EP0270217B1 - Bleach-fixing solution having good processing performance and method for processing light-sensitive material using the same - Google Patents
Bleach-fixing solution having good processing performance and method for processing light-sensitive material using the same Download PDFInfo
- Publication number
- EP0270217B1 EP0270217B1 EP19870308819 EP87308819A EP0270217B1 EP 0270217 B1 EP0270217 B1 EP 0270217B1 EP 19870308819 EP19870308819 EP 19870308819 EP 87308819 A EP87308819 A EP 87308819A EP 0270217 B1 EP0270217 B1 EP 0270217B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleach
- group
- general formula
- carbon atoms
- fixing 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.)
- Expired - Lifetime
Links
- 238000012545 processing Methods 0.000 title claims description 54
- 239000000463 material Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 87
- 150000003839 salts Chemical class 0.000 claims description 60
- -1 silver halide Chemical class 0.000 claims description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 229910052709 silver Inorganic materials 0.000 claims description 47
- 239000004332 silver Substances 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 30
- 239000003446 ligand Substances 0.000 claims description 24
- 238000004061 bleaching Methods 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 150000001340 alkali metals Chemical group 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical group [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 7
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 7
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 6
- 235000019252 potassium sulphite Nutrition 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 4
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000002587 enol group Chemical group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 239000000243 solution Substances 0.000 description 203
- 238000002474 experimental method Methods 0.000 description 71
- 239000000839 emulsion Substances 0.000 description 32
- 238000003860 storage Methods 0.000 description 27
- 239000007844 bleaching agent Substances 0.000 description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 20
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000000975 dye Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 150000007524 organic acids Chemical class 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003755 preservative agent Substances 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 230000002335 preservative effect Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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 5
- 238000009825 accumulation Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 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 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- 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 4
- 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 4
- 229910021612 Silver iodide Inorganic materials 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 229940045105 silver iodide Drugs 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- SRPOMGSPELCIGZ-UHFFFAOYSA-N disulfino carbonate Chemical compound OS(=O)OC(=O)OS(O)=O SRPOMGSPELCIGZ-UHFFFAOYSA-N 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 3
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 3
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- GVEYRUKUJCHJSR-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C(C)=C1 GVEYRUKUJCHJSR-UHFFFAOYSA-N 0.000 description 1
- 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
- UOMQUZPKALKDCA-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UOMQUZPKALKDCA-UHFFFAOYSA-K 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 229940090898 Desensitizer Drugs 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 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
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 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
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 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
- 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
- RVPQGUIKVDNENB-UHFFFAOYSA-L disodium hydrogen sulfite pentane-2,4-dione Chemical compound [Na+].[Na+].OS([O-])=O.OS([O-])=O.CC(=O)CC(C)=O RVPQGUIKVDNENB-UHFFFAOYSA-L 0.000 description 1
- TYZVRCWJCJVTRC-UHFFFAOYSA-L disodium;butanedial;hydrogen sulfite Chemical compound [Na+].[Na+].OS([O-])=O.OS([O-])=O.O=CCCC=O TYZVRCWJCJVTRC-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229960005102 foscarnet Drugs 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- JGEMYUOFGVHXKV-OWOJBTEDSA-N fumaraldehyde Chemical compound O=C\C=C\C=O JGEMYUOFGVHXKV-OWOJBTEDSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 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
- 239000000843 powder Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AWOBIMIIHDHGAK-UHFFFAOYSA-M sodium hydrogen sulfite pentan-2-one Chemical compound [Na+].OS([O-])=O.CCCC(C)=O AWOBIMIIHDHGAK-UHFFFAOYSA-M 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate 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
- YNJORDSKPXMABC-UHFFFAOYSA-M sodium;2-hydroxypropane-2-sulfonate Chemical compound [Na+].CC(C)(O)S([O-])(=O)=O YNJORDSKPXMABC-UHFFFAOYSA-M 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
- ALDWJWJHFFRLCZ-UHFFFAOYSA-M sodium;butan-2-one;hydrogen sulfite Chemical compound [Na+].OS([O-])=O.CCC(C)=O ALDWJWJHFFRLCZ-UHFFFAOYSA-M 0.000 description 1
- DTKWNTFUNKRCSS-UHFFFAOYSA-M sodium;hydrogen sulfite;propanal Chemical compound [Na+].CCC=O.OS([O-])=O DTKWNTFUNKRCSS-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 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
- 150000003585 thioureas Chemical class 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
Definitions
- This invention relates to a bleach-fixing solution, and particularly to a bleach-fixing solution that can achieve rapid processing when applied in a light-sensitive material for photographing.
- the desilvering of light-sensitive materials for photographing in which a highly sensitive silver iodobromide-rich emulsion is used is carried out separately in a bleaching step and a fixing step.
- DTPA ⁇ Fe complex salt a diethylenetriaminepentaacetic acid ferric complex salt
- DTPA ⁇ Fe complex salt a diethylenetriaminepentaacetic acid ferric complex salt
- the above DTPA ⁇ Fe complex salt can satisfy the above properties when used in the higher pH range, specifically, at about pH 7 to 9.
- ammonia gas may be readily generated when used in such a pH range, so that there has been a problem undesirable from a viewpoint of the work environment if the developing is carried out in a small room.
- EP-A-0 173 540 discloses a color forming method using a light-sensitive silver halide color photographic material having red, green and blue sensitive layers with a total thickness of 25 microns or less.
- the method involves involves inagewise exposure folllowed by color development in the presence of a dye forming coupler.
- the silver is removed from the developed material using a bleach-fixing solution.
- the bleach-fixing solution may contain one or more organic acid ferric complexes such as ethylamine diamine tetraacetic acid and 1,2-diaminopropane tetraacetic acid.
- the present inventors have continued further studies to find, as a result, that the lowering of the desilvering ability and the inferiority in the color reproduction that are considered to be caused by the above-mentioned accumulation of ferrous ions can be solved at the same time and the problem of the generation of ammonia gas can be solved by using a bleach-fixing solution having the pH aminopolycarboxylic ferric complex salt.
- Some compounds of the compounds represented respectively by General Formulas (II) and (III) of this invention are known to be used in a bleach-fixing solution containing an ethylenediaminetetraacetic acid iron (III) complex (hereinafter "EDTA ⁇ Fe) as a bleaching agent, as disclosed, for example, in Japanese Publication No. 39985/1979/ However, it was revealed that such compounds may gradually release sulfite ions when used in the bleach-fixing solution containing the above EDTA ⁇ Fe, so that aldehydes or ketones may be accumulated and the desilvering speed may be gradually lowered.
- EDTA ⁇ Fe ethylenediaminetetraacetic acid iron
- a first object of this invention is to provide a bleach-fixing solution made feasible for rapid processing of a light-sensitive photographic material for photographing.
- a second object of this invention is to provide a bleach-fixing solution free from generation of ammonia gas and desirable from the viewpoint of work environment.
- a third object of this invention is further to provide a bleach-fixing solution that can delay the occurrence of the precipitation even during storage with time to attain a stable bleach-fixing performance.
- a fourth object of this invention is to provide a bleach-fixing solution that can improve the bleach stain at a non-image portion of a light-sensitive material when the processing with low replenishment is carried out.
- a bleach-fix solution for processing a light-sensitive silver halide photographic material for photographing wherein said solution has a pH ranging from between 3.0 to 6.8, contains a ferric complex salt having a ligand comprising a compound represented by the Formulas I-1 and I-2 shown below, and further contains at least one of;
- R2 and R3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and M represents an alkali metal atom or an ammonium group,
- R4 and R5 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; M represents an alkali metal atom or an ammonium group; and n represents an integer of 0 to 6,
- R2 represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl-substituted alkyl group having 1 to 5 carbon atoms, or ( ⁇ CH2)n6COOH; and n4, n5 and n6 each represents an integer of 1 or 2,
- n7 and n9 each represent an integer of 0 to 3
- n8 represents an integer of 1 to 3, provided that the sum of n7, n8 and n9 is 2 or more
- R3 and R4 each represent a hydrogen atom, a hydroxyl-substituted alkyl group having 1 to 3 carbon atoms, or a carboxyl-substituted alkyl group having 1 or 2 carbon atoms;
- R5 and R6 each represent a hydrogen atom or a hydroxyl-substituted phenyl group;
- R7, R8, R9 and R10 each represent a hydrogen atom or a hydroxyl-substituted alkyl group having 1 to 3 carbon atoms, provided that R7, R8, R9 and R10 each may combine to form a ring having 5 to 8 carbon atoms;
- n10 and n11 each represent an integer of 1 to 3; and
- n12 represents an integer of 0 to 4,
- n13 represents an integer of 1 to 8.
- the ferric complex salt having a ligand comprising the compound represented by the Formulas I-1 and I-2 may be used also in the form of a free acid (hydrogen salt), or may also be used in the form of a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amines, for example, triethanolamine.
- alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amines, for example, triethanolamine.
- Preferably used are a potassium salt, a sodium salt and an ammonium salt.
- At least one of these ferric complex salts of this invention may be used, but two or more of these can also be used in combination. It is also possible to use them in combination with any ferric complex salts outside this invention.
- the ferric complex salt can be used in any amount in the bleach-fixing solution of this invention so long as it is in an amount sufficient for obtaining the effect of this invention.
- overly high concentration of the ferric complex salt may cause the deterioration of shelf stability of the bleach-fixing solution, and, on the other hand, overly low concentration of the ferric complex salt may cause the deterioration of desilvering performance and color reproduction performance.
