobizing agents as described above but may also be contained in the alkaline processing liquid used for developing the imaging element.
- the neutralization liquid • preferably contains buffer ions, e.g. phosphate buffer or citrate buffer to establish in said liquid a pH value ranging from 5.0 to 7.0.
- the neutralization solution can further contain bactericides, e.g. phenol, thymol or 5-bromo-5-nitro-l,3-dioxan as described in EP 0,150,517.
- the photographic silver halide emulsions used in accordance with the above described imaging elements can be prepared from soluble silver salts and soluble halides according to different methods as described e.g. by P. Glafkides in "Chimie et Physique Photographique", Paul Montel, Paris (1967) , by G.F. Duffin in “Photographic Emulsion Chemistry", The Focal Press, London (1966) , and by V.L. Zelikman et al in “Making and Coating Photographic Emulsion", The Focal Press, London (1966) .
- the photographic silver halide emulsions used according to the present invention can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition.
- the silver halide can be precipitated according to the single-jet method or the double-jet method.
- the silver halide particles of the photographic emulsions used according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
- the emulsion or emulsions preferably consist principally of silver chloride while a fraction of silver bromide is present ranging from 1 mole % to 40 mole %.
- the emulsions may belong to the core/shell type well known to those skilled in the art in the sense that substantially all the bromide is concentrated in the core.
- This core contains preferably 10 to 40 % of the total silver halide precipitated, while the shell consists preferably of 60 to 90 % of the total silver halide precipitated.
- the average size of the silver halide grains may range from 0.10 to 0.70 ⁇ m , preferably from 0.25 to 0.45 ⁇ .
- the size distribution of the silver halide particles of the photographic emulsions to be used according to the present invention can be ho odisperse or heterodisperse.
- a homodisperse size distribution is obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.
- Rhodium containing compounds or a mixture of both are added.
- concentration of these added compounds ranges from 10 —8 to 10—3 mole per mole of AgNOg, preferably between 10 —7 and 10—6 mole per mole of
- the emulsions can be chemically sensitized e. . by adding sulphur-containing compounds during the chemical ripening stage e.g. allyl isothiocyanate, allyl thiourea, and sodium thiosulphate. Also reducing agents e.g. the tin compounds described in BE-P 493,464 and
- polyamines such as diethylene triamine or derivatives of aminomethane-sulphonic acid can be used as chemical sensitizers.
- Suitable chemical sensitizers are noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium. This method of chemical sensitization has been described in the article of R.KOSLO SKY, Z. Wiss. Photogr. Photophys. Photochem.
- the emulsions of the DTR element can be spectrally sensitized according to the spectral emission of the exposure source for which the DTR element is designed.
- Suitable sensitizing dyes for the visible spectral region include methine dyes such as those described by F.M. Ha er in "The
- Cyanine Dyes and Related Compounds 1964 r John Wiley & Sons.
- Dyes that can be used for this purpose include cyanine dyes r merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
- Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
- the spectral sensitizers can be added to the photographic emulsions in the form of an aqueous solution, a solution in an organic solvent or in the form of a dispersion.
- the silver halide emulsions may contain the usual stabilizers e.g. homopolar or salt-like compounds of mercury with aromatic or heterocycli ⁇ rings such as mercaptotriazoles, simple mercury salts, sulphonium mercury double salts and other mercury compounds.
- suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, especially those substituted with hydroxy or amino groups. Compounds of this kind have been described by BIRR in Z. Wiss. Photogr. Photophys. Photochem. 47, 2-27 (1952) .
- Other suitable stabilizers are i.a. heterocyclic mercapto compounds e.g. phenylmercaptotetrazole, quaternary benzothiazole derivatives, and benzotriazole.
- Preferred compounds are mercapto substituted pyrimidine derivatives as disclosed in US-P 3,692,527.
- the silver halide emulsions may contain pH controlling ingredients.
- the emulsion layer is coated at a pH value below the isoelectric point of the gelatin to improve the stability characteristics of the coated layer.
- Other ingredients such as antifogging agents, development accelerators, wetting agents, and hardening agents for gelatin may be present.
