JPS6392952A - Bleach-fix bath having excellent quick processability - Google Patents
Bleach-fix bath having excellent quick processabilityInfo
- Publication number
- JPS6392952A JPS6392952A JP23859886A JP23859886A JPS6392952A JP S6392952 A JPS6392952 A JP S6392952A JP 23859886 A JP23859886 A JP 23859886A JP 23859886 A JP23859886 A JP 23859886A JP S6392952 A JPS6392952 A JP S6392952A
- Authority
- JP
- Japan
- Prior art keywords
- bleach
- present
- solution
- salt
- fix solution
- 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
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 silver halide Chemical class 0.000 claims description 34
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000004061 bleaching Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 159000000000 sodium salts Chemical class 0.000 abstract description 2
- 159000000001 potassium salts Chemical class 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 15
- 239000007844 bleaching agent Substances 0.000 description 11
- 238000011161 development Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229940045105 silver iodide Drugs 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910004504 HfF4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960005102 foscarnet Drugs 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 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
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- VTAIGULUTDIFOG-UHFFFAOYSA-J thorium(4+) tetrathiocyanate Chemical compound [S-]C#N.[Th+4].[S-]C#N.[S-]C#N.[S-]C#N VTAIGULUTDIFOG-UHFFFAOYSA-J 0.000 description 1
- MDMUQRJQFHEVFG-UHFFFAOYSA-J thorium(iv) iodide Chemical compound [I-].[I-].[I-].[I-].[Th+4] MDMUQRJQFHEVFG-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- 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］
本発明は漂白定着液に関し、詳しくは固形用感光材Ｈに
適用して迅速処理化を達成できる漂白定着液に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a bleach-fix solution, and more particularly to a bleach-fix solution that can be applied to solid photosensitive materials H to achieve rapid processing.
［発明の背景］
現在、高感度高沃臭化銀乳剤を用いた囮彩用感光材料の
脱銀処理は漂白工程と定着工程が別々に行われている。[Background of the Invention] Currently, in the desilvering treatment of light-sensitive materials for decoy coloring using high-sensitivity silver iodobromide emulsions, a bleaching step and a fixing step are performed separately.
本発明者等は上記躍影用感光材料の脱銀処理の簡略化お
よび迅速化を図るため、漂白と定着を一浴で処理Ｊる漂
白定着処理化を検討してきた。In order to simplify and speed up the desilvering process of the photographic photographic material, the present inventors have investigated a bleach-fixing process in which bleaching and fixing are performed in one bath.
その検討の中で、上記漂白定着液としては、液保存性お
よび１りられる色素画像の復色不良の梵生等の１Ｍ点か
ら従来から０１−１が高い領域で使用することが有利で
あるとされ、その高１）ＨｆＦ４域で優れた脱銀能力を
有する漂白剤を探索した結果、本発明者等は種々のアミ
ノポリカルボン酸鉄錯体の中でもジエヂレントリアミン
五酢酸第２鉄鉗塩（ＤＴＰＡ −Ｆｃ鉗塩）が脱銀速度
、得られる色ＭＩｉＴｊ像の復色性および漂白定着液の
経時保存性を満足できるものとして提案してきた。（特
開昭６０−１３４２３８号、同 （３０−１３０７３８
号、同 ６Ｏ−１３（３７４４号等）
ｈ ｆ’！ｉ！ Ｄ Ｔ ＰΔ−ＦｅｇＭ塩は、ｐＨが
高い領域、具体的には約ｐ［１７〜９という範囲で上記
の如くの特性を満足できるものであるが、かかるｐＨ領
域ではアンモニアガスが発生し易く、狭い室内で現像処
理を行う際には作業環境上好ましく、ない点を有してい
た。さらに、感光材料を長期にわたり処理した際の経時
において、漂白定着液中に第１鉄イオンのＮ積に起因す
ると考えられる脱銀能力の低下と復色不良が発生するこ
とがわかってきた。In this study, it was found that it is advantageous to use the above bleach-fix solution in the area where 01-1 is conventionally high due to the 1M point, such as 1M point, which has poor solution storage stability and poor color recovery of dye images. As a result of searching for a bleaching agent with excellent desilvering ability in the high 1) HfF4 range, the present inventors found that among various aminopolycarboxylic acid iron complexes, ferric triamine salt of diadienetriaminepentaacetate was used. (DTPA-Fc salt) has been proposed as one that satisfies the desilvering rate, the recoloring property of the resulting color MIiTj image, and the storage stability of the bleach-fix solution over time. (Unexamined Japanese Patent Publication No. 60-134238, same (30-130738)
No. 6O-13 (No. 3744, etc.) h f'! i! D T PΔ-FegM salt can satisfy the above characteristics in a high pH region, specifically in the range of about p[17 to 9, but in such a pH region, ammonia gas is likely to be generated. This method is unfavorable in terms of working environment when developing in a narrow room. Furthermore, it has been found that when photographic materials are processed over a long period of time, desilvering ability decreases and color restoration failure occurs, which is thought to be caused by the N product of ferrous ions in the bleach-fix solution.
上記の欠点について詳細に検討を加えた結果、第１鉄イ
オンの蓄積は、漂白定着液のｐＨに大きく依存し、さら
に一定の０１１以上では処理した際の経時において、通
常漂白剤として用いられている゛アミノポリカルボン酸
鉄錯塩に共通して起こる問題点であることがわかった。As a result of a detailed study on the above drawbacks, we found that the accumulation of ferrous ions is highly dependent on the pH of the bleach-fix solution, and that at a certain pH level of 011 or higher, over a certain period of time during processing, the accumulation of ferrous ions is not normally used as a bleaching agent. It was found that this is a problem that commonly occurs with aminopolycarboxylic acid iron complex salts.
本発明者等は、さらに検討を続けた結果、特定の低いＩ
ｌＨ賊でかつ特定のアミノポリカルボン酸鉄錯塩を用い
ることにより、上記第１鉄イＡンの蓄積に起因すると考
えられる脱銀能力の低下と復色不良が同時に解決され、
かつアンモニアガスの発生も解消されることを見い出し
た。As a result of further investigation, the present inventors discovered that a specific low I
By using a specific aminopolycarboxylic acid iron complex salt that is 1H-rich, the decrease in desilvering ability and poor color recovery, which are thought to be caused by the accumulation of ferrous ion, can be solved at the same time.
It has also been found that the generation of ammonia gas can also be eliminated.
また、該漂白定着液の実用化に際して、特定の保恒剤を
特定のｍ以上用いることにより、上記問題点の改良効果
に悪影響を与えることなく、連続処理時における漂白定
着液の経時保存性の劣化を良好に防止できることを見い
出し本発明を為１に到ったものである。In addition, when putting the bleach-fix solution into practical use, by using a specific preservative with a specific m or more, it is possible to improve the storage stability of the bleach-fix solution over time during continuous processing without adversely affecting the improvement effect of the above problems. We have discovered that deterioration can be effectively prevented, and have thus arrived at the present invention.
