JPH03101728A - Method for processing silver halide photosensitive material - Google Patents
Method for processing silver halide photosensitive materialInfo
- Publication number
- JPH03101728A JPH03101728A JP23927889A JP23927889A JPH03101728A JP H03101728 A JPH03101728 A JP H03101728A JP 23927889 A JP23927889 A JP 23927889A JP 23927889 A JP23927889 A JP 23927889A JP H03101728 A JPH03101728 A JP H03101728A
- Authority
- JP
- Japan
- Prior art keywords
- fixer
- silver halide
- photosensitive material
- emulsion
- processing
- 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.)
- Pending
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 61
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 45
- 239000004332 silver Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 59
- 238000012545 processing Methods 0.000 title description 36
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 125000000656 azaniumyl group Chemical group [H][N+]([H])([H])[*] 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 7
- 125000004429 atom Chemical group 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229910052751 metal Chemical group 0.000 abstract 1
- 239000002184 metal Chemical group 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 29
- 239000000975 dye Substances 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000011161 development Methods 0.000 description 25
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 22
- 230000001235 sensitizing effect Effects 0.000 description 22
- 238000005406 washing Methods 0.000 description 21
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 18
- 108010010803 Gelatin Proteins 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 229920000159 gelatin Polymers 0.000 description 15
- 239000008273 gelatin Substances 0.000 description 15
- 235000019322 gelatine Nutrition 0.000 description 15
- 235000011852 gelatine desserts Nutrition 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000007792 addition Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 238000003672 processing method Methods 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229940001482 sodium sulfite Drugs 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 235000010338 boric acid Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 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
- 239000012141 concentrate Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 3
- 229940116357 potassium thiocyanate Drugs 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 2
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000000843 anti-fungal effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000006179 pH buffering agent Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 2
- 229940043349 potassium metabisulfite Drugs 0.000 description 2
- 235000010263 potassium metabisulphite Nutrition 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- GKSPIZSKQWTXQG-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-[1-(pyridin-2-yldisulfanyl)ethyl]benzoate Chemical compound C=1C=C(C(=O)ON2C(CCC2=O)=O)C=CC=1C(C)SSC1=CC=CC=N1 GKSPIZSKQWTXQG-UHFFFAOYSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 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
- AYNPIRVEWMUJDE-UHFFFAOYSA-N 2,5-dichlorohydroquinone Chemical compound OC1=CC(Cl)=C(O)C=C1Cl AYNPIRVEWMUJDE-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- RDRWXZDNMNAEAA-UHFFFAOYSA-N 2-sulfonylacetamide Chemical compound NC(=O)C=S(=O)=O RDRWXZDNMNAEAA-UHFFFAOYSA-N 0.000 description 1
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical compound C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 1
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- SOVXTYUYJRFSOG-UHFFFAOYSA-N 4-(2-hydroxyethylamino)phenol Chemical compound OCCNC1=CC=C(O)C=C1 SOVXTYUYJRFSOG-UHFFFAOYSA-N 0.000 description 1
- HDGMAACKJSBLMW-UHFFFAOYSA-N 4-amino-2-methylphenol Chemical compound CC1=CC(N)=CC=C1O HDGMAACKJSBLMW-UHFFFAOYSA-N 0.000 description 1
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 1
- JNOJDURFZLCLSX-UHFFFAOYSA-N O.O.O.[Na].[Na] Chemical compound O.O.O.[Na].[Na] JNOJDURFZLCLSX-UHFFFAOYSA-N 0.000 description 1
- KDCJDNFHDCTZMN-UHFFFAOYSA-N OCC(CC(CCCS(O)(=O)=O)CC(CO)O)O Chemical compound OCC(CC(CCCS(O)(=O)=O)CC(CO)O)O KDCJDNFHDCTZMN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AJCODISBBXVCCF-UHFFFAOYSA-J dialuminum disulfate Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AJCODISBBXVCCF-UHFFFAOYSA-J 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 210000001951 dura mater Anatomy 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FIDOKWKZNVJFDX-UHFFFAOYSA-N ethene;2-(2-hydroxyethoxy)ethanol Chemical group C=C.C=C.OCCOCCO FIDOKWKZNVJFDX-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 150000002473 indoazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- ATGAWOHQWWULNK-UHFFFAOYSA-I pentapotassium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ATGAWOHQWWULNK-UHFFFAOYSA-I 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- DGPIGKCOQYBCJH-UHFFFAOYSA-M sodium;acetic acid;hydroxide Chemical compound O.[Na+].CC([O-])=O DGPIGKCOQYBCJH-UHFFFAOYSA-M 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はハロゲン化銀感光材料の現像処理方法に関する
ものであり、特に増感色素に起因する残色性や、定着性
、及び処理後の画像保存性が改良された現像処理方法に
関するものである．（従来の技術）
ハロゲン化銀感光材料（以下感材という）が、自動現像
機（以下自現機という）で処理されるとき現像液や定着
液が処理される量に応じて自現機の各処理タンクに補充
されるのが一般的である。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for developing silver halide light-sensitive materials, and in particular, it relates to residual color caused by sensitizing dyes, fixing properties, and post-processing. This paper relates to a processing method with improved image preservation. (Prior Art) When a silver halide photosensitive material (hereinafter referred to as a photosensitive material) is processed in an automatic processor (hereinafter referred to as an automatic processor), the amount of developing solution and fixer applied to the automatic processor depends on the amount of processing solution. Generally, each processing tank is replenished.
この補充液量は例えば現像液ならば所望の現像活性が得
られるように、現像反応によって現像液中に１積される
反応物質を希釈し、また酸化反応によって劣化した分を
新たに補なうことで決められる．定着液ならば、感材か
ら未感光のハロゲン化銀を熔解して定着液中に銀が蓄積
し、またハライドイオンがｌｉ，ｆｌシて定着能を低下
させ、また色素の溶出能力を低下させるので、新たに補
充液が補充されるわけである．通常定着液の補充量は感
光材料１ｄ当たり、０．６Ｎ〜０．９ｌ程度であった．
ところが近年、写真感材の現像処理にも、環境保全の立
場から、これらの処理廃液を少しでも滅らしたいという
要望が益々強くなっている．しかし、補充液量を低下さ
せれば、それに殆んど反比例して銀はより多く蓄積され
、ハライドイオン中でもヨードイオンはより多く蓄積さ
れて、定着能力は低下する。また、感材中に含まれる増
感色素は処理中に溶出し終わらないで処理後の感材中に
着色を残すいわゆる残色の問題を引き起したりするので
、補充液低減の強い要望があるにもかかわらず、簡単に
は実現できなかった．一方、エレクトロニクス分野の進
歩発展に伴ない、すべての分野に迅速性が要求されるよ
うになっておりハロゲン化銀写真の分野でも例外ではな
い．特に例えばグラフィンクアーツ感材、Ｘレイ用感材
、スキャナー用感材、ＣＲＴ画像記録用感材のような現
像処理において迅速処理の必要性は益々高くなってきて
いる．
迅速処理にすればする程、単位時間内により多くの感材
を処理できる。すわなち、より小さな自現機で高能力の
自現機となるというメリットもあって迅速化の意義は大
きい．
しかし現像処理の迅速化に伴ない上記の定着性能並びに
残色の問題はより大きくなることは言うまでもない．更
には水洗も短かくなって処理後の画像保存性も悪くなる
などの問題も出てくる．（発明の目的）
本発明の目的は第一にハロゲン化銀感光材料の定着液の
補充量を低減する処理方法を提供することにあり、第二
に定着液の補充量を低減したときの定着性能を高く維持
し、増感色素による残色の問題を解決した処理方法を提
供することにある。For example, in the case of a developer, this amount of replenisher dilutes the reactant accumulated in the developer by the development reaction so that the desired development activity can be obtained, and also replenishes the amount degraded by the oxidation reaction. It can be determined by In the case of a fixer, unexposed silver halide from the photosensitive material is melted, silver accumulates in the fixer, and halide ions are released, reducing the fixing ability and the dye elution ability. Therefore, new replenisher fluid is added. Normally, the amount of replenishment of fixer was about 0.6 N to 0.9 liters per 1 d of light-sensitive material. However, in recent years, there has been an increasing desire to eliminate as much processing waste liquid as possible from the standpoint of environmental conservation in the processing of photographic materials. However, if the amount of replenisher is reduced, more silver will be accumulated in almost inverse proportion to it, and more iodide ions will be accumulated among halide ions, resulting in a decrease in fixing ability. In addition, the sensitizing dye contained in the photosensitive material does not completely elute during processing, causing the problem of so-called residual color, which leaves color in the photosensitive material after processing, so there is a strong desire to reduce the amount of replenisher. Despite this, it was not easy to achieve. On the other hand, with the progress and development of the electronics field, speed is now required in all fields, and the field of silver halide photography is no exception. In particular, the need for rapid processing is increasing, especially in the development of Graphic Arts photosensitive materials, X-ray photosensitive materials, scanner photosensitive materials, CRT image recording photosensitive materials, and the like. The faster the processing is done, the more sensitive material can be processed within a unit time. In other words, speeding up the process is of great significance as it has the advantage of being a highly capable machine with a smaller size. However, it goes without saying that as development processing speeds up, the above-mentioned problems with fixing performance and residual color become more serious. Furthermore, problems arise, such as shorter washing times and poor image preservation after processing. (Objects of the Invention) The first object of the present invention is to provide a processing method for reducing the amount of fixer replenishment for silver halide photosensitive materials, and secondly, to provide a processing method for reducing the amount of fixer replenishment for silver halide photosensitive materials. The object of the present invention is to provide a processing method that maintains high performance and solves the problem of residual color caused by sensitizing dyes.