- the silver halide emulsion layer may comprise light-screening dyes that absorb scattering light and thus promote the image sharpness. Suitable light-absorbing dyes are described in i.a. US-P 4,092,168, US-P 4,311,787, DE-P 2,453,217, and GB-P 1,907,440.
- the layer containing physical development nuclei is preferably free of hydrophilic binder but may comprise small amounts upto 30% by weight of the total weight of said layer of a hydrophilic colloid e.g. polyvinyl alcohol to improve the hydrophilicity of the surface.
- Preferred development nuclei for use in accordance with the present invention are sulphides of heavy metals e.g. sulphides of antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, platinum, silver, and zinc.
- Other suitable development nuclei are salts such as e.g. selenides, polyselenides, polysulphides, mercaptans, and tin (II) halides.
- Heavy metals, preferably silver, gold, platinum, palladium, and mercury can be used in colloidal form.
- Especially suitable development nuclei in connection with the present invention are palladium sulphide nuclei or metallic silver nuclei.
- the initiated diffusion transfer was allowed to continue for 30 s to form a silver image on the aluminium foil.
- Each of the 4 developed monosheet layer assemblages was then rinsed for 1 min. with a water jet to remove all the layers above the silver image so as to expose it. Both elements were then guided to a finishing solution having the following composition: 10% aqueous n-hexadecyl trimethyl ammonium chloride 25 ml
- solution 1 mercapto polymer 1 (see below) 10% p-C 9 H 19 -C 6 H 5 -0(-CH 2 -CH 2 0) 3 QH 1.0%
- the polymer is represented by its recurring unit(s) and the indices in the above table for polymers 2 and 3 represent the weight % of the branched and non-branched units in these polymers.
- Polymers 2 and 3 are respectively the polymers LP-32 and LP-3 commercially available rom Thiokol Chemicals.
- Each of the 4 printing plates obtained was placed on an Heidelberg offset printing press, type GTO, marketed by HEIDELBERGER DRUCKMASCHINEN AG, D-6900 Heidelberg, West-Germany.
- An imaging element as described in example 1 was imaged and processed as described in example 1 with the exception that wiping with a starter solution was omitted and that the finishing solution of example 1 was replaced by a finishing solution of the following composition: polymer of starter solution 3 of example 1 2.5% p-C 9 H 19 -CgH 5 -O(-CH 2 -CH 2 O) 30 H 0.25%
- lithographic printing plate was used to print as described in example 1. 100000 copies of good quality were obtained and only the 5 first copies had to be disposed.
- An imaging element as described in example 1 was imaged an processed as described in example 1 with the exception that a starter solution was used with the following composition:
- polymer of starter solution 3 of example 1 0.25% p-C 9 H 19 -CgH 5 -O(-CH 2 -CH 2 O) 30 H 0.025% polystyrene 2.5% polystyrene sulfonic acid 0.25%
- the thus obtained printing plate was used to print as described in example 1. 100000 copies of good quality were obtained and only the 5 first copies had to be disposed.
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Abstract
The present invention provides a method for obtaining a lithographic printing plate comprising the steps of: information-wise exposing an imaging element comprising on a support a silver halide emulsion layer and a layer containing physical development nuclei, developing said information-wise exposed imaging element according to the DTR-process in the presence of developing agent(s) and silver halide solvent(s), treating the obtained silver image with a solution containing a hydrophobic polymer comprising mercapto groups. A thus obtained lithographic printing plate shows an increased printing endurance and the number of copies before a copy of constant quality is obtained is reduced.
Description
DESCRIPTION
A METHOD FOR INCREASING THE HYDROPHOBICI Y OF A SILVER IMAGE.
*
1. Field of the invention.
The present invention relates to a method for hydrophobizing a silver image obtained according to the silver salt diffusion transfer process so that said silver image can be used in a lithographic printing process.
2. Background of the invention.
The principles of the silver complex diffusion transfer reversal process, hereinafter called DTR-process, have been described e.g. in TJS-P 2,352,014 and in the book "Photographic Silver Halide Diffusion Processes" by Andre Rott and Edith eyde - The Focal Press - London and New York, (1972) .
