EP0426181B1 - Process for developing silver halide colour reversal photograhic material - Google Patents
Process for developing silver halide colour reversal photograhic material Download PDFInfo
- Publication number
- EP0426181B1 EP0426181B1 EP90120955A EP90120955A EP0426181B1 EP 0426181 B1 EP0426181 B1 EP 0426181B1 EP 90120955 A EP90120955 A EP 90120955A EP 90120955 A EP90120955 A EP 90120955A EP 0426181 B1 EP0426181 B1 EP 0426181B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- silver
- layer
- emulsion
- grains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silver halide Chemical class 0.000 title claims description 95
- 229910052709 silver Inorganic materials 0.000 title claims description 84
- 239000004332 silver Substances 0.000 title claims description 84
- 238000000034 method Methods 0.000 title claims description 48
- 239000000463 material Substances 0.000 title claims description 33
- 239000000839 emulsion Substances 0.000 claims description 86
- 238000011161 development Methods 0.000 claims description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 27
- 230000035945 sensitivity Effects 0.000 claims description 16
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 15
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 15
- 229940045105 silver iodide Drugs 0.000 claims description 15
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 13
- 230000003595 spectral effect Effects 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 76
- 238000012545 processing Methods 0.000 description 31
- 238000005406 washing Methods 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 27
- 230000000694 effects Effects 0.000 description 26
- 238000004061 bleaching Methods 0.000 description 25
- 239000002253 acid Substances 0.000 description 18
- 230000006641 stabilisation Effects 0.000 description 17
- 238000011105 stabilization Methods 0.000 description 17
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 14
- 235000002639 sodium chloride Nutrition 0.000 description 14
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 13
- 108010010803 Gelatin Proteins 0.000 description 12
- 229920000159 gelatin Polymers 0.000 description 12
- 239000008273 gelatin Substances 0.000 description 12
- 235000019322 gelatine Nutrition 0.000 description 12
- 235000011852 gelatine desserts Nutrition 0.000 description 12
- 238000011160 research Methods 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 9
- 230000000087 stabilizing effect Effects 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 235000019445 benzyl alcohol Nutrition 0.000 description 5
- 238000005282 brightening Methods 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000004989 p-phenylenediamines Chemical class 0.000 description 5
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 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 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 239000007844 bleaching agent Substances 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 3
- 235000019252 potassium sulphite Nutrition 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 101100221809 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cpd-7 gene Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 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
- 150000001639 boron compounds Chemical class 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- ZJEFVRRDAORHKG-UHFFFAOYSA-M potassium;2-hydroxy-5-sulfobenzoate Chemical compound [K+].OC1=CC=C(S(O)(=O)=O)C=C1C([O-])=O ZJEFVRRDAORHKG-UHFFFAOYSA-M 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229960004025 sodium salicylate Drugs 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical group C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 1
- 229940116368 1,2-benzisothiazoline-3-one Drugs 0.000 description 1
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical compound O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- IHDKBHLTKNUCCW-UHFFFAOYSA-N 1,3-thiazole 1-oxide Chemical class O=S1C=CN=C1 IHDKBHLTKNUCCW-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
- ZQXIMYREBUZLPM-UHFFFAOYSA-N 1-aminoethanethiol Chemical compound CC(N)S ZQXIMYREBUZLPM-UHFFFAOYSA-N 0.000 description 1
- XEFAJZOBODPHBG-UHFFFAOYSA-N 1-phenoxyethanol Chemical class CC(O)OC1=CC=CC=C1 XEFAJZOBODPHBG-UHFFFAOYSA-N 0.000 description 1
- FBJAGEQLOUPXHL-UHFFFAOYSA-N 1-sulfanylethanesulfonic acid Chemical compound CC(S)S(O)(=O)=O FBJAGEQLOUPXHL-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- JBAITADHMBPOQQ-UHFFFAOYSA-N 2-(1h-benzimidazol-2-yl)-1,3-thiazole Chemical compound C1=CSC(C=2NC3=CC=CC=C3N=2)=N1 JBAITADHMBPOQQ-UHFFFAOYSA-N 0.000 description 1
- QADPIHSGFPJNFS-UHFFFAOYSA-N 2-(1h-benzimidazol-2-ylmethyl)-1,3-thiazole Chemical compound N=1C2=CC=CC=C2NC=1CC1=NC=CS1 QADPIHSGFPJNFS-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QTLHLXYADXCVCF-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methylanilino)ethanol Chemical compound OCCN(CC)C1=CC=C(N)C(C)=C1 QTLHLXYADXCVCF-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
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- PDHFSBXFZGYBIP-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical compound OCCSCCSCCO PDHFSBXFZGYBIP-UHFFFAOYSA-N 0.000 description 1
- GRUVVLWKPGIYEG-UHFFFAOYSA-N 2-[2-[carboxymethyl-[(2-hydroxyphenyl)methyl]amino]ethyl-[(2-hydroxyphenyl)methyl]amino]acetic acid Chemical compound C=1C=CC=C(O)C=1CN(CC(=O)O)CCN(CC(O)=O)CC1=CC=CC=C1O GRUVVLWKPGIYEG-UHFFFAOYSA-N 0.000 description 1
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 1
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- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- RILRIYCWJQJNTJ-UHFFFAOYSA-M sodium;3-carboxy-4-hydroxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(S([O-])(=O)=O)=CC=C1O RILRIYCWJQJNTJ-UHFFFAOYSA-M 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical group [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical class SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZOPCDOGRWDSSDQ-UHFFFAOYSA-N trinonyl phosphate Chemical compound CCCCCCCCCOP(=O)(OCCCCCCCCC)OCCCCCCCCC ZOPCDOGRWDSSDQ-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/50—Reversal development; Contact processes
Definitions
- the present invention relates to a process for developing silver halide color reversal photographic materials excellent in color reproducibility.
- a color reversal photographic material has a plurality of silver halide emulsion layers different in color sensitivity such as a red sensitive layer, a green sensitive layer and a blue sensitive layer on a support.
- the color reversal photographic material which has been image exposed to a polychromatic object is first subjected to black-and-white silver development at a first developing stage, and then the residual silver halide is color developed at a second developing stage through a chemical or optical fogging stage to form cyan, magenta and yellow color images.
- a dye image usually formed on each color sensitive layer by polychromatic exposure is different from a dye image produced by monochromatic exposure.
- this difference is mainly caused by the transfer of a development restrainer such as iodine ions generated between the emulsion layers different in color sensitivity at the black-and-white developing stage.
- a development restrainer such as iodine ions generated between the emulsion layers different in color sensitivity at the black-and-white developing stage.
- the dye image difference between the polychromatic exposure and the monochromatic exposure caused by such development is called a multilayer effect or an inter image effect as described in Hudson and Horton, Journal of the Optical Society of America 42 (No. 9), pp. 663 to 669 (1976), and known to be available for improving sharpness and color reproducibility.
- JP-A-51-128528 discloses a process for enhancing the multilayer effect given to a sensitive silver halide emulsion layer by introducing an emulsion which has fogged the surfaces of silver halide grains into the sensitive silver halide emulsion layer.
- Research Disclosure No. 13553 (1975) also discloses a process for application of the preferable multilayer effect by iodine ions in a color reversal photographic material, which comprises adding an emulsion containing a silver halide so as to release the iodine ion such as AgBrI, AgClI or AgBrClI to at least one layer to which the multilayer effect is applied, adding a hydrophilic colloid as well as usual emulsion grains to at least one layer to which the multilayer effect is given, and further adding another surface fogging emulsion.
- the above-described references do not fully disclose the features of the more preferred sensitive silver halide emulsion in enhancing the multi layer effect utilizing the fogging emulsion.
- the sensitive silver halide emulsion is developed depending on the amount of exposure.
- the silver halide emulsion grains not developed are subjected to the color developing processing through the fogging stage.
- This color developing stage is required to develop all the residual silver halide to develop color, so that its developing activity is designed to be high. For this reason, it is substantially almost impossible to make the multilayer effect function at the color developing stage, and, in the color reversal photographic materials, the multilayer effect is substantially determined by the black-and-white developing stage.
- the developing solution has the effect of dissolving the emulsion grains.
- This solubility is controlled by the iodine ions diffused by the development of the other layers, whereby the multilayer effect is obtained.
- the multilayer effect is produced according to many mechanisms, the most important mechanism of them is the above one.
- EP-A-0 272 675 describes a silver halide photographic material comprising a support having thereon at least one silver halide emulsion layer composed of one or more layers, wherein the silver halide emulsion contained in at least one layer of the silver halide emulsion layer is chemically sensitized so that silver halide grains in the emulsion have at least one maximum value of the latent image number in distribution thereof in the inside of the silver halide grains and the position where the maximum value(s) exists is at a depth of less than 0.01 ⁇ m from the surface of the grains, and the emulsion also has a latent image number of at least 1/5 of the largest maximum value but less than the largest maximum value on the surface of the grains.
- US-A-4 804 616 describes a method for continuously processing a color reversal photographic material. After black and white development, the color reversal photographic material is rinsed in a bath wherein the replenishing amount per unit area of the photographic material is 3 to 50 times as much as the amount of processing solution carried over from the preceding bath in terms of volume ratio and the pH is 9.5 or below.
- US-A-4 839 268 describes a silver halide color reversal photosensitive material comprising a plurality of silver halide emulsion layers on a substrate, wherein 50 % or more of the total projected area of silver halide grains contained in at least one of said silver halide emulsion layers is occupied by tabular silver iodobromide grains having an average thickness of 0.5 micron or less, an average diameter of 0.5 micron or more, an average aspect ratio of at least 5/1, and a silver iodide content of 4.0 mol % or less, and said tabular silver iodobromide grains are negative-type silver halide grains forming a latent image mainly inside the grains.
- the object of the present invention is attained by a process for developing a silver halide color reversal photographic material comprising a support having provided thereon at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, wherein at least one silver halide emulsion layer contains tabular silver halide grains having an aspect ratio of at least 5 occupying at least 50% of all silver halide grains existing in the same layer as a projected area, and having a mean sphere-corresponding grain size of 0.30 ⁇ m or less, which comprises developing said color reversal photographic material with a black-and-white developing solution for 100 seconds or less.
- the mean sphere-corresponding grain size of the silver halide emulsion grains contained in at least one emulsion layer is 0.25 ⁇ m or less.
- the lower limit thereof is preferably 0.1 ⁇ m from the view point of sensitivity.
- the measuring methods of the mean sphere-corresponding grain size of silver halide grains are described in detail, for example, in James, The Theory of Photographic Process , the 4th edition, page 100. Such methods include methods using an optical microscope, an electron microscope and a coulter counter. When the size of such a degree as the size of the emulsion grains of the present invention is measured, a method is preferably used in which the thickness of the grains is determined from the projected area of the grains and the length of shadows obtained by shadowing, using an electron microscope, the volume of each grain is determined therefrom, and the mean sphere-corresponding grain size is determined from the mean value thereof.