本発明の第三の目的はハロゲン化銀感光材料を迅速処理
する方法を提供することにあり、第四に処理後の画像保
存性を改良する処理方法を提供することにあり、第五に
処理コストを低減した処理方法を提供することにある．
（発明の構或）
本発明の目的は、ハロゲン化銀感光材料を露光現像した
後で定着するに際し、定着液補充量を感光材料１ｍ２あ
たり０，！Ｍ！以下とし、かつ定着液中に下記一般式（
Ｉ）で表される化合物を含有させることにより達戒され
た．
一般式（Ｉ）
Ｎ冨＝Ｎ
ＳＭ
式中、Ｘはアミノ基またはアンモニオ基を表わす．Ｌは
アルキレンを表わす．Ｍは水素原子またはアルカリ金属
を表わす．
本発明において用いられる一般式（１）において、Ｘで
表わされるアξノ基は置換されていてもよく、置換基と
して好ましいものは炭素数１から６までのアルキル基、
炭素数２から６までのヒドロキシアルキル基、炭素数２
から６までのスルホアルキル基、炭素数２から１０まで
のカルボキシアルキル基、炭素数２から６までのアルヵ
ンスルホニルアルキル基、炭素数ｌから１０までのアシ
７Ｌ４Ｅ、炭素数６から１０までのアレーンスルボニル
基、炭素数２から１０までのアルコキシアルキル基など
が好ましく、また置換基どうしで環状アミノ基を形成し
てもよい．
Ｘで表わされるアンモニオ基は置換されていてもよ＜、
置換基として好ましいものは炭素数１から６までのアル
キル基、炭素数２から６までのヒドロキシアルキル基、
炭素数２から６までのスルホアルキル基、炭素数２から
１０までのカルボキシアルキル基、炭素数２から６まで
のアルカンスルホニルアルキル基、炭素数２から１０ま
でのアルコキシアルキル基などが好ましく、また置ｔａ
基どうしで環状アンモニオ基を形威してもよい．Ｌで表
わされるアルキレンとしては炭素数２から８までのもの
が好ましく、途中に酸素原子または硫黄原子で介されて
いてもよい．
Ｍで表わされるアルカリ金属としてはナトリウム、カリ
ウムなどを挙げることができる．以下に本発明において
用いられる一般式（１）で表わされる化合物の具体例を
示すが、本発明はこれらに限定されるものではない．
ＳＮａ
これらの化合物については特開昭５ｌ−１４７５号、同
５３−５０１６９号に記載の方法で合或することができ
る．
上記一般式（Ｉ）で表される本発明の化合物は、定着液
中において、５Ｘ１０−’モル／ｌ〜１０−１モル／ｌ
、好ましくはＩＯ−４モル／ｊ！〜５Ｘ１０−１モル／
ｊ２，更に好ましくは１０−ｓモル／ｌ〜２×１０−８
モル／ｌの濃度を保つように使用される．本発明の化合
物を含む定着液の補充液量は感光材料Ｉｎ？当たり０．
５Ｊ以下である．好ましい補充量は感光材料の種類や使
用する自動現像機の構造によって異なるが、０．４ｌ以
下、更に０．３ｌ以下が好ましい．
定着液の補充量を少なくすると現像液のキャリーオーバ
ーによる定着液のｐＨ上昇が発生しやすくなるので、定
着液中には通常より高濃度のｐ Ｈ緩衝剤（酢酸、硼酸
など）を用いることが好ましい．定着液中のｐＨ緩衝剤
の濃度は通常０、３モル／１程度であるが、本発明のよ
うな低補充システムでは０．５モル／ｅ以上、特に０．
５モル／ｌ〜０．７モル／Ｅ程度のｐＨ緩衝剤を定着液
に含有させることが好ましい．現像液のキャリーオーバ
ーの影響を少なくするために現像と定着の間にリンス浴
または酸性の浴を設けてもよい．定着液の補充量を少な
くすると、定着液中のヨードイオンの量が増加するが、
本発明の化合物は平衡定着液組威になったときの定着液
中のヨードイオンの濃度が０．６粟リモル／ｌ以上にな
ったとき、特に１１リモル／Ｉｌ以上になったときに有
効である．なおここで平衡定着液組成とは、ある補充量
で感光材料を無限にランニング処理した時に収斂する定
着液＆Ｉｉｒｓ．をいうが、通常は、ある補充量で感光
材料をランニング処理してタンク液量の２倍の量を補充
した時点の定着液の組威で代替することができる．
定着液は定着剤としてチオ硫酸塩を含む水溶液であり、
ｐＨ３．８以上、好ましくは４．２〜７．０を有する．
更に好ましくはｐＨ４．２〜５．５である．
定着剤としてはチオ硫酸ナトリウム、チオ硫酸アンモニ
ウムなどがあるが、定着速度の点からチオ硫酸アンモニ
ウムが特に好ましい．定着剤の使用量は適宜変えること
ができ、−Ｓには約０． １〜約６モル／ｌである．
定着液には硬膜剤として作用する水溶性アルミニウム塩
を含んでもよく、それらには、例えば塩化アルミニウム
、硫酸アルξニウム、カリ明ばんなどがある．
定着液には、酒石酸、クエン酸、グルコン酸あるいはそ
れらの誘導体を単独で、あるいは２種以上、併用するこ
とができる．これらの化合物は定着液１１につきｏ．ｏ
ｏｓモル以上含むものが有効で、特に０．０１モル／ｌ
−０．０３モル／１が特に有効である．
定着液には所望により硬膜剤（ｉＪＥ酸アルミニウムの
ようなアル稟ニウム塩など）、保恒剤（例えば、亜硫酸
塩、重亜硫酸塩）、ｐＨｉ［整剤（例えば、硫酸）、硬
水軟化能のあるキレート剤や特開昭６２−７８５５ｌ号
記載の化合物を含むことができる．
本発明に用いる定着補充液は上記定着液と同様の戒分を
含むものであることが好ましいが、一部の威分を変更し
たり、組戒比率を変えたものでもよい．定着補充液は濃
縮液の形で供給し、希釈して使用されるのが好ましい．
濃縮液は１剤として調製されても、また２剤以上の形態
にして使用時に混合するようにしてもよい．後者の場合
それぞれのパートを収納した容器を一体に結合すれば取
扱が容易になり好ましい．
本発明の現像処理方法は基本的に、露光したハロゲン化
銀感光材料を現像、定着、水洗、乾燥する工程からなる
．
本発明の現像処理に使用する現像液に用いる現像主薬に
は良好な性能を得やすい点で、ジヒドロキシベンゼン類
と１−フエニル−３−ビラゾリドン類の組合せが最も好
ましい．勿論この他にｐアミノフェノール系現像主薬を
含んでもよい．本発明に用いるジヒドロキシベンゼン現
像主薬としてはハイドロキノン、クロロハイドロキノン
、プロムハイドロキノン、イソプロビルハイドロキノン
、メチノレハイドロキノン、２．３−ジクロロハイドロ
キノン、２．５−ジクロロハイドロキノン、２．３−ジ
ブロムハイドロキノン、２．５−ジメチルハイドロキノ
ンなどがあるが特にハイドロキノンが好ましい．
本発明に用いるｐ−アミノフェノール系現像主薬として
はＮ−メチルーｐ−アミノフェノール、ｐ−アミノフェ
ノール、Ｎ−（β−ヒドロキシエチル）−ｐ−アミノフ
ェノール、Ｎ−（４−ヒドロキシフェニル）グリシン、
２−メチルーｐ−アミノフェノール、ｐ−ペンジルアミ
ノフェノール等があるが、なかでもＮ−メチルーｐ−ア
ミノフェノールが好ましい．
本発明に用いる３−ビラゾリドン系現像主薬としては１
−フエニル−３−ビラゾリドン、ｌ−フェニルー４，４
−ジメチル−３−ビラゾリドン、１−フエニルー４−メ
チル−４−ヒドロキシメチル−３−ビラゾリドン、１−
フェニル−４．４ージヒドロキシメチル−３−ビラゾリ
ドン、ｌ−フェニルー５−メチル−３−ビラゾリドン、
１−ｐ一アミノフエニル−４，４−ジメチル−３−ビラ
ゾリドン、１−ｐ−｝リルー４．４−ジメチル３−ビラ
プリドン、１−１）−トリル−４−メチル４−ヒドロキ
シメチル−３−ビラゾリドン、などがある．
現像主薬は通常０．０１モル／ｌ〜１．２モル／ｌの量
で用いられるのが好ましい．
本発明の現像処理に用いる亜硫酸塩の保恒剤としては亜
硫酸ナトリウム、亜硫酸カリウム、亜硫酸リチウム、亜
硫酸アンモニウム、重亜硫酸ナトリウム、メタ重亜硫酸
カリウム、などがある．亜硫酸塩は０．２モル／ｌ以上
特に０．４モル／ｌ以上が好ましい．また、上限は２．
５モル／ｌまでとするのが好ましい。A third object of the present invention is to provide a method for rapidly processing silver halide photosensitive materials, a fourth object is to provide a processing method that improves image storage stability after processing, and a fifth object is to provide a processing method for rapidly processing silver halide photosensitive materials. The objective is to provide a processing method that reduces costs. (Structure of the Invention) It is an object of the present invention to reduce the amount of fixer replenishment to 0,! M! The general formula (
By containing the compound represented by I), the precepts were attained. General formula (I) N-value=N SM In the formula, X represents an amino group or an ammonio group. L represents alkylene. M represents a hydrogen atom or an alkali metal. In the general formula (1) used in the present invention, the ξ group represented by X may be substituted, and preferred substituents include an alkyl group having 1 to 6 carbon atoms;
Hydroxyalkyl group having 2 to 6 carbon atoms, 2 carbon atoms
to 6 sulfoalkyl groups, carboxyalkyl groups with 2 to 10 carbon atoms, alkanesulfonylalkyl groups with 2 to 6 carbon atoms, ace7L4E with 1 to 10 carbon atoms, 7L4E with 6 to 10 carbon atoms, An arenesulfonyl group, an alkoxyalkyl group having 2 to 10 carbon atoms, and the like are preferred, and substituents may combine to form a cyclic amino group. The ammonio group represented by X may be substituted.
Preferred substituents are alkyl groups having 1 to 6 carbon atoms, hydroxyalkyl groups having 2 to 6 carbon atoms,
A sulfoalkyl group having 2 to 6 carbon atoms, a carboxyalkyl group having 2 to 10 carbon atoms, an alkanesulfonylalkyl group having 2 to 6 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and the like are preferable. ta
The groups may form a cyclic ammonio group. The alkylene represented by L preferably has 2 to 8 carbon atoms, and an oxygen atom or sulfur atom may be present in the middle. Examples of the alkali metal represented by M include sodium and potassium. Specific examples of the compound represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited thereto. SNa These compounds can be synthesized by the method described in JP-A-51-1475 and JP-A-53-50169. The compound of the present invention represented by the above general formula (I) may be present in a fixing solution of 5X10-' mol/l to 10-1 mol/l.
, preferably IO-4 mol/j! ~5X10-1 mol/
j2, more preferably 10-s mol/l to 2 x 10-8
It is used to maintain a concentration of mol/l. The amount of replenisher of the fixer containing the compound of the present invention is the amount of the photosensitive material In? Hit 0.
It is less than 5J. The preferred replenishment amount varies depending on the type of photosensitive material and the structure of the automatic processor used, but is preferably 0.4 liters or less, more preferably 0.3 liters or less. If the amount of fixer replenishment is reduced, the pH of the fixer will likely increase due to developer carryover, so it is recommended to use a pH buffering agent (acetic acid, boric acid, etc.) with a higher concentration than usual in the fixer. preferable. The concentration of the pH buffer in the fixer is usually about 0.3 mol/e, but in a low replenishment system like the present invention, it is more than 0.5 mol/e, especially 0.3 mol/e.
It is preferable that the fixing solution contains a pH buffering agent of about 5 mol/l to 0.7 mol/E. A rinsing bath or an acidic bath may be provided between development and fixing to reduce the effect of developer carryover. When the amount of fixer replenishment is reduced, the amount of iodine ions in the fixer increases, but
The compound of the present invention is effective when the concentration of iodine ions in the fixer reaches an equilibrium fixer composition of 0.6 lmol/l or higher, particularly 11 lmol/l or higher. be. Note that the equilibrium fixer composition here refers to the fixer & IIrs. However, normally, it can be replaced by the strength of the fixer at the time when the photosensitive material is subjected to running processing with a certain amount of replenishment and twice the amount of tank liquid is refilled. The fixer is an aqueous solution containing thiosulfate as a fixing agent;
It has a pH of 3.8 or higher, preferably 4.2 to 7.0.
More preferably, the pH is 4.2 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, but ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and -S is about 0. 1 to about 6 mol/l. The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum ξ sulfate, potassium alum, and the like. The fixing solution may contain tartaric acid, citric acid, gluconic acid, or their derivatives alone or in combination. These compounds are added at o.o. per fixer 11. o
Those containing more than os mole are effective, especially 0.01 mole/l
-0.03 mol/1 is particularly effective. The fixer may optionally contain a hardening agent (such as an aluminum salt such as aluminum iJE acid), a preservative (such as a sulfite or a bisulfite), a pH adjustment agent (such as sulfuric acid), and water softening ability. It may contain certain chelating agents and compounds described in JP-A-62-78551. The fixer replenisher used in the present invention preferably contains the same precepts as the above-mentioned fixer, but it may be one in which some of the preservatives are changed or the composition ratio is changed. It is preferable that the fixing replenisher be supplied in the form of a concentrated solution and used after being diluted.
The concentrate may be prepared as a single agent, or it may be in the form of two or more agents and mixed at the time of use. In the latter case, it is preferable to combine the containers containing each part into one unit, as this makes handling easier. The development processing method of the present invention basically consists of the steps of developing, fixing, washing with water, and drying the exposed silver halide photosensitive material. The combination of dihydroxybenzenes and 1-phenyl-3-virazolidones is most preferred as the developing agent used in the developer used in the development process of the present invention, since it is easy to obtain good performance. Of course, a p-aminophenol type developing agent may also be included. Examples of dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, promhydroquinone, isoprobylhydroquinone, methinohydroquinone, 2.3-dichlorohydroquinone, 2.5-dichlorohydroquinone, 2.3-dibromhydroquinone, 2. Examples include 5-dimethylhydroquinone, but hydroquinone is particularly preferred. Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine,
There are 2-methyl-p-aminophenol, p-pendylaminophenol, etc., among which N-methyl-p-aminophenol is preferred. As the 3-virazolidone developing agent used in the present invention, 1
-phenyl-3-virazolidone, l-phenyl-4,4
-dimethyl-3-virazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-virazolidone, 1-
Phenyl-4,4-dihydroxymethyl-3-virazolidone, l-phenyl-5-methyl-3-virazolidone,
1-p-aminophenyl-4,4-dimethyl-3-vilazolidone, 1-p-}lylu-4,4-dimethyl-3-vilapridone, 1-1)-tolyl-4-methyl 4-hydroxymethyl-3-vilazolidone, and so on. The developing agent is preferably used in an amount of usually 0.01 mol/l to 1.2 mol/l. Sulfite preservatives used in the development process of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The amount of sulfite is preferably 0.2 mol/l or more, particularly 0.4 mol/l or more. Also, the upper limit is 2.
Preferably it is up to 5 mol/l.
本発明の現像処理に用いる現像液のｐＨは９から１３ま
での範囲のものが好ましい．更に好ましくはｐＨ１０か
らｌ２までの範囲である。The pH of the developer used in the development process of the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 10 to 12.