In the DTR-process non-developed silver halide of an information-wise exposed photographic silver halide emulsion layer material is transformed with a so-called silver halide solvent into soluble silver complex compounds which are allowed to diffuse into an image-receiving element and are reduced therein with a developing agent, generally in the presence of physical development nuclei, to form a silver image having reversed image density values ("DTR-image") with respect to the black silver image obtained in the exposed areas of the photographic material.
A DTR-image bearing material can be used as a planographic printing plate wherein the DTR-silver image areas form the water-repellant ink-receptive areas on a water-receptive ink-repellant background. The DTR-image can be formed in the image-receiving layer of a sheet or web material which is a separate element with respect to the photographic silver halide emulsion material (a so-called two-sheet DTR element) or in the image-receiving layer of a so-called single-support-element, also called mono-sheet element, which contains at least one photographic silver halide emulsion layer integral with an image-receiving layer
in water permeable relationship therewith. It is the latter mono-sheet version which is preferred for the preparation of offset printing plates by the DTR method.
To obtain a lithographic printing plate with good printing properties it is necessary to improve the hydrophobicity of the silver image obtained using the DTR-process. For this purpose hydrophobizing agents are used. These agents are commonly added to a processing liquid used during processing of an information-wise exposed DTR-imaging element e.g. to the developing liquid, the neutralization liquid etc.. Alternatively they may also be applied after development of the plate using a so-called finishing liquid or starter solution. Known hydrophobizing agents are e.g. those described in US-P 3,776,728, and TJS-P 4,563,410. Specific examples are 5-n-heptyl-2-mercapto-l,3,4,-oxadiazol and 3-mercapto-4-acetamido-5-n.heptyl-l,2,4-triazole.
Although the printing properties of a lithographic printing plate obtained according to the DTR-process can be improved using the above mentioned hydrophobizing agents some of these printing properties still need to be improved. For example the first copies obtained are generally of low quality and have to be disposed. For printing jobs requiring a small number of copies it is especially important to limit the number of initial copies that have to be disposed. On the other hand some printing jobs require a high printing endurance i.e. the quality of the copies needs to be constant over a large number of copies.
3. Summary of the invention.
It is an object of the present invention to provide a method for obtaining a lithographic printing plate according to the DTR-process using hydrophobizing agents by which the printing properties of said printing plate can be improved.
Further objects of the present invention will become clear from the description hereinafter.
According to the present invention a method is provided for obtaining a lithographic printing plate comprising the steps of developing an information-wise exposed imaging element according to
the DTR-process and treating said information-wise exposed imaging element during or after said development with a liquid containing a hydrophobic polymer comprising mercapto-groups.
4. Detailed description of the present invention.
It has been found that the printing properties of a lithographic printing plate obtained according to the DTR-process can be improved by adding a hydrophobic polymer containing mercapto-groups to one or more liquids used for processing an information-wise exposed imaging element to a lithographic printing plate or by treating a lithographic printing plate obtained according to the DTR-process with a finishing liquid or starter solution comprising a polymer containing mercapto-groups so that the hydrophobicity of the obtained silver image is improved.
Hydrophobic polymers for use in accordance with the method of the present invention may be polymers that contain mercapto-groups in the side chain or polymers that are mercapto terminated. Specific examples are mercapto terminated polymers and copolymers of vinyl monomers e.g. acrylate, methacrylate, vinyl chloride, vinylidene chloride, styrenes etc., mercapto terminated epoxy resins, mercapto terminated polysulphides, polysiloxanes having mercapto groups in the side chain etc.. Preferably used are mercapto terminated polysulphides or polysiloxanes having a mercapto group in the side chain.
The mercapto containing polymers used in accordance with the present invention may be prepared using the well known polymerization methods e.g. radical polymerization or polycondensation. Alternatively they may be prepared by polymer modification reactions.
In order to improve the hydrophobicity of the silver image it is essential that the polymers are hydrophobic. By the term "hydrophobic polymer" is meant that said polymers do not dissolve in water i.e. their solubility is lower than 0.05% by weight and preferably lower than 0.01% by weight.