- it may be usually used preferably in the range of 0.02 to 1.30 mol/lit., more preferably 0.10 to 1.20 mol/lit.
- the effect of this invention can be preferably exhibited when used in the range of 0.20 to 0.80 mol/lit.
- the bleach-fixing solution of this invention may be appropriately in the pH range of pH 3.0 to 6.8, because sulfite gas may be generated at less than pH 3.0 and the effect of this invention may be insufficient if the pH is higher than 6.8. It can be used at any pH so long as it is used in this pH range, but is preferably used at pH 4.0 to 6.7, particularly preferably H 5.0 to 6.5, taking account of the solubility of various iron salts at low temperature the odor of the sulfite gas generated from sulfite ions in addition to desilvering performance and color reproduction.
- the bleach-fixing solution of this invention may preferably contain a variety of sulfites therein, and these sulfites may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, etc.
- At least one compound selected from the compounds represented respectively by General Formulas (II) and (III) may be used as a preservative in the bleach-fixing solution of this invention.
- the alkyl group having 1 to 8 carbon atoms may preferably include an alkyl group having 1 to 4 carbon atoms.
- One of the preferred compounds included in the carbonyl bisulfite addition compound represented by General Formula (II) is a compound wherein R2 is a hydrogen atom and R3 is an alkyl group having 1 to 4 carbon atoms, and another of them is a compound wherein R2 and R3 each are in alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 8 carbon atoms may preferably include an alkyl group having 1 or 2 carbon atoms.
- n which represents an integer of 0 to 6, may preferably be an integer of 1 to 4.
- One of the preferred compounds included in the carbonyl bis-sulfite addition compound represented by General Formula (III) is a compound wherein R4 and R5 each are a hydrogen atom and n is an integer of 1 to 4. Another of them is a compound wherein R4 and R5 each are an alkyl group having 1 or 2 carbon atoms and n is an integer of 1 to 4.
- the polymer having a unit of a pyrrolidone nucleus in the molecular structure (hereinafter called "vinyl pyrrolidone polymer of this invention") will be described below.
- the vinyl pyrrolidone polymer of this invention may comprise either a homopolymer of vinyl pyrrolidone alone or a copolymer thereof with additional copolymerizable monomer(s), but it is required to be water-soluble as a polymer.
- the above additional monomer copolymerizable with vinyl pyrrolidone may typically include, for example, vinyl esters, acrylates, methacrylates, acrylic acids, methacrylic acid, styrene, etc.
- the vinyl esters may include for example, vinyl acetate, vinyl propionate, vinyl butyrate.
- the acrylic esters may include, for example, methyl ester, ethyl ester, butyl ester, 2-ethyl hexyl ester, etc.
- the copolymerization ratio may preferably be selected in the range of 5 to 100 mol % based on the vinyl pyrrolidone.
- the average molecular weight of the vinyl pyrrolidone polymer of this invention may preferably in the range of 500 to 800,000 more preferably 2,000 to 400,000
- the determination of the average molecular weight of the polymer can be carried out according to a usual method, for example, according to the following:
- Typical examples of the vinyl pyrrolidone polymer of this invention are shown below, but by no means limited to these.
- the amount for the addition of the above vinyl pyrrolidone polymer of this invention may vary depending on the type of the polymer, the polymerization degree and so forth, but approximately may preferably in the range of 0.1 to 100 g, more preferably 0.2 to 50 g, still more preferably 0.3 to 20 g, and particularly preferably 0.5 to 10 g, per liter of the bleach-fixing solution of this invention.
- the vinyl pyrrolidone polymer of this invention may be added in the bleach-fixing solution by, for example, adding it directly as it is in the form of powder, or may be added by dissolving it in a solvent such as water.
- the above vinyl pyrrolidone polymer of this invention may be more preferably used for the purpose of better improving the shelf stability of the bleach-fixing solution, when a sulfite or a sulfite-releasable compound (for example, carbonyl bisulfite addition compounds disclosed in Japanese Patent Publication No. 38895/1979) is used in combination with it.
- a sulfite or a sulfite-releasable compound for example, carbonyl bisulfite addition compounds disclosed in Japanese Patent Publication No. 38895/1979
- the sulfite or the sulfite-releasable compound may preferably be contained in an amount of 1 x 10 ⁇ 3 mol or more per liter of the bleach-fixing solution of this invention. It may be used more preferably in an amount of not less than 0.02 mol and not more than 2.0 mols, still more preferably not less than 0.05 mol and not more than 1.3 mols, and most preferably not less than 0.09 mol and not more than 0.9 mol.
- the above sulfite may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, etc.
- the ferric complex salt having a ligand Comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) may be used also in the form of a free acid (hydrogen salt), or may also be used in the form of a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amine salts, for example, triethanolamine salt, etc.
- alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amine salts, for example, triethanolamine salt, etc.
- Preferably used are a potassium salt, a sodium salt and an ammonium salt.
- the ferric complex salt having a ligand comprising the compound represented by Formulas I-1 and I-2 and ferric complex salt having a ligand comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) of this invention may preferably be in the range of 1 mol % to 95 mol %, more preferably 5 mol % to 90 mol %, and most preferably 10 mol % to 80 mol %, based on the total amount of these.
- the ferric complex salt having a ligand comprising the compound represented by Formulas I-1 and I-2 and that having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) of this invention can be used in any amount in the bleach-fixing solution of this invention so long as it is in an amount sufficient for obtaining the effect of this invention.
- overly high concentration of the ferric complex salt may cause the deterioration of shelf stability of the bleach-fixing solution, and, on the other hand, overly low concentration of the ferric complex salt may cause the deterioration of desilvering performance and color reproduction performance.
- the effect of this invention can be preferably exhibited when used in the range of 0.20 to 0.80 mol/lit.
- ferric complex salt having a ligand comprising the compound represented by General Formula (I) and ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) of this invention are used in combination, so that the shelf stability can be improved while maintaining the good desilvering and color reproduction performances inherent in the bleach-fixing solution of this invention.
- the bleach-fixing solution of the present embodiment may preferably contain a sulfite and/or a sulfite-releasable compound in order to further improve the shelf stability.
- a sulfite and/or a sulfite-releasable compound may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, formaldehyde bisulfite addition compounds, etc.
- These compounds may be used in an amount of 0.001 mol to 2.0 mols, preferably 0.001 mol to 1.3 mols, most preferably 0.01 mol to 0.9 mol, per liter of the bleach-fixing solution of this invention.
- the silver halide fixing agent to be contained in the bleach-fixing solution of this invention may include a compound capable of forming a water-soluble complex salt through the reaction with the silver halide used in usual fixing, typically including, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thioureas, thioethers, highly concentrated bromides, iodides, etc.
- These fixing agents can be used in an amount of not less than 5 g/lit., preferably not less than 50 g/lit., or more preferably not less than 70 g/lit. and in the amount of the range they can be dissolved.
- the bleach-fixing solution of this invention may contain various additives.
- the additives are alkali halides or ammonium halides, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc.
- the bleach-fixing solution of this invention may contain, alone or in combination of two or more of, pH buffering agents including boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium, carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may further contain every kind of brightening agents, anti-foaming agents, surface active agents and mildewproofing agents.
- pH buffering agents including boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium, carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may further contain every kind of brightening agents, anti-foaming agents, surface active agents and mildewproofing agents.
- organic chelating agents such as acetyl acetone, phosphonocarboxylic acid, pholyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, stabilizers such as nitroalcohol and nitrate, solubilizing agents such as alkanolamine, anti-stain agents such as organic amine, other additives, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide.
- organic chelating agents such as acetyl acetone, phosphonocarboxylic acid, pholyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, stabilizers such as nitroalcohol and nitrate, solubilizing agents such as alkanolamine, anti-stain agents such as organic amine, other additives, and organic solvents
- a bleach accelerator may preferably be used in the bleach-fixing solution of this invention.
- the compounds described in Japanese Unexamined Patent Publication No. 19851/1987 and, to exhibit the effect of this invention with good results, the compounds represented respectively by General Formulas (A-I) to (A-Iv) shown below.
- Q1 represents a group of atoms necessary for the formation of a nitrogen-containing heterocyclic ring (including those condensed with a saturated or unsaturated ring of 5 or 6 members); R1 represents a hydrogen atom, an alkali metal atom, or an alkyl group, provided that Q ⁇ have the same meaning as defined for Q1.
- R2 and R3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.
- R and R ⁇ each have the same meaning as R2 and R3, X ⁇ have the same meaning as X;
- Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic group, an alkyl group or M represents a divalent metal atom;
- R ⁇ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including those condensed with an unsaturated ring of 5 or 6 members) or an amino group; and
- n1 to n6 and m1 to m5 each represent an integer of 1 to 6.
- B represents an alkylene group having 1 to 6 carbon atoms
- Y represents -N ⁇ or -CH ⁇
- R4 and R5 each have the same meaning as R2 and R3, provided that R4 and R5 each may represent -B-SZ, or R2 and R3, and R4 and R5 each may combine to form a ring.
- the compound represented by the above formula may include compounds of enol form and salts thereof.
- R6 and R7 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B1-S-Z1, provided that R6 and R7 may combine to form a ring.
- Y1 represents ⁇ N- or ⁇ CH-;
- B1 represents an alkylene group having 1 to 6 carbon atoms;
- Z1 represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, or and n7 represents an integer of 1 to 6.
