JPH02232654A - Processing method for silver halide color photographic sensitive material - Google Patents
Processing method for silver halide color photographic sensitive materialInfo
- Publication number
- JPH02232654A JPH02232654A JP5344889A JP5344889A JPH02232654A JP H02232654 A JPH02232654 A JP H02232654A JP 5344889 A JP5344889 A JP 5344889A JP 5344889 A JP5344889 A JP 5344889A JP H02232654 A JPH02232654 A JP H02232654A
- Authority
- JP
- Japan
- Prior art keywords
- bleach
- bleaching
- color
- processing
- acid
- 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
- 239000000463 material Substances 0.000 title claims abstract description 44
- -1 silver halide Chemical class 0.000 title claims description 60
- 229910052709 silver Inorganic materials 0.000 title claims description 45
- 239000004332 silver Substances 0.000 title claims description 45
- 238000003672 processing method Methods 0.000 title description 9
- 238000004061 bleaching Methods 0.000 claims abstract description 65
- 238000012545 processing Methods 0.000 claims abstract description 59
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 5
- 125000000656 azaniumyl group Chemical group [H][N+]([H])([H])[*] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 80
- 239000000975 dye Substances 0.000 description 65
- 239000007844 bleaching agent Substances 0.000 description 51
- 239000000839 emulsion Substances 0.000 description 42
- 239000010410 layer Substances 0.000 description 33
- 230000001235 sensitizing effect Effects 0.000 description 31
- 235000002639 sodium chloride Nutrition 0.000 description 31
- 150000003839 salts Chemical class 0.000 description 27
- 239000003795 chemical substances by application Substances 0.000 description 25
- 239000002253 acid Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 24
- 238000011161 development Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 17
- 108010010803 Gelatin Proteins 0.000 description 15
- 230000000694 effects Effects 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
- 238000011282 treatment Methods 0.000 description 13
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910001447 ferric ion Inorganic materials 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 8
- 230000005070 ripening Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 5
- 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 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 150000004989 p-phenylenediamines Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 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
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying 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
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003567 thiocyanates Chemical class 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 101000618467 Hypocrea jecorina (strain ATCC 56765 / BCRC 32924 / NRRL 11460 / Rut C-30) Endo-1,4-beta-xylanase 2 Proteins 0.000 description 2
- 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 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 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
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- ZJEFVRRDAORHKG-UHFFFAOYSA-M potassium;2-hydroxy-5-sulfobenzoate Chemical compound [K+].OC1=CC=C(S(O)(=O)=O)C=C1C([O-])=O ZJEFVRRDAORHKG-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 150000003548 thiazolidines Chemical class 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- CCVYRRGZDBSHFU-UHFFFAOYSA-N (2-hydroxyphenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC=C1O CCVYRRGZDBSHFU-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical compound O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- IZNLVYVGSDBDMV-UHFFFAOYSA-N 1-(2-bromoethyl)pyridin-1-ium Chemical compound BrCC[N+]1=CC=CC=C1 IZNLVYVGSDBDMV-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- QADPIHSGFPJNFS-UHFFFAOYSA-N 2-(1h-benzimidazol-2-ylmethyl)-1,3-thiazole Chemical compound N=1C2=CC=CC=C2NC=1CC1=NC=CS1 QADPIHSGFPJNFS-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
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- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- JZWFDVDETGFGFC-UHFFFAOYSA-N salacetamide Chemical group CC(=O)NC(=O)C1=CC=CC=C1O JZWFDVDETGFGFC-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 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
- QWSDEEQHECGZSL-UHFFFAOYSA-M sodium;acetaldehyde;hydrogen sulfite Chemical compound [Na+].CC=O.OS([O-])=O QWSDEEQHECGZSL-UHFFFAOYSA-M 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical class [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 150000004886 thiomorpholines Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- TZIAJEIDZDBZNC-UHFFFAOYSA-J tripotassium sodium carbonic acid hydroxylamine sulfurous acid bromide iodide sulfate Chemical compound S(=O)(=O)([O-])[O-].NO.[I-].[K+].[Br-].[K+].C(O)(O)=O.[K+].S(=O)(O)O.[Na+] TZIAJEIDZDBZNC-UHFFFAOYSA-J 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Chemical class 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)
本発明は露光されたハロゲン化銀カラー写真感光材料(
以下カラー感光材料という)を現像、漂白、定着する現
像処理方法(以下単に処理という)に間するものであり
、特に漂白作用を促進して、処理時間を短縮化するとと
もに充分な漂白を行って画質の良好なカラー写真画像を
形成することができる改良された現像処理方法に関する
ものである.
(従来の技術冫
一般に、カラー感光材料の処理の基本工程は、発色現像
工程と脱銀工程である.すなわち、露光されたカラー感
光材料を、発色現像工程に入れる.ここでは、カラー現
像主薬によりハロゲン化銀が還元されて根を生ずるとと
もに、酸化されたカラー現像主薬は発色剤(カブラーと
通称する)と反応して色素の百像を与える.しかるのち
に、カラー感光材料を脱銀工程に入れる.ここでは、酸
化剤(漂白剤と通称する)の作用により前の工程で生じ
た銀が酸化されたのち、娘イオンの錯化剤に(定着剤と
通称される)よって溶解されカラー感光材料から除かれ
る.したがって、これらの工程を経たカラー感光材料に
は色素画像のみが出来上がる.実際の現像処理は、上記
の二つの基本工程のほかに、画像の写真的、物理的品質
を保つため、あるいは画像の保存性を良くするため等の
補助的な工程を含んでいる。たとえば、処理中の感光層
の過度の軟化を防ぐための硬膜浴、現像反応を効果的に
停止させる停止浴、画像を安定化させる画像安定浴ある
いは支持体のバ,キング層を除くための脱膜浴などが挙
げられる.
また上記した脱銀工程も、漂白浴と定着浴をそれぞれ別
浴として二工程で行なう場合と、迅速処理化、省力化を
目的として処理工程をより節略化し、漂白荊と定着剤を
共存させた漂白定着浴により一工程で行なう場合とがあ
る.
近年、カラー感光材料の処理において、処理の迅速簡略
化と環境汚染防止が要請されている観点から、第2鉄イ
オン錯塩(例えば、アミノボリカルボン酸第二鉄イオン
錯塩、等、とくにエチレンジアミンテトラ酢酸鉄(l[
I)iff塩)を主体とした漂白処理方法が主に利用さ
れている。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an exposed silver halide color photographic light-sensitive material (
This method is used to develop, bleach, and fix (hereinafter simply referred to as "processing") a color photosensitive material (hereinafter referred to as a color photosensitive material).In particular, it accelerates the bleaching action, shortens the processing time, and performs sufficient bleaching. This paper relates to an improved processing method that can form color photographic images with good image quality. (Prior art) In general, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. That is, the exposed color photosensitive material is put into the color development step. While the silver halide is reduced to form roots, the oxidized color developing agent reacts with a color former (commonly called a coupler) to give a dye image.The color photosensitive material is then subjected to a desilvering process. Here, the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly known as a bleaching agent), and then dissolved by a daughter ion complexing agent (commonly known as a fixing agent) to produce color photosensitizers. Therefore, the color light-sensitive material that has gone through these steps will only have a dye image.In addition to the two basic steps mentioned above, the actual development process also involves other steps to maintain the photographic and physical quality of the image. , or includes auxiliary processes to improve image storage stability, etc.For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing, and a stop bath to effectively stop the development reaction. , an image stabilizing bath to stabilize the image, and a film removal bath to remove the backing layer of the support.The above-mentioned desilvering process is also a two-step process in which the bleaching bath and fixing bath are separate baths. In some cases, the processing steps are simplified for the purpose of speeding up processing and saving labor, and in other cases, the process is carried out in one step using a bleach-fixing bath in which bleaching agents and fixing agents coexist.In recent years, in the processing of color photosensitive materials, , from the viewpoint of rapid and simple processing and prevention of environmental pollution, ferric ion complex salts (e.g., aminobocarboxylic acid ferric ion complex salts, etc.), especially iron ethylenediaminetetraacetate (l[
Bleaching treatment methods mainly using I) if salt) are mainly used.
しかしながら、第2鉄イオン錯塩は酸化力が比較的小さ
く漂白力が不充分なため、これを漂白剤として用いたも
のはたとえば塩臭化銀乳剤を主体とする低惑度のカラー
感光材料を漂白処理もしくは漂白定着処理する場合には
、一応所望の目的を達することができるが、塩臭沃化銀
あるいは沃炎化銀乳剤を主体とし、かつ色増感された高
感度のカラー惑光材才]、とくに高銀量乳剤を用いてい
る盪影用カラー反転感光材料、擾影用力ラーネガ感光材
料を処理する場合には、漂白作用が不十分で脱銀不良に
なったり、漂白するのに長時間を要するという欠点を有
する.
カラー感光材料では、一mに色増感の目的で増感色素が
用いられる.特に高感度化をめざして、高恨化又は高ア
スペクト比の平仮粒子を用いる場合、ハロゲン化銀表面
に吸着した増感色素が、/Mロゲン化銀の現像で生成さ
れた銀の漂白を阻害すると考えられる.
第2鉄イオン錯塩以外の漂白剤としては、過硫酸塩が知
られており、通常、過硫酸塩は塩化物を含有させて漂白
液として使用される.しかしながら、過硫酸塩を用いた
漂白液の欠点は、第2鉄イオン讃塩よりさらに漂白力が
弱く、漂白するのに著しく長時間を有することである.
一般に公害性又は機器に対する腐食性のない漂白剤は漂
白力が弱いという関係があり、それ故に漂白力の弱い漂
白剤、特に第2鉄イオン錯塩又は過硫酸塩を使用した漂
白液もしくは漂白定着液の漂白能力を増加させることが
望まれている.従来、エチレンジアミンテトラ酢酸鉄塩
の如き第2軽イオン酢塩を漂白剤とする漂白液もしくは
漂白定着液の漂白能力を高める手段として種々の漂白促
進剤を処理浴に添加することが提案されている.
例えば米国特許第3893858号明細書、英国特許第
1138842号明細書、特開昭53一141623号
公報に記載されている如き種々のメルカブト化合物、特
開昭5195630号公報に記載されている如きジスル
フィド結合を有する化合物、特公昭53−9854号公
報に記載されている如きチアゾリジン誘導体、特開昭5
3−94927号公報に記載されている如きイソチオ尿
素誘導体、特公昭45−8506号公叩、特公昭49−
26586号公報に記載されている如きチオ尿素誘導体
、特開昭49−42349号公報に記載されている如き
チオアミド化合物、特開昭55−26506号公報に記
載されている如きジチオカルバミン酸塩類等があげられ
る.これらの漂白促進剤の中には、確かに漂白促進効果
を有するものがあるが、その効果は必ずしも十分ではな
く、また特に漂白定着液中においては、安定性が極めて
悪く短時間に効果を失って実用に適したものでは必ずし
もなかった.
さらに、他の漂白促進剤として、たとえば、米国特許3
.748,136号明細書に記載されている如きオニウ
ム化合物、特公昭5 4 − 1. 2 0 56号公
報に記載されている如きフエニレン連結アンモニウム塩
、米国特許4.552.834号明細書に記載されてい
る如きアミン化合物等がある.これらの化合物は漂白液
や漂白定着液中で安定であるが、漂白促進効果が弱く、
これらも必ずしも実用に適したものではなかった.
また、特公昭60−24936号公報に記載されている
化合物は、一定程度の漂白促進効果を有しているが、必
ずしも満足しうるちのではない.また、特開昭61−2
0945号公報に記載されているメルカブトチアジアゾ
ール化合物は漂白液や漂白定着液中で安定であり、しか
も漂白促進効果も大きい。しかし,ここに記載されてい
る化合物は、疲労した漂白液や漂白定着液では、必ずし
も充分な漂白促進効果を示さないことがわかった。However, since ferric ion complex salts have relatively low oxidizing power and insufficient bleaching power, they can be used as bleaching agents to bleach color light-sensitive materials with low bleaching properties, such as silver chlorobromide emulsions. In the case of processing or bleach-fixing, the desired purpose can be achieved to a certain extent, but it is necessary to use a color sensitized high-sensitivity color luminescent material that is mainly composed of silver chloriobromoiodide or silver iodoflame emulsion. ], In particular, when processing color reversal light-sensitive materials for shadows and color negative light-sensitive materials for shadows that use emulsions with a high silver content, the bleaching effect may be insufficient, resulting in poor desilvering, or bleaching may take a long time. It has the disadvantage that it requires In color photosensitive materials, sensitizing dyes are used for the purpose of color sensitization. In particular, when using highly grained or high aspect ratio tabular grains with the aim of increasing sensitivity, the sensitizing dye adsorbed on the silver halide surface inhibits the bleaching of the silver produced by the development of /M silver halide. This is thought to inhibit Persulfates are known as bleaching agents other than ferric ion complex salts, and persulfates are usually used as bleaching solutions in the form of chlorides. However, the disadvantage of bleaching solutions using persulfates is that they have weaker bleaching power than ferric ion salts and take a significantly longer time to bleach. In general, bleaching agents that are not polluting or corrosive to equipment have weak bleaching power, and therefore, bleaching agents with weak bleaching power, especially bleach solutions or bleach-fix solutions using ferric ion complex salts or persulfates. It is desired to increase the bleaching ability of Conventionally, it has been proposed to add various bleaching accelerators to processing baths as a means of increasing the bleaching ability of bleaching solutions or bleach-fixing solutions that use a second light ion acetate salt such as iron ethylenediaminetetraacetate as a bleaching agent. .. For example, various mercabuto compounds as described in U.S. Pat. thiazolidine derivatives as described in Japanese Patent Publication No. 53-9854;
Isothiourea derivatives such as those described in Japanese Patent Publication No. 3-94927, Japanese Patent Publication No. 8506/1986, Japanese Patent Publication No. 49/1983
Thiourea derivatives as described in JP-A No. 26586, thioamide compounds as described in JP-A-49-42349, dithiocarbamates as described in JP-A-55-26506, etc. It will be done. Some of these bleach accelerators do have the effect of accelerating bleaching, but their effect is not necessarily sufficient, and they are extremely unstable, especially in bleach-fix solutions, and lose their effectiveness in a short period of time. However, it was not necessarily suitable for practical use. Additionally, other bleach accelerators, such as U.S. Pat.
