EP0595031A1 - Process for the production of silver halide emulsions - Google Patents
Process for the production of silver halide emulsions Download PDFInfo
- Publication number
- EP0595031A1 EP0595031A1 EP93115452A EP93115452A EP0595031A1 EP 0595031 A1 EP0595031 A1 EP 0595031A1 EP 93115452 A EP93115452 A EP 93115452A EP 93115452 A EP93115452 A EP 93115452A EP 0595031 A1 EP0595031 A1 EP 0595031A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- mol
- emulsion
- compounds
- histidine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 88
- -1 silver halide Chemical class 0.000 title claims abstract description 67
- 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 description 28
- 230000008569 process Effects 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 108010010803 Gelatin Proteins 0.000 claims abstract description 20
- 239000008273 gelatin Substances 0.000 claims abstract description 20
- 229920000159 gelatin Polymers 0.000 claims abstract description 20
- 235000019322 gelatine Nutrition 0.000 claims abstract description 20
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 20
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 18
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims abstract description 14
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 5
- 150000003378 silver Chemical class 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 3
- 150000004866 oxadiazoles Chemical class 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 150000003230 pyrimidines Chemical class 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- 150000003557 thiazoles Chemical class 0.000 claims description 3
- 150000002916 oxazoles Chemical class 0.000 claims description 2
- 150000004867 thiadiazoles Chemical class 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract 3
- 235000013339 cereals Nutrition 0.000 description 26
- 150000004820 halides Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000010931 gold Substances 0.000 description 7
- 239000004848 polyfunctional curative Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000005070 ripening Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000001016 Ostwald ripening Methods 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229940065287 selenium compound Drugs 0.000 description 3
- 150000003343 selenium compounds Chemical class 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000004891 diazines Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 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 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NCNYEGJDGNOYJX-NSCUHMNNSA-N (e)-2,3-dibromo-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Br)=C(/Br)C=O NCNYEGJDGNOYJX-NSCUHMNNSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical class C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-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
- 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
- IWAGGDFROAISJT-UHFFFAOYSA-N 1h-isoquinoline-2-carboxylic acid Chemical compound C1=CC=C2C=CN(C(=O)O)CC2=C1 IWAGGDFROAISJT-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
- WAVYAFBQOXCGSZ-UHFFFAOYSA-N 2-fluoropyrimidine Chemical compound FC1=NC=CC=N1 WAVYAFBQOXCGSZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene 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
- 150000001412 amines Chemical class 0.000 description 1
- ISLGHAYMGURDSU-UHFFFAOYSA-N aminomethanesulfinic acid Chemical class NCS(O)=O ISLGHAYMGURDSU-UHFFFAOYSA-N 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical group C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000001719 carbohydrate derivatives Chemical class 0.000 description 1
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- 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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- 239000000701 coagulant Substances 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 235000015927 pasta Nutrition 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical class [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 1
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- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229940095574 propionic acid Drugs 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
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 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
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/015—Apparatus or processes for the preparation of emulsions
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/07—Substances influencing grain growth during silver salt formation
Definitions
- the invention relates to a method for producing silver halide emulsions, in which emulsions of different solubility are mixed and redissolved.
- Silver halide emulsions are generally prepared by precipitating silver halide in a binder, preferably gelatin as the binder.
- the silver halide can be precipitated by adding an aqueous solution of a silver salt to a gelatin-containing halide solution.
- the size of the silver halide grains obtained is inter alia controlled by the temperature of the solution, the run-in time and the excess of halide.
- the grain size and the grain size distribution of the silver halide grains of the emulsions obtained are still determined primarily by the so-called Ostwald ripening. Under the Ostwald ripening is the dissolution Easily soluble silver halide grains are understood to be the action of silver halide solvents and subsequent separation of the dissolved silver halide on less soluble silver halide grains.
- the more readily soluble silver halide emulsion used in these processes is preferably a fine grain silver halide emulsion with an average grain diameter smaller than that of the less soluble silver halide emulsion.
- the advantages of the specified redeployment procedures include: in controlled Ostwald ripening and above all in avoiding local silver ion oversaturation.
- Examples of known silver halide solvents are: halides, preferably alkali and ammonium halides, in particular bromides or chlorides; Ammonia; Thiocyanates, especially alkali or ammonium thiocyanate; Sulfites, especially alkali or ammonium sulfites; Thiosulfate; organic amines; Thioether and imidazole derivatives.
- Suitable thioethers are described, for example, in US Pat. Nos. 3,271,157, 3,507,657, 3,531,289 and 3,574,628. Particularly suitable thioethers are also described in German Offenlegungsschriften 2,614,862 and 2,824,249. Suitable imidazole derivatives are described in US Pat German Offenlegungsschrift 27 58 711.
- the object of the invention is therefore to find a process for the production of highly sensitive, fine-grained silver halide emulsions which have low fog.
- the invention therefore relates to a process for the preparation of a silver halide emulsion with up to 20 mol% AgI by precipitation of a silver halide emulsion A with up to 100 mol% AgI and addition of a silver halide emulsion B with up to 40 mol% AgI and an average grain size of at most 0.25 ⁇ m, emulsion B in aqueous gelatin solution always being more soluble than emulsion A either because of its grain size or because of its iodide content, in the presence of at least two compounds from the series imidazole, histidine ( ⁇ -amino- ⁇ -imidazolyl - (5) -pro-pionic acid) and other monocyclic, free of SH groups, 5- or 6-membered, heterocyclic compounds with at least one ring nitrogen atom, which form poorly soluble silver salts in weakly acidic to neutral aqueous solution, which with the addition of ammonia go back into solution at pH> 9, one of the at least two
- Monocyclic compounds are understood to mean those which have no fused rings in the entire molecule.
- Grain size is always understood to mean the diameter of the same-volume ball.
- the iodide content of emulsion A is preferably 10 to 90 mol%.
- Suitable are e.g. Imidazoles, oxazoles, thiazoles, triazoles, thiadiazoles, oxadiazoles, pyridines, tetrazoles and pyrimidines which are substituted by alkyl, preferably having up to 4 carbon atoms such as methyl, ethyl, isopropyl; Alkenyl such as allyl; Aryl such as phenyl, halogen such as chlorine or bromine, carboxylic acid groups or derivatives such as carbalkoxy or carbonamido: sulfonic acid groups, sulfonamide, sulfones, thioethers such as methylthio or carboxyalkylthio; substituted or unsubstituted amino groups can be substituted.
- alkyl preferably having up to 4 carbon atoms such as methyl, ethyl, isopropyl
- Alkenyl such as allyl
- Aryl such as phen
- the solution is preferably carried out at an E Ag value of -20 to -120 mV, in particular -40 to -100 mV, at a pH of 4 to 10, in particular 6 to 8 and a temperature of 40 to 90 ° C. especially 50 to 75 ° C. Under these conditions, the redissolution is usually complete after 20 minutes (E Ag is the potential between a silver electrode and a saturated calomel electrode).
- the gelatin / silver halide weight ratio expressed as the amount of silver nitrate used, is preferably 0.05 to 1.0, in particular 0.1 to 0.5, when the solution is redissolved.
- Emulsions A and B expressed as the amount of silver nitrate used, are preferably mixed with one another in a weight ratio of 1: 1 to 1:20, preferably 1: 2 to 1:10.
- Emulsions A and B are essentially silver bromoiodide emulsions. They can also contain small amounts of silver chloride.
- the grain size of emulsion A ranges in particular from 0.1 to 1.5 ⁇ m, the grain size of emulsion B in particular from 0.01 to 0.2 ⁇ m.
- the emulsion A If the iodide content of emulsion A is between 40 and 90 mol%, the emulsion consists predominantly of grains with about 40 mol% AgI and pure AgI grains.
- the iodide content of emulsion A can be adjusted by appropriate selection of the mixture of soluble halides intended for the precipitation.
- An emulsion with a lower iodide content can also be precipitated first and then converted to the desired higher iodide content with the addition of KI.
- emulsion A is first prepared as a precipitate, which can optionally be concentrated and desalted.