- Ar represents a divalent arylene group or a divalent organic group comprising the combination of an aryl group with an oxygen and/or an alkylene group;
- B2 and B3 each represent a lower alkylene group;
- R8, R9, R10 and R11 each represent a hydroxyl-substituted lower alkyl group;
- x and y each represent 0 or 1.
- G ⁇ represents an anion; and
- z represents 0, 1 or 2.
- the bleaching accelerator may preferably added in an amount ranging from about 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.05 to 15 g, per liter of the bleach-fixing solution of this invention.
- the bleach-fixing solution of this invention can preferably be also applied in the low replenishment processing.
- iodide ions are accumulated in the bleach-fixing solution of this invention.
- the bleach-fixing solution of this invention may cause substantially no lowering of the desilvering performance even by the accumulation of iodide ions, but also it may hardly cause surprisingly any density increase at a non-image portion (the so-called fogging) also when a light-sensitive material is dipped in the bleach-fixing solution without taking the step of rinsing such as washing with water after color developing processing.
- the iodide ions may preferably be contained in the bleach-fixing solution in an amount of not less than 0.0005 mol/lit. More preferably, it may preferably contained in the bleached-fixing solution in an amount of not less than 0.001 mol/lit.
- the processing time when using the bleach-fixing solution of this invention may be not longer than 3 minutes and 30 seconds without any problems, but may preferably be not longer than 3 minutes, more preferably in 2 minutes and 30 seconds.
- the bleach-fixing solution of this invention may be used at a temperature of 80°C or less, desirably 55°C or less, and most preferably 45°C or less. It can also desirably be used while suppressing evaporation or the like.
- the bleach-fixing solution of this invention can be applied in any light-sensitive silver halide photographic materials so long as they are light-sensitive photographic materials for photographing.
- they may preferably be light-sensitive materials employing a highly sensitive silver iodobromide emulsion having a silver iodide content of not less than 0.5 mol %, more preferably not less than 1 mol % per liter.
- the bleach-fixing solution of this invention may be used as a processing solution for bleach-fixing immediately after the color developing of the above light-sensitive silver halide photographic material for photographing, or, alternatively, used as a bleach-fixing solution after the color developing and after the processing such as washing, rinsing or stopping, or further may be used as a bleach-fixing solution after the pre-fixing was carried out after the color developing.
- the processing by use of the bleach-fixing solution of this invention may be also followed by washing with water, and thereafter may be followed by stabilizing. It can be also applied in the multi-step counter current stabilizing technique in which the washing step is omitted or the amount of water for the washing is extremely reduced as disclosed in Japanese Unexamined Patent Publication No.
- the silver halide emulsion for photographing that can be applied in this invention can be chemically sensitized according to a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.
- An antifoggant, a stabilizer and so forth can be added in the silver halide emulsion.
- a binder for the emulsion gelatin can be used advantageously.
- Emulsion layers and other hydrophilic colloid layers can be hardened, and also can contain a plasticizer, a dispersion of a water-soluble or slightly soluble synthetic polymer (i.e., latex).
- Couplers can be used in the emulsion layers of a light-sensitive color photographic material.
- a compound capable of releasing photographically useful fragments such as development accelerators, bleaching accelerators, developers, silver halide solvents, color torning agents, hardening agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers through the coupling with a colored coupler, a competing coupler and an oxidized product of a developing agent.
- the light-sensitive material can be provided with auxiliary layers such as a filter layer, a halation-preventive layer and an irradiation-preventive layer. These layers and/or emulsion layers may also contain a dye that may flow out from the light-sensitive material or may be bleached during development processing.
- a matte agent, a lubricant, an image-stabilizing agent, a surface active agent, a color fog preventive agent, a development accelerator, a development retarder or a bleaching accelerator may be added in the light-sensitive material.
- a support there can be used paper laminated with polyethylene or the like, a polyethylene terephthalate film, baryta paper, cellulose triacetate, etc.
- a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 88 mg per 100 cm2.
- the above emulsion layers comprised silver iodobromide having a silver iodide mol % of about 4.3 %, and there were used the following (Y-1) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the following (M-1) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the following (C-1) as a cyan coupler in the red-sensitive silver halide emulsion layer.
- a sensitizing dye, a hardening agent and a spreading agent were added to the respective emulsion layers.
- a light-sensitive silver halide color negative materials thus prepared was used as a sample. Using samples obtained by cutting the above sample into pieces and subjected to wedge exposure according a conventional method, processing was carried out according to the following steps with use of a processing apparatus for pieces (hereinafter called "hand developing").
- the bleach-fixing solutions available after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm2/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution has an air contact area of 10 cm2 based on 1 liter of the bleach-fixing solution), and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
- the residual silver amount (mg/dm2) at the maximum density portion of the film samples was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
- bleach-fixing solutions Nos. 1-1 and 2-1 used in the above Experiment 1 the types of the preservatives in the bleach-fixing solutions and the concentration for the addition were changed as shown in Table 3 below and the pH was adjusted to 6.0, to prepare bleach-fixing solutions Nos. 9-1 to 9-3 and Nos. 10-1 to 10-3.
- the above bleach-fixing solutions the light-sensitive materials corresponding to those in Experiment 1 were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
- the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 3.
- the bleach-fixing solutions in which the organic acid which forms the comparative ferric complex salt and the preservative are used can delay the occurrence of precipitation to have good shelf stability even when stored with time, and also can achieve good desilvering performance and color reproduction performance of a dye image to be obtained by use of said solution.
- the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing the bisulfite addition compound of this invention can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
- the bleach-fixing solutions of this invention had no ammoniacal odor at all.
- Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 1.
- the bisulfite addition compound and exemplary compound No. II-4 in the bleach-fixing solutions were used in concentration of 0.25 mol/lit.
- the types of the bleaching agents were selected as shown in Table 4, and the concentration of the bleaching agents was varied as shown in Table 4.
- the pH of the bleach-fixing solutions was adjusted to 6.0
- bleach-fixing solutions of this invention particularly those having the content of bleaching agent in the range of 0.02 mol/lit. to 1.30 mol.lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with time.
- Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 1.
- the preservative in bleach-fixing solution No. 1-1 used in Experiment 1 of Example 1 was replaced by exemplary compound No. II-6 (concentration: 0.2 mol/lit), the bleaching agent and the amount thereof were changed as shown in Table 5, and the concentration of KI in the bleach-fixing solutions was varied as shown in Table 5
- the pH of the bleach-fixing solutions was adjusted to 6.0.
- the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
- D R1 transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
- the difference between D R1 and D R2 was determined ( ⁇ D R ) to evaluate the magenta stain.
- Bleach-fixing solutions Nos. 1-11 to 1-16 and Nos. 2-21 to 2-26 were prepared in the same manner as in Experiment 1 of Example 1 except that, in the bleach-fixing solutions No. 1-1 and No. 2-1 prepared in Experiment 1 of Example 1, the pH was adjusted to 6.0 exemplary compound No. II-4 (concentration: 0.1 mol/lit.) was used as the preservative, and the bleaching accelerator was added as shown in Table 6 below.
- the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored.
- the bleach-fixing solutions outside this invention which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.
- a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 90 mg per 100 cm2.
- the above emulsion layers comprised silver iodobromide having silver iodide mol % of about 4.1 %, and there were used the above (Y-l) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the above (M-l) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the above (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer.
- conventional additives such as a sensitizing dye, a hardening agent and a spreading agent were added.
- a light-sensitive silver halide color negative materials thus prepared was used as a sample.
- the bleach-fixing solutions after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm2/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution have an air contact area of 10 cm2 based on 1 liter of the bleach-fixing solution), and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
- the residual silver amount (mg/dm2) at the maximum density portion of the film samples was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
- Exemplary vinyl pyrrolidone polymer (2) in bleach-fixing solution No. 13 used in the above Experiment 1 was changed for a control, exemplary vinyl pyrrolidone polymers Nos. (1), (3) and (5), repsectively, and the pH was adjusted to 6.0, to prepare bleach-fixing solutions Nos. 16-1 to 16-5.
- Light-sensitive materials corresponding to those in Experiment 1 and employing the above bleach-fixing solutions were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
- the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 9.
- the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing polyvinyl pyrrolidone of this invention can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
- the bleach-fixing solutions of this invention had no ammoniacal odor at all.
- Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 5.
- the ammonium sulfite concentration in the bleach-fixing solutions was controlled to 12 g/lit.
- the types of the bleaching agents were selected as shown in Table 10, and the concentration of the bleaching agents was varied as shown in Table 10.
- the pH of the bleach-fixing solutions was adjusted to 6.0.
- bleach-fixing solutions of this invention particularly those having the content of bleaching agent in the range of 0.02 mol/lit, to 1.30 mol/lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with a time.
- Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 5.
- the bleaching agent in bleach-fixing solution No. 11-1 used in Experiment 1 of Example 5 as the bleach-fixing solution and the amount thereof were changed as shown in Table 11, and the concentration of KI in the bleach-fixing solutions was varied as shown in Table 11.
- the pH of the bleach-fixing solutions was adjusted to 6.0.
- the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
- D R1 transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
- the different between D R1 and D R2 was determined ( ⁇ D R ) to evaluate the magenta stain.
- Bleach-fixing solutions Nos. 11-11 to 11-16 and Nos. 13-32 to 13-37 were prepared in the same manner as in Experiment 1 of Example 5 except that, in the bleach-fixing solutions Nos. 11-1 and No. 13-1 prepared in Experiment 1 of Example 5, the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 12 below.
- the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored.