.. Onium compounds as described in No. 748,136, Japanese Patent Publication No. 54-1. Examples include phenylene-linked ammonium salts as described in US Pat. No. 2,056, and amine compounds as described in US Pat. No. 4,552,834. These compounds are stable in bleach and bleach-fix solutions, but have weak bleaching accelerating effects;
These were not necessarily suitable for practical use either. Furthermore, the compounds described in Japanese Patent Publication No. 60-24936 have a certain degree of bleaching accelerating effect, but are not necessarily satisfactory. Also, JP-A-61-2
The mercabutothiadiazole compound described in Japanese Patent No. 0945 is stable in bleaching solutions and bleach-fixing solutions, and also has a large bleaching accelerating effect. However, it has been found that the compounds described herein do not necessarily exhibit sufficient bleaching accelerating effects in tired bleaching solutions and bleach-fixing solutions.
(発明が解決しようとする課題}
このように、これらの漂白促進剤の多くは必ずしも充分
満足し得る漂白促進効果を奏せず、また、漂白促進効果
は優れていても、処理液中での安定性に欠けるため処理
液の有効寿命が短くなり長期保存に耐え得ないという欠
点を有するものが多い.本発明の第1の目的は、毒性が
低く公害防止の要請に適合し、漂白速度において優れた
カラー感光材料の処理方法を提供することである.本発
明の第2の目的は、漂白力の弱い漂白剤、特に第2鉄イ
オン諸塩又は過硫酸塩を用いる漂白処理もしくは漂白定
着処理において他の写真特性を悪化させずに漂白力を高
める方法を掃供することである.
本発明の第40口的は、とくに逼影感度を有するカラー
感光材料を迅速に漂白もしくは漂白定着することのでき
る方法を提供することである.本発明の第5の目的は、
疲労した漂白液や漂白定着液でも、迅速に漂白もしくは
漂白定着することのできる方法を提供することである,
(課題を解決するための手段)
本発明の前記の諸目的は、露光されたカラー感光材料を
、下記一殻式(+)で表わされる化合物を含有する漂白
能を有する処理液で処理することで達成された.
一般式(1)
(式中、Lは、置喚されてもよいアルキレン基を表わし
、炭素数1〜6のWl換されてもよいアルキレン基が好
ましい.Xは、アルキル置換された四級アンモニオ基、
あるいは窒素原子を少なくとも一つ含む不飽和のへテロ
環基を表わす.このヘテロ環基の窒素原子は四級化され
てもよい.アルキル置換された四級アンモニオ基として
は、トリメチルアンモニオ、トリエチルアンモニオなど
があげられるが、トリメチルアンモニオ基が好ましい.
Aは対アニオンで、nは、Xが四級化されている窒素を
含むときはlで、四級化されている窒素原子を含まない
ときは0である.対アニオンとしては、塩素イオン、臭
素イオン、硫酸イオン、p−トルエンスルホナートイオ
ン、オギザラートイオンなどがあげられる.沃素イオン
は好ましくない.上記へテロ環基としては、ビリジル基
、ビラジル基、ビリミジニル基、ビリジニウム基、イミ
ダゾリル基、イミダゾリウム基、トリアゾリル基、ピラ
ゾリル基、ブリニル基、トリアジニル基があげられる.
窒素はLとの結合部で四級化してもよいし、Lとの非結
合部で四級化してもよい.Mは水素原子あるいはアルカ
リ金属原子(例えば、Na % K )アンモニウム基
(例えば、トリメチルアンモニウム、ジメチルベンジル
アンモニウム)を表わす.
Xとしては、窒素原子を少なくとも1つ含む不飽和のへ
テロ環が好ましく、特に、ビリジル基、イミダゾリル蟇
が好ましい.
本発明の漂白能を有する処理液とは、漂白液または漂白
定着液のことをいう.
一般式口)の化合物は、漂白液又は漂白定着液に含有さ
れる.漂白液又は漂白液に直接添加してもよいし、それ
らの補充液に添加してもよい.あるいは、それらの前浴
の漂白促進浴や定着液に添加してもよい.漂白液又は漂
白定着液又はそれらの補充液に添加されるのが好ましい
.添加する場合の添加量としては、好ましくは1xio
”’からI X 1 0 −’sol / l、より好
ましくはIXIO−3から2X10−”moI /l,
最も好まし《は2 X 1 (I”からI X 1 0
−”mol / 1である.一般式(1)の化合物は漂
白促進剤として単独で用いても良いし2種以上使用して
も良い.本発明化合物は特異的に大きな漂白促進能を有
し、しかも漂白能を有する処理液中で安定で、現在一般
的に行なわれているような自動現像機を用いた長期連続
処理にも充分使用可能である.次に本発明の具体的化合
物を配すが、これらに限られるものではない.
+11
Co!H
0H
特開昭62−139346号、同62−174755号
に本発明の化合物をカラー感光材料中に含有させる技術
が開示されているが、これらはインターイメージ効果を
改良することを目的としたカラー反転材料に関するもの
である.
特開昭63−106656号には、本発明の化合物の存
在下で現像処理する技術が開示されているが、これは造
核促進剤としての使用であり、直接ボジ感材中に含有さ
せるか、発色現像中に存在させることが開示されている
のみである.本発明は、一般式(1)の化合物を漂白能
を有する処理液中に含有させるもので、前記の技術とは
、使用形態も、使用目的も異ることは明らかである.
本発明の化合物の合成は一般によく知られた方法により
容易に合成することができるが、例として具体的方法を
以下に記す.
化合物(3)の合成
2、5−ジメルカブトチアジアゾール10gとクロ口エ
チルトリメチルアンモニウムクロリドi0.6gのア七
トニトリル溶液にビリジン5,3gを加え、4時間加熱
還流した.生じた結晶をメタノールとエタノールで再結
晶し、化合物《3》を得た.収19g(50%)
化合物αlの合成
2,5−ジメルカブトチアジアゾール6.1gとN−ブ
ロモエチルビリジニウムブ口ミドl0.8gのアセトニ
トリル溶液100Miにヒ’) ’2 7 3 .4g
を加え、3時間加熱還流した.生じた結晶をメタノール
300Miから再結晶することにより、化合物01を得
た.収flt8.3g (61%)他の化合物も同様に
合成できる.
本発明は脱銀工程として漂白浴、漂白定着浴、定着浴等
を組み合わしたいかなる処理においても効果を発揮する
.脱銀工程としては例えば下記のものが挙げられるが、
これらに限定はされない.患l 漂白一定着
嵐2 漂白一水洗一定着
?&L3 漂白〜漂白定着
嵐4 漂白一漂白定着一定着
嵐5 定着一漂白定着
隘6 漂白定着
脱銀工程としては漂白定着工程を有する工程が本発明の
効果が大きく好ましい.特に、上記ぬ6が最も好ましい
.
また、脱銀工程は通常発色現像工程の後に行なわれるが
、これらの間に水洗やリンス、漂白促進などの浴を設け
ても良い.
さらに、各工程は順流または向流の多段処理方式が好ま
しい.特に2段または3段の向流方式が好ましい.
本発明において、漂白能を有する処理液に用いられる漂
白剤としては、公知のあらゆるものが使用可能であるが
、特に、漂白液にはアミノポリカルボン酸第二鉄錯塩及
び過硫酸塩が好まし《、漂白定着液にはアミノボリカル
ボン酸第二鉄錯塩が好ましい.アミノボリカルボン酸第
二鉄謹塩は、第二鉄イオンとアミノボリカルボン酸又は
その塩との錯体であり、アミノボリカルボン酸の代表例
としては以下の通りである.
A−1 エチレンジアミン四酢酸
A−2 ジエチレントリアミン五酢酸A−31.3−
ジアミノプロパン四酢酸A−41.2−ジアミノブロバ
ン四酢酸A−5 エチレンジアミンーN−(β−オキ
シエチル)−N,N’.N’一三酢酸
A−6 ニトリロ三酢酸
A−71.2−シクロヘキサンジアミン四酢酸
A−8 イミノジ酢酸
A−9 ジヒドロキジエチルグリシンA−10 エチ
ルエーテルジアミン四酢酸A−11 グリコールエー
テルジアミン四酢酸A−12 エチレンジアミンテト
ラブロビオン酸などを挙げることができるが、これらの
例示化合物に限定されない.
これらの化合物の中では特にA−1〜A−3、A−7、
A−8、A−11が好ましい.アミノポリカルボン酸第
2鉄錯塩は錯塩の形で使用しても良いし、第2鉄塩、例
えば硫酸第2鉄、塩化第2鉄、硝酸第2鉄、g酸第2鉄
アンモニウム、燐酸第2鉄などとアミノボリカルボン酸
を用いて溶液中で第2鉄イオン錯塩を形成させてもよい
.錯塩の形で使用する場合は、1種類の錯塩を用いても
よいし、又2種類以上の錯塩を用いてもよい.一方、第
2鉄塩とアミノポリカルポン酸を用いて溶液中で錯塩を
形成する場合は第2鉄塩を1種類又は2種類以上使用し
てもよい.更にアミノポリカルボン酸をimi又は2種
類以上使用してもよい.また、いずれの場合にも、アミ
ノポリカルボン酸を第2鉄イオン錯塩を形成する以トに
過剰に用いるのが好ましい.
アミノボリカルポン酸及びその第二鉄錯塩は通常、アル
カリ金属塩やアンモニウム塩の形で使用するのが好まし
く、特にアンモニウム塩が溶解性の点で好ましい.
また上記の第2鉄イオン措体を含む漂白能を有する処理
液には鉄以外のコバルト、銅等の金属イオン詔塩が入っ
ていてもよい.
過硫酸塩としてはアンモニウム塩、カリウム塩、ナトリ
ウム塩、などが挙げられる.
さらに、漂白能を存する処理液中もし《はこれらの前浴
中には本発明の漂白促進剤の他に従来漂白促進剤として
知られている化合物を添加することができる.このよう
な漂白促進剤については、例えば、米国特許第3,89
3,858号明細書、ドイツ特許第1,290.812
号明細書、英国特許第1.138,842号明細書、特
開昭53−95630号、同60−24936号、同6
l−20945号公報、リサーチ・ディスクロージャー
第17129号(1978年7月号)に記載のメルカブ
ト基またはジスルフィド基を有する化合物、特開昭50
−140129号公報に記載のチアゾリジン誘導体、米
国特許第3,706,561号明細書に記載のチオ尿素
誘導体、特開昭58−16235号公報に記載の沃化物
、ドイツ特許第2,748,430号明細書に記載のポ
リエチレンオキサイド類、特公昭4 5−8 8 3
6号公報に記載のポリアミン化合物などを用いることが
できる.特に好ましくは英国特許第1.138.842
号明細書記載のようなメルカブト化合物が好ましい.
これらの漂白促進剤は本発明の漂白能を有する処理液の
前浴に添加して使用することもできる.本発明において
漂白能を有する処理液には、漂白剤及び上記化合物の他
に、臭化物、例えば臭化カリウム、臭化ナトリウム、臭
化アンモニウム又は塩化物、例えば塩化カリウム、塩化
ナトリウム、塩化アンモニウムなどの再ハロゲン化剤を
含むことができる.再ハロゲン化剤の濃度は漂白液1ク
あたりO.1〜5モル、好ましくは0.5〜3モルであ
る.他に、硝酸ナトリウム、硝酸アンモニウム等の硝酸
塩、硼酸、硼砂、メタ硼酸ナトリウム、酢酸、酢酸ナト
リウム、炭酸ナトリウム、炭酸カリウム、亜燐酸、燐酸
、燐酸ナトリウム、クエン酸、クエン酸ナトリウム、酒
石酸などのp }{緩衝能を有する1種類以上の無機酸
、有機酸及びこれらの塩、硫酸アンモニウムなどの金属
腐食防止剤、蛍光増白剤、消泡剤、界面活性剤、ポリビ
ニルビロリドン、メタノールなど通常漂白液に用いるこ
とが公知の添加剤を添加することができる.本発明にお
いて、漂白液11当りの漂白剤の量は0.05モル〜1
モルであり、好ましくは0.1モル〜0.5モルである
.
また漂白液のpHは、漂白剤がアミノボリカルボン酸第
二鉄塩の場合2.5〜8.0、特に3.5〜6.5にな
ることが好ましく、過硫酸塩の場合0。5〜8,0、好
ましくは2. 0〜4.0である.漂白液の温度はlO
〜60℃で処理可能であるが好ましくは30〜50℃、
より好ましくは35〜45℃である.漂白液の補充量は
感光材籾l ffiあたり50〜200(ldが好まし
いがより好ましくは100〜500−である.
本発明において漂白定着液11当りの漂白剤の量は0.
05モル〜0.5モルであり、好ましくはO.1モル〜
0.4モルである.
また漂白定着液中には定着剤としてチオ硫酸ナトリウム
、チオ硫酸アンモニウム、ヂオ硫酸アンモニウムナトリ
ウム、チオ硫酸カリウムの如きチオ硫酸塩、チオシアン
酸ナトリウム、千オシアン酸アンモニウム、チオシアン
酸カリウムの如きチオシアン酸塩、千オ尿素、チオエー
テル等を用いることができる.これら定着剤の量は漂白
定着液1i当り0.3モル〜3モル、好ましくは0.5
モル〜2モルである.
漂白定着液には、保恒剤としての亜硫酸塩、例えば亜硫
酸ナトリウム、亜硫酸カリウム、亜硫酸アンモ二ウム及
び、ヒドロヰシルアミン、ヒドラジン、アルデヒド化合
物の重亜硫酸塩付加物、例えばアセトアルデヒド重亜硫
酸ナトリウムなどを含有させることができる.
漂白定着液のpHは4.0〜9,0、好ましくは5.0
〜8.0、より好ましくは6.0〜7.5である.
また、漂白定着液の好ましい温度範囲は漂白液の場合と
同じである.