The polymers containing mercapto-groups used in accordance with the present invention are preferably used in the form of a
dispersion or emulsion e.g. in an aqueous processing liquid or in an aqueous finishing liquid. Surfactants used for making said dispersion may be ionic or non-ionic surfactants e.g. a block copolymer of ethylene oxide and propylene oxide, alkylsulphonates, alkylarylsulphonates, alkylaryl substituted ethylene oxides, polyethylenoxides containing an acetylenic group such as surfynol 104, surfynol 465, surfynol 440 etc. all available from Air Reduction Chemical Company New York.. It is important with respect to the present invention that a stable dispersion or emulsion of the mercapto containing polymer is prepared. To obtain a stable dispersion the polymers containing mercapto-groups used in accordance with the present invention are preferably of low molecular weight. For example the weight average molecular weight of the preferably used mercapto terminated polysulphide is preferably between 1000 and 30000 most preferably between 1000 and 10000.
The dispersion of the mercapto-containing polymers according to the present invention may be mixed with dispersion of hydrophobic polymers not containing a mercapto-group. It has indeed been found that the concentration of said polymers containing mercapto groups can be lowered by the addition of a dispersion of another hydrophobic polymer not containing mercapto groups while still maintaining good printing properties. Such o fers an ecological advantage. Suitable hydrophobic polymers not containing mercapto groups are e.g. polystyrene, poly(meth) crylates, polyethylene etc..
The concentration of the mercapto containing polymers used in accordance with the present invention is preferably between 0.05% by weight and 40% by weight most preferably between 0.1% and 30% by weight.
The mercapto containing polymers according to the present invention may be used in combination with low molecular weight hydrophobizing agents e.g. those described in US-P 3,776,728, and US-P 4,563,410. Said low molecular weight hydrophobizing agents may be present in the same liquid that contains the mercapto containing polymers or may be present in another liquid used for obtaining a lithographic printing plate according to the DTR-process.
According to a preferred mode of the present invention a DTR-
imaging element comprising in the order given on an anodized and roughened aluminium support a layer containing physical development nuclei, an optional hydrophilic layer as disclosed in e.g. EP-A-483415 and EP-A-410500 and a silver halide emulsion is information-wise exposed and subsequently developed in the presence of developing agent (s) and silver halide solvent (s) . After said development the plate is rinsed with water to remove the silver halide emulsion layer and any other optional layers so that the silver image is exposed. The plate is then preferably treated with a finishing solution comprising a polymer containing mercapto- groups. The concentration of said polymer in said finishing solution is preferably between 0.05% by weight and 20% by weight.
Silver halide developing agents for use in accordance with the present invention are preferably of the p-dihydroxybenzene type, e.g. hydroquinone, methylhydroquinone or chlorohydroquinone, preferably in combination with an auxiliary developing agent being a l-phenyl-3-pyrazolidinone-type developing agent and/or p-monomethylaminophenol. Particularly useful auxiliary developing agents are of the phenidone type e.g. l-phenyl-3-pyrazolidinone, l-phenyl-4-monomethyl-3-pyrazolidinone, and l-phenyl-4,4-dimethyl-3-pyrazolidinone. However other developing agents can be used. Said developing agents may be contained in an alkaline processing liquid but are preferably contained in one or more layers of the imaging element. In the latter case the alkaline processing liquid merely serves as an alkaline activating liquid.
The pH of said alkaline processing liquid is preferably between 12 and 14 and may be established by an organic and/or inorganic alkali agent. Examples of suitable alkali agents are e.g. sodium hydroxide, carbonates, secundary and/or tertiary alkanolamines, amines etc. or mixtures thereof.
It is furthermore essential that the DTR-process is carried out in the presence of (a) silver halide solvent (s) . Said silver halide solvent(s) can be present in one or more layers comprised in the imaging element but are preferably comprised in the alkaline processing liquid. Suitable silver halide solvents for use in accordance with the present invention are e.g. thiosulphate or thiocyanate. Further interesting silver halide complexing agents,
are cyclic imides, preferably combined with alkanolamines, as described in US-P 4,297,430 and US-P 4,355,090 and 2-mercaρtobenzoic acid derivatives as described in US-P 4,297,429, preferably combined with alkanolamines or with cyclic imides and alkanolamines.
