JPH037104B2 - - Google Patents
Info
- Publication number
- JPH037104B2 JPH037104B2 JP11016981A JP11016981A JPH037104B2 JP H037104 B2 JPH037104 B2 JP H037104B2 JP 11016981 A JP11016981 A JP 11016981A JP 11016981 A JP11016981 A JP 11016981A JP H037104 B2 JPH037104 B2 JP H037104B2
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- group
- compound
- polymerization
- photographic
- 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
Links
- -1 Silver halide Chemical class 0.000 claims description 121
- 229910052709 silver Inorganic materials 0.000 claims description 61
- 239000004332 silver Substances 0.000 claims description 61
- 229920002554 vinyl polymer Polymers 0.000 claims description 27
- 238000011161 development Methods 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 230000005660 hydrophilic surface Effects 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004001 thioalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000012644 addition polymerization Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000839 emulsion Substances 0.000 description 35
- 238000006116 polymerization reaction Methods 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- 108010010803 Gelatin Proteins 0.000 description 18
- 229920000159 gelatin Polymers 0.000 description 18
- 239000008273 gelatin Substances 0.000 description 18
- 235000019322 gelatine Nutrition 0.000 description 18
- 235000011852 gelatine desserts Nutrition 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 239000000126 substance Substances 0.000 description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 206010070834 Sensitisation Diseases 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000008313 sensitization Effects 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229940052303 ethers for general anesthesia Drugs 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism 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
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 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 1
- LGJWFDONNSEVGG-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C=CC1=CC=CC=C1C=C LGJWFDONNSEVGG-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- YLVACWCCJCZITJ-UHFFFAOYSA-N 1,4-dioxane-2,3-diol Chemical compound OC1OCCOC1O YLVACWCCJCZITJ-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- SIQZJFKTROUNPI-UHFFFAOYSA-N 1-(hydroxymethyl)-5,5-dimethylhydantoin Chemical compound CC1(C)N(CO)C(=O)NC1=O SIQZJFKTROUNPI-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- YKUDHBLDJYZZQS-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one Chemical compound OC1=NC(Cl)=NC(Cl)=N1 YKUDHBLDJYZZQS-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WHJDYNKUABBTRF-UHFFFAOYSA-N C(C=C)(=O)OCCN(C(=O)OCC)CCCN(C(=O)OCC)CCOC(C=C)=O Chemical compound C(C=C)(=O)OCCN(C(=O)OCC)CCCN(C(=O)OCC)CCOC(C=C)=O WHJDYNKUABBTRF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- LIQDVINWFSWENU-UHFFFAOYSA-K aluminum;prop-2-enoate Chemical compound [Al+3].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C LIQDVINWFSWENU-UHFFFAOYSA-K 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical class OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 description 1
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 230000001934 delay Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- PCAXGMRPPOMODZ-UHFFFAOYSA-N disulfurous acid, diammonium salt Chemical class [NH4+].[NH4+].[O-]S(=O)S([O-])(=O)=O PCAXGMRPPOMODZ-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- JOXWSDNHLSQKCC-UHFFFAOYSA-N ethenesulfonamide Chemical class NS(=O)(=O)C=C JOXWSDNHLSQKCC-UHFFFAOYSA-N 0.000 description 1
- OMNSJWQRKOCQOJ-UHFFFAOYSA-N ethenyl benzenesulfonate;potassium Chemical compound [K].C=COS(=O)(=O)C1=CC=CC=C1 OMNSJWQRKOCQOJ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 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
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Chemical class 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
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- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 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 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
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- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pentâ4âenâ2âone Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000008130 triterpenoid saponins Chemical class 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
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/0285—Silver salts, e.g. a latent silver salt image
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Description
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The present invention relates to a method for forming images using polymers. In particular, the present invention relates to a method of selectively producing a polymer compound in a portion corresponding to a photographic latent image by the action of a silver halide photographic emulsion and a reducing agent. Various methods have been proposed for forming images by polymerizing vinyl compounds to produce polymeric compounds through the action of light. Direct photopolymerization using silver halide as a catalyst has also been proposed (UK Patent No. 866631, S. Levinos et al. Photographic Science and Engineering).