［発明の目的］
従って、本発明の第一の目的は躍彰用写真感光材料に適
用して前記欠点を解決し、迅速処理化を可能にした漂白
定着液を提供することにある。本発明の第二の目的は、
アンモニアガスの発生がなく、作業環境上好ましい漂白
定着液の提供にある。[Object of the Invention] Therefore, the first object of the present invention is to provide a bleach-fixing solution which can be applied to photographic materials for high performance and which solves the above-mentioned drawbacks and enables rapid processing. The second object of the present invention is to
To provide a bleach-fixing solution that does not generate ammonia gas and is favorable in terms of working environment.
［発明の構成］
本発明の上記目的は撮影用ハロゲン化銀写真感光材料を
漂白定着づる処理液にＪ３いて、咳液のｐＨが３．０〜
６．８の範囲にあり、かつ下記一般式［Ｉ］で示される
化合物を配位子とする第２鉄鉗塩を含有し、さらに亜硫
酸塩を０．０５モル／１以上含有する漂白定着液により
達成された。[Structure of the Invention] The above-mentioned object of the present invention is to provide a processing solution for bleaching and fixing a silver halide photographic light-sensitive material for photographing, so that the pH of the cough fluid is 3.0 to 3.0.
6.8, a bleach-fixing solution containing a ferric salt having a compound represented by the following general formula [I] as a ligand, and further containing 0.05 mol/1 or more of a sulfite. achieved by.
−・般式［１１
（式中、Ｒ＋ は水素原子または低級アルキル基を表わ
し、ｎｌ、ｎ２および「１３はそれぞれＯ〜３の整数を
表わず。但し、ｎｌ 、’２およびｎ３の合計は３また
は４の整数であり、
１で１
数の総（１１は３以上である。）
［発明の具体的構成］
本発明の漂白定着液には、一般式［Ｉ］で示される化合
物を配位子とする第２鉄銘塩が用いられる。- General formula [11 (In the formula, R+ represents a hydrogen atom or a lower alkyl group, and nl, n2 and "13 each do not represent an integer from O to 3. However, the sum of nl, '2 and n3 is is an integer of 3 or 4, and 1 is the sum of 1 (11 is 3 or more) [Specific constitution of the invention] The bleach-fixing solution of the present invention contains a compound represented by the general formula [I]. The ferric salt known as Ishi is used.
一般式［Ｉ］において、１（１としては好ましくは水素
原子である。また、
【＜
数の総和の最も好ましくは３である。In the general formula [I], 1 (1 is preferably a hydrogen atom. [< The sum of the numbers is most preferably 3.
以下、一般式［Ｉ］で示される化合物の好ましい具体例
を示ず。Preferred specific examples of the compound represented by the general formula [I] are not shown below.
以舌°戸゛白
例示化合１カ
上記一般式［ｉ］で示される化合物を配位子とりる第２
鉄錯塩（以下、本発明の第２鉄錯塩という）は、フリー
の酸（水素塩）としても用いられるが、対温としてナト
リウム塩、カリウム塩、リチウム塩等のアルカリ金属塩
、もしくはアンモニウム塩、または水溶性アミン塩、例
えばｌ・リエタノールアミン塩等としても用いることが
できる。The first example compound is a second compound having the compound represented by the above general formula [i] as a ligand.
The iron complex salt (hereinafter referred to as the ferric complex salt of the present invention) is also used as a free acid (hydrogen salt), but as a counter temperature, it can be used as an alkali metal salt such as sodium salt, potassium salt, lithium salt, or ammonium salt. Alternatively, it can also be used as a water-soluble amine salt, such as l-liethanolamine salt.
好ましくはカリウム塩、ナトリウム塩及びアンモニウム
塩が使われる。これらの本発明の第２鉄錯塩は少なくと
も１種用いればよいが、２種以上を併用することもでき
る。さらに本発明外の第２鉄釦塩と併用とすることもで
きる。Preferably potassium, sodium and ammonium salts are used. At least one type of these ferric complex salts of the present invention may be used, but two or more types can also be used in combination. Furthermore, it can also be used in combination with ferric button salts other than those of the present invention.
上記例示の本発明の第２鉄釦塩の中では好ましくは、例
示化合物（Ｉ−１）、（Ｉ−２）および（！−３）を配
位子として用いる第２鉄１１ Ｊ！！である。さらに、
例示化合物Ｎ０６（Ｉ−１）、（Ｉ−２）および（Ｉ−
３）の中でも溶解性の点から（Ｉ−１）、（Ｉ−２）を
用いることが特に好ましく、本発明の目的の効果客種々
の点を鑑みると、（Ｉ−１）を用いることが本発明にお
いて最も好ましい。Among the above-exemplified ferric button salts of the present invention, ferric 11 J! using exemplified compounds (I-1), (I-2) and (!-3) as ligands is preferable. ! It is. moreover,
Exemplary compounds N06 (I-1), (I-2) and (I-
Among 3), it is particularly preferable to use (I-1) and (I-2) from the viewpoint of solubility, and from the viewpoint of various effects aimed at the present invention, it is preferable to use (I-1). Most preferred in the present invention.
本発明の第２鉄ｆｆｌ塩は、本発明の漂白定着液中本発
明の効果を１７６、ｍであればいかなる川でも用いられ
るが、第２鉄紹ｉ！！漢度が高くなりづざると、漂白定
着液の保存性が劣化し、一方、第２鉄！ｉ塩の′ａ度が
低すぎると１１１２銀性能ど復色性能が劣化する。従っ
て通常０．０２〜１．３０モル／ｌの範囲で用いること
が好ましく、０，１０〜１，２０モル／ｌの範囲で用い
ることがにり好ましい。特に０．２０〜０．８０モル／
２の範囲で用いると本発明の効果を良好に奏し好ましい
。The ferric ffl salt of the present invention can be used in any river as long as the effect of the present invention is 176, m in the bleach-fix solution of the present invention; ! If the iron content becomes too high, the shelf life of the bleach-fix solution will deteriorate, and on the other hand, ferric iron! If the degree of 'a' of the i salt is too low, the color restoration performance such as the performance of 1112 silver will deteriorate. Therefore, it is usually preferable to use the amount in the range of 0.02 to 1.30 mol/l, and more preferably in the range of 0.10 to 1,20 mol/l. Especially 0.20 to 0.80 mol/
When used in the range of 2, the effects of the present invention can be favorably exhibited and it is preferable.
