USH1294H - Silver halide photographic emulsion - Google Patents
Silver halide photographic emulsion Download PDFInfo
- Publication number
- USH1294H USH1294H US07/989,508 US98950892A USH1294H US H1294 H USH1294 H US H1294H US 98950892 A US98950892 A US 98950892A US H1294 H USH1294 H US H1294H
- Authority
- US
- United States
- Prior art keywords
- emulsion
- silver
- silver halide
- grains
- mol
- 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.)
- Abandoned
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 148
- -1 Silver halide Chemical class 0.000 title claims abstract description 113
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 109
- 239000004332 silver Substances 0.000 title claims abstract description 109
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 46
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 7
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 19
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 52
- 238000000034 method Methods 0.000 description 41
- 239000007864 aqueous solution Substances 0.000 description 35
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 32
- 239000000975 dye Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 238000012545 processing Methods 0.000 description 29
- 238000002360 preparation method Methods 0.000 description 28
- 206010070834 Sensitisation Diseases 0.000 description 24
- 230000008313 sensitization Effects 0.000 description 24
- 238000007792 addition Methods 0.000 description 22
- 238000011161 development Methods 0.000 description 19
- 239000011780 sodium chloride Substances 0.000 description 16
- 108010010803 Gelatin Proteins 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 229920000159 gelatin Polymers 0.000 description 15
- 239000008273 gelatin Substances 0.000 description 15
- 235000019322 gelatine Nutrition 0.000 description 15
- 235000011852 gelatine desserts Nutrition 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 150000004820 halides Chemical class 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 12
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 12
- 230000001235 sensitizing effect Effects 0.000 description 12
- 230000003595 spectral effect Effects 0.000 description 12
- 150000002367 halogens Chemical class 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 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 6
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- PVGBHEUCHKGFQP-UHFFFAOYSA-M sodium;(1z)-n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylethanimidate Chemical compound [Na+].CC(=O)[N-]S(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-M 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229960005323 phenoxyethanol Drugs 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FYHIXFCITOCVKH-UHFFFAOYSA-N 1,3-dimethylimidazolidine-2-thione Chemical compound CN1CCN(C)C1=S FYHIXFCITOCVKH-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- MKPCNMXYTMQZBE-UHFFFAOYSA-N 7h-purin-6-amine;sulfuric acid;dihydrate Chemical compound O.O.OS(O)(=O)=O.NC1=NC=NC2=C1NC=N2.NC1=NC=NC2=C1NC=N2 MKPCNMXYTMQZBE-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000000843 anti-fungal effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000009428 plumbing Methods 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical class OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical class C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical class C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical class C1=C[se]C=N1 ODIRBFFBCSTPTO-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
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical compound SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 description 1
- WFXLRLQSHRNHCE-UHFFFAOYSA-N 2-(4-amino-n-ethylanilino)ethanol Chemical compound OCCN(CC)C1=CC=C(N)C=C1 WFXLRLQSHRNHCE-UHFFFAOYSA-N 0.000 description 1
- PHPYXVIHDRDPDI-UHFFFAOYSA-N 2-bromo-1h-benzimidazole Chemical class C1=CC=C2NC(Br)=NC2=C1 PHPYXVIHDRDPDI-UHFFFAOYSA-N 0.000 description 1
- AYPSHJCKSDNETA-UHFFFAOYSA-N 2-chloro-1h-benzimidazole Chemical class C1=CC=C2NC(Cl)=NC2=C1 AYPSHJCKSDNETA-UHFFFAOYSA-N 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical class C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical class O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- GCABLKFGYPIVFC-UHFFFAOYSA-N 3-(1-benzofuran-2-yl)-3-oxopropanenitrile Chemical compound C1=CC=C2OC(C(CC#N)=O)=CC2=C1 GCABLKFGYPIVFC-UHFFFAOYSA-N 0.000 description 1
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical class C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical class SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- XBTWVJKPQPQTDW-UHFFFAOYSA-N 4-n,4-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C(C)=C1 XBTWVJKPQPQTDW-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 1
- GIQKIFWTIQDQMM-UHFFFAOYSA-N 5h-1,3-oxazole-2-thione Chemical compound S=C1OCC=N1 GIQKIFWTIQDQMM-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- 208000002109 Argyria Diseases 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HGSWSFXRNHFOSI-UHFFFAOYSA-N [Fe].[Re] Chemical compound [Fe].[Re] HGSWSFXRNHFOSI-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- IGUSGFIPWBSXSQ-UHFFFAOYSA-L aluminum disodium sulfate Chemical compound [Na+].[Na+].[Al+3].[O-]S([O-])(=O)=O IGUSGFIPWBSXSQ-UHFFFAOYSA-L 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000002216 antistatic agent Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
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- 239000011668 ascorbic acid Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical class O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical class C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical class C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
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- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
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- 125000001165 hydrophobic group Chemical group 0.000 description 1
- AKCUHGBLDXXTOM-UHFFFAOYSA-N hydroxy-oxo-phenyl-sulfanylidene-$l^{6}-sulfane Chemical class SS(=O)(=O)C1=CC=CC=C1 AKCUHGBLDXXTOM-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- PTFYQSWHBLOXRZ-UHFFFAOYSA-N imidazo[4,5-e]indazole Chemical compound C1=CC2=NC=NC2=C2C=NN=C21 PTFYQSWHBLOXRZ-UHFFFAOYSA-N 0.000 description 1
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- OVWGAGKOPGNUGC-UHFFFAOYSA-N n,3-diphenylpropanamide Chemical class C=1C=CC=CC=1NC(=O)CCC1=CC=CC=C1 OVWGAGKOPGNUGC-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
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- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 1
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- 150000003142 primary aromatic amines Chemical class 0.000 description 1
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- LETVJWLLIMJADE-UHFFFAOYSA-N pyridazin-3-amine Chemical compound NC1=CC=CN=N1 LETVJWLLIMJADE-UHFFFAOYSA-N 0.000 description 1
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- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
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- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
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- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
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- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
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- 230000002087 whitening effect Effects 0.000 description 1
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Classifications
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- 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
- G03C2001/091—Gold
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- 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
- G03C2001/095—Disulfide or dichalcogenide compound
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- 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
- G03C2001/096—Sulphur sensitiser
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- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
- G03C2005/168—X-ray material or process
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- 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
- G03C2200/00—Details
- G03C2200/44—Details pH value
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- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/16—X-ray, infrared, or ultraviolet ray processes
Definitions
- the present invention relates to a silver halide photographic emulsion, and more particularly to a tabular silver chlorobromide emulsion having a high silver chloride content or a tabular silver chloride emulsion each having high sensitivity, and which emulsions are well adapted to rapid processing.
- a high-sensitivity negative type photographic light-sensitive material generally employs a silver iodobromide emulsion; however, in order to satisfy the above noted requirements, a silver chlorobromide emulsion or a silver chloride emulsion having a high solubility is useful.
- a silver chlorobromide emulsion or a silver chloride emulsion having a high solubility is useful.
- tabular silver halide grains provide favorable properties with respect to sensitivity, graininess, sharpness, color sensitizing efficiency, etc.
- Silver halide grains having a high silver chloride content i.e., as high as 50 mol %
- high silver chloride content grains generally have a cubic structure.
- tabular grains having a high silver chloride content various specific means must be employed.
- Methods for preparing tabular silver chlorobromide grains are known including, for example, (1) simultaneously introducing an aqueous solution of a chloride and an aqueous solution of a silver salt in a dispersion medium in the presence of ammonia by a double jet method as described in JP-B-64-8324 (the term "JP-B" as used herein means an "examined Japanese patent publication"), (2) reacting an aqueous silver salt solution and an aqueous solution of a chloride-containing halide in the presence of aminoazaindene and a thioether bond-containing peptizer as described in JP-B-64-8326, (3) simultaneously introducing an aqueous solution of a silver salt, an aqueous solution of a chloride, and an aqueous solution of a bromide to a dispersion medium while keeping the mol ratio of chloride ion to bromide ion in the range of from 1.6:1 to 258:1, and keeping the total concentration
- a silver chlorobromide emulsion tends to fog and has a low light sensitivity as compared to a silver iodobromide emulsion.
- the application of a silver chlorobromide emulsion is limited to color photo- graphic papers and light-sensitive materials for making printing plates using a relatively high intensity exposure.
- JP-A-58-95736, JP-A-58-108533, JP-A-60-222844, and JP-A-60-222845 disclose that for imparting high sensitivity to a high silver chloride content emulsion, it is effective to form a grain structure having a high silver bromide content layer in the silver halide grains.
- the present inventors have found that although high sensitivity is obtained using these techniques, desensitization tends to occur when pressure is applied to the emulsion. Also, tabular silver halide grains having a uniform grain size distribution are difficult to prepare, such that the emulsion is not practically employed. Furthermore, it has also been found that by using these methods, it is difficult to sufficiently improve the reciprocity law failure of the high silver chloride content emulsion.
- JP-A-51-139323, JP-A-59-171947 and British Patent 2,109,576A described that high sensitivity is obtained and the reciprocity law failure is improved by introducing to the silver halide emulsion a compound of a metal belonging to Group VIII of the Periodic Table.
- U.S. Pat. No. 4,269,927 describes that high sensitivity is obtained by incorporating cadmium, lead, zinc, or a mixture thereof in a surface latent image-type high silver chloride content emulsion having a silver chloride content of at least 80 mol %.
- European Patent 336426Al discloses a technique of obtaining high sensitivity by forming a high silver chloride content emulsion in the presence of six-coordinate complex of rhenium, ruthenium, or osmium having a cyan ligand.
- the sensitivity attained is far inferior to that of a silver iodobromide emulsion which is generally used.
- An object of the present invention is to provide a high silver chloride content emulsion which is well adapted to rapid processing and having a sensitivity as high as that of a silver iodobromide emulsion.
- the present inventors have discovered that the above object is attained by providing a photographic silver halide emulsion comprising silver chlorobromide grains containing at least 80 mol % silver chloride or silver chloride grains, wherein tabular grains having a thickness of less than 0.5 ⁇ m, a diameter of at least 0.5 ⁇ m, and an aspect ratio of at least 2/1 account for at least 50% of the total projected area of the silver halide grains, and said tabular grains are formed in the presence of a compound of metal belonging to Group VIII of the Periodic Table.