- the further supply of substance, which is carried out according to the invention by adding emulsion B, can be set up in such a way that more than 50 mol%, preferably more than 80 mol%, of the silver halide used is added in the form of emulsion B.
- Emulsion B can also be concentrated and desalted.
- emulsion B and the silver halide solvents to be used according to the invention can be added simultaneously or at different times, all at once or in several parts or continuously.
- concentrations of the silver halide emulsions B and A used can be varied within wide limits.
- the amount of the silver halide solvent to be used according to the invention can generally be easily determined in a series of tests and, in the case of imidazole and histidine, is preferably between 10 ⁇ 5 and 2.0 mol per mol of silver halide used, in particular between 10 ⁇ 3 and 0.3 mol per Mol used silver halide and in the case of compounds other than imidazole and histidine preferably 10 ⁇ 6 and 0.5 mol per mol of silver halide used.
- emulsions can in principle be prepared for a wide variety of photographic materials, e.g. Negative working emulsions with high surface sensitivity, negative working emulsions with high internal sensitivity, directly positive working emulsions that can be superficially veiled or superficially unveiled, emulsions with layered grain structure, print-out emulsions, reverse emulsions, emulsions for black and white and for color materials as well as with defined grain distribution and halide topography , in particular with a defined halide, in particular iodide gradient.
- photographic materials e.g. Negative working emulsions with high surface sensitivity, negative working emulsions with high internal sensitivity, directly positive working emulsions that can be superficially veiled or superficially unveiled, emulsions with layered grain structure, print-out emulsions, reverse emulsions, emulsions for black and white and for color materials as well as with defined grain distribution and halide
- the silver halide emulsions prepared according to the invention and the starting emulsions A and B can either be solidified, pasta-coated and soaked in a known manner or can also be coagulated with a coagulating agent and then washed, as is known, for example, from German Offenlegungsschrift 2,614,862. Desalination is particularly advantageously carried out by ultrafiltration.
- the emulsion produced according to the invention and optionally also the starting emulsions, in particular emulsion A, can be chemically sensitized, for example by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate.
- sulfur-containing compounds for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate.
- Reducing agents for example, the tin compounds described in the Belgian patent specifications 493 464 or 568 687, and also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, for example in accordance with the Belgian patent specification 547 323, can be used.
- Selenium compounds are also suitable.
- Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z. Wis. Phot. 46, 65-72 (1951).
- Both emulsion A and emulsion B can be added with foreign ions for doping during the precipitation. This addition is also possible before, during and after the redeployment.
- Suitable compounds are for example Ir- and. Rh compounds.
- Both emulsion A and emulsion B can be subjected to reduction ripening during the precipitation. Such reduction sensitization is also possible before, during and after the redissolution.
- Suitable compounds for this are, for example, thiosulfonic acid derivatives, H2O2 and mercury (II) compounds.
- polyalkylene oxide derivatives for example with polyethylene oxide with a molecular weight between 1,000 and 20,000, furthermore with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
- the condensation products have a molecular weight of at least 700, preferably more than 1,000.
- these sensitizers can of course be used in combination, as in the Belgian patent 536 278 and in the British patent 727,982.
- the emulsions can also be optically sensitized, for example with the usual polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
- polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
- sensitizers are described in FM Hamer: "The Cyanine Dyes and Related Compounds" 1964, Interscience Publishers, John Wiley and Sons.
- the emulsions can contain the usual stabilizers, e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
- stabilizers e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
- azaindenes preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are in Birr: Z. Wiss. Phot. 47 (1952), 2-58.
- Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenylmercapto compounds, quaternary benzothiazole derivatives and benzotriazole.
- gelatin as a binder or protective colloid for the photographic emulsion according to the invention
- other colloids can also be used.
- various high molecular weight synthetic hydrophilic materials such as graft polymers of gelatin and other high molecular weight materials; Proteins such as albumin, casein and the like; Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate and the like; Saccharide derivatives such as sodium alginate, starch derivatives and the like; Homopolymers or copolymers, such as polyvinyl alcohol, partially acetalized polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.
- Suitable gelatin graft polymers that can be used in the present invention are those obtained by grafting homopolymers or copolymers of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof, e.g. the esters, amides, acrylonitrile, styrene on gelatin. Graft polymers of gelatin with polymers of acrylic acid, methacrylic acid, acrylamide, methacrylamide and hydroxyalkyl methacrylates are particularly preferred.
- the emulsions can be hardened in a customary manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
- formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
- the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type.
- hardeners are e.g. in German laid-open specification 2 263 602 or in British patent 1 266 655.
- hardeners examples include diazine derivatives containing alkyl or arylsulfonyl groups, derivatives of hydrogenated diazines or triazines, such as, for example, 1,3,5, -hexahydrotriazine, fluorine-substituted diazine derivatives, for example fluoropyrimidine, esters of 2-substituted, 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acid, vinyl sulfonic acid hardeners, carbodiimide or carbamoyl hardeners can also be used, as described, for example, in German Offenlegungsschriften 2,263,602, 2,225,230 and 1,808,685, French Patent 1,491,807 and German Patent 872 153 and DD-A-7218.
- Other useful resins are described, for example, in British Patent 1,268,550.
- the present invention can be applied to both black and white and color photographic images.
- Colored photographic images can e.g. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of color-giving p-phenylenediamine developers to form dyes.
- the color couplers can, for example, be added to the color developer according to the principle of the so-called development process.
- the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers.
- the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
- the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone, indazolone or pyrazoloazole type usually being used.
- the blue-sensitive layer can contain a non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
- Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publication "Color coupler” by W. Pelz in “Messages from the research laboratories of Agfa, Leverkusen / Kunststoff", Volume III (1961) and K. Venkataraman in "The Chemistry of Synthetic Cyes", Vol. 4, 341 -387, Academic Press, 1971.
- 2-equivalent couplers can be used as further non-diffusing color couplers; these contain a removable substituent in the coupling point, so that they only require two equivalents of silver halide to form the color, in contrast to the usual 4-equivalent couplers.
- the 2-equivalent couplers that can be used include, for example, the known DIR couplers, in which the cleavable residue is released as a diffusing development inhibitor after reaction with color developer oxidation products.
- the so-called white couplers can be used to improve the properties of the photographic material, which provide a colorless coupling product.
- the non-diffusing color couplers and coloring compounds are added to the light-sensitive silver halide emulsions or other casting solutions by customary known methods. If the compounds are soluble in water or alkali, they can be added to the emulsions in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide.
- non-diffusing color couplers and coloring compounds are water- or alkali-insoluble compounds, they can be emulsified in a known manner, for example by dissolving these compounds in a low-boiling organic solvent directly with the silver halide emulsion or initially with an aqueous gelatin solution is mixed, whereupon the organic solvent is removed in a conventional manner. A gelatin emulsate of the respective compound thus obtained is then mixed with the silver halide emulsion.
- coupler solvents or oil formers are additionally used to emulsify such hydrophobic compounds; these are generally higher-boiling organic compounds which include the compounds in the form of oily droplets which split off and emulsify in the silver halide emulsions and do not diffuse color couplers and development inhibitors.
- coupler solvents or oil formers are generally higher-boiling organic compounds which include the compounds in the form of oily droplets which split off and emulsify in the silver halide emulsions and do not diffuse color couplers and development inhibitors.
- the emulsions prepared according to the invention can be applied to the customary layer supports, for example supports made from cellulose esters such as cellulose acetate or cellulose acetobutyrate, furthermore polyesters, in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane.
- cellulose esters such as cellulose acetate or cellulose acetobutyrate
- polyesters in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane.
- paper supports which can optionally contain water-impermeable polyolefin layers, for example made of polyethylene or polypropylene, and supports made of glass or metal.
- the emulsion B used in the examples below is a silver bromide emulsion which has an average grain size of 0.05 ⁇ m and contains 1.25 mol of silver halide per kg and 18 g of gelatin per kg.
- the AgBrI emulsion A1 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg.
- the average grain size is 0.4 ⁇ m, the iodide content is 25 mol%.
- 3000 g of emulsion B are mixed with 1500 g of emulsion A1 and digested in the presence of the substances listed in Table 1 at 65 ° C, pH 7.5 and an E Ag value of -60 mV until the redissolution is complete ( after about 20 minutes). It is then coagulated, washed and finally redispersed with the addition of water and gelatin. Then an optimal ripening with gold and sulfur compounds is carried out.