ｐＨの設定のために用いるアルカリ剤には水酸化ナトリ
ウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム
、第三リン酸ナトリウム、第三リン酸カリウムの如きｐ
Ｈ調節剤を含む．
特開昭６２−１８６２５９号（ホウ酸塩〉、特開昭６
０ − ９ ３ ４．３ ３号（例えば、サッカロース
、アセトオキシム、５−スルホサルチル酸〉、リン酸塩
、炭酸塩などの緩衝剤を用いてもよい．また上記現像液
には硬膜剤を用いてもよい．硬膜剤としてはジアルデヒ
ド系硬膜剤またはその重亜硫酸塩付加物が好ましく用い
られるが、その具体例を挙げればグルタルアルデヒド、
又はこの重亜硫酸塩付加物などがある．
上記威分以外に用いられる添加剤としては、臭化ナトリ
ウム、臭化カリウム、沃化カリウムの如き現像抑制剤：
エチレングリコール、ジエチレングリコール、トリエチ
レングリコール、ジメチルホルムアミド、メチルセロソ
ルブ、ヘキシレングリコール、エタノール、メタノール
の如き有機溶剤：１−フェニルー５−メルカブトテトラ
ゾール、２−メルカブトベンツイ竃ダゾール〜５−スル
ホン酸ナトリウム塩等のメルカブト系化合物、５ーニト
ロインダゾール等のインダゾール系化合物、５−メチル
ベンットリアゾール等のペンットリアゾール系化合物な
どのカブリ防止剤を含んでもよく、 Ｒｅｓｅａｒｃｈ
Ｄｉｓｃｌｏｓｕｒｅ第１７６巻、ｍｌ７６４３、第
Ｍ項（１２月号、１９７８年）に記載された現像促進剤
や更に必要に応じて色調剤、界面活性剤、消泡剤、硬水
軟化剤、特開昭５６−１０６２４４号記載のアミノ化合
物などを含んでもよい．
本発明の現像処理においては現像液に銀汚れ防止剤、例
えば特開昭５６−２４３４７号、特願平１−１８７７０
０号に記載の化合物を用いることができる．
本発明の現像液には、特開昭５６−１０６２４４号に記
載のアルカノールアミンなどのアミノ化合物を用いるこ
とができる．
この他Ｌ．Ｆ．Ａメイソン著「フォトグラフインク・プ
ロセシング・ケξストリー」、フォーカル・プレス刊（
１９６６年）の２２６〜２２９真、米国特許第２，１９
３，０１５号、同２，５９２，３６２号、特開昭４８−
６４９３３号などに記載のものを用いてもよい．
本発明の迅速処理には、感光材料の膨潤百分率を後述の
ように小さく （好ましくは１５０％〜５０％）して、
処理硬膜は弱くした方がよい．すなわち現像中における
硬膜はない方がより好ましく、定着中の硬膜もない方が
より好ましいが、定着液のｐＨを４．６以上にして、硬
膜反応を弱くしてもよい．こうすることによって、現像
液、定着液とも各々１液からなる補充剤を構戒すること
ができ、補充液の調製には単なる水で希釈するだけです
むという利点も生ずる．
上記本発明のハロゲン化銀写真感光材料の現像処理方法
では、現像、定着工程の後、該感光材料ｉｎ？当り、３
Ｅ以下の補充量（Ｏも含む、すなわちため水水洗）の水
洗水又は安定化液で処理することもできる．
すなわち、節水処理が可能となるのみならず、自現機設
置の配管が不要とすることができる。Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator. JP-A-62-186259 (borates), JP-A-62-186259
0 - 9 3 4.3 Buffers such as No. 3 (e.g., saccharose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may be used.Also, a hardening agent may be used in the above developer. As the hardening agent, dialdehyde hardening agents or their bisulfite adducts are preferably used, and specific examples include glutaraldehyde,
Or this bisulfite adduct. Additives used in addition to the above ingredients include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol: 1-phenyl-5-mercabutotetrazole, 2-mercabutobenzikadazole ~ 5-sodium sulfonate It may contain antifoggants such as merkabut compounds such as salts, indazole compounds such as 5-nitroindazole, penttriazole compounds such as 5-methylbenttriazole, etc.
Development accelerators described in Disclosure Vol. 176, ml7643, Section M (December issue, 1978), as well as color toning agents, surfactants, antifoaming agents, water softeners, and JP-A-1988 It may also contain the amino compound described in No.-106244. In the development process of the present invention, a silver stain preventive agent is added to the developer, for example, in Japanese Patent Application Laid-Open No. 56-24347, Japanese Patent Application No. 1-18770.
The compound described in No. 0 can be used. In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used. Besides this, L. F. “Photographic Ink Processing Cases” by A. Mason, published by Focal Press (
226-229 (1966), U.S. Patent No. 2,19
No. 3,015, No. 2,592,362, Japanese Unexamined Patent Publication No. 1973-
Those described in No. 64933 may also be used. For the rapid processing of the present invention, the swelling percentage of the light-sensitive material is reduced (preferably 150% to 50%) as described below.
It is better to weaken the treated dura mater. That is, it is more preferable that there is no hardening film during development, and it is even more preferable that there is no hardening film during fixing, but the pH of the fixing solution may be set to 4.6 or higher to weaken the hardening reaction. By doing so, it is possible to use a replenisher consisting of a single solution for both the developer and the fixer, and there is also the advantage that the replenisher only needs to be diluted with water to prepare the replenisher. In the above-mentioned method for developing a silver halide photographic light-sensitive material of the present invention, after the development and fixing steps, the light-sensitive material in? Hit, 3
It is also possible to process with rinsing water or stabilizing liquid at a replenishment amount (including O, ie, reservoir water rinsing) of less than E. In other words, not only can water be saved, but also piping for installing an automatic processor can be eliminated.
補充量を少なくする方法として、古くより多段向流方式
（例えば２段、３段など）が知られている．この多段向
流方式を本発明に適用すれば定着後の感光材料はだんだ
んと清浄な方向、つまり定着液で汚れていない処理液の
方に順次接触して処理されて行くので、更に効率の良い
水洗がなされる．
上記の節水処理又は無配管処理には、水洗水又は安定化
液に防黴手段を施すことが好ましい．防黴手段としては
、特開昭６０−２６３９３９号に記された紫外線照射法
、同６０−２６３９４０号に記された磁場を用いる方法
、同６１−１３ｌ６３２号に記されたイオン交換樹脂を
用いて純水にする方法、特開昭６２−１１５ｌ５４号、
同６２−１５３９５２号、同６２−２２０９５ｌ号、同
６２−２０９５３２号に記載の防菌剤を用いる方法を用
いることができる．
更には、Ｌ． Ｅ． Ｗｅｓｔ，“−ａｔｅｒ Ｑｕａ
ｌｉｔｙ Ｃｒｉｔｅｒｉａ”Ｐｈｏｔｏ． Ｓｃｉ，
＆ Ｅｎｇ． Ｖｏｌ． ９ｔｍ６ （１ ９
６ ５）、Ｍ． Ｌ Ｂｅａｃｈ＋ ”Ｍｉｃｒｏｂｉ
ｏｌｏｇｉｃａｌ Ｇｒｏｗｔｈｓ ｉｎＭｏｔｉｏｎ
−Ｐｉｃｔｕｒｅ Ｐｒｏｃｅｓｓｉｎｇ’ ＳＭＰＴ
Ｅ Ｊｏｕｒｎａｌ Ｖｏｌ．８ ５， （１ ９
７ ６） 、Ｒ． ０． Ｄｅｅｇａｎ． ”Ｐｈｏｔ
ｏＰｒｏｃｅｓｓｉｎｇ Ｗａｓｈ Ｗａｔｅｒ Ｂｉ
ｏｃｉｄｅｓ” Ｊ． ＩｍａｇｉｎｇＴｅｃｈｌ Ｏ
， Ｎａ６ （１ ９ ８ ４）及び特開昭５７−８５
４２号、同５７−５８１４３号、同５Ｂ−１０５ｌ４５
号、同５７−１３２１４６号、同５８１８６３１号、同
５７−９７５３０号、同５７１５７２４４号などに記載
されている防菌剤、防黴剤、界面活性剤などを併用する
こともできる。As a method to reduce the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multistage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. For the above-mentioned water-saving treatment or piping-free treatment, it is preferable to apply anti-mold measures to the washing water or stabilizing liquid. Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-13l632. How to make pure water, JP-A-62-115l54,
Methods using antibacterial agents described in No. 62-153952, No. 62-22095l, and No. 62-209532 can be used. Furthermore, L. E. West, “-ater Qua
ity Criteria"Photo.Sci,
& Eng. Vol. 9tm6 (1 9
6 5), M. L Beach+ ”Microbi
Logical Growths inMotion
-Picture Processing' SMPT
E Journal Vol. 8 5, (1 9
7 6), R. 0. Deegan. ”Photo
oProcessing Wash Water Bi
ocides” J. ImagingTechl O
, Na6 (1984) and JP-A-57-85
No. 42, No. 57-58143, No. 5B-105l45
Antibacterial agents, antifungal agents, surfactants, and the like described in Japanese Patent No. 57-132146, Japanese No. 5818631, Japanese No. 57-97530, Japanese Japanese Patent No. 57157244, etc. can also be used in combination.
更に、水洗浴又は安定化浴には、Ｒ． Ｔ． Ｋｒｅｉ
ｍａｎ著、Ｊ． Ｉｍａｇｅ． Ｔｅｃｈ １ ０ ，
（６１ ２ ４ ２頁（１ ９ ８ ４）に記載され
たイソチアゾリン系化合物、ＲｅｓｅａｒｃｈＤｉｓｃ
ｌｏｓｕｒｅ第２０５巻、＆２０５２６ （１９８１
年５月号）に記載されたイソチアゾリン系化合物、同第
２２８巻、隠２２８４５ （１９８３年４月号）に記載
されたイソチアゾリン系化合物、特開昭６２−２０９５
３２号に記載された化合物、特願平１−９１５３３号に
記載された銀イオン放出剤などを防菌剤（Ｍｉｃｒｏｂ
ｉｏｃｉｄｅ）として併用することもできる．
その他、「防菌防黴の化学」堀口博著、三共出版（昭５
７）、ｒ防菌防黴技術ハンドブック」日本防菌防黴学会
・博報堂（昭和６１）に記載されているような化合物を
含んでもよい．
本発明の方法において少量の水洗水で水洗するときには
特開昭６３−１８３５０号に記載のスクイズローラー洗
浄槽を設けることがより好ましい．また、特開昭６３−
１４３５４８号のような水洗工程の横或をとることも好
ましい．
更に、本発明の方法で水洗又は安定化浴に防黴手段を施
した水を処理に応じて補充することによって生ずる水洗
又は安定化浴からのオーバーフロー液の一部又は全部は
特開昭６０−２３５ｌ３３号に記載されているようにそ
の前の処理工程である定着能を有する処Ｅｌｉ液に利用
することもできる．本発明のハロゲン化銀感光材料は、
上記の少なくとも現像、定着、水洗（又は安定化）及び
乾燥の工程を含む自動現像機で処理されるとき、現像か
ら乾燥までの工程を９０秒以内で完了させること、即ち
、感光材料の先端が現像液に浸漬され始める時点から、
定着、水洗（又は安定化）工程を経て乾燥されて、同先
端が乾燥ゾーンを出てくるまでの時間（いわゆるＤｒｙ
ｔｏ Ｄｒｙの時間）が９０秒以内であること、特に
７０秒以内であることが好ましい．より好ましくは、こ
のＤｒｙ ｔｏ Ｄｒｙの時間が６０秒以内である．
本発明において「現像工程時間」又は「現像時間」とは
、前述のように処理する感光材料の先端が自現機の現像
タンク液に浸漬してから次の定着液に浸漬するまでの時
間、「定着時間」とは定着タンク液に浸漬してから次の
水洗タンク液（安定液）に浸漬するまでの時間「水洗時
間」とは、水洗タンク液に浸漬している時間をいう．ま
た「乾燥時間」とは、通常３５℃〜１００℃、好ましく
は４０℃〜８０℃の熱風が吹きつけられる乾燥ゾーンが
、自現機には設置されており、その乾燥ゾーンに入って
いる時間をいう。Furthermore, the washing bath or stabilization bath contains R. T. Krei
by J. man. Image. Tech 1 0,
(Isothiazoline compounds described on page 61 2 4 2 (1 9 8 4), Research Disc
Losure Volume 205, &20526 (1981
Isothiazoline compounds described in Vol. 228, Hidden 22845 (April 1983 issue), JP-A-62-2095
The compound described in No. 32, the silver ion release agent described in Japanese Patent Application No. 1-91533, and the like are used as antibacterial agents (Microb.