本発明の漂白定着液は、ｐ＋−＋ ３．０未満では亜硫
酸ガス発生のため、またｐＨＧ、８．にり高ければ本発
明の効果が不充分のため、そのｐＨ範囲はｐＨ３，０〜
６．８であり、このＤ）ｌｆｆＩ域であればいかなるｐ
Ｈでも用いることができるが脱銀性と復色性の他に、各
種鉄塩の低温時の溶解性、亜硫酸イオンより発生する亜
硫酸ガス臭気を考えるとＩ）Ｌ１４．０〜６．１で用い
ることが好ましく、特にｐ ）−１５、θ〜６．５で用
いることが最も好ましい。The bleach-fix solution of the present invention has a p+-+ of less than 3.0 because of sulfur dioxide gas generation, and a pH of less than 8.0. If the pH is too high, the effect of the present invention is insufficient, so the pH range is from pH 3.0 to
6.8, and any p in this D)lffI area
H can also be used, but considering the desilvering and recoloring properties, the solubility of various iron salts at low temperatures, and the odor of sulfur dioxide gas generated from sulfite ions, it is used in I) L14.0 to 6.1. It is particularly preferable to use p ) -15, θ ~ 6.5.
本発明では保存安定性を向上させるため漂白定着液中の
亜１ｔ［イオンを０．０５モル以上存在さける。従来漂
白定着液では、漂白定着液中の亜硫酸イオンは実用上問
題のない保存安定性を右づる限り、できるだ番）（Ｉｔ
＜抑えるのが良いとされてぎた。In the present invention, in order to improve storage stability, the presence of 0.05 mol or more of nitrous ions in the bleach-fix solution is avoided. In conventional bleach-fix solutions, the sulfite ions in the bleach-fix solutions are as high as possible as long as storage stability is maintained without any practical problems.
<It was thought that it was better to suppress it.
りなわら亜硫酸イオンの濃度を高くザると、アミノポリ
カルボン酸鉄（ｌｉｔ）錯体と亜硫酸イオンとの反応が
急速に進行して鉄（ｎ）錯体が生成しやすくなるため、
脱銀、復色能力が低下してしまう。If the concentration of sulfite ions is increased, the reaction between the aminopolycarboxylic acid iron (lit) complex and sulfite ions will proceed rapidly, making it easier to generate iron (n) complexes.
Desilvering and color restoring ability will decrease.
しかしながら本発明の漂白定着液では、液中の亜硫酸イ
オン濃度を増加さＵても！［、復色能力の低下が極めて
少ないことを見い出し本発明に至ったものである。However, in the bleach-fix solution of the present invention, even if the concentration of sulfite ions in the solution is increased! [The inventors have discovered that the deterioration in color restoration ability is extremely small, leading to the present invention.
本発明に於いて亜硫酸イオンを漂白定着液に供給するた
めに、種々の亜硫酸塩が使用されるが、これらの亜硫Ｍ
ｌとしては、亜５ＡＭアンモニｆクム、亜硫酸ナトリウ
ム、亜ＵＡ耐カリウム、亜硫酸水素ナトリウム、亜硫酸
水素カリウム、メタｍ亜ｔａ Ｆａナトリウム等があげ
られる。In the present invention, various sulfites are used to supply sulfite ions to the bleach-fix solution.
I include 5AM ammonium cum, sodium sulfite, UA resistant potassium, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium meta ta Fa, and the like.
本発明では亜硫酸イオンを漂白定着液１２当り０．０５
モル以上含有Ｊれば良いが、好ましくは０．０５ Ｅル
以上２．〇七ル以下であり、より好ましくは０．０７モ
ル以上１．３モル以下、最も好ましくは０．０９ ｒニ
ル以上０．９モル以下で使用される。In the present invention, sulfite ions are added at 0.05% per 12% of the bleach-fix solution.
It is sufficient if the content is 0.05 mol or more, but preferably 0.05 mol or more2. The amount is preferably 0.07 mol or more and 1.3 mol or less, most preferably 0.09 mol or more and 0.9 mol or less.
本発明の漂白定着液に含ませるハロゲン化銀定着剤とし
ては通常の定着処理に用いられるようなハロゲン化銀と
反応して水溶性の錯塩を形成する化合物、例えばチオ硫
酸カリウム、チオ硫酸ナトリウム、ヂオ硫酸アンモニウ
ムの如きチオ硫酸塩、チオシアン酸カリウム、チオシア
ン酸すトリウム、ヂオシアン酸アンモニウムの如ぎチオ
シアン酸塩、ヂオ尿素、チオエーテル、高濃度の臭化物
、ヨウ化物等がその代表的なものである。これらの定着
剤は５Ｇ／Ｆ！以上、好ましくは５０ｇ／４以上、Ｊ：
り好ましくは７０ａ／Ｉｔ以」ユ溶解できる範囲の聞で
使用できる。The silver halide fixing agent to be included in the bleach-fixing solution of the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium diosulfate, potassium thiocyanate, thorium thiocyanate, thiocyanates such as ammonium diocyanate, diourea, thioethers, and high concentrations of bromide and iodide. . These fixatives are 5G/F! or more, preferably 50g/4 or more, J:
It can be used within a range where it can be dissolved, preferably 70a/It or more.
本発明の漂白定着液は、種々の添加剤を含むことができ
る。添加剤としては、特にアルカリハライ°ドまたはア
ンモニウムハライド、例えば臭化カリ１クム、臭化ナト
リウム、塩化ナトリウム、臭化アンモニウム、沃化カリ
ウム、沃化すトリウム、沃化アンモニウム等を含有させ
ることが望ましい。The bleach-fix solution of the present invention can contain various additives. As additives, it is particularly desirable to contain alkali halides or ammonium halides, such as 1cum potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, thorium iodide, ammonium iodide, etc. .
本発明の漂白定着液にはｔｍｑ、硼砂、水酸化すトリウ
ム、水酸化カリ１クム、炭酸ナトリウム、炭酸カリウム
、■炭酸す１〜リウム、ｍ炭ｆｆＪ ７Ｊリウム、酢酸
、酢酸す１−リウム、水酸化アンモニウム等の各種の塩
からなるｐ］−１緩衝剤を単独であるいは２種以上組合
せて含有せしめることができる。さらにまた、各種の蛍
光増白剤や消泡剤あるいは界面活性剤や防ばい剤を含有
せしめることもできる。The bleach-fixing solution of the present invention contains tmq, borax, sthorium hydroxide, 1 cum of potassium hydroxide, sodium carbonate, potassium carbonate, 1~lium carbonate, 7J lium m carbon, acetic acid, 1-lium acetate, [p]-1 buffer consisting of various salts such as ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained.
またアセチルアセトン、ホスホノカルボン酸、ポリリン
酸、有機ボスホン酸、オキシカルボン酸、ポリカルボン
酸、ジカルボン酸及びアミノポリカルボン酸等の有機キ
レート剤あるいはニトロアルコール、ＶＩ酸塩等の安定
剤、アルカノールアミン等の可溶化剤、有機アミン等の
スティン防止剤、その他の添加物や、メタノール、ジメ
チルホルムアミド、ジメチルスルホキシド等の有機溶媒
を適宜含有せしめることができる。Also, organic chelating agents such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic bosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid, and aminopolycarboxylic acid, stabilizers such as nitro alcohol, VI salts, alkanolamines, etc. A solubilizing agent, an anti-stinting agent such as an organic amine, other additives, and an organic solvent such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be appropriately contained.