- the bleach-fixing solutions outside this invention which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.
- a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 93 mg per 100 cm2.
- the above emulsion layers comprised silver iodobromide having silver iodide mol % of about 5.0 %, and there were used the above (Y-l) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the above (M-l) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the above (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer.
- a sensitizing dye, a hardening agent and a spreading agent were added to the respective emulsion layers.
- a light-sensitive silver halide color negative materials thus prepared was used as a sample.
- the bleach-fixing solutions available after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm2/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution have an air contact area of 10 cm2 based in 1 liter of the bleach-fixing solution, and the above processing was again repeated with use of the bleach-fixing solutions available after storage.
- the residual silver amount (mg/dm2) at the maximum density portion of the film samples was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
- the concentration and combination of the ferric complex salt comprising the organic acid in bleach-fixing solution No. 19 used in the above Experiment 1 was varied as shown in Table 15 below to prepare bleach-fixing solutions Nos. 22-1 to 24-10.
- the light-sensitive materials corresponding to those in Experiment 1 were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1.
- the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 15.
- the bleach-fixing solutions according to this invention in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing a ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas of General Formulas (IV) to (VII) can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability.
- the bleach-fixing solutions of this invention had no ammoniacal odor at all.
- bleach-fixing solutions of this invention particularly those having the content of bleaching agent in the range of 0.02 mol/lit. to 1.30 mol/lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with time.
- the samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as D R1 .
- D R1 transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as D R2 .
- the difference between D R1 and D R2 was determined ( ⁇ D R ) to evaluate the magenta stain. Results obtained are shown together in Table 19.
- Bleach-fixing solutions Nos. 17-21 to 17-26 and Nos. 19-31 to 19-36 were prepared in the same manner as in Experiment 1 of Example 9 except that, in bleach-fixing solutions No. 17-1 and No. 19-1 prepared in Experiment 1 of Example 9, the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 20 below.
- the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored, even if the bleach-fixing time is shortened.
- the bleach-fixing solutions outside this invention which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.
Description
- This invention relates to a bleach-fixing solution, and particularly to a bleach-fixing solution that can achieve rapid processing when applied in a light-sensitive material for photographing.
- At present, the desilvering of light-sensitive materials for photographing in which a highly sensitive silver iodobromide-rich emulsion is used is carried out separately in a bleaching step and a fixing step.
- In an attempt to achieve a simple and rapid desilvering of the above light-sensitive materials for photographing, the present inventors have made studies on a bleach-fixing system in which the bleaching and fixing are carried out in a monobath.
- In the course of that studies, as it has been conventionally considered advantageous for the above bleach-fixing solution to be used in a higher pH range from viewpoints of the shelf stability of a solution and the inferior color reproduction that may occur on a resulting dye image, researches were made for a bleaching agent that can have a good desilvering ability in such a high pH range. As a result, the present inventors have proposed that, among various aminopolycarboxylic acid iron complexes, a diethylenetriaminepentaacetic acid ferric complex salt (hereinafter "DTPA·Fe complex salt") can satisfy the desilvering speed, the color reproduction of a resulting color image and the shelf stability with time, of a bleach-fixing solution (Japanese Unexamined Patent Publications No. 134238/1985, No. 130738/1985, No. 136744/1985, etc.).
- The above DTPA·Fe complex salt can satisfy the above properties when used in the higher pH range, specifically, at about pH 7 to 9. However, ammonia gas may be readily generated when used in such a pH range, so that there has been a problem undesirable from a viewpoint of the work environment if the developing is carried out in a small room. In addition, with lapse of time when a lightsensitive material is processed over a long period of time, it has become clearer that there may occur a lowering of the desilvering ability and an inferiority in the color reproduction that are considered to be caused by the accumulation of ferrous ions in a bleach-fixing solution.
- As a result of detailed studies on the above disadvantages, it was found that the accumulation of ferrous ions largely depends on the pH of the bleach-fixing solution, and, at the pH more than a certain value, this is a problem that may commonly occur in the aminopolycarboxylic acid iron complex salts usually used as a bleaching agent, with lapse of time when processing is carried out.
-
- EP-A-0 173 540 discloses a color forming method using a light-sensitive silver halide color photographic material having red, green and blue sensitive layers with a total thickness of 25 microns or less. The method involves involves inagewise exposure folllowed by color development in the presence of a dye forming coupler. The silver is removed from the developed material using a bleach-fixing solution. The bleach-fixing solution may contain one or more organic acid ferric complexes such as ethylamine diamine tetraacetic acid and 1,2-diaminopropane tetraacetic acid.
- The present inventors have continued further studies to find, as a result, that the lowering of the desilvering ability and the inferiority in the color reproduction that are considered to be caused by the above-mentioned accumulation of ferrous ions can be solved at the same time and the problem of the generation of ammonia gas can be solved by using a bleach-fixing solution having the pH aminopolycarboxylic ferric complex salt.
- The present inventors have also made further studies to find the facts as shown below, thus accomplishing this invention.
- It became clear that, when the bleach-fixing solution is put into practical use, a particular preservative may be used in not less than a particular amount, whereby the shelf stability with time of the bleach-fixing solution can be advantageously prevented from being deteriorated at the time of continuous processing without adversely affecting the effect of improving the above problems.
- It was also found that although conventional bleach-fixing solution using sulfite in a lower concentration have caused precipitation in a relatively shorter time by storage, at least one of the compounds selected from the compounds represented respectively by General Formulas (II) and (III) of this invention as described below may be used, so that the precipitation can be made not to be readily caused and the shelf stability can be improved.
- Some compounds of the compounds represented respectively by General Formulas (II) and (III) of this invention are known to be used in a bleach-fixing solution containing an ethylenediaminetetraacetic acid iron (III) complex (hereinafter "EDTA·Fe) as a bleaching agent, as disclosed, for example, in Japanese Publication No. 39985/1979/ However, it was revealed that such compounds may gradually release sulfite ions when used in the bleach-fixing solution containing the above EDTA·Fe, so that aldehydes or ketones may be accumulated and the desilvering speed may be gradually lowered.
- In contrast thereto, it was revealed that a particular aminopolycarboxylic acid iron complex salt may be used in a bleach-fixing solution used in a particular lower pH range, whereby the shelf stability can be particularly remarkably improved without lowering the good desilvering and color reproduction performances possessed by the bleach-fixing solution.
- It was also found that a particular polyvinyl pyrrolidone may be used when the bleach-fixing solution is put into practical use, whereby it becomes possible to delay the occurrence of the precipitation of silver sulfide during storage with time, without adversely affecting the effect of improving the aforesaid problems, and also it becomes possible to improve the bleach stain at a non-image portion that may be readily generated when the bleach-fixing solution is used in the processing with low replenishment. This invention has thus been accomplished.
- Accordingly, a first object of this invention is to provide a bleach-fixing solution made feasible for rapid processing of a light-sensitive photographic material for photographing.
- A second object of this invention is to provide a bleach-fixing solution free from generation of ammonia gas and desirable from the viewpoint of work environment.
- A third object of this invention is further to provide a bleach-fixing solution that can delay the occurrence of the precipitation even during storage with time to attain a stable bleach-fixing performance.
- A fourth object of this invention is to provide a bleach-fixing solution that can improve the bleach stain at a non-image portion of a light-sensitive material when the processing with low replenishment is carried out.
- The above objects of this invention can be achieved by a bleach-fix solution for processing a light-sensitive silver halide photographic material for photographing, wherein said solution has a pH ranging from between 3.0 to 6.8, contains a ferric complex salt having a ligand comprising a compound represented by the Formulas I-1 and I-2 shown below, and further contains at least one of;
- (i) at least one of the compounds represented respectively by General Formula (II) and General Formula (III) shown below;
- (ii) a water-soluble polymer having a unit of pyrrolidone nucleus in the molecular structure; and
- (iii) a ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII),
-
-
-
-
-
wherein R₃ and R₄ each represent a hydrogen atom, a hydroxyl-substituted alkyl group having 1 to 3 carbon atoms, or a carboxyl-substituted alkyl group having 1 or 2 carbon atoms; R₅ and R₆ each represent a hydrogen atom or a hydroxyl-substituted phenyl group; R₇, R₈, R₉ and R₁₀ each represent a hydrogen atom or a hydroxyl-substituted alkyl group having 1 to 3 carbon atoms, provided that R₇, R₈, R₉ and R₁₀ each may combine to form a ring having 5 to 8 carbon atoms; n₁₀ and n₁₁ each represent an integer of 1 to 3; and n₁₂ represents an integer of 0 to 4, -
-
- The ferric complex salt having a ligand comprising the compound represented by the Formulas I-1 and I-2 may be used also in the form of a free acid (hydrogen salt), or may also be used in the form of a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amines, for example, triethanolamine. Preferably used are a potassium salt, a sodium salt and an ammonium salt. At least one of these ferric complex salts of this invention may be used, but two or more of these can also be used in combination. It is also possible to use them in combination with any ferric complex salts outside this invention.
- The ferric complex salt can be used in any amount in the bleach-fixing solution of this invention so long as it is in an amount sufficient for obtaining the effect of this invention. However, overly high concentration of the ferric complex salt may cause the deterioration of shelf stability of the bleach-fixing solution, and, on the other hand, overly low concentration of the ferric complex salt may cause the deterioration of desilvering performance and color reproduction performance. Accordingly, it may be usually used preferably in the range of 0.02 to 1.30 mol/lit., more preferably 0.10 to 1.20 mol/lit. Particularly, the effect of this invention can be preferably exhibited when used in the range of 0.20 to 0.80 mol/lit.