- silver halide grains used in the present invention monodisperse emulsions narrow in grain size distribution or polydisperse emulsions wide in grain size distribution may be used.
- At least one sensitive emulsion layer contains the tabular silver halide emulsion grains having a mean sphere-corresponding grain size of 0.30 ⁇ m or less and an aspect ratio of at least 5 so as to occupy at least 50% of all silver halide grains existing in the same layer as a projected area. It is further preferred that at least one layer contains tabular silver halide emulsion grains having an aspect ratio of at least 8 so as to occupy at least 50% of all silver halide grains existing in the same layer as a projected area.
- the aspect ratio called here means the ratio of diameter to thickness of the emulsion grain.
- the diameter of the silver halide grain means the diameter of a circle whose area is the same as the projected area of the grain.
- the tabular silver halide grain has two planes parallel to each other, and the thickness called here is represented by the distance between the two parallel planes constituting the tabular silver halide grain.
- silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and silver chloride may be used as the tabular silver halide grains.
- silver bromide and silver iodobromide are preferably used.
- the tabular silver halide grains can be prepared by suitable combinations of methods known in the art.
- the tabular silver halide grains can be obtained by simultaneous addition of silver and a halogen solution with maintaining the pBr value as relatively low as 1.3 or less.
- the size of the tabular silver halide grains can be adjusted by temperature control, selection of the kind or amount of solvent, selection of the kind of silver salt used on grain growth and control of the addition rate of the halide.
- solvents for silver halides can be used as required.
- the solvents for silver halides frequently used include ammonia, thioethers and thiourea compounds.
- thioethers for the thioethers, reference can be made to U.S. Patents 3,271,157, 3,790,387 and 3,574,628.
- the above-described at least one sensitive emulsion layer means at least one layer of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer.
- Each of the above-described emulsion layers may consist of a plurality of layers having a similar spectral sensitivity as long as at least one of those layers meets the above-described requirements.
- a low-sensitive emulsion layer is preferably used from the viewpoint of sensitivity.
- an emulsion layer in most close proximity thereto meets the above-described requirements.
- This yellow colloidal silver is known to be prepared by various methods.
- Silver halide grains used in the present invention other than the tabular silver halide grains which have a mean sphere-corresponding grain size of 0.30 ⁇ m or less and an aspect ratio of at least 5, are hereinafter described.
- the silver halide grains may have a regular crystal form such as a cubic, an octahedral or a tetradecahedral form, an irregular crystal form such as a spherical or a tabular form, crystalline defects such as a twin plane, or a composite form thereof.
- the silver halide grains may be fine grains having a grain size of about 0.2 ⁇ m or less or large sized grains having a projected area diameter of up to about 10 ⁇ m.
- the silver halide grains may be used as a monodisperse emulsion or a polydisperse emulsion.
- a monodisperse emulsion having a coefficient of variation of not more than 20% is preferably used.
- Such photographic silver halide emulsions can be prepared by using the methods described in Research Disclosure No. 17643, pages 22 and 23, I. "Emulsion Preparation and Types" (December, 1978), ibid. , No. 18716 (November, 1979), P. Glafkides, Chimie et Physique Photographique , (Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966) and V.L. Zelikman et al, Making and Coating Photograhic Emulsion (Focal Press, 1964).
- the silver halide emulsions used in the photographic materials of the present invention are generally subjected to physical ripening, chemical ripening and spectral sensitization, and then used.
- the above-described emulsion grains may be of a so-called surface latent image type in which latent images are mainly formed on the surface of the grains or of a so-called internal latent image type in which the latent images are mainly formed in the insides of the grains. Additives used in such stages are described in Research Disclosure No. 17643 and ibid. , No. 18716, and the corresponding portions are summarized in a table shown later.
- the crystal structure may be uniform, or the interior and the exterior of the grain may be composed of different halogen compositions, respectively.
- the crystal structure may also be a laminar structure.
- Silver halides different in composition may be joined together by epitaxial junction. Further, silver halides may be joined to compounds other than silver halides, such as silver rhodanine and lead oxide.
- Dye image stabilizers Page 25 9. Hardeners Page 26 Page 651, left column 10. Binders Page 26 - ditto - 11. Plasticizers, lubricants Page 27 Page 650, right column 12. Coating aids, surfactants Pages 26 to 27 - ditto - 13. Antistatic agents Page 27 - ditto -
- phenoxyethanol compounds in addition to phenol, there can be used phenoxyethanol compounds, p-hydroxybenzoic butylate, Proxel (benzoisothiazoline) and sodium salicylate.
- color couplers can be used in the present invention. Specific examples thereof are described in the patent specifications cited in the above-described Research Disclosure No. 17643, VII-C to G.
- yellow couplers there can be preferably used the compounds described, for example, in US-A 3,933,501, 4,022,620, 4,326,024 and 4,401,752, JP-B-58-10739 (the term "JP-B” as used herein means an "examined Japanese patent publication"), GB-B-1,425,020 and 1,476,760.
- magenta couplers 5-pyrazolone and pyrazoloazole compounds are preferably used, and there are particularly preferred the compounds described in US-A-4,310,619 and 4,351,987, EP-A-73,636, US-A-3,061,432 and 3,725,067, Research Disclosure , No. 24220 (June, 1984), JP-A-60-33552, Research Disclosure , No. 24230 (June, 1984), JP-A-60-43659, US-A-4,500,630 and 4,540,654.
- Cyan couplers include phenol and naphthol compounds, and there are preferably used the compounds described in US-A-4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, DE-A-3,329,729, EP-A-121,365, US-A-3,446,622, 4,333,999, 4,451,559 and 4,427,767, and EP-A-161,626.
- couplers which give formed dyes having appropriate diffusivity there are preferably used the compounds described in US-A-4,366,237, GB-B-2,125,570, EP-B-96,570 and DE-A-3,234,533.
- Couplers which release photographically useful residues in coupling can also be preferably used in the present invention.
- DIR couplers which release development inhibitors there are preferred the compounds described in JP-A-57-151944, JP-A-57-154234, JP-A-60-184248 and U.S. Patent 4,248,962 cited in the above-described Research Disclosure , No. 17643, Item VII-F.
- couplers which release nucleating agents or development accelerators in the form of images on development there are preferably used the compounds described in GB-B-2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840.
- couplers which can be used in the photographic materials in the present invention include the competitive couplers described in US-A-4,130,427, the multiequivalent couplers described in US-A-4,283,472, 4,338,393 and 4,310,618, the couplers which release DIR redox compounds described in JP-A-60-185950, and the couplers which release dyes recolored after separation described in EP-A-173,302.
- the couplers used in the present invention can be incorporated in the photographic materials by various known dispersion methods.
- the first developing (black-and-white developing) stage for the color reversal photographic materials of the present invention is conducted for 100 seconds or less. When this stage is conducted for 60 seconds or less, the effect of the present invention becomes more remarkable. It is preferred from the viewpoint of productivity that the first developing time is shorter.
- the stages from black-and-white development (first development) to color development are as follows:
- Each of the washing stages in procedures 1 to 3 can be replaced by the rinsing stage described in US-A-4,804,616 to simplify the processing and reduce the amount of liquid wastes.
- black-and-white developing agents can be used alone or in combination.
- Such developing agents include dihydroxybenzenes such as hydroquinone; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone; aminophenols such as N-methyl-p-aminophenol; 1-phenyl-3-pyrazoline; ascorbic acid; and heterocyclic compounds such as a condensed compound of a 1,2,3,4-tetrahydroquinoline ring and an indolene ring described in US-A-4,067,872.
- the black-and-white developing solutions used in the present invention may contain preservatives such as sulfites and bisulfites; buffers such as carbonates, boric acid, borates and alkanolamines; alkali agents such as hydroxides and carbonates; solubilizing auxiliaries such as polyethylene glycol and esters thereof; water softeners such as aminopolycarboxylic acids and organic phosphonic acids; pH regulators, for example, organic acids such as acetic acid; sensitizers such as quaternary ammonium salts; development accelerators; surface active agents; antifoaming agents; hardening agents; antifoggants such as potassium iodide, potassium bromide and benzotriazole; and viscosity imparting agents, if necessary.
- preservatives such as sulfites and bisulfites
- buffers such as carbonates, boric acid, borates and alkanolamines
- alkali agents such as hydroxides and carbonates
- the black-and-white developing solutions used in the present invention are required to contain compounds acting as solvents for silver halides, the above-described sulfites added as the preservatives generally play its role.
- Specific examples of the sulfites include K 2 SO 3 , Na 2 SO 3 , K 2 S 2 O 5 , Na 2 S 2 O 5 , K 2 S 2 O 3 and Na 2 S 2 O 3 .
- this black-and-white developing solution contains at least one kind of rhodanide.
- rhodanides include potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate.
- the content of these compounds is preferably 0.01 to 50 g/l, and more preferably 0.05 to 10 g/l.
- the pH of the black-and-white developing solutions is selected so as to give a desired density and contrast, and ranges from about 8.5 to about 11.5.
- Reversal baths used after the black-and-white development can contain fogging agents known in the art.
- fogging agents include stannous ion complex salts such as stannous ion-organic phosphoric acid complex salts (US-A-3,617,282), stannous ion-organic phosphonocarboxylic acid complex salts (JP-B-56-32616) and stannous ion-aminopolycarboxylic acid complex salts (GB-B-1,209,050); boron compounds such as hydrogenated boron compounds (US-A-2,984,567) and heterocyclic amineborane compounds (British Patent 1,011,000).
- the pH of the fogging baths extends over a wide range from an acidic side to a basic side of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
- optical reversal processing by reexposure may be carried out.
- the reversal stage can be omitted by adding the above-described fogging agents to the color developing solutions.
- aromatic primary amine color developing agents used in the color developing solutions in the present invention.
- p-Phenylenediamine derivatives are preferable. Typical examples thereof are shown below, but the p-phenylenediamine derivatives are not limited thereto.
- compounds D-2, D-4, D-5 and D-6 are particularly preferable.
- p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates.
- the above aromatic primary amine developing agents are used preferably in an amount of about 0.1 to about 20 g, and more preferably in an amount of about 0.5 to 15 g per liter of developing solution.
- a color developing solution substantially free from benzyl alcohol may be used.
- the color developing solution substantially free from benzyl alcohol means a color developing solution containing benzyl alcohol at a concentration of not more than 3 ⁇ 10 -2 mol per liter of developing solution, preferably free from benzyl alcohol.
- the sulfites contained in the color developing solutions used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite and potassium metabisulfite.