- the compound of a metal belonging to group VIII of the Period Table for use in the present invention includes compounds of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc., and typical examples of the compound are ferric chloride, potassium ferricyanide, cobalt chloride, cobalt nitrate, luteo salt, nickel chloride, nickel sulfate, ruthenium chloride, ruthenium hydroxide, rhodium chloride, ammonium hexachlorodinate, palladium chloride, palladium nitrate, potassium hexachloropalladate, osmium chloride, iridium chloride (IrCl 3 or IrCl 4 ), potassium iridate chloride, ammonium hexachloroiridate, ammonium hexachloroplatinate, and potassium hexachloroplatinate.
- ferric chloride potassium ferricyanide
- iron rhenium, ruthenium, and osmium are preferred and in particular, the six-coordination complex of iron, rhenium, ruthenium, or osmium having 4 cyan ligands as described in European Patent 336426Al exhibit an excellent effect for increasing the sensitivity.
- the addition amount of the compound of a metal belonging to Group VIII of the Periodic Table is from 1 ⁇ 10 -8 to 1 ⁇ 10 -2 mol, and preferably from 1 ⁇ 10 -6 to 1 ⁇ 10 -3 mol per mol of silver halide contained in the emulsion.
- the metal of Group VIII is contained in the tabular grains.
- the metal of Group VIII contained in the high silver chloride content grains may be uniformly distributed over the entire grain or may be localized in the central portion of the grain, or may largely exist in the outside portion of the grain as opposed to the central portion of the grain.
- the metal of Group VIII is largely present in the outside portions but not in the central portion of the grain.
- the tabular high silver chloride content grains for use in the present invention may be obtained by referring to the above-described conventional methods in accordance with the intended application of the emulsion.
- a method of preparing tabular high silver chloride grains by controlling the pH of the system for forming the grains in the range of from 4.5 to 8.5 using adenine as described in Japanese Patent Application No. Hei-1-254439 and a method of using a bispyridinium salt as a crystal appearance controlling agent as described in Japanese Patent Application Nos. Sho-62-267476 and Hei-1-276527 are useful for providing a narrow grain size distribution and high sensitivity.
- the high silver chloride content grains of the present invention have a silver chloride content of at least 80 mol %, preferably at least 90 mol %, and more preferably at least 95 mol %.
- the residue remaining silver halide content of the high silver chloride content grains may be composed of silver bromide.
- a phase mainly composed of silver bromide may be localized near the surface of the grains, or the silver halide grains may be core/shell type grains.
- the tabular silver halide grains of the present invention have an aspect ratio (diameter/thickness ratio) of at least 2/1, preferably from 2/1 to 20/1, and more preferably from 3/1 to 8/1.
- the diameter of a tabular grain is the diameter of a circle having the same area as the projected area of the grain.
- the diameter of the tabular grain is at least 0.5 ⁇ m, and preferably from 0.7 to 4 ⁇ m.
- the thickness of a tabular grain is the distance between two main parallel planes facing each other in the planes constituting the tabular grain.
- the thickness of the tabular grains is less than 0.5 ⁇ m, and preferably less than 0.3 ⁇ m.
- the grain size distribution of the silver halide grains of the present invention may be monodisperse or polydisperse, but a monodisperse generally having a coefficient of variation of 25% or less and particularly from 10 to 20% is preferred.
- the coefficient of variation is a quotient obtained by dividing a standard deviation of grain size (expressed in terms of diameter of circle equivalent to projected area) by a mean grain size).
- a silver halide solvent may be used.
- Useful silver halide solvents include, for example, thiocyanates as described, e.g., in U.S. Pat. Nos. 2,222,264, 2,448,534, and 3,320,069; thioether compounds as described, e.g., in U.S. Pat. Nos.
- a method for increasing the addition rate, addition amount, and addition concentration of an aqueous silver salt solution (e.g., an aqueous solution of AgNO 3 ) and an aqueous halide solution (e.g., an aqueous solution of NaCl) over time is preferably used for increasing the rate of growth of the grains in the production of the silver halide grains.
- the tabular silver halide emulsion of the present invention is not necessarily chemically sensitized but, if necessary, may be subjected to chemical sensitization.
- Useful chemical sensitization methods include gold sensitization as described, e.g., in U.S. Pat. Nos. 2,448,060 and 3,320,069, sulfur sensitization using a sulfur-containing compound as described, e.g., in U.S. Pat. No. 2,222,264, selenium sensitization using a selenium compound, reduction sensitization with a tin salt, thiourea dioxide, polyamine, etc., as described, e.g., in U.S. Pat. Nos. 2,487,850, 2,518,698, and 2,521,925, and a combination of these methods.
- a gold sensitization method, a sulfur sensitization method, or a combination thereof is particularly preferred.
- the photographic silver halide emulsion of the present invention can further contain ordinary silver halide grains in addition to the silver halide grains of the invention.
- the tabular high silver chloride content grains account for at least 50%, preferably at least 70%, and particularly preferably at least 90% of the total projected area of all of the silver halide grains.
- the photographic silver halide emulsion of the present invention may be mixed with other photographic silver halide emulsions and in this case, it is preferred that the tabular high silver chloride grains of the present invention account for at least 50% of the total projected area of the silver halide grains in such a mixed emulsion.
- the photographic silver halide emulsion of the present invention may be spectrally sensitized by a methine dye, etc.
- spectral sensitizing dyes for use in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
- Particularly useful dyes include cyanine dyes, merocyanine dyes, and complex cyanine dyes.
- the above dyes can contain a basic heterocyclic nucleus usually utilized for cyanine dyes, including a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc.; a nucleus formed by fusing an aliphatic hydrocarbon ring to the above-noted nuclei, and a nucleus formed by fusing an aromatic hydrocarbon ring to the above-noted nuclei, such as an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucle
- Merocyanine dyes or complex merocyanine dyes for use in the present invention may contain a 5-membered or 6-membered heterocyclic nucleus such as a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazoline-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodaine nucleus, a thiobarbituric acid, etc., as a nucleus having a ketomethylene structure.
- a 5-membered or 6-membered heterocyclic nucleus such as a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazoline-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodaine nucleus, a thiobarbituric acid,
- the spectral sensitizing dyes may be added to the silver halide emulsion at any step during the preparation of the emulsion.
- the spectral sensitizing dyes may be added in the step after completing chemical sensitization but before coating, the spectral sensitizing dyes can be added simultaneously with the addition of a chemical sensitizer to simultaneously carry out spectral sensitization and chemical sensitized as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, the spectral sensitizing dyes may be added before chemical sensitization as described in JP-A-58-113928, and the spectral sensitizing dyes may be added before completion of the precipitation of the silver halide grains to initiate the spectral sensitization.
- the above-described spectral sensitizing dyes may be separately added at different times during the preparation of the emulsion as described in U.S. Pat. No. 4,225,666. Namely, a portion of the sensitizing dye may be added prior to chemical sensitization and the remainder can be added after chemical sensitization. Thus, the spectral sensitizing dyes may be added as in the method described in U.S. Pat. No. 4,183,756, or may be added at any step of forming the silver halide grains.
- the amount of the spectral sensitizing dye added to the emulsion is from 4 ⁇ 10 -6 to 8 ⁇ 10 -3 mol, and preferably from 5 ⁇ 10 -5 to 2 ⁇ 10 -3 mol per mol of the silver halide.
- the silver halide emulsion of the present invention can be used for color photographic light-sensitive materials and black-and-white light-sensitive materials.
- the color photographic light-sensitive materials which advantageously contain the silver halide emulsion of the present invention include color photographic papers, color photographic films for photographing, color reversal films, etc., and the black-and-white light-sensitive materials include X-ray films, general photographic films for photographing, light-sensitive film for making printing plates, but the emulsion of the present invention is particularly preferably used for X-ray films.
- azoles e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, aminotriazoles, and benzotriazoles
- heterocyclic mercapto compounds e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobezimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly, 1-phenyl-5-mercaptotetrazole); mercaptopyrimidine, and mercaptotriazine
- thioketo compounds such as oxazolinethione, etc.
- Color couplers for use in the present invention include non-diffusible couplers having a hydrophobic group (i.e., a "ballast group") in the molecule thereof, or polymerized couplers are preferred.
- the coupler may be four-equivalent or two equivalent to silver ion.
- the silver halide emulsion of the present invention may further contain a colored coupler having a color correction effect or a DIR coupler which releases a development inhibitor upon development.
- the emulsion may contain a colorless DIR coupling compound which forms a colorless product by a coupling reaction and releases a development inhibitor.
- yellow couplers examples include acylacetamide couplers (e.g., benzylacetanilides and pivaloylacetanilides).
- examples of the cyan couplers are naphthol couplers and phenol couplers.
- phenolic couplers having an ethyl group at the meta-position of the phenol 2,5-diacylamino-substituted phenolic couplers, phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and couplers having a sulfonamido group or an amido group at the 5-position of the naphthol as described in U.S. Pat. Nos.
- Couplers Two or more kinds of the above noted couplers may be incorporated in the same emulsion layer, or the same coupler may be incorporated into two or more different layers to satisfy the characteristics required for the photographic light-sensitive material.
- the silver halide emulsion of the present invention may further contain a fading inhibitor and typical examples of the fading inhibitor are hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols such as bis-phenols, etc., gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives formed by silylating or alkylating the phenolic hydroxy group of each of these compounds. Also, metal complexes such as bis(salicylaldoxymate) nickel complex and bis(N,N-dialkyldithiocarbamate) nickel complex can be used.
- the processing temperature is usually selected from the range of from 18° C. to 50° C., but the processing temperature may be lower than 18° C. or higher than 50° C. According to the intended application, a black-and-white process for forming silver images or a color development process including a development for forming color images can be used.
- known developing agents such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminophenol) can be used alone or in combination thereof.
- dihydroxybenzenes e.g., hydroquinone
- 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone
- aminophenols e.g., N-methyl-p-aminophenol
- the color developer is generally composed of an alkaline aqueous solution containing a color developing agent.
- a color developing agent known primary aromatic amine color developing agents such as phenylenediamines [e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-( ⁇ -hydroxyethyl)aniline, 3-methyl-4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl ")aniline, and 4-amino-3-methyl-N-ethyl-N-(- ⁇ -methoxyethyl)aniline]can be used.
- the developer may further contain a pH buffers such as sulfites, carbonates, borates, and phosphates of alkali metals and a development inhibitor or antifoggants such as bromides, iodides, and organic antifoggants.