漂白定着液の補充量としては惑光材#04+.n{あた
り300dから3 0 0 0adが好ましいが、より
好ましくは300dから1 0 0 0R!である.本
発明の化合物は特開昭61−75352号公報に記載さ
れたような漂白一漂白定着工程にも使用できる.この場
合、漂白液または漂白定着液の片方に添加しても良いし
、両方に添加しても良い.本発明の処理方法において定
着液には前記漂白定着液に含まれる化合物を全て含むこ
とができる.定着液のp Hは3,Q〜9.0、好まし
くは5..0〜8.05処理時間は20秒〜10分が好
ましく、30秒〜4分がより好ましい.含まれる定着剤
の好ましい濃度及び好ましい温度は前記漂白定着液と同
じである.
本発明の脱銀工程における各処理液の撹拌はできるだけ
強化されていることが、脱銀処理時間短縮の点から好ま
しい.撹拌手段としては、特開昭62−183460号
や同62−183461号に記載のような方法などが挙
げられ、噴流を衝突させる手段の場合には、衝突までの
時間は感光材料が処理液に導入されてから15秒以内に
行うのが好ましい.
本発明においてクロスオーバー時間(惑光材料が処理液
から出て、次の処理液に入るまでの空中時間)は、10
秒以内が好ましく、より好ましくは、5秒以内である.
漂白、漂白定着または定着工程のすぐ後に水洗または安
定化工程が続く場合、これらのオーバーフロー液の一部
または全部を漂白、漂白定着、定着などの処理液へ導入
することが好ましい。(Problems to be Solved by the Invention) As described above, many of these bleach accelerators do not necessarily have a sufficiently satisfactory bleach accelerating effect, and even if they have an excellent bleach accelerating effect, they do not work well in the processing solution. Many of them have the disadvantage that the effective life of the processing solution is shortened due to lack of stability and cannot withstand long-term storage.The first object of the present invention is to provide a solution that has low toxicity, meets the requirements for pollution prevention, and has a high bleaching rate. It is an object of the present invention to provide an excellent method for processing color light-sensitive materials.A second object of the present invention is to provide a bleaching process or a bleach-fixing process using a bleaching agent with weak bleaching power, especially ferric ion salts or persulfates. It is an object of the present invention to provide a method for increasing bleaching power without deteriorating other photographic properties.A 40th object of the present invention is to provide a method for quickly bleaching or bleach-fixing color light-sensitive materials, especially those having high shadow sensitivity. The fifth object of the present invention is to provide a method that allows
To provide a method that can quickly bleach or bleach-fix even with a tired bleach solution or bleach-fix solution.
(Means for Solving the Problems) The above-mentioned objects of the present invention are to process an exposed color photosensitive material with a processing solution having bleaching ability and containing a compound represented by the following one-shell formula (+). It was achieved with. General formula (1) (In the formula, L represents an optionally substituted alkylene group, preferably an alkylene group having 1 to 6 carbon atoms and optionally substituted with Wl. X is an alkyl-substituted quaternary ammonium base,
Alternatively, it represents an unsaturated heterocyclic group containing at least one nitrogen atom. The nitrogen atom of this heterocyclic group may be quaternized. Examples of the alkyl-substituted quaternary ammonio group include trimethylammonio and triethylammonio, with trimethylammonio being preferred.
A is a counter anion, and n is 1 when X contains a quaternized nitrogen atom, and 0 when X does not contain a quaternized nitrogen atom. Examples of counter anions include chloride ion, bromide ion, sulfate ion, p-toluenesulfonate ion, and oxalate ion. Iodine ions are not preferred. Examples of the heterocyclic group include a biridyl group, a biradyl group, a birimidinyl group, a viridinium group, an imidazolyl group, an imidazolium group, a triazolyl group, a pyrazolyl group, a brinyl group, and a triazinyl group.
Nitrogen may be quaternized at the bonding site with L, or may be quaternized at the non-bonding site with L. M represents a hydrogen atom or an alkali metal atom (eg, Na % K ) or an ammonium group (eg, trimethylammonium, dimethylbenzylammonium). As X, an unsaturated heterocycle containing at least one nitrogen atom is preferable, and a pyridyl group and an imidazolyl group are particularly preferable. The processing solution having bleaching ability in the present invention refers to a bleaching solution or a bleach-fixing solution. The compound of the general formula (2) is contained in a bleach solution or a bleach-fix solution. It may be added directly to the bleaching solution or bleach solution, or to its replenisher. Alternatively, it may be added to the bleach accelerating bath or fixing solution as a pre-bath. Preferably, it is added to the bleach or bleach-fix solution or their replenisher. When added, the amount of addition is preferably 1xio
"' to IX10-'sol/l, more preferably IXIO-3 to 2X10-'mol/l,
Most preferably << is 2 X 1 (I" to I X 1 0
-"mol/1. The compound of general formula (1) may be used alone as a bleach accelerator, or two or more types may be used. The compound of the present invention has a specifically large bleach accelerating ability. Moreover, it is stable in a processing solution with bleaching ability, and can be fully used for long-term continuous processing using an automatic processor, which is currently commonly used. However, the invention is not limited to these. +11 Co!H 0H Japanese Patent Application Laid-open Nos. 139346/1982 and 174755/1987 disclose a technique for incorporating the compound of the present invention into a color photosensitive material. These relate to color reversal materials aimed at improving the interimage effect. JP-A-63-106656 discloses a technique of developing in the presence of the compound of the present invention. This is used as a nucleation accelerator, and it is only disclosed that it is directly included in a positive sensitive material or is present during color development.The present invention discloses that the compound of general formula (1) is used as a nucleation accelerator. It is obvious that the compound of the present invention is contained in a processing solution having bleaching ability, and is different from the above-mentioned technique in terms of usage form and purpose.The compound of the present invention can be easily synthesized by a generally well-known method. The specific method is described below as an example. Synthesis of Compound (3) Add pyridine 5 to a seventonitrile solution of 10 g of 2,5-dimercabutothiadiazole and 0.6 g of chloroethyltrimethylammonium chloride i. , and heated under reflux for 4 hours. The resulting crystals were recrystallized from methanol and ethanol to obtain compound <<3>>. Yield: 19 g (50%) Synthesis of compound αl 2,5-dimercabutothiadiazole 6 .1g and 0.8g of N-bromoethylpyridinium bucchimid in 100Mi of acetonitrile solution.'273.4g
was added and heated under reflux for 3 hours. Compound 01 was obtained by recrystallizing the resulting crystals from 300 Mi of methanol. Yield flt8.3g (61%) Other compounds can be synthesized in the same way. The present invention is effective in any treatment that combines a bleach bath, bleach-fix bath, fix bath, etc. as a desilvering process. Examples of the desilvering process include the following:
It is not limited to these. Case 1 Bleach and constant wear Arashi 2 Bleach and wash and constant wear? &L3 Bleach-bleach-fixing storm 4 Bleach-bleach-fixing constant-fixing storm 5 Fixing-bleach-fixing stage 6 As the bleach-fixing desilvering process, a process having a bleach-fixing process is preferable because the effects of the present invention are large. In particular, No. 6 above is most preferred. Further, although the desilvering step is usually carried out after the color development step, a bath for washing, rinsing, bleaching acceleration, etc. may be provided between these steps. Furthermore, it is preferable that each step be carried out in a forward or countercurrent multi-stage treatment system. A two-stage or three-stage countercurrent system is particularly preferred. In the present invention, all known bleaching agents can be used in the processing solution having bleaching ability, but aminopolycarboxylic acid ferric complex salts and persulfates are particularly preferable for the bleaching solution. 《Aminobolycarboxylic acid ferric complex salt is preferable for the bleach-fix solution. Aminoborigarboxylic acid ferric salt is a complex of ferric ion and aminoborigarboxylic acid or its salt, and representative examples of aminoborigarboxylic acids are as follows. A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-31.3-
Diaminopropanetetraacetic acid A-41.2-Diaminopropanetetraacetic acid A-5 Ethylenediamine-N-(β-oxyethyl)-N,N'. N' Monotriacetic acid A-6 Nitrilotriacetic acid A-71.2-Cyclohexanediaminetetraacetic acid A-8 Iminodiacetic acid A-9 Dihydroxydiethylglycine A-10 Ethyl ether diamine tetraacetic acid A-11 Glycol ether diamine tetraacetic acid A -12 Examples include ethylenediaminetetrabrobionic acid, but are not limited to these exemplified compounds. Among these compounds, A-1 to A-3, A-7,
A-8 and A-11 are preferred. Aminopolycarboxylic acid ferric complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium g-acid, ferric phosphate, etc. A ferric ion complex salt may be formed in a solution using diiron or the like and an aminoborigarboxylic acid. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, one or more types of ferric salts may be used. Furthermore, imi or two or more types of aminopolycarboxylic acids may be used. In any case, it is preferable to use the aminopolycarboxylic acid in excess to form the ferric ion complex. Aminobocarboxylic acid and its ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, with ammonium salts being particularly preferred from the viewpoint of solubility. Further, the above-mentioned treatment liquid having bleaching ability and containing ferric ion solution may also contain metal ion salts other than iron, such as cobalt and copper. Examples of persulfates include ammonium salts, potassium salts, and sodium salts. Furthermore, in addition to the bleaching accelerator of the present invention, compounds conventionally known as bleaching accelerators may be added to the pre-bath of the processing solution that has bleaching ability. Such bleach accelerators are described, for example, in U.S. Pat.
3,858, German Patent No. 1,290.812
specification, British Patent No. 1,138,842, JP-A-53-95630, JP-A-60-24936, JP-A-6
Compounds having a mercabuto group or a disulfide group described in Publication No. 1-20945, Research Disclosure No. 17129 (July 1978 issue), JP-A-1988
-140129, thiazolidine derivatives, US Patent No. 3,706,561, thiourea derivatives, JP-A-58-16235, iodides, German Patent No. 2,748,430 Polyethylene oxides described in the specification of Japanese Patent Publication No. 4 5-8 8 3
Polyamine compounds described in Publication No. 6 can be used. Particularly preferably British Patent No. 1.138.842
Mercabut compounds such as those described in the specification are preferred. These bleaching accelerators can also be used by being added to the prebath of the processing solution having bleaching ability of the present invention. In the present invention, in addition to bleaching agents and the above-mentioned compounds, the processing liquid having bleaching ability may contain bromides such as potassium bromide, sodium bromide, ammonium bromide, or chlorides such as potassium chloride, sodium chloride, ammonium chloride, etc. May contain rehalogenating agents. The concentration of the rehalogenating agent is O. The amount is 1 to 5 mol, preferably 0.5 to 3 mol. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. {One or more types of inorganic acids, organic acids and their salts with buffering capacity, metal corrosion inhibitors such as ammonium sulfate, optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, ordinary bleaching solutions such as methanol, etc. Additives known to be used can be added. In the present invention, the amount of bleach per 11 bleaching solutions is 0.05 mol to 1
mol, preferably 0.1 mol to 0.5 mol. Further, the pH of the bleaching solution is preferably 2.5 to 8.0, particularly 3.5 to 6.5 when the bleach is a ferric salt of aminobolycarboxylic acid, and 0.5 when the bleach is a persulfate. ~8.0, preferably 2. It is between 0 and 4.0. The temperature of the bleach solution is lO
It can be processed at ~60°C, but preferably 30~50°C,
More preferably it is 35-45°C. The replenishment amount of the bleaching solution is 50 to 200 (ld is preferable, but more preferably 100 to 500) per 1 ffi of the photosensitive material. In the present invention, the amount of bleach per 11 bleach-fixing solutions is 0.
05 mol to 0.5 mol, preferably 0.05 mol to 0.5 mol. 1 mole ~
It is 0.4 mole. The bleach-fix solution also contains fixing agents such as thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium diosulfate, and potassium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate; Urea, thioether, etc. can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.5 mol per liter of bleach-fixing solution.
mol to 2 mol. The bleach-fix solution contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydrocylamine, hydrazine, and aldehyde compounds, such as acetaldehyde sodium bisulfite. It can be included. The pH of the bleach-fix solution is 4.0 to 9.0, preferably 5.0.
-8.0, more preferably 6.0-7.5. Furthermore, the preferred temperature range for the bleach-fix solution is the same as that for the bleach solution. The amount of replenishment of bleach-fixing solution is as follows. 300d to 3000ad per n{ is preferable, and more preferably 300d to 1000R! It is. The compounds of the present invention can also be used in the bleach-bleach-fix process as described in JP-A-61-75352. In this case, it may be added to either the bleach solution or the bleach-fix solution, or to both. In the processing method of the present invention, the fixing solution can contain all the compounds contained in the bleach-fixing solution. The pH of the fixer is 3.Q to 9.0, preferably 5. .. 0 to 8.05 The processing time is preferably 20 seconds to 10 minutes, more preferably 30 seconds to 4 minutes. The preferred concentration and temperature of the fixing agent contained are the same as those for the bleach-fixing solution. In the desilvering process of the present invention, it is preferable that the stirring of each processing solution be as strong as possible from the viewpoint of shortening the desilvering process time. Examples of stirring means include methods described in JP-A-62-183460 and JP-A No. 62-183461. In the case of a means of colliding jets, the time until the collision is such that the photosensitive material is absorbed into the processing solution. It is preferable to do this within 15 seconds after introduction. In the present invention, the crossover time (time in the air from when the photosensitive material leaves the processing solution to when it enters the next processing solution) is 10
It is preferably within seconds, more preferably within 5 seconds. When a bleaching, bleach-fixing or fixing step is immediately followed by a washing or stabilizing step, it is preferred to introduce some or all of these overflow liquids into the bleaching, bleach-fixing, fixing, etc. processing solution.
本発明に使用することのできるカラー現像液中には、公
知の芳香族第一級アミンカラー現像主薬を含有する.好
ましい例はp−フエニレンジアミン誘導体であり、代表
例を以下に示すがこれらに限定されるものではない。The color developer that can be used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.