- the amount of the sulfites added to the developing solutions is preferably 1 ⁇ 10 -5 to 5 ⁇ 10 -2 mol, more preferably 1 ⁇ 10 -4 to 5 ⁇ 10 -2 mol, and further more preferably 1 ⁇ 10 -4 to 2 ⁇ 10 -2 mol per liter of developing solution.
- preservatives there may be contained various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349 and aromatic polyhydroxy compounds described in U.S. Patent 3,746,544, as required.
- the aromatic polyhydroxy compounds are preferably added.
- the pH of the color developing solutions used in the present invention is preferably 9 to 14, and more preferably 9 to 13.
- To the color developing solutions can be added other known constituent compounds of the color developing solutions.
- the buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
- the buffers used in the present invention are not limited to these compounds.
- the above-described buffers are added to the color developing solutions preferably in an amount of at least 0.1 mol/l, and particularly preferably in an amount of 0.1 to 0.4 mol/l.
- various chelating agents can be used in the color developing solutions as suspending agents for calcium or magnesium or to improve the stability of the color developing solutions.
- organic acid compounds are preferably used.
- the chelating agents include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Specific examples thereof include, but are not limited to, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N′,N′-tetramethylenediphosphonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycoletherdiaminetetraacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and N,N′-bis(2-hydroxybenzyl)ethylened
- These chelating agents may be added in any amount as long as the amount is enough to block metal ions in the color developing solutions. For example, they are added in an amount of about 0.1 to about 10 g/l.
- Any development accelerators may be added to the color developing solutions as required.
- Such development accelerators include p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554, quaternary ammonium salts described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, amine compounds described in US-A-2,494,903, 3,128,182, 4,230,796 and 3,253,919, JP-B-41-11431, US-A-2,482,546, 2,596,926 and 3,582,346, polyalkylene oxides described in JP-B-37-16088, JP-B-42-25201, US-A-3,128,183, JP-B-41-11431, JP-B-42-23883 and US-A-3,532,501, 1-phenyl-3-pyrazolidone compounds and imidazole compounds.
- any antifoggants may be added as required.
- the antifoggants there can be used alkaline metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants.
- the organic antifoggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.
- the color developing solutions used in the present invention may contain fluorescent brightening agents.
- fluorescent brightening agents 4,4′-diamino-2,2′-disulfostilbene compounds are preferably used. They are added in an amount of 0 to 5 g/l, and preferably in an amount of 0.1 to 4 g/l.
- the processing temperature of the color developing solutions in the present invention is 20 to 50°C, and preferably 30 to 40°C.
- the processing time is 20 seconds to 8 minutes, and preferably 30 seconds to 6 minutes. It is preferred that the replenishment rate of the color developing solutions is minimized.
- the replenishment rate is however 100 to 3,000 ml/m 2 of photographic material, preferably 100 to 2,500 ml/m 2 , and more preferably 100 to 2,000 ml/m 2 .
- the color developing bath may be divided into two or more baths as required, and the foremost bath or the hindmost bath thereof may be replenished with the color developing solution to shorten the developing time and reduce the replenishment rate.
- the color developing solutions used in the present invention may contain so-called competitive compounds such as citrazinic acid, J acid and H acid which react with the oxidation product of the color developing agents to form colorless compounds.
- the photographic materials are subjected to the bleaching processing or the bleach-fixing processing after color development. These processing may be carried out immediately after color development without any other processing stages, or after processing stages such as termination, compensation and washing after the color developing stage.
- Solutions used for the above-described compensation may contain aminopolycarboxylic acids such as ethylenediaminetetraacetlc acid and diethylenetriaminepentaacetic acid; sulfites such as sodium sulfite and ammonium sulfite; and bleaching accelerators such as thioglycerin, aminoethanethiol and sulfoethanethiol.
- the compensating solutions contain sorbitan esters of fatty acids substituted with ethylene oxide described in U.S. Patent 4,839,262 or polyoxyethylene compounds described in US-A-4,059,446 and Research Disclosure , Vol. 191, No. 19104 (1980).
- Bleaching agents used in bleaching solutions and/or bleach-fixing solutions include ferric complex salts of aminopolycarboxylic acids and peroxide such as sodium persulfate.
- the ferric complex salts of aminopolycarboxylic acids are preferably used.
- aminopolycarboxylic acids of such ferric complex salts include ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, glycoletherdiaminetetraacetic acid, cyclohexanediaminetetraacetic acid, 1,4-diaminobutanetetraacetic acid, 1,2-propylenediaminetetraacetic acid, thioglycoletherdiaminetetraacetic acid, 1,3-butylenediaminetetraacetic acid and methyliminodiacetic acid.
- the above-described bleaching agents are added in an amount of 0.05 to 1 mol per liter of bleaching solution or blech-fixing solution, and preferably in an amount of 0.1 to 0.5 mol.
- aminopolycarboxylates may be added to the bleaching solutions and/or the bleach-fixing solutions used in the present invention.
- the aminopolycarboxylates are added preferably in an amount of 0.0001 mol to 0.1 mol/l, and more preferably in an amount of 0.003 to 0.05 mol/l.
- aminopolycarboxylates and the ferric complex salts thereof are usually used in the form of alkali metal salts or ammonium salts.
- the ammonium salts are preferable because of their excellent solubility and bleaching ability.
- bleaching accelerators may be added to the bleaching solutions and/or the bleach-fixing solutions used in the present invention.
- bleaching accelerators there are preferably used, for example, mercapto group- or disulfide group-containing compounds described in US-A-3,893,858, DE-C-1,290,812, GB-B-1,138,842, JP-A-53-95630 and Research Disclosure , No. 17129 (July, 1978).
- the bleaching accelerators are added in an amount of 0.01 to 20 g per liter of solution having bleaching ability, and preferably in an amount of 0.1 to 10 g.
- the bleaching solutions and/or the bleach-fixing solutions used in the present invention may contain rehalogenating agents such as bromides (for example, potassium bromide, sodium bromide and ammonium bromide) and chlorides (for example, potassium chloride, sodium chloride and ammonium chloride) in addition to the bleaching agents and the above-described compounds.
- rehalogenating agents such as bromides (for example, potassium bromide, sodium bromide and ammonium bromide) and chlorides (for example, potassium chloride, sodium chloride and ammonium chloride) in addition to the bleaching agents and the above-described compounds.
- concentration of the rehalogenating agents is 0.1 to 5 mols per liter of bleaching solution, and preferably 0.5 to 3 mols.
- nitrates such as sodium nitrate and ammonium nitrate
- inorganic acids, organic acids and salts thereof having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid.
- the bleach-fixing solutions and/or fixing solutions used in the present invention may contain thiosulfates as fixing agents.
- the thiosulfates are added in an amount of 0.1 to 3 mols/l, and preferably in an amount of 0.3 to 2 mols/l.
- the thiosulfate compounds include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate and magnesium thiosulfate.
- ammonium thiosulfate is preferably used because of its good solubility and highest rate of fixing.
- thiocyanic acid compounds particularly the ammonium salt thereof
- thiourea thioethers
- urea urea and the like
- the total concentration of these supplementary fixing agents or fixing accelerators and the thiosulfate compounds is 1.11 to 3.0 mols/l, and preferably 1.4 to 2.8 mols/l.
- the bleach-fixing solutions and/or the fixing solutions used in the present invention may contain sulfites such as sodium sulfite, potassium sulfite and ammonium sulfite, hydroxylamine and hydrazine as preservatives. Further, they may contain various fluorescent brightening agents, antifoaming agents, surface active agents and organic solvents such as polyvinyl pyrrolidone and methanol. In particular, it is preferred that the sulfinic acid compounds described in JP-A-62-143048 are used as the preservatives.
- aminopolycarboxylic acids and organic phosphonic acids are preferably added to the solutions.
- 1-hydroxyethylidene-1,1-diphosphonic acid is effective.
- These compounds are added in an amount of 0.01 to 0.3 mol/l, and preferably in an amount of 0.05 to 0.2 mol/l, which is particularly effective in the fixing solutions.
- the pH of the bleaching solutions and/or the bleach-fixing solutions used in the present invention is generally 1 to 9, preferably 1.5 to 7.5, and more preferably 2.0 to 7.0. In particular, it is preferred that the pH of the bleaching solutions is 2.0 to 5.0. Within the preferred range of pH, little fogging takes place in bleaching and the silver removal property is also excellent.
- the pH of the fixing solutions used in the present invention is usually 5.0 to 9.0, and particularly preferably 5.5 to 7.5.
- additives may be added to rinsing water used in the washing stage as so desired.
- water softeners such as inorganic phosphoric acid compounds, aminopolycarboxylic acids and organic phosphoric acid compounds; disinfectants and antifungal agents to prevent various bacteria and duckweeds from proliferating such as isothiazolone, organic chlorine disinfectants and benzotriazole; and surface active agents to prevent dry load and unevenness.
- disinfectants and antifungal agents to prevent various bacteria and duckweeds from proliferating such as isothiazolone, organic chlorine disinfectants and benzotriazole
- surface active agents to prevent dry load and unevenness.
- Processing solutions for stabilizing dye images are used as stabilizing solutions used in the stabilization stage.
- solutions having a pH of 3 to 6 and buffering ability can be used, and solutions containing aldehydes such as glutaraldehyde.
- Formalin is unfavorable in terms of environmental pollution.
- ammonium compounds metal compounds such as Bi and Al, fluorescent brightening agents, chelating agents such as EDTA and 1-hydroxyethylidene-1,1-diphosphonic acid, disinfectants, antifungal agents, hardening agents, surface active agents and the like.
- Thiazolone compounds such as 5-chloro-2-mwethylisothiazoline-3-one and 1,2-benzisothiazoline-3-one are effective as the antifungal agents.
- alkanolamines are preferably added to the stabilizing solutions.
- the pH of the stabilizing solutions used in the present invention is 3 to 8, and preferably 5 to 7.
- the temperature of the stabilizing solutions is preferably 5 to 45°C, and more preferably 10 to 40°C. It is preferred that a multistage countercurrent process is used as the washing stage or the stabilization stage.
- the number of stages is preferably 2 to 4. Two or more kinds of stabilizing solutions may be used in multiple stage.
- the replenishment rate is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount of the solution brought in from the preceding bath per unit area.
- water used in the washing stage or the stabilization stage are preferred water deionized with an ion-exchange resin to Ca and Mg concentrations of 5 mg/l or less, respectively, and water sterilized with a halogen bactericidal lamp or an ultraviolet bactericidal lamp, in addition to tap water.
- Cubic grains of silver iodobromide (silver iodide: 2.5 mol%) were prepared by the controlled double jet process in the presence of ammonia.
- the mean sphere-corresponding grain size of the resulting grains was 0.35 ⁇ m.
- the grains were subjected to chemical sensitization simultaneously using gold and sulfur.