It can also be used together as ioside). In addition, "Chemistry of anti-bacterial and anti-mildew" by Hiroshi Horiguchi, Sankyo Publishing (Showa 5)
7), ``Handbook of Antibacterial and Antifungal Technology'', Japanese Society of Antibacterial and Antifungal Research, Hakuhodo (1988). When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide a squeeze roller washing tank as described in JP-A-63-18350. Also, JP-A-63-
It is also preferable to use a water washing process as in No. 143548. Furthermore, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water according to the treatment according to the method of the present invention, is used in Japanese Patent Application Laid-Open No. 1986-1999. As described in No. 235l33, it can also be used in the treatment Eli liquid that has fixing ability, which is the previous treatment step. The silver halide photosensitive material of the present invention is
When processed with an automatic processor that includes at least the above steps of development, fixing, washing (or stabilization), and drying, the process from development to drying must be completed within 90 seconds, that is, the leading edge of the photosensitive material must be From the point when it begins to be immersed in the developer,
The time it takes for the tip to come out of the drying zone after being dried through the fixing, water washing (or stabilization) process (the so-called Dry
It is preferable that the drying time (time to dry) is within 90 seconds, particularly within 70 seconds. More preferably, this dry-to-dry time is within 60 seconds. In the present invention, "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed as described above is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution; "Fixing time" is the time from immersion in the fixing tank solution until immersion in the next washing tank solution (stabilizing solution). "Washing time" is the time during which the product is immersed in the washing tank solution. Furthermore, "drying time" refers to the time the machine is in the drying zone, which is usually equipped with a drying zone where hot air is blown at a temperature of 35°C to 100°C, preferably 40°C to 80°C. means.
上記のＤｒｙ ｔｏ Ｄｒｙ ７ ０秒以内の迅速処理
を達或するためには、現像時間が２０秒以内、好ましく
は１５秒以内で可能だからであるが、その現像温度は２
５℃〜５０℃が好ましく、３０℃〜４０℃がより好まし
い．
本発明によれば定着温度及び時間は約２０℃〜約５０℃
で６秒〜２０秒が好ましく、３０℃〜４０℃で６秒〜１
５秒がより好ましい．この範囲内で十分な定着ができ、
残色を生じない程度に増感色素を溶出させることができ
る．
水洗または安定浴温度及び時間は０〜５０℃で６秒〜２
０秒が好ましくは、１５℃〜４０℃で６秒から１５秒が
より好ましい．
本発明の方法によれば、現像、定着及び水洗（又は安定
化）された写真材料は水洗水をしぼり切る、すなわちス
クイズローラーを経て乾燥される．乾燥は約４０℃〜約
１００℃で行なわれ、乾燥時間は周囲の状態によって適
宜変えられるが、通常は約５秒〜３０秒でよく、特によ
り好ましくは４０℃〜８０℃で約５秒〜２０秒である．
本発明の感材／処理システムでＤｒｙ ｔｏ Ｄｒｙで
７０秒以下の現像処理をするときには、迅速処理特有の
現像ムラを防止するために特開昭６３−１５ｌ９４３号
明細書に記載されているようなゴム材質のローラーを現
像タンク出口のローラーに適用することや、特開昭６３
−１５ｌ９４４号明細書に記載されているように現像液
タンク内の現像液攪拌のための吐出流速をｌＯｍｉ分以
上にすることや更には、特開昭６３−２６４７５８号明
細書に記載されているように、少なくとも現像処理中は
待機中より強い攪拌をすることがより好ましい．更には
本発明のような迅速処理のためには、特に定着液タンク
のローラーの構或は、定着速度を速めるために、対向ロ
ーラーであることがより好ましい．対向ローラーで構戒
することによって、ローラーの本数を少なくでき、処理
タンクを小さくできる．すなわち自現機をよりコンパク
トにすることが可能となる．
本発明の感光材料の現像処理方法には、写真感光材とし
て、特に限定はなく、一１に黒白感光材料が主として用
いられる他にカラー感光材料にも用いることができる．
特に医療画像のレーザープリンター用写真材料や印刷用
スキャナー感材並びに、医療用直接撮影Ｘ−レイ感材、
医療用間接撮影Ｘ−レイ感材、ＣＲＴ画像記録用感材な
どに用いることができる．本発明は特に銀画像を観察す
る白黒感光材料の処理に適している．
本発明に従う迅速現像に適する感光材料を製造するには
、例えば以下の如き方法の一つ又は二つ以上の方法の組
合せで実現できる．
■ 沃素含量の少ない乃至は含有しないハロゲン化銀を
用いる．即ち、沃化銀の含量がＯ〜５モル％の、塩化銀
、臭化銀、塩臭化銀、沃臭化銀、塩沃臭化銀等を用いる
．
■ ハロゲン化銀乳剤に水溶性イリジウム塩を含有させ
る．
■ ハロゲン化銀乳剤層における塗布１！量を少なくす
る。例えば片面で１〜３．５ｇ／ｒｒｒ、好ましくは１
〜３ｇ／ｒｄとする．
■ 乳剤中のハロゲン化銀の平均粒子サイズを小さくす
る．例えば１．０μ以下、好ましくは０．７μ以下とす
る。In order to achieve the above-mentioned dry-to-dry rapid processing within 70 seconds, the development time can be within 20 seconds, preferably within 15 seconds, but the development temperature is 2.
The temperature is preferably 5°C to 50°C, more preferably 30°C to 40°C. According to the present invention, the fixing temperature and time are about 20°C to about 50°C.
6 seconds to 20 seconds at 30℃ to 40℃, preferably 6 seconds to 1 seconds at 30℃ to 40℃
5 seconds is more preferable. Sufficient fixation can be achieved within this range,
The sensitizing dye can be eluted to the extent that no residual color occurs. Water washing or stabilization bath temperature and time are 0 to 50℃ for 6 seconds to 2
0 seconds is preferable, and 6 seconds to 15 seconds at 15°C to 40°C is more preferable. According to the method of the invention, the developed, fixed and washed (or stabilized) photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is carried out at a temperature of about 40°C to about 100°C, and the drying time can be changed appropriately depending on the surrounding conditions, but it is usually about 5 seconds to 30 seconds, particularly preferably about 5 seconds to 80°C. It is 20 seconds.
When carrying out dry-to-dry development processing in 70 seconds or less using the sensitive material/processing system of the present invention, in order to prevent uneven development peculiar to rapid processing, a method such as that described in JP-A-63-151943 is used. Applying a roller made of rubber to the roller at the outlet of the developing tank, and
- As described in the specification of No. 15l944, the discharge flow rate for stirring the developer in the developer tank is set to 10mi minutes or more, and furthermore, as described in the specification of JP-A-63-264758. Therefore, it is more preferable to stir the film more strongly at least during the development process than during standby. Furthermore, for rapid processing as in the present invention, it is particularly preferable that the roller structure of the fixer tank be opposed rollers in order to increase the fixing speed. By using opposing rollers, the number of rollers can be reduced and the processing tank can be made smaller. In other words, it is possible to make the automatic processor more compact. The method of developing a photosensitive material of the present invention is not particularly limited as a photographic photosensitive material, and firstly, black and white photosensitive materials are mainly used, but it can also be used for color photosensitive materials.
In particular, photographic materials for laser printers for medical images, scanner sensitive materials for printing, medical direct photography X-ray sensitive materials,
It can be used for medical indirect photography X-ray photosensitive materials, CRT image recording photosensitive materials, etc. The present invention is particularly suitable for processing black and white photosensitive materials in which silver images are observed. The production of a photosensitive material suitable for rapid development according to the present invention can be achieved by, for example, one of the following methods or a combination of two or more methods. ■ Use silver halide with low or no iodine content. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., having a silver iodide content of 0 to 5 mol %, are used. ■ Adding a water-soluble iridium salt to the silver halide emulsion. ■ Coating in silver halide emulsion layer 1! Reduce quantity. For example, 1 to 3.5 g/rrr on one side, preferably 1
~3g/rd. ■ Reduce the average grain size of silver halide in the emulsion. For example, it is 1.0μ or less, preferably 0.7μ or less.
■ 乳剤中のハロゲン化銀粒子として平板状粒子、例え
ばアスベクト比４以上のもの、好ましくは５以上のもの
を用いる．
■ ハロゲン化銀感光材料の膨潤百分率を２００％以下
にする．
写真乳剤中のハロゲン化銀粒子は、立方体、八面体、十
四面体のような規則的な結晶体を有するいわゆるレギュ
ラー粒子でもよく、また球状などのような変則的な結晶
形を持つもの、双晶面などの結晶欠陥を持つもの、平板
状粒子あるいはそれらの複合形でもよい。(2) Tabular grains, for example those with an aspect ratio of 4 or more, preferably 5 or more, are used as silver halide grains in the emulsion. ■ Reduce the swelling percentage of silver halide photosensitive materials to 200% or less. The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. They may be grains with crystal defects such as twin planes, tabular grains, or composites thereof.
平板状粒子アスベクト比は、平板状粒子個々の粒子の投
影面積と等しい面積を有する円の直径の平均値と、平板
状粒子個々の粒子厚みの平均値との比で与えられる．本
発明において平板状粒子である場合の好ましい粒子形態
としてはアスペクト比４以上２０未満、より好ましくは