本発明の漂白定着液には漂白促進剤を用いることが好ま
しく、例えば特願昭ＧＯ−１６０り４３＠等に記載され
る化合物を用いることがＣき、下記一般式［Δ〜１］〜
［Δ〜ＩＶ ］に示される化合物を用いることが本発明
の効果を良好に奏し好ましい。It is preferable to use a bleach accelerator in the bleach-fixing solution of the present invention, and for example, compounds described in Japanese Patent Application No. 160-160-43@ can be used, and the following general formulas [Δ~1]~
It is preferable to use the compounds shown in [Δ to IV] because they exhibit the effects of the present invention well.
一般式［Δ−ＩＦ
１式中、Ｑｌは含窒素へテロ環（５〜６員の不飽和環ま
たは飽和環が縮合しているものち含む）を形成するに必
要な原子ｆ！Ｆを表わし、Ｒ１は水素またはアルキル基
を表わず。但し、−Ｑ′はＱｌと同浅である。、Ｊ
一般式［八−Ｈ］
［式中、Ｒ２ＪＪよびＲ３はそれぞれ水素原子、炭素原
子数′１〜Ｇのアルキル基、ヒドロキシ基、カルボキシ
基、アミノ基、炭素原子数１〜３のアシル基、アリール
基ｊ：たはアルク゛ニル基を表わす。General formula [Δ-IF 1 In the formula, Ql is an atom f! required to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed)! F and R1 does not represent hydrogen or an alkyl group. However, -Q' is as shallow as Ql. , J General formula [8-H] [In the formula, R2JJ and R3 are each a hydrogen atom, an alkyl group having 1 to G carbon atoms, a hydroxy group, a carboxy group, an amino group, and an acyl group having 1 to 3 carbon atoms. , represents an aryl group or an alkynyl group.
Δは
又はｎ＋ｌｌ１ｌｉのへゾロ環残基（５〜６員の不飽和
１１が縮合しているものち含む）を表わし、Ｘは−Ｓ、
−〇または＝ Ｎ Ｒ”を表わす。ここで、ＲＪ３よび
Ｒ′はそれぞれＲ２およびＲ３と同義、Ｘ′はＸと同義
、Ｚは水素原子、アルカリ金属原子、アンモニウム基、
アミノ基、含窒素へゾロ環残基、アルキル基、または
原子を表わし、Ｒｎは水素原子、炭素原子数１〜６のア
ルキル基、シクロアルキル基、アリール基、ヘテロ環残
基（５〜６員の不飽和環が縮合しているものも含む）ま
たはアミノ基を表わし、ｎ１〜ｎ（３およびｌ１１１へ
・ｒａ５はそれぞれ１〜６の整数を表わす。Ｂは炭素原
子数１〜６のアルキレン基を表わし、Ｙは−Ｎ＜または
−〇Ｈくを表わし、Ｒ４およびＲ５はそれぞれＲ２およ
びＲ３と同義である。但し、Ｒ４およびＲ５はそれぞれ
−Ｂ−８Ｚを表わしてもよく、またＲ２とＲ３、ＲとＲ
’ 、Ｒ４とＲ５はそれぞれ結合して環を形成して゛も
よい。Δ represents or n+ll1li hezolocyclic residue (including those in which 5- to 6-membered unsaturated 11 are condensed), X is -S,
-〇 or = NR''. Here, RJ3 and R' have the same meaning as R2 and R3, respectively, X' has the same meaning as X, and Z is a hydrogen atom, an alkali metal atom, an ammonium group,
It represents an amino group, a nitrogen-containing hezocyclic residue, an alkyl group, or an atom, and Rn represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (5 to 6 (including those in which unsaturated rings are condensed) or an amino group, n1 to n (3 and l111 and ra5 each represent an integer of 1 to 6. B is an alkylene group having 1 to 6 carbon atoms. , Y represents -N< or -〇H, and R4 and R5 have the same meanings as R2 and R3, respectively.However, R4 and R5 may each represent -B-8Z, and R2 and R3 , R and R
', R4 and R5 may each be combined to form a ring.
なお、該式で表わされる化合物はエノール化体Ｊ３よび
その塩も含む、、］
一般式［△−Ｉｌｌ ］
ｂ
＼Ｙ、−（［３，−３瑞Ｚ１
１丈。In addition, the compound represented by this formula also includes the enolated compound J3 and its salt. ] General formula [Δ-Ill ] b \Y, -([3,-3Zui Z1 1 length.
［式中、１テロおよび１り７はそれぞれ水素原子、炭素
原子数１〜６のアルキル基、ヒドロキシキ、カルボキシ
基、アミノ基、炭素原子数１〜３のアシル基、アリール
！ｊ１アルケニル基または−８＋ −３−Ｚ＋ を表わ
す。但し、Ｒ６とＲ７は結合して環を形成してもよい。[In the formula, 1tero and 17 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, or an aryl group! j1 represents an alkenyl group or -8+ -3-Z+. However, R6 and R7 may be combined to form a ring.
Ｙｌは Ｎ−または Ｃｌ−１−を表わし、Ｂ１は炭素
原子数１〜６のアルキレン基を表わし、７１は水素原子
、アルカリ金属原子、アンモニウム基、アミン基、含窒
素へゾロ環残基また１よ
−３−Ｂ＋ −Ｙｌ を表わす。０７は１〜６
＼□７
一般式［△−ＩＶ Ｊ
（Ｇ’）７゜
式中、△ｒは２価のアリール基またはアリール基と酸素
原子Ｊ３よび／もしくはアルキレン基とを組みあわせｌ
Ｃ２価の有（幾基を表わし、Ｂ２およびＢ３はそれぞれ
低級アルキレン基を表わし、Ｒ８、Ｒｓ、Ｒ＋ｏおよび
Ｒ＋＋はそれぞれヒドロキシ置換低級アル４ニル基を表
わし、Ｘ ｄ３よびｙはそれぞれ０または１を表わず。Yl represents N- or Cl-1-, B1 represents an alkylene group having 1 to 6 carbon atoms, and 71 represents a hydrogen atom, an alkali metal atom, an ammonium group, an amine group, a nitrogen-containing hezorocyclic residue or 1 represents yo-3-B+ -Yl. 07 is 1-6
\□7 General formula [△-IV J (G')7゜In the formula, △r is a divalent aryl group or a combination of an aryl group and an oxygen atom J3 and/or an alkylene group.
B2 and B3 each represent a lower alkylene group, R8, Rs, R+o and R++ each represent a hydroxy-substituted lower alkyl group, and X d3 and y each represent 0 or 1. Not shown.
Ｇ′はアニオンを表わし、ｌは０．１または２を表わす
。G' represents an anion, and l represents 0.1 or 2.
以下、木梵明に好ましく用いられる漂白促進剤の具体例
を承り。Below are specific examples of bleaching accelerators that are preferably used for Mokubonmei.