- the emulsion thus obtained was named Emulsion A. 60% by weight of the emulsion grains had grain sizes within 18% from the mean grain size.
- a cubic grain emulsion having a mean sphere-corresponding grain size of 0.27 ⁇ m was prepared by adjusting the temperature in forming the grains of Emulsion A.
- the resulting grains were silver iodobromide grains containing 2.5 mol% of silver iodide.
- Emulsion C This emulsion was subjected to chemical sensitization simultaneously using gold and sulfur.
- the tabular silver halide emulsion thus obtained was named Emulsion C.
- the grains of Emulsion C had a mean sphere-corresponding grain size of 0.35 ⁇ m.
- Emulsion D which had a mean sphere-corresponding grain size of 0.28 ⁇ m, in which 53% of all grains as a projected area were composed of grains having an aspect ratio of at least 5, and which contained 2.5% of silver iodide.
- Emulsion E which had a mean sphere-corresponding grain size of 0.21 ⁇ m, in which 53% of all grains as a projected area were composed of grains having an aspect ratio of at least 5, and which contained 2.5% of silver iodide.
- Emulsion F which had a mean sphere-corresponding grain size of 0.21 ⁇ m, in which 55% of all grains as a projected area were composed of grains having an aspect ratio of at least 8, and which contained 2.5% of silver iodide.
- Phenoxyethanol was added to Emulsions A to F as a preservative in an amount of 40,000 ppm based on gelatin.
- a paper support both sides of which had been laminated with polyethylene was coated with the following first to twelfth layers to prepare a multilayer color photographic material, which was named Sample 101.
- Polyethylene on the side of the first layer to be coated contained titanium oxide as a white pigment and a slight amount of ultramarine as a bluing dye.
- each sensitive layer is shown below.
- Numerals for the components indicate coated amounts represented in g/m 2 .
- Numerals for the silver halides indicate coated amounts converted to silver.
- Silver iodobromide EM1 (silver iodide: 4 mol%, mean grain size: 0.4 ⁇ m, cubic) spectrally sensitized with red-sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.06
- Silver iodobromide EM2 (silver iodide: 5 mol%, mean grain size: 0.50 ⁇ m, cubic) spectrally sensitized with red-sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.10 Gelatin 1.00 Cyan coupler (ExC-1) 0.14 Cyan coupler (ExC-2) 0.07 Antifading agent (Cpd-2, Cpd-3, Cpd-4 and Cpd-9 in equivalent amounts) 0.12 Dispersion medium (Cpd-5) for coupler 0.03 Solvent (Solv-1, Solv-2 and Solv-3) for coupler 0.06
- Silver iodobromide EM3 (silver iodide: 6 mol%, mean grain size: 0.75 ⁇ m, twin) spectrally sensitized with red-sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.15 Gelatin 1.00 Cyan coupler (ExC-1) 0.20 Cyan coupler (ExC-2) 0.10 Antifading agent (Cpd-2, Cpd-3, Cpd-4 and Cpd-9 in equivalent amounts) 0.15 Dispersion medium (Cpd-5) for coupler 0.03 Solvent (Solv-1, Solv-2 and Solv-3) for coupler 0.10
- Silver iodobromide EM4 (silver iodide: 3.5 mol%, mean grain size: 0.6 ⁇ m, twin) spectrally sensitized with green-sensitizing dye (ExS-4) 0.10 Magenta coupler (ExM-1) 0.05 Magenta coupler (ExM-2) 0.05 Antifading agent (Cpd-9) 0.10 Stain inhibitor (Cpd-10) 0.01 Stain inhibitor (Cpd-11) 0.001 Stain inhibitor (Cpd-12) 0.01 Dispersion medium (Cpd-5) for coupler 0.05 Solvent (Solv-4 and Solv-6) for coupler 0.15
- Silver iodobromide EM7 (silver iodide: 2.5 mol%, mean grain size: 1.2 ⁇ m, twin) spectrally sensitized with blue-sensitizing dyes (ExS-5 and ExS-6) 0.25 Gelatin 1.00 Yellow coupler (ExY-1) 0.40 Stain inhibitor (Cpd-11) 0.002 Antifading agent (Cpd-6) 0.10 Dispersion medium (Cpd-5) for coupler 0.15 Solvent (Solv-2) for coupler 0.10
- Fine grains of silver chlorobromide (silver chloride: 97 mol%, mean grain size: 0.2 ⁇ m) 0.07 Modified poval 0.02 Gelatin 1.50 Gelatin hardener (H-1) 0.17
- alkanol XC Du Pont de Nemours Co.
- sodium alkylbenzenesulfonate as emulsifying dispersion aids
- succinic ester and Magefac F-120 (Dainippon Ink & Chemical Inc.) as coating aids.
- Cpd ⁇ 19, Cpd-20 and Cpd-21 were used as stabilizers in the silver halide-containing layers and the colloidal silver-containing layers.
- the compounds used in Example are shown below: Cpd-8 Polyethylacrylate
- Samples 102 to 106 were prepared by replacing Emulsion A contained in the sixth layer of Sample 101 by Emulsions B to F, respectively. Further, Sample 107 was prepared by replacing yellow colloidal silver contained in the fifth layer of Sample 104 by black colloidal silver.
- Emulsion Mean Sphere-Corresponding Grain Size Form Colloidal Silver of Fifth Layer ( ⁇ m) 101 (Comparison) A 0.35 Cubic Yellow colloidal silver 102 (Comparison) B 0.27 Cubic Yellow colloidal silver 103 (Comparison) C 0.35 Tabular aspect ratio: 5 Yellow colloidal silver 104 (Invention) D 0.28 Tabular aspect ratio: 5 Yellow colloidal silver 105 (Invention) E 0.21 Tabular aspect ratio: 5 Yellow colloidal silver 106 (Invention) F 0.21 Tabular aspect ratio: 8 Yellow colloidal silver 107 (Invention) D 0.28 Tabular aspect ratio: 5 Black colloidal silver
- Pentasodium nitrilo-N,N,N-trimethylenephosphonate 0.6 g Pentasodium diethylenetriaminepentaacetate 4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1.2 g Potassium carbonate 35.0 g Potassium hydroquinonemonosulfonate 25.0 g Diethylene glycol 15.0 ml 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g Potassium bromide 0.5 g Potassium iodide 5.0 mg Water to make 1 l (pH: 9.70)
- Benzyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Pentasodium nitrilo-N,N,N-trimethylene phosphonate 0.5 g Pentasodium diethylenetriaminepentaacetate 2.0 g Sodium sulfite 2.0 g Potassium carbonate 25.0 g Hydroxylamine sulfate 3.0 g N-Ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g Potassium bromide 0.5 g Potassium iodide 1.0 mg Water to make 1 l (pH: 10.40)
- processing procedure (I) was same as with processing procedure (I) except the time of the first development (black-and-white development) was 55 seconds.
- the multilayer effect is preferably enhanced.
- the multilayer effect is more enhanced compared with the case that the layer does not contain yellow colloidal silver.
- the effect of the present invention is remarkable when the time of the black-and-white development is short.
- the color reversal photographic materials which give the sufficient multilayer effect are obtained.
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Description
- The present invention relates to a process for developing silver halide color reversal photographic materials excellent in color reproducibility.
- Usually, a color reversal photographic material has a plurality of silver halide emulsion layers different in color sensitivity such as a red sensitive layer, a green sensitive layer and a blue sensitive layer on a support. The color reversal photographic material which has been image exposed to a polychromatic object is first subjected to black-and-white silver development at a first developing stage, and then the residual silver halide is color developed at a second developing stage through a chemical or optical fogging stage to form cyan, magenta and yellow color images. A dye image usually formed on each color sensitive layer by polychromatic exposure is different from a dye image produced by monochromatic exposure. In the case of the color reversal photographic material, this difference is mainly caused by the transfer of a development restrainer such as iodine ions generated between the emulsion layers different in color sensitivity at the black-and-white developing stage. The dye image difference between the polychromatic exposure and the monochromatic exposure caused by such development is called a multilayer effect or an inter image effect as described in Hudson and Horton, Journal of the Optical Society of America 42 (No. 9), pp. 663 to 669 (1976), and known to be available for improving sharpness and color reproducibility.
- As a technique to enhance the multilayer effect, JP-A-51-128528 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") discloses a process for enhancing the multilayer effect given to a sensitive silver halide emulsion layer by introducing an emulsion which has fogged the surfaces of silver halide grains into the sensitive silver halide emulsion layer.
- Research Disclosure No. 13553 (1975) also discloses a process for application of the preferable multilayer effect by iodine ions in a color reversal photographic material, which comprises adding an emulsion containing a silver halide so as to release the iodine ion such as AgBrI, AgClI or AgBrClI to at least one layer to which the multilayer effect is applied, adding a hydrophilic colloid as well as usual emulsion grains to at least one layer to which the multilayer effect is given, and further adding another surface fogging emulsion. However, the above-described references do not fully disclose the features of the more preferred sensitive silver halide emulsion in enhancing the multi layer effect utilizing the fogging emulsion.
- At the black-and-white developing stage of the color reversal photographic materials the sensitive silver halide emulsion is developed depending on the amount of exposure. At that time, the silver halide emulsion grains not developed are subjected to the color developing processing through the fogging stage. This color developing stage is required to develop all the residual silver halide to develop color, so that its developing activity is designed to be high. For this reason, it is substantially almost impossible to make the multilayer effect function at the color developing stage, and, in the color reversal photographic materials, the multilayer effect is substantially determined by the black-and-white developing stage.
- At this black-and-white developing stage, the developing solution has the effect of dissolving the emulsion grains. This solubility is controlled by the iodine ions diffused by the development of the other layers, whereby the multilayer effect is obtained. Although the multilayer effect is produced according to many mechanisms, the most important mechanism of them is the above one.
- The emulsion dissolving effect of this developing solution is enhanced with increasing the developing time. Hence, when the processing time of the black-and-white developing stage is short, it is difficult to apply the sufficient multilayer effect to the conventional color reversal photographic materials, compared to the case in which the processing time is long.
- EP-A-0 272 675 describes a silver halide photographic material comprising a support having thereon at least one silver halide emulsion layer composed of one or more layers, wherein the silver halide emulsion contained in at least one layer of the silver halide emulsion layer is chemically sensitized so that silver halide grains in the emulsion have at least one maximum value of the latent image number in distribution thereof in the inside of the silver halide grains and the position where the maximum value(s) exists is at a depth of less than 0.01 µm from the surface of the grains, and the emulsion also has a latent image number of at least 1/5 of the largest maximum value but less than the largest maximum value on the surface of the grains.
- US-A-4 804 616 describes a method for continuously processing a color reversal photographic material. After black and white development, the color reversal photographic material is rinsed in a bath wherein the replenishing amount per unit area of the photographic material is 3 to 50 times as much as the amount of processing solution carried over from the preceding bath in terms of volume ratio and the pH is 9.5 or below.