Science & Engineering) Vol. 6, pp. 222-226 (1962)). In this reaction, the products generated by photolysis of silver halide are thought to act as direct catalysts for polymerization, and the sensitivity is not as high as that of reducing silver halide grains by normal development. Not obtained. Furthermore, after the exposed silver halide emulsion grains are developed with an ordinary developer, a vinyl compound is polymerized using the resulting silver image or unreacted silver halide as a catalyst to form a polymer compound. It has also been proposed to generate images in the form of images (Belgium Patent No. 642477, etc.). This reaction has the disadvantage that the development operation and the polymerization operation must be carried out separately. Developing exposed silver halide with a reducing compound in the presence of a vinyl compound and causing polymerization of the vinyl compound by the oxidation product or its intermediate product produced in the process is as follows:
Such a reaction is carried out using a so-called benzenoid compound, which already has two or more hydroxyl groups, amino groups, alkyl, or aryl-substituted amino groups at mutually ortho or para positions on the benzene ring, as a reducing agent. (U.S. Pat. No. 3,019,104, G. Oster. Nature, Vol. 180, p. 1275 (1957)). However, in this example of a reaction using a benzenoid compound, only an increase in the optical density of the silver image of silver halide was observed, and an increase in viscosity that directly supported the formation of polymers, or the generation of reaction heat was confirmed. No isolation of the produced polymer was performed. Furthermore, other researchers have reported that they were not successful in follow-up testing (S. Levinos and
FWH Mueller, Photographic Science & Engineering, Vol. 6, p. 222 (1962)). Then, in the presence of exposed silver halide, a vinyl compound is polymerized using a resorzine, naphthol, pyrazolone, or hydrazine compound as a polymerization initiator, as described in Japanese Patent Publication Nos. 11149-1986 and 50-1999.
No. 10488, No. 45-30338, No. 46-21723, No. 47
â18585, No. 46-6581, No. 47-14667, No. 47
â14668, No. 47-14669, No. 47-12638, No.
47-20741, 49-1569, 49-1570, 49-1569, 49-1570,
No. 49-48769 and No. 49-10697. Although these inventions produced polymers of vinyl compounds, the sensitivity was still not sufficient. Furthermore, an invention using hydroquinone or the like as a polymerization initiator is disclosed in JP-A-55-149939,
This is because a polymerization reaction occurs in the areas where the silver halide has not been reduced, that is, in the non-exposed areas, and a negative image is formed with respect to the silver halide image. This is still not sufficient in terms of sensitivity. It is an object of the present invention to provide a sensitive method for polymerizing vinyl compounds in the presence of exposed silver halide. Another object of the present invention is to provide a highly sensitive silver halide photosensitive material capable of obtaining a positive polymer image relative to a silver halide image. Another purpose is to provide a highly sensitive printing plate by forming a polymer image on a metal plate such as aluminum. The inventors have discovered that reduction of silver halide in the presence of a vinyl compound using the phenolic compounds described below can cause polymerization of the vinyl compound. Moreover, when a silver halide photographic emulsion is used as the silver halide, the reaction occurs more quickly when the silver halide microcrystals contain development nuclei, and therefore, if appropriate reaction conditions and reaction time are selected, the development nuclei can be removed. Polymerization can occur selectively only in the areas where the silver halide grains containing the silver halide grains are present. The present invention is achieved by taking advantage of the above facts. That is, the present invention involves the application of a silver halide photographic emulsion layer having a photographic latent image in the presence of a vinyl compound capable of polymerizing at least one of the phenolic compounds in the area where the latent image is present. Optionally, this is accomplished by causing the polymerization of the vinyl compound to occur on a metal surface with a hydrophilic surface. A photographic latent image is an image-like change that occurs in a silver halide photographic emulsion due to the action of electromagnetic waves or particle beams and is normally invisible to the naked eye, but becomes a visible image when developed. It is something. In emulsions that produce normal negative images, a latent image is created by the formation of development nuclei in silver halide grains that are irradiated with electromagnetic waves or particle beams, whereas in direct positive emulsions, development nuclei that were initially present in all grains are irradiated. to disappear depending on
``Fundamentals of Photographic Theory'' by James and Huggins.