５以上１０未満である．さらに粒子の厚みは０．３μ以
下が好ましく、特に０．２μ以下が好ましい．平板状粒
子は全粒子の好ましくは８０重量％、より好ましくは９
０重量％以上存在することが好ましい．
ハロゲン化銀の粒径は、狭い分布を有する単分散乳剤で
もよく、あるいは広い分布を有する多分散乳剤でもよい
．
本発明に使用できるハロゲン化銀写真乳剤は、公知の方
法で製造でき、例えばＲｅｓｅａｒｃｈ ｌｌｉｓｃｌ
ｏｓｕｒｅ．磁１７６４３ （１９７８年１２月〉、２
２〜２３頁、″Ｌ乳剤製造（εｓ１ｕＩｓｌｏｎ ｐｒ
ｅｐａｒａｔｉｏｎ ａｎｄｔｙｐｅｓ） ’および同
、隘１Ｂ７１６ （１９７９年１１月）、６４８真に記
載の方法に従うことができる．
本発明に用いられる写真乳剤は、グラフヰデ著「写真の
化学と物理Ｊ，ボールモンテル社刊（Ｐ．Ｇ］ａｆｋｌ
ｄｅｓ，Ｃｈｅｍｉｃ ａｔ Ｐｈｙｓｉｑｕｅ Ｐｈ
ｏｔｏｇｒａｐｈｉｑｕｅＰａｕｌ Ｍｏｎｔｅｌ，
１ ９ ６ ７ ） 、ダフィン著「写真乳剤化学」、
フォーカルプレス社刊（Ｇ．Ｆ． Ｄｕｆｆｉｎ．Ｐｈ
ｏｔｏｇｒａｐｈｉｃ Ｅｍｕｌｓｉｏｎ Ｃｈｅｍｉ
ｓｔｒｙ（Ｆｏｃａｌ Ｐｒｅｓｓ＋１９６６）、ゼリ
クマンら著「写真乳剤の製造と塗布」、フォーカルプレ
ス社刊（Ｖ． Ｌ． Ｚｅｌｉｋｍａｎｅｔ ａｌ，
Ｍａｋｉｎｇ ａｎｄ Ｃｏａｔｉｎｇ Ｐ
ｈｏｔｏｇｒａｐｈｉｃＥｓｕｌｓｉｏｎ＋ Ｆｏｃａ
ｌ Ｐｒｅｓｓ＋ １ ９ ６ ４ ）などに記載され
た方法を用いて調製することができる．本発明に用いら
れるハロゲン化銀粒子の形或時には粒子の成長をコント
ロールするためにハロゲン化ｉ！溶剤として例えばアン
モニア、ロダンカリ、ロダンアンモン、チオエーテル化
合物（例えば米国特許第３．２７１，１５７号、同第３
，５７４，６２８号、同第３，７０４，１３０号、同第
４，２９７，４３９号、同第４．２７６．３７４号など
）、チオン化合物（例えば特開昭５３−１４４，３１９
号、同第５３−８２，４０８号、同第５５７７．７３７
号など〉、アミン化合物（例えば特開昭５４−１００，
７１７号など）などを用いることかできる．
本発明においては、水溶性ロジウム塩や前述の如き水溶
性イリジウム塩を用いることができる．本発明における
可溶性根塩と可溶性ハロゲン塩を反応させる形式として
は片側混合法、同時混合法、それらの組合せなどのいず
れを用いてもよい．粒子を銀イオン過剰の下において形
威させる方法（いわゆる逆混合法）を用いることもでき
る．同時混合法の一つの形式としてハロゲン化銀の生成
される液相中のｐＡｇを一定に保つ方法、すなわちいわ
ゆるコントロールド・ダブルジェット法を用いることが
でき、この方法によると、結晶形が規則的で粒子サイズ
が均一に近いハロゲン化銀乳剤が与えられる．
本発明の方法で用いるハロゲン化銀乳剤は化学増感して
いることが好ましい．
化学増感する場合は、ｉｌ常のイオウ増感、還元増感、
貴金属増感及びそれらの組合せが用いられる．
さらに具体的な化学増感剤としては、アリルチ？カルバ
ミド（Ａｌｌｙｌ ｔｈｉｏｃａｒｂａｍｔｄｅ）、チ
オ尿素、チオサルフェート、チオエーテルやシスチンな
どの硫黄増感剤；ボタシウムク口ロオーレイト、オーラ
ス、チオサルフエートやボタシウムク口ロバラデート（
Ｐｏｔａｓｓｉｕａ＋ ｃｈｌｏｒｏ Ｐａｌｌａｄａ
ｔｅ）などの貴金属増感剤：塩化スズ、フェニルヒドラ
ジンやレダクトンなどの還元増感剤などを挙げることが
できる．
本発明に用いられるハロゲン化銀乳剤は、公知の分光増
感色素によって必要に応じて分光増感される．用いられ
る分光増感色素としては、例えばヘイマー著、′ヘテロ
サイクリック・コンパウンズーザ・シアニン・ダイズ・
アンド・リレイテイッド・コンバウンズ１、ジッン・ウ
ィーリ−・アンド・サンズ（１９６４年刊） （Ｆ．
Ｍ． Ｈａｍｅｒ＋”Ｈｅｔｅｒｏｃｙｃｌｉｃ Ｃ
ｏｍｐｏｕｎｄｓ Ｔｈｅ Ｃｙａｎｉｎｅ Ｄｙ
ｅｓａｎｄ Ｒｅｌａｔｅｄ Ｃｏｍｐｏｕｎｄｓ″，
Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ（１９６４）．
やスターマー著、′ヘテロサイクリック・コンバウンズ
■スペシャル・トピックス・イン・ヘテロサイクリック
・ケミストリージッン・ウィーリ−・アンド・サンズ（
１ ９ ７ ７年刊） ＣＤ． Ｍ． Ｓｔｕｒａａｒ
＋ ”Ｈｅｔｅｒｏｃｙｃｌｉｃ Ｃｏｍｐｏｕｎｄｓ
− Ｓｐｅｃｉａｌ Ｔｏｐｉｃｓ ｉｎ Ｈ
ｅｔｅｒｏｃｙｃｌｉｃ Ｃｈｅｍｉｓｔｒｙ ，
Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ （ １ ９
７ ７ ） ．などに記載されている、シアニン、メロ
シアニン、ログシアニン、スチリル、ヘミシアニン、オ
キソノール、ペンジリデン、ホロボーラーなどを用いる
ことができるが、特にシアニンおよびメロシアニンが好
ましい．
本発明で好ましく使用しうる増感色素としては、特開昭
６０−１３３４４２号、同６１−７５３３９号、同６２
−６２５ｌ号、同５９−２１２８２７号、同５０−１２
２９２８号、同５９−１８０１５５３号等に記載された
一般式で表わされるシアニン色素、メロシアニン色素等
が挙げられる．具体的には、特開昭６０−１３３４４２
号の第（８）〜（１１）頁、特開昭６１−７５３３９号
の第（５）〜（７）頁、第（２４〉〜（２５）頁、特開
昭６ ２−６ ２ ５ｌ号の第（ＩＯ）〜（１５）頁、
特開昭５９−２１２８２７号の第（５）〜（７〉頁、特
開昭５０−１２２９２８号の第（７〉〜（９）頁、特開
昭５９−１８０５５３号の第（７）〜（１８）頁等に記
述されているスペクトルの青領域、緑領域、赤領域ある
いは赤外領域にハロゲン化銀を分光増感する増感色素を
挙げることができる．
これらの増感色素は単独に用いてもよいが、それらの組
合わせを用いてもよく、増感色素の組合わせは特に、強
色増感の目的でしばしば用いられる．増感色素とともに
、それ自身分光増感作用を持たない色素あるいは可視光
を実質的に吸収しない物質であって、強色増感を示す物
質を乳剤中に含んでもよい．例えば、含窒素異節環核基
であって置換されたアミノスチルベン化合物（例えば米
国特許第２，９３３，３９０号、同３，６３５．７２１
号に記載のもの）、芳香族有機酸ホルムアルデヒド縮合
物（例えば米国特許第３，７４３．５ＩＯ号に記載のも
の）、カド旦ウム塩、アザインデン化合物などを含んで
もよい．米国特許第３．６１５，６１３号、同３，６１
５．６４１号、同３，６１７，２９５号、同３，６３５
，７２１号に記載の組合わせは特に有用である．
上記の増感色素はハロゲン化銀１モル当り５×１０−’
モル〜５Ｘ１０−”モル、好ましくは１×ｔｏ−”モル
〜ｔｘｉｏ−”モル、特に好ましくは２ｘｔｏ−’モル
〜５Ｘ１０−’モルの割合でハロゲン化銀写真乳剤層中
に含有される．
前記の増感色素は、直接乳剤層へ分散することができる
．また、これらはまず適当な溶媒、例えばメチルアルコ
ール、エチルアルコール、メチルセロソルブ、アセトン
、水、ビリジンあるいはこれらの混合溶媒などの中に溶
解され、溶液の形で乳剤へ添加することもできる．また
、溶解に超音波を使用することもできる．また、前記の
増感色素の添加方法としては米国特許第３，４６９，９
８７号明細書などに記載のごとき、色素を揮発性の有４
！！溶媒に溶解し、該溶液を親水性コロイド中に分散し
、この分散物を乳剤中に添加する方法、特公昭４６−２
４１８５号などに記載のごとき、水不溶性色素を熔解す
ることなしに水溶性溶剤中に分散させ、この分散物を乳
剤へ添加する方法；特公昭６１−４５２１７号に記載の
ごとき、水不溶性色素を水系溶媒中にて機械的に粉砕、
分散させ、この分散物を乳剤へ添加する方法；米国特許
第３，８２２．１３５号明細書に記載のごとき、界面活
性剤に色素を溶解し、該溶液を乳剤中へ添加する方法；
特開昭５ｌ−７４６２４号に記載のごとき、レッドシフ
トさせる化合物を用いて溶解し、該溶液を乳剤中へ添加
する方法；特閉昭５０−８０８２６号に記載のごとき色
素を実質的に水を含まない酸に溶解し、該乳剤を乳剤中
に添加する方法などが用いられる．その他、乳剤への添
加には米国特許第２，９１２，３４３号、同第３３４２
．６０５号、同第２，９９６，２８７号、同第３，４２
９，８３５号などに記載の方法も用いられる．また上記
の増感色素は適当な支持体上に塗布される前にハロゲン
化銀乳剤中に一様に分散してよいが、勿論ハロゲン化銀
乳剤の調製のどの過程にも分散することができる．
上記の増感色素は、さらに他の増感色素を組合せて用い
ることができる．例えば米国特許第３，７０３．３７７
号、同第２，６８８，５４５号、同第３，３９７，０６
０号、同第３， ６１５， ６３５号、同第３，６２
８，９６４号、英国特許第１，２４２，５８８号、同第
１，２９３，８６２号、特公昭４３−４９３６号、同４
４−１４０３０号、同４３−１０７７３号、米国特許３
，４１６．９２７号、特公昭４３−４９３０号、米国特
許第２，６１５，６１３号、同第３． ６１５，
６３２号、同第３．６１７．２９５号、同第３．６３５
，７２１号などに記載の増感色素を用いることができる
．
本発明に従い本発明のハロゲン化銀感光材料を迅速処理
するためには、ハロゲン化銀感光材料の膨潤百分率を２
００％以下にすることが好ましい．一方、膨潤百分率を
低くしすぎると、現像、定着、水洗などの速度が低下す
るため必要以上に下げることは好ましくない．
好ましい膨潤百分率としては２００％以下３０％以上、
特に１５０％以下５０％以上が好ましい．膨潤百分率を
２００％以下とするためには例えば、感光材料に用いる
硬膜剤の使用量を増加させることなどによって当業者で
あれば容易にコントロールすることができる．
膨潤百分率は、ｉａ）写真材料を３８℃５０％相対湿度
で３日間インキュベーシッン処理し、（ｂ）！！水性コ
ロイド層の厚みを測定し、（Ｃｌ該写真材料は２１℃蒸
留水に３分間浸漬し、そして＋ｄｌ工程中》で測定した
親水性コロイド層の厚みと比較して、層の厚みの変化の
百分率を測定することによって求めることができる．
本発明に用いうる硬膜剤としては例えばアルデヒド化合
物、米国特許第３．２８８，７７５号等に記載されてい
る活性ハロゲンを有する化合物、米国特許第３，６３５
，７１８号等に記載されている反応性のエチレン性不飽
和基を持つ化合物、米国特許第３，０９１，５３７号等
に記載されているエボキシ化合物、ムコクロル酸のよう
なハロゲノカルボキシアルデヒド等の有機化合物が知ら
れている．中でもビニルスルホン系硬膜剤が好ましい．
更には高分子硬膜剤も好ましく用いることができる．
高分子硬膜剤としては活性ビニル基、あるいはその前駆
体となる基を有するボリマーが好ましく、中でも特開昭
５６−１４２５２４号に記載されている様な、長いスペ
ーサーによって活性ビニル基、あるいはその前駆体とな
る基がボリマー主鎖に結合されているようなボリマーが
特に好ましい．上記の膨潤百分率を達威するためのこれ
らの硬膜剤の添加量は、使用する硬膜剤のｌＩ類やゼラ
チン種によって異なる．
本発明の迅速処理においては、乳剤層中及び／又はその
他の親水性コロイド層中に現像処理工程に於で流出する
ような有機物質を含有せしめることが好ましい．流出す
る物質がゼラチンの場合は硬膜剤によるゼラチンの架橋
反応にかかわらないゼラチン種が好ましく、たとえばア
セチル化ゼラチンやフタル化ゼラチンなどがこれに該当
し、分子量は小さいものが好ましい．一方、ゼラチン以
外の高分子物質としては米国特許第３，２７１，１５８
号に記載されているようなポリアクリルアミド、あるい
はまたポリビニールアルコール、ポリビニルビロリドン
などの親水性ボリマーを有効に用いることができ、デキ
ストランやサフカローズ、ブルラン、などのｔｉｌ！も
有効である．中でもポリアクリルアξドやデキストラン
が好ましく、ポリアクリルアミドは特に好ましい物質で
ある．これらの物質の平均分子量は好ましくは２万以下
、より好ましくは１万以下が良い．この他に、Ｒｅｓｅ
ａｒｃｈ Ｄｉｓｃｌｏｓｕｒｅ第１７６巻、Ｎａｌ７
６４３、第■項（１２月号、１９７８年）に記載された
カブリ防止剤や安定化剤を用いることができる．本発明
の現住処理方法は、米国特許第４，２２４．４０１号、
同第４，１６８，９７７号、同第４，１６６，７４２号
、同第４，３１１．７８１号、同第４，２７２，６０６
号、同第４，２２１，８５７号、同第４，２４３，７３
９号等に記載されているヒドラジン誘導体を用いて超硬
調で感度の高い写真特性を得ることができるハロゲン化
銀感光材料の画像形成処理に応用できる．ヒドラジン誘
導体としては、ＲＥＳＥＡＲＣＨ ＤＩＳＣＬＯＳＵＲ
ＥＮａ２３５ｌ６ （１９８３年１１月号、Ｐ．３４６
）およびそこに引用された文献の他、米国特許第４．０
８０．２０７号、同第４，２６９，９２９号、同第４，
２７６，３６４号、同第４， ２７８． ７４８号
、同第４，３８５．１０８号、同第４．４５９，３４７
号、同第４．５６０．６３８号、同第４，４７８，９２
８号、英国特許第２．０１１，３９１Ｂ号、特開昭６０
−１７９７３４号に記載されたものを用いることができ
る．ヒドラジン誘導体は、ハロゲン化１９１モルあたり
ＩＸＩＯ−’モルないし５ Ｘ １ ０−”モル含有さ
れるのが好ましく、特にＩＸＩＯ−’モルないし２Ｘ１
０””モルの範囲が好ましい添加量である．
また、この場合において用いる現像液には、硬調化促進
剤として米国特許４，２６９．９２９号に記載のアミノ
化合物を含んでもよい．以下に実施例を挙げて本発明を
更に詳細に説明すζ．
実施例ｌ
乳剋凶亘盟
水ｌＩ中にゼラチン３０ｇ、臭化カリ６ｇを加え６０℃
に保った容器中に攪拌しながら硝酸銀水溶液（硝酸銀と
して５ｇ）と沃化カリ０．１５ｇを含む臭化カリ水溶液
を１分間かけてダブルジェット法で添加した，さらに硝
酸銀水溶液（硝酸銀として１４５ｇ）と沃化カリ４．２
ｇを含む臭化カリ水溶液をダブルジェット法で添加した
．この時の添加流速は、添加終了時の流速が、添加開始
時の５倍となるように流量加速をおこなった．添加終了
後、沈降法により３５℃にて可溶性塩類を除去したのち
４０℃に昇温してゼラチン７５ｇを追添し、ｐＨを６．
７に調整した．得られた乳剤は投影面積直径が０６ ９
８μｍ、平均厚み０．１３８μｍの平板状粒子で、沃化
銀含量は３モル％であった．この乳剤に、金、イオウ増
感を併用して化学増感をほどこし、乳剤を調製した．工
真杜粧坐里製
表面保護層として、ゼラチンの他にポリスチレンスルホ
ン酸ソーダ、ポリメチルメタクリレート微粒子（平均粒
子サイズ３．０μｍ）、ポリエチレンオキサイド、およ
び硬膜剤などを含有したゼラチン水溶液を用いた．上記
乳剤増感色素アンヒドロー５．５′−ジークロロー９−
エチル−３．３′−ジ（３−スルホブロビル〉オキサカ
ルボシアニンハイドロオキサイドナトリウム塩５００■
／ｌモルＡｇと沃化カリ２００■／ｌモルＡｇを添加し
た．さらに安定剤として４−ヒドロキシー６−メチル−
１．３，３ａ，７−テトラザインデンと２，６−ビス（
ヒドロキシアミン）−４−ジエチルアミノー１．３．５
−｝リアジン、乾燥カブリ防止剤としてトリメチロール
プロパン、塗布助剤、硬膜剤を添加して塗布液とし、ポ
リエチレンテレフタレート支持体の両側に各々表面保護
層と同時に塗布乾燥することにより、写真材料を作威し
た．写真材料の塗布銀量は両面で３．７ｇ／ｄである．
処差九抜
現像液及び定着液（１１処方は次の通りである．Ｅ』レ
叉
ジエチレントリアミン五酢酸 ２ｇ１−フヱ
ニル−３−ビラゾリドン ２，３ｇヒドロキノン
３０ｇ５〜ニトロインダゾール
０．２５ｇ５−メチルベンゾトリアゾール
０．０２ｇ臭化カリウム
１ｇ無水亜硫酸ナトリウム ６０ｇ
水酸化カリウム ３０ｇ炭酸カ
リウム ５ｇ硼Ｍ
６ｇジエチレングリコー
ル ２０ｇグルタルアルデヒド
５ｇ水を加えて全量を１１とする
（ｐＨはｉｏ．ｓｏに調整した．）
定置換１±と
チオ硫酸アンモニウム（ ７ ０ ｗｔ／ｖｏ１％）２
０（ｌｄ
亜硫酸ナトリウム（無水） ２０、Ｏｇチオ硫
酸ナトリウム・五水塩 １０ｇ酒石酸
３．０ｇ
０．
１ ５．
２．
３５．
ｌ．
（ｐＨは４．２０に調整する．
エチレンジアξン四酢酸二
ナトリウム・二水塩
硫酸アルミニウム
硫酸
氷酢酸
水を加えて
自現機のタンクには現像液として、上記補充液１ｌに対
して臭化カリウム２ｇ及び酢酸（９０％〉４ｇを含む水
溶液（スターター）２０Ｍｌを添加した液を使用し、以
後感材が処理される毎に、補充液を一定の割合で補充し
た．定着液は自現機のタンクにも補充液と同一＆ｌ威の
液を使った．上記の感材を四切サイズで各５００枚次の
ような種々の条件下で処理したときの処理液の増感色素
による残色（５００枚目）画像安定性及び定着速度は以
下の通りである．
？施例 ２
裏最色遁製
水１ｌに臭化カリ５ｇ、ゼラチン２５．６ｇ、チオエー
テル ＨＯ（ＣＩ１■）＊Ｓ（ＣＨｉ）＊Ｓ（ＣＨｚ）
ｘＯＨ の５％水溶液２．５ｃｃを添加し６６℃に保
った溶液中へ、攪拌しながら硝酸銀８．３３ｇの水溶液
と、臭化カリ５．９４ｇ，沃化カリ０．７２６ｇを含む
水溶液とをダブルジェント法により４５秒間で添加した
．続いて臭化カリ２６ ９ｇを添加したのち、硝酸銀８
．３３ｇを含む水溶液を２４分かけて添加したのち二酸
化チオ尿素（下記構造）を０．ｌ■添加した．
“”Ｎ＞ｓｏ．■
ＨＮ
このあと２５％アンモニア溶液２０ｃｃ、５０％ＮＨ４
ＮＯ−１０ｃｃで添加して２０分間物理熟威したのち
ＩＮの硫酸２ ４ ０ ｃｃを添加して中和した．引き
続いて硝酸銀１５３．３４ｇの水溶液と臭化力＋ｆの水
溶液を、電位ｐＡｇ８．２に保ちながらコントロールダ
ブルジェット法で４０分間で添加した。この時の流量は
添加終了時の流量が、添加開始時の流量の９倍となるよ
う加速した．添加終了後２Ｎのチオシアン酸カリウム溶
液１５ｃｃを添加し、さらに１％の沃化カリ水溶液４５
ｃｃを３０秒かけて添加した。このあと温度を３５℃に
下げ、沈降法により可溶性塩類を除去したのち、４０℃
昇温しでゼラチン７６ｇとプロキセル７６■およびフェ
ノキシエタノール７６０■を添加し、苛性ソーダと臭化
カリによりｐＨ６．５０、ｐＡｇ８．２０に調整した．
温度を５６℃に昇温したのち、４−ヒドロキシ−６−メ
チル−１．３．３ａ．７−テトラザインデン１８６■を