- US-A-4 839 268 describes a silver halide color reversal photosensitive material comprising a plurality of silver halide emulsion layers on a substrate, wherein 50 % or more of the total projected area of silver halide grains contained in at least one of said silver halide emulsion layers is occupied by tabular silver iodobromide grains having an average thickness of 0.5 micron or less, an average diameter of 0.5 micron or more, an average aspect ratio of at least 5/1, and a silver iodide content of 4.0 mol % or less, and said tabular silver iodobromide grains are negative-type silver halide grains forming a latent image mainly inside the grains.
- It is therefore an object of the present invention to provide a process giving the sufficient multilayer effect even in processing in which the black-and-white developing time is short.
- The object of the present invention is attained by a process for developing a silver halide color reversal photographic material comprising a support having provided thereon at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, wherein at least one silver halide emulsion layer contains tabular silver halide grains having an aspect ratio of at least 5 occupying at least 50% of all silver halide grains existing in the same layer as a projected area, and having a mean sphere-corresponding grain size of 0.30 µm or less, which comprises developing said color reversal photographic material with a black-and-white developing solution for 100 seconds or less.
- It is preferred that the mean sphere-corresponding grain size of the silver halide emulsion grains contained in at least one emulsion layer is 0.25 µm or less. The lower limit thereof is preferably 0.1 µm from the view point of sensitivity.
- The measuring methods of the mean sphere-corresponding grain size of silver halide grains are described in detail, for example, in James, The Theory of Photographic Process, the 4th edition, page 100. Such methods include methods using an optical microscope, an electron microscope and a coulter counter. When the size of such a degree as the size of the emulsion grains of the present invention is measured, a method is preferably used in which the thickness of the grains is determined from the projected area of the grains and the length of shadows obtained by shadowing, using an electron microscope, the volume of each grain is determined therefrom, and the mean sphere-corresponding grain size is determined from the mean value thereof.
- As the silver halide grains used in the present invention, monodisperse emulsions narrow in grain size distribution or polydisperse emulsions wide in grain size distribution may be used.
- In the present invention, at least one sensitive emulsion layer contains the tabular silver halide emulsion grains having a mean sphere-corresponding grain size of 0.30 µm or less and an aspect ratio of at least 5 so as to occupy at least 50% of all silver halide grains existing in the same layer as a projected area. It is further preferred that at least one layer contains tabular silver halide emulsion grains having an aspect ratio of at least 8 so as to occupy at least 50% of all silver halide grains existing in the same layer as a projected area. The aspect ratio called here means the ratio of diameter to thickness of the emulsion grain.
- Further, the diameter of the silver halide grain means the diameter of a circle whose area is the same as the projected area of the grain. In general, the tabular silver halide grain has two planes parallel to each other, and the thickness called here is represented by the distance between the two parallel planes constituting the tabular silver halide grain.
- Any of silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and silver chloride may be used as the tabular silver halide grains. However, silver bromide and silver iodobromide are preferably used. In particular, it is preferred that silver iodobromide having a silver iodide content of 0.01 to 30 mol%, more preferably 0.5 to 10 mol%, is used.
- Methods for preparation of the tabular silver halide grains are hereinafter described.
- The tabular silver halide grains can be prepared by suitable combinations of methods known in the art.
- For example, the tabular silver halide grains can be obtained by simultaneous addition of silver and a halogen solution with maintaining the pBr value as relatively low as 1.3 or less.
- The size of the tabular silver halide grains can be adjusted by temperature control, selection of the kind or amount of solvent, selection of the kind of silver salt used on grain growth and control of the addition rate of the halide.
- When the tabular silver halide grains of the present invention is prepared, solvents for silver halides can be used as required.
- The solvents for silver halides frequently used include ammonia, thioethers and thiourea compounds. For the thioethers, reference can be made to U.S. Patents 3,271,157, 3,790,387 and 3,574,628.
- In addition, methods for preparation of the tabular silver halide grains are described in Gutoff, Photographic Science and Engineering, Vol. 14, pages 248 to 257 (1970), US-A-4,434,226, 4,414,310, 4,433,048 and 4,439,520 and GB-B-2,112,157.
- The above-described at least one sensitive emulsion layer means at least one layer of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer. Each of the above-described emulsion layers may consist of a plurality of layers having a similar spectral sensitivity as long as at least one of those layers meets the above-described requirements. However, a low-sensitive emulsion layer is preferably used from the viewpoint of sensitivity. When a layer having yellow colloidal silver is contained, it is preferred that an emulsion layer in most close proximity thereto meets the above-described requirements.
- This yellow colloidal silver is known to be prepared by various methods.
- S. Inoue, Preparative Experiments of Inorganic Chemistry, page 647 discloses the method of reducing silver nitrate with dextrin under alkaline conditions, the method of reducing silver nitrate with tannin under alkaline conditions, the method of reducing silver nitrate with hydrazine and the method of reducing silver oxide with sodium carbonate and hydrogen peroxide in the presence of a silver sol reduced with phosphorus.
- Silver halide grains used in the present invention, other than the tabular silver halide grains which have a mean sphere-corresponding grain size of 0.30 µm or less and an aspect ratio of at least 5, are hereinafter described. The silver halide grains may have a regular crystal form such as a cubic, an octahedral or a tetradecahedral form, an irregular crystal form such as a spherical or a tabular form, crystalline defects such as a twin plane, or a composite form thereof.
- The silver halide grains may be fine grains having a grain size of about 0.2 µm or less or large sized grains having a projected area diameter of up to about 10 µm. The silver halide grains may be used as a monodisperse emulsion or a polydisperse emulsion. A monodisperse emulsion having a coefficient of variation of not more than 20% is preferably used.
- Such photographic silver halide emulsions can be prepared by using the methods described in Research Disclosure No. 17643, pages 22 and 23, I. "Emulsion Preparation and Types" (December, 1978), ibid., No. 18716 (November, 1979), P. Glafkides, Chimie et Physique Photographique, (Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966) and V.L. Zelikman et al, Making and Coating Photograhic Emulsion (Focal Press, 1964).
- The monodisperse emulsions described in US-A-3,574,628 and 3,655,394 and GB-B-1,413,748 are also preferably used.
- The silver halide emulsions used in the photographic materials of the present invention are generally subjected to physical ripening, chemical ripening and spectral sensitization, and then used. The above-described emulsion grains may be of a so-called surface latent image type in which latent images are mainly formed on the surface of the grains or of a so-called internal latent image type in which the latent images are mainly formed in the insides of the grains. Additives used in such stages are described in Research Disclosure No. 17643 and ibid., No. 18716, and the corresponding portions are summarized in a table shown later.
- The crystal structure may be uniform, or the interior and the exterior of the grain may be composed of different halogen compositions, respectively. The crystal structure may also be a laminar structure. Silver halides different in composition may be joined together by epitaxial junction. Further, silver halides may be joined to compounds other than silver halides, such as silver rhodanine and lead oxide.
- Mixtures of grains of various crystal forms may be used.
- Known photographic additives which can be used in the present invention are also described in the two Research Disclosure references mentioned above, and the corresponding portions are indicated in the table shown later.
Kind of Additive RD 17643 RD 18716 1. Chemical sensitizers Page 23 Page 648, right column 2. Sensitivity increasing agents - ditto - 3. Spectral sensitizers, supersensitizers Pages 23 to 24 Page 648, right column to page 649, right column 4. Brightening agents Page 24 5. Antifoggants and stabilizers Pages 24 to 25 Page 649, right column 6. Light absorbers, filter dyes, ultraviolet absorbers Pages 25 to 26 Page 649, right column to page 650, left column 7. Stain inhibitors Page 25, right column Page 650, left column to right column 8. Dye image stabilizers Page 25 9. Hardeners Page 26 Page 651, left column 10. Binders Page 26 - ditto - 11. Plasticizers, lubricants Page 27 Page 650, right column 12. Coating aids, surfactants Pages 26 to 27 - ditto - 13. Antistatic agents Page 27 - ditto - - As preservatives, in addition to phenol, there can be used phenoxyethanol compounds, p-hydroxybenzoic butylate, Proxel (benzoisothiazoline) and sodium salicylate.
- Various color couplers can be used in the present invention. Specific examples thereof are described in the patent specifications cited in the above-described Research Disclosure No. 17643, VII-C to G.
- As yellow couplers, there can be preferably used the compounds described, for example, in US-A 3,933,501, 4,022,620, 4,326,024 and 4,401,752, JP-B-58-10739 (the term "JP-B" as used herein means an "examined Japanese patent publication"), GB-B-1,425,020 and 1,476,760.
- As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferably used, and there are particularly preferred the compounds described in US-A-4,310,619 and 4,351,987, EP-A-73,636, US-A-3,061,432 and 3,725,067, Research Disclosure, No. 24220 (June, 1984), JP-A-60-33552, Research Disclosure, No. 24230 (June, 1984), JP-A-60-43659, US-A-4,500,630 and 4,540,654.
- Cyan couplers include phenol and naphthol compounds, and there are preferably used the compounds described in US-A-4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, DE-A-3,329,729, EP-A-121,365, US-A-3,446,622, 4,333,999, 4,451,559 and 4,427,767, and EP-A-161,626.
- As couplers which give formed dyes having appropriate diffusivity, there are preferably used the compounds described in US-A-4,366,237, GB-B-2,125,570, EP-B-96,570 and DE-A-3,234,533.
- Typical examples of polymerized dye-forming couplers are described in US-A-3,451,820, 4,080,211 and 4,367,282, and GB-B-2,102,173.
- Couplers which release photographically useful residues in coupling can also be preferably used in the present invention. As DIR couplers which release development inhibitors, there are preferred the compounds described in JP-A-57-151944, JP-A-57-154234, JP-A-60-184248 and U.S. Patent 4,248,962 cited in the above-described Research Disclosure, No. 17643, Item VII-F.
- As couplers which release nucleating agents or development accelerators in the form of images on development, there are preferably used the compounds described in GB-B-2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840.
- Other couplers which can be used in the photographic materials in the present invention include the competitive couplers described in US-A-4,130,427, the multiequivalent couplers described in US-A-4,283,472, 4,338,393 and 4,310,618, the couplers which release DIR redox compounds described in JP-A-60-185950, and the couplers which release dyes recolored after separation described in EP-A-173,302.
- The couplers used in the present invention can be incorporated in the photographic materials by various known dispersion methods.
- Examples of high boiling solvents which can be used in oil-in-water dispersion methods are described in US-A-2,322,027.
- The stages and effects of latex dispersion methods and specific examples of latexes for impregnation are described in US-A-4,199,363, DE-A-2,541,274 and 2,541,230.