D−IN,N−ジエチルーp−フェニレンジアミン
D−2 2−アミノー5−ジエチルアミノトルエン
D−3 2−アミノー5−(N一エチルーN−ラウリル
アミノ)トルエン
D−4 4−(N一エチルーN−(β−ヒドロキシエ
チル)アミノ〕アニリン
D−5 2−メチル〜4−〔N一エチルーN−(β−ヒ
ドロキシエチル)アミノ〕アニリン
D−6 4−アミノー3−メチルーN−エチルーN−(
β一(メタンスルホンアミド)エチル)一アニリン
D−7 N−(2−アミノー5−ジエチルアミノフエ
ニルエチル)メタンスルホンアミドD−8N,N−ジエ
チルーp−フエニレンジアミン
D−9 4−アミノー3−メチルーN一エチルーN−メ
トキシエチルアニリン
D−10 4−アミノー3−メチルーN一エチルーN
一β一エトキシエチルアニリン
D−11 4−アミノー3−メチルーN−エチルN−
β−ブトキシエチルアニリン
上記p−フェニレンジアミン誘導体のうち特に好ましく
は例示化合物D−5である.
また、これらのp−フエニレンジアミン誘導体は硫酸塩
、塩酸塩、亜硫酸塩、p−トルエンスルホン酸塩などの
塩であってもよい.該芳香族一級アミン現像主薬の使用
量は現像液11当り好ましくは約0.1g〜約20g、
より好ましくは約0.5g〜約10gの濃度である.
又、カラー現像液には保恒剤として、亜硫酸ナトリウム
、亜硫酸カリウム、重亜硫酸ナトリウム、重亜硫酸カリ
ウム、メタ亜硫酸ナトリウム、メタ亜硫酸カリウム等の
亜硫酸塩や、カルボニル亜硫酸付加物を必要に応じて添
加することができる.しかしながら、カラー現像液の発
色性向上のためには亜硫酸イオンは実質的に含有しない
方が好ましい.ここでいう“実質的に含有しない”とは
、カラー現像液11当り、亜硫酸ナトリウム換算で0.
5g/1以下、好まし《は0.2g/e以下、より好ま
しくは、全く、含有しないことである。D-IN,N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5-(N-ethyl-N-laurylamino)toluene D-4 4-(N-ethyl-N- (β-hydroxyethyl)amino]aniline D-5 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline D-6 4-amino-3-methyl-N-ethyl-N-(
β-(methanesulfonamido)ethyl)-aniline D-7 N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8 N,N-diethyl-p-phenylenediamine D-9 4-amino-3- Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N
-β-Ethoxyethylaniline D-11 4-Amino-3-methyl-N-ethyl N-
β-Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred. Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per developer solution 11,
More preferably, the concentration is about 0.5 g to about 10 g. In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to. However, in order to improve the color development properties of the color developer, it is preferable that the color developer contains substantially no sulfite ions. "Substantially not containing" as used herein means 0.00% in terms of sodium sulfite per 11 parts of color developer.
5 g/e or less, preferably 0.2 g/e or less, more preferably no content at all.
又、前記カラー現像主薬を直接、保恒する化合物として
、各種ヒドロキシルアミン類、特開昭63−43138
号記載のヒドロキサム61l!¥、同63 − 1 4
. 6 0 4 1号記載のヒドラジン類や、ヒドラジ
ド類、同63−44657号及び同63−58443号
記載のフェノール類、同63−44656号記載のα−
ヒドロキシケトン類やα−アミノケトン類、及び/又は
、同63−36244号記載の各種糖類を添加するのが
好ましい.又、上記化合物と併用して、特開昭63〜4
235号、同63−24254号、同63−21647
号、同63−146040号、同63−27841号、
及び同63−25654号等に記載のモノアミン類、同
63−30845号、同63−146040号、同63
−43139号等に記載のジアミン類、同63−216
47号、及び同63−26655号記載のポリアミン類
、同63−44655号記載のポリアミン類、同63−
53551号記載のニトロキシラジカル類、IiW63
−43140号、及び63−53549号記載のアルコ
ール類、同63−56654号記載のオキシム類、及び
同63−239447号記載の3級アミン類を使用する
のが好ましい.
その他保恒剤として、特開昭57−44148号及び同
57−53749号に記載の各種金属類、特開昭59−
180588号記載のサリチルtllM、特開昭54−
3532号記載のアルカノールアミン類、特開昭56−
94349号記載のポリエチレンイミン類、米国特許第
3,746.544号記載の芳香族ポリヒドロヰシ化合
物等を必要に応じて含有しても良い.特に芳香族ポリヒ
ドロキシ化合物の添加が好ましい.
本発明に使用されるカラー現像液は、好ましくはpH9
〜l2、より好ましくは9〜11,Oであり、そのカラ
ー現像液には、その他に既知の現像液成分の化合物を含
ませることができる.上記PHを保持するためには、各
種緩衝剤を用いるのが好ましい.
緩衝剤の具体例としては、度酸ナトリウム、炭酸カリウ
ム、重炭酸ナトリウム、重炭酸カリウム、リン酸三ナト
リウム、リン酸三カリウム、リン酸二ナトリウム、リン
酸二カリウム、ホウ酸ナトリウム、ホウ酸カリウム、四
ホウ酸ナトリウム(ホウ砂)、四ホウ酸カリウム、O−
ヒドロキシ安息香酸ナトリウム(サリチル酸ナトリウム
)%O一ヒドロキシ安息香酸カリウム、5−スルホー2
−ヒド口キジ安、ワ、香酸ナトリウム(5−スルホサリ
チル酸ナトリウム)、5−スルホー2−ヒドロキシ安息
香酸カリウム(5−スルホサリチル酸カリウム)などを
挙げることができる.しかしながら本発明は、これらの
化合物に限定されるものではない.
該緩衝剤のカラー現像液への添加量は、0.1モル/1
以上であることが好ましく、特に0.1モル/1〜0.
4モル/1であることが特に好ましい,
その他、カラー現像液中にはカルシウムやマグネシウム
の沈澱防止剤として、あるいはカラー現像液の安定性向
上のために、各種キレート剤を用いることができる.
キレート剤としては有機酸化合物が好ましく、例えばア
ミノボリカルボン酸類、有機ホスホン酸類、ホスホノカ
ルボン酸頚をあげることができる.以下に具体例を示す
がこれらに限定されるものでなはい.
ニトリロ三酢酸、ジエチレントリアミン五酢酸、エチレ
ンジアミン四酢酸、N,N,N−トリメチレンホスホン
酸、エチレンジアミンーN, NN’,N’−テトラ
メチレンホスホン酸、トランスシクロヘキサンジアミン
四酢酸、1,2−ジアミノプロパン四酢酸、ヒドロキシ
ェチルイミノジ酢酸、グリコールエーテルジアミン四酢
酸、エチレンジアミンオルトヒド口キシフエニル酢酸、
2ーホスホノブタン−1.2.4−}リカルボン酸、l
−ヒドロキシエチリデン−1,l−ジホスホン酸、N,
N’−ビス(2−ヒト′ロキシベンジル)エチレンジア
ミンーN,N’−ジ酢酸、これらのキレート荊は必要に
応じて2種以上併用しても良い.
これらのキレート剤の添加量はカラー現像液中の金属イ
オンを封鎖するのに充分な量であれば良い.例えば11
当り0.1g〜log程度である。In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, JP-A-63-43138
Hydroxam 61l described in the issue! ¥, 63-14
.. Hydrazines and hydrazides described in No. 6041, phenols described in No. 63-44657 and No. 63-58443, and α- described in No. 63-44656.
It is preferable to add hydroxyketones, α-aminoketones, and/or the various sugars described in No. 63-36244. In addition, in combination with the above compounds, JP-A-63-4
No. 235, No. 63-24254, No. 63-21647
No. 63-146040, No. 63-27841,
and monoamines described in No. 63-25654, etc., No. 63-30845, No. 63-146040, No. 63
Diamines described in No.-43139 etc., No. 63-216
No. 47, and the polyamines described in No. 63-26655, the polyamines described in No. 63-44655, and No. 63-26655,
Nitroxy radicals described in No. 53551, IiW63
It is preferable to use the alcohols described in No. 43140 and No. 63-53549, the oximes described in No. 63-56654, and the tertiary amines described in No. 63-239447. Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicyl tllM described in No. 180588, JP-A-54-
Alkanolamines described in No. 3532, JP-A-56-
The polyethyleneimine described in US Pat. No. 94349, the aromatic polyhydrolysate compound described in US Pat. No. 3,746.544, etc. may be contained as necessary. Particularly preferred is the addition of aromatic polyhydroxy compounds. The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11,0, and the color developer may contain other known developer component compounds. In order to maintain the above pH, it is preferable to use various buffering agents. Specific examples of buffering agents include sodium peroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and potassium borate. , Sodium Tetraborate (Borax), Potassium Tetraborate, O-
Sodium hydroxybenzoate (sodium salicylate)% O-potassium hydroxybenzoate, 5-sulfo2
- Hydroxylene chloride, sodium fragrant (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds. The amount of the buffer added to the color developer is 0.1 mol/1
It is preferable that the amount is more than 0.1 mol/1 to 0.1 mol/1.
A ratio of 4 mol/1 is particularly preferred. In addition, various chelating agents may be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer. The chelating agent is preferably an organic acid compound, such as aminobocarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but are not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N, NN',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropane Tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid,
2-phosphonobutane-1.2.4-}licarboxylic acid, l
-hydroxyethylidene-1,l-diphosphonic acid, N,
N'-bis(2-human'roxybenzyl)ethylenediamine-N,N'-diacetic acid, two or more of these chelates may be used in combination if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to log per unit.
カラー現像液には、必要により任意の現像促進剤を添加
することができる.しかしながら、本発明のカラー現像
液は、公害性、調液性及び色汚染防止の点で、ベンジル
アルコールを実t的に含有しない場合が好ましい.ここ
で「実質的に」とは現像液1l当たり2一以下、好まし
くは全く含有しないことを意味する.
その他現像促進剤としては、特公昭37−16088号
、同37−5987号、同38−7826号、同44−
12380号、同45−9019号及び米国特許第3,
813,247号等に表わされるチオエーテル系化合物
、特開昭52−49829号及び同50−15554号
に表わされるp−フエニレンジアミン系化合物、特開昭
50−137726号、特公昭44−30074号、特
開昭56−156826号及び同52−43429号、
等に表わされる4級アンモニウム塩類、米国特許第2,
494,903号、同3,128,182号、同4,2
30,796号、同3,253,919号、特公昭41
−11431号、米国特許第2,482,546号、同
2. 596, 926号及び同3,582,34
6号等に記載のアミン系化合物、特公昭37−1608
8号、同42−25201号、米国特許第3,128.
183号1特公昭41−11431号、同42−238
83号及び米国特許第3,532,501号等に表わさ
れるポリアルキレンオキサイド、その他1−フエニル−
3−ビラゾリドン類、イミダゾール類、等を必要に応し
て添加することができる。Any development accelerator can be added to the color developer if necessary. However, it is preferable that the color developer of the present invention does not actually contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means that the developer contains less than 2 parts per liter of developer, preferably not at all. Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, and JP-B-Sho 44-30074. , JP-A-56-156826 and JP-A-52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2,
No. 494,903, No. 3,128,182, No. 4,2
No. 30,796, No. 3,253,919, Special Publication No. 1977
-11431, U.S. Patent No. 2,482,546, 2. 596, 926 and 3,582,34
Amine compounds described in No. 6 etc., Japanese Patent Publication No. 37-1608
No. 8, No. 42-25201, U.S. Patent No. 3,128.
No. 183 1 Special Publication No. 41-11431, No. 42-238
83 and U.S. Pat. No. 3,532,501, etc., and other 1-phenyl-
3-Vyrazolidones, imidazoles, etc. can be added as necessary.
本発明においては、必要に応じて、任意のカブリ防止剤
を添加できる.カブリ防止剤としては、塩化ナトリウム
、臭化カリウム、沃化カリウムの如きアルカリ金属ハロ
ゲン化物及び有機力ブリ防止剤が使用できる.有機力ブ
リ防止剤としては、例えばペンゾトリアゾール、6−ニ
トロベンズイミグゾール、5−ニトロインイングゾール
、5一メチルベンゾトリアゾール、5−ニトロペンゾト
リアゾール、5−クロローベンゾl− IJアゾール、
2−チアゾリルーペンズイミダゾール、2−チアゾリル
メチルーベンズイミダゾール、インダゾール、ヒドロキ
シアザインドリジン、アデニンの如き含窒素へテロ環化
合物を代表例としてあげることができる.
本発明に使用されるカラー現像液には、螢光増白剤を含
有してもよい.螢光増白剤としては、44゛−ジアミノ
ー2.2′−ジスルホスチルベン系化合物が好ましい。In the present invention, any antifoggant can be added as necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic anti-brittle agents include penzotriazole, 6-nitrobenzimiguzole, 5-nitroiningzole, 5-methylbenzotriazole, 5-nitropenzotriazole, 5-chlorobenzol-IJ azole,
Representative examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylpenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, and adenine. The color developer used in the present invention may contain a fluorescent brightener. As the fluorescent brightener, 44'-diamino-2,2'-disulfostilbene compounds are preferred.
添加量は0〜5g/1好ましくは0.1g〜4g/1で
ある.
又、必要に応じてアルキルスルホン酸、アリーホスホン
酸、脂肪族カルボン酸、芳香族カノレボン酸等の各種界
面活性剤を添加しても良い。The amount added is 0 to 5 g/1, preferably 0.1 g to 4 g/1. Furthermore, various surfactants such as alkylsulfonic acid, aryphosphonic acid, aliphatic carboxylic acid, and aromatic canolebonic acid may be added as necessary.
本発明のカラー現像液の処理温度は20〜50℃好まし
くは30〜45℃である.処理時間は20秒〜5分好ま
しくは30秒〜3分である.補充量は少ない方が好まし
いが、感光材料1一当り100〜150〇一好ましくは
ioo〜800−である.更に好ましくは100−〜4
00−である.又、カラー現像浴は必要に応して2浴以
上に分割し、最前浴あるいは最後浴からカラー現像補充
液を補充し、現像時間の短縮化や補充量の低減を実施し
ても良い.
本発明の処理方法はカラー反転処理にも用いうる.本発
明ではこのときに用いる黒白現像液として通常知られて
いるカラー写真感光材料の反転処理に用いられる黒白第
1現像液と呼ばれるものもしくは、黒白感光材料の処理
に用いられるものが使用できる.また一般に黒白現像液
に添加されるよく知られた各種の添加剤を含有せしめる
ことができる.