Photographic Theory)â 2nd edition Morgam&
Published by Morgam., 1960, see Chapters 3 and 4). The silver halide photographic emulsion used in the present invention is
Ordinary silver halide photographic emulsions that produce development nuclei in the irradiated areas due to the action of electromagnetic waves or particle beams, that is, produce negative images upon development, can also be used, and they can also be used to create image-like irradiation with light. It is also possible to use a so-called direct positive emulsion in which a greater number of development nuclei exist in halogen silver grains in the other areas than in the exposed areas. In the present invention, silver halide photographic emulsions used for ordinary development processing can be conveniently used as silver halide photographic emulsions capable of producing negative images. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide photographic emulsions can be used. The photographic emulsion used in the present invention can be subjected to chemical sensitization and optical sensitization as applied to ordinary photographic emulsions. That is, as chemical sensitization, sulfur sensitization, noble metal sensitization, and reduction sensitization can be performed (for example, P. Glafkides Chimic Photographique).
2nd edition Photocinema PaulMontel Paris (Photocinema PaulMontel Paris) 1957 No. 247
(See pages 301 to 301). The Theory of the Photographic Process
See Chapter 5 of Photographic Process, 4th edition, Macmillan, 1977. or,
For optical sensitization, optical sensitizing dyes used in ordinary photography such as cyanine dyes and merocyanine dyes (for example, Shinichi Kikuchi et al., Scientific Photography Handbook, Volume 2, Maruzen Publishing, 1959)
2013, pp. 15-24) are valid. The emulsion used in the present invention may also contain stabilizers such as those used in conventional photography. Direct positive silver halide photographic emulsions that can be used in the present invention can be prepared by utilizing solarization, Herschel effect, Kleiden effect, and Sabatier effect. An explanation of these effects is, for example, CEK
The Theory of the Photographic Process by Mees
To make direct positive silver halide emulsions, use solarization as described in Chapters 6 and 7 of The Photographic Process, Second Edition (MACMILLAN, 1954). It is sufficient to prepare a type of silver halide photographic emulsion that is easy to develop, and to expose the entire surface of the emulsion to light in advance or to make it work with chemicals so that it can be sufficiently developed without image exposure. Examples of how to prepare such emulsions can be found, for example, in British Patent Nos. 443,245 and 462,730. The Hersiel effect is caused by exposing silver halide to long-wavelength light that has been exposed to light or made fully developable by chemicals; A silver halide emulsion containing a large amount of silver chloride is advantageous, and a desensitizing dye such as pinacrybutol yellow or phenosafranin may be added to promote the Herschel effect. Methods for producing direct positive emulsions using the Herschel effect are found in, for example, British Patent No. 667,206 and US Pat. No. 2,857,273. In order to obtain a direct positive image using the Kleiden effect, it is necessary to give a short image exposure at high illuminance, followed by a full-surface exposure at a relatively low effective light-intensity, and only after this full-surface exposure, Areas that did not receive high-intensity image exposure become developable. The Sabatier effect is produced by exposing a silver halide emulsion to light in an imagewise manner, and then exposing the entire surface to light while immersed in a developer or by being exposed to chemical agents. This occurs by creating developability in areas that have not been exposed. The Glidden effect and the Sabatier effect can easily occur practically when using a silver halide emulsion in which the initial exposure tends to produce development nuclei inside the grains rather than on the grain surfaces. be able to. Methods for producing emulsions that are likely to generate such internal development nuclei are described, for example, in US Pat. No. 2,592,250, US Pat. ing. Positives can also be made using core shell emulsions. Methods for making core-shell emulsions are described in US Pat. No. 3,761,276 and US Pat. No. 3,206,313. The above photographic emulsion consists of a system in which silver halide grains are dispersed in a solution of a polymeric substance, and gelatin is widely used as the polymeric substance, but other hydrophilic colloids can also be used. can. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid (polyacrylic acid, Various synthetic hydrophilic polymeric substances can be used, such as single or copolymers of polymethacrylic acid and glycidyl acrylate or glycidyl methacrylate (ester bonded to each other), polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.
As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples are U.S. Patent No. 2614928, U.S. Patent No. 3132945,
3186846, 3312553, British Patent No. 861414,
It is described in No. 1033189, No. 1005784, and Japanese Patent Publication No. 42-26845. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. . Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like.