The alkaline processing liquid preferably also contains a preserving agent having antioxidation activity, e.g. sulphite ions provided e.g. by sodium or potassium sulphite. For example, the aqueous alkaline solution comprises sodium sulphite in an amount ranging from 0.15 to 1.0 mol/1. Further may be present a thickening agent, e.g. hydroxyethylcellulose and carboxymethylcellulose, fog inhibiting agents, e.g. potassium bromide, potassium iodide and a benzotriazole which is known to improve the printing endurance, calcium-sequestering compounds, anti-sludge agents, and hardeners including latent hardeners.
The mercapto containing polymers used in accordance with the present invention may also be added to the alkaline processing liquid in addition to one or more low molecular weight hydrophobizing agents, e.g. those described in US-P 3,776,728, and US-P 4,563,410, that may be present in said processing liquid.
Development acceleration can be accomplished with the aid of various compounds to the alkaline processing liquid and/or one or more layers of the imaging element, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-P 3,038,805 - 4,038,075 - 4,292,400 - 4,975,354.
According to another embodiment of the present invention an imaging element comprising on a support &.g. a paper or resin support in the order given a silver halide emulsion layer and a surface layer containing physical development nuclei is information- wise exposed and developed in the presence of developing agent(s) and silver halide solven (s) using an alkaline processing liquid as described above. Said development step is preferably followed by a neutralization step using a neutralization liquid to lower the plate surface after development. The mercapto containing polymers used in accordance with the present invention are preferably contained -in the neutralization liquid optionally in combination with low molecular weight hydrophobizing agents as described above but may
also be contained in the alkaline processing liquid used for developing the imaging element. The neutralization liquid •preferably contains buffer ions, e.g. phosphate buffer or citrate buffer to establish in said liquid a pH value ranging from 5.0 to 7.0. The neutralization solution can further contain bactericides, e.g. phenol, thymol or 5-bromo-5-nitro-l,3-dioxan as described in EP 0,150,517.
The photographic silver halide emulsions used in accordance with the above described imaging elements can be prepared from soluble silver salts and soluble halides according to different methods as described e.g. by P. Glafkides in "Chimie et Physique Photographique", Paul Montel, Paris (1967) , by G.F. Duffin in "Photographic Emulsion Chemistry", The Focal Press, London (1966) , and by V.L. Zelikman et al in "Making and Coating Photographic Emulsion", The Focal Press, London (1966) .
The photographic silver halide emulsions used according to the present invention can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition. The silver halide can be precipitated according to the single-jet method or the double-jet method.
The silver halide particles of the photographic emulsions used according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
According to the present invention the emulsion or emulsions preferably consist principally of silver chloride while a fraction of silver bromide is present ranging from 1 mole % to 40 mole %. The emulsions may belong to the core/shell type well known to those skilled in the art in the sense that substantially all the bromide is concentrated in the core. This core contains preferably 10 to 40 % of the total silver halide precipitated, while the shell consists preferably of 60 to 90 % of the total silver halide precipitated.
The average size of the silver halide grains may range from
0.10 to 0.70 μm , preferably from 0.25 to 0.45 μ .
The size distribution of the silver halide particles of the photographic emulsions to be used according to the present invention can be ho odisperse or heterodisperse. A homodisperse size distribution is obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.
Preferably during the precipitation stage Iridium and/or
Rhodium containing compounds or a mixture of both are added. The concentration of these added compounds ranges from 10 —8 to 10—3 mole per mole of AgNOg, preferably between 10 —7 and 10—6 mole per mole of
AgNOg. This results in the building in in the silver halide crystal lattice of minor amounts of Iridium and/or Rhodium, so-called
Iridium and/or Rhodium dopants. As known to those skilled in the art numerous scientific and patent publications disclose the addition of
Iridium or Rhodium containing compounds or compounds containing other elements of Group VIII of the Periodic System during emulsion prepara io .