代表的な添加剤としては、1−フエニル−3ビラゾリド
ン、メトールおよびノ1イドロキノンのような現像主薬
、亜硫酸塩のような保恒剤、水酸化ナトリウム、炭酸ナ
トリウム、炭酸カリウム等のアルカリから成る促進剤、
臭化カリウムや、2−メチルベンツイミダゾール、メチ
ルベンツチアゾール等の無機性もしくは、有機性の抑制
剤、ポリリン酸塩のような硬水軟化剤、微量のヨウ化物
や、メルカブト化合物から成る現像抑制剤をあげること
ができる.
本発明の処理方法は、前述した発色現像、漂白、漂白定
着などの処理工程からなっている.ここで、漂白定着工
程の後には、水洗及び安定化などの処理工程を行なうこ
とが一般的に行なわれているが、漂白定着工程後、実質
的な水洗を行なわず安定化処理を行なう簡便な処理方法
を用いることもできる.
水洗工程に用いられる水洗水には、必要に応じて公知の
添加剤を含有させることができる.例えば、無機リン酸
、アミノポリカルボン酸、有機1Jン酸等の硬水軟化剤
、各種バクテリアや藻の増殖を防止する・殺菌剤・防ぽ
い剤(例えば、イソチアゾロン、有機塩素系殺菌剤、ペ
ンゾトリアゾーノレ等)、乾燥負荷、ムラを防止するた
めの界面活性剤などを用いることができる.または、l
,[i,West”Water Quality Cr
iteria’,Phot.Sci.and Eng.
vol.9.k6、page3 4 4 〜3 5 9
(1 9 6 5)等に記載の化合物を用いることも
できる.安定化工程に用いる安定液としては、色素画像
を安定化される処理液が用いられる.例えば、pH3〜
6の緩衝能を有する液、アルデヒド(例えば、ホルマリ
ン)を含有した液などを用いることができる.安定液に
は、必要に応じてアンモニウム化合物、Bi,Aj!な
どの金属化合物、螢光増白剤、キレート剤(例えば、l
−ヒドロキジエチリデン−1,1−ジホスホン酸)、殺
苗剤、防ぽい剤、硬膜剤、アルカノールアミン、界面活
性剤などを用いることができる.
また水洗工程や安定化工程は、多段向流方式が好ましく
、段数としては2〜4段が好ましい.補充量としては単
位面積当り前浴からの持込挺の1〜50倍、好ましくは
2〜30倍、より好ましくは2〜15倍である.
これらの水洗工程もしくは・安定化工程に用いられる水
としては、水道水の他、イオン交換樹脂などによってC
a,Mg濃度を5tz/1以下に脱イオン処理した水、
ハロゲン、紫外線殺菌灯等により殺菌された水を使用す
るのが好ましい.以上のを光材料の各処理工程において
、自動現像機による連続処理を行なった場合、窪発によ
る処理液の濃縮が起きることがあり、特に処理量が少な
い場合や処理液の開口面積が大きい場合に顕著となる.
このような処理液の1縮を補正するため、適当量の水ま
たは補正液を補充することが好ましい.
本発明は種々のカラー感光材料に適用することができる
.一般用若しくは映画用のカラーネガフィルム、スライ
ド用若しくはテレビ用のカラー反転フィルム、カラーペ
ーパー、カラーボジフィルム及びカラー反転ペーパー、
直接ボジカラー感光材料等を代表例として挙げることが
できる.本発明に用いられるハロゲン化銀乳剤は、リサ
ーチ・ディスクロージャー、voL 1 7 6, I
te僧陽!7643、■〕項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カラー写真惑光材料に
は、臭化銀、沃臭化銀、沃塩臭化銀、塩臭化銀および塩
化銀のいずれのハロゲン化銀を用いてもよい.
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を有するいわゆるレギュラ
ー粒子でもよく、また球状、板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あ
るいはそれらの複合形でもよい.また種々の結晶形の粒
子の混合物を用いてもよい.
ハロゲン化銀の粒径は、0,1ミクロン以下の微粒子で
も投影面積直径が10ミクロンに至る迄の大サイズ粒子
でもよく、狭い分布を有する単分散乳剤でも、あるいは
広い分布を有する多分散乳剤でもよい.
また単分散乳剤としては、平均粒子直径が約0.1ミク
ロンより大きいハロゲン化銀粒子で、その少なくとも約
95重董%が平均粒子直径の±40%内にあるような乳
剤が代表的である。平均粒子直径が約0.25〜2ミク
ロンであり、少なくとも約95重量%又は数量で少なく
とも約95%のハロゲン化銀粒子を平均粒子直径±20
λ6の範囲内としたような乳剤を本発明で使用できる.
結晶構造は一様なものでも、内部と外部とが異質なハロ
ゲン組成からなる物でもよく、1口状構造をなしていて
もよい。これらの乳剤粒子は、英国特許第i.027,
146号、米国特許第3,505,068号、同4.4
4.4.877号および特開昭60−143331号等
に開示されている.また、エビタキシャル接合によって
組成の異なるハロゲン化銀が接合されていてもよい.本
発明に用いられるハロゲン化銀写真乳剤に平板状粒子を
用いることによって、増感色素による色増悪効率の向上
を含む惑度の向上、惑度の粒状性の関係の改良、シャー
プネスの改良、現像進行性の改良、カバリングバワーの
向上、クロスオーバーの改善などが達成できる.ここで
平板状ハロゲン化銀粒子とは、その直径/厚みの比が5
以上のものであり、例えば8を越えるものや5以上8以
下のものがある.
高感度カラー感光材料に用いるものには沃臭化銀が特に
好ましい.沃臭化銀の場合、沃化銀含有量は、通常40
モル%以下であり、好ましくは30モル%以下、より好
ましくは2〜20モル%である.また、プリント用カラ
ー感光材料には塩化銀、奥化銀、塩臭化銀が特に好まし
い.平板状粒子は均一なハロゲン組成からなるものであ
りでも異なるハロゲン組成を有する2以上の相からなる
ものであってもよい.例えば、沃臭化銀を用いる場合、
この沃臭化根平板状粒子はそれぞれ沃化物含有量の異な
る複数の相からなる相状構造を有するものを用いること
もできる。特開昭58−113928号あるいは特開昭
59−99433号等において、平板状ハロゲン化根粒
子のハロゲン組成およびハロゲンの粒子内分布の好まし
い例が記載されている.
本発明における平板状ハロゲン化銀粒子の好ましい使用
方法としては、リサーチ・ディスクロージャー隘225
3411983年I月)、同隘25330 (1985
年5月)に詳細に記述されており、そこでは例えば平板
状粒子の厚みと光学的性質の関係に基づいた使用法が開
示されている.ハロゲン化銀乳剤は、通常、物理熟成、
化学増感及び分光増悪を行ったものを使用する.物理熟
成の過程において、種々の多価金属イオン不純物(カド
ミウム、亜鉛、鉛、銅、タリウム、鉄、ルテニウム、ロ
ジウム、パラジウム、オスミウム、イリジウム、白金な
どの塩もしくは詣塩など)を導入することもできる.
ハロゲン化銀粒子形成の熟成を促進するにはハロゲン化
銀溶剤が有用である.例えば熟成を促進するのに過剰量
のハロゲンイオンを反応器中に存在せしめることが知ら
れている。ハロゲンイオン以外の熟成剤としては、アン
モニアあるいは、アミン化合物、チオシアネート塩、例
えばアルカリ金属チオシアネート塩、特にナトリウム及
びカリウムチオシアネート塩、並びにアンモニウムチオ
シアネート塩を用いることができる.チオシアネート熟
成剤を用いることは米国特許第2,222,264号、
同2,448,534号および同3,320,069号
に教示が見られる.また米国特許第3,271.157
号、同3,574,628号および同3,737,3i
3号に記載されるような常用されるチオエーテル熟成剤
を用いることもできる.あるいは特開昭53−8240
8号、同5 3 − 1 4 4 3 1. 9号に開
示されているような千オン化合物を用いることもできる
.
ハロゲン化銀乳荊の化学増感は、金化合物とチオシアネ
ート化合物の存在下に、または米国特許第3,857.
711号、同4,266.018号および同4,054
、457号に記載される硫黄含有化合物もしくはハイボ
、チオ尿素系化合物、ロダニン系化合物などの硫黄含有
化合物の存在下に行うのが好ましい.
本発明に用いられるハロゲン化銀写真乳剤は、メチン色
素類その他によって分光増感されてもよい.特に有用な
色素は、シアニン色素、メロシアニン色素、および複合
メロシアニン色素に属する色素である.
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侍に、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.
これらの色素などとしては、リサーチ・ディスクロージ
ャー、vol. 1 7 6、Item kl 7
6 4 3、IV(1978年12月)に記載されたも
のを用いうる.
本発明に用いられるハロゲン化銀乳剤を分光増感する際
には、乳剤調製のどの段階でも行なうことができる.米
国特許第4.183,756号および同4,225,6
66号では、ハロゲン化銀粒子形成の安定な該の形成以
後に分光増感色素を乳剤に添加することにより、写真感
度の増加やハロゲン化銀粒子による分光増感色素の吸着
の強化などの利点があることが開示されている。The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. Although it is preferable that the replenishment amount be small, it is preferably 100 to 1,500, preferably 1,000 to 800, per 1 photosensitive material. More preferably 100- to 4
It is 00-. Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment. The processing method of the present invention can also be used for color reversal processing. In the present invention, the black-and-white developer to be used at this time can be a so-called black-and-white first developer, which is commonly known and used in the reversal processing of color photographic light-sensitive materials, or a developer used in the processing of black-and-white light-sensitive materials. In addition, various well-known additives that are generally added to black and white developers can be included. Typical additives include developing agents such as 1-phenyl-3-virazolidone, metol and noihydroquinone, preservatives such as sulfites, and promoters consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. agent,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, trace amounts of iodide, and development inhibitors consisting of mercabuto compounds. I can give it to you. The processing method of the present invention comprises processing steps such as color development, bleaching, and bleach-fixing as described above. Here, after the bleach-fixing process, processing steps such as water washing and stabilization are generally performed, but there is a simple method of performing stabilization processing without actually washing with water after the bleach-fixing process. You can also use processing methods. The rinsing water used in the rinsing process may contain known additives as necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic 1J phosphoric acid, etc., disinfectants and anti-fungal agents that prevent the growth of various bacteria and algae (e.g. isothiazolone, organochlorine disinfectants, penzo triazole, etc.), drying load, surfactants to prevent unevenness, etc. can be used. Or l
,[i,West”Water Quality Cr
iteria', Photo. Sci. and Eng.
vol. 9. k6, page 3 4 4 ~ 3 5 9
(1 9 6 5) etc. can also be used. The stabilizing solution used in the stabilization process is a processing solution that can stabilize dye images. For example, pH 3~
A solution having a buffering capacity of 6, a solution containing an aldehyde (for example, formalin), etc. can be used. The stabilizing solution contains ammonium compounds, Bi, Aj!, if necessary. metal compounds such as fluorescent brighteners, chelating agents (e.g. l
-hydroxydiethylidene-1,1-diphosphonic acid), seedlingicides, anti-fungal agents, hardeners, alkanolamines, surfactants, etc. can be used. Further, the water washing step and the stabilization step are preferably performed using a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area. In addition to tap water, the water used in these washing steps or stabilization steps includes carbon
a, water that has been deionized to have a Mg concentration of 5 tz/1 or less;
It is preferable to use water that has been sterilized using halogen or ultraviolet germicidal lamps. In each of the above processing steps for optical materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to depression may occur, especially when the processing amount is small or the opening area of the processing solution is large. It becomes noticeable.
In order to correct such shrinkage of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid. The present invention can be applied to various color photosensitive materials. Color negative film for general use or movies, color reversal film for slides or television, color paper, color body film and color reversal paper,
Direct physical color photosensitive materials are a typical example. The silver halide emulsion used in the present invention is described in Research Disclosure, vol 1 7 6, I
te monk! 7643, [1]]. The silver halide color photographic material used in the present invention may contain any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Silver halide grains in photographic emulsions may be so-called regular grains with regular crystals such as cubes, octahedrons, and tetradecahedrons, or may have irregular crystal shapes such as spherical or plate shapes. It may be a crystal, a crystal with crystal defects such as twin planes, or a combination thereof. Also, a mixture of particles of various crystal forms may be used. The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good. A typical monodisperse emulsion is an emulsion in which silver halide grains have an average grain diameter of more than about 0.1 micron, and at least about 95% of the grains are within ±40% of the average grain diameter. . The average grain diameter is between about 0.25 and 2 microns, and at least about 95% by weight or at least about 95% by number of silver halide grains have an average grain diameter of ±20 microns.
Emulsions within the range of λ6 can be used in the present invention.
The crystal structure may be uniform, the inside and outside may have different halogen compositions, or the crystal structure may be a one-hole structure. These emulsion grains are described in British Patent No. i. 027,
No. 146, U.S. Pat. No. 3,505,068, U.S. Patent No. 4.4
4.4.877 and Japanese Patent Application Laid-Open No. 143331/1983. Further, silver halides having different compositions may be joined by evitaxial joining. By using tabular grains in the silver halide photographic emulsion used in the present invention, it is possible to improve the clarity, including the improvement of the efficiency of color enhancement by the sensitizing dye, to improve the relationship between the clarity and the graininess, to improve sharpness, and to improve the development Improvements in progression, covering power, and crossover can be achieved. Here, tabular silver halide grains have a diameter/thickness ratio of 5.