- the average grain size is 0.7 ⁇ m, the iodide content 7 mol%.
- the AgBrI emulsion A2 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg.
- the average grain size is 0.7 ⁇ m, the iodide content is 40 mol%.
- emulsion B 9000 g of emulsion B are mixed with 1500 g of emulsion A2 and digested in the presence of the substances listed in Table 2 at 60 ° C., pH 7.5 and an E Ag value of -60 mV until the redissolution is complete ( after about 20 minutes).
- the further processing corresponds to Example 1.
- the average grain size is 1.1 ⁇ m, the iodide content 4.7 mol%.
- the AgBrI emulsion A3 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg.
- the average grain size is 0.5 ⁇ m
- the iodide content is 70 mol%
- an iodide content of 30 mol% first being precipitated and then converted to the stated iodide content by adding KI.
- the average grain size is 1.1 ⁇ m, the iodide content is 12 mol%.
- Both the emulsions produced after 1.1 and after 1.3 are subjected to an optimal ripening of gold sulfur as well as an optimal ripening, in which, in addition to gold and sulfur compounds, selenium compounds are also present. Suitable selenium compounds for this are described for example in EP 428 041, 458 278, 476 345.
- example 1.3 according to the invention there is a significantly greater increase in sensitivity due to the addition of selenium than in example 1.1 not according to the invention.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Silberhalogenidemulsionen, bei dem Emulsionen unterschiedlicher Löslichkeit gemischt und umgelöst werden.The invention relates to a method for producing silver halide emulsions, in which emulsions of different solubility are mixed and redissolved.
Silberhalogenidemulsionen werden im allgemeinen durch Fällen von Silberhalogenid in einem Bindemittel hergestellt, wobei als Bindemittel vorzugsweise Gelatine verwendet wird. Die Fällung des Silberhalogenids kann dadurch erfolgen, daß zu einer gelatinehaltigen Halogenidlösung eine wäßrige Lösung eines Silbersalzes zugefügt wird. Die Größe der erhaltenen Silberhalogenidkörner wird u.a. durch die Temperatur der Lösung, die Einlaufzeit und den Halogenidüberschuß gesteuert.Silver halide emulsions are generally prepared by precipitating silver halide in a binder, preferably gelatin as the binder. The silver halide can be precipitated by adding an aqueous solution of a silver salt to a gelatin-containing halide solution. The size of the silver halide grains obtained is inter alia controlled by the temperature of the solution, the run-in time and the excess of halide.
Die Korngröße und die Korngrößenverteilung der Silberhalogenidkörner der erhaltenen Emulsionen werden weiterhin vor allem durch die sogenannte Ostwald-Reifung bestimmt. Unter der Ostwald-Reifung wird die Auflösung leichter löslicher Silberhalogenidkörner unter der Einwirkung von Silberhalogenidlösungsmitteln und anschließende Abscheidung des gelösten Silberhalogenids an schwerer löslichen Silberhalogenidkörnern verstanden.The grain size and the grain size distribution of the silver halide grains of the emulsions obtained are still determined primarily by the so-called Ostwald ripening. Under the Ostwald ripening is the dissolution Easily soluble silver halide grains are understood to be the action of silver halide solvents and subsequent separation of the dissolved silver halide on less soluble silver halide grains.
Es ist weiterhin bekannt, die wäßrigen Lösungen eines Silbersalzes und eines Halogenids gleichzeitig in eine Vorlage einlaufen zu lassen (Doppelstrahl-Verfahren).It is also known to run the aqueous solutions of a silver salt and a halide into a receiver at the same time (double-jet method).
Zur Herstellung von Silberhalogenidemulsionen sind auch Verfahren bekannt, Emulsionen unterschiedlicher Korngröße zu mischen und in Gegenwart von Silberhalogenidlösungsmitteln eine Umlösung zu bewirken. Eine Voraussetzung für derartige Verfahren ist, daß die bei der Umlösung verwendeten Silberhalogenidkristalle unterschiedliche Löslichkeit aufweisen. Unterschiedliche Löslichkeiten können durch unterschiedliche Korngröße und/oder unterschiedliche Halogenidzusammensetzung hervorgerufen werden. Derartige Verfahren sind aus den US-Patentschriften 2 146 983, 3 206 313, 3 317 322, der deutschen Auslegeschrift 1 207 791, den Referat von D. Markocki und W. Romer in "Korpuskular Photographie", IV (1963), Seiten 149 ff., aus "Zhurnal Nauchnoi Prikladnoi Fotografi Kinematografi 5, No. 2 (1960), Seiten 81-83 und EP-PS 42 060 bekannt.For the production of silver halide emulsions, processes are also known for mixing emulsions of different grain sizes and for effecting a redissolution in the presence of silver halide solvents. A prerequisite for such processes is that the silver halide crystals used in the redissolution have different solubilities. Different solubilities can be caused by different grain size and / or different halide composition. Such methods are described in US Pat. Nos. 2,146,983, 3,206,313, 3,317,322, German Auslegeschrift 1,207,791, D. Markocki and W. Romer in "Korpuskular Photographie", IV (1963), page 149 ff., from "Zhurnal Nauchnoi Prikladnoi Fotografi Kinematografi 5, No. 2 (1960), pages 81-83 and EP-PS 42 060 known.
Die bei diesen Verfahren verwendete leichter lösliche Silberhalogenidemulsion ist vorzugsweise eine feinkörnige Silberhalogenidemulsion mit einem mittleren Korndurchmesser, der kleiner istals der der schwerer löslichen Silberhalogenidemulsion.The more readily soluble silver halide emulsion used in these processes is preferably a fine grain silver halide emulsion with an average grain diameter smaller than that of the less soluble silver halide emulsion.
Die Vorteile der angegebenen Umlöseverfahren liegen u.a. in der kontrollierten Ostwald-Reifung und vor allem in der Vermeidung örtlicher Silberionenübersättigungen.The advantages of the specified redeployment procedures include: in controlled Ostwald ripening and above all in avoiding local silver ion oversaturation.
Als Silberhalogenidlösungsmittel sind beispielsweise bekannt: Halogenide, vorzugsweise Alkali und Ammoniumhalogenide, insbesondere Bromide oder Chloride; Ammoniak; Thiocyanate, insbesondere Alkali oder Ammoniumthiocyanat; Sulfite, insbesondere Alkali oder Ammoniumsulfite; Thiosulfat; organische Amine; Thioether und Imidazolderivate. Geeignete Thioether sind beispielsweise beschrieben in den US-Patentschriften 3 271 157, 3 507 657, 3 531 289 und 3 574 628. Besonders geeignete Thioether sind weiterhin beschrieben in den deutschen Offenlegungsschriften 2 614 862 und 2 824 249. Geeignete Imidazolderivate sind beschrieben in der deutschen Offenlegungsschrift 27 58 711.Examples of known silver halide solvents are: halides, preferably alkali and ammonium halides, in particular bromides or chlorides; Ammonia; Thiocyanates, especially alkali or ammonium thiocyanate; Sulfites, especially alkali or ammonium sulfites; Thiosulfate; organic amines; Thioether and imidazole derivatives. Suitable thioethers are described, for example, in US Pat. Nos. 3,271,157, 3,507,657, 3,531,289 and 3,574,628. Particularly suitable thioethers are also described in German Offenlegungsschriften 2,614,862 and 2,824,249. Suitable imidazole derivatives are described in US Pat German Offenlegungsschrift 27 58 711.
Durch die genannten Verfahren lassen sich sowohl hochempfindliche als auch feinkörnige Silberhalogenidemulsionen herstellen, jedoch ist es bisher nicht gelungen, beide Eigenschaften in einem ausreichenden Maß gemeinsam zu realisieren.Both high-sensitivity and fine-grain silver halide emulsions can be produced by the processes mentioned, but it has not hitherto been possible to achieve both properties to a sufficient extent together.