Examples of these are U.S. Pat. Nos. 2,763,625, 2,831,767,
It is described in No. 2956884, etc. Typical synthetic hydrophilic polymer substances include West German patent applications (OLS)
No. 2312708, U.S. Patent No. 3620751, U.S. Patent No. 3879205,
This is described in Japanese Patent Publication No. 7561/1973. The phenol compound used in the present invention is represented by the following general formula. general formula In the formula, R 1 represents an alkyl group or a substituted alkyl group, R 2 and Râ² 2 each represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a halogen atom, and R 3 and
Râ² 3 is hydrogen, alkyl group, substituted alkyl group,
Represents an aryl group, substituted aryl group, aralkyl group, alkoxy group, thioalkyl group, or halogen atom. Among these, R 2 and R' 2 are each hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group, and R 3 and R' 3 are each hydrogen, an alkyl group, or a substituted alkyl group. , an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, and a thioalkyl group are more preferred in terms of the effects of the present invention. Examples of the compounds used in the present invention include the following compounds. The phenol compound of the present invention has a higher oxidation potential than the developing agents (hydroquinone, catechol, metol, p-phenylenediamine) of ordinary silver halide emulsions, and is difficult to reduce silver halide. It is rarely used for development. In addition, the phenol compound of the present invention is usually used as a polymerization inhibitor to improve the storage stability of monomers, and as an antioxidant for plastics, rubber, etc. Examples of use as a polymerization initiator as in the present invention include do not have. Although it is stated in the aforementioned Japanese Patent Publication No. 49-10697 that p-methoxyphenol may be added, this is only as a polymerization inhibitor, and p-methoxyphenol etc. accelerate the polymerization reaction. There is nothing written about it. As described above, it is revolutionary to use p-methoxyphenol, which has been conventionally used as a polymerization inhibitor, as a polymerization initiator as in the present invention. Furthermore, the phenol compound of the present invention had a faster development polymerization rate than resorcinol. The reaction mechanism in which polymerization of vinyl compounds occurs as a result of the reduction of silver halide by the phenol compound is still unclear. However, since compounds that undergo radical polymerization are generally available, the reaction proceeds in an aqueous solution, and oxygen delays the polymerization reaction, it is thought that polymerization proceeds by a radical mechanism. It is not yet clear whether radicals are generated directly by the reaction between the phenol compound and silver halide, or whether radicals are generated by further interaction with water, oxygen, etc. in the system. If the irradiated silver halide is reduced with the phenol compound and then the vinyl compound is added to the reaction system, no polymerization is observed, so the polymerization of the vinyl compound occurs at the same time as the silver halide is reduced. It is clear that this will occur. Therefore, it is considered that an intermediate product between silver halide and the phenol compound contributes to the reaction. It is believed that an intermediate product between silver halide and the phenol compound contributes to the reaction. In the so-called tanning development method, which cross-links gelatin using the oxidation product of a developing agent, which is a well-known method for forming images using polymers by utilizing the photosensitivity of silver halide, the resulting image is formed on gelatin. It is limited to products that have been crosslinked. However, the polymer images obtained in the present invention have various properties depending on the vinyl compound used, so it is possible to obtain properties such as printing durability and chemical resistance that cannot be obtained with gelatin crosslinked images. It is characterized by being able to. Furthermore, in the method of the present invention, the presence of sulfite ions in the system promotes polymerization of the vinyl compound. Sulfite ions may be added as compounds that already contain sulfite ions, such as alkali metal or ammonium sulfites or bisulfites, or may be added as alkali metal or ammonium pyrosulfites or bisulfites. It may also be added as a substance that decomposes in an aqueous solution to generate sulfite ions, such as an adjunct with an aldehyde such as formaldehyde or glyoxal. The appropriate amount of sulfite ion to be added depends on the phenol compound used, the type and amount of vinyl monomer, and the system.