例示化合物 （△−１） （Δ−２） （△−３） （△−４） （Ａ−５） （△−６） （Δ−７） Ｈ，Ｎ−ＣＳ Ｎ １１ Ｎ １１ ＣＳ−Ｎ ＩＩ。Exemplary compound (△-1) (Δ-2) (△-3) (△-4) (A-5) (△-6) (Δ-7) H, N-CS N 11 N 11 CS-N II.
（△−９）
漂白促進剤の添加量は本発明の漂白定着液１！当り約０
．０１〜１００ｇの範囲で用いるのが好ましく、さらに
、０．０５〜５０（＋が好ましく、特にａｔましくは０
．０５〜１５（ｌである。(Δ-9) The amount of bleach accelerator added is 1 in the bleach-fix solution of the present invention! Approximately 0 hits
．． It is preferable to use it in the range of 0.01 to 100 g, and more preferably 0.05 to 50 (+ is preferable, especially at or 0.
．． 05-15 (l.
近年、公害負荷低減及び処理液コストの低減の目的から
低補充化が行なわれるが、本発明の漂白定着液も低補充
化に適用して好ましい。この時、本発明の漂白定着液中
にヨウ素イオンの蓄積が起こることが予想される。従来
、ヨウ素イオンの蓄積は、脱銀速度の低下をもたらすこ
とが知られているが、本発明の漂白定着液では、ヨウ素
イオンの蓄積によっても脱銀性が実質的に低下しないば
かりか、驚くべきことに、発色現像処理後水洗工程等洗
浄工程を経ることなく、漂白定着液に浸漬される場合に
も未露光部のｍ度上昇（いわゆるカプリ）がほとんど起
こらないことが明らかとなった。In recent years, low replenishment has been carried out for the purpose of reducing pollution load and processing solution cost, and the bleach-fixing solution of the present invention is also preferably applied to low replenishment. At this time, it is expected that iodine ions will accumulate in the bleach-fix solution of the present invention. Conventionally, it has been known that the accumulation of iodine ions causes a decrease in the desilvering rate, but in the bleach-fix solution of the present invention, not only does the accumulation of iodine ions not substantially reduce the desilvering performance, but surprisingly Interestingly, it has become clear that even when the film is immersed in a bleach-fix solution without going through a washing process such as a water washing process after color development, the m degree increase (so-called capri) in the unexposed area hardly occurs.
この時ヨウ素イオンは漂白定着液に０．０００５モル／
ｌ以上含右することが好ましく、より好ましくは、漂白
定着液に０．００１モル／１以上含有することが好まし
い、。At this time, iodine ions are added to the bleach-fix solution at 0.0005 mol/
It is preferable that the bleach-fixing solution contains 0.001 mol/1 or more, more preferably 0.001 mol/1 or more.
本発明の漂白定着液による処理時間は３分３０秒以下で
あれば良いが、好ましくは３分以下、より好ましくは２
分３０秒以内で用いることである。The processing time with the bleach-fix solution of the present invention may be 3 minutes and 30 seconds or less, preferably 3 minutes or less, more preferably 2 minutes or less.
It should be used within minutes and 30 seconds.
本発明の漂白定着液の温度は８０℃以下で使用されるが
、望ましくは５５℃以下、最も好ましくは４５℃以下で
使用される。又蒸発等を抑えて使用づるのが望ましい。The bleach-fix solution of the present invention is used at a temperature of 80°C or lower, preferably 55°C or lower, most preferably 45°C or lower. It is also desirable to use it while suppressing evaporation.
上記本発明の漂白定着液は、ｌｌ１ｌ影用ハロゲン化銀
写真感光材料であればいかなるハロゲン化銀写真感光材
料でも適用できる。具体的に好ましくは沃化銀含有率が
０．５モル％以上、さらに好ましくは１モル％以上含有
する＾感度沃臭化銀乳剤を用いた感光材料であることが
好ましい。The above bleach-fix solution of the present invention can be applied to any silver halide photographic material as long as it is a silver halide photographic material for shadows. Specifically, a photosensitive material using a sensitive silver iodobromide emulsion having a silver iodide content of 0.5 mol % or more, more preferably 1 mol % or more is preferable.
本発明の漂白定着液は、上記踊影、用ハロゲン化銀写真
感光材料を発色現像後、直ちに漂白定着する処理液とし
て用いてもよいし、発色現像後、水洗又はリンス又は停
止等の処理を行った後の漂白室゛着処理液として用いて
もよく、さらに発色現像後に前定着処理を行った後の漂
白定着処理液として用いてもよい。また、本発明の漂白
定着液による処理の摂、水洗処理し、その後安定化処理
してらよいし、水洗処理１稈を省略もしくは水洗水間を
極端に低減する特開昭５７−８５４３号に記載の多段向
流安定化処理技術や、特開昭５８−１４８３４号公報に
記載されているような水洗代替処理液による処理技術に
適用することもできる。また、発色現像、漂白定着、水
洗等の工程の他に硬膜、中和、黒白現像、反転、少量水
洗工程等、必要に応じて各種の補助工程が付加されても
よい。The bleach-fix solution of the present invention may be used as a processing solution for bleaching and fixing the silver halide photographic light-sensitive material for photographic use immediately after color development, or may be used as a processing solution for washing, rinsing, stopping, etc. after color development. It may be used as a bleach-fixing solution after color development has been carried out, or as a bleach-fixing solution after pre-fixing has been carried out after color development. Furthermore, it is possible to perform treatment with the bleach-fix solution of the present invention, washing with water, and then stabilizing, as described in JP-A No. 57-8543, which omit one culm washing process or extremely reduce the time between washings. The present invention can also be applied to the multi-stage countercurrent stabilization treatment technology described in JP-A-58-14834, and the treatment technology using a washing alternative treatment liquid as described in Japanese Patent Laid-Open No. 14834/1983. In addition to the steps of color development, bleach-fixing, and washing with water, various auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary.
本発明に適用できる撮影用ハロゲン化銀乳剤は、常法に
より化学増感することができ、増感色素を用いて、所望
の波長域に光学的に増感できる。The photographic silver halide emulsion applicable to the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.
ハロゲン化銀乳剤には、カブリ防止剤、安定剤等を加え
ることができる。該乳剤のバインダーとしては、ゼラチ
ンを用いるのが右利である。Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is preferably used as the binder for the emulsion.
乳剤層、その他の親水性コＬ：ｌイド層は、硬膜するこ
とができ、又、可塑剤、水不溶性又はｆｉｔ溶性合成ポ
リマーの分散物（ラテックス）を含有さけることができ
る。The emulsion layer and other hydrophilic co-L:lid layers may be hardened and may contain plasticizers, dispersions (latex) of water-insoluble or fit-soluble synthetic polymers.
カラー写真用感光材料の乳剤層には、カプラーが用いら
れる。A coupler is used in the emulsion layer of a light-sensitive material for color photography.