Aufgabe der Erfindung ist daher, ein Verfahren zur Herstellung hochempfindlicher, feinkörniger Silberhalogenidemulsionen zu finden, die niedrigen Schleier aufweisen.The object of the invention is therefore to find a process for the production of highly sensitive, fine-grained silver halide emulsions which have low fog.
Diese Aufgabe wird durch ein verbessertes Umlöseverfahren gelöst.This task is solved by an improved redeployment process.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung einer Silberhalogenidemulsion mit bis zu 20 Mol-% AgI durch Fällen einer Silberhalogenidemulsion A mit bis zu 100 Mol-% AgI und Zugabe einer Silberhalogenidemulsion B mit bis zu 40 Mol-% AgI und einer mittleren Korngröße von höchstens 0,25 µm, wobei die Emulsion B in wäßriger Gelatinelösung stets entweder aufgrund iher Korngröße oder aufgrund ihres Iodidgehaltes gegenüber Emulsion A die größere Löslichkeit aufweist, in Gegenwart von wenigstens zwei Verbindungen aus der Reihe Imidazol, Histidin (α-Amino-β-imidazolyl-(5)-pro-pionsäure) und anderen monocyclischen, von SH- Gruppen freien, 5- oder 6-gliedrigen, heterocyclischen Verbindungen mit wenigstens einem Ringstickstoffatom, die in schwach saurer bis neutraler wäßriger Lösung schwerlösliche Silbersalze bilden, die unter Zusatz von Ammoniak bei pH > 9 wieder in Lösung gehen, wobei eine der wenigstens zwei Verbindungen Imidazol oder Histidin und wenigstens eine andere Verbindung nicht Imidazol oder Histidin ist.The invention therefore relates to a process for the preparation of a silver halide emulsion with up to 20 mol% AgI by precipitation of a silver halide emulsion A with up to 100 mol% AgI and addition of a silver halide emulsion B with up to 40 mol% AgI and an average grain size of at most 0.25 µm, emulsion B in aqueous gelatin solution always being more soluble than emulsion A either because of its grain size or because of its iodide content, in the presence of at least two compounds from the series imidazole, histidine (α-amino-β-imidazolyl - (5) -pro-pionic acid) and other monocyclic, free of SH groups, 5- or 6-membered, heterocyclic compounds with at least one ring nitrogen atom, which form poorly soluble silver salts in weakly acidic to neutral aqueous solution, which with the addition of ammonia go back into solution at pH> 9, one of the at least two compounds imidazole or histidine and little At least one other compound is not imidazole or histidine.
Unter monocyclischen Verbindungen werden solche verstanden, die im gesamten Molekül keine anellierten Ringe besitzen. Unter Korngröße wird stets der Durchmesser der volumengleichen Kugel verstanden.Monocyclic compounds are understood to mean those which have no fused rings in the entire molecule. Grain size is always understood to mean the diameter of the same-volume ball.
Der Iodidgehalt der Emulsion A beträgt vorzugsweise 10 bis 90 Mol-%.The iodide content of emulsion A is preferably 10 to 90 mol%.
Geeignet sind z.B. Imidazole, Oxazole, Thiazole, Triazole, Thiadiazole, Oxadiazole, Pyridine, Tetrazole und Pyrimidine, die durch Alkyl, vorzugsweise mit bis zu 4 C-Atomen wie Methyl, Ethyl, Isopropyl; Alkenyl wie Allyl; Aryl wie Phenyl, Halogen wie Chlor oder Brom, Carbonsäuregruppen oder Derivate wie Carbalkoxy oder Carbonamido: Sulfonsäuregruppen, Sulfonamid, Sulfone, Thioether wie Methylthio oder Carboxyalkylthio; substituierte oder unsubstituierte Aminogruppen substituiert sein können.Suitable are e.g. Imidazoles, oxazoles, thiazoles, triazoles, thiadiazoles, oxadiazoles, pyridines, tetrazoles and pyrimidines which are substituted by alkyl, preferably having up to 4 carbon atoms such as methyl, ethyl, isopropyl; Alkenyl such as allyl; Aryl such as phenyl, halogen such as chlorine or bromine, carboxylic acid groups or derivatives such as carbalkoxy or carbonamido: sulfonic acid groups, sulfonamide, sulfones, thioethers such as methylthio or carboxyalkylthio; substituted or unsubstituted amino groups can be substituted.
Die Umlösung erfolgt vorzusgweise bei einem EAg-Wert von -20 bis -120 mV, insbesondere -40 bis -100 mV, bei einem pH-Wert von 4 bis 10, insbesondere 6 bis 8 und einer Temperatur von 40 bis 90°C, insbesondere 50 bis 75°C. Die Umlösung ist unter diesen Bedingungen üblicherweise nach 20 Minuten abgeschlossen (EAg ist das Potential zwischen einer Silberelektrode und einer gesättigten Kalomelelektrode).The solution is preferably carried out at an E Ag value of -20 to -120 mV, in particular -40 to -100 mV, at a pH of 4 to 10, in particular 6 to 8 and a temperature of 40 to 90 ° C. especially 50 to 75 ° C. Under these conditions, the redissolution is usually complete after 20 minutes (E Ag is the potential between a silver electrode and a saturated calomel electrode).
Das Gelatine/Silberhalogenid-Gewichtsverhältnis, ausgedrückt als eingesetzte Silbernitratmenge, beträgt bei der Umlösung bevorzugt 0,05 bis 1,0, insbesondere 0,1 bis 0,5.The gelatin / silver halide weight ratio, expressed as the amount of silver nitrate used, is preferably 0.05 to 1.0, in particular 0.1 to 0.5, when the solution is redissolved.
Die Emulsionen A und B, ausgedrückt als eingesetzte Silbernitratmenge, werden vorzusgweise im Gewichtsverhältnis 1:1 bis 1:20 miteinander gemischt, vorzugsweise 1:2 bis 1:10. Die Emulsionen A und B sind im wesentlichen Silberbromidiodidemulsionen. Sie können auch geringe Anteile Silberchlorid enthalten. Die Korngröße der Emulsion A reicht insbesondere von 0,1 bis 1,5 µm, die Korngröße der Emulsion B insbesondere von 0,01 bis 0,2 µm.Emulsions A and B, expressed as the amount of silver nitrate used, are preferably mixed with one another in a weight ratio of 1: 1 to 1:20, preferably 1: 2 to 1:10. Emulsions A and B are essentially silver bromoiodide emulsions. They can also contain small amounts of silver chloride. The grain size of emulsion A ranges in particular from 0.1 to 1.5 μm, the grain size of emulsion B in particular from 0.01 to 0.2 μm.
Sofern der Iodidgehalt der Emulsion A zwischen 40 und 90 Mol-% liegt, besteht die Emulsion überwiegend aus Körnern mit etwa 40 Mol-% AgI und reinen AgI-Körnern.If the iodide content of emulsion A is between 40 and 90 mol%, the emulsion consists predominantly of grains with about 40 mol% AgI and pure AgI grains.
Der Iodidgehalt der Emulsion A kann durch entsprechende Wahl der für die Fällung vorgesehenen Mischung löslicher Halogenide eingestellt werden. Es kann aber auch zunächst eine Emulsion mit geringerem Iodidanteil gefällt und anschließend unter Zusatz von KI zum gewünschten höheren Iodidgehalt konvertiert werden.The iodide content of emulsion A can be adjusted by appropriate selection of the mixture of soluble halides intended for the precipitation. An emulsion with a lower iodide content can also be precipitated first and then converted to the desired higher iodide content with the addition of KI.
Geeignete SH-gruppenfreie N-Heterocyclen sind nachfolgend angegeben:Suitable SH group-free N-heterocycles are given below:
Nicht geeignete Verbindungen sind z.B.
- a)
- b)
- a)
- b)
In einer bevorzugten Ausführungsform wird zunächst als Vorfällung die Emulsion A hergestellt, die gegebenenfalls konzentriert und entsalzt werden kann. Die weitere Substanzzufuhr, die erfindungsgemäß durch Zugabe der Emulsion B erfolgt, kann dabei so eingerichtet werden, daß mehr als 50 Mol-%, vorzugsweise mehr als 80 Mol-% des eingesetzten Silberhalogenids in der Form der Emulsion B zugesetzt wird. Auch die Emulsion B kann konzentriert und entsalzt werden.In a preferred embodiment, emulsion A is first prepared as a precipitate, which can optionally be concentrated and desalted. The further supply of substance, which is carried out according to the invention by adding emulsion B, can be set up in such a way that more than 50 mol%, preferably more than 80 mol%, of the silver halide used is added in the form of emulsion B. Emulsion B can also be concentrated and desalted.