It is effective to use 0.002 mol or more, especially 0.01 mol or more per reaction system, which varies depending on pH etc. The addition of sulfites to photographic developers is well known. In this case, the sulfite is thought to prevent auto-oxidation of the developing agent by reacting with oxidation products of the developing agent such as hydroquinone para-aminophenol, and also prevent the development reaction from occurring non-uniformly. (e.g. CEK Mees)
Author, The Theory of the Photographic Process
Photographic Process (2nd edition) published by Macmillan, 1954 (see page 652)). In the present invention, since the intermediate product of the oxidation of the phenol compound by silver halide initiates polymerization, the polymerization promoting effect of the sulfite salt is due to the effect of removing the oxidation product in the ordinary developer as described above. It must be noted that this is fundamentally different. If the sulfite simply scavenges oxidation products, polymerization should rather be inhibited. In addition, sulfite is a well-known compound as a reducing agent in redox reactions, and polymerization using a silver halide-sulfite ion system may be considered, but in the experiments conducted in the present invention, phenolic compounds as described in the present invention were not used. In its absence, the resulting polymerization was almost negligible. Although the mechanism of action of sulfite in the present invention is not clear, it seems reasonable to assume that it prevents the polymerization inhibition effect caused by oxygen. Further, the development and polymerization of the phenolic compound used in the present invention can be accelerated by the combined use of a small amount of a conventional photographic developer or by prebathing with a conventional photographic developer. This means that resorcinols, meta-aminophenols, phenols,
- Just as development and polymerization with pyrazolones, naphthols, hydrazine derivatives, etc. are promoted by the combined use of small amounts of conventional photographic developers. As a normal photographic developer like this,
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ãéåç»åãåŸããæ床ã¯æ¥µããŠçäœãã€ãã[Formula] (where A and B are -OH, -NH2 or -NHR, where n represents an integer of 4 or less, R is an alkyl group having a total carbon number of 4 or less,
It represents a group selected from a hydroalkyl group, an alkoxyalkyl group and an alkylsulfonamidoalkyl group, or an aryl group. ), 1-aryl-3-oxopyrazolidines, and 1-aryl-3-iminopyrazolidines. Although these conventional photographic developers do not have the effect of causing polymerization by themselves, they can accelerate the polymerization reaction by promoting the developing effect of a reducing agent that has the effect of initiating polymerization. In the present invention, the vinyl compound used is a liquid or solid addition-polymerizable compound at room temperature, or a mixture thereof. Such compounds include acrylamide, acrylonitrile, N-hydroxymethylacrylamide, methacrylamide, N-t-
Butylacrylamide, methacrylic acid, acrylic acid, calcium acrylate, aluminum acrylate, sodium acrylate, methacrylamide, methyl methacrylate, methyl acrylate, ethyl acrylate, 2-acrylamide-2
-Methylpropanesulfonic acid, vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine,
Examples include 2-methyl-N-vinylimidazole, potassium vinylbenzenesulfonate, and vinylcarzol. Compounds having two or more vinyl groups are particularly advantageous in the present invention, and can be used in combination with a compound having one vinyl group as described above, or alone as a compound having a plurality of vinyl groups such as this. Use with. Examples of such compounds include N,N'-methylene bisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinyl ether, divinylbenzene bisphenol. -A- Dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, bisoxyethylated bisphenol -A-
diacrylate, dipentaerythritol hexaacrylate or unsaturated monomers containing urethane groups such as di-(2'-methacryloxyethyl)
Examples include reaction products of diol mono(meth)acrylates and diisocyanates such as -2,4-tolylene diurethane and di-(2'-acryloxyethyl)trimethylene diurethane. In the present invention, a water-soluble vinyl compound may be used, or a water-insoluble vinyl compound may be added in the form of an emulsion or dissolved in a suitable solvent for polymerization. Emulsification can be carried out according to a conventional method in the presence of a surfactant and/or a polymer compound using a suitable stirring device. This reaction generally proceeds well under alkaline conditions, but the most appropriate pH varies depending on the type and concentration of silver halide, phenol compound, and medium polymer compound, and the reaction temperature, and the reaction is possible at a pH of about 8 or higher.