- The bleach-fixing solution of this invention may be appropriately in the pH range of pH 3.0 to 6.8, because sulfite gas may be generated at less than pH 3.0 and the effect of this invention may be insufficient if the pH is higher than 6.8. It can be used at any pH so long as it is used in this pH range, but is preferably used at pH 4.0 to 6.7, particularly preferably H 5.0 to 6.5, taking account of the solubility of various iron salts at low temperature the odor of the sulfite gas generated from sulfite ions in addition to desilvering performance and color reproduction.
- The bleach-fixing solution of this invention may preferably contain a variety of sulfites therein, and these sulfites may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, etc.
- Embodiment i) of this invention will be described below.
- As embodiment i), at least one compound selected from the compounds represented respectively by General Formulas (II) and (III) (hereinafter referred to as the bisulfite addition compound of this compound) may be used as a preservative in the bleach-fixing solution of this invention.
- In General Formula (II), the alkyl group having 1 to 8 carbon atoms, represented respectively by R₂ and R₃, may preferably include an alkyl group having 1 to 4 carbon atoms.
- One of the preferred compounds included in the carbonyl bisulfite addition compound represented by General Formula (II) is a compound wherein R₂ is a hydrogen atom and R₃ is an alkyl group having 1 to 4 carbon atoms, and another of them is a compound wherein R₂ and R₃ each are in alkyl group having 1 to 4 carbon atoms.
- In General Formula (III), the alkyl group having 1 to 8 carbon atoms, represented respectively by R₄ and R₅, may preferably include an alkyl group having 1 or 2 carbon atoms.
- The symbol n, which represents an integer of 0 to 6, may preferably be an integer of 1 to 4.
- One of the preferred compounds included in the carbonyl bis-sulfite addition compound represented by General Formula (III) is a compound wherein R₄ and R₅ each are a hydrogen atom and n is an integer of 1 to 4. Another of them is a compound wherein R₄ and R₅ each are an alkyl group having 1 or 2 carbon atoms and n is an integer of 1 to 4.
- Specific examples of the bisulfite addition compound of this invention are shown below, but by no means limited to these.
- Exemplary bisulfite addition compounds:
- II-1 Sodium acetaldehyde bisulfite
- II-2 Sodium propionaldehyde bisulfite
- II-3 Sodium butylaldehyde bisulfite
- II-4 Sodium acetone bisulfite
- II-5 Sodium butanone bisulfite
- II-6 Sodium pentanone bisulfite
- III-1 Sodium succinaldehyde bisbisulfite
- III-2 Sodium glutalaldehyde bisbisulfite
- III-3 Sodium β-methylglutalaldehyde bisbisulfite
- III-4 Sodium maleic dialdehyde bisbisulfite
- III-5 Sodium 2,4-pentanedione bisbisulfite
- Embodiment ii) of this invention will be described below.
- It has been conventionally known in, for example, Japanese Patent Publication No. 38938/1975, etc. that polyvinyl pyrrolidone is used in a bleach-fixing solution for the purpose of maintaining the bleaching power in a long term storage. However, in the prior arts including these, there has been a disadvantage that the ethylenediamine-tetraacetic acid ferric complex salt conventionally having been frequently used as a bleaching agent of bleach-fixing solutions tends to cause, when used in the acidic range, a trouble of the color reproduction inferiority particularly with regard to light-sensitive materials for highly sensitive photographing which contains silver in a large amount. However, in this invention, where a particular aminopolycarboxylic acid ferric complex salt and polyvinyl pyrrolidone are used in combination in the bleach-fixing solution having the pH of 3 to 6.8, it was found that there is surprisingly no disadvantage of the color reproduction inferiority, and the precipitation of silver sulfide characteristically occurring in bleach-fixing solutions can be prevented from being occurred, and also the effect aimed at in this invention as mentioned above can be exhibited, thus accomplishing this invention.
- The polymer having a unit of a pyrrolidone nucleus in the molecular structure (hereinafter called "vinyl pyrrolidone polymer of this invention") will be described below.
- The vinyl pyrrolidone polymer of this invention may comprise either a homopolymer of vinyl pyrrolidone alone or a copolymer thereof with additional copolymerizable monomer(s), but it is required to be water-soluble as a polymer.
- The above additional monomer copolymerizable with vinyl pyrrolidone may typically include, for example, vinyl esters, acrylates, methacrylates, acrylic acids, methacrylic acid, styrene, etc. The vinyl esters may include for example, vinyl acetate, vinyl propionate, vinyl butyrate. The acrylic esters may include, for example, methyl ester, ethyl ester, butyl ester, 2-ethyl hexyl ester, etc. In the case of the copolymer of these, the copolymerization ratio may preferably be selected in the range of 5 to 100 mol % based on the vinyl pyrrolidone.
- There is no particular limitation in the average molecular weight of the vinyl pyrrolidone polymer of this invention, but it may preferably in the range of 500 to 800,000 more preferably 2,000 to 400,000
- The determination of the average molecular weight of the polymer can be carried out according to a usual method, for example, according to the following:
- Precisely 1,000 g of a polymer sample is weighed and introduced in a 100 ml messflask, to which distilled water is added to prepare a 1 % aqueous solution, and the viscosity of the aqueous solution and that of the water serving as a solvent are measured, respectively. There was utilized a Ubbelohde's capillary viscometer for the measurement of the viscosity. The viscometer holding the solution to be measured was hanged in a thermostat and kept to stand at 20°C ± 0.01°C for 30 minutes to measure gauges. An average value for several times was taken and a relative viscosity was calculated from the relation represented by the following formula:
Based on the relative viscosity, the value K is determined according to Fikentscher's viscosity formula (see Physikalische U. Technologische Prüfungsverfahren fur Lacke und ihre Rohstoffe, 1953 Edit.), and the average molecular weight is determined from the value K according to a usual method. - Typical examples of the vinyl pyrrolidone polymer of this invention are shown below, but by no means limited to these.
-
- (1) Polyvinyl pyrrolidone (average molecular weight: about 40,000)
- (2) Polyvinyl pyrrolidone (average molecular weight: about 9,000)
- (3) Polyvinyl pyrrolidone (average molecular weight: about 16,000
- (4) Vinyl pyrrolidone/vinyl acetate copolymer
(copolymerization molar ratio: 7:3)
(average molecular weight: 4,000) - (5) Vinyl pyrrolidone/methyl acrylate copolymer
(copolymerization molar ratio: 7:3)
(average molecular weight: 1,000) - (6) Vinyl pyrrolidone/ethyl acrylate copolymer
(copolymerization molar ratio: 7:3)
(average molecular weight: 25,000) - (7) Vinyl pyrrolidone/butyl acrylate copolymer
(copolymerization molar ratio: 7:3)
(average molecular weight: 7,000) - (8) Vinyl pyrrolidone/2-ethyl hexyl acrylate copolymer
(copolymerization molar ratio: 7:3)
(average molecular weight: 18,000) - (9) Vinyl pyrrolidone/styrene copolymer
(copolymerization molar ratio: 1:3)
(average molecular weight: 20,000) - The amount for the addition of the above vinyl pyrrolidone polymer of this invention may vary depending on the type of the polymer, the polymerization degree and so forth, but approximately may preferably in the range of 0.1 to 100 g, more preferably 0.2 to 50 g, still more preferably 0.3 to 20 g, and particularly preferably 0.5 to 10 g, per liter of the bleach-fixing solution of this invention.
- The vinyl pyrrolidone polymer of this invention may be added in the bleach-fixing solution by, for example, adding it directly as it is in the form of powder, or may be added by dissolving it in a solvent such as water.
- In embodiment (ii) of this invention, the above vinyl pyrrolidone polymer of this invention may be more preferably used for the purpose of better improving the shelf stability of the bleach-fixing solution, when a sulfite or a sulfite-releasable compound (for example, carbonyl bisulfite addition compounds disclosed in Japanese Patent Publication No. 38895/1979) is used in combination with it.
- In this embodiment ii), the sulfite or the sulfite-releasable compound may preferably be contained in an amount of 1 x 10⁻³ mol or more per liter of the bleach-fixing solution of this invention. It may be used more preferably in an amount of not less than 0.02 mol and not more than 2.0 mols, still more preferably not less than 0.05 mol and not more than 1.3 mols, and most preferably not less than 0.09 mol and not more than 0.9 mol.
- The above sulfite may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, etc.
- Embodiment iii) of this invention will be described below.
- Preferred examples of the compounds represented respectively by General Formulas (IV) to (VII), used in embodiment iii) are shown below.
-
The ferric complex salt having a ligand Comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) may be used also in the form of a free acid (hydrogen salt), or may also be used in the form of a counter salt including alkali metal salts such as a sodium salt, a potassium salt and a lithium salt or an ammonium salt, or water soluble amine salts, for example, triethanolamine salt, etc. Preferably used are a potassium salt, a sodium salt and an ammonium salt. - In the bleach-fixing solution of the present embodiment, where the ferric complex salt having a ligand comprising the compound represented by Formulas I-1 and I-2 and ferric complex salt having a ligand comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) of this invention are used, the latter ferric complex salt may preferably be in the range of 1 mol % to 95 mol %, more preferably 5 mol % to 90 mol %, and most preferably 10 mol % to 80 mol %, based on the total amount of these.