更に色補正の効果を有しているカラードカプラー、競合
カプラー及び現像主薬の酸化体とのカップリングによっ
て現像促進剤、漂白促進剤、現像剤、ハロゲン化銀溶剤
、調色剤、１ａ膜剤、カブリ剤、カブリ防止剤、化学増
感剤、分光増感剤、及び減感剤のような写真的に有用な
フラグメントを放出゛する化合物が用いることができる
。Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a 1a film agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.
感光材料には、フィルタ一層、ハレーション防止層、イ
ラジェーション防止層等の補助層を設けることができる
。これらの層中及び／又は乳剤層中には現象処理中に感
光材料から流出するかもしくは漂白される染料が含有さ
せられてもよい。The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes which are leached or bleached from the light-sensitive material during processing.
感光材料には、マット剤、滑剤、画像安定剤、界面活性
剤、色カブリ防止剤、現像促進剤、現像遅延剤や漂白促
進剤を添加できる。A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.
支持体としては、ポリエチレン等をラミネートした紙、
ポリエチレンテレフタレートフィルム、バライタ紙、三
酢酸セルロース等を用いることがぐきる。As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.
し実施例］
以下、実／７Ｉ！ｉＶＡによって本発明の訂ＩＩＩを説
明づるが、これにより本発明の実／７Ｉ態様が限定され
るものではない。Example] The following is real/7I! Although the iVA describes Revision III of the present invention, it is not intended to limit the Real/7I aspect of the present invention.
実施例−１
（実験１）
トリア上デー１〜フイルムベース上にハレーション防止
層及びＵラヂン層を設けこの上に赤感性ハロゲン化銀乳
剤層、緑感性ハロゲン化銀乳剤層、黄色コロイド銀を含
有するフィルタ一層及び青感性ハロゲン化銀乳剤層を総
体の銀ｍが１００ Ｃ１２当り８８Ｉ１ｇになるよう塗
布した。上記の乳剤層は沃化銀のモル％が約４．３％の
沃臭化銀であり。この際、青感性ハロゲン化銀乳剤層に
はイエローカプラーとして下記（Ｙ−１）、緑感性ハロ
ゲン化銀乳剤層には、マゼンタカプラーとして下記（Ｍ
−１）、赤感性ハロゲン化銀乳剤層にはシアンカプラー
として下記（Ｃ−１＞を用い、各乳剤層にはそれぞれ増
感色素、硬膜剤及び延展割等通常の添加剤を加えた。こ
のようにして１ｑられたハロゲン化銀カラーネガ感光４
４石を試料として用いた。Example-1 (Experiment 1) An antihalation layer and a U radiation layer were provided on the film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a yellow colloidal silver were contained thereon. A single filter layer and a blue-sensitive silver halide emulsion layer were coated to give a total silver m of 88 I1 g/100 C12. The emulsion layer described above is silver iodobromide with a molar percentage of silver iodide of about 4.3%. At this time, the following yellow coupler (Y-1) is used in the blue-sensitive silver halide emulsion layer, and the following magenta coupler (M) is used in the green-sensitive silver halide emulsion layer.
-1) The following (C-1>) was used as a cyan coupler in the red-sensitive silver halide emulsion layer, and usual additives such as a sensitizing dye, a hardening agent, and a spreader were added to each emulsion layer. Silver halide color negative exposure 4
Four stones were used as samples.
イエにｌ−カプラー（Ｙ−１）
マゼンタカプラー（Ｍ−１）
ｙ
シアンカプラー（Ｃ−’Ｉ）
この試料をピースに＃ｉ断し、常法に従って模型露光を
与えたものを用い、次の工程に従ってピース用処理装置
を用いて処理（以下、手用処理と称する）を行った。Yellow, l-coupler (Y-1), magenta coupler (M-1), cyan coupler (C-'I) This sample was cut into #i pieces, exposed to model light according to the usual method, and then the following Processing (hereinafter referred to as manual processing) was performed using a piece processing device according to the steps.
処理工程 処理温度（”Ｃ）槽数 処理時間１発色現
像 ３７．８ １槽 ３９１５秒２漂白定着
３７．８ １ Ｊ凸 ４分２０秒３水
洗 ３０〜３４ ２槽 ４分２０秒４安
定 ３０〜３４ １槽 ２分１０秒５乾
燥
発色現像液、漂白定着・液及び安定液は以下のものを使
用した。Processing process Processing temperature ("C) Number of tanks Processing time 1 color development 37.8 1 tank 3915 seconds 2 bleach-fixing 37.8 1 J convex 4 minutes 20 seconds 3 water
Washing 30-34 2 tanks 4 minutes 20 seconds 4 yen
Constant 30-34 1 tank 2 minutes 10 seconds 5 drying
The following drying color developing solution, bleach-fixing solution, and stabilizing solution were used.
［発色現像液１
［漂白定着液］
［安定液］
表 １
表 １ （続ぎ）
」二記処理１１１白定首液を開口比率１０Ｃｍ’／り（
一般の自動用ＩＩＩに相当づる開口条ｔ’［であり、１
２の漂白定着液に対して、１０Ｃｎ’の空気接触面積を
有している事を意味する。）で、３８℃、１週間の経時
保存し、保存後の漂白定着液を用いて上記処理を再び行
なった。処理役のフィルム試別（漂白定着液のＩ！時保
存前後のそれぞれ）の最高濃度部の残ｆ８銀ｍ （ｍｇ
／ ｄｍ’ ）を蛍光Ｘ線法により、測定し、さらに、
シアン色素１１度をザクラ光電溌度計Ｐ ＤΔ−６５（
小西六写真工業［４１１製）を用いて復色率を測定した
。[Color developing solution 1 [Bleach-fixing solution] [Stabilizing solution] Table 1 Table 1 (Continued) 2 Processing 111 White fixing solution with an aperture ratio of 10 cm'/l (
Opening strip t' [corresponding to general automatic III, and 1
This means that it has an air contact area of 10Cn' with respect to the bleach-fix solution of 2. ) at 38° C. for one week, and the above treatment was performed again using the bleach-fix solution after storage. Residual f8 silver m (mg
/dm') by the fluorescent X-ray method, and further,
Cyan dye 11 degrees was measured using Zakura Photoelectric Visibility Meter P DΔ-65 (
The color recovery rate was measured using Konishiroku Photo Industry Co., Ltd. [411].
上記表２より、本発明に係わる右傾酸第２鉄錯塩を用い
て、ｐＨ３，０〜６．８の領域の漂白定着液を使用する
際には、経時保存の如何にかかわらず、残留銀も少なく
、かつ復色率も良好であることが判る。特に、ｌ’１）
−１が４．０〜６．７の時θ・よ＋、１Ｎ時で、ｐＨが
５．０〜６．５の際にとりわけ特に良好であることが判
る。From Table 2 above, when using the dextral ferric acid complex salt according to the present invention and a bleach-fix solution in the pH range of 3.0 to 6.8, residual silver can be removed regardless of how it is stored over time. It can be seen that the color recovery rate is small and the color restoration rate is also good. In particular, l'1)
It can be seen that when -1 is 4.0 to 6.7, θ·yo + is 1N, and the pH is particularly good when pH is 5.0 to 6.5.