9 or above is particularly convenient. When using a photographic emulsion by coating it on a support,
This photosensitive material can be irradiated with electromagnetic radiation or particle beams and then immersed in an alkaline aqueous solution to allow the reaction to proceed. The reducing agent or vinyl compound may be contained in this alkaline aqueous solution, or may be contained in the photosensitive material. The reaction can be easily stopped by making the system acidic, for example, pH 5 or less, but it is also possible to remove reactants by cooling, washing, dissolving silver halide with a photographic fixer, or inhibiting polymerization. It can also be stopped by adding agents to the system. When the vinyl compound monomer is added to the photosensitive material from the beginning, the weight of the vinyl compound used is 1/30 to 30 times, especially 1/4 to 4 times, the weight of the polymer compound added in advance. It's convenient. The silver halide used is preferably 1/1000 to 2 times the weight, particularly 4/1000 to 1/2 times the weight of the polymer compound used in advance. In addition, when the phenol compound of the present application is added to the sensitive material in advance, and when the vinyl compound and the phenol compound are contained in the same layer, the weight of the phenol compound is 3/100 or more of the weight of the vinyl compound used, Preferably 4/
100 or more, and when it is contained in a layer different from the vinyl compound, it is conveniently in a range of 1/10 to 20 moles per mole of silver halide used. The phenol compound may be dissolved in water or an organic solvent, or dissolved in water or an organic solvent with the addition of a suitable surfactant, and may be added at the time of preparing the sensitive material. When adding a vinyl compound to a processing solution, it is usually advantageous to have a concentration as high as possible, and the amount added to the solution is rather limited by the solubility of the vinyl compound used in the processing solution. When adding a phenol compound used as a reducing agent to the processing solution, the optimum concentration varies somewhat depending on the compound used, but the concentration is between 1/1000 mol and 5 mol/1.
mole is appropriate, especially 1/50 to 1 mole,
For vinyl compounds, it is convenient to have a weight ratio of 3/100 or more, preferably 4/100 or more. Further, when adding the phenol compound, it may be added as an aqueous solution or an organic solvent, and a surfactant may be further added to solubilize it. The light-sensitive material of the present invention may contain an inorganic or organic hardening agent. . For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), activated vinyl compound (1,3,
5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl) methyl ether, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucochloric acid, enoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc. can be used alone or in combination. A specific example is the U.S. patent
No. 1870354, No. 2080019, No. 2726162, No.
No. 2870013, No. 2983611, No. 2992109, No.
No. 3047394, No. 3057723, No. 3103437, No. 3047394, No. 3057723, No. 3103437, No.
No. 3321313, No. 3325287, No. 3362827, No. 3321313, No. 3325287, No. 3362827, No.
No.3539644, No.3543292, British Patent No.676628, No.3543292, British Patent No.676628,
No. 825544, No. 1270578, German Patent No. 872153,
It is described in No. 1090427, Special Publication No. 34-7133, No. 46-1872, etc. The photosensitive material used in the present invention may contain various known surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, and prevention of adhesion. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides) , polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and non-ionic materials such as urethanes or ethers. surfactants; triterpenoid saponins, alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates,
Alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups: amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amine imides, Amphoteric surfactants such as amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphoniums or sulfoniums containing aliphatic or heterocyclic rings. Cationic surfactants such as salts can be used. Specific examples of these surfactants are listed in the U.S. patent.
No. 2240472, No. 2831766, No. 3158484, No.
No. 3210191, No. 3294540, No. 3507660, British Patent No. 1012495, No. 1022878, No. 1179290, British Patent No.
No. 1198450, Japanese Unexamined Patent Publication No. 117414, US patent
No. 2739891, No. 2823123, No. 3068101, No.
No. 3415649, No. 3666478, No. 3756828, British Patent No. 1397218, US Patent No. 3133816, No. 3441413,
Same No. 3475174, No. 3545974, No. 3726683, Same No.
No. 3843368, Belgian Patent No. 731126, British Patent
No. 1138514, No. 1159825, No. 1374780, Tokko Akira
40-378, 40-379, 43-13822, U.S. Patent No. 2271623, 2288226, 2944900, U.S. Pat.
No. 3253919, No. 3671247, No. 3772021, No.
3589906, 3666478, 3754924, West German patent application OLS 1961638, Japanese Patent Application Laid-Open No. 50-59025, etc. In the present invention, any electromagnetic waves or particle beams to which ordinary photographic emulsions are sensitive can be used as the electromagnetic waves or particle beams that can be used to obtain photographic images. That is, particle beams such as visible light, ultraviolet rays, infrared rays of 1.3 ÎŒm or less, X-rays, gamma rays, electron beams, and Alpha rays can be applied. In particular, conventional methods, such as tungsten lamps, fluorescent lamps, mercury lamps, xenon, arc lamps, carbon arc lamps, xenon flash lamps, halogen lamps, light emitting diodes, cathode ray tubes, flying spots, discharge tubes such as clotue tubes, argon lasers, etc. Any of various known light sources such as laser light can be used.