- In this invention, most effective from a viewpoint of overall performances for the desilvering, color reproduction and shelf stability is the combination of the compound represented by Formulas I-1 and I-2 with the compound VI-3 or VI-7. Particularly effective is the combination of I-1 with VI-7 or the combination of I-2 with VI-7.
- The ferric complex salt having a ligand comprising the compound represented by Formulas I-1 and I-2 and that having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) of this invention can be used in any amount in the bleach-fixing solution of this invention so long as it is in an amount sufficient for obtaining the effect of this invention. However, overly high concentration of the ferric complex salt may cause the deterioration of shelf stability of the bleach-fixing solution, and, on the other hand, overly low concentration of the ferric complex salt may cause the deterioration of desilvering performance and color reproduction performance. Accordingly, it may be usually used preferably in the range of 0.02 to 1.30 mol/lit., more preferably 0.10 to 1.20 mol/lit., in the total amount of them. Particularly, the effect of this invention can be preferably exhibited when used in the range of 0.20 to 0.80 mol/lit.
- In the present embodiment, there can be found a feature in that the ferric complex salt having a ligand comprising the compound represented by General Formula (I) and ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) of this invention are used in combination, so that the shelf stability can be improved while maintaining the good desilvering and color reproduction performances inherent in the bleach-fixing solution of this invention.
- In general, it is known to use several kinds of bleaching agents in combination in order to improve various performances. For example, Research Disclosure No. 24023 (April, 1984) discloses a technique in which several kinds of bleaching agents are added by mixing them in a bleaching solution for the purpose of improving the color reproduction inferiority, stain and air oxidation rate.
- However, the fact has been unknown at all that the shelf stability of the bleach-fixing solution of this invention can be remarkably improved by adding the ferric complex salt having a ligand comprising at least one of the compounds represented respectively by General Formulas (IV) to (VII) to ferric complex salt having a ligand comprising the compound represented by Formulas I-1 and I-2. Also, this is a surprising fact that can not be obvious, considering that there can be no effect of improving the shelf stability even with use of the bleach-fixing solution having the composition of this invention if the pH is outside the range of this invention, and that there can be no effect of improving the shelf stability even with the pH inside the range of this invention if the combination comprises bleaching agents other than those of this invention.
- The bleach-fixing solution of the present embodiment may preferably contain a sulfite and/or a sulfite-releasable compound in order to further improve the shelf stability. Such compounds may include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite, sodium metabisulfite, formaldehyde bisulfite addition compounds, etc.
- These compounds may be used in an amount of 0.001 mol to 2.0 mols, preferably 0.001 mol to 1.3 mols, most preferably 0.01 mol to 0.9 mol, per liter of the bleach-fixing solution of this invention.
- The silver halide fixing agent to be contained in the bleach-fixing solution of this invention may include a compound capable of forming a water-soluble complex salt through the reaction with the silver halide used in usual fixing, typically including, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thioureas, thioethers, highly concentrated bromides, iodides, etc. These fixing agents can be used in an amount of not less than 5 g/lit., preferably not less than 50 g/lit., or more preferably not less than 70 g/lit. and in the amount of the range they can be dissolved.
- The bleach-fixing solution of this invention may contain various additives. Preferably contained as the additives are alkali halides or ammonium halides, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc.
- The bleach-fixing solution of this invention may contain, alone or in combination of two or more of, pH buffering agents including boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium, carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It may further contain every kind of brightening agents, anti-foaming agents, surface active agents and mildewproofing agents. It may also appropriately contain organic chelating agents such as acetyl acetone, phosphonocarboxylic acid, pholyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, stabilizers such as nitroalcohol and nitrate, solubilizing agents such as alkanolamine, anti-stain agents such as organic amine, other additives, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide.
- A bleach accelerator may preferably be used in the bleach-fixing solution of this invention. For example, there can be used the compounds described in Japanese Unexamined Patent Publication No. 19851/1987, and, to exhibit the effect of this invention with good results, the compounds represented respectively by General Formulas (A-I) to (A-Iv) shown below.
-
In the formula Q₁ represents a group of atoms necessary for the formation of a nitrogen-containing heterocyclic ring (including those condensed with a saturated or unsaturated ring of 5 or 6 members); R₁ represents a hydrogen atom, an alkali metal atom,
or an alkyl group, provided that Qʹ have the same meaning as defined for Q₁. -
In the formula, R₂ and R₃ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group. A represents a group of;
-SZ
or a heterocyclic residual group with a valence of n₁ (including those condensed with an unsaturated ring of 5 or 6 members); and X represents =S, =O or =NRʺ. Here R and Rʹ each have the same meaning as R₂ and R₃, Xʹ have the same meaning as X; Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic group, an alkyl group or
M represents a divalent metal atom;
Rʺ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including those condensed with an unsaturated ring of 5 or 6 members) or an amino group; and n₁ to n₆ and m₁ to m₅ each represent an integer of 1 to 6. B represents an alkylene group having 1 to 6 carbon atoms; Y represents -N〈 or -CH〈, R₄ and R₅ each have the same meaning as R₂ and R₃, provided that R₄ and R₅ each may represent -B-SZ, or R₂ and R₃, and R₄ and R₅ each may combine to form a ring. - The compound represented by the above formula may include compounds of enol form and salts thereof.
-
In the formula, R₆ and R₇ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B₁-S-Z₁, provided that R₆ and R₇ may combine to form a ring. Y₁ represents 〉N- or 〉CH-; B₁ represents an alkylene group having 1 to 6 carbon atoms; Z₁ represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residual group, or
and n₇ represents an integer of 1 to 6. -
In the formula, Ar represents a divalent arylene group or a divalent organic group comprising the combination of an aryl group with an oxygen and/or an alkylene group; B₂ and B₃ each represent a lower alkylene group; R₈, R₉, R₁₀ and R₁₁ each represent a hydroxyl-substituted lower alkyl group; and x and y each represent 0 or 1. Gʹ represents an anion; and z represents 0, 1 or 2. - Specific examples of the bleaching accelerators preferably usable in this invention are shown below.
-
- Recent years, a low replenishment processing is carried out for the purposes of decreasing an environmental load and decreasing the cost for processing solutions. The bleach-fixing solution of this invention can preferably be also applied in the low replenishment processing. Here, it is expected that iodide ions are accumulated in the bleach-fixing solution of this invention. Although the accumulation of iodide ions is conventionally known to bring about a lowering of the desilvering speed, it became clear that not only the bleach-fixing solution of this invention may cause substantially no lowering of the desilvering performance even by the accumulation of iodide ions, but also it may hardly cause surprisingly any density increase at a non-image portion (the so-called fogging) also when a light-sensitive material is dipped in the bleach-fixing solution without taking the step of rinsing such as washing with water after color developing processing.
- In this occasion, the iodide ions may preferably be contained in the bleach-fixing solution in an amount of not less than 0.0005 mol/lit. More preferably, it may preferably contained in the bleached-fixing solution in an amount of not less than 0.001 mol/lit.
- The processing time when using the bleach-fixing solution of this invention may be not longer than 3 minutes and 30 seconds without any problems, but may preferably be not longer than 3 minutes, more preferably in 2 minutes and 30 seconds.
- The bleach-fixing solution of this invention may be used at a temperature of 80°C or less, desirably 55°C or less, and most preferably 45°C or less. It can also desirably be used while suppressing evaporation or the like.
- The bleach-fixing solution of this invention can be applied in any light-sensitive silver halide photographic materials so long as they are light-sensitive photographic materials for photographing. Specifically, they may preferably be light-sensitive materials employing a highly sensitive silver iodobromide emulsion having a silver iodide content of not less than 0.5 mol %, more preferably not less than 1 mol % per liter.
- The bleach-fixing solution of this invention may be used as a processing solution for bleach-fixing immediately after the color developing of the above light-sensitive silver halide photographic material for photographing, or, alternatively, used as a bleach-fixing solution after the color developing and after the processing such as washing, rinsing or stopping, or further may be used as a bleach-fixing solution after the pre-fixing was carried out after the color developing. The processing by use of the bleach-fixing solution of this invention may be also followed by washing with water, and thereafter may be followed by stabilizing. It can be also applied in the multi-step counter current stabilizing technique in which the washing step is omitted or the amount of water for the washing is extremely reduced as disclosed in Japanese Unexamined Patent Publication No. 8543/1982 or the processing technique in which a washing-substitutive processing solution is used as disclosed in Japanese Unexamined Patent Publication No. 14834/1983. If necessary, in addition to the steps such as color developing, bleach-fixing and washing, there can be also added various auxiliary steps such as hardening, neutralizing, black and white developing, reversing, and washing with a small amount of water.
- The silver halide emulsion for photographing that can be applied in this invention can be chemically sensitized according to a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.
- An antifoggant, a stabilizer and so forth can be added in the silver halide emulsion. As a binder for the emulsion, gelatin can be used advantageously.
- Emulsion layers and other hydrophilic colloid layers can be hardened, and also can contain a plasticizer, a dispersion of a water-soluble or slightly soluble synthetic polymer (i.e., latex).
- Couplers can be used in the emulsion layers of a light-sensitive color photographic material.
- There can be also used a compound capable of releasing photographically useful fragments such as development accelerators, bleaching accelerators, developers, silver halide solvents, color torning agents, hardening agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers through the coupling with a colored coupler, a competing coupler and an oxidized product of a developing agent.
- The light-sensitive material can be provided with auxiliary layers such as a filter layer, a halation-preventive layer and an irradiation-preventive layer. These layers and/or emulsion layers may also contain a dye that may flow out from the light-sensitive material or may be bleached during development processing.