The emulsions can be chemically sensitized e. . by adding sulphur-containing compounds during the chemical ripening stage e.g. allyl isothiocyanate, allyl thiourea, and sodium thiosulphate. Also reducing agents e.g. the tin compounds described in BE-P 493,464 and
568,687, and polyamines such as diethylene triamine or derivatives of aminomethane-sulphonic acid can be used as chemical sensitizers.
Other suitable chemical sensitizers are noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium. This method of chemical sensitization has been described in the article of R.KOSLO SKY, Z. Wiss. Photogr. Photophys. Photochem.
46, 65-72 (1951) .
The emulsions of the DTR element can be spectrally sensitized according to the spectral emission of the exposure source for which the DTR element is designed.
Suitable sensitizing dyes for the visible spectral region include methine dyes such as those described by F.M. Ha er in "The
Cyanine Dyes and Related Compounds", 1964r John Wiley & Sons. Dyes that can be used for this purpose include cyanine dyesr merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
The spectral sensitizers can be added to the photographic emulsions in the form of an aqueous solution, a solution in an organic solvent or in the form of a dispersion.
The silver halide emulsions may contain the usual stabilizers e.g. homopolar or salt-like compounds of mercury with aromatic or heterocycliσ rings such as mercaptotriazoles, simple mercury salts, sulphonium mercury double salts and other mercury compounds. Other suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, especially those substituted with hydroxy or amino groups. Compounds of this kind have been described by BIRR in Z. Wiss. Photogr. Photophys. Photochem. 47, 2-27 (1952) . Other suitable stabilizers are i.a. heterocyclic mercapto compounds e.g. phenylmercaptotetrazole, quaternary benzothiazole derivatives, and benzotriazole. Preferred compounds are mercapto substituted pyrimidine derivatives as disclosed in US-P 3,692,527.
The silver halide emulsions may contain pH controlling ingredients. Preferably the emulsion layer is coated at a pH value below the isoelectric point of the gelatin to improve the stability characteristics of the coated layer. Other ingredients such as antifogging agents, development accelerators, wetting agents, and hardening agents for gelatin may be present. The silver halide emulsion layer may comprise light-screening dyes that absorb scattering light and thus promote the image sharpness. Suitable light-absorbing dyes are described in i.a. US-P 4,092,168, US-P 4,311,787, DE-P 2,453,217, and GB-P 1,907,440.
The layer containing physical development nuclei is preferably free of hydrophilic binder but may comprise small amounts upto 30% by weight of the total weight of said layer of a hydrophilic colloid e.g. polyvinyl alcohol to improve the hydrophilicity of the surface. Preferred development nuclei for use in accordance with the present invention are sulphides of heavy metals e.g. sulphides of antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, platinum, silver, and zinc. Other suitable development nuclei are salts such as e.g. selenides, polyselenides, polysulphides, mercaptans, and tin (II) halides. Heavy metals, preferably silver, gold, platinum, palladium,
and mercury can be used in colloidal form. Especially suitable development nuclei in connection with the present invention are palladium sulphide nuclei or metallic silver nuclei.
More details about the imaging elements used in accordance with the present invention and described in the above two embodiments can be found in e.g. EP-A-483415, EP-A-410500, US-P-4.824.760, US-P 4,297,430, US-P 4,355,090, US-P 4,297,429 and EP-A-423399. The invention will now be illustrated by the following examples without however limiting it thereto.
EXAMPLE 1
4 equal imaging elements were made according to the invention sample of example 1 described in EP-A-483415.
- The imaging elements were identically exposed through a contact screen in a process-camera and immersed for 8 s at 25°C in a freshly made developing solution (pH=13 (25°C) ) having the following ingredients in a CR 430 processor marketed by AGFA-GEVAERT, Belgium: carboxymethylσellulose 18 g sodium hydroxide 22.5 g anhydrous sodium sulphite 120 g hydroquinone 20 g l-phenyl-3-pyrazolidinone 3 g potassium bromide 0.75 g anhydrous sodium thiosulphate 7.5 g ethylene diamine tetraacetic acid tetrasodium salt 3.2 g demineralized water to make 1000 ml
The initiated diffusion transfer was allowed to continue for 30 s to form a silver image on the aluminium foil.