Exposure times range from 1/1000 seconds to 50 seconds, as well as exposures shorter than 1/1000 seconds, such as 1/1000 seconds using xenon flash lamps, cathode ray tubes, and laser light.
Exposures of 10 4 to 1/10 6 seconds can also be used,
Exposures longer than 50 seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. When using the method of the present invention to record images,
Differences in physical and chemical properties such as solubility, adhesiveness, and dyeability between vinyl compounds and their polymers can be utilized in various ways. By taking advantage of the difference in solubility, by dissolving the unpolymerized portion after irradiation and reaction, the image created by the polymer substance remains only in the irradiated area, creating an image. can be formed. In this case, it is more convenient for the initially added polymer compound to be dissolved away together with unreacted monomers. For this reason, the polymer compounds contained in the system from the beginning are either so-called two-dimensional linear forms with almost no crosslinking, or the main chains or crosslinks are easily severed. It is convenient that the polymer compound produced by the one-sided reaction is a so-called three-dimensional crosslinked polymer.
For this purpose, it is convenient to use the aforementioned compound having a plurality of vinyl groups alone or in combination with a compound having one vinyl group. However, even if the generated polymeric substance is a two-dimensional soluble polymeric substance, as a result of interaction with the polymeric compound added in advance, some parts of the polymeric substance are generated by reaction and others are not. It is not essential to use monomers with multiple vinyl groups, since there are often significant differences in solubility between the parts (eg, in the case of polyacrylic acid and gelatin). Metals with hydrophilic surfaces used in the present invention include aluminum (including aluminum alloys);
Metals such as zinc, iron, copper, etc. are suitable, and these metals may be laminated or vapor deposited onto paper or plastic film to form a composite support, or may serve as a support on their own. good. Among these supports, aluminum plates and composite sheets in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 18327/1984 are preferred. These supports are subjected to treatments such as surface treatment or formation of a hydrophilic layer, if necessary, in order to obtain a hydrophilic surface. There are various types of hydrophilic treatment. In the case of a support having a surface of metal, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. It is preferable. Additionally, U.S. Patent No.
As described in the specification of US Pat. No. 2,714,066, an aluminum plate is grained and then immersed in an aqueous sodium silicate solution, and an aluminum plate is anodized as described in US Pat. No. 3,181,461. Furthermore, those treated by immersion in an aqueous solution of an alkali metal silicate are also suitably used. The above-mentioned anodizing treatment can be carried out using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either alone or in combination. Among them, it is particularly preferably carried out by passing an electric current through an aluminum plate in an aqueous solution of phosphoric acid, sulfuric acid or a mixture thereof. Additionally, U.S. Patent No.
Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Additionally, British Patent No.
Also preferred is an aluminum plate which is electrolyzed with alternating current in a hydrochloric acid electrolyte and then anodized in a sulfuric acid electrolyte, as described in No. 1208224. Further, it is preferable to provide an undercoat layer of a cellulose resin containing a water-soluble salt of a metal such as zinc on the aluminum plate anodized in the above process in order to prevent scum during printing. Example 1 A 2S aluminum plate mechanically grained by the method disclosed in JP-A-48-33911 was immersed in a 2% sodium hydroxide aqueous solution kept at 40°C for 1 minute to corrode a part of the surface. . After washing with water, it was immersed in a sulfuric acid-chromic acid solution for about 1 minute to expose the pure aluminum surface. It was immersed in 20% sulfuric acid kept at 30°C, anodized for 2 minutes at a DC voltage of 1.5V and a current density of 3A/dm 2 , then washed with water and dried. Also, 75 mol% silver chloride under red safety light,
A silver halide emulsion consisting of 24.5 mole percent silver bromide and 0.5 mole percent silver iodide was prepared in methanol solution with poly-N-vinylpyrrolidone (2 g/g silver) as the protective colloid binder. The average grain size of the silver halide was 0.20 ÎŒm. To this silver halide emulsion were added 4 g of pentaerythritol tetraacrylate and 0.017 mol (2 g) of Phenol Compound Example 1 per 1 g of silver, and the mixture was coated on the above aluminum plate to obtain a sample. Coated silver amount is 0.8g/
It was m2 . This sample was placed in close contact with a step wedge with a step difference of 0.15 (â³logE), exposed for 1 second to an ultra-high pressure mercury lamp through a gray filter with an optical density of 1.0, and then exposed to the following developer at 40°C for 30 seconds under red safety light. Soaked. Sodium sulfite 14g Phenol compound Example 1 0.9 mol The pH was adjusted to 10.2 with sodium hydroxide and water was added. 1 Then, unpolymerized parts were removed by washing with warm water to obtain a polymerized image. Example 2 A polymerized image was obtained in the same manner as in Example 1, except that the compounds shown in Table 1 were used in place of Phenol Compound Example 1. Example 3 A polymerized image was obtained in the same manner as in Example 1 except that dipentaerythritol hexaacrylate was used instead of pentaerythritol tetraacrylate. Comparative Example 1 A sample was prepared and processed in the same manner as in Example 1 except that resorcinol was used in place of Phenol Compound Example 1, and a polymerized image was obtained, but the sensitivity was extremely low.