Die Zugabe der Emulsion B sowie der erfindungsgemäß zu verwendenden Silberhalogenidlösungsmittel kann grundsätzlich gleichzeitig oder zu unterschiedlichen Zeiten, auf einmal oder in mehreren Teilen oder kontinuierlich erfolgen. Die Konzentrationen der benutzten Silberhalogenidemulsionen B und A kann in weiten Grenzen variiert werden. Die Menge der erfindungsgemäß zu verwendenden Silberhalogenidlösungsmittel läßt sich im allgemeinen in einer Versuchsreihe leicht ermitteln und liegt im Fall von Imidazol und Histidin vorzugsweise zwischen 10⁻⁵ und 2,0 Mol pro Mol eingesetztem Silberhalogenid, insbesondere zwischen 10⁻³ und 0,3 Mol pro Mol eingesetztem Silberhalogenid und im Fall der von Imidazol und Histidin verschiedenen Verbindungen vorzugsweise 10⁻⁶ und 0,5 Mol pro Mol eingesetzten Silberhalogenid.In principle, emulsion B and the silver halide solvents to be used according to the invention can be added simultaneously or at different times, all at once or in several parts or continuously. The concentrations of the silver halide emulsions B and A used can be varied within wide limits. The amount of the silver halide solvent to be used according to the invention can generally be easily determined in a series of tests and, in the case of imidazole and histidine, is preferably between 10⁻⁵ and 2.0 mol per mol of silver halide used, in particular between 10⁻³ and 0.3 mol per Mol used silver halide and in the case of compounds other than imidazole and histidine preferably 10⁻⁶ and 0.5 mol per mol of silver halide used.
Erfindungsgemäß können grundsätzlich Emulsionen für die verschiedensten photographischen Materialien hergestellt werden, z.B. negativarbeitende Emulsionen mit hoher Oberflächenempfindlichkeit, negativarbeitende Emulsionen mit hoher Innenempfindlichkeit, direkt positiv arbeitende Emulsionen, die oberflächlich verschleiert oder oberflächlich unverschleiert sein können, Emulsionen mit geschichtetem Kornaufbau, print-out Emulsionen, Umkehremulsionen, Emulsionen für Schwarzweiß und für Colormaterialien sowie mit definierter Kornverteilung und Halogenidtopographie, insbesondere mit definiertem Halogenid-, insbesondere Iodidgradienten.According to the invention, emulsions can in principle be prepared for a wide variety of photographic materials, e.g. Negative working emulsions with high surface sensitivity, negative working emulsions with high internal sensitivity, directly positive working emulsions that can be superficially veiled or superficially unveiled, emulsions with layered grain structure, print-out emulsions, reverse emulsions, emulsions for black and white and for color materials as well as with defined grain distribution and halide topography , in particular with a defined halide, in particular iodide gradient.
Die erfindungsgemäß hergestellten Silberhalogenidemulsionen sowie die Ausgangsemulsionen A und B können zur Entfernung der wasserlöslichen Salze entweder in bekannter Weise erstarrt, genudelt und gewässert werden oder auch mit einem Koagulierungsmittel koaguliert und anschließend gewaschen werden, wie es beispielsweise aus der deutschen Offenlegungsschrift 2 614 862 bekannt ist. Die Entsalzung erfolgt besonders vorteilhaft durch Ultrafiltration.To remove the water-soluble salts, the silver halide emulsions prepared according to the invention and the starting emulsions A and B can either be solidified, pasta-coated and soaked in a known manner or can also be coagulated with a coagulating agent and then washed, as is known, for example, from German Offenlegungsschrift 2,614,862. Desalination is particularly advantageously carried out by ultrafiltration.
Die erfindungsgemäß hergestellte Emulsion sowie auch gegebenenfalls die Ausgangsemulsionen, insbesondere die Emulsion A können chemisch sensibilisiert werden, z.B. durch Zusatz schwefelhaltiger Verbindungen bei der chemischen Reifung, beispielsweise Allylisothiocyanat, Allylthioharnstoff, Natriumthiosulfat. Als chemische Sensibilisatoren können ferner auch Reduktionsmittel, z.B. die in den belgischen Patentschriften 493 464 oder 568 687 beschriebenen Zinnverbindungen, ferner Polyamine wie Diethylentriamin oder Aminomethylsulfinsäure-Derivate, z.B. gemäß der belgischen Patentschrift 547 323, verwendet werden. Weiterhin geeignet sind Selenverbindungen.The emulsion produced according to the invention and optionally also the starting emulsions, in particular emulsion A, can be chemically sensitized, for example by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate. Reducing agents, For example, the tin compounds described in the Belgian patent specifications 493 464 or 568 687, and also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, for example in accordance with the Belgian patent specification 547 323, can be used. Selenium compounds are also suitable.
Geeignet als chemische Sensibilisatoren sind auch Edelmetalle bzw. Edelmetallverbindungen wie Gold, Platin, Palladium, Iridium, Ruthenium oder Rhodium. Diese Methode der chemischen Sensibilisierung ist in dem Artikel von R. Koslowsky, Z. Wis. Phot. 46, 65-72 (1951), beschrieben.Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z. Wis. Phot. 46, 65-72 (1951).
Sowohl der Emulsion A als auch der Emulsion B können während der Fällung Fremdionen zur Dotierung zugefügt werden. Dieser Zusatz ist auch vor, während und nach der Umlösung möglich. Geeignete Verbindungen sind beispielsweise Ir- u. Rh-Verbindungen.Both emulsion A and emulsion B can be added with foreign ions for doping during the precipitation. This addition is also possible before, during and after the redeployment. Suitable compounds are for example Ir- and. Rh compounds.
Sowohl die Emulsion A als auch die Emulsion B kann während der Fällung einer Reduktionsreifung unterzogen werden. Eine solche Reduktionssensibilisierung ist auch vor, während und nach der Umlösung möglich.Both emulsion A and emulsion B can be subjected to reduction ripening during the precipitation. Such reduction sensitization is also possible before, during and after the redissolution.
Diese Maßnahme und geeignete Verbindungen sind z.B. in EP 348 934, 368 304, 369 424, 371 338, 369 491, 378 841, 404 142, 435 270, 435 355 und US 4 917 997 beschrieben.This measure and suitable connections are described, for example, in EP 348 934, 368 304, 369 424, 371 338, 369 491, 378 841, 404 142, 435 270, 435 355 and US 4 917 997.
Weiterhin kann es vorteilhaft sein, entweder bei nachfolgenden Fällungsschritten oder vor der chemischen Sensibilisierung einen Oxidationsschritt durchzuführen. Geeignete Verbindungen hierzu sind beispielsweise Thiosulfonsäurederivate, H₂O₂ und Quecksilber(II)-verbindungen.Furthermore, it can be advantageous to carry out an oxidation step either in subsequent precipitation steps or before chemical sensitization. Suitable compounds for this are, for example, thiosulfonic acid derivatives, H₂O₂ and mercury (II) compounds.
Es ist ferner möglich, die Emulsionen mit Polyalkylenoxid-Derivaten zu sensibilisieren, z.B. mit Polyethylenoxid eines Molekulargewichtes zwischen 1.000 und 20.000, ferner mit Kondensationsprodukten von Alkylenoxiden und aliphatischen Alkoholen, Glykolen, cyclischen Dehydratisierungsprodukten von Hexitolen, mit alkylsubstituierten Phenolen, aliphatischen Carbonsäuren, aliphatischen Aminen, aliphatischen Diaminen und Amiden. Die Kondensationsprodukte haben ein Molekulargewicht von mindestens 700, vorzugsweise von mehr als 1.000. Zur Erzielung besonderer Effekte kann man diese Sensibilisatoren selbstverständlich kombiniert verwenden, wie in der belgischen Patentschrift 536 278 und in der britischen Patentschrift
727 982 beschrieben.It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, for example with polyethylene oxide with a molecular weight between 1,000 and 20,000, furthermore with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a molecular weight of at least 700, preferably more than 1,000. To achieve special effects, these sensitizers can of course be used in combination, as in the Belgian patent 536 278 and in the British patent
727,982.