- A matte agent, a lubricant, an image-stabilizing agent, a surface active agent, a color fog preventive agent, a development accelerator, a development retarder or a bleaching accelerator may be added in the light-sensitive material.
- As a support, there can be used paper laminated with polyethylene or the like, a polyethylene terephthalate film, baryta paper, cellulose triacetate, etc.
- Details of this invention will be described below by Examples, but the embodiment of this invention are by no means limited by these.
- On a triacetate film support, a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 88 mg per 100 cm². The above emulsion layers comprised silver iodobromide having a silver iodide mol % of about 4.3 %, and there were used the following (Y-1) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the following (M-1) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the following (C-1) as a cyan coupler in the red-sensitive silver halide emulsion layer. To the respective emulsion layers, a sensitizing dye, a hardening agent and a spreading agent were added. A light-sensitive silver halide color negative materials thus prepared was used as a sample.
Using samples obtained by cutting the above sample into pieces and subjected to wedge exposure according a conventional method, processing was carried out according to the following steps with use of a processing apparatus for pieces (hereinafter called "hand developing"). - As for the color developing solution, bleach-fixing solution and stabilizing solution, the solutions as shown below were used.
[Color developing solution] Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 5.0 g Sodium bromide 1.2 g Potassium iodide 2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g Sodium diethylenetriaminepentaacetate 2.0 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoamiline sulfate 4.5 g Potassium hydroxide 1.2 g Made up to 1 liter by adding water, and adjusted to pH 10.06 with use of sodium hydroxide or 20 % sulfuric acid. [Bleach-fixing solution] Ferric ammonium complex salt of organic acid as shown in Table 1 0.25 mol Ammonium thiosulfate (a 70 % solution) 300 ml Preservative shown in Table 1 Amount shown in Table 1 Silver powder 2.0 g Made up to 1 liter in total amount by adding water, and adjusted the pH as shown in Table 1 with use of acetic acid and ammonia water. [Stablizing solution] Formalin (a 37 % aqueous solution) 2 ml Conidax (produced by Konishiroku Photo Industry Co., Ltd.) 5 ml Made up to 1 liter by adding water. - The bleach-fixing solutions available after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm²/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution has an air contact area of 10 cm² based on 1 liter of the bleach-fixing solution), and the above processing was again repeated with use of the bleach-fixing solutions available after storage. After the processing, the residual silver amount (mg/dm²) at the maximum density portion of the film samples (the respective samples available before and after the storage with time, of the bleach-fixing solutions) was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
-
- It is understood from the above Table 2 that in the case the bleach-fixing solutions with pH range of 3.0 to 6.8 are used with use of the organic acid ferric complex salt according to this invention, there is seen only small residual silver and good color reproduction percentage regardless of whether the solutions were stored with time. In particular, good results are obtained when the pH is 4.0 to 6.7, and particularly good results are obtained when the pH is 5.0 to 6.5.
- However, according to the comparative bleach-fixing solutions employing a comparative EDTA as the organic acid result in insufficient desilvering performance and color reproduction performance regardless of whether the solutions were stored with time.
- Similar effect was confirmed also when exemplary compounds Nos. II-1 and III-1 used as preservatives in the above bleach-fixing solutions Nos. 1-1 to 8-9 are replaced by II-2 to II-6 and III-2 to III-5, respectively.
- In bleach-fixing solutions Nos. 1-1 and 2-1 used in the above Experiment 1, the types of the preservatives in the bleach-fixing solutions and the concentration for the addition were changed as shown in Table 3 below and the pH was adjusted to 6.0, to prepare bleach-fixing solutions Nos. 9-1 to 9-3 and Nos. 10-1 to 10-3. Using the above bleach-fixing solutions, the light-sensitive materials corresponding to those in Experiment 1 were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1. Using the bleach-fixing solutions stored with time, the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 3.
- Also, after storage for 1 week, the storage was further continued under the open ratio of 10 times to visually observe the days elapsing before the precipitation occurred.
-
- As will be clear from Table 3, it is understood that, in contrast to the comparative bleach-fixing solutions in which the organic acid which forms the comparative ferric complex salt and the preservative are used, the bleach-fixing solutions in which the organic acid which forms the ferric complex salt of this invention and the bisulfite addition compound are used can delay the occurrence of precipitation to have good shelf stability even when stored with time, and also can achieve good desilvering performance and color reproduction performance of a dye image to be obtained by use of said solution.
- It is seen from the results in the above Experiment 1 and Experiment 2 that the bleach-fixing solutions according to this invention, in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing the bisulfite addition compound of this invention can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability. In addition, the bleach-fixing solutions of this invention had no ammoniacal odor at all.
- Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 1. Here, however, the bisulfite addition compound and exemplary compound No. II-4 in the bleach-fixing solutions were used in concentration of 0.25 mol/lit., the types of the bleaching agents were selected as shown in Table 4, and the concentration of the bleaching agents was varied as shown in Table 4. The pH of the bleach-fixing solutions was adjusted to 6.0
- After storage with time, the same evaluation as in Experiment 1 of Example 1 was carried out. Results are shown in Table 4.
-
- As will be clear from Table 4, among the bleach-fixing solutions of this invention, particularly those having the content of bleaching agent in the range of 0.02 mol/lit. to 1.30 mol.lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with time.
- Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 1. Here, however, as the preservative in the bleach-fixing solutions, the preservative in bleach-fixing solution No. 1-1 used in Experiment 1 of Example 1 was replaced by exemplary compound No. II-6 (concentration: 0.2 mol/lit), the bleaching agent and the amount thereof were changed as shown in Table 5, and the concentration of KI in the bleach-fixing solutions was varied as shown in Table 5 The pH of the bleach-fixing solutions was adjusted to 6.0.
- After storage with time, evaluation on the desilvering performance was carried out in the same manner as in Experiment 1 of Example 1. Results obtained as shown in Table 5.
- The samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as DR1. Next, after color developing was carried out in the same manner as in Experiment 1 of Example 1, the transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as DR2. The difference between DR1 and DR2 was determined (ΔDR) to evaluate the magenta stain.
- As will be clear from Table 5, in the comparative bleach-fixing solutions, the addition of KI can make small the magenta stain, but the desilvering performance is greatly lowered. However, in the bleach-fixing solutions of this invention, not only the addition of KI can suppress the magenta stain to a lower level, but also the desilvering performance is only slightly lowered to obtain good results.
- Bleach-fixing solutions Nos. 1-11 to 1-16 and Nos. 2-21 to 2-26 were prepared in the same manner as in Experiment 1 of Example 1 except that, in the bleach-fixing solutions No. 1-1 and No. 2-1 prepared in Experiment 1 of Example 1, the pH was adjusted to 6.0 exemplary compound No. II-4 (concentration: 0.1 mol/lit.) was used as the preservative, and the bleaching accelerator was added as shown in Table 6 below.
- Using the bleach-fixing solutions thus obtained, evaluation was carried out in the same manner as in Experiment 1 an Experiment 2 of Example 1 except that the bleach-fixing time 4 minutes 20 seconds in Experiment 1 was set to 3 minutes 15 seconds.
-
- As will be clear from Table 6, in the case the bleach accelerator is added, the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored. In contrast thereto, the bleach-fixing solutions outside this invention, which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.
- On a triacetate film support, a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 90 mg per 100 cm². The above emulsion layers comprised silver iodobromide having silver iodide mol % of about 4.1 %, and there were used the above (Y-l) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the above (M-l) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the above (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer. To the respective emulsion layers, conventional additives such as a sensitizing dye, a hardening agent and a spreading agent were added. A light-sensitive silver halide color negative materials thus prepared was used as a sample.
-
- As for the color developing solution, bleach-fixing solution and stabilizing solution, the solutions as shown below were used.
[Color developing solution] Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 5.0 g Sodium bromide 1.2 g Potassium iodide 1.2 g Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g Sodium diethylenetriaminepentaacetate 2.0 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate 4.5 g Potassium hydroxide 1.2 g Made up to 1 liter by adding water, and adjusted to pH 10.06 with use of sodium hydroxide or 20 % sulfuric acid. [Bleach-fixing solution] Ferric ammonium complex salt of organic acid as shown in Table 7 0.25 mol Ammonium thiosulfate (a 70 % solution) 300 ml Ammonium sulfite 10 g Exemplary vinyl pyrrolidone polymer (2) 1.0 g Silver powder 2.0 g Made up to 1 liter in total amount by adding water, and adjusted the pH as shown in Table 7 with use of acetic acid and ammonia water. [Stablilizing solution] Formalin (a 37 % aqueous solution 2 ml Conidax (produced by Konishiroku Photo Industry Co., Ltd.) 5 ml Made up to 1 liter by adding water. - The bleach-fixing solutions after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm²/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution have an air contact area of 10 cm² based on 1 liter of the bleach-fixing solution), and the above processing was again repeated with use of the bleach-fixing solutions available after storage. After the processing, the residual silver amount (mg/dm²) at the maximum density portion of the film samples (the respective samples available before and after the storage with time, of the bleach-fixing solutions) was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photoelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
-
- It is understood from the above Table 8 that in the case the bleach-fixing solutions with pH range of 3.0 to 6.8 are used with use of the organic acid ferric complex salt according to this invention, there is seen only small residual silver and good color reproduction percentage regardless of whether the solutions were stored with time. In particular, good results are obtained when the pH is 4.0 to 6.7, and particularly good results are obtained when the pH is 5.0 to 6.5.