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ç©ãåŸãã[Table] Example 4 A sample was prepared by the method described in Example 1, and the following
A polymerized image was obtained by processing in the same manner as in Example 1, except that development was performed at 40° C. for 8 minutes. Sodium sulfite 14g Adjust the pH to 10.2 with sodium hydroxide, then add water to bring it to 1. When the polymerized image samples obtained in Examples 1, 2, 3, and 4 were mounted on a Hamadastar 500CD printer and printed using a commercially available dampening solution, more than 5,000 good prints were obtained.
Claims (1)
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éžæçã«ããã«ååç©ã芪氎æ§è¡šé¢ãæããéå±
é¢äžã§éåãããããšãç¹åŸŽãšããå°å·çäœè£œæ¹
æ³ã äžè¬åŒ åŒäžãR1ã¯ã¢ã«ãã«åºåã¯çœ®æã¢ã«ãã«åºã
è¡šãããR2åã³Râ²2ã¯åã æ°ŽçŽ ãã¢ã«ãã«åºã眮
æã¢ã«ãã«åºãã¢ãªãŒã«åºã眮æã¢ãªãŒã«åºãã¢
ã©ã«ãã«åºåã¯ããã²ã³ååãè¡šãããR3åã³
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è¡šããã[Scope of Claims] 1. Silver halide having development nuclei is reduced using a phenol compound represented by the following general formula in the presence of at least one vinyl compound capable of addition polymerization. A method for producing a printing plate, characterized in that a vinyl compound is selectively polymerized in silver on a metal surface having a hydrophilic surface. general formula In the formula, R 1 represents an alkyl group or a substituted alkyl group, R 2 and Râ² 2 each represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, or a halogen atom, and R 3 and
Râ² 3 is hydrogen, alkyl group, substituted alkyl group,
Represents an aryl group, substituted aryl group, aralkyl group, alkoxy group, thioalkyl group, or halogen atom.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11016981A JPS5810745A (en) | 1981-07-14 | 1981-07-14 | Printing plate making method |
DE19823206030 DE3206030A1 (en) | 1981-02-19 | 1982-02-19 | Process for formation of polymeric images and printing plates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11016981A JPS5810745A (en) | 1981-07-14 | 1981-07-14 | Printing plate making method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5810745A JPS5810745A (en) | 1983-01-21 |
JPH037104B2 true JPH037104B2 (en) | 1991-01-31 |
Family
ID=14528792
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11016981A Granted JPS5810745A (en) | 1981-02-19 | 1981-07-14 | Printing plate making method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5810745A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011119292A3 (en) * | 2010-03-25 | 2012-01-19 | Vgensys, Ltd. | Support truss for hinged overhead door |
-
1981
- 1981-07-14 JP JP11016981A patent/JPS5810745A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011119292A3 (en) * | 2010-03-25 | 2012-01-19 | Vgensys, Ltd. | Support truss for hinged overhead door |
Also Published As
Publication number | Publication date |
---|---|
JPS5810745A (en) | 1983-01-21 |
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