添加して１０分後に増感色素（下記構造式）を５２０１
Ｉｇ添加した．更に１０分後にチオ硫酸ナトリウム５水
和物３．４■チオシアン酸カリ１４０■、塩化金酸３．
１■を乳剤に添加し、７０分後に急冷して固化させて乳
剤とした。The tabular grain aspect ratio is given as the ratio of the average diameter of a circle having an area equal to the projected area of each tabular grain to the average grain thickness of each tabular grain. In the present invention, the preferred grain form in the case of tabular grains is an aspect ratio of 4 or more and less than 20, more preferably 5 or more and less than 10. Further, the thickness of the particles is preferably 0.3μ or less, particularly preferably 0.2μ or less. The tabular grains preferably account for 80% by weight of the total grains, more preferably 9% by weight of the total grains.
Preferably, it is present in an amount of 0% by weight or more. The grain size of silver halide may be a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution. The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, by Research lliscl.
osure. Magnetic 17643 (December 1978), 2
Pages 2-23, "L emulsion production (εs1uIslon pr
1B716 (November 1979), 648. The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Graffide, published by Beaumontel (P.G.) afkl.
des, Chemical at Physique Ph
otographiquePaul Montel,
1967), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (G.F. Duffin.Ph
otographic Emulsion Chemi
stry (Focal Press+1966), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V. L. Zelikmanet al,
Making and coating P
photographyEsulsion+ Foca
It can be prepared using the method described in 1 Press+ 1964). In order to control the shape and sometimes grain growth of the silver halide grains used in the present invention, the i! Examples of solvents include ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. Nos. 3,271,157 and 3).
, No. 574,628, No. 3,704,130, No. 4,297,439, No. 4.276.374, etc.), thione compounds (e.g., JP-A No. 144,319/1983)
No. 53-82,408, No. 5577.737
etc.), amine compounds (e.g. Japanese Patent Application Laid-Open No. 54-100,
717 etc.). In the present invention, water-soluble rhodium salts and water-soluble iridium salts as described above can be used. In the present invention, the soluble root salt and the soluble halogen salt may be reacted by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof. It is also possible to use a method in which particles are formed under an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method of keeping the pAg in the liquid phase in which silver halide is produced constant, that is, a so-called controlled double jet method, can be used. According to this method, the crystal form is regular. gives a silver halide emulsion with nearly uniform grain size. The silver halide emulsion used in the method of the present invention is preferably chemically sensitized. For chemical sensitization, conventional sulfur sensitization, reduction sensitization,
Noble metal sensitization and combinations thereof are used. As a more specific chemical sensitizer, Allylchi? Sulfur sensitizers such as carbamides, thioureas, thiosulfates, thioethers and cystine;
Potassiua+ chloro Pallada
Examples include noble metal sensitizers such as tin chloride, reduction sensitizers such as phenylhydrazine, and reductones. The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. The spectral sensitizing dye used is, for example, 'Heterocyclic Compounds of Cyanine Soybean' by Hamer.
& Related Combines 1, Ginn, Wheelie & Sons (1964) (F.
M. Hamer+”Heterocyclic C
compounds The Cyanine Dy
esand Related Compounds'',
John Wiley & Sons (1964).
and Starmer, ``Heterocyclic Combinations■Special Topics in Heterocyclic Chemistry, Gene Wiley & Sons (
1977) CD. M. Sturaar
＋”Heterocyclic Compounds
-Special Topics in H
eterocyclic chemistry,
John Wiley & Sons (19
7 7). Cyanine, merocyanine, logocyanine, styryl, hemicyanine, oxonol, penzylidene, holoborer, etc., which are described in , etc., can be used, but cyanine and merocyanine are particularly preferred. Sensitizing dyes that can be preferably used in the present invention include JP-A-60-133442, JP-A-61-75339, and JP-A-62
-625l No. 59-212827, No. 50-12
Examples include cyanine dyes and merocyanine dyes represented by the general formulas described in No. 2928 and No. 59-1801553. Specifically, Japanese Patent Application Laid-Open No. 60-133442
pages (8) to (11) of JP-A-61-75339, pages (5)-(7), and pages (24-25) of JP-A-61-75339, JP-A-61-75339. pages (IO) to (15) of
JP-A No. 59-212827, pages (5) to (7), JP-A-50-122928, pages (7>-(9), JP-A-59-180553, pages (7) to () Examples include sensitizing dyes that spectrally sensitize silver halide in the blue region, green region, red region, or infrared region of the spectrum as described on page 18).These sensitizing dyes can be used alone. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.Along with sensitizing dyes, dyes that do not themselves have spectral sensitizing properties may be used. Alternatively, the emulsion may contain a substance that does not substantially absorb visible light and exhibits supersensitization.For example, an aminostilbene compound substituted with a nitrogen-containing heterocyclic ring group (for example, Patent No. 2,933,390, Patent No. 3,635.721
(described in US Pat. No. 3,743.5IO), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743.5IO), caddanium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613, U.S. Patent No. 3,61
No. 5.641, No. 3,617,295, No. 3,635
, 721 is particularly useful. The above sensitizing dye is 5 x 10-' per mole of silver halide.
It is contained in the silver halide photographic emulsion layer in a proportion of mol to 5X10-'' mol, preferably 1xto-'' mol to txio-'' mol, particularly preferably 2xto-' mol to 5X10-'' mol. Sensitizing dyes can be directly dispersed into the emulsion layer, or they are first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixture thereof. The sensitizing dye can be added to the emulsion in the form of a solution.Ultrasonic waves can also be used for dissolution.Also, as a method for adding the sensitizing dye, US Pat.
As described in Specification No. 87, etc., dyes are volatile
! ! A method of dissolving in a solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion, Japanese Patent Publication No. 46-2
A method of dispersing a water-insoluble dye in a water-soluble solvent without melting it and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 45217-1985; Mechanically pulverized in an aqueous solvent;
a method of dispersing the dye and adding the dispersion to an emulsion; a method of dissolving the dye in a surfactant and adding the solution into an emulsion, as described in U.S. Pat. No. 3,822,135;
A method of dissolving a red-shifting compound using a red-shifting compound and adding the solution into an emulsion as described in JP-A No. 50-80826; A method of dissolving the emulsion in an acid-free emulsion and adding the emulsion to the emulsion is used. Other additions to emulsions include U.S. Patent Nos. 2,912,343 and 3342.
．． No. 605, No. 2,996,287, No. 3,42
The method described in No. 9,835 etc. can also be used. The sensitizing dyes described above may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but can of course also be dispersed during any step in the preparation of the silver halide emulsion. ．． The above-mentioned sensitizing dyes can be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3,703.377
No. 2,688,545, No. 3,397,06
No. 0, No. 3, 615, 635, No. 3, 62
8,964, British Patent No. 1,242,588, British Patent No. 1,293,862, Japanese Patent Publication No. 43-4936, British Patent No. 4
No. 4-14030, No. 43-10773, U.S. Patent 3
, No. 416.927, Japanese Patent Publication No. 43-4930, U.S. Patent No. 2,615,613, No. 3. 615,
No. 632, No. 3.617.295, No. 3.635
, No. 721, etc. can be used. In order to rapidly process the silver halide photosensitive material of the present invention according to the present invention, the swelling percentage of the silver halide photosensitive material must be set to 2.