Die Emulsionen können auch optisch sensibilisiert sein, z.B. mit den üblichen Polymethinfarbstoffen wie Neutrocyaninen, basischen oder sauren Carbocyaninen, Rhodacyaninen, Hemicyaninen, Styrylfarbstoffen, Oxonolen und ähnlichen. Derartige Sensibilisatoren sind in F.M. Hamer: "The Cyanine Dyes and related Compounds" 1964, Interscience Publishers, John Wiley and Sons, beschrieben.The emulsions can also be optically sensitized, for example with the usual polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like. Such sensitizers are described in FM Hamer: "The Cyanine Dyes and Related Compounds" 1964, Interscience Publishers, John Wiley and Sons.
Die Emulsionen können die üblichen Stabilisatoren enthalten, z.B. homöopolare oder salzartige Verbindungen des Quecksilbers mit aromatischen oder heterocyclischen Ringen wie Mercaptotriazole, einfache Quecksilbersalze, Sulfoniumquecksilberdoppelsalze und andere Quecksilberverbindungen. Als Stabilisatoren sind ferner geeignet Azaindene, vorzugsweise Tetra- oder Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind in Birr: Z. Wiss. Phot. 47 (1952), 2-58, beschrieben. Weitere geeignete Stabilisatoren sind u.a. heterocyclische Mercaptoverbindungen, z.B. Phenylmercaptoverbindungen, quaternäre Benzthiazol-Derivate und Benzotriazol.The emulsions can contain the usual stabilizers, e.g. homeopolar or salt-like compounds of mercury with aromatic or heterocyclic rings such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Also suitable as stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are in Birr: Z. Wiss. Phot. 47 (1952), 2-58. Other suitable stabilizers include heterocyclic mercapto compounds, e.g. Phenylmercapto compounds, quaternary benzothiazole derivatives and benzotriazole.
Erfindungsgemäß ist es von Vorteil, als Bindemittel oder Schutzkolloid für die erfindungsgemäße photographische Emulsion Gelatine zu verwenden, es können aber auch andere Kolloide verwendet werden. So können beispielsweise verschiedene synthetische hydrophile Materialien mit einem hohen Molekulargewicht, wie Pfropfpolymere von Gelatine und anderen Materialien mit einem hohem Molekulargewicht; Proteine, wie Albumin, Casein und dgl.; Cellulosederivate, wie Hydroxyethylcellulose, Carboxymethylcellulose, Cellulosesulfat und dgl.; Saccharidderivate, wie Natriumalginat, Stärkederivate und dgl.; Homopolymere oder Copolymere, wie Polyvinylalkohol, teilweise acetalisierter Polyvinylalkohol, Poly-N-vinylpyrrolidon, Polyacrylsäure, Polymethacrylsäure, Polyacrylamid, Polyvinylimidazol und Polyvinylpyrazol eingesetzt werden.According to the invention, it is advantageous to use gelatin as a binder or protective colloid for the photographic emulsion according to the invention, but other colloids can also be used. For example, various high molecular weight synthetic hydrophilic materials such as graft polymers of gelatin and other high molecular weight materials; Proteins such as albumin, casein and the like; Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate and the like; Saccharide derivatives such as sodium alginate, starch derivatives and the like; Homopolymers or copolymers, such as polyvinyl alcohol, partially acetalized polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.
Geeignete Gelatine-Propfpolmere, die erfindungsgemäß verwendet werden können, sind solche, die erhalten werden durch Aufpfropfen von Homopolymeren oder Copolymeren von Vinylmonomeren, wie Acrylsäure, Methacrylsäure, Derivaten davon, z.B. den Estern, Amiden, Acrylnitril, Styrol auf Gelatine. Bevorzugt sind insbesondere Pfropfpolymere von Gelatine mit Polymeren der Acrylsäure, Methacrylsäure, des Acrylamids, Methacrylamids und der Hydroxyalkylmethacrylate.Suitable gelatin graft polymers that can be used in the present invention are those obtained by grafting homopolymers or copolymers of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof, e.g. the esters, amides, acrylonitrile, styrene on gelatin. Graft polymers of gelatin with polymers of acrylic acid, methacrylic acid, acrylamide, methacrylamide and hydroxyalkyl methacrylates are particularly preferred.
Die Emulsionen können in üblicher Weise gehärtet sein, beispielsweise mit Formaldehyd oder halogensubstituierten Aldehyden, die eine Carboxylgruppe enthalten wie Mucobromsäure, Diketonen, Methansulfonsäureester und Dialdehyden.The emulsions can be hardened in a customary manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
Weiterhin können die photographischen Schichten mit Härtern des Epoxidtyps, des heterocyclischen Ethylenimins oder des Acryloyltyps gehärtet werden. Beispiele derartiger Härter sind z.B. in der deutschen Offenlegungsschrift 2 263 602 oder in der britischen Patentschrift 1 266 655 beschrieben. Weiterhin ist es auch möglich, die Schichten gemäß dem Verfahren der deutschen Offenlegungsschrift 2 218 009 zu härten, um farbphotographische Materialien zu erzielen, die für eine Hochtemperaturverarbeitung geeignet sind.Furthermore, the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type. Examples of such hardeners are e.g. in German laid-open specification 2 263 602 or in British patent 1 266 655. Furthermore, it is also possible to harden the layers in accordance with the process of German Offenlegungsschrift 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing.
Es ist ferner möglich, die photographischen Schichten bzw. die farbphotographischen Mehrschichtenmaterialien mit Härtern der Diazin-, Triazin- oder 1,2-Dihydrochinolin-Reihe zu härten, wie in den britischen Patentschriften 1 193 290, 1 251 091, 1 306 544, 1 266 655, der französischen Patentschrift 71 02 716 oder der deutschen Offenlegungsschrift 2 332 317 beschrieben ist. Beispiele derartiger Härter sind alkyl- oder arylsulfonylgruppenhaltige Diazin-Derivate, Derivate von hydrierten Diazinen oder Triazinen, wie z.B. 1,3,5,-Hexahydrotriazin, fluorsubstituierte Diazin-Derivate, z.B. Fluorpyrimidin, Ester von 2-substituierten, 1,2-Dihydrochinolin- oder 1,2-Dihydroisochinolin-N-carbonsäure, Brauchbar sind weiterhin Vinylsulfonsäurehärter, Carbodiimid- oder Carbamoylhärter, wie z.B. in den deutschen Offenlegungsschriften 2 263 602, 2 225 230 und 1 808 685, der französischen Patentschrift 1 491 807, der deutschen Patentschrift 872 153 und der DD-A-7218 beschrieben. Weitere brauchbare Härzer sind bespielsweise in der britischen Patentschrift 1 268 550 beschrieben.It is also possible to coat the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series to harden, as described in British Patents 1 193 290, 1 251 091, 1 306 544, 1 266 655, French Patent 71 02 716 or German Laid-Open Specification 2 332 317. Examples of such hardeners are diazine derivatives containing alkyl or arylsulfonyl groups, derivatives of hydrogenated diazines or triazines, such as, for example, 1,3,5, -hexahydrotriazine, fluorine-substituted diazine derivatives, for example fluoropyrimidine, esters of 2-substituted, 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acid, vinyl sulfonic acid hardeners, carbodiimide or carbamoyl hardeners can also be used, as described, for example, in German Offenlegungsschriften 2,263,602, 2,225,230 and 1,808,685, French Patent 1,491,807 and German Patent 872 153 and DD-A-7218. Other useful resins are described, for example, in British Patent 1,268,550.