しかるに、比較のＤ Ｔ Ｉ） Ａを有機酸として用い
た比較の漂白定着液によればｐ１１７〜８で経時保存前
は脱銀性能及び復色性能は４少めで良好であるが、１週
間の保存後には不充分なる性能となってしまう。さらに
、Ｅ Ｄ Ｔ Ａは、経時保存の如何にかかわらづ”、
脱銀性能及び復色性能が不充分なものであることが判る
。However, according to the comparative bleach-fix solution using DTI) A as the organic acid, the desilvering performance and recoloring performance were good with p117 to 8 before storage over time, with 4 less. After storage, the performance becomes insufficient. Furthermore, EDTA, regardless of how it is stored over time,
It can be seen that the desilvering performance and recoloring performance are insufficient.
（実験２）
前記（実験１）で用いた漂白定着液ＮＯ１２及びＮ０１
３の亜Ｕ１１Ｍ、アンモニウムの添加ｍを下記表３に示
す餡にそれぞれ変化さＵ漂白定着液Ｎ ０．２−１１〜
３−２１を調製した。該漂白定着液を用いた実験１の感
材を処理し、１りられた処理後の漂白定着液を実験１と
同様に経時保存し、この経時保存漂白定着液を用いて、
脱銀性能及び復色性能を実ｋｉｌと同様に測定し表３に
０１１！て示した。(Experiment 2) Bleach-fix solutions NO12 and N01 used in the above (Experiment 1)
3, U11M and ammonium addition m were changed to the bean paste shown in Table 3 below, respectively. U bleach-fix solution N 0.2-11~
3-21 was prepared. The photosensitive material of Experiment 1 using the bleach-fix solution was processed, and the processed bleach-fix solution was stored over time in the same manner as in Experiment 1, and using this time-preserved bleach-fix solution,
Desilvering performance and recoloring performance were measured in the same manner as the actual kil, and Table 3 shows 011! It was shown.
また１週間保存後、さらに間口比率を１０倍にして保存
をつづけ沈澱の発生が生じるまでの日数を目視にて観察
した。After one week of storage, storage was continued with the frontage ratio increased to 10 times, and the number of days until precipitation occurred was visually observed.
表ご３ ＃ 沈１２ｙｌ！生までの日数で承り。Table 3 # Shen 12yl! Accepted by number of days until birth.
上記表３より、明らかな様に、亜硫酸塩濃度が０．０５
５■ル／１上の際に沈澱の発生が少なく、残菌銀及び復
色率ｂ Ｉ） Ｔ Ｉ”Δ−１：ｃと比較して、極めて
良好であり、実技的に優れたものであった。As is clear from Table 3 above, the sulfite concentration is 0.05
5■L/1, there is less precipitation, residual bacteria silver and color recovery rate b I) T I"Δ-1: It is extremely good compared to c, and is excellent in practical terms. there were.
とりわけ、０．０５〜２．０’Ｅル／１、さらに特に０
．０１〜１．３モル／ｌ、さらに、とりわけ特に０．０
９〜０．９■ル／１の際に、本発明の目的の効果を良好
に奏することが判る。In particular, 0.05 to 2.0'E/1, more especially 0
．． 01-1.3 mol/l, more especially 0.0
It can be seen that the desired effects of the present invention are well achieved when the ratio is 9 to 0.9 μl/1.
以上の実験１および実験２の結果より、本発明の漂白定
着液、即ちＩ）ｌ−（が３．０〜６．８の範囲で一般式
［Ｉ］で示される化合物を配位子とする第２鉄錯塩を含
有し、ざらに亜硫酸Ｊ！！ ０．０５５■ル／２上含有
する漂白定着処理液は、特に経時保存後においても優れ
た脱銀性能を有し、復色不良の発生も良好に防止され、
さらに保存安定性も良好であることがわかる。なＪ３、
本発明の漂白定着液はアンモニア臭は全くないものであ
った。From the results of Experiment 1 and Experiment 2 above, it was found that the bleach-fix solution of the present invention, that is, I) l-( is in the range of 3.0 to 6.8 and the compound represented by the general formula [I] is used as a ligand) A bleach-fixing solution containing ferric complex salts and containing sulfite J!! 0.055 μl/2 has excellent desilvering performance, especially after storage over time, and prevents the occurrence of poor color restoration. is also well prevented,
Furthermore, it can be seen that the storage stability is also good. Na J3,
The bleach-fix solution of the present invention had no ammonia odor at all.
実施例−２
実施例−１の実験１と同様に漂白定着液を経時保存させ
た。ただし、ここでは漂白定着液中の亜硫酸アンモニウ
ムの濃度を２０ｇ／ｆｆｉ、漂白剤の種類を表４に記載
しｌζ如くとし、漂白剤の濃度を表４の如く変化させた
。また漂白定着液のｐＨを６．０とした。Example 2 A bleach-fix solution was stored over time in the same manner as in Experiment 1 of Example 1. However, here, the concentration of ammonium sulfite in the bleach-fix solution was 20 g/ffi, the type of bleaching agent was as shown in Table 4, and the concentration of the bleaching agent was varied as shown in Table 4. Further, the pH of the bleach-fix solution was set to 6.0.
経時保存後実施例−１の実験１と同様の評価を行ない、
結果を表４に示した。After storage over time, the same evaluation as in Experiment 1 of Example-1 was performed,
The results are shown in Table 4.
次にすべての漂白定着液を実施例−１の実験２と同様に
継続して保存し、１１１化りるまでの１コ数を測定し、
結果を表４に併Ｕて示した。Next, all the bleach-fixing solutions were continuously stored in the same manner as in Experiment 2 of Example-1, and the number of 1 pieces until they reached 111 was measured.
The results are also shown in Table 4.
ｔ、、／ｌ ｔｌ−
表４Ｊ：り明らかなように、本発明の漂白定着液の中で
も、特に漂白剤の含有量が０．０２ Ｅル／り〜１．３
０ ［−ル／ｌ、好ましくは０．１０〜１．２０モル、
！、さらに好ましくは０．２０〜０．８モル／りの範囲
であれば、経時保存しても脱銀及び復色能力は高くかつ
硫化までの１１数が良い良好な漂白定着液であることが
わかる。t,,/l tl- Table 4J: As is clear, among the bleach-fixing solutions of the present invention, the bleaching agent content is particularly high from 0.02 E/l to 1.3
0 [-l/l, preferably 0.10 to 1.20 mol,
! , more preferably in the range of 0.20 to 0.8 mol/liter, it is a good bleach-fixing solution that has high desilvering and restoring ability even after storage over time, and has a good number of 11 until sulfurization. Recognize.