For example, there are those that exceed 8 and those that are greater than or equal to 5 and less than or equal to 8. Silver iodobromide is particularly preferred for use in high-sensitivity color photosensitive materials. In the case of silver iodobromide, the silver iodide content is usually 40
It is mol% or less, preferably 30 mol% or less, more preferably 2 to 20 mol%. Furthermore, silver chloride, silver chloride, and silver chlorobromide are particularly preferred for color photosensitive materials for printing. The tabular grains may have a uniform halogen composition or may consist of two or more phases having different halogen compositions. For example, when using silver iodobromide,
The iodobromide tabular grains may have a phase structure consisting of a plurality of phases each having a different iodide content. In JP-A-58-113928 and JP-A-59-99433, preferred examples of the halogen composition of tabular halogenated root particles and the intra-particle distribution of halogen are described. A preferred method of using tabular silver halide grains in the present invention is as described in Research Disclosure 225
341 I, 1983), same issue 25330 (1985
(May, 2013), which discloses, for example, a method of use based on the relationship between the thickness of tabular grains and optical properties. Silver halide emulsions are usually subjected to physical ripening,
Use those that have undergone chemical sensitization and spectral enhancement. During the physical ripening process, various polyvalent metal ion impurities (salts or pilgrim salts of cadmium, zinc, lead, copper, thallium, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.) may be introduced. can. Silver halide solvents are useful for accelerating the ripening of silver halide grain formation. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in U.S. Pat. No. 2,222,264;
Teachings can be found in No. 2,448,534 and No. 3,320,069. Also, U.S. Patent No. 3,271.157
No. 3,574,628 and No. 3,737,3i
Commonly used thioether ripening agents such as those described in No. 3 can also be used. Or JP-A-53-8240
No. 8, 5 3-1 4 4 3 1. It is also possible to use 1,000-ion compounds such as those disclosed in No. 9. Chemical sensitization of silver halide milk in the presence of gold compounds and thiocyanate compounds or as described in US Pat. No. 3,857.
No. 711, No. 4,266.018 and No. 4,054
It is preferable to carry out the reaction in the presence of a sulfur-containing compound such as a sulfur-containing compound described in No. 457, or a sulfur-containing compound such as Hybo, a thiourea compound, or a rhodanine compound. The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used in Samurai for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. These dyes are described in Research Disclosure, vol. 1 7 6, Item kl 7
6 4 3, IV (December 1978) may be used. Spectral sensitization of the silver halide emulsion used in the present invention can be carried out at any stage of emulsion preparation. U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66 discloses that by adding a spectral sensitizing dye to the emulsion after the formation of stable silver halide grains, advantages such as increased photographic sensitivity and enhanced adsorption of the spectral sensitizing dye by the silver halide grains are obtained. It has been disclosed that there is.
本発明の写真感光材料の写真乳剤層には感度上昇、コン
トラスト上昇、または現像促進の目的でたとえばポリア
ルキレンオキシドまたはそのエーテル、エステル、アミ
ンなどの誘導体、チオエーテル化合物、チオモルフォリ
ン類、四級アンモニウム塩化合物、ウレタン誘導体、尿
素誘導体、イミダゾール誘導体、3−ビラゾリドン類等
を含んでもよい,
本発明に用いられるハロゲン化銀写真乳剤には、感光材
料の製造工程、保存中あるいは写真処理中のカブリを防
止し、あるいは写真性能を安定化させるなどの目的で、
種々の化合物を含有させることができる.すなわちアゾ
ール頚、例えばペンゾチアゾリウム類、ニトロイミダゾ
ール類、ニトロベンズイミダゾール類、クロロペンズイ
ミダゾール類、プロモベンズイミダゾール類、メルカブ
トチアゾール類、メルカブトベンゾチアゾール類、メル
カブトベンズイミダゾール類、メルカブトチアジアゾー
ル類、アミノトリアゾール類、ペンゾトリアゾール類、
ニトロペンゾトリアゾール類、メルカプトテトラゾール
類(特に1−フェニルー5−メルカブトテトラゾール)
など;メルカブトピリミジン類1メルカブトトリアジン
類;例えばオキサゾリンチオンのようなチオケト化合物
;アザインデン類、例えばトリアザインデン類、テトラ
アザインデン類(特に4−ヒドロキシ置換(13.3a
,?)テトラアザインデン類)、ペンタアザインデン類
など:ベンゼンチオスルフォン酸、ベンゼンスルフィン
酸、ベンゼンスルフォン酸アミド等のようなカブリ防止
剤または安定剤として知られた多くの化合物を加えるこ
とができる。The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. The silver halide photographic emulsion used in the present invention, which may contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-virazolidones, etc., is free from fog during the manufacturing process, storage, or photographic processing of the light-sensitive material. For the purpose of preventing or stabilizing photographic performance,
It can contain various compounds. That is, azole necks, such as penzothiazoliums, nitroimidazoles, nitrobenzimidazoles, chloropenzimidazoles, promobenzimidazoles, mercabutothiazoles, mercabutobenzothiazoles, mercabutobenzimidazoles, mercabut Thiadiazoles, aminotriazoles, penzotriazoles,
Nitropenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
merkabutopyrimidines; merkabutotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (13.3a
,? ) Tetraazaindenes), Pentaazaindenes, etc. Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.
また、色カブリ防止剤もしくは混色防止剤として、ハイ
ドロキノン誘導体、アミノフェノール誘導体、アミン類
、没食子酸誘導体、カテコール誘導体、アスコルビン酸
誘導体、無呈色カブラースルホンアミドフェノール誘導
体などを含有してもよい.
本発明に用いられる感光材料には、公知の退色防止剤を
用いることができる。公知の退色防止剤としてはハイド
ロキノン類、6−ヒドロキシクロマン類、5−ヒドロキ
シクマラン類、スビロクロマン類、p−アルコキシフェ
ノール類、ビスフェノール類を中心としたヒンダードフ
ェノール類、没食子酸誘導体、メチレンジオキシベンゼ
ン類、アミノフェノール類、ヒンダートアミン類および
これら各化合物のフェノール性水酸基をシリル化、アル
キル化したエーテルもしくはエステル誘導体が代表例と
して挙げられる.
本発明に用いられる感光材料において、親水性コロイド
層中に紫外線吸収荊を添加することができる.
紫外線吸収剤の典型例はRD24239 (1984年
6月)などに記載されている。Further, as a color antifogging agent or a color mixing prevention agent, hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplersulfonamide phenol derivatives, etc. may be contained. Known anti-fading agents can be used in the photosensitive material used in the present invention. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, subirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, and methylenedioxy. Representative examples include benzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. In the photosensitive material used in the present invention, an ultraviolet absorbing layer can be added to the hydrophilic colloid layer. Typical examples of ultraviolet absorbers are described in RD24239 (June 1984).
本発明に用いられる感光材料は塗布助剤、帯電防止、ス
ベリ性改良、乳化分散、接着防止および写真特性改良(
たとえば現像促進、硬調化、増惑)など種々の目的で一
種以上の界面活性剤を含んでもよい.
本発明に用いられる感光材料は、フィルター染料として
、またはイラジエーションもしくはハレーション防止そ
の他種々の目的のために親水性コロイド層中に水溶性染
料を含有してもよい。このような染料として、オキソノ
ール染料、ヘミオキソノール染料、スチリル染料、メロ
シアニン染料、アントラキノン染料、アゾ染料が好まし
く使用され、この他にシアニン染料、アゾメチン染料、
トリアゾールメタン染料、フタ口シアニン染料も有用で
ある.油溶性染料を氷中油滴分散法により乳化して親水
性コロイド層に添加することもできる。The photosensitive material used in the present invention is used as a coating aid, antistatic, improves sliding properties, emulsification and dispersion, prevents adhesion, and improves photographic properties (
For example, one or more surfactants may be included for various purposes such as accelerating development, increasing contrast, and increasing clarity. The photosensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes,
Triazole methane dyes and lid cyanine dyes are also useful. An oil-soluble dye can also be emulsified by an oil-in-ice dispersion method and added to the hydrophilic colloid layer.
以上の工程で使用することのできる添加剤は、リサーチ
・ディスクロージャーml7643及び−1. 8 7
1 6に記載されており、後掲の表にまとめた.
内崖劃1且 RD17643
1 化学増感剤 23頁
2感度上昇剤
4 増 白 剤 24頁色素画像安定剤
硬 膜 剤
バインダー
可塑剤、潤滑剤
25頁
26頁
26頁
27真
その該当箇所を
1?D18716
648頁右欄
同上
651頁左欄
同上
650頁右欄
また、ホルムアルデヒドガスによる写真性能の劣化を防
止するために、米国特許4,411,987号や同4,
435.503号に記載されたホルムアルデヒドと反応
して、固定化できる化合物を感光材料に添加することが
好ましい.本発明には種々のカラーカブラーを使用する
ことができ、その具体例はリサーチ・ディスクロージャ
ー (RD)魚17643、■一〇−Gに記載された特
許に記載されている。色素形成カブラーとしては、滅色
法の三原色(すなわち、イエローマゼンタおよびシアン
)を発色現像で与えるカプラーが重要であり、耐拡散性
の、4当量または2当量カブラーの具体例は前述RD1
7643、■一〇およびD項記載の特許に記載されたカ
ブラーの外、下記のものを本発明で好ましく使用できる
.イエローカブラーとしては、例えば米国特許第3,9
33,501号、同4,022,620号、同4,32
6.024号、同4,401,752号、同4,248
.961号、特公昭58−10739号、英国特許第1
.425.020号、同1,476,760号、米国特
許第3.973.968号、同4,314,023号、
同4、511,649号、欧州特許第249,473A
号等に記載のものが好ましい.
マゼンタカブラーとしては5−ピラゾロン系及びビラゾ
ロアゾール系の化合物が好ましく、米国特許第4,31
0,619号、同4, 351. 897号、欧州
特許第73,636号、米国特許第3 061.43
2号、同3,725.064号、RD磁24220 (
1984年6月)、特開昭60−33552号、RD?
b24.230 (1984年6月)、特開昭60−4
3659号、同6172238号、同60−35730
号、同55−1. 1 8 0 3 4号、同60−1
85951号、米国特許第4.500,630号、同4
,540.654号、同4,556,630号、WO
(PCT)88/04.795号等に記載のものが持に
好ましい。Additives that can be used in the above steps are Research Disclosure ml7643 and -1. 8 7
16, and summarized in the table below. Inner cliff 1 and RD17643 1 Chemical sensitizer page 23 2 Sensitivity enhancer 4 Brightening agent page 24 Dye image stabilizer Hardener Binder Plasticizer, lubricant 25 page 26 page 26 page 27 True 1? D18716 Page 648 Right column Same as above Page 651 Left column Same as above Page 650 Right column In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503. A variety of color couplers can be used with the present invention, examples of which are described in the patents listed in Research Disclosure (RD) Fish 17643, 10-G. As a dye-forming coupler, a coupler that provides the three primary colors (i.e., yellow magenta and cyan) in a color development process is important, and a specific example of a diffusion-resistant 4-equivalent or 2-equivalent coupler is the above-mentioned RD1.
In addition to the couplers described in the patents described in No. 7643, Section 10 and Section D, the following can be preferably used in the present invention. As a yellow coupler, for example, U.S. Patent Nos. 3 and 9
No. 33,501, No. 4,022,620, No. 4,32
No. 6.024, No. 4,401,752, No. 4,248
.. No. 961, Special Publication No. 58-10739, British Patent No. 1
.. 425.020, U.S. Patent No. 1,476,760, U.S. Patent No. 3.973.968, U.S. Patent No. 4,314,023,
4,511,649, European Patent No. 249,473A
Preferably, those listed in the No. As the magenta coupler, 5-pyrazolone type and virazoloazole type compounds are preferable, and US Pat.
No. 0,619, 4, 351. 897, European Patent No. 73,636, U.S. Patent No. 3 061.43
No. 2, No. 3,725.064, RD Magnet 24220 (
June 1984), JP-A-60-33552, RD?
b24.230 (June 1984), JP-A-60-4
No. 3659, No. 6172238, No. 60-35730
No. 55-1. 18034, 60-1
85951, U.S. Pat. No. 4,500,630, U.S. Pat.
, No. 540.654, No. 4,556,630, WO
(PCT) No. 88/04.795 and the like are particularly preferred.
シアンカブラーとしては、フェノール系及びナフトール
系カブラーが挙げられ、米国特許第4.052.212
号、同4,146,396号、同4,228,233号
、同4,296,200号、同2,369,929号、
同2, 801, 1.71号、同2,772,162
号、同2、895,82G号、同3,772,002号
、同3.758308号、同4,334,011号、同
4,327,173号、***特許公開第3.329.7
29号、欧州特許第121,365A号、同24945
3八号、米国特許第3.4.46,622号、同4,3
33,999号、同4,753.871号、同4,45
1,559号、同4,427,767号、同4,690
,889号、同4.254212号、同4,296.1
99号、特開昭61−42658号等に記載のものが好
ましい.発色色素の不要吸収を補正するためのカラード
・カブラーは、RDぬ17643の■−G項、米国特許
第4.,163.670号、特公昭57−39413号
、米国特許第4,004,929号、同4,138.2
58号、英国特許第1.146368号に記載のものが
好ましい.また、米国特許第4..774,181号に
記載のカップリング時に放出された蛍光色素により発色
色素の不要吸収を補正するカプラーや、米国特許第4,
777,120号に記載の現像主薬と反応して色素を形
成しうる色素プレカーサー基を離脱基として有するカブ
ラーを用いることも好ましい.
発色色素が適度な拡散性を有するカブラーとしては、米
国特許第4.366,237号、英国特許第2.125
,570号、欧州特許第96,570号、***特許(公
開》第3,234.533号に記載のものが好ましい.
ボリマー化された色素形成カブラーの典型例は、米国特
許第3,451,820号、同4,080,211号、
同4,367,282号、同4,409,320号、同
4,576,910号、英国特許2.102.173号
等に記載されている.カップ電届/グに伴って写真的に
有用な残基を放出するカブラーもまた本発明で好ましく
使用できる.現像抑制剤を放出するDIRカブラーは、
前述のRD17643、■〜F項に記載された特許、特
開昭5 7 − 1 5 1 9 4. 4号、同57
−154234号、同6 0 − 1 8 4 2 4
. 8号、同63−37346号、米国特許4.248
.962号、同4,782,01.2号に記載されたも
のが好ましい.現像時に画像状に造核剤もしくは現像促
進剤を放出するカブラーとしては、英国特許第2,09
7,140号、同2,131..188号、特開昭59
−157638号、同5 9 − 1 7 0 8 4
. 0号に記載のものが好ましい.