Die vorliegende Erfindung kann sowohl für die Herstellung schwarz-weißer als auch farbiger photographischer Bilder angewendet werden. Farbige photographische Bilder können z.B. nach dem bekannten Prinzip der chromogenen Entwicklung in Anwesenheit von Farbkupplern, die mit dem Oxidationsprodukt von farbgebenenden p-Phenylendiamin-Entwicklern unter Bildung von Farbstoffen reagieren, hergestellt werden.The present invention can be applied to both black and white and color photographic images. Colored photographic images can e.g. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of color-giving p-phenylenediamine developers to form dyes.
Die Farbkuppler können beispielsweise dem Farbentwickler nach dem Prinzip des sogenannten Einentwicklungsverfahrens zugesetzt werden. In einer bevorzugten Ausführungsform enthält das photographische Material selbst die üblichen Farbkuppler, die in der Regel den Silberhalogenidschichten einverleibt sind. So kann die rotempfindliche Schicht beispielswiese einen nicht-diffundierenden Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes enthalten, in der Regel einen Kuppler vom Phenol- oder α-Naphtholtyp. Die grünempfindliche Schicht kann beispielsweise mindestens einen nicht-diffundierenden Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes enthalten, wobei üblicherweise Farbkuppler vom Typ des 5-Pyrazolons, des Indazolons oder der Pyrazoloazole Verwendung finden. Die blauempfindliche Schicht kann beispielswiese einen nicht-diffundierenden Farbkuppler zur Erzeugung des gelben Teilfarbenbildes, in der Regel einen Farbkuppler mit einer offenkettigen Ketomethylengruppierung enthalten. Farbkuppler dieser Art sind in großer Zahl bekannt und in einer Vielzahl von Patentschriften beschrieben. Beispielhaft sei hier auf die Veröffentlichung "Farbkuppler" von W. Pelz in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/München", Band III (1961) und K. Venkataraman in "The Chemistry of Synthetic Cyes", Vol. 4, 341-387, Academic Press, 1971, hingewiesen.The color couplers can, for example, be added to the color developer according to the principle of the so-called development process. In a preferred embodiment the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers. For example, the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or α-naphthol type. The green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone, indazolone or pyrazoloazole type usually being used. For example, the blue-sensitive layer can contain a non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping. Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publication "Color coupler" by W. Pelz in "Messages from the research laboratories of Agfa, Leverkusen / Munich", Volume III (1961) and K. Venkataraman in "The Chemistry of Synthetic Cyes", Vol. 4, 341 -387, Academic Press, 1971.
Als weitere nicht-diffundierende Farbkuppler können 2-Äquivalentkuppler verwendet werden; diese enthalten in der Kupplungsstelle einen abspaltbaren Substituenten, so daß sie zur Farbbildung nur zwei Äquivalente Silberhalogenid benötigen im Unterschied zu den üblichen 4-Äquivalentkupplern. Zu den einsetzbaren 2-Äquivalent-Kupplern gehören beispielsweise die bekannten DIR-Kuppler, bei denen der abspaltbare Rest nach Reaktion mit Farbentwickleroxidationsprodukten als diffundierender Entwicklungsinhibitor in Freiheit gesetzt wird. Weiterhin können zur Verbesserung der Eigenschaften des photographischen Materials die sogenannten Weißkuppler eingesetzt werden, die ein farbloses Kupplungsprodukt liefern.2-equivalent couplers can be used as further non-diffusing color couplers; these contain a removable substituent in the coupling point, so that they only require two equivalents of silver halide to form the color, in contrast to the usual 4-equivalent couplers. The 2-equivalent couplers that can be used include, for example, the known DIR couplers, in which the cleavable residue is released as a diffusing development inhibitor after reaction with color developer oxidation products. Furthermore, the so-called white couplers can be used to improve the properties of the photographic material, which provide a colorless coupling product.
Die nicht-diffundierenden Farbkuppler und farbgebenden Verbindungen werden den lichtempfindlichen Silberhalogenidemulsionen oder sonstigen Gießlösungen nach üblichen bekannten Methoden zugesetzt. Wenn es sich um wasser- oder alkalilösliche Verbindungen handelt, können sie den Emulsionen in Form von wäßrigen Lösungen, gegebenenfalls unter Zusatz von mit Wasser mischbaren organischen Lösungsmitteln wie Ethanol, Aceton oder Dimethylformamid, zugesetzt werden. Soweit es sich bei den nicht-diffundierenden Farbkupplern und farbgebende Verbindungen um wasser- bzw. alkaliunlösliche Verbindungen handelt, können sie in bekannter Weise emulgiert werden, z.B. indem eine Lösung dieser Verbindungen in einem niedrigsiedenden organischen Lösungsmittel direkt mit der Silberhalogenidemulsion oder zunächst mit einer wäßrigen Gelatinelösung vermischt wird, worauf das organische Lösungsmittel in üblicher Weise entfernt wird. Ein so erhaltenes Gelatineemulgat der jeweiligen Verbindung wird anschließend mit der Silberhalogenidemulsion vermischt. Gegebenenfalls verwendet man zur Einemulgierung derartiger hydrophober Verbindungen zusätzlich noch sogenannte Kupplerlösungsmittel oder Ölformer; das sind in der Regel höhersiedende organische Verbindungen, die die in den Silberhalogenidemulsionen zu emulgierenden, nicht-diffundierenden Farbkuppler und Entwicklungsinhibitor abspaltenden Verbindungen in Form öliger Tröpfchen einschließen. Verwiesen sei in diesem Zusammenhang beispielsweise auf die US-Patentschriften 2 322 027, 2 533 514, 3 689 271, 3 764 336 und 3 765 897.The non-diffusing color couplers and coloring compounds are added to the light-sensitive silver halide emulsions or other casting solutions by customary known methods. If the compounds are soluble in water or alkali, they can be added to the emulsions in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. If the non-diffusing color couplers and coloring compounds are water- or alkali-insoluble compounds, they can be emulsified in a known manner, for example by dissolving these compounds in a low-boiling organic solvent directly with the silver halide emulsion or initially with an aqueous gelatin solution is mixed, whereupon the organic solvent is removed in a conventional manner. A gelatin emulsate of the respective compound thus obtained is then mixed with the silver halide emulsion. If necessary, so-called coupler solvents or oil formers are additionally used to emulsify such hydrophobic compounds; these are generally higher-boiling organic compounds which include the compounds in the form of oily droplets which split off and emulsify in the silver halide emulsions and do not diffuse color couplers and development inhibitors. In this connection, reference is made, for example, to US Pat. Nos. 2,322,027, 2,533,514, 3,689,271, 3,764,336 and 3,765,897.
Die erfindungsgemäß hergestellten Emulsionen können auf die üblichen Schichtträger aufgetragen werden, z.B. Träger aus Celluloseestern wie Celluloseacetat oder Celluloseacetobutyrat, ferner Polyester, insbesondere Polyethylenterephthalat oder Polycarbonate, insbesondere auf Basis von Bisphenylolpropan. Geeignet sind ferner Papierträger, die gegebenenfalls wasserundurchlässige Polyolefinschichten, z.B. aus Polyethylen oder Polypropylen, enthalten können, ferner Träger aus Glas oder Metall.The emulsions prepared according to the invention can be applied to the customary layer supports, for example supports made from cellulose esters such as cellulose acetate or cellulose acetobutyrate, furthermore polyesters, in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane. Also suitable are paper supports, which can optionally contain water-impermeable polyolefin layers, for example made of polyethylene or polypropylene, and supports made of glass or metal.
Die in den nachstehenden Beispielen eingesetzte Emulsion B ist eine Silberbromidemulsion, die eine mittlere Korngröße von 0,05 µm aufweist und 1,25 mol Silberhalogenid pro kg sowie 18 g Gelatine pro kg enthält.The emulsion B used in the examples below is a silver bromide emulsion which has an average grain size of 0.05 μm and contains 1.25 mol of silver halide per kg and 18 g of gelatin per kg.
Die AgBrI-Emulsion A1 wird mit Hilfe eines Doppelstrahlverfahrens hergestellt und enthält 1 mol Silberhalogenid und 32 g Gelatine pro kg. Die mittlere Korngröße liegt bei 0,4 µm, der Iodidgehalt bei 25 mol-%.The AgBrI emulsion A1 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg. The average grain size is 0.4 µm, the iodide content is 25 mol%.