- To the photographic materials used in the present invention can be preferably added the development inhibiting compound-releasing hydroquinones described in US-A-3,379,529 and 3,639,417, and the development inhibiting compound-releasing naphthohydroquinones described in Research Disclosure, No. 18264 (June, 1979).
- Appropriate supports which can be used in the present invention are described, for example, in the above-described Research Disclosure, No. 17643, page 28 and ibid., No. 18716, the right column of page 647 to the left column of page 648.
- Processing solutions and processing stages for the color reversal photographic materials of the present invention are hereinafter described.
- The first developing (black-and-white developing) stage for the color reversal photographic materials of the present invention is conducted for 100 seconds or less. When this stage is conducted for 60 seconds or less, the effect of the present invention becomes more remarkable. It is preferred from the viewpoint of productivity that the first developing time is shorter.
- Of the processing stages for the color reversal photographic materials of the present invention, the stages from black-and-white development (first development) to color development are as follows:
- 1. Black and white development - Washing - Reversal - Color development
- 2. Black and white development - Washing - Optical reversal - Color development
- 3. Black and white development - Washing - Color-development
- Each of the washing stages in procedures 1 to 3 can be replaced by the rinsing stage described in US-A-4,804,616 to simplify the processing and reduce the amount of liquid wastes.
- The stages after the color development are hereinafter described.
- 4. Color development - Compensation - Bleaching - Fixing - Washing - Stabilization
- 5. Color development - Washing - Bleaching - Fixing - Washing - Stabilization
- 6. Color development - Compensation - Bleaching - Washing - Fixing - Washing - Stabilization
- 7. Color-development - Washing - Bleaching - Washing - Fixing - Washing - Stabilization
- 8. Color development - Bleaching - Fixing - Washing - Stabilization
- 9. Color development - Bleaching - Bleach-fixing - Washing - Stabilization
- 10. Color development - Bleaching - Bleach-fixing - Fixing - Washing - Stabilization
- 11. Color development - Bleaching - Washing - Fixing - Washing - Stabilization
- 12. Color development - Compensation - Bleach-fixing - Washing - Stabilization
- 13. Color development - Washing - Bleach-fixing - Washing - Stabilization
- 14. Color development - Bleach-fixing - Washing - Stabilization
- 15. Color development - Fixing - Bleach-fixing - Washing - Stabilization
- In processing procedures 4 to 15, the washing stages just before the stabilization stages may be eliminated and the final stabilization stages may not be carried out. Any one of procedures 1 to 3 described above is combined with any one of procedures 4 to 15 to form a color reversal procedure.
- Processing solutions used in the color reversal procedures of the present invention are hereinafter described.
- For the black-and-white developing solutions, known black-and-white developing agents can be used alone or in combination. Such developing agents include dihydroxybenzenes such as hydroquinone; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone; aminophenols such as N-methyl-p-aminophenol; 1-phenyl-3-pyrazoline; ascorbic acid; and heterocyclic compounds such as a condensed compound of a 1,2,3,4-tetrahydroquinoline ring and an indolene ring described in US-A-4,067,872.
- The black-and-white developing solutions used in the present invention may contain preservatives such as sulfites and bisulfites; buffers such as carbonates, boric acid, borates and alkanolamines; alkali agents such as hydroxides and carbonates; solubilizing auxiliaries such as polyethylene glycol and esters thereof; water softeners such as aminopolycarboxylic acids and organic phosphonic acids; pH regulators, for example, organic acids such as acetic acid; sensitizers such as quaternary ammonium salts; development accelerators; surface active agents; antifoaming agents; hardening agents; antifoggants such as potassium iodide, potassium bromide and benzotriazole; and viscosity imparting agents, if necessary.
- Although the black-and-white developing solutions used in the present invention are required to contain compounds acting as solvents for silver halides, the above-described sulfites added as the preservatives generally play its role. Specific examples of the sulfites include K2SO3, Na2SO3, K2S2O5, Na2S2O5, K2S2O3 and Na2S2O3.
- In the present invention, it is preferred that this black-and-white developing solution contains at least one kind of rhodanide. Particularly preferred examples of the rhodanides include potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate. The content of these compounds is preferably 0.01 to 50 g/ℓ, and more preferably 0.05 to 10 g/ℓ.
- The pH of the black-and-white developing solutions is selected so as to give a desired density and contrast, and ranges from about 8.5 to about 11.5.
- Reversal baths used after the black-and-white development can contain fogging agents known in the art. Such fogging agents include stannous ion complex salts such as stannous ion-organic phosphoric acid complex salts (US-A-3,617,282), stannous ion-organic phosphonocarboxylic acid complex salts (JP-B-56-32616) and stannous ion-aminopolycarboxylic acid complex salts (GB-B-1,209,050); boron compounds such as hydrogenated boron compounds (US-A-2,984,567) and heterocyclic amineborane compounds (British Patent 1,011,000). The pH of the fogging baths (reversal baths) extends over a wide range from an acidic side to a basic side of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9. Instead of the use of the reversal bath, optical reversal processing by reexposure may be carried out. Further, the reversal stage can be omitted by adding the above-described fogging agents to the color developing solutions.
- As aromatic primary amine color developing agents used in the color developing solutions in the present invention. p-Phenylenediamine derivatives are preferable. Typical examples thereof are shown below, but the p-phenylenediamine derivatives are not limited thereto.
- D-1:
- N,N-Diethyl-p-phenylenediamine
- D-2:
- 2-Amino-5-diethylaminotoluene
- D-3:
- 2-Amino-5-(N-ethyl-N-laurylamino)toluene
- D-4:
- 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline
- D-5:
- 2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline
- D-6:
- 4-Amino-3-methyl-N-ethyl-N-[β-methanesulfonamide)ethyl]aniline
- D-7:
- N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide
- D-8:
- N,N-dimethyl-p-phenylenediamine
- D-9:
- 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
- D-10:
- 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline
- D-11:
- 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline
- Of the above-described p-phenylenediamine derivatives, compounds D-2, D-4, D-5 and D-6 are particularly preferable.
- These p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The above aromatic primary amine developing agents are used preferably in an amount of about 0.1 to about 20 g, and more preferably in an amount of about 0.5 to 15 g per liter of developing solution.
- In the present invention, a color developing solution substantially free from benzyl alcohol may be used. The color developing solution substantially free from benzyl alcohol means a color developing solution containing benzyl alcohol at a concentration of not more than 3×10-2 mol per liter of developing solution, preferably free from benzyl alcohol.
- The sulfites contained in the color developing solutions used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite and potassium metabisulfite. The amount of the sulfites added to the developing solutions is preferably 1×10-5 to 5×10-2 mol, more preferably 1×10-4 to 5×10-2 mol, and further more preferably 1×10-4 to 2×10-2 mol per liter of developing solution.
- In addition, as preservatives, there may be contained various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349 and aromatic polyhydroxy compounds described in U.S. Patent 3,746,544, as required. In particular, the aromatic polyhydroxy compounds are preferably added.
- The pH of the color developing solutions used in the present invention is preferably 9 to 14, and more preferably 9 to 13. To the color developing solutions can be added other known constituent compounds of the color developing solutions.
- It is preferred to use various buffers to maintain the above-described pH.
- Specific examples of the buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the buffers used in the present invention are not limited to these compounds.
- The above-described buffers are added to the color developing solutions preferably in an amount of at least 0.1 mol/ℓ, and particularly preferably in an amount of 0.1 to 0.4 mol/ℓ.
- Moreover, various chelating agents can be used in the color developing solutions as suspending agents for calcium or magnesium or to improve the stability of the color developing solutions.
- As the chelating agents, organic acid compounds are preferably used. Examples of the chelating agents include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Specific examples thereof include, but are not limited to, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N′,N′-tetramethylenediphosphonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycoletherdiaminetetraacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and N,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid. Two or more kinds of these chelating agents may be used in combination as required.
- These chelating agents may be added in any amount as long as the amount is enough to block metal ions in the color developing solutions. For example, they are added in an amount of about 0.1 to about 10 g/ℓ.
- Any development accelerators may be added to the color developing solutions as required. Such development accelerators include p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554, quaternary ammonium salts described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, amine compounds described in US-A-2,494,903, 3,128,182, 4,230,796 and 3,253,919, JP-B-41-11431, US-A-2,482,546, 2,596,926 and 3,582,346, polyalkylene oxides described in JP-B-37-16088, JP-B-42-25201, US-A-3,128,183, JP-B-41-11431, JP-B-42-23883 and US-A-3,532,501, 1-phenyl-3-pyrazolidone compounds and imidazole compounds.
- In the present invention, any antifoggants may be added as required. As the antifoggants, there can be used alkaline metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants. Typical examples of the organic antifoggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.
- The color developing solutions used in the present invention may contain fluorescent brightening agents. As the fluorescent brightening agents, 4,4′-diamino-2,2′-disulfostilbene compounds are preferably used. They are added in an amount of 0 to 5 g/ℓ, and preferably in an amount of 0.1 to 4 g/ℓ.
- There may be further added various surface active agents such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids and aromatic carboxylic acids as so desired.
- The processing temperature of the color developing solutions in the present invention is 20 to 50°C, and preferably 30 to 40°C. The processing time is 20 seconds to 8 minutes, and preferably 30 seconds to 6 minutes. It is preferred that the replenishment rate of the color developing solutions is minimized. The replenishment rate is however 100 to 3,000 ml/m2 of photographic material, preferably 100 to 2,500 ml/m2, and more preferably 100 to 2,000 ml/m2.
- Further, the color developing bath may be divided into two or more baths as required, and the foremost bath or the hindmost bath thereof may be replenished with the color developing solution to shorten the developing time and reduce the replenishment rate.
- Furthermore, for the purpose of controlling the gradient, the color developing solutions used in the present invention may contain so-called competitive compounds such as citrazinic acid, J acid and H acid which react with the oxidation product of the color developing agents to form colorless compounds.
- In the present invention, the photographic materials are subjected to the bleaching processing or the bleach-fixing processing after color development. These processing may be carried out immediately after color development without any other processing stages, or after processing stages such as termination, compensation and washing after the color developing stage.
- Solutions used for the above-described compensation may contain aminopolycarboxylic acids such as ethylenediaminetetraacetlc acid and diethylenetriaminepentaacetic acid; sulfites such as sodium sulfite and ammonium sulfite; and bleaching accelerators such as thioglycerin, aminoethanethiol and sulfoethanethiol. For the purpose of preventing scum formation, it is preferred that the compensating solutions contain sorbitan esters of fatty acids substituted with ethylene oxide described in U.S. Patent 4,839,262 or polyoxyethylene compounds described in US-A-4,059,446 and Research Disclosure, Vol. 191, No. 19104 (1980).