実施例−３
実施例−１の実験１と同様に漂白定着液を経時保存させ
た。ただし、ここでは漂白定着液中の漂白剤及び添加ｍ
を表５の如くとし、漂白定着液中の１り１のｒＡ度を表
５の如く変化させた。また漂白定着液中のｐＨを６．０
とした。Example 3 A bleach-fix solution was stored over time in the same manner as in Experiment 1 of Example 1. However, here, the bleaching agent in the bleach-fix solution and the additive m
were as shown in Table 5, and the degree of rA in the bleach-fix solution was varied as shown in Table 5. Also, the pH in the bleach-fix solution was adjusted to 6.0.
And so.
経時保存後実施例−１の実験１と同様に脱銀１１ヒ力の
評価を行ない結果を表５に記載した。After storage over time, the desilvering strength was evaluated in the same manner as in Experiment 1 of Example-1, and the results are shown in Table 5.
また処理後の試料を、ＣＮ Ｋ −４基準処理（小西六
写真工業カラーネガ処理）に従って漂白及び定性処理を
施こし残存銀を完全に除いた後に、τ？ピンク色素の透
過１１１度をＪＩＱ定してこの値をＤＩｈ とした。次
に実施例−１の実験１ど同様に発色現象を行った後、Ｃ
ＮＫ−’Ｉ基準処理に従って漂白及び定着処理した試わ
）のマピンタ色素の透過Ｉｔ（［を測定し、この値をＤ
Ｒ２とした。【）２．と０１？２の差を求める（ΔＤ１
２）ことにＪ：す、７じンタステインを評価した。。Further, the treated sample was subjected to bleaching and qualitative treatment according to the CN K-4 standard treatment (Konishi Roku Photo Industry Color Negative Processing) to completely remove residual silver, and then τ? The transmission of the pink pigment at 111 degrees was determined by JIQ, and this value was defined as DIh. Next, after performing the coloring phenomenon in the same manner as in Experiment 1 of Example-1, C.
The transmission of Mapinta dye (It) was measured and this value was calculated as D
It was set to R2. [)2. Find the difference between and 01?2 (ΔD1
2) In particular, J:S.7-gintastein was evaluated. .
表５から明らかなＪ：うに、比較の漂白定着液では、Ｋ
１の添加ににってマゼンタスティンは小さくなるが脱銀
能力が大きく低下づる。しかし本発明の漂白定着液では
、Ｋ１の添加によりマゼンタスティンが低く押えられる
一方、脱銀能力のイ〔下が小さく良好な結果が１７られ
た。It is clear from Table 5 that J: sea urchin, and in the comparative bleach-fix solution, K
By adding 1, the magentastin becomes smaller, but the desilvering ability is greatly reduced. However, in the bleach-fix solution of the present invention, while magentastin was suppressed to a low level by the addition of K1, good results were obtained with a small decrease in desilvering ability.
実施Ｖ／４−４
実施例−１の実Ｍ１において調製した漂白定着液Ｎ０．
１−１および３−１にＪ３いて、ｐＨを６．０とし漂白
促進剤を下記表６に示す如くに添加した以外は同様にし
て、漂白定着液ＮＯ４１−１１〜１−１６および３−３
２〜３−３７を調製した。Implementation V/4-4 Bleach-fix solution N0. prepared in Example M1 of Example-1.
Bleach-fix solutions No. 41-11 to 1-16 and No. 3-3 were prepared in the same manner except that the pH was adjusted to 6.0 and the bleach accelerator was added as shown in Table 6 below.
2-3-37 was prepared.
４りられた漂白定着液を用いて、実験１にＪ５ける漂白
定着時４分２０秒を３分１５秒とした以外は、実施例−
１の実験１ ’６３よび２と同様の評価を打つｌこ 。Example 4 except that the bleach-fixing time in J5 in Experiment 1 was changed from 4 minutes 20 seconds to 3 minutes 15 seconds using the bleach-fix solution prepared in Example 4.
The same evaluation as in Experiments 1 and 2 was made.
表６より、漂白Ｃ？進剤を添加した時には本発明の漂白
定着液１よ保存によっても脱銀性、復色性Ｌ１３よび保
存性のいずれも良りｒな効果を維持できるのに対して本
発明外の漂白定着液は、調製直後の場合はいずれも効果
があったが保存により脱１１４１と塩性性Ｊ３よび保存
性が更に劣化することが明らかとなった。From Table 6, bleaching C? When a promoter is added, the bleach-fix solution 1 of the present invention can maintain good effects in terms of desilvering properties, recoloring properties L13, and preservability even after storage, whereas the bleach-fix solutions other than the present invention It was found that, although both were effective immediately after preparation, storage further deteriorated de-1141, saltiness of J3, and storage stability.
Claims (1)
において、該液のｐＨが３．０〜６．８の範囲にあり、
かつ下記一般式［ I ］で示される化合物を配位子とす
る第２鉄錯塩を含有し、さらに亜硫酸塩を０．０５モル
／ｌ以上含有することを特徴とする漂白定着液。 一般式［ I ］ ▲数式、化学式、表等があります▼ （式中、Ｒ＿１は水素原子または低級アルキル基を表わ
し、ｎ＿１、ｎ＿２およびｎ＿３はそれぞれ０〜３の整
数を表わす。但し、ｎ＿１、ｎ＿２およびｎ＿３の合計
は３または４の整数であり、 ▲数式、化学式、表等があります▼における炭素原子数
の総和は３以上である。）[Scope of Claims] A processing solution for bleaching and fixing silver halide photographic light-sensitive materials, the pH of which is in the range of 3.0 to 6.8;
A bleach-fixing solution characterized by containing a ferric complex salt having a compound represented by the following general formula [I] as a ligand, and further containing sulfite in an amount of 0.05 mol/l or more. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a lower alkyl group, and n_1, n_2 and n_3 each represent an integer from 0 to 3. The sum of and n_3 is an integer of 3 or 4, and the total number of carbon atoms in ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is 3 or more.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23859886A JPS6392952A (en) | 1986-10-07 | 1986-10-07 | Bleach-fix bath having excellent quick processability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23859886A JPS6392952A (en) | 1986-10-07 | 1986-10-07 | Bleach-fix bath having excellent quick processability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6392952A true JPS6392952A (en) | 1988-04-23 |
Family
ID=17032572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23859886A Pending JPS6392952A (en) | 1986-10-07 | 1986-10-07 | Bleach-fix bath having excellent quick processability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6392952A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6397953A (en) * | 1986-10-15 | 1988-04-28 | Fuji Photo Film Co Ltd | Processing method for silver halide color photographic sensitive material |
| JPH01319037A (en) * | 1988-06-20 | 1989-12-25 | Fuji Photo Film Co Ltd | Method of processing silver halide color photographic sensitive material |
-
1986
- 1986-10-07 JP JP23859886A patent/JPS6392952A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6397953A (en) * | 1986-10-15 | 1988-04-28 | Fuji Photo Film Co Ltd | Processing method for silver halide color photographic sensitive material |
| JPH01319037A (en) * | 1988-06-20 | 1989-12-25 | Fuji Photo Film Co Ltd | Method of processing silver halide color photographic sensitive material |
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