Each of the 4 developed monosheet layer assemblages was then rinsed for 1 min. with a water jet to remove all the layers above the silver image so as to expose it. Both elements were then guided to a finishing solution having the following composition:
10% aqueous n-hexadecyl trimethyl ammonium chloride 25 ml
20% aqueous solution of polystyrene sulphonic acid 100 ml potassium nitrate 12.5 g citric acid 20.0 g l-phenyl-5-mercaptotetrazole 2.0 g sodium hydroxide 5.5 g water to make 1000 ml pH (20°C) = 4
3 of these elements were respectively wiped with a starter solution 1, 2 and 3 having the following composition:
solution 1: mercapto polymer 1 (see below) 10% p-C9H19-C6H5-0(-CH2-CH20) 3QH 1.0%
solution 2: mercapto polymer 2 (see below) 5% p-C9H19-C6H5-0(-CH2-CH20) 3QH 0.5%
solution 3: mercapto polymer 3 (see below) 0.6% p-C9H19-C6H5-0(-CH2-CH20) 30H 0.5%
Solution number mercapto polymer
CH,
. o—Si
(CH2)3-SH
(*) The polymer is represented by its recurring unit(s) and the indices in the above table for polymers 2 and 3 represent the weight % of the branched and non-branched units in these polymers. Polymers 2 and 3 are respectively the polymers LP-32 and LP-3 commercially available rom Thiokol Chemicals.
Each of the 4 printing plates obtained was placed on an Heidelberg offset printing press, type GTO, marketed by HEIDELBERGER DRUCKMASCHINEN AG, D-6900 Heidelberg, West-Germany.
Each printing plate was inked with a commercially available KAST + EHINGER 123W ink and then used for printing copy sheets of paper. The results for each of the samples are shown in table 1.
(*) number of copies that had to be disposed before a copy of constant quality was obtained.
From the above table 1 it can be seen that the printing characteristics of the plate can be improved using a polymer containing mercapto groups.
EXAMPLE 2
An imaging element as described in example 1 was imaged and processed as described in example 1 with the exception that wiping with a starter solution was omitted and that the finishing solution of example 1 was replaced by a finishing solution of the following
composition: polymer of starter solution 3 of example 1 2.5% p-C9H19-CgH5-O(-CH2-CH2O)30H 0.25%
NaOH 1.5% citric acid 2.3%
NaH2P04 2.3%
KN03 1.4%
The thus obtained lithographic printing plate was used to print as described in example 1. 100000 copies of good quality were obtained and only the 5 first copies had to be disposed.
EXAMPLE 3
An imaging element as described in example 1 was imaged an processed as described in example 1 with the exception that a starter solution was used with the following composition:
polymer of starter solution 3 of example 1 0.25% p-C9H19-CgH5-O(-CH2-CH2O)30H 0.025% polystyrene 2.5% polystyrene sulfonic acid 0.25%
The thus obtained printing plate was used to print as described in example 1. 100000 copies of good quality were obtained and only the 5 first copies had to be disposed.
Claims
I. A method for obtaining a lithographic printing plate comprising the steps of:
- information-wise exposing an imaging element comprising on a support a silver halide emulsion layer and a layer containing physical development nuclei, **
- developing said information-wise exposed imaging element according to the DTR-process in the presence of developing agent(s) and silver halide solven (s),
- treating the obtained silver image with a solution containing a hydrophobic polymer comprising mercapto groups.
2. A method according to claim 1 wherein said solution containing said hydrophobic polymer comprising mercapto groups is a developing liquid.
3. A method according to claim 1 wherein said treatement with a solution containing a hydrophobic polymer comprising mercapto groups is carried out after development of said imaging element.
4. A method according to any of claims 1 to 3 wherein said hydrophobic polymer containing mercapto groups is a mercapto terminated hydrophobic polymer.
5. A method according to any of claims 1 to 3 wherein said hydrophobic polymer containing mercapto groups is a hydrophobic polymer containing mercapto groups in the side chain.