- Bleaching agents used in bleaching solutions and/or bleach-fixing solutions include ferric complex salts of aminopolycarboxylic acids and peroxide such as sodium persulfate. In particular, the ferric complex salts of aminopolycarboxylic acids are preferably used. Preferred examples of aminopolycarboxylic acids of such ferric complex salts include ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, glycoletherdiaminetetraacetic acid, cyclohexanediaminetetraacetic acid, 1,4-diaminobutanetetraacetic acid, 1,2-propylenediaminetetraacetic acid, thioglycoletherdiaminetetraacetic acid, 1,3-butylenediaminetetraacetic acid and methyliminodiacetic acid.
- The above-described bleaching agents are added in an amount of 0.05 to 1 mol per liter of bleaching solution or blech-fixing solution, and preferably in an amount of 0.1 to 0.5 mol. In addition to the above-described complex salts of iron(III) with the aminopolycarboxylic acids, aminopolycarboxylates may be added to the bleaching solutions and/or the bleach-fixing solutions used in the present invention.
- The aminopolycarboxylates are added preferably in an amount of 0.0001 mol to 0.1 mol/ℓ, and more preferably in an amount of 0.003 to 0.05 mol/ℓ.
- It is preferred that the aminopolycarboxylates and the ferric complex salts thereof are usually used in the form of alkali metal salts or ammonium salts. In particular, the ammonium salts are preferable because of their excellent solubility and bleaching ability.
- Various bleaching accelerators may be added to the bleaching solutions and/or the bleach-fixing solutions used in the present invention.
- As such bleaching accelerators, there are preferably used, for example, mercapto group- or disulfide group-containing compounds described in US-A-3,893,858, DE-C-1,290,812, GB-B-1,138,842, JP-A-53-95630 and Research Disclosure, No. 17129 (July, 1978).
- The bleaching accelerators are added in an amount of 0.01 to 20 g per liter of solution having bleaching ability, and preferably in an amount of 0.1 to 10 g.
- The bleaching solutions and/or the bleach-fixing solutions used in the present invention may contain rehalogenating agents such as bromides (for example, potassium bromide, sodium bromide and ammonium bromide) and chlorides (for example, potassium chloride, sodium chloride and ammonium chloride) in addition to the bleaching agents and the above-described compounds. The concentration of the rehalogenating agents is 0.1 to 5 mols per liter of bleaching solution, and preferably 0.5 to 3 mols. In addition, there can be added known additives which can be usually used in the bleaching solutions, for example, nitrates such as sodium nitrate and ammonium nitrate; and one or more kinds of inorganic acids, organic acids and salts thereof having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid.
- The bleach-fixing solutions and/or fixing solutions used in the present invention may contain thiosulfates as fixing agents. The thiosulfates are added in an amount of 0.1 to 3 mols/ℓ, and preferably in an amount of 0.3 to 2 mols/ℓ.
- The thiosulfate compounds include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate and magnesium thiosulfate. In particular, ammonium thiosulfate is preferably used because of its good solubility and highest rate of fixing.
- In addition to the above-described thiosulfate compounds, there can be used thiocyanic acid compounds (particularly the ammonium salt thereof), thiourea, thioethers, urea and the like as the fixing agents or fixing accelerators of the bleach-fixing solutions and/or the fixing solutions used in the present invention. The total concentration of these supplementary fixing agents or fixing accelerators and the thiosulfate compounds is 1.11 to 3.0 mols/ℓ, and preferably 1.4 to 2.8 mols/ℓ.
- The bleach-fixing solutions and/or the fixing solutions used in the present invention may contain sulfites such as sodium sulfite, potassium sulfite and ammonium sulfite, hydroxylamine and hydrazine as preservatives. Further, they may contain various fluorescent brightening agents, antifoaming agents, surface active agents and organic solvents such as polyvinyl pyrrolidone and methanol. In particular, it is preferred that the sulfinic acid compounds described in JP-A-62-143048 are used as the preservatives.
- Further, for the purpose of stabilizing the solution, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the solutions. In particular, 1-hydroxyethylidene-1,1-diphosphonic acid is effective. These compounds are added in an amount of 0.01 to 0.3 mol/ℓ, and preferably in an amount of 0.05 to 0.2 mol/ℓ, which is particularly effective in the fixing solutions.
- The pH of the bleaching solutions and/or the bleach-fixing solutions used in the present invention is generally 1 to 9, preferably 1.5 to 7.5, and more preferably 2.0 to 7.0. In particular, it is preferred that the pH of the bleaching solutions is 2.0 to 5.0. Within the preferred range of pH, little fogging takes place in bleaching and the silver removal property is also excellent.
- The pH of the fixing solutions used in the present invention is usually 5.0 to 9.0, and particularly preferably 5.5 to 7.5.
- Known additives may be added to rinsing water used in the washing stage as so desired. For example, there can be used water softeners such as inorganic phosphoric acid compounds, aminopolycarboxylic acids and organic phosphoric acid compounds; disinfectants and antifungal agents to prevent various bacteria and duckweeds from proliferating such as isothiazolone, organic chlorine disinfectants and benzotriazole; and surface active agents to prevent dry load and unevenness. There can also be used the compounds described in L.E. West, "Water Quality Criteria", Phot. Sci. and Eng. 9, No. 6, 343-359 (1965).
- Processing solutions for stabilizing dye images are used as stabilizing solutions used in the stabilization stage. For example, there can be used solutions having a pH of 3 to 6 and buffering ability, and solutions containing aldehydes such as glutaraldehyde. Formalin is unfavorable in terms of environmental pollution. In the stabilizing solutions can be used ammonium compounds, metal compounds such as Bi and Al, fluorescent brightening agents, chelating agents such as EDTA and 1-hydroxyethylidene-1,1-diphosphonic acid, disinfectants, antifungal agents, hardening agents, surface active agents and the like. Thiazolone compounds such as 5-chloro-2-mwethylisothiazoline-3-one and 1,2-benzisothiazoline-3-one are effective as the antifungal agents.
- In order to prevent thiosulfate ions brought into the stabilizing solutions with the photographic materials from sulfurating, alkanolamines are preferably added to the stabilizing solutions.
- The pH of the stabilizing solutions used in the present invention is 3 to 8, and preferably 5 to 7. The temperature of the stabilizing solutions is preferably 5 to 45°C, and more preferably 10 to 40°C. It is preferred that a multistage countercurrent process is used as the washing stage or the stabilization stage. The number of stages is preferably 2 to 4. Two or more kinds of stabilizing solutions may be used in multiple stage. The replenishment rate is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount of the solution brought in from the preceding bath per unit area.
- As water used in the washing stage or the stabilization stage are preferred water deionized with an ion-exchange resin to Ca and Mg concentrations of 5 mg/ℓ or less, respectively, and water sterilized with a halogen bactericidal lamp or an ultraviolet bactericidal lamp, in addition to tap water.
- The present invention will be further illustrated in greater detail with reference to the following example, which are however not to be construed as limiting the invention.
- Cubic grains of silver iodobromide (silver iodide: 2.5 mol%) were prepared by the controlled double jet process in the presence of ammonia. The mean sphere-corresponding grain size of the resulting grains was 0.35 µm. The grains were subjected to chemical sensitization simultaneously using gold and sulfur. The emulsion thus obtained was named Emulsion A. 60% by weight of the emulsion grains had grain sizes within 18% from the mean grain size.
- A cubic grain emulsion having a mean sphere-corresponding grain size of 0.27 µm was prepared by adjusting the temperature in forming the grains of Emulsion A. The resulting grains were silver iodobromide grains containing 2.5 mol% of silver iodide.
- 60% by weight of the emulsion grains had grain sizes within 15% from the mean grain size.
- To 1 ℓ of water were added 30 g of gelatin and 10.3 g of potassium bromide, and then Solutions I and II shown in Table 1 were simultaneously added thereto with stirring for 15 minutes in a vessel maintained at 60°C.
- In the resulting tabular silver halide grains, 53% of all grains as a projected area were composed of grains having an aspect ratio of at least 5, and the content of silver iodide was 2.5 mol%.
- This emulsion was subjected to chemical sensitization simultaneously using gold and sulfur. The tabular silver halide emulsion thus obtained was named Emulsion C. The grains of Emulsion C had a mean sphere-corresponding grain size of 0.35 µm.
TABLE 1 Solution I Solution II AgNO3 (g) 100.0 - H2O (cc) 561 542 KBr (g) - 72.8 KI (g) - 2.5 - By adjusting the temperature in forming grains of Emulsion C, there was obtained Emulsion D which had a mean sphere-corresponding grain size of 0.28 µm, in which 53% of all grains as a projected area were composed of grains having an aspect ratio of at least 5, and which contained 2.5% of silver iodide.
- By adjusting the temperature in forming grains of Emulsion D, there was obtained Emulsion E which had a mean sphere-corresponding grain size of 0.21 µm, in which 53% of all grains as a projected area were composed of grains having an aspect ratio of at least 5, and which contained 2.5% of silver iodide.
- By adjusting the temperature in forming grains of Emulsion E, there was obtained Emulsion F which had a mean sphere-corresponding grain size of 0.21 µm, in which 55% of all grains as a projected area were composed of grains having an aspect ratio of at least 8, and which contained 2.5% of silver iodide.
- Phenoxyethanol was added to Emulsions A to F as a preservative in an amount of 40,000 ppm based on gelatin.
- A paper support both sides of which had been laminated with polyethylene was coated with the following first to twelfth layers to prepare a multilayer color photographic material, which was named Sample 101. Polyethylene on the side of the first layer to be coated contained titanium oxide as a white pigment and a slight amount of ultramarine as a bluing dye.
- The composition of each sensitive layer is shown below. Numerals for the components indicate coated amounts represented in g/m2. Numerals for the silver halides indicate coated amounts converted to silver.