- a pH buffers such as sulfites, carbonates, borates, and phosphates of alkali metals
- a development inhibitor or antifoggants such as bromides, iodides, and organic antifoggants.
- the developer may further contain a water softener, a preservative such as hydroxylamine, etc., an organic solvent such as benzyl alcohol, diethylene glycol, etc., a development accelerator such as polyethylene glycol, quaternary ammonium salts, amines, etc., a dye-forming coupler, a competing coupler, a fogging agent such as sodium boron hydride, etc., an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, etc., a tackifier, the polycarboxylic acid series chelating agent described in U.S. Pat. No. 4,083,723, and the antioxidant described in West German Patent Application (OLS) 2,622,950.
- a water softener such as hydroxylamine, etc.
- a preservative such as hydroxylamine, etc.
- an organic solvent such as benzyl alcohol, diethylene glycol, etc.
- a development accelerator such as polyethylene glycol, quaternary ammonium salts
- the developer may further contain a silver staining inhibitor such as the compounds described in JP-A-56-24347.
- the developer for use in accordance with the present invention can contain an amino compound such as the alkanolamine described in JP-A-56-106244.
- a fix solution for processing a photographic material containing the silver halide emulsion of the present invention is an aqueous solution containing a thiosulfate having a pH of at least 3.8, preferably from 4.2 to 7.0, and more preferably from 4.5 to 5.5.
- Useful fixing agents include sodium thiosulfate and ammonium thiosulfate, but ammonium thiosulfate is particularly preferred in view of its rapid fixing rate.
- the amount of the fixing agent varies depending on the intended application, but is generally from about 0.1 mol/liter to about 6 mol/liter.
- the fix solution may contain a water-soluble aluminum salt as a hardening agent, and examples of the aluminum compound are aluminum chloride, aluminum sulfate, and potassium alum.
- the fix solution can further contain tartaric acid, citric acid, gluconic acid and the derivatives thereof alone or as a mixture thereof.
- the addition amount of these additives is effectively at least 0.005 mol, and particularly from 0.01 mol/liter to 0.03 mol/liter per liter of the fix solution.
- the fix solution can, if desired, contain a preservative (e.g., sulfites and hydrogensulfites), a pH buffer (e.g., acetic acid and boric acid), a pH controlling agent (e.g., sulfuric acid), a chelating agent having a water softening ability, and the compound described in JP-A-62-78551.
- a preservative e.g., sulfites and hydrogensulfites
- a pH buffer e.g., acetic acid and boric acid
- a pH controlling agent e.g., sulfuric acid
- a chelating agent having a water softening ability e.g., sodium bicarbonate
- the photographic material can be processed with wash water or a stabilization solution having a replenishment rate of less than 3 liters (including 0, i.e., water washing with stored water) per square meter of the photographic material processed.
- a multistage countercurrent system may be used as a method of reducing the amount of the water washing replenisher.
- the multistage countercurrent system is applied for processing a photographic light-sensitive materials containing the silver halide emulsion of the present invention, the light-sensitive material is successively processed with a cleaner processing solution (without being stained by the residual fix solution), such that washing is carried out more efficiently.
- Useful antifungal treatments include a method of irradiating ultraviolet rays as described in JP-A-60-26393, a method of using a magnetic field as described in JP-A-60-263940, a method of forming pure water using ion-exchange resins as described in JP-A-61-131632, and a method of using antibacterial agents as described in JP-A-62-115439, JP-A-62-153952, JP A-62-220951, and A-2-209532.
- the wash bath or the stabilization bath can contain the isothiazoline series compounds described in Kriman, J. Image Tech 10, (6), 242(1984), the isothiazoline series compounds described in Research Disclosure, Vol. 205, RD 20526 (May, 1981), the isothiazoline compounds described in ibid., Vol. 228, RD 22845 (April, 1983), and the compounds described in JP-A-62-209532 as microbiocides.
- wash step is carried out using a small amount of wash water, it is preferred to use a wash bath having a squeeze roller as described in JP-A-62-32460. Also, the wash step constitution described in JP-A-63-143548 is preferably used.
- the steps from development to drying are preferably completed within 50 seconds.
- the time from immersion of the top end of the light-sensitive material in the developer to the time that the top end emerges from a drying zone after being fixed, washed (or stabilized) and dried i.e., the dry-to-dry time
- the dry-to-dry time is not more than 50 seconds. It is more preferred that the dry-to-dry time is not more than 30 seconds.
- the reason that rapid processing having a dry-to-dry time of not more than 50 seconds can be attained is that the development process can be carried out within 15 seconds.
- the development temperature is preferably from 25° C. to 50° C., and more preferably from 30° C. to 40° C.
- the fixing temperature and time are preferably from about 20° C. to about 50° C. and 5 seconds to 20 seconds, and more preferably from 30° C. to 40° C. and from 5 seconds to 10 seconds.
- wash or stabilization temperature and time are preferably from 0° C. to 50° C. and from 5 seconds to 20 seconds, and more preferably from 15° C. to 40° C. and from 5 seconds to 15 seconds.
- the processing fluids remaining wash water in or on the photographic light-sensitive material after being developed, fixed and washed (or stabilizer) is preferably removed by drying through a squeeze roller. Drying is carried out at a temperature of from about 40° C. to about 100° C. and the drying time can be properly adjusted according to the surrounding ambient conditions and is usually from about 5 seconds to 20 seconds, and more preferably from about 5 seconds to 10 seconds at a temperature of from 40° C. to 80° C.
- a rubber roller is preferably applied to the roller at the outlet of the development tank as described in JP-A-63-151943, or the jet speed for stirring the developer in the developing tank is increased to at least 10 meters/min. as described in JP-A-63-151944.
- the roller construction of the fixing tank preferably employs a counter roller.
- a counter roller By employing a counter roller, the number of rollers is reduced and the processing tank size can be reduced. That is, a compact automatic processor can be employed for processing a light-sensitive material containing the silver halide emulsion of the present invention.
- an aqueous solution containing 136 g of silver nitrate and an aqueous solution containing 1.904 g of potassium bromide and 45.86 g of sodium chloride (2nd addition) were added thereto with vigorous stirring at 63° C. After keeping the mixture at 63° C. for 5 minutes, the temperature was lowered and the mixture was desalted and washed with water. Furthermore, 90.0 g of limed gelatin was added to the emulsion thus obtained, and pH and pAg thereof were adjusted to 7.1 and 7.5, respectively.
- the silver halide emulsion thus obtained contained cubic silver halide grains having a side length of 0.8 ⁇ m.
- comparison emulsion-2 The same procedure as for preparing comparison emulsion-1 was employed except that iron was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K 4 [Fe(CN) 6 ] in an amount of 1 ⁇ 10 -4 mol per mol of silver in the system, to prepare the comparison emulsion 2.
- comparison emulsion-3 The same procedure as for preparing comparison emulsion-1 was employed except that ruthenium was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K 4 [Ru(CN) 6 ] in an amount of 1 ⁇ 10 -4 mol per mol of silver in the system, to prepare the comparison emulsion 3.
- the silver halide emulsion thus obtained contained cubic silver halide grains having an edge length of 0.78 ⁇ m.
- comparison example 4 The same procedure as for preparing comparison example 4 was employed, except that iron was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K 4 [Fe(CN) 6 ] in an amount of 1 ⁇ 10 -4 mol per mol of silver in the system, to prepare the comparison emulsion 5.
- comparison emulsion 6 The same procedure as for preparing comparison emulsion 4 was employed, except that ruthenium was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K 4 [Ru(CN) 6 ] in an amount of 1 ⁇ 10 -4 mol per mol of silver in the system, to prepare the comparison emulsion 6.
- the temperature was lowered and the emulsion thus formed was desalted and washed with water. Furthermore, after adding gelatin, the pH and pAg thereof were adjusted to 7.1 to 7.5, respectively. The weight ratio of gelatin to silver nitrate was adjusted to the same value (by weight) as that of comparison emulsions 1 to 6.
- the tabular silver halide grains thus obtained had a thickness of 0.19 ⁇ m, a diameter of 1.45 ⁇ m, and an aspect ratio of 7.6.
- the silver chloride emulsion was prepared as follows.
- the pH value of the solution (1) containing adenine sulfate and NaCl maintained at 75° C. was adjusted to 7.0 and while vigorously stirring the solution, the solution (2) and the solution (3) were simultaneously added to the solution over a period of 5 minutes at constant addition rates. Then, the solution (4) and the solution (5) were simultaneously added thereto at constant addition rates over a period of 40 minutes to provide a silver chloride emulsion.
- the tabular silver halide grains thus prepared had a diameter of 1.4 ⁇ m, a thickness of 0.20 ⁇ m, and an aspect ratio of 7.0.
- a base was prepared by forming a subbing layer having a coated amount of gelatin of 84 mg/m 2 on a polyethylene terephthalate base of 175 ⁇ m in thickness.
- each of the above-described coating compositions were simultaneously coated on the above-noted support together with the following coating composition for a surface protective layer.
- the silver halide coverage was 2.0 g/m 2 (in terms of silver).
- the coating composition for the surface protective layer is as shown below.
- photographic light-sensitive materials 1 to 12 as shown in Table 1 were prepared.
- Each of the photographic materials 1 to 12 thus prepared was imagewise exposed for 1/50 sec. using a light source of 365.5 nm in wavelength and processed using following developer (I) and fix solution (I), and then dried.
- the development was carried out for 15 seconds at 30° C. and the fix was carried out for 10 seconds at 30° C.
- the sensitivity was evaluated as the reciprocal of the exposure amount necessary for obtaining blackened extent of 0.3+fog value, relative to the sensitivity of photographic material 1 defined as 100.
- a silver halide emulsion was prepared in the same manner as emulsion 4 of Example 1. However, in this case, after completing the 1st and 2nd additions of the alkali halide, an aqueous solution containing 1.19 g of potassium bromide was added to carry out halogen conversion at the surface of the silver halide grains. Thereafter, the emulsion was dealt and washed. Then, 90 g of gelatin and 3 g of phenoxy ethanol were added, and the pH and pAg were adjusted to 6.5 and 7.5, respectively, to obtain the emulsion 13.
- a silver halide emulsion was prepared in the same manner as emulsion 10 in Example 1. However, in this case, after completing the addition of the solutions (4) and (5) an aqueous solution containing 1.19 g of potassium bromide was added to the emulsion to carry out halogen conversion of the surface of the silver halide grains.