It is preferable to keep it below 00%. On the other hand, if the swelling percentage is too low, the speed of development, fixing, washing, etc. will be reduced, so it is not preferable to lower the swelling percentage more than necessary. The preferred swelling percentage is 200% or less and 30% or more,
Particularly preferred is 150% or less and 50% or more. A person skilled in the art can easily control the swelling percentage to 200% or less by, for example, increasing the amount of hardening agent used in the photosensitive material. The swelling percentage was determined by ia) incubating the photographic material at 38°C and 50% relative humidity for 3 days, and (b)! ! The thickness of the aqueous colloid layer was measured and compared with the thickness of the hydrophilic colloid layer measured (the photographic material was immersed in distilled water at 21° C. for 3 minutes and during the +dl step) to determine the change in layer thickness. It can be determined by measuring the percentage. Examples of hardening agents that can be used in the present invention include aldehyde compounds, active halogen-containing compounds described in U.S. Pat. No. 3,288,775, and U.S. Pat. ,635
, 718, etc., epoxy compounds described in U.S. Pat. No. 3,091,537, etc., and organic compounds such as halogenocarboxaldehydes such as mucochloric acid. compounds are known. Among these, vinyl sulfone hardeners are preferred.
Furthermore, polymer hardeners can also be preferably used. The polymer hardener is preferably a polymer having an active vinyl group or a group that is a precursor thereof, and in particular, a long spacer as described in JP-A No. 56-142524 is used to harden an active vinyl group or its precursor. Particularly preferred are polymers in which the body groups are bonded to the main chain of the polymer. The amount of these hardeners added to achieve the above swelling percentage varies depending on the type of hardener used and the type of gelatin. In the rapid processing of the present invention, it is preferred that the emulsion layer and/or other hydrophilic colloid layers contain organic substances that would flow out during the development process. When the substance to be discharged is gelatin, it is preferable to use a type of gelatin that is not involved in the crosslinking reaction of gelatin by a hardening agent, such as acetylated gelatin or phthalated gelatin, and preferably one with a small molecular weight. On the other hand, as a polymer substance other than gelatin, U.S. Patent No. 3,271,158
Hydrophilic polymers such as polyacrylamide, or alternatively polyvinyl alcohol, polyvinylpyrrolidone, etc. can be effectively used, such as dextran, safka rose, bullulan, etc. is also valid. Among these, polyacrylamide and dextran are preferred, and polyacrylamide is particularly preferred. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. In addition to this, Rese
arch Disclosure Volume 176, Nal7
Antifoggants and stabilizers described in No. 643, Section 2 (December issue, 1978) can be used. The current treatment method of the present invention is disclosed in U.S. Patent No. 4,224.401;
Same No. 4,168,977, Same No. 4,166,742, Same No. 4,311.781, Same No. 4,272,606
No. 4,221,857, No. 4,243,73
It can be applied to the image forming process of silver halide photosensitive materials that can obtain ultra-high contrast and high-sensitivity photographic properties using the hydrazine derivatives described in No. 9 and other publications. As a hydrazine derivative, RESEARCH DISCLOSUR
ENa235l6 (November 1983 issue, P.346
) and references cited therein, as well as U.S. Pat.
No. 80.207, No. 4,269,929, No. 4,
No. 276,364, No. 4, 278. No. 748, No. 4,385.108, No. 4.459,347
No. 4,560.638, No. 4,478,92
No. 8, British Patent No. 2.011,391B, Japanese Unexamined Patent Publication No. 1983
-179734 can be used. The hydrazine derivative is preferably contained in an amount of IXIO-' mol to 5 X 10-'' mol, particularly IXIO-' mol to 2
The preferred addition amount is in the range of 0"" mole. Further, the developer used in this case may contain an amino compound described in US Pat. No. 4,269,929 as a high contrast accelerator. The present invention will be explained in more detail with reference to Examples.ζ. Example 1 Add 30 g of gelatin and 6 g of potassium bromide to milk and water at 60°C.
A silver nitrate aqueous solution (5 g as silver nitrate) and a potassium bromide aqueous solution containing 0.15 g of potassium iodide were added over 1 minute using the double jet method while stirring into a container kept at Potassium iodide 4.2
An aqueous solution of potassium bromide containing g was added using the double jet method. The addition flow rate at this time was accelerated so that the flow rate at the end of addition was five times that at the start of addition. After the addition, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, 75 g of gelatin was added, and the pH was adjusted to 6.
Adjusted to 7. The resulting emulsion has a projected area diameter of 069
The grains had a tabular shape of 8 μm and an average thickness of 0.138 μm, and the silver iodide content was 3 mol %. This emulsion was chemically sensitized using gold and sulfur sensitization to prepare an emulsion. As the surface protective layer made by Koshin Toshozari, an aqueous gelatin solution containing sodium polystyrene sulfonate, polymethyl methacrylate fine particles (average particle size 3.0 μm), polyethylene oxide, and a hardening agent in addition to gelatin was used. ．． The above emulsion sensitizing dye Anhydro 5.5'-Dichloro 9-
Ethyl-3.3'-di(3-sulfobrovir>oxacarbocyanine hydroxide sodium salt 500■
/l mol Ag and 200 µ/l mol Ag of potassium iodide were added. Furthermore, as a stabilizer, 4-hydroxy-6-methyl-
1.3,3a,7-tetrazaindene and 2,6-bis(
Hydroxyamine)-4-diethylamino1.3.5
-}Ryazine, trimethylolpropane as a drying anti-fog agent, a coating aid, and a hardening agent are added to form a coating solution, which is coated on both sides of a polyethylene terephthalate support at the same time as a surface protective layer, and dried to prepare a photographic material. I created it. The amount of coated silver on both sides of the photographic material was 3.7 g/d. Processing difference 9 developer and fixer (11 The formulation is as follows.
30g5~Nitroindazole 0.25g5-Methylbenzotriazole
0.02g potassium bromide
1g anhydrous sodium sulfite 60g
Potassium hydroxide 30g Potassium carbonate 5g
6g diethylene glycol 20g glutaraldehyde
Add 5 g of water to bring the total volume to 11 (pH was adjusted to io.so.) Constant substitution 1± and ammonium thiosulfate (70 wt/vo 1%) 2
0 (ld Sodium sulfite (anhydrous) 20, Og Sodium thiosulfate pentahydrate 10 g Tartaric acid 3.0 g 0. 1 5. 2. 35. l. (Adjust the pH to 4.20. Sodium/dihydrate aluminum sulfate aluminum sulfate glacial acetic acid water was added to the tank of the automatic processor as a developer, and 20 ml of an aqueous solution (starter) containing 2 g of potassium bromide and 4 g of acetic acid (90%) per 1 liter of the above replenisher was added. Afterwards, each time the photosensitive material was processed, it was replenished with replenisher at a fixed rate.The same fixer solution as the replenisher was also used in the tank of the automatic processing machine. When 500 sheets each of the above-mentioned photosensitive materials were processed in a quarter-cut size under the following various conditions, the residual color (500th sheet) image stability and fixing speed due to the sensitizing dye in the processing solution were as follows: Yes. ?Example 2 5 g of potassium bromide, 25.6 g of gelatin, thioether HO (CI1■) * S (CHi) * S (CHz) in 1 liter of Ura-Saishokuton Seisui.
2.5 cc of a 5% aqueous solution of xOH was added and kept at 66°C, and while stirring, an aqueous solution of 8.33 g of silver nitrate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide were added. It was added in 45 seconds using the gent method. Subsequently, after adding 269 g of potassium bromide, 8 g of silver nitrate was added.
．． An aqueous solution containing 33 g was added over 24 minutes, and then 0.0 g of thiourea dioxide (structure below) was added. l■ Added. “”N>so. ■ HN After this, 20cc of 25% ammonia solution, 50% NH4
After adding 10 cc of NO and physically ripening for 20 minutes, 240 cc of IN sulfuric acid was added to neutralize. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of bromidating power +f were added over 40 minutes by a controlled double jet method while maintaining the potential pAg at 8.2. At this time, the flow rate was accelerated so that the flow rate at the end of addition was nine times the flow rate at the start of addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 45 cc of 1% potassium iodide aqueous solution was added.
cc was added over 30 seconds. After this, the temperature was lowered to 35°C, soluble salts were removed by the sedimentation method, and then the temperature was lowered to 35°C.
While the temperature was raised, 76 g of gelatin, 76 ml of Proxel, and 760 ml of phenoxyethanol were added, and the pH was adjusted to 6.50 and pAg to 8.20 with caustic soda and potassium bromide. After raising the temperature to 56°C, 4-hydroxy-6-methyl-1.3.3a. 10 minutes after adding 7-tetrazaindene 186■, add the sensitizing dye (the following structural formula) to 5201
Ig was added. After a further 10 minutes, 3.4 parts of sodium thiosulfate pentahydrate, 140 parts of potassium thiocyanate, and 3.4 parts of potassium thiocyanate were added.
1 was added to the emulsion, and 70 minutes later, it was rapidly cooled and solidified to form an emulsion.