-
Gelatin 1.30 -
Black colloidal silver 0.10 Gelatin 0.70 -
Silver iodobromide EM1 (silver iodide: 4 mol%, mean grain size: 0.4 µm, cubic) spectrally sensitized with red-sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.06 Silver iodobromide EM2 (silver iodide: 5 mol%, mean grain size: 0.50 µm, cubic) spectrally sensitized with red-sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.10 Gelatin 1.00 Cyan coupler (ExC-1) 0.14 Cyan coupler (ExC-2) 0.07 Antifading agent (Cpd-2, Cpd-3, Cpd-4 and Cpd-9 in equivalent amounts) 0.12 Dispersion medium (Cpd-5) for coupler 0.03 Solvent (Solv-1, Solv-2 and Solv-3) for coupler 0.06 -
Silver iodobromide EM3 (silver iodide: 6 mol%, mean grain size: 0.75 µm, twin) spectrally sensitized with red-sensitizing dyes (ExS-1, ExS-2 and ExS-3) 0.15 Gelatin 1.00 Cyan coupler (ExC-1) 0.20 Cyan coupler (ExC-2) 0.10 Antifading agent (Cpd-2, Cpd-3, Cpd-4 and Cpd-9 in equivalent amounts) 0.15 Dispersion medium (Cpd-5) for coupler 0.03 Solvent (Solv-1, Solv-2 and Solv-3) for coupler 0.10 -
Yellow colloidal silver 0.02 Gelatin 1.00 Color mixing inhibitor (Cpd-6 and Cpd-7) 0.08 Solvent (Solv-4 and Solv-5) for color mixing inhibitor 0.16 Polymer latex (Cpd-8) 0.10 -
-
Silver iodobromide EM4 (silver iodide: 3.5 mol%, mean grain size: 0.6 µm, twin) spectrally sensitized with green-sensitizing dye (ExS-4) 0.10 Magenta coupler (ExM-1) 0.05 Magenta coupler (ExM-2) 0.05 Antifading agent (Cpd-9) 0.10 Stain inhibitor (Cpd-10) 0.01 Stain inhibitor (Cpd-11) 0.001 Stain inhibitor (Cpd-12) 0.01 Dispersion medium (Cpd-5) for coupler 0.05 Solvent (Solv-4 and Solv-6) for coupler 0.15 -
Yellow colloidal silver 0.20 Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.06 Solvent (Solv-4 and Solv-5) for color mixing inhibitor 0.15 Polymer latex (Cpd-8) 0.10 -
-
Silver iodobromide EM7 (silver iodide: 2.5 mol%, mean grain size: 1.2 µm, twin) spectrally sensitized with blue-sensitizing dyes (ExS-5 and ExS-6) 0.25 Gelatin 1.00 Yellow coupler (ExY-1) 0.40 Stain inhibitor (Cpd-11) 0.002 Antifading agent (Cpd-6) 0.10 Dispersion medium (Cpd-5) for coupler 0.15 Solvent (Solv-2) for coupler 0.10 -
-
Fine grains of silver chlorobromide (silver chloride: 97 mol%, mean grain size: 0.2 µm) 0.07 Modified poval 0.02 Gelatin 1.50 Gelatin hardener (H-1) 0.17 - Further, to each layer were added alkanol XC (Du Pont de Nemours Co.) and sodium alkylbenzenesulfonate as emulsifying dispersion aids, and a succinic ester and Magefac F-120 (Dainippon Ink & Chemical Inc.) as coating aids. Cpd∼19, Cpd-20 and Cpd-21 were used as stabilizers in the silver halide-containing layers and the colloidal silver-containing layers. The compounds used in Example are shown below:
Cpd-8 Polyethylacrylate
- Solv-1
- Di(2-ethylhexyl) phthalate
- Solv-2
- Trinonyl phosphate
- Solv-3
- Di(3-methylhexyl) phthalate
- Solv-4
- Tricresyl phosphate
- Solv-5
- Dibutyl phthalate
- Solv-6
- Trioctyl phosphate
- H-1
- 1,2-Bis(vinylsulfonylacetamido)ethane
- Samples 102 to 106 were prepared by replacing Emulsion A contained in the sixth layer of Sample 101 by Emulsions B to F, respectively. Further, Sample 107 was prepared by replacing yellow colloidal silver contained in the fifth layer of Sample 104 by black colloidal silver. These features are summarized in Table 2.
TABLE 2 Emulsion of Sixth Layer Sample No. Emulsion Mean Sphere-Corresponding Grain Size Form Colloidal Silver of Fifth Layer (µm) 101 (Comparison) A 0.35 Cubic Yellow colloidal silver 102 (Comparison) B 0.27 Cubic Yellow colloidal silver 103 (Comparison) C 0.35 Tabular aspect ratio: 5 Yellow colloidal silver 104 (Invention) D 0.28 Tabular aspect ratio: 5 Yellow colloidal silver 105 (Invention) E 0.21 Tabular aspect ratio: 5 Yellow colloidal silver 106 (Invention) F 0.21 Tabular aspect ratio: 8 Yellow colloidal silver 107 (Invention) D 0.28 Tabular aspect ratio: 5 Black colloidal silver - Two film pieces were prepared from each of these Samples 101 to 107. One was exposed through an optical wedge using a white light source and the other was exposed through an optical wedge using a green light source. These exposed Samples were processed by the following processing procedure (I):
-
First development (black-and-white development) 38°C 75 seconds Washing 38°C 90 seconds Reversal exposure 100 lux or more 1 second or more Color development 38°C 135 seconds Washing 38°C 45 seconds Bleach-fixing 38°C 120 seconds Washing 38°C 135 seconds -
Pentasodium nitrilo-N,N,N-trimethylenephosphonate 0.6 g Pentasodium diethylenetriaminepentaacetate 4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1.2 g Potassium carbonate 35.0 g Potassium hydroquinonemonosulfonate 25.0 g Diethylene glycol 15.0 ml 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g Potassium bromide 0.5 g Potassium iodide 5.0 mg Water to make 1 ℓ (pH: 9.70) -
Benzyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Pentasodium nitrilo-N,N,N-trimethylene phosphonate 0.5 g Pentasodium diethylenetriaminepentaacetate 2.0 g Sodium sulfite 2.0 g Potassium carbonate 25.0 g Hydroxylamine sulfate 3.0 g N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g Potassium bromide 0.5 g Potassium iodide 1.0 mg Water to make 1 ℓ (pH: 10.40) -
- After processing, sensitometry was conducted for magenta image formed on the above-described Samples. For each Sample, the sensitivity ratio of the magenta image of the test piece exposed to green light to the magenta image of the test piece exposed to white light was determined. The results are shown in Table 3.
- Then, Samples 101 to 107 were exposed in the same manner as described above, and processed by the following processing procedure (II).
- The same as with processing procedure (I) except the time of the first development (black-and-white development) was 55 seconds.
- The results are also shown in Table 3.
TABLE 3 Processing Procedure Sensitivity Ratio of Magenta Image Exposed to Green Light to That Exposed to White Light (at a density of 0.6) Sample No. Processing Time of Black-and-White Development (sec) 101 (Comparison) I 75 1.37 102 (Comparison) I 75 1.66 103 (Comparison) I 75 1.42 104 (Invention) I 75 1.79 105 (Invention) I 75 1.90 106 (Invention) I 75 2.01 107 (Invention) I 75 1.71 101 (Comparison) II 55 1.10 102 (Comparison) II 55 1.35 103 (Comparison) II 55 1.16 104 (Invention) II 55 1.51 105 (Invention) II 55 1.65 106 (Invention) II 55 1.77 107 (Invention) II 55 1.42 - As the sensitivity ratio of monochromatic exposure to white light exposure is higher, the multilayer effect becomes larger, resulting in a color reversal photographic light-sensitive material showing color reproducibility of high chroma.
- As apparent from Table 3, when the form of the emulsion grains contained in the sixth layer is tabular, the multilayer effect is preferably enhanced. The smaller the mean sphere-corresponding grain size is and the higher the aspect ratio is, the higher effect is obtained.
- When the layer adjacent to the emulsion layer contains yellow colloidal silver, the multilayer effect is more enhanced compared with the case that the layer does not contain yellow colloidal silver.
- Further, the shorter the time of the black-and-white development is, the less the multilayer effect becomes. However, the effect of the present invention is remarkable when the time of the black-and-white development is short.
- According to the present invention, even in the processing in which the time of the first development is short, the color reversal photographic materials which give the sufficient multilayer effect are obtained.
Claims (9)
- A process for developing a silver halide color reversal photographic material comprising a support having provided thereon at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, wherein at least one silver halide emulsion layer contains tabular silver halide grains having an aspect ratio of at least 5 occupying at least 50% of all silver halide grains existing in the same layer as a projected area, and having a mean sphere-corresponding grain size of 0.30 µm or less, which comprises developing said color reversal photographic material with a black-and-white developing solution for 100 seconds or less.
- A process as claimed in claim 1, in which the time of black-and-white development is 60 seconds or less.
- A process as claimed in claim 1, in which the aspect ratio of the tabular silver halide grains is at least 8.
- A process as claimed in claim 1, in which the black-and-white developing solution contains a rhodanide.
- A process as claimed in claim 1, in which the mean sphere-corresponding grain size of said tabular silver halide grain is 0.25 µm or less.
- A process as claimed in claim 1, in which said tabular silver halide grain is a silver iodobromide having a silver iodide content of 0.01 to 30 mol%.
- A process as claimed in claim 1, in which the silver halide color reversal photographic material contains a silver having a yellow colloidal silver.
- A process as claimed in claim 7, in which said tabular silver halide grain is contained in an adjacent layer to the layer having a yellow colloidal silver.
- A process claimed in claim 1, in which said tabular silver halide grain is contained in the most low-sensitive emulsion layer when each of said emulsion layers consists of a plurality of layers having a similar spectral sensitivity.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP283990/89 | 1989-10-31 | ||
JP28399089 | 1989-10-31 | ||
JP22742590A JPH03200963A (en) | 1989-10-31 | 1990-08-29 | Method for developing silver halide color reversal photographic sensitive material |
JP227425/90 | 1990-08-29 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0426181A2 EP0426181A2 (en) | 1991-05-08 |
EP0426181A3 EP0426181A3 (en) | 1991-07-10 |
EP0426181B1 true EP0426181B1 (en) | 1996-10-16 |
Family
ID=26527663
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90120955A Expired - Lifetime EP0426181B1 (en) | 1989-10-31 | 1990-10-31 | Process for developing silver halide colour reversal photograhic material |
Country Status (2)
Country | Link |
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EP (1) | EP0426181B1 (en) |
DE (1) | DE69028895T2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0547983B1 (en) * | 1991-12-19 | 1995-10-04 | Eastman Kodak Company | Reversal photographic element and processing thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63129341A (en) * | 1986-11-19 | 1988-06-01 | Fuji Photo Film Co Ltd | Silver halide color reversal photographic sensitive material |
JPS63264740A (en) * | 1986-12-22 | 1988-11-01 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
JPS63158546A (en) * | 1986-12-22 | 1988-07-01 | Fuji Photo Film Co Ltd | Silver halide color reversal photosensitive material |
JP2588740B2 (en) * | 1988-03-03 | 1997-03-12 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
-
1990
- 1990-10-31 EP EP90120955A patent/EP0426181B1/en not_active Expired - Lifetime
- 1990-10-31 DE DE1990628895 patent/DE69028895T2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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& JP-A-1 223451 (FUJI) 06 September 1989, * |
Also Published As
Publication number | Publication date |
---|---|
DE69028895D1 (en) | 1996-11-21 |
DE69028895T2 (en) | 1997-05-07 |
EP0426181A3 (en) | 1991-07-10 |
EP0426181A2 (en) | 1991-05-08 |
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