- a silver halide emulsion was prepared in the same manner as emulsion 11 in Example 1.
- a silver chlorobromide emulsion was prepared as follows.
- the emulsion was desalted by an ordinary flocculation method and washed with water, and after adding thereto gelatin, the pH and pAg were adjusted to 6.4 and 7.5 at 40° C. to provide a tabular grain silver chloride emulsion.
- the silver chloride emulsion thus prepared contained more than 80% (projected area) tabular grains having a thickness of less than 0.5 ⁇ m, a diameter of at least 0.5 ⁇ m, and aspect ratio of 2 or more and having parallel (111) planes.
- the tabular silver halide grains had a mean projected area of 1.8 ⁇ m 2 , a mean thickness of 0.22 ⁇ m, and a mean aspect ratio of 6.9.
- a superfine grain silver bromide emulsion (grain size of about 0.05 ⁇ m) in an amount to provide 1 mol % silver bromide to silver chloride, and ripening was carried out for 10 minutes at 60° C. to provide an emulsion before chemical sensitization.
- the chemical ripening time was 30 minutes.
- Photographic materials 17 to 20 were prepared and evaluated in the same manner as in Example 1. The development process was carried out for 10 seconds at 35° C.
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Abstract
A photographic silver halide emulsion comprising silver chlorobromide grains containing at least 80 mol % silver chloride or silver chloride grains is disclosed, wherein tabular grains having a thickness of less than 0.5 μm, a diameter of at least 0.5 μm and an aspect ratio of at least 2/1 account for at least 50% of the total projected area of the silver halide grains, and the tabular grains are formed in the presence of a compound of metal belonging to Group VIII of the Periodic Table. The high silver chloride content emulsion has a sensitivity as high as that of a silver iodobromide emulsion.
Description
This is a continuation of application Ser. No. 07/662,591, filed Mar. 1, 1991, abandoned.
The present invention relates to a silver halide photographic emulsion, and more particularly to a tabular silver chlorobromide emulsion having a high silver chloride content or a tabular silver chloride emulsion each having high sensitivity, and which emulsions are well adapted to rapid processing.
In photographic processing for photographic light-sensitive materials, it is desired to shorten the processing time and reduce the amount of waste solutions that are generated in processing.
A high-sensitivity negative type photographic light-sensitive material generally employs a silver iodobromide emulsion; however, in order to satisfy the above noted requirements, a silver chlorobromide emulsion or a silver chloride emulsion having a high solubility is useful. On the other hand, for reducing the amount of processing waste, it is desirable to increase the image density using a smaller amount of silver, and also it is well known in the art that tabular silver halide grains provide favorable properties with respect to sensitivity, graininess, sharpness, color sensitizing efficiency, etc.
Silver halide grains having a high silver chloride content, i.e., as high as 50 mol %, (hereinafter, "high silver chloride content grains") generally have a cubic structure. To form tabular grains having a high silver chloride content, various specific means must be employed.
Methods for preparing tabular silver chlorobromide grains are known including, for example, (1) simultaneously introducing an aqueous solution of a chloride and an aqueous solution of a silver salt in a dispersion medium in the presence of ammonia by a double jet method as described in JP-B-64-8324 (the term "JP-B" as used herein means an "examined Japanese patent publication"), (2) reacting an aqueous silver salt solution and an aqueous solution of a chloride-containing halide in the presence of aminoazaindene and a thioether bond-containing peptizer as described in JP-B-64-8326, (3) simultaneously introducing an aqueous solution of a silver salt, an aqueous solution of a chloride, and an aqueous solution of a bromide to a dispersion medium while keeping the mol ratio of chloride ion to bromide ion in the range of from 1.6:1 to 258:1, and keeping the total concentration of halogen ions in the range of from 0.10 to 0.90 normal as described in JP-A-58-111936 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), (4) introducing silver ion into a dispersion medium containing at least 0.5 molar chloride ion and a gelatin deflocculant formed from methionine of less than 30 μmol per gram as described in JP-A-62-163046, (5) contacting a chloride-containing halide and a water-soluble silver salt in a dispersion medium in the presence of a crystal habit changing amount of aminoazapyridine and the salt thereof as described in JP-A-63-281149, (6) mixing an aqueous silver salt solution and an aqueous halide solution in the presence of thiourea or a thiourea derivative or using a gold compound as described in JP-A-63-213836, (7) forming the silver halide grains in the presence of a compound having a sulfur ion in a heterocyclic ring thereof as described in JP-A-63-2043, and (8) forming the silver halide grains in the presence of a carbonyl compound containing a sulfur ion in the molecule thereof or a sulfone compound as described in JP-A-63-41845.
However, a silver chlorobromide emulsion tends to fog and has a low light sensitivity as compared to a silver iodobromide emulsion. Also, the application of a silver chlorobromide emulsion is limited to color photo- graphic papers and light-sensitive materials for making printing plates using a relatively high intensity exposure.
For solving the above noted problems of high silver chloride content emulsions, various techniques have been proposed.
For example, JP-A-58-95736, JP-A-58-108533, JP-A-60-222844, and JP-A-60-222845 disclose that for imparting high sensitivity to a high silver chloride content emulsion, it is effective to form a grain structure having a high silver bromide content layer in the silver halide grains. The present inventors have found that although high sensitivity is obtained using these techniques, desensitization tends to occur when pressure is applied to the emulsion. Also, tabular silver halide grains having a uniform grain size distribution are difficult to prepare, such that the emulsion is not practically employed. Furthermore, it has also been found that by using these methods, it is difficult to sufficiently improve the reciprocity law failure of the high silver chloride content emulsion.
JP-A-51-139323, JP-A-59-171947 and British Patent 2,109,576A described that high sensitivity is obtained and the reciprocity law failure is improved by introducing to the silver halide emulsion a compound of a metal belonging to Group VIII of the Periodic Table.
Also, U.S. Pat. No. 4,269,927 describes that high sensitivity is obtained by incorporating cadmium, lead, zinc, or a mixture thereof in a surface latent image-type high silver chloride content emulsion having a silver chloride content of at least 80 mol %.
However, by using the above-described method, although a small increase in sensitivity and improvement in reciprocity law failure is observed, the resulting high silver chloride content emulsion does not provide practically useful performance.
Furthermore, European Patent 336426Al discloses a technique of obtaining high sensitivity by forming a high silver chloride content emulsion in the presence of six-coordinate complex of rhenium, ruthenium, or osmium having a cyan ligand.
However, the sensitivity attained is far inferior to that of a silver iodobromide emulsion which is generally used.
An object of the present invention is to provide a high silver chloride content emulsion which is well adapted to rapid processing and having a sensitivity as high as that of a silver iodobromide emulsion.
The present inventors have discovered that the above object is attained by providing a photographic silver halide emulsion comprising silver chlorobromide grains containing at least 80 mol % silver chloride or silver chloride grains, wherein tabular grains having a thickness of less than 0.5 μm, a diameter of at least 0.5 μm, and an aspect ratio of at least 2/1 account for at least 50% of the total projected area of the silver halide grains, and said tabular grains are formed in the presence of a compound of metal belonging to Group VIII of the Periodic Table.
The invention is explained in detail below.
The compound of a metal belonging to group VIII of the Period Table for use in the present invention includes compounds of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc., and typical examples of the compound are ferric chloride, potassium ferricyanide, cobalt chloride, cobalt nitrate, luteo salt, nickel chloride, nickel sulfate, ruthenium chloride, ruthenium hydroxide, rhodium chloride, ammonium hexachlorodinate, palladium chloride, palladium nitrate, potassium hexachloropalladate, osmium chloride, iridium chloride (IrCl3 or IrCl4), potassium iridate chloride, ammonium hexachloroiridate, ammonium hexachloroplatinate, and potassium hexachloroplatinate.
Of the metals belonging to Group VIII of the Periodic Table for use in the present invention, iron rhenium, ruthenium, and osmium are preferred and in particular, the six-coordination complex of iron, rhenium, ruthenium, or osmium having 4 cyan ligands as described in European Patent 336426Al exhibit an excellent effect for increasing the sensitivity.
The addition amount of the compound of a metal belonging to Group VIII of the Periodic Table is from 1×10-8 to 1×10-2 mol, and preferably from 1×10-6 to 1×10-3 mol per mol of silver halide contained in the emulsion.
In the present invention, by forming the tabular high silver chloride content grains in the presence of a compound of a metal belonging to Group VIII of the Periodic Table, the metal of Group VIII is contained in the tabular grains.
The metal of Group VIII contained in the high silver chloride content grains may be uniformly distributed over the entire grain or may be localized in the central portion of the grain, or may largely exist in the outside portion of the grain as opposed to the central portion of the grain.
In the present invention, it is preferred that the metal of Group VIII is largely present in the outside portions but not in the central portion of the grain.
The tabular high silver chloride content grains for use in the present invention may be obtained by referring to the above-described conventional methods in accordance with the intended application of the emulsion. However, a method of preparing tabular high silver chloride grains by controlling the pH of the system for forming the grains in the range of from 4.5 to 8.5 using adenine as described in Japanese Patent Application No. Hei-1-254439 and a method of using a bispyridinium salt as a crystal appearance controlling agent as described in Japanese Patent Application Nos. Sho-62-267476 and Hei-1-276527 are useful for providing a narrow grain size distribution and high sensitivity.
The high silver chloride content grains of the present invention have a silver chloride content of at least 80 mol %, preferably at least 90 mol %, and more preferably at least 95 mol %.
The residue remaining silver halide content of the high silver chloride content grains may be composed of silver bromide. In this case, a phase mainly composed of silver bromide may be localized near the surface of the grains, or the silver halide grains may be core/shell type grains.
The tabular silver halide grains of the present invention have an aspect ratio (diameter/thickness ratio) of at least 2/1, preferably from 2/1 to 20/1, and more preferably from 3/1 to 8/1.
The diameter of a tabular grain is the diameter of a circle having the same area as the projected area of the grain. In the present invention, the diameter of the tabular grain is at least 0.5 μm, and preferably from 0.7 to 4 μm.
The thickness of a tabular grain is the distance between two main parallel planes facing each other in the planes constituting the tabular grain. In the present invention, the thickness of the tabular grains is less than 0.5 μm, and preferably less than 0.3 μm.
The grain size distribution of the silver halide grains of the present invention may be monodisperse or polydisperse, but a monodisperse generally having a coefficient of variation of 25% or less and particularly from 10 to 20% is preferred. The coefficient of variation is a quotient obtained by dividing a standard deviation of grain size (expressed in terms of diameter of circle equivalent to projected area) by a mean grain size).