その他、米国特許第4,130,427号等に記載の競
争カブラー、米国特許第4.,283.472号、同4
..338,393号、同4,310,618号等に記
載の多当量カブラー、特開昭60−185950号、特
開昭62−24252号等に記載のDIRレドックス化
合物放出力ブラーDIRカブラー放出力ブラー、DIR
カブラー放出レドンクス化合物もしくはDIRレドノク
ス放出レドンクス化合物、欧州特許第173,302A
号に記載の離脱後復色する色素を放出するカブラー、R
D陽1 1. 4 4 9、同24241、特開昭61
−201247号等に記載の漂白促進剤放出カブラー、
米国特許第4,553.477号等に記載のりガンド放
出力ブラー、特開昭63−75747号に記載のロイコ
色素を放出するカブラー米国特許第4,774,181
号に記載の蛍光色素を放出するカブラー等も用いること
ができる.
本発明に使用するカブラーは、種々の公知の分散方法例
えば.水中油滴分散法、ラテノクス分散法、固体分散法
、アルカリ分散法などにより感光材事4に導入できる.
水中油滴分散法に用いられる高沸点溶媒の例は米国特許
第2.322.027号などに記載されている.
ラテックス分散法の工程、効果及び含浸用のラテックス
の具体例は、米国特許第4、199,363号、***特
許出111(OLS)第2.541274号及び同2.
54.1,230号などに記載されている.
また、これらのカブラーは前記の高沸点有機溶媒の存在
下または不存在下でローダブルラテノクスボリマ−(例
えば米国特許第4,203.7J6号)に含浸させて、
または水不溶性かつ有機溶媒可溶性のボリマーに溶かし
て親水性コロイド水}容液に乳化分散させることができ
る。Cyan couplers include phenolic and naphthol based couplers, and are described in U.S. Patent No. 4.052.212.
No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929,
2, 801, 1.71, 2,772,162
No. 2, 895,82G, No. 3,772,002, No. 3.758308, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3.329.7
No. 29, European Patent No. 121,365A, European Patent No. 24945
No. 38, U.S. Patent No. 3.4.46,622, U.S. Patent No. 4,3
No. 33,999, No. 4,753.871, No. 4,45
No. 1,559, No. 4,427,767, No. 4,690
, No. 889, No. 4.254212, No. 4,296.1
No. 99, JP-A-61-42658, etc. are preferred. Colored couplers for correcting unnecessary absorption of color-forming dyes are described in Section 1-G of RD No. 17643, U.S. Patent No. 4. , 163.670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,138.2
No. 58 and British Patent No. 1.146368 are preferred. Also, U.S. Patent No. 4. .. No. 774,181, a coupler that corrects unnecessary absorption of a coloring dye by the fluorescent dye released during coupling, and U.S. Pat.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 777,120. As a coupler in which a coloring dye has an appropriate diffusivity, U.S. Patent No. 4.366,237 and British Patent No. 2.125
Preferred are those described in U.S. Pat. No. 820, No. 4,080,211,
It is described in 4,367,282, 4,409,320, 4,576,910, British Patent 2,102,173, etc. Couplers that release photographically useful residues upon cupping are also suitable for use in the present invention. DIR couplers that release development inhibitors are
Patents described in the above-mentioned RD17643, Items ① to F, JP-A-57-15194. No. 4, 57
-154234, 60-18424
.. No. 8, No. 63-37346, U.S. Patent No. 4.248
.. Those described in No. 962 and No. 4,782,01.2 are preferred. British Patent No. 2,09 discloses a coupler that releases a nucleating agent or a development accelerator imagewise during development.
No. 7,140, No. 2,131. .. No. 188, JP-A-59
-157638, 59-17084
.. The one described in No. 0 is preferred. In addition, competitive couplers described in U.S. Patent No. 4,130,427, etc., and U.S. Patent No. 4. , No. 283.472, 4
.. .. 338,393, multi-equivalent couplers described in 4,310,618, etc.; DIR redox compound release power blurrs described in JP-A-60-185950, JP-A-62-24252, etc.; DIR redox compound release power blurrs; ,DIR
Couvlar-Releasing Redonx Compound or DIR Redonox-Releasing Redonx Compound, European Patent No. 173,302A
A coupler that releases a dye that restores color after separation as described in
D Yang 1 1. 4 4 9, 24241, JP-A-61
Bleach accelerator releasing coupler described in No.-201247 etc.
Gand release force blur described in U.S. Pat. No. 4,553.477, etc.; leuco dye-releasing coupler described in JP-A-63-75747; U.S. Pat. No. 4,774,181
Couplers that emit fluorescent dyes as described in this issue can also be used. The coupler used in the present invention can be dispersed using a variety of known dispersion methods, for example. It can be introduced into photosensitive materials by oil-in-water dispersion, latex dispersion, solid dispersion, alkali dispersion, etc. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Patent No. 2.322.027 and others. The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.
54.1,230 etc. These couplers can also be impregnated into loadable latex polymers (e.g., U.S. Pat. No. 4,203.7J6) in the presence or absence of the above-mentioned high-boiling organic solvents.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid solution.
又、カブラー分散媒としてボリマーを用いる方法もあり
、特公昭48−30494号、同51一39835号、
米国特許第3.619、195号、***特許1,957
.467号に種々の記載がある.
好ましくは、国際公開番号W08 8/0 0 7 2
3号明細書の第12〜30頁に記載の単独重合体または
共重合体が用いられる.特にアクリルアミド系ボリマー
の使用が色像安定化等の上で好ましい。There is also a method of using a polymerer as a coupler dispersion medium, as described in Japanese Patent Publication No. 48-30494, Japanese Patent Publication No. 51-39835,
U.S. Patent No. 3,619,195, West German Patent No. 1,957
.. There are various descriptions in No. 467. Preferably, International Publication No. W08 8/0 0 7 2
The homopolymers or copolymers described on pages 12 to 30 of the specification of No. 3 are used. In particular, the use of acrylamide polymers is preferred from the viewpoint of color image stabilization.
本発明に使用できる適当な支持体は、例えば、前述のR
D.陽17643の28頁、および同嵐18716の6
47頁右欄から648頁左欄に記載されている.
(実施例)
以下に本発明の実施例を示すが本発明はこれらに限定さ
れるものではない。Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. Yang 17643, page 28, and Arashi 18716, 6
It is described from the right column on page 47 to the left column on page 648. (Example) Examples of the present invention are shown below, but the present invention is not limited thereto.
(実施例−口
下塗りを施した三酢酸セルロースフイルム支持体上に、
下記に示すような組成の各層を重層塗布し、多層カラー
感光材料である試料101を作製した.
(感光層組成)
各成分に対応する数字は、g/n{単位で表した塗布量
を示し、ハロゲン化銀については、恨換算の塗布量を示
す.ただし増感色素については、同−Hのハロゲン化m
1モルに対する塗布量をモル単位で示す.
(試料10l)
第1層(ハレーション防止層)
黒色コイイド銀 根 0,18ゼラチン
0.40第211(中間層)
乳削H
S艮 0 . 0 92.5−ジーt−ベン
タデシ
ルハイドロキノン
EX− 1
EX−3
EX− 1 2
tJ−1
IJ−2
U−3
HBS−1
HBS−2
ゼラチン
第3層(第1赤感乳剤層)
乳剤A
乳剤B
増感色素I
増悪色素a
増悪色素■
EX−2
EX−10
U−1
tJ−2
恨 O。 10
銀0.15
9xio−’
1。 8 X 1 0−’
3.IX10−’
0. 335
0.020
0.030
0.015
U−3
HBS−2
ゼラヂン
第4層(第2赤感乳剤N)
乳剤F
増感色素1
増惑色素■
増感色素■
EX− 2
EX−3
EX−10
U−1
tJ−2
tJ − 3
H B S − 2
ゼラチン
第51J(第3赤感乳剤層》
乳剤I
増感色素■
増感色素■
0.030
0.060
0. 9 0
銀 0.90
5. IXIOづ
1.4X10−’
2.3X].O−’
0. 400
0.050
0.0!5
0.080
0.040
0.080
0.060
1. 5 0
壇艮 l . 5 0
5.4XIO−’
1.4XIO−’
増悪色素■
E X−3
EX−4
EX−2
HBS−1
HBS−2
ゼラチン
第6層(中間層)
EX−5
+{ B S − 1
ゼラチン
第7N(第1緑感乳剤層)
乳剤A
乳剤B
増感色素■
増感色素■
増感色素■
EX−6
EX− 1
EX−7
?×1 0′■4
0.0!.0
0.083
0.097
0. 22
0,10
1. 50
0.080
0.020
0. 8 0
? 0. 15
i10.l5
3。 OXIO′■S
1. OXIO−″
3.8X10−’
0.260
0.040
0.065
EX−8
+4 B S − 1
H B S − 3
ゼラチン
第8層(第2緑感乳剤層)
乳剤C
増感色素V
増感色素■
増感色素■
EX−6
EX−8
EX−7
HBS− 1
HBS−3
ゼラチン
第9層(第3緑感乳剤層)
乳剤D
増感色素■
増感色素■
増感色素■
0.025
o.ioo
O.010
0, 66
?!0.4.5
2.lXlO−’
7.OXI.O′■S
2.6XIO−’
0.105
0.029
0. 029
0.160
0.008
0, 60
!I l。60
3.5X10−’
8.0XlO−’
3.OX1.0−’
EX−1.3 0.
01.SEX−11
0、 1 00EX−1
0. 025HBS−1
0.25HBS−2
0. 10ゼラチン
1.50第lO層(イエローフィルター
層)
黄色コロイド恨 銀 0.05EX−5
0.158BS−1.
0.08ゼラチン
0.50第11層(第1青感乳剤層)
乳剤A 銀 0.08乳剤B
l?IO.07乳剤E
t!0.07増感色素■
3.5XIQ−’EX−9
0。721EX−8 0
.042HBS−1 0.28
ゼラチン 1.10第12層(
第2青感乳剤層)
乳剤F
増悪色素■
EX−9
EX−10
HBS−1
ゼラチン
第13層(第3青感乳剤層)
乳剤G
増感色素■
EX−9
HBS−1
ゼラチン
第14層(第1保護層)
乳剤H
U−4
U−5
HBS−1
ゼラチン
第15層(第2保護層)
銀 0. 45
2.lX10−’
0.154
0. 00?
0. 0 5
0. 7 8
銀 0.77
2. 2X10−’
0. 20
0. 07
0, 69
ボリメチルアクリレート粒
子(直径約1.5μm)
S−1
ゼラチン
各層には上記の成分の他に、
−1や界面活性剤を添加した.
0. 5 4
0, 20
1. 20
ゼラチン硬化剤H
EX−1
EX−4
ON
EX−6
EX−3
EX
EX
EX
U−1
CI
CI
(t)c4Ht
EX−10
CI+3
U−2
0H
(t)C,H.
tJ−3
0H
(t)C4H*
U−4
x:y−10
=30
(wt%)
Uv
H B S − 1
トリクレジルホスフエート
H B S − 2
ジーn−プチルフタレート
増感色素r
増進色素U
増感色素■
S−1
l1
■
CI!−Cll Sor−CHg−CONH CH
z増感色素m
増感色素■
以上の様に作成した試料を35m/m巾に裁断し、露光
量5CMSでウェンジ露光したのち、以下に記載の処理
工程及び処理液にて、漂白定着液の累fi補充量がその
母液タンク容量の2倍になるまで、連続処理(ランニン
グ処理)を行った。(Example - On a base coated cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below. (Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/n{units, and for silver halide, the coating amount is expressed in terms of weight. However, for sensitizing dyes, the halogenated m of -H
The coating amount per mole is shown in moles. (Sample 10l) 1st layer (antihalation layer) Black coid silver root 0.18 gelatin
0.40 No. 211 (middle layer) Milking H
S 艮 0. 0 92.5-d-t-bentadecylhydroquinone EX- 1 EX-3 EX- 1 2 tJ-1 IJ-2 U-3 HBS-1 HBS-2 Gelatin third layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye I Enhanced dye a Enhanced dye ■ EX-2 EX-10 U-1 tJ-2 O. 10 Silver 0.15 9xio-' 1. 8 X 1 0-' 3. IX10-' 0. 335 0.020 0.030 0.015 U-3 HBS-2 4th layer of geladine (second red-sensitive emulsion N) Emulsion F Sensitizing dye 1 Sensitizing dye ■ Sensitizing dye ■ EX- 2 EX-3 EX- 10 U-1 tJ-2 tJ-3 HBS-2 Gelatin No. 51J (Third red-sensitive emulsion layer) Emulsion I Sensitizing dye■ Sensitizing dye■ 0.030 0.060 0.9 0 Silver 0.90 5. 5.4XIO-'1.4XIO-' Exacerbating dye ■ EX-3 EX-4 EX-2 HBS-1 HBS-2 Gelatin 6th layer (intermediate layer) EX-5 +{ B S - 1 Gelatin 7th N ( 1st green emulsion layer) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX- 1 EX-7 ?x1 0'■4 0.0!.0 0.083 0. 097 0.22 0.10 1.50 0.080 0.020 0.8 0 ? 0.15 i10.l5 3. OXIO'■S 1. OXIO-''3.8X10-' 0.260 0.040 0 .065 EX-8 +4 B S - 1 H B S - 3 Gelatin 8th layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 EX-7 HBS- 1 HBS-3 Gelatin 9th layer (third green emulsion layer) Emulsion D Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ 0.025 o.ioo O.010 0, 66 ?! 0.4. 5 2.lXlO-'7.OXI.O'■S2.6XIO-' 0.105 0.029 0.029 0.160 0.008 0, 60 !I l.60 3.5X10-' 8.0XlO -'3.OX1.0-' EX-1.3 0.
01. SEX-11
0, 1 00EX-1
0. 025HBS-1
0.25HBS-2
0. 10 gelatin
1.50th 1O layer (yellow filter layer) Yellow colloid silver 0.05EX-5
0.158BS-1.