１
Ｓｏ，Ｎａ Ｓｏ，得られた乳剤
は全粒子の投影面積の総和の９９．５％がアスペクト比
３以上の粒子からなり、アスペクト比２以上すべての粒
子についての平均の投影面積直径は１．３５μｍ，標準
偏差２２．３％、厚みの平均は０．２００μｍでアスペ
クト比は６．８であった．
乳剋塗奄放食Ａ監
乳剤にハロゲン化銀ｌモルあたり、下記の薬品を添加し
て塗布液とした．
・ポリマーラテックス
（ポリ（エチルアクリレート
／メタクリル酸）−９７／
３） ２５．０ｇ・硬膜剤
１．２−ビス（スルホニルア
セトアミド〉エタン ３，Ｏｇ・２，６−
ビス（ヒドロキシアミ
ノ）−４−ジエチルアミノー
１，３．５−トリアジン ８０■・ポリアク
リル酸ナトリウム
（平均分子！ ４，１万） ４．０ｇ・ポリス
チレンスルホン酸カリウム
（平均分子量 ６０万） ｌ．ｏｇ・ポリ
アクリルアミド
（平均分子量 ４．５万） ２４ｇ叉且生立這
盟
ブルー着色した厚さ１７５μｍのポリエチレンテレフタ
レートベースの両面に下記の塗布量の下塗層を設けたベ
ースを準備した．
・ゼラチン ８４■／ｒｒｒイ
ＣＨＲＣＨ力ｔ一−−べｃｕｔｃｕ石ＣＯ．
ＣＨ，
１７■／耐
互ｍ因４製
前記塗布液を表面保護層塗布液と同時に厚み１７５μｍ
の透明ＰＥＴ支持体上に塗布した．塗布銀量は片面あた
り２，Ｏｇ／ｒｒｌとし両面に塗布した．
表面保護層は各成分が、下記の塗布量となるように調製
し、写真材料を調製した．
１４ｍκ聳
・ゼラチン
・ポリアクリルアミド
（平均分子Ｎ ４．５万）
・ポリアクリル酸ソーダ
（平均分子１ ４０万）
・ｐ−ｔ−オクチルフエノキシジ
グリセリルプチルスルホン化
物のナトリウム塩
・ポリ（重合度１０）オキシエチ
レンセチルエーテル
・ポリ（重合度１０）オキシエチ
レンーボリ（重合度３）オキ
シグリセリルｐ−オクチルフ
エノキシエーテル
・４−ヒドロキシ−６−メチル
１，３．３ａ，？−テトラザ
インデン
・２−クロロハイドロキノン
・ Ｃ＊ＦＩｑＳＯｓκ
２蚕及
１． １５ｇ／ｍ
０． ２５
０． ０ ２
０． ０ ２
０．０３５
０．０１
０．０１５５
０．１５４ｇ
０．００３
Ｃ３Ｈ，
・ ＣｓＦ＋ｔｓＯｘＮ＋ＣＨ１ナ「士ＣＨ！’ＦｒＳ
ＯｓＮａ０．００１
ＣＪｔ
・ ＣｓＦ ＋ ｔｓＯｔＮ −｛ＣＨ＊ＣＩＩｇＯ｝
−ｒｒ−｛ＣＨｔＣＨＣＨｚＯ） ａＨ０．００３
・ポリメチルメタクリレート
（平均粒径３．５μｍ）
・ポリ （メチルメタクリレート／
メタクリレート）（モル比７
：３、平均粒径２．５μｍ）
処理剤の調製（濃縮液処方）
現像液
Ｐａｒｔ Ａ
水酸化カリウム ３３０ ｇ
亜硫酸カリウム ６３０ｇ
亜硫酸ナトリウム ２４０ｇ
炭酸カリウム ９０ｇ
ホウ酸 ４５ｇ
０．０２５
０．０２０
２２ｇ
４２ｇ
１６ｇ
６ｇ
３ｇ
ジエチレングリコール
ジエチレントリアミン
五酢酸
３．３′−ジチオビス
ヒド口桂皮酸
５−メチルベンゾトリ
アゾール
ハイドロキノン
臭化カリウム
水を加えて
Ｐａｒｔ Ｂ
トリエチレングリコール
氷酢酸
５−ニトロインダゾール
１−フエニル−３
ビラ
ゾリドン
水を加えて
１８０ｇ
３０ｇ
３ｇ
０．２２５ ｇ
４５０ｇ
１５ｇ
４１２５ｄ
１２ｇ
２ｇ
０．２ｇ
０．０１５ ｇ
３０ｇ
Ｉｇ
２７５ｄ
５２５ｇ
１０２．６ ｇ
３５ｇ
７．６ｇ （９０％）
３．７５ ｇ
０．２５ｇ
３４．５ ｇ
７５０＋ｄ
２．３ｇ
５〇一
Ｐａｒｔ Ｃ
グルタルアルデヒド
（５０＋ｓｔ／ｗｔ％） １５０ｇメタ重
亜硫酸カリウム １５０ｇ
水を加えて ７５０ｄ
スターター
氷酢酸 ２７ｇ
臭化カリウム ２００ｇ
水を加えて ２０００ ｄ
定豊換里
チオ硫酸アンモニウム＜７０ｗｔ／ｖｏＩ ％）１０ｇ
１０ｇ
５〇一
２００ｓｄ
硫酸（３６Ｎ） ３．９ｇ硫酸
アルミニウム １０ｇ１− （Ｎ，
Ｎ−ジメチルアミノ）
エチル−５−メルカブトテトラ
ゾール １ｇ水で
４００ｄｐＨ４．６５
上記現像液濃縮液をポリエチレンの容器に各パート毎に
充填した．この容器はパー｝Ａ，Ｂ，Ｃの各容器が一つ
に連結されている．
また上記定着液濃縮液もポリエチレンの容器に充填した
．
エチレンジア稟ン四酢酸・ニ
ナトリウム・三水塩
千オ硫酸ナトリウム・五水塩
亜硫酸ナトリウム
ホウ酸
酒石酸
氷酢酸
水酸化ナトリウム
０．０３ｇ
ｌｏｇ
２５ｇ
４ｇ
３． ２ｇ
３１．５ｇ
１１ｇ
これらの現像液、定着液を次のような割合で自現機の現
像タンク、定着液タンクに、それぞれ自現機に設置され
ている定量ポンプを使って満たした．
現像液 定着液
（ｐＨ １０．５０）
現像液タンクにはこれにスターターを３００一添加した
．水洗タンクには水道水を満たし、タンクの底に、Ｎａ
ｔＯ／ＢｔＯｓ ／ Ｓｉｎｇから威る溶解性ガラスに
ＡｇｚＯを０．５％（ｗｔ）含む銀除放剤〔商品名 バ
イオシェアＳＧ（近畿パイプ技研■製）〕５０ｇを不織
布に包んだ袋４ヶを沈めた．前記の感光材料にＸ一線露
光を与え、上記の自現機及び処理液を上記のような割合
で四切サイズ（１″ＯインチＸ１２インチ）８枚処理さ
れる毎に補充をしながら現像処理した．
水洗水は毎分流量１（ｌで、感光材料が処理されている
間は同期して電磁弁が開いて供給（約１ｌ／四切りサイ
ズｌ枚）され、一日の作業終了時には自動的に電磁弁が
開いて、全部水を抜いた．こうして１日平均１５０枚の
ランニング処理を２ケ月続けた．結果を第２表に示す．
化合物Ａ（比較用）
第１表および第２表から明らかなように、本発明の化合
物を用いることにより低補充量でも定着性、残色、画像
安定性の点で全く問題のない処理が可能になることがわ
かる．1 So, Na So, in the resulting emulsion, 99.5% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all the grains with an aspect ratio of 2 or more is 1. 35 μm, standard deviation 22.3%, average thickness 0.200 μm, and aspect ratio 6.8. The following chemicals were added per mole of silver halide to Emulsion A to prepare a coating solution.・Polymer latex (poly(ethyl acrylate/methacrylic acid)-97/3) 25.0g ・Hardening agent 1.2-bis(sulfonylacetamide>ethane 3,Og・2,6-
Bis(hydroxyamino)-4-diethylamino-1,3.5-triazine 80■ Sodium polyacrylate (average molecular weight 4,100,000) 4.0g Potassium polystyrene sulfonate (average molecular weight 600,000) l. A base containing 24 g of OG polyacrylamide (average molecular weight: 45,000) and a 175 μm thick polyethylene terephthalate base colored with raw material blue and having an undercoat layer of the following coating amount on both sides was prepared.・Gelatin 84■/rrrI CHRCH force t--becutcu stone CO. CH, 17■/The above coating solution made from Mutual Factor 4 was applied to a thickness of 175 μm at the same time as the surface protective layer coating solution.
It was coated on a transparent PET support. The amount of silver applied was 2.0 g/rrl per side, and the coating was applied to both sides. The surface protective layer was prepared so that the coating amount of each component was as shown below, and a photographic material was prepared. 14mκ聳・Gelatin・Polyacrylamide (average molecule N 45,000) ・Sodium polyacrylate (average molecule 1 400,000) ・Sodium salt of pt-octylphenoxy diglycerylbutyl sulfonate・Poly(degree of polymerization 10) ) Oxyethylene cetyl ether/poly(degree of polymerization 10) Oxyethylene-poly(degree of polymerization 3) Oxyglyceryl p-octyl phenoxy ether/4-hydroxy-6-methyl 1,3.3a,? -Tetrazaindene・2-chlorohydroquinone・C*FIqSOsκ 2 Silkworm and 1. 15g/m 0. 25 0. 0 2 0. 0 2 0.035 0.01 0.0155 0.154g 0.003 C3H, ・ CsF + tsOxN + CH1Na ``SCH!'FrS
OsNa0.001 CJt・CsF + tsOtN −{CH*CIIgO}
-rr-{CHtCHCHzO) aH0.003 ・Polymethyl methacrylate (average particle size 3.5 μm) ・Poly(methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2.5 μm) Preparation of processing agent (concentrated solution Prescription) Developer Part A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 240 g Potassium carbonate 90 g Boric acid 45 g 0.025 0.020 22 g 42 g 16 g 6 g 3 g Diethylene glycol diethylene triamine pentaacetic acid 3.3'-dithiobishydrocinnamate 5-methyl Add benzotriazole hydroquinone Potassium bromide water Part B Triethylene glycol Glacial acetic acid 5-nitroindazole 1-phenyl-3 Add water vilazolidone 180g 30g 3g 0.225 g 450g 15g 4125d 12g 2g 0.2g 0.015 g 30g Ig 275d 525g 102.6 g 35g 7.6g (90%) 3.75 g 0.25g 34.5 g 750+d 2.3g 501 Part C Glutaraldehyde (50+st/wt%) 150g Potassium metabisulfite 150g Add water 750d Starter glacial acetic acid 27g Potassium bromide 200g Add water 2000d Sadatoyo Kasuri ammonium thiosulfate <70wt/voI%) 10g 10g 501 200sd Sulfuric acid (36N) 3.9g Aluminum sulfate 10g 1- (N ，
N-dimethylamino) Ethyl-5-mercabutotetrazole 1g with water
400dpH4.65 The above developer concentrate was filled into polyethylene containers for each part. This container consists of containers A, B, and C connected together. The above fixer concentrate was also filled into a polyethylene container. Ethylenediaminetetraacetic acid, disodium trihydrate, sodium periosulfate, pentahydrate, sodium sulfite, boric acid, tartaric acid, glacial sodium acetate hydroxide 0.03g log 25g 4g 3. 2g 31.5g 11g These developer and fixer solutions were filled in the developing tank and fixer tank of an automatic processor in the following proportions using metering pumps installed in the automatic processor. Developer Solution Fixer (pH 10.50) 300ml of starter was added to the developer tank. Fill the washing tank with tap water, and add Na to the bottom of the tank.
tO/BtOs/Sing's soluble glass silver release agent containing 0.5% (wt) AgzO [Product name: Bioshare SG (manufactured by Kinki Pipe Giken)] 4 bags containing 50g wrapped in non-woven fabric. It sank. The above-mentioned photosensitive material is subjected to single-line X-ray exposure, and developed using the above-mentioned automatic processor and processing solution while replenishing it every time 8 sheets of four-cut size (1"0" x 12") are processed at the above ratio. Washing water is supplied at a flow rate of 1 (l) per minute, and a solenoid valve opens synchronously while the photosensitive material is being processed (approximately 1 liter/1 piece of quarter-cut size). Then, the solenoid valve opened and all the water was drained.In this way, running processing continued for two months, averaging 150 sheets per day.The results are shown in Table 2.Compound A (for comparison) Tables 1 and 2 As is clear from the above, it is clear that by using the compound of the present invention, it is possible to perform processing without any problems in terms of fixability, residual color, and image stability even with a low replenishment amount.
Claims (1)
、かつ定着液中に下記一般式（ I ）で表される化合物
を含有することを特徴とするハロゲン化銀感光材料の処
理方法。 一般式（ I ） ▲数式、化学式、表等があります▼ 式中、Ｘはアミノ基またはアンモニオ基を表し、Ｌはア
ルキレン基を表す。Ｍは水素原子またはアルカリ金属を
表す。[Scope of Claims] A silver halide characterized in that the fixer replenishment amount is 0.5 liters or less per 1 m^2 of the photosensitive material, and the fixer contains a compound represented by the following general formula (I). How to process photosensitive materials. General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, X represents an amino group or an ammonio group, and L represents an alkylene group. M represents a hydrogen atom or an alkali metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23927889A JPH03101728A (en) | 1989-09-14 | 1989-09-14 | Method for processing silver halide photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23927889A JPH03101728A (en) | 1989-09-14 | 1989-09-14 | Method for processing silver halide photosensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03101728A true JPH03101728A (en) | 1991-04-26 |
Family
ID=17042376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23927889A Pending JPH03101728A (en) | 1989-09-14 | 1989-09-14 | Method for processing silver halide photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03101728A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04337729A (en) * | 1991-05-14 | 1992-11-25 | Fuji Photo Film Co Ltd | Processing method for silver halide color photographic sensitive material and photographic bleach-fixing composition |
| JPH04340951A (en) * | 1991-05-17 | 1992-11-27 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material and developing method for that |
| JPH04365038A (en) * | 1991-06-11 | 1992-12-17 | Fuji Photo Film Co Ltd | Processing for silver halogenide color photosensitive material |
| JPH0566540A (en) * | 1991-09-09 | 1993-03-19 | Fuji Photo Film Co Ltd | Processing method of photographic light-sensitive material |
| US5434035A (en) * | 1993-12-29 | 1995-07-18 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to improve desilvering |
| US5508150A (en) * | 1993-12-29 | 1996-04-16 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to prevent iron retention |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62123460A (en) * | 1985-11-22 | 1987-06-04 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide color photographic sensitive material |
| JPS644739A (en) * | 1987-06-29 | 1989-01-09 | Fuji Photo Film Co Ltd | Development of silver halide sensitive material |
-
1989
- 1989-09-14 JP JP23927889A patent/JPH03101728A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62123460A (en) * | 1985-11-22 | 1987-06-04 | Konishiroku Photo Ind Co Ltd | Treatment of silver halide color photographic sensitive material |
| JPS644739A (en) * | 1987-06-29 | 1989-01-09 | Fuji Photo Film Co Ltd | Development of silver halide sensitive material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04337729A (en) * | 1991-05-14 | 1992-11-25 | Fuji Photo Film Co Ltd | Processing method for silver halide color photographic sensitive material and photographic bleach-fixing composition |
| JPH04340951A (en) * | 1991-05-17 | 1992-11-27 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material and developing method for that |
| JPH04365038A (en) * | 1991-06-11 | 1992-12-17 | Fuji Photo Film Co Ltd | Processing for silver halogenide color photosensitive material |
| JPH0566540A (en) * | 1991-09-09 | 1993-03-19 | Fuji Photo Film Co Ltd | Processing method of photographic light-sensitive material |
| US5434035A (en) * | 1993-12-29 | 1995-07-18 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to improve desilvering |
| US5508150A (en) * | 1993-12-29 | 1996-04-16 | Eastman Kodak Company | Fixer additives used in combination with iron complex based bleaches to prevent iron retention |
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