In the preparation of the silver halide grains of the present invention, a silver halide solvent may be used. Useful silver halide solvents include, for example, thiocyanates as described, e.g., in U.S. Pat. Nos. 2,222,264, 2,448,534, and 3,320,069; thioether compounds as described, e.g., in U.S. Pat. Nos. 3,271,157, 3,574,628, 3,704,130, 4,297,439, and 4,276,347; thion compounds and thiourea compounds as described, e.g., JP-A-53-144319, JP-A-53-82408, and JP-A-55-77737, and amine compounds as described, e.g., in JP-A-54-100717. Also, ammonia can be used as the silver halide solvent together with the above-described silver halides to the extent that adverse effects do not result.
In the present invention, a method for increasing the addition rate, addition amount, and addition concentration of an aqueous silver salt solution (e.g., an aqueous solution of AgNO3) and an aqueous halide solution (e.g., an aqueous solution of NaCl) over time is preferably used for increasing the rate of growth of the grains in the production of the silver halide grains.
The above methods are described, e.g., in British Patent 1,335,925, U.S. Pat. Nos. 3,672,900, 3,650,757, and 4,242,445, JP-A-55-142329, JP-A-55-158124, JP-A-58-113927, JP-A-58-113928, JP-A-58-111934, and JP-A-58-111936.
The tabular silver halide emulsion of the present invention is not necessarily chemically sensitized but, if necessary, may be subjected to chemical sensitization.
Useful chemical sensitization methods include gold sensitization as described, e.g., in U.S. Pat. Nos. 2,448,060 and 3,320,069, sulfur sensitization using a sulfur-containing compound as described, e.g., in U.S. Pat. No. 2,222,264, selenium sensitization using a selenium compound, reduction sensitization with a tin salt, thiourea dioxide, polyamine, etc., as described, e.g., in U.S. Pat. Nos. 2,487,850, 2,518,698, and 2,521,925, and a combination of these methods.
For the silver halide emulsion of the present invention, a gold sensitization method, a sulfur sensitization method, or a combination thereof is particularly preferred.
The photographic silver halide emulsion of the present invention can further contain ordinary silver halide grains in addition to the silver halide grains of the invention.
In the photographic silver halide emulsion of the present invention containing tabular high silver chloride content grains, the tabular high silver chloride content grains account for at least 50%, preferably at least 70%, and particularly preferably at least 90% of the total projected area of all of the silver halide grains.
The photographic silver halide emulsion of the present invention may be mixed with other photographic silver halide emulsions and in this case, it is preferred that the tabular high silver chloride grains of the present invention account for at least 50% of the total projected area of the silver halide grains in such a mixed emulsion.
The photographic silver halide emulsion of the present invention may be spectrally sensitized by a methine dye, etc. Examples of spectral sensitizing dyes for use in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes include cyanine dyes, merocyanine dyes, and complex cyanine dyes.
The above dyes can contain a basic heterocyclic nucleus usually utilized for cyanine dyes, including a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc.; a nucleus formed by fusing an aliphatic hydrocarbon ring to the above-noted nuclei, and a nucleus formed by fusing an aromatic hydrocarbon ring to the above-noted nuclei, such as an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc., can be used for the above-described dyes. These nuclei may be substituted on carbon atoms thereof.
Merocyanine dyes or complex merocyanine dyes for use in the present invention may contain a 5-membered or 6-membered heterocyclic nucleus such as a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazoline-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodaine nucleus, a thiobarbituric acid, etc., as a nucleus having a ketomethylene structure.
Examples of sensitizing dyes for use in the present invention include the compounds described in Research Disclosure, Vol. 176 (RD 17643), IV, page 23 (December, 1978), and the literature references cited therein.
The spectral sensitizing dyes may be added to the silver halide emulsion at any step during the preparation of the emulsion. For example, the spectral sensitizing dyes may be added in the step after completing chemical sensitization but before coating, the spectral sensitizing dyes can be added simultaneously with the addition of a chemical sensitizer to simultaneously carry out spectral sensitization and chemical sensitized as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, the spectral sensitizing dyes may be added before chemical sensitization as described in JP-A-58-113928, and the spectral sensitizing dyes may be added before completion of the precipitation of the silver halide grains to initiate the spectral sensitization.
Furthermore, the above-described spectral sensitizing dyes may be separately added at different times during the preparation of the emulsion as described in U.S. Pat. No. 4,225,666. Namely, a portion of the sensitizing dye may be added prior to chemical sensitization and the remainder can be added after chemical sensitization. Thus, the spectral sensitizing dyes may be added as in the method described in U.S. Pat. No. 4,183,756, or may be added at any step of forming the silver halide grains.
The amount of the spectral sensitizing dye added to the emulsion is from 4×10-6 to 8×10-3 mol, and preferably from 5×10-5 to 2×10-3 mol per mol of the silver halide.
The silver halide emulsion of the present invention can be used for color photographic light-sensitive materials and black-and-white light-sensitive materials.
The color photographic light-sensitive materials which advantageously contain the silver halide emulsion of the present invention include color photographic papers, color photographic films for photographing, color reversal films, etc., and the black-and-white light-sensitive materials include X-ray films, general photographic films for photographing, light-sensitive film for making printing plates, but the emulsion of the present invention is particularly preferably used for X-ray films.
There is no particular restriction on the photographic materials to which the emulsion of the present invention is applied. Additives for use in the silver halide emulsion of the present invention are described in Research Disclosures, Vol. 176 (RD 17643) and Vol. 187 (RD 18716).
The above noted portions of RD 17643 and RD 18716 concerning the use of additives are summarized in the following table.
______________________________________ Kind of Additives RD 17643 RD 18716 ______________________________________ 1. Chemical Sensitizer Page 23 Page 648, right column 2. Sensitivity -- Page 648, Increasing Agent right column 3. Spectral Sensitizer Pages 23 Page 648, right and Super Color to 24 column to page Sensitizer 649, right column 4. Whitening Agent Page 24 -- 5. Antifoggant and Pages 24 Page 649, Stabilizer to 25 right column 6. Light-Absorber, Pages 25 Page 649, right Filter Dye and Ultra- to 26 column to page violet Absorber 650, left column 7. Stain Inhibitor Page 25, Page 650, left right to right column column 8. Dye Image Stabilizer Page 25 -- 9. Hardener Page 26 Page 651, left column 10. Binder Page 26 Page 651, left column 11. Plasticizer Page 27 Page 650, Lubricant right column 12. Coating Aid Pages 26 Page 650, Surface Active Agent to 27 right column 13. Antistatic Agent Page 27 Page 650, right column ______________________________________
Of the above-described additives, as anti-foggants and stabilizers, azoles (e.g., benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, aminotriazoles, and benzotriazoles); heterocyclic mercapto compounds (e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobezimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly, 1-phenyl-5-mercaptotetrazole); mercaptopyrimidine, and mercaptotriazine); the above-noted heterocyclic mercapto compounds having a water-solubilizing group such as a carboxy group and a sulfon group; thioketo compounds such as oxazolinethione, etc.; azaindenes[e.g., triazaindenes, tetraazaindenes (particularly, 4-hydroxy-substituted 1,3,3a,7-tetraazaindenes), and pentaazaindenes]; benzenethiosulfonic acids; benzenesulfinic acids; benzenesulfonamide, etc., are preferably used.
Color couplers for use in the present invention, include non-diffusible couplers having a hydrophobic group (i.e., a "ballast group") in the molecule thereof, or polymerized couplers are preferred. The coupler may be four-equivalent or two equivalent to silver ion. Furthermore, the silver halide emulsion of the present invention may further contain a colored coupler having a color correction effect or a DIR coupler which releases a development inhibitor upon development. Also, the emulsion may contain a colorless DIR coupling compound which forms a colorless product by a coupling reaction and releases a development inhibitor.
Examples of the magenta coupler for use in the present invention include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers. Examples of the yellow couplers are acylacetamide couplers (e.g., benzylacetanilides and pivaloylacetanilides). Also, examples of the cyan couplers are naphthol couplers and phenol couplers. As the cyan coupler, phenolic couplers having an ethyl group at the meta-position of the phenol, 2,5-diacylamino-substituted phenolic couplers, phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and couplers having a sulfonamido group or an amido group at the 5-position of the naphthol as described in U.S. Pat. Nos. 3,772,002, 2,772,162, 3,758,308, 4,126,396, 4,334,011, 4,327,173, 3,446,622, 4,333,999, 4,451,559, and 4,427,767 are preferred in that the images thereby formed have an excellent fastness.
Two or more kinds of the above noted couplers may be incorporated in the same emulsion layer, or the same coupler may be incorporated into two or more different layers to satisfy the characteristics required for the photographic light-sensitive material.
The silver halide emulsion of the present invention may further contain a fading inhibitor and typical examples of the fading inhibitor are hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols such as bis-phenols, etc., gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives formed by silylating or alkylating the phenolic hydroxy group of each of these compounds. Also, metal complexes such as bis(salicylaldoxymate) nickel complex and bis(N,N-dialkyldithiocarbamate) nickel complex can be used.
For processing the photographic light-sensitive material containing the silver halide emulsion of the present invention, known processes can be used and also known processing solutions can be used for this purpose.
The processing temperature is usually selected from the range of from 18° C. to 50° C., but the processing temperature may be lower than 18° C. or higher than 50° C. According to the intended application, a black-and-white process for forming silver images or a color development process including a development for forming color images can be used.
For black-and-white development, known developing agents such as dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminophenol) can be used alone or in combination thereof.
The color developer is generally composed of an alkaline aqueous solution containing a color developing agent. As the color developing agent, known primary aromatic amine color developing agents such as phenylenediamines [e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-(β-hydroxyethyl)aniline, 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl ")aniline, and 4-amino-3-methyl-N-ethyl-N-(-β-methoxyethyl)aniline]can be used.
Other color developing agents for use in the present invention are described in L. F. A. Mason, Photoqraphic Processinq Chemistry, pages 226 to 229, (published by The Focal Press, 1966), U.S. Pat. Nos. 2,193,015 and 2,592,364, and JP-A-48-64933.
The developer may further contain a pH buffers such as sulfites, carbonates, borates, and phosphates of alkali metals and a development inhibitor or antifoggants such as bromides, iodides, and organic antifoggants.