0.08 gelatin
0.50 11th layer (first blue-sensitive emulsion layer) Emulsion A Silver 0.08 Emulsion B
l? IO. 07 Emulsion E
T! 0.07 sensitizing dye■
3.5XIQ-'EX-9
0.721EX-8 0
.. 042HBS-1 0.28
Gelatin 1.10 12th layer (
Emulsion F Enhanced dye ■ EX-9 EX-10 HBS-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion G Sensitizing dye ■ EX-9 HBS-1 Gelatin 14th layer ( 1st protective layer) Emulsion HU-4 U-5 HBS-1 Gelatin 15th layer (2nd protective layer) Silver 0. 45 2. lX10-' 0.154 0. 00? 0. 0 5 0. 7 8 Silver 0.77 2. 2X10-' 0. 20 0. 07 0, 69 Polymethyl acrylate particles (approximately 1.5 μm in diameter) S-1 In addition to the above ingredients, -1 and a surfactant were added to each gelatin layer. 0. 5 4 0, 20 1. 20 Gelatin hardening agent H EX-1 EX-4 ON EX-6 EX-3 EX EX EX U-1 CI CI (t)c4Ht EX-10 CI+3 U-2 0H (t)C,H. tJ-3 0H (t)C4H* U-4 x:y-10 =30 (wt%) Uv HBS-1 Tricresyl phosphate HBS-2 Jean-n-butyl phthalate sensitizing dye r Enhancement dye U Sensitizing dye ■ S-1 l1 ■ CI! -Cll Sor-CHg-CONH CH
z Sensitizing dye M Sensitizing dye Continuous processing (running processing) was performed until the cumulative fi replenishment amount became twice the capacity of the mother liquor tank.
表2 処理方法
工 程 処理時間 処理温度 補充量 ’lンク容量
発色現像 3分15秒 38℃ 45Id51漂白定
着(2)2分OO秒 38℃ 50d 31
方式.
水洗(2) 20秒 35℃ 3〇一
安 定 25秒 35℃ 20lR
1乾 燥 50秒 65℃補充量は3
5n巾1m長さ当たり
次に、処理液の組成を記す.
(発色現像液)
(漂白定着液)母液、補充液共通
母液(g)補充液(g)
ジエチレントリアミン
五酢酸
1−ヒド口キシエチリ
デンー1.1−ジホ
スホン酸
亜硫酸ナトリウム
炭酸カリウム
臭化カリウム
ヨウ化カリウム
ヒドロキシルアミン硫
酸塩
4−(N一エチルーN
一β−ヒドロキシエ
チルアミノ)−2=
メチルアニリン硫酸
塩
水を加えて
p H
2.0
3.0
4.0
30.0
1.4
1.5vt
2.4
4.5
1.Oa
10.05
2.2
2.8
5.5
1,OI
10.10
単位(g)
エチレンジアミン四酢酸第二
鉄アンモニウムニ水塩
エチレンジアミン四酢酸ニナ
トリウム塩
亜硫酸アンモニウム
千オ硫酸アンモニウム水溶液
(70%)
漂白促進剤(表2)
水を加えて
pH
(安定液)母液、補充液共通
90. 0
5.0
Q d
〇一
〇j!
ホルマリン(37%)
単位(g)
2,〇一
ポリオキシエチレンーp−モ
ノノニルフェニルエーテル
(平均重合度10)
エチレンジアミン四酢酸二ナ
トリウム塩
0. 30
0. 05
水を加えて 1.Olp}{
5.0〜8.0(水洗水)母
液、補χ液共通
水道水をH型強酸性カチオン交換樹脂(ロームアンドハ
ース社製アンバーラントIR−120B)と、OH型ア
ニオン交換樹脂(同アンバーライトIR−400)を充
填した混床式カラムに通水してカルシウム及びマグネシ
ウムイオン濃度を3■/I以下に処理し、続いて二塩化
イソシアヌール酸ナトリウム20■/j!と硫酸ナトリ
ウム0.15g/1を添加した.この液のpHは6.5
〜7.5の範囲にある.
漂白定着液の漂白促進剤を表3のように変化させてラン
ニング処理を行った.それぞれの漂白促進剤の脱銀性を
ランニング終了時の試料の最高濃度部(D■ax部)及
び未露光部(Dmin部)の残存銀量で比較した.最高
濃度部と未露光部の残存銀量が少ないほどそれぞれ漂白
性、定着性がよいことを示す.残存銀量は、螢光X線分
析により求めた.結果を表3に示した.実施例中の本発
明の化合物は本文中の具体例の番号で表わした.
尚、実施例にて使用した比較化合物の構造は、以下の通
りである.
漂白促進剤
(英国特許1,138.842号記載の化合物)(特開
昭61−20945号記載の化合物)表3
表3から明らかなように本発明の漂白促進剤は、ランニ
ング処理時においても漂白促進能が著しく向上した上、
定着を遅らせることなく良好な結果が得られた.
実施例−2
実施例−1の処理方法を以下のように変更して漂白定t
f液の累積補充量がその母液タンク容量の表5
(C)
(特開昭61−20945号記載の化合物)2倍になる
までランニング処理を行った.実施例−1と同様の方法
で残存銀量を比較した.結果を表5に示した.
表4 処理方法
工 程 処理時間 処理温度 補充量発色現像 3分
15秒 38℃
漂白定着 4分00秒 38℃ 40*145一
タンク容量
5e
6l
水洗f21 20秒 35℃
安 定 25秒 35℃
乾 燥 50秒 65℃
補充量は351巾1m長さ当たり
30R!
20期l
2e
2P
(D)
(特開昭61−20945号記載の化合物)結果から明
らかなように本発明の漂白促進剤は、漂白定着工程を一
浴とし、さらに漂白定着液の補充量を減少して、液疲労
がさらに進行した場合においても漂白促進効果の低下が
少なく、優れた効果を示す.
実施例−3
実施例−1で作成した試料101を下記処理方法及び処
理液にて実施例−1と同様にランニング処理し、最高濃
度部(D+wax)と未露光部(llIlin)の残存
限量で漂白促進削の脱根性を比較した.結果を表7に示
した.
表6 処理方法
工 程 処理時間 処理温度 補充量 +シク容量発
色現像 3分15秒 38℃ 45m 10N
漂 白 2分00秒 38℃ 20d
41漂白定着 3分15秒 38℃ 3〇一水洗(
2)1分00秒 35℃
安 定 40秒 38℃
乾 燥 1分15秒 55℃補充量は351
一巾1m長さ当たり
次に、処理液の組成を示す.
(発色現像液)
実施例1と同じ
(漂白液)母液、補充液共通
3〇一
2〇一
8l
4l
4l
単位
(g)
エチレンジアミン四酢酸第二
鉄アンモニウムニ水塩
エチレンジアミン四酢酸二ナ
トリウム塩
臭化アンモニウム
硝酸アンモニウム
アンモニア水(27%)
漂白促進剤(表7)
120.0
l O. 0
1.00.0
1 0, 0
150.Oml
3 X 1 0 −”gol
水を加えて
p H
(漂白定着液)母液、補充液共通
エチレンジアミン四酢酸第二
鉄アンモニウムニ水塩
エチレンジアミン四酢酸二ナ
トリウム塩
亜硫酸ナトリウム
チオ硫酸アンモニウム水溶液
アンモニア水(27%)
pH
(水洗水)
実施例1と同じ
(安定液)
実施例lと同じ
1.01
6.3
単位
<g)
5.
12.
24 0,
6,
Q ml
Q d
表7Table 2 Processing Method Step Processing Time Processing Temperature Replenishment Amount Ink Capacity Color Development 3 minutes 15 seconds 38℃ 45Id51 Bleach-Fixing (2) 2 minutesOO seconds 38℃ 50d 31
method. Water washing (2) 20 seconds 35℃ 301 Stable 25 seconds 35℃ 20lR
1 Drying 50 seconds 65℃ Replenishment amount is 3
5n width and 1m length Next, the composition of the treatment liquid is described. (Color developer) (Bleach-fix solution) Mother liquor, replenisher Common mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-hydrooxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine Sulfate 4-(N-ethyl-N-β-hydroxyethylamino)-2= Add methylaniline sulfate water to pH 2.0 3.0 4.0 30.0 1.4 1.5vt 2.4 4 .5 1. Oa 10.05 2.2 2.8 5.5 1, OI 10.10 Unit (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium sulfite Ammonium periosulfate aqueous solution (70%) Bleach Accelerator (Table 2) Add water to pH (stabilizing solution) common to mother liquor and replenisher solution: 90. 0 5.0 Q d 〇1〇j! Formalin (37%) Unit (g) 2,01 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0. 30 0. 05 Add water 1. Olp}{
5.0 to 8.0 (Washing water) Mother liquor and χ compensator Common tap water was mixed with H-type strongly acidic cation exchange resin (Amberlant IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). Water was passed through a mixed bed column packed with IR-400) to reduce the concentration of calcium and magnesium ions to 3/I or less, followed by sodium dichloride isocyanurate 20/J! and 0.15 g/1 sodium sulfate were added. The pH of this solution is 6.5
It is in the range of ~7.5. Running treatments were performed by changing the bleach accelerator in the bleach-fix solution as shown in Table 3. The desilvering properties of each bleach accelerator were compared based on the amount of silver remaining in the highest density area (Dax area) and unexposed area (Dmin area) of the sample at the end of the run. The smaller the amount of residual silver in the highest density area and the unexposed area, the better the bleaching and fixing properties, respectively. The amount of residual silver was determined by fluorescent X-ray analysis. The results are shown in Table 3. Compounds of the present invention in Examples are indicated by the numbers of specific examples in the text. The structures of the comparative compounds used in the examples are as follows. Bleach accelerator (compound described in British Patent No. 1,138.842) (compound described in JP-A-61-20945) Table 3 As is clear from Table 3, the bleach accelerator of the present invention is effective even during running treatment. In addition to significantly improving bleaching promotion ability,
Good results were obtained without delaying fixation. Example-2 The treatment method of Example-1 was changed as follows to achieve bleaching
Running treatment was carried out until the cumulative replenishment amount of the f solution was twice the mother liquor tank capacity. The amount of residual silver was compared using the same method as in Example-1. The results are shown in Table 5. Table 4 Processing method Step Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38°C Bleach-fixing 4 minutes 00 seconds 38°C 40*145 - Tank capacity 5e 6l Water washing F21 20 seconds 35°C Stability 25 seconds 35°C Drying 50 seconds 65℃ Refill amount is 30R per 1m length of 351 width! 20 period l 2e 2P (D) (Compound described in JP-A No. 61-20945) As is clear from the results, the bleach accelerator of the present invention uses a single bath in the bleach-fixing process and further increases the amount of replenishment of the bleach-fixing solution. Even when the bleaching effect decreases and liquid fatigue progresses further, the bleaching accelerating effect does not decrease much and exhibits an excellent effect. Example-3 Sample 101 prepared in Example-1 was subjected to running treatment in the same manner as in Example-1 using the following treatment method and processing solution, and the remaining amount of the highest density part (D+wax) and unexposed part (llIlin) was We compared the derooting properties of bleach-accelerated cutting. The results are shown in Table 7. Table 6 Processing method Step Processing time Processing temperature Replenishment amount + Shikaku capacity color development 3 minutes 15 seconds 38℃ 45m 10N
Bleach 2 minutes 00 seconds 38℃ 20d
41 Bleach fixing 3 minutes 15 seconds 38℃ 301 Washing with water (
2) 1 minute 00 seconds 35℃ Stable 40 seconds 38℃ Dry 1 minute 15 seconds 55℃ Replenishment amount is 351
The composition of the treatment liquid per width and length of 1m is shown below. (Color developer) Same as Example 1 (Bleach solution) Mother solution and replenisher common 3012018l 4l 4l Unit (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt bromide Ammonium nitrate Ammonium aqueous ammonia (27%) Bleach accelerator (Table 7) 120.0 l O. 0 1.00.0 1 0, 0 150. Oml 3 ) pH (Washing water) Same as Example 1 (Stable liquid) Same as Example 1 1.01 6.3 Unit <g) 5. 12. 24 0, 6, Q ml Q d Table 7
Claims (1)
を有する処理液で処理する方法において、該漂白能を有
する処理液が下記一般式〔 I 〕で表わされる化合物の
少なくとも一種を含有することを特徴とするハロゲン化
銀カラー写真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、Lは置換されてもよいアルキレン基を表わし、
Xは、アルキル置換された四級アンモニオ基、あるいは
窒素原子を少なくとも一つ含む不飽和のヘテロ環基を表
わし、Mは水素原子、アルカリ金属又は、アンモニウム
基を表わし、Aは対アニオンを表わし、nは、Xが四級
化されている窒素原子を含むとき1で四級化されている
窒素原子を含まないとき0である。)[Scope of Claims] In a method of processing an imagewise exposed silver halide color photographic light-sensitive material with a processing liquid having bleaching ability, the processing liquid having bleaching ability contains at least one of the compounds represented by the following general formula [I]. A method for processing a color photographic material containing one type of silver halide. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, L represents an optionally substituted alkylene group,
X represents an alkyl-substituted quaternary ammonio group or an unsaturated heterocyclic group containing at least one nitrogen atom, M represents a hydrogen atom, an alkali metal or an ammonium group, A represents a counter anion, n is 1 when X contains a quaternized nitrogen atom, and 0 when X does not contain a quaternized nitrogen atom. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5344889A JPH02232654A (en) | 1989-03-06 | 1989-03-06 | Processing method for silver halide color photographic sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5344889A JPH02232654A (en) | 1989-03-06 | 1989-03-06 | Processing method for silver halide color photographic sensitive material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02232654A true JPH02232654A (en) | 1990-09-14 |
Family
ID=12943138
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5344889A Pending JPH02232654A (en) | 1989-03-06 | 1989-03-06 | Processing method for silver halide color photographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02232654A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5439132A (en) * | 1977-06-01 | 1979-03-26 | Coulter Systems Corp | Make up attachment apparatus of make up camera and making up method |
JPS6120945A (en) * | 1984-07-10 | 1986-01-29 | Fuji Photo Film Co Ltd | Method for processing color photograph |
JPS63106656A (en) * | 1986-06-12 | 1988-05-11 | Fuji Photo Film Co Ltd | Method for forming direct positive image |
-
1989
- 1989-03-06 JP JP5344889A patent/JPH02232654A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5439132A (en) * | 1977-06-01 | 1979-03-26 | Coulter Systems Corp | Make up attachment apparatus of make up camera and making up method |
JPS6120945A (en) * | 1984-07-10 | 1986-01-29 | Fuji Photo Film Co Ltd | Method for processing color photograph |
JPS63106656A (en) * | 1986-06-12 | 1988-05-11 | Fuji Photo Film Co Ltd | Method for forming direct positive image |
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