Jeweils 3000 g der Emulsion B werden mit 1500 g der Emulsion A1 vermischt und in Gegenwart der in Tabelle 1 angegebenen Substanzen bei 65°C, pH 7,5 und einen EAg-Wert von -60 mV digeriert, bis die Umlösung abgeschlossen ist (etwa nach 20 Minuten). Anschließend wird koaguliert, gewaschen und schließlich unter Zusatz von Wasser- und Gelatine redispergiert. Danach wird eine optimale Reifung mit Gold- und Schwefelverbindungen durchgeführt. Die mittlere Korngröße beträgt 0,7 µm, der Iodidgehalt 7 mol-%.3000 g of emulsion B are mixed with 1500 g of emulsion A1 and digested in the presence of the substances listed in Table 1 at 65 ° C, pH 7.5 and an E Ag value of -60 mV until the redissolution is complete ( after about 20 minutes). It is then coagulated, washed and finally redispersed with the addition of water and gelatin. Then an optimal ripening with gold and sulfur compounds is carried out. The average grain size is 0.7 µm, the iodide content 7 mol%.
Die AgBrI-Emulsion A2 wird mit Hilfe eines Doppelstrahlverfahrens hergestellt und enthält 1 mol Silberhalogenid und 32 g Gelatine pro kg. Die mittlere Korngröße liegt bei 0,7 µm, der Iodidgehalt bei 40 mol-%.The AgBrI emulsion A2 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg. The average grain size is 0.7 µm, the iodide content is 40 mol%.
Jeweils 9000 g der Emulsion B werden mit 1500 g der Emulsion A2 vermischt und in Gegenwart der in Tabelle 2 angegebenen Substanzen bei 60°C, pH 7,5 und einem EAg-Wert von -60 mV digeriert, bis die Umlösung abgeschlossen ist (nach etwa 20 Minuten). Die weitere Bearbeitung entspricht Beispiel 1. Die mittlere Korngröße beträgt 1,1 µm, der Iodidgehalt 4,7 mol-%.In each case 9000 g of emulsion B are mixed with 1500 g of emulsion A2 and digested in the presence of the substances listed in Table 2 at 60 ° C., pH 7.5 and an E Ag value of -60 mV until the redissolution is complete ( after about 20 minutes). The further processing corresponds to Example 1. The average grain size is 1.1 µm, the iodide content 4.7 mol%.
Die AgBrI-Emulsion A3 wird mit Hilfe eines Doppelstrahlverfahrens hergestellt und enthält 1 mol Silberhalogenid und 32 g Gelatine pro kg. Die mittlere Korngröße beträgt 0,5 µm, der Jodidgehalt 70 mol-%, wobei zunächst mit einem Iodidgehalt von 30 mol-% gefällt und anschießend durch Zugabe von KI bis zum angegebenen Iodidgehalt konvertiert wird.The AgBrI emulsion A3 is produced using a double jet process and contains 1 mol of silver halide and 32 g of gelatin per kg. The average grain size is 0.5 µm, the iodide content is 70 mol%, with an iodide content of 30 mol% first being precipitated and then converted to the stated iodide content by adding KI.
Jeweils 5800 g der Emulsion B werden mit 1500 g der Emulsion A3 vermischt und in Gegenwart der in Tabelle 3 angegebenen Substanzen bei 70°C, pH 7,5 und EAg-60 mV digeriert, bis die Umlösung nach etwa 20 Minuten abgeschlossen ist, Die weitere Bearbeitung entspricht Beispiel 1.5800 g of emulsion B are mixed with 1500 g of emulsion A3 and digested in the presence of the substances listed in Table 3 at 70 ° C., pH 7.5 and E Ag -60 mV until the redissolution is complete after about 20 minutes, The further processing corresponds to example 1.
Die mittlere Korngröße beträgt 1,1 µm, der Iodidgehalt 12 mol-%.
Sowohl die nach 1.1 als auch nach 1.3 hergestellten Emulsionen werden neben einer optimalen Goldschwefelreifung auch einer optimalen Reifung unterzogen, bei der neben Gold- und Schwefelverbindungen auch Selenverbindungen anwesend sind. Geeignete Selenverbindungen hierfür sind beispielsweise in EP 428 041, 458 278, 476 345 beschrieben.
Beim erfindungsgemäßen Beispiel 1.3 findet eine wesentlich größere Steigung der Empfindlichkeit durch den Reifzusatz Selen statt als beim nicht erfindungsgemäßen Beispiel 1.1.In example 1.3 according to the invention there is a significantly greater increase in sensitivity due to the addition of selenium than in example 1.1 not according to the invention.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4233714 | 1992-10-07 | ||
| DE4233714A DE4233714A1 (en) | 1992-10-07 | 1992-10-07 | Process for the preparation of silver halide emulsions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0595031A1 true EP0595031A1 (en) | 1994-05-04 |
| EP0595031B1 EP0595031B1 (en) | 1997-12-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93115452A Expired - Lifetime EP0595031B1 (en) | 1992-10-07 | 1993-09-24 | Process for the production of silver halide emulsions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5427904A (en) |
| EP (1) | EP0595031B1 (en) |
| JP (1) | JPH06202257A (en) |
| DE (2) | DE4233714A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19933258A1 (en) | 1999-07-15 | 2001-01-18 | Agfa Gevaert Ag | Preparation of silver halide emulsions |
| US6451520B1 (en) * | 2000-07-29 | 2002-09-17 | Agfa-Gevaert | Color photographic silver halide material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002759A2 (en) * | 1977-12-29 | 1979-07-11 | Agfa-Gevaert AG | Photosensitive photographic material, its fabrication process and use |
| EP0006543A1 (en) * | 1978-06-27 | 1980-01-09 | Agfa-Gevaert AG | Light-sensitive photographic material, process for making it and its use for realising photographic images |
| EP0042060A2 (en) * | 1980-05-23 | 1981-12-23 | Agfa-Gevaert AG | Process for preparing silver halide emulsions, photographic materials, and process for the production of photographic images |
| EP0421740A1 (en) * | 1989-10-03 | 1991-04-10 | Konica Corporation | Silver halide photographic light-sensitive material with high-sensitivity and improved fog and granularity and method of its production |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE414540A (en) * | 1935-04-05 | |||
| US3206313A (en) * | 1961-05-15 | 1965-09-14 | Eastman Kodak Co | Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity |
| US3317322A (en) * | 1965-08-27 | 1967-05-02 | Eastman Kodak Co | Photographic emulsions having high internal sensitivity |
| US5273871A (en) * | 1990-10-03 | 1993-12-28 | Konica Corporation | Silver halide photographic emulsion and silver halide color photographic light-sensitive material incorporating it |
-
1992
- 1992-10-07 DE DE4233714A patent/DE4233714A1/en not_active Withdrawn
-
1993
- 1993-09-24 US US08/125,737 patent/US5427904A/en not_active Expired - Fee Related
- 1993-09-24 EP EP93115452A patent/EP0595031B1/en not_active Expired - Lifetime
- 1993-09-24 DE DE59307852T patent/DE59307852D1/en not_active Expired - Fee Related
- 1993-10-06 JP JP5272903A patent/JPH06202257A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0002759A2 (en) * | 1977-12-29 | 1979-07-11 | Agfa-Gevaert AG | Photosensitive photographic material, its fabrication process and use |
| EP0006543A1 (en) * | 1978-06-27 | 1980-01-09 | Agfa-Gevaert AG | Light-sensitive photographic material, process for making it and its use for realising photographic images |
| EP0042060A2 (en) * | 1980-05-23 | 1981-12-23 | Agfa-Gevaert AG | Process for preparing silver halide emulsions, photographic materials, and process for the production of photographic images |
| EP0421740A1 (en) * | 1989-10-03 | 1991-04-10 | Konica Corporation | Silver halide photographic light-sensitive material with high-sensitivity and improved fog and granularity and method of its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06202257A (en) | 1994-07-22 |
| EP0595031B1 (en) | 1997-12-17 |
| US5427904A (en) | 1995-06-27 |
| DE59307852D1 (en) | 1998-01-29 |
| DE4233714A1 (en) | 1994-04-14 |
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