Also, if necessary, the developer may further contain a water softener, a preservative such as hydroxylamine, etc., an organic solvent such as benzyl alcohol, diethylene glycol, etc., a development accelerator such as polyethylene glycol, quaternary ammonium salts, amines, etc., a dye-forming coupler, a competing coupler, a fogging agent such as sodium boron hydride, etc., an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, etc., a tackifier, the polycarboxylic acid series chelating agent described in U.S. Pat. No. 4,083,723, and the antioxidant described in West German Patent Application (OLS) 2,622,950.
Furthermore, in the development processing of the photographic material containing the silver halide emulsion of the present invention, the developer may further contain a silver staining inhibitor such as the compounds described in JP-A-56-24347.
The developer for use in accordance with the present invention can contain an amino compound such as the alkanolamine described in JP-A-56-106244.
Additionally the compounds described in L. F. A. Mason, Photoqraphic Processing Chemistry, pages 226-229, (published by The Focal Press, (1966)), U.S. Pat. Nos. 2,193,015 and 2,592,364, and JP-A-48-64933 can be also used in the developer.
A fix solution for processing a photographic material containing the silver halide emulsion of the present invention is an aqueous solution containing a thiosulfate having a pH of at least 3.8, preferably from 4.2 to 7.0, and more preferably from 4.5 to 5.5.
Useful fixing agents include sodium thiosulfate and ammonium thiosulfate, but ammonium thiosulfate is particularly preferred in view of its rapid fixing rate. The amount of the fixing agent varies depending on the intended application, but is generally from about 0.1 mol/liter to about 6 mol/liter.
The fix solution may contain a water-soluble aluminum salt as a hardening agent, and examples of the aluminum compound are aluminum chloride, aluminum sulfate, and potassium alum.
Also, the fix solution can further contain tartaric acid, citric acid, gluconic acid and the derivatives thereof alone or as a mixture thereof. The addition amount of these additives is effectively at least 0.005 mol, and particularly from 0.01 mol/liter to 0.03 mol/liter per liter of the fix solution.
The fix solution can, if desired, contain a preservative (e.g., sulfites and hydrogensulfites), a pH buffer (e.g., acetic acid and boric acid), a pH controlling agent (e.g., sulfuric acid), a chelating agent having a water softening ability, and the compound described in JP-A-62-78551.
For rapid processing, it is advantageous to reduce the swelling percentage (preferably from 150% to 50%) of the photographic light-sensitive material and to reduce the hardening action by processing. For the measurement of swelling percentage, a reference may be made to U.S. Pat. No. 4,414,304. Thus, hardening is preferably not conducted during development or fixing. The hardening reaction in fixing is diminished by increasing the pH of the fix solution above 4.6.
In the processing of the silver halide photo-graphic material containing the emulsion of the present invention, after the development and fix step, the photographic material can be processed with wash water or a stabilization solution having a replenishment rate of less than 3 liters (including 0, i.e., water washing with stored water) per square meter of the photographic material processed.
In other words, in the processing of a photographic material containing the emulsion of the present invention, water-saving processing is practically conducted and also plumbing for an automatic processor is not necessarily required.
As a method of reducing the amount of the water washing replenisher, a multistage (e.g., 2 or 3 stage) countercurrent system may be used. When the multistage countercurrent system is applied for processing a photographic light-sensitive materials containing the silver halide emulsion of the present invention, the light-sensitive material is successively processed with a cleaner processing solution (without being stained by the residual fix solution), such that washing is carried out more efficiently.
For the above-described water-saving processing or non-plumbing processing, it is preferred to apply an antifungal treatment to the wash water or the stabilization solution.
Useful antifungal treatments include a method of irradiating ultraviolet rays as described in JP-A-60-26393, a method of using a magnetic field as described in JP-A-60-263940, a method of forming pure water using ion-exchange resins as described in JP-A-61-131632, and a method of using antibacterial agents as described in JP-A-62-115439, JP-A-62-153952, JP A-62-220951, and A-2-209532.
Furthermore, the antibacterial agents, antifungal agents, surface active agents, etc., described in L. E. West, "Water Quality Criteria", Photo. Sci. & Eng., Vol. 9, No. 6, (1965), M. W. Beach, "Microbiological Growth in Motion-Picture Processing", SMPTE Journal, Vol. 85, (1976), R. O. Deegan, "Photo Processing Wash Water Biocides", J. Imaging Tech. 10, No. 6 (1984), and JP-A-57-8542, JP-A-57-58143, JP-A-58-105145, JP-A-57-132146, JP-A-58-18631, JP-A-57-97530, JP-A-57-157244, etc., can also be used.
Moreover, the wash bath or the stabilization bath can contain the isothiazoline series compounds described in Kriman, J. Image Tech 10, (6), 242(1984), the isothiazoline series compounds described in Research Disclosure, Vol. 205, RD 20526 (May, 1981), the isothiazoline compounds described in ibid., Vol. 228, RD 22845 (April, 1983), and the compounds described in JP-A-62-209532 as microbiocides.
When wash step is carried out using a small amount of wash water, it is preferred to use a wash bath having a squeeze roller as described in JP-A-62-32460. Also, the wash step constitution described in JP-A-63-143548 is preferably used.
When the silver halide light-sensitive material containing the silver halide emulsion of the present invention is processed by an automatic processor including the steps of at least development, fix, and wash (or stabilization), the steps from development to drying are preferably completed within 50 seconds. Namely, the time from immersion of the top end of the light-sensitive material in the developer to the time that the top end emerges from a drying zone after being fixed, washed (or stabilized) and dried (i.e., the dry-to-dry time), is not more than 50 seconds. It is more preferred that the dry-to-dry time is not more than 30 seconds.
The reason that rapid processing having a dry-to-dry time of not more than 50 seconds can be attained is that the development process can be carried out within 15 seconds. The development temperature is preferably from 25° C. to 50° C., and more preferably from 30° C. to 40° C.
Also, the fixing temperature and time are preferably from about 20° C. to about 50° C. and 5 seconds to 20 seconds, and more preferably from 30° C. to 40° C. and from 5 seconds to 10 seconds.
Furthermore, the wash or stabilization temperature and time are preferably from 0° C. to 50° C. and from 5 seconds to 20 seconds, and more preferably from 15° C. to 40° C. and from 5 seconds to 15 seconds.
In accordance with the present invention, the processing fluids remaining wash water in or on the photographic light-sensitive material after being developed, fixed and washed (or stabilizer) is preferably removed by drying through a squeeze roller. Drying is carried out at a temperature of from about 40° C. to about 100° C. and the drying time can be properly adjusted according to the surrounding ambient conditions and is usually from about 5 seconds to 20 seconds, and more preferably from about 5 seconds to 10 seconds at a temperature of from 40° C. to 80° C.
When the photographic light-sensitive material containing the silver halide emulsion of the present invention is processed in a dry-to-dry time of not more than 50 seconds, and to prevent the formation of uneven development which tends to occur in rapid processing, a rubber roller is preferably applied to the roller at the outlet of the development tank as described in JP-A-63-151943, or the jet speed for stirring the developer in the developing tank is increased to at least 10 meters/min. as described in JP-A-63-151944.
Furthermore, for increasing the fixing speed or for increasing the dissolving speed of dyes contained in the light-sensitive material, the roller construction of the fixing tank preferably employs a counter roller. By employing a counter roller, the number of rollers is reduced and the processing tank size can be reduced. That is, a compact automatic processor can be employed for processing a light-sensitive material containing the silver halide emulsion of the present invention.
The invention is further described in detail by reference to the following examples, but the invention is not to be construed as being limited to these examples.
To an aqueous solution of 3% limed gelatin was added 3.3 g of sodium chloride followed by addition of 3.2 ml of an aqueous solution of 1% N,N'-dimethylimidazolidine-2-thione. To the solution were added an aqueous solution containing 34 g of silver nitrate and an aqueous solution containing 0.476 g of potassium bromide and 11.47 g of sodium chloride (1st addition) at 63° C. with vigorous stirring. Then, an aqueous solution containing 136 g of silver nitrate and an aqueous solution containing 1.904 g of potassium bromide and 45.86 g of sodium chloride (2nd addition) were added thereto with vigorous stirring at 63° C. After keeping the mixture at 63° C. for 5 minutes, the temperature was lowered and the mixture was desalted and washed with water. Furthermore, 90.0 g of limed gelatin was added to the emulsion thus obtained, and pH and pAg thereof were adjusted to 7.1 and 7.5, respectively. The silver halide emulsion thus obtained contained cubic silver halide grains having a side length of 0.8 μm.
The same procedure as for preparing comparison emulsion-1 was employed except that iron was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K4 [Fe(CN)6 ] in an amount of 1×10-4 mol per mol of silver in the system, to prepare the comparison emulsion 2.
The same procedure as for preparing comparison emulsion-1 was employed except that ruthenium was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K4 [Ru(CN)6 ] in an amount of 1×10-4 mol per mol of silver in the system, to prepare the comparison emulsion 3.
To an aqueous solution of 3% limed gelatin was added 3.3 g of sodium chloride followed by addition of 3.2 ml of an aqueous solution of 1% N,N'-dimethylimidazolidine-2-thione. To the solution were added an aqueous solution containing 34 g of silver nitrate and an aqueous solution containing 11.7 g of sodium chloride (1st addition) with vigorous stirring at 63° C. Then, an aqueous solution containing 136 g of silver nitrate and an aqueous solution containing 46.8 g of sodium chloride were added thereto (2nd addition) with vigorous stirring at 63° C. After keeping the emulsion thus obtained at 63° C. for 5 minutes, the temperature was lowered, and the emulsion was desalted and washed with water. Furthermore, 90.0 g of limed gelatin and 3 g of phenoxy ethanol were added, and the pH and pAg thereof were adjusted to 7.1 and 7.5, respectively.
The silver halide emulsion thus obtained contained cubic silver halide grains having an edge length of 0.78 μm.
The same procedure as for preparing comparison example 4 was employed, except that iron was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K4 [Fe(CN)6 ] in an amount of 1×10-4 mol per mol of silver in the system, to prepare the comparison emulsion 5.
The same procedure as for preparing comparison emulsion 4 was employed, except that ruthenium was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K4 [Ru(CN)6 ] in an amount of 1×10-4 mol per mol of silver in the system, to prepare the comparison emulsion 6.