6. A method according to claim 4 wherein said hydrophobic polymer is a mercapto terminated polysulphid .
7. A method according to 5 wherein said hydrophobic polymer is a polysiloxane containing mercapto groups in the side chain.
8. A method according to claims 6 or 7 wherein said hydrophobic polymer containing mercapto groups has a weight average molecular weight between lOOOg/mol and 30000g/mol.
9. A method according to any of the above claims wherein said solution containing said hydrophobic polymer containing mercapto groups further contains a hydrophobic polymer not containing mercapto groups.
10. A method according to any of the above claims wherein said hydrophobic polymer containing mercapto groups is contained in said solution in an amount between 0.05% by weight and 40% by weight.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP91203094.7 | 1991-11-27 | ||
EP91203094 | 1991-11-27 |
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Publication Number | Publication Date |
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WO1993011468A1 true WO1993011468A1 (en) | 1993-06-10 |
Family
ID=8208038
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP1992/002590 WO1993011468A1 (en) | 1991-11-27 | 1992-11-11 | A method for increasing the hydrophobicity of a silver image |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5399457A (en) * | 1993-10-15 | 1995-03-21 | Minnesota Mining And Manufacturing Company | Process for reducing sludge in diffusion transfer printing plates |
EP0676670A1 (en) * | 1994-04-08 | 1995-10-11 | Agfa-Gevaert N.V. | A method for making improved lithographic printing plates according to the silver salt diffusion transfer process |
EP0697282A1 (en) * | 1994-07-11 | 1996-02-21 | Agfa-Gevaert N.V. | Process for the prodcution of a printing plate by inkjet |
EP0681219A3 (en) * | 1994-04-08 | 1996-04-10 | Agfa Gevaert Nv | A method for making an offset printing plate according to the silver salt diffusion transfer process. |
EP0720054B1 (en) * | 1994-12-27 | 1999-04-14 | Mitsubishi Paper Mills, Ltd. | Process for preparing printing plate |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3161508A (en) * | 1958-08-29 | 1964-12-15 | Eastman Kodak Co | Process of lithographic printing |
DE1622743B1 (en) * | 1961-03-30 | 1971-06-03 | Agfa Ag | Process for the production of planographic printing forms with an aluminum base |
US4160670A (en) * | 1976-08-10 | 1979-07-10 | Mitsubishi Paper Mills, Ltd. | Lithographic printing plate material |
-
1992
- 1992-11-11 WO PCT/EP1992/002590 patent/WO1993011468A1/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3161508A (en) * | 1958-08-29 | 1964-12-15 | Eastman Kodak Co | Process of lithographic printing |
DE1622743B1 (en) * | 1961-03-30 | 1971-06-03 | Agfa Ag | Process for the production of planographic printing forms with an aluminum base |
US4160670A (en) * | 1976-08-10 | 1979-07-10 | Mitsubishi Paper Mills, Ltd. | Lithographic printing plate material |
Non-Patent Citations (2)
Title |
---|
DATABASE WPIL Week 8107, Derwent Publications Ltd., London, GB; AN 81-10378D * |
RESEARCH DISCLOSURE. no. 161, September 1977, HAVANT GB pages 23 - 24 R.J.KEMP ET AL 'Lithographic printing plates' * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5399457A (en) * | 1993-10-15 | 1995-03-21 | Minnesota Mining And Manufacturing Company | Process for reducing sludge in diffusion transfer printing plates |
EP0676670A1 (en) * | 1994-04-08 | 1995-10-11 | Agfa-Gevaert N.V. | A method for making improved lithographic printing plates according to the silver salt diffusion transfer process |
EP0681219A3 (en) * | 1994-04-08 | 1996-04-10 | Agfa Gevaert Nv | A method for making an offset printing plate according to the silver salt diffusion transfer process. |
EP0697282A1 (en) * | 1994-07-11 | 1996-02-21 | Agfa-Gevaert N.V. | Process for the prodcution of a printing plate by inkjet |
EP0720054B1 (en) * | 1994-12-27 | 1999-04-14 | Mitsubishi Paper Mills, Ltd. | Process for preparing printing plate |
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