By referring to the method described in Example 1 of JP-A-63-281149, a tabular grain silver chlorobromide emulsion containing 1.5 mol % silver bromide was formed. In this case, 0.08 g of 4-aminopyrazolo[3,4,d]-pyrimidine was added as a crystal growth modifier, and the pH value was adjusted to 4.5.
After forming the silver halide grains, the temperature was lowered and the emulsion thus formed was desalted and washed with water. Furthermore, after adding gelatin, the pH and pAg thereof were adjusted to 7.1 to 7.5, respectively. The weight ratio of gelatin to silver nitrate was adjusted to the same value (by weight) as that of comparison emulsions 1 to 6.
The tabular silver halide grains thus obtained had a thickness of 0.19 μm, a diameter of 1.45 μm, and an aspect ratio of 7.6.
The same procedure as for preparing Comparison Example 7 was employed, except that iron was added in the form of an aqueous solution of K4 [Fe(CN)6 ] to the aqueous alkali halide solutions in an amount of 1×10-4 mol per mol of silver in the system, to prepare the emulsion 8 of the invention.
The same procedure as for preparing Comparison Example 7 was employed, except that ruthenium was added to the aqueous alkali halide solutions in the form of an aqueous solution of K4 [Ru(CN)6 ] in an amount of 1×10-4 mol per mol of silver in the system, to prepare the emulsion 9 of the present invention.
The silver chloride emulsion was prepared as follows.
______________________________________ Solution (1): Inactive Gelatin 30 g Adenine Sulfate 0.186 g [(C.sub.5 H.sub.5 N.sub.5).sub.2.H.sub.2 SO.sub.4.2H.sub.2 O] NaCl 7.8 g Water 1450 ml Solution (2): AgNO.sub.3 20 g Water to make 50 ml Solution (3): NaCl 6.5 g Water to make 50 ml Solution (4): AgNO.sub.3 150 g Water to make 400 ml Solution (5): NaCl 52 g Water to make 400 ml ______________________________________
The pH value of the solution (1) containing adenine sulfate and NaCl maintained at 75° C. was adjusted to 7.0 and while vigorously stirring the solution, the solution (2) and the solution (3) were simultaneously added to the solution over a period of 5 minutes at constant addition rates. Then, the solution (4) and the solution (5) were simultaneously added thereto at constant addition rates over a period of 40 minutes to provide a silver chloride emulsion.
After desalting by flocculation and washing with water, 90 g of gelatin and 3 g of phenoxy ethanol were added to the emulsion, and pH and pAg thereof were adjusted to 7.1 and 7.5, respectively
The tabular silver halide grains thus prepared had a diameter of 1.4 μm, a thickness of 0.20 μm, and an aspect ratio of 7.0.
The same procedure as for preparing the emulsion 10 was employed, except that iron was added to the solution (5) in the form of an aqueous solution of K4 [Fe(CN)6 ] in an amount of 1×10-4 mol per mol of silver in the system, to prepare the emulsion 11 of the invention.
The same procedure as for preparing the emulsion 10 was employed, except that ruthenium was added to the solution (5) in the form of an aqueous solution of K4 [Ru(CN)6 ] in an amount of 1×10-4 mol per mol of silver in the system, to prepare the emulsion 12 of the invention.
To each of the emulsions 1 to 12 were added the following components per mol of silver halide to provide corresponding coating compositions.
______________________________________ Polymer Latex: [poly(ethyl acrylate/ 20.0 g methacrylic acid) = 97/3] Hardening Agent: 1,2-Bis(vinylsulfonyl- 2.4 g acetamido)ethane 2,6-Bis(hydroxyamino)-4- 76 mg diethylamino-1,3,5-triazine Sodium Polyacrylate (mean molecular 2.1 g weight 41,000) Potassium Polystyrenesulfonate 1.0 g (mean molecular weight 600,000) Dextran (molecular weight 39,000) 23.6 g Trimethylolpropane 9.8 g ##STR1## 0.03 g ______________________________________
A base was prepared by forming a subbing layer having a coated amount of gelatin of 84 mg/m2 on a polyethylene terephthalate base of 175 μm in thickness.
Each of the above-described coating compositions were simultaneously coated on the above-noted support together with the following coating composition for a surface protective layer. The silver halide coverage was 2.0 g/m2 (in terms of silver).
The coating composition for the surface protective layer is as shown below. Thus, photographic light-sensitive materials 1 to 12 as shown in Table 1 were prepared.
______________________________________ Content of Surface Protective Layer Coated Amount ______________________________________ Gelatin 1.138 g/m.sup.2 Dextran (mean molecular weight 0.228 g/m.sup.2 39,000) 4-Hydroxy-6-methyl-1,3,3a,7- 0.0155 g/m.sup.2 tetraazaindene Sodium Polyacrylate (mean 0.023 g/m.sup.2 molecular weight 400,000) ##STR2## 0.0225 g/m.sup.2 C.sub.16 H.sub.33 O(CH.sub.2 CH.sub.2 O) .sub.10 H 0.035 g/m.sup.2 ##STR3## 0.005 g/m.sup.2 C.sub.8 F.sub.17 SO.sub.3 K 0.0053 g/m.sup.2 Polymethyl Methacrylate 0.088 g/m.sup.2 (mean grain size 3.7 μm) Proxicel (available from I.C.I. Co) 0.0006 g/m.sup.2 ______________________________________
Each of the photographic materials 1 to 12 thus prepared was imagewise exposed for 1/50 sec. using a light source of 365.5 nm in wavelength and processed using following developer (I) and fix solution (I), and then dried.
______________________________________ Developer (I) Hydroquinone 10 g 4-Hydromethyl-4-methyl-1- 1 g phenyl-3-pyrazolidone Potassium Chloride 10 g Ascorbic Acid 10 g pH adjusted to 9.5 Water to make 1 liter Fix Solution (I) Ammonium Thiosulfate 200 g Sodium Sulfite (anhydrous) 20 g Boric Acid 8 g Ethylenediaminetetraacetic Acid 0.1 g Di-Sodium Aluminum Sulfate 15 g Sulfuric Acid 2 g Glacial Acetic Acid 22 g Water to make 1.0 liter pH adjusted to 4.2 ______________________________________
The development was carried out for 15 seconds at 30° C. and the fix was carried out for 10 seconds at 30° C.
The sensitivity was evaluated as the reciprocal of the exposure amount necessary for obtaining blackened extent of 0.3+fog value, relative to the sensitivity of photographic material 1 defined as 100.
The results are shown in Table 1.
TABLE 1 __________________________________________________________________________ Amount of Photographic Halogen Grain Metal Metal Salt Sensi- Material Composition Form Salt Used (mol/mol-Ag) tivity __________________________________________________________________________ Cl 98 mol % 1 Cubic None 0 100 Br 2 mol % Cl 98 mol % 2 " K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 105 Br 2 mol % Cl 98 mol % 3 " K.sub.4 [Ru(CN).sub.6 ] 1 × 10.sup.-4 105 Br 2 mol % 4 Cl 100 mol % " None 0 100 5 " " K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 115 6 " " K.sub.4 [Ru(CN).sub.6 ] 1 × 10.sup.-4 110 Cl 98.5 mol % 7 Tabular None 0 90 Br 1.5 mol % Cl 98.5 mol % 8* Tabular K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 120 Br 1.5 mol % Cl 98.5 mol % 9* Tabular K.sub.4 [Ru(CN).sub.6 ] 1 × 10.sup.-4 120 Br 1.5 mol % 10 Cl 100 mol % " None 0 90 11* " " K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 135 12* " " K.sub.4 [Ru(CN).sub.6 ] 1 × 10.sup.-4 130 __________________________________________________________________________ *Invention
From the results shown in Table 1, it is seen that in the comparison of emulsions 1, 4, 7, and 10 containing no metal salt, cubic silver halide grains have a higher sensitivity than tabular silver halide grains. This result is obtained because the light absorption of tabular silver halide grains is less than that of cubic silver halide grains. However, when the silver halide grains are formed in the presence of iron or ruthenium, the tabular silver halide grains exhibit remarkedly higher sensitivity than the cubic silver halide grains despite less light absorption. The above results clearly show the effect of the present invention.
A silver halide emulsion was prepared in the same manner as emulsion 4 of Example 1. However, in this case, after completing the 1st and 2nd additions of the alkali halide, an aqueous solution containing 1.19 g of potassium bromide was added to carry out halogen conversion at the surface of the silver halide grains. Thereafter, the emulsion was dealt and washed. Then, 90 g of gelatin and 3 g of phenoxy ethanol were added, and the pH and pAg were adjusted to 6.5 and 7.5, respectively, to obtain the emulsion 13.
The same procedure as for preparing emulsion 13 was employed, except that iron was added to the aqueous alkali halide solutions being added in the 1st and 2nd additions in the form of an aqueous solution of K4 [Fe(CN)6 ] in an amount of 1×10-4 mol per mol of silver in the system, to prepare the emulsion 14.
A silver halide emulsion was prepared in the same manner as emulsion 10 in Example 1. However, in this case, after completing the addition of the solutions (4) and (5) an aqueous solution containing 1.19 g of potassium bromide was added to the emulsion to carry out halogen conversion of the surface of the silver halide grains.
Then, after desalting and washing with water, 90 g of gelatin and 3 g of phenoxy ethanol were added to the emulsion, and the pH and pAg thereof were adjusted to 6.5 and 7.5, respectively, to obtain the emulsion 15.
A silver halide emulsion was prepared in the same manner as emulsion 11 in Example 1.
In this case, however, after completing the addition of the solutions (4) and (5), an aqueous solution containing 1.19 g of potassium bromide was added to the emulsion to carry out halogen conversion of the surface of the silver halide grains.
By following the same procedure as Example 1, photographic materials 13 to 16 were prepared and were evaluated as in Example 1.
The results obtained are shown in Table 2 below.
TABLE 2 __________________________________________________________________________ Amount of Photographic Halogen Grain Metal Metal Salt Sensi- Material Composition Form Salt Used (mol/mol-Ag) tivity __________________________________________________________________________ 4 Cl 100 mol % Cubic None 0 100 Cl 99 mol % 13 " None 0 145 Br 1 mol % (Halogen conversion) Cl 99 mol % 14 " K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 160 Br 1 mol % (Halogen conversion) 10 Cl 100 mol % Tabular None 0 90 Cl 99 mol % 15 " None 0 130 Br 1 mol % (Halogen conversion) Cl 99 mol % 16* " K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 195 Br 1 mol % (Halogen conversion) __________________________________________________________________________ *Invention
From the results shown in Table 2, it can be seen that the effects of the present invention are further enhanced by using silver halide grains subjected to halogen conversion.
The same procedure as for preparing emulsion 5 was employed to prepare a silver halide emulsion which was not chemically sensitized. In this case, however, the pH and pAg were adjusted to 7.1 and 6.95, respectively.
To the emulsion, the following components were successively added to chemically sensitize the emulsion at 60° C.
______________________________________ (per mol of silver) ______________________________________ NaCl 1.79 × 10.sup.-2 mol KBr 1 × 10.sup.-2 mol Chloroauric Acid 5 × 10.sup.-5 mol Sodium Thiosulfate 5 × 10.sup.-5 mol 4-Hydroxy-6-methyl-1,3,3a,7- 5 × 10.sup.-3 mol tetraazaindene ______________________________________
Chemical ripening was carried out for 30 minutes after adding 4 hydroxy-6-methyl-1,3,3a,7-tetraazaindene.
The same procedure as for preparing the emulsion 11 of invention was employed to prepare emulsion which was not chemically sensitized. In this case, however, the pH and pAg thereof were adjusted to 7.1 and 6.95, respectively. The silver halide was then chemically sensitized in the same manner as emulsion 17 to obtain the emulsion 18 of the invention.
A silver chlorobromide emulsion was prepared as follows.
__________________________________________________________________________ Solution (1): Inactive Gelatin 30 g ##STR4## 0.8 g NaCl 4 g Water to make 1750 ml Solution (2): AgNO.sub.3 34 g Water to make 200 ml Solution (3): NaCl 12.5 g Water to make 200 ml Solution (4): AgNO.sub.3 102 g Water to make 600 ml Solution (5): NaCl 37.5 g Water to make 600 ml __________________________________________________________________________
To the solution (1) kept at 35° C. with vigorous stirring were simultaneously added the solution (2) and the solution (3) over a period of 10 minutes.
Furthermore, after raising the temperature of the mixture to 75° C., the solution (4) and the solution (5) were simultaneously added thereto over a period of 30 minutes.
The emulsion was desalted by an ordinary flocculation method and washed with water, and after adding thereto gelatin, the pH and pAg were adjusted to 6.4 and 7.5 at 40° C. to provide a tabular grain silver chloride emulsion.
The silver chloride emulsion thus prepared contained more than 80% (projected area) tabular grains having a thickness of less than 0.5 μm, a diameter of at least 0.5 μm, and aspect ratio of 2 or more and having parallel (111) planes. The tabular silver halide grains had a mean projected area of 1.8 μm2, a mean thickness of 0.22 μm, and a mean aspect ratio of 6.9.
To the tabular silver chloride emulsion was added a superfine grain silver bromide emulsion (grain size of about 0.05 μm) in an amount to provide 1 mol % silver bromide to silver chloride, and ripening was carried out for 10 minutes at 60° C. to provide an emulsion before chemical sensitization.
After adjusting, the pH and pAg of the emulsion to 7.1 and 7.8, respectively, the following components were successively added to chemically sensitize the emulsion at 60° C.
______________________________________ (per mol of silver) ______________________________________ NaCl 1.79 × 10.sup.-2 mol Chloroauric Acid 5 × 10.sup.-2 mol Sodium Thiosulfate 2 × 10.sup.-5 mol 4-Hydroxy-6-methyl-1,3,3a,7- 5 × 10.sup.-3 mol tetraazaindene ______________________________________
The chemical ripening time was 30 minutes.
The same procedure as for preparing the emulsion 19 was employed, except that iron was added to the solution (5) in the form of an aqueous solution of K4 [Fe(CN)6 ] in an amount of 1×10-4 per mol of silver in the system. Then, the emulsion was chemically sensitized in the same manner as emulsion 19.
Photographic materials 17 to 20 were prepared and evaluated in the same manner as in Example 1. The development process was carried out for 10 seconds at 35° C.
The results are shown in Table 3 below, wherein the sensitivity is indicated relative to the photographic material 4 defined as 100.
TABLE 3 __________________________________________________________________________ Amount of Photographic Halogen Grain Metal Metal Salt Chemical Sensi- Material Composition Form Salt Used (mol/mol-Ag) Sensitization tivity __________________________________________________________________________ 4 Cl 100 mol % Cubic None 0 None 100 17 Cl 99 mol % " K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 Gold 8500 sensitization + Br 1 sulfur sensitization 18* Cl 99 mol % Tabular K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 Gold 11200 sensitization + Br 1 sulfur sensitization 19 Cl 99 mol % " None 0 Gold 7950 sensitization + Br 1 sulfur sensitization 20* Cl 99 mol % " K.sub.4 [Fe(CN).sub.6 ] 1 × 10.sup.-4 Gold 12600 sensitization + Br 1 sulfur sensitization __________________________________________________________________________ *Invention
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (9)
1. A photographic silver halide emulsion comprising silver chorobromide grains containing at least 98.5 mol % silver chloride or silver chloride grains, wherein tabular grains having a thickness of less than 0.5 μm, a diameter of at least 0.5 μm and an aspect ratio of at least 2/1 account for at least 50% of the total projected area of the silver halide grains, and said tabular grains are formed in the presence of a compound of a metal belonging to Group VIII of the Periodic Table selected from the group consisting of iron, ruthenium and osmium.
2. A photographic silver halide emulsion as in claim 1, wherein the compound of a metal belonging to Group VIII of the Periodic Table is present in an amount of from 1×10-8 to 1×10-2 mol per mol of silver halide contained in the emulsion.
3. A photographic silver halide emulsion as in claim 1, wherein the tabular grains have an aspect ratio of from 3/1 to 8/1.
4. A photographic silver halide emulsion as in claim 1, wherein the tabular grains have a diameter of from 0.7 to 4 μm.
5. A photographic silver halide emulsion as in claim 1, wherein the tabular grains have a thickness of less than 0.3 μm.
6. A photographic silver halide emulsion as in claim 1, wherein the tabular grains account for at least 70% of the total projected area of the silver halide grains.
7. A photographic silver halide emulsion as in claim 1, wherein the silver chlorobromide grains contain at least 99% mol % silver chloride.
8. A photographic silver halide emulsion as in claim 1, wherein said tabular grains comprise a localized silver bromide phase near the surface of the grains.
9. A light-sensitive silver halide photographic material comprising a support having thereon at least one hydrophilic colloid layer, at least one layer of which is a light-sensitive silver halide emulsion layer comprising silver chlorobromide grains containing at least 98.5 mol % silver chloride or silver chloride grains, wherein tabular grains having a thickness of less than 0.5 μm, a diameter of at least 0.5 μm and an aspect ratio of at least 2/1 account for at least 50% of the total projected area of the silver halide grains, and said tabular grains are formed in the presence of a compound of a metal belonging to Group VIII of the Periodic Table selected from the group consisting of iron, ruthenium and osmium.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US07/989,508 USH1294H (en) | 1990-03-02 | 1992-12-11 | Silver halide photographic emulsion |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP2-51165 | 1990-03-02 | ||
JP5116590A JPH03252649A (en) | 1990-03-02 | 1990-03-02 | Emulsion for silver halide photography |
US66259191A | 1991-03-01 | 1991-03-01 | |
US07/989,508 USH1294H (en) | 1990-03-02 | 1992-12-11 | Silver halide photographic emulsion |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US66259191A Continuation | 1990-03-02 | 1991-03-01 |
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USH1294H true USH1294H (en) | 1994-03-01 |
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ID=27294231
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US07/989,508 Abandoned USH1294H (en) | 1990-03-02 | 1992-12-11 | Silver halide photographic emulsion |
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US (1) | USH1294H (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5508152A (en) * | 1992-12-07 | 1996-04-16 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide photographic material |
EP0731382A1 (en) * | 1995-02-21 | 1996-09-11 | Agfa-Gevaert N.V. | Method for processing an exposed photographic silver halide material |
EP0736797A2 (en) * | 1995-04-05 | 1996-10-09 | Konica Corporation | A silver halide photographic light-sensitive material and a manufacturing method of a silver halide emulsion |
US5637446A (en) * | 1994-06-14 | 1997-06-10 | Fuji Photo Film Co., Ltd. | Silver halide emulsion and photographic material having the same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2448060A (en) | 1945-08-30 | 1948-08-31 | Eastman Kodak Co | Photographic emulsions sensitized with salts of metals of group viii of the periodicarrangement of the elements |
US4783398A (en) | 1986-06-20 | 1988-11-08 | Fuji Photo Film Co., Ltd. | Photographic silver halide emulsion containing tabular grains of high chloride content |
US4952491A (en) | 1987-09-10 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive material and method of developing the same |
US5057402A (en) | 1988-01-18 | 1991-10-15 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US5166044A (en) | 1989-12-18 | 1992-11-24 | Fuji Photo Film Co., Ltd. | Silver halide emulsion and photographic material using same |
-
1992
- 1992-12-11 US US07/989,508 patent/USH1294H/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2448060A (en) | 1945-08-30 | 1948-08-31 | Eastman Kodak Co | Photographic emulsions sensitized with salts of metals of group viii of the periodicarrangement of the elements |
US4783398A (en) | 1986-06-20 | 1988-11-08 | Fuji Photo Film Co., Ltd. | Photographic silver halide emulsion containing tabular grains of high chloride content |
US4952491A (en) | 1987-09-10 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Photographic light-sensitive material and method of developing the same |
US5057402A (en) | 1988-01-18 | 1991-10-15 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US5166044A (en) | 1989-12-18 | 1992-11-24 | Fuji Photo Film Co., Ltd. | Silver halide emulsion and photographic material using same |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5508152A (en) * | 1992-12-07 | 1996-04-16 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide photographic material |
US5637446A (en) * | 1994-06-14 | 1997-06-10 | Fuji Photo Film Co., Ltd. | Silver halide emulsion and photographic material having the same |
EP0731382A1 (en) * | 1995-02-21 | 1996-09-11 | Agfa-Gevaert N.V. | Method for processing an exposed photographic silver halide material |
EP0736797A2 (en) * | 1995-04-05 | 1996-10-09 | Konica Corporation | A silver halide photographic light-sensitive material and a manufacturing method of a silver halide emulsion |
EP0736797A3 (en) * | 1995-04-05 | 1996-10-30 | Konica Corporation | A silver halide photographic light-sensitive material and a manufacturing method of a silver halide emulsion |
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