- However, according to the comparative bleach-fixing solutions employing a comparative DTPA as the organic acid, the desilvering performance and color reproduction performance, though very good before storage with time at pH 7 or 8, become insufficient after storage for 1 week. It is further understood that the employment of EDTA results in insufficient desilvering performance and color reproduction performance regardless of whether the solutions were stored with time.
- Exemplary vinyl pyrrolidone polymer (2) in bleach-fixing solution No. 13 used in the above Experiment 1 was changed for a control, exemplary vinyl pyrrolidone polymers Nos. (1), (3) and (5), repsectively, and the pH was adjusted to 6.0, to prepare bleach-fixing solutions Nos. 16-1 to 16-5. Light-sensitive materials corresponding to those in Experiment 1 and employing the above bleach-fixing solutions were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1. Using the bleach-fixing solutions stored with time, the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 9.
- Also, after storage for 1 week, the storage was further continued under the open ratio of 10 times to visually observe the days elapsing before the precipitation occurred.
-
- As will be clear from the above Table 8, it is understood that the employment of the vinyl pyrrolidone polymer according to this invention can not only greatly prolong the days elapsing before the precipitation occurs but also achieve good results for the residual silver amount and color reproduction performance.
- In addition, the tests same as in Experiment 2 were repeated except that exemplary vinyl pyrrolidone polymer (5) used in Experiment No. 5-55 of Experiment 2 was replaced by (7), (8), (9) and (4), respectively, to obtain substantially the same results as those for No. 5-55 of Experiment 2.
- It is seen from the results in the above Experiment 1 and Experiment 2 that the bleach-fixing solutions according to this invention, in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing polyvinyl pyrrolidone of this invention can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability. In addition, the bleach-fixing solutions of this invention had no ammoniacal odor at all.
- Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 5. Here, however, the ammonium sulfite concentration in the bleach-fixing solutions was controlled to 12 g/lit., the types of the bleaching agents were selected as shown in Table 10, and the concentration of the bleaching agents was varied as shown in Table 10. The pH of the bleach-fixing solutions was adjusted to 6.0.
- After storage with time, the same evaluation as in Experiment 1 of Example 5 was carried out. Results are shown in Table 10.
-
- As will be clear from Table 10, among the bleach-fixing solutions of this invention, particularly those having the content of bleaching agent in the range of 0.02 mol/lit, to 1.30 mol/lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with a time.
- Bleach-fixing solutions were stored with time in the same manner as in Experiment 1 of Example 5. Here, however, the bleaching agent in bleach-fixing solution No. 11-1 used in Experiment 1 of Example 5 as the bleach-fixing solution and the amount thereof were changed as shown in Table 11, and the concentration of KI in the bleach-fixing solutions was varied as shown in Table 11. The pH of the bleach-fixing solutions was adjusted to 6.0.
- After storage with time, evaluation on the desilvering performance was carried out in the same manner as in Experiment 1 of Example 5. Results obtained are shown in Table 11.
- The samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as DR1. Next, after color developing was carried out in the same manner as in Experiment 1 of Example 5, the transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as DR2. The different between DR1 and DR2 was determined (ΔDR) to evaluate the magenta stain.
- As will be clear from Table 11, in the comparative bleach-fixing solutions, the addition of KI can make small the magenta stain, but the desilvering performance is greatly lowered. However, in the bleach-fixing solutions of this invention, not only the addition of KI can suppress the magenta stain to a lower level, but also the desilvering performance is only slightly lowered to obtain good results.
- Bleach-fixing solutions Nos. 11-11 to 11-16 and Nos. 13-32 to 13-37 were prepared in the same manner as in Experiment 1 of Example 5 except that, in the bleach-fixing solutions Nos. 11-1 and No. 13-1 prepared in Experiment 1 of Example 5, the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 12 below.
- Using the bleach-fixing solutions thus obtained evaluation was carried out in the same manner as in Experiment 1 and Experiment 2 of Example 5 except that the bleach-fixing time 4 minutes 20 seconds in Experiment 1 was set to 3 minutes 15 seconds.
-
- As will be clear from Table 12, in the case the bleaching accelerator is added, the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored. In contrast thereto, the bleach-fixing solutions outside this invention, which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.
- On a triacetate film support, a halation-preventive layer and a gelatin layer were provided, and coated thereon were a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer so as to give a total silver amount of 93 mg per 100 cm². The above emulsion layers comprised silver iodobromide having silver iodide mol % of about 5.0 %, and there were used the above (Y-l) as a yellow coupler in the blue-sensitive silver halide emulsion layer, the above (M-l) as a magenta coupler in the green-sensitive silver halide emulsion layer, and the above (C-l) as a cyan coupler in the red-sensitive silver halide emulsion layer. To the respective emulsion layers, a sensitizing dye, a hardening agent and a spreading agent were added. A light-sensitive silver halide color negative materials thus prepared was used as a sample.
-
- As for the color developing solution, bleach-fixing solution and stabilizing solution, the solutions as shown below were used.
[Color developing solution] Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium hydrogencarbonate 5.0 g Sodium bromide 1.2 g Potassium iodide 2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g Sodium diethylenetriaminepentaacetate 2.0 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoamiline sulfate 4.5 g Potassium hydroxide 1.2 g Made up to 1 liter by adding water, and adjusted to pH 10.06 with use of sodium hydroxide or 20 % sulfuric acid. [Bleach-fixing solution] Ferric ammonium complex salt of organic acid as shown in Table 13 Amount as shown in Table 13 Ammonium thiosulfate (a 70 % solution) 300 ml Ammonium sulfite 5 g Silver powder 2.0 g Made up to 1 liter in total amount by adding water, and adjusted the pH as shown in Table 13 with use of acetic acid and ammonia water. [Stablizing solution] Formalin (a 37 % aqueous solution) 2 ml Conidax (produced by Konishiroku Photo Industry Co., Ltd. 5 ml Made up to 1 liter by adding water. - The bleach-fixing solutions available after the above processing were stored with time for 1 week at 38°C under the open ratio of 10 cm²/lit. (which is the open condition corresponding to that of usual automatic processing machine, and meant that the solution have an air contact area of 10 cm² based in 1 liter of the bleach-fixing solution, and the above processing was again repeated with use of the bleach-fixing solutions available after storage. After the processing, the residual silver amount (mg/dm²) at the maximum density portion of the film samples (the respective samples available before and after the storage with time, of the bleach-fixing solutions) was measured according to a fluorescent X-ray method, and the cyan dye density was further measured with use of Sakura Photelectric Densitometer PDA-65 (produced by Konishiroku Photo Industry Co., Ltd.) to determine the color reproduction percentage.
-
- It is understood from the above Table 14 that in the case the bleach-fixing solutions with pH range of 3.0 to 6.8 are used with combined use of the organic acid ferric complex salt according to this invention, there is seen only small residual silver and good color reproduction percentage regardless of whether the solutions were stored with time.
- The concentration and combination of the ferric complex salt comprising the organic acid in bleach-fixing solution No. 19 used in the above Experiment 1 was varied as shown in Table 15 below to prepare bleach-fixing solutions Nos. 22-1 to 24-10. Using the above bleach-fixing solutions, the light-sensitive materials corresponding to those in Experiment 1 were processed, and the resulting bleach-fixing solutions having been used for the processing were stored with time in the same manner as in Experiment 1. Using the bleach-fixing solutions stored with time, the desilvering performance and color reproduction performance were measured in the same manner as in Experiment 1 to obtain the results shown together in Table 15.
- Also, after storage for 1 week, the storage was further continued under the open ratio of 10 times to visually observe the days elapsing before the precipitation occurred.
-
- As will be clear from Table 15, it is understood that the combined use of the bleaching agents of General Formula (I) and of at least one selected from General Formulas (IV) to (VII) can achieve the effect of improving the shelf stability in the pH range of 3.0 to 6.8, and good results can be obtained particularly at pH 4.0 to pH 6.7, more particularly at pH 5.0 to 6.5.
- Using bleach-fixing solutions Nos. 19-4 and 20-4 used in Experiment 1, the experiments same as in Experiment 2 were repeated. Here, however, the concentration of the organic acid ferric complex salt and the organic acid ferric complex salt to be used in combination were varied as shown in Table 16, and the pH was adjusted to 6.0.
-
- As will be clear from Table 16, it is understood that only the combination of the organic acid ferric complex salts of this invention can show good desilvering performance, color reproduction performance and shelf stability. It is also understood that there can be exhibited higher effect of improving the shelf stability particularly in the combination of I-1 with VI-3 or VI-7, the combination of I-2 with VI-3 or VI-7, and the combination of I-3 with VI-3 or VI-7, and preferred are the combination of I-1 with VI-7 and the combination of I-2 with VI-7.
- Using bleach-fixing solution No. 19-4 used in Experiment 1, the tests same as in Experiment 2 were repeated. Here, however, the composition of the organic acid ferric complex salt was varied as shown in Table 17, and the pH was adjusted to 5.5
-
- As will be clear from Table 17, it is understood that substantially good results can be obtained when the ferric complex salt of organic acid VI-7 is used in the range of 1 mol % to 95 mol %, and goods results for all the desilvering, color reproduction and storage performances can be obtained particularly when it is used in the range of 5 mol % to 90 mol %, more particularly 10 mol % to 80 mol %.
- It is seen from the results in the above Experiment 1 to Experiment 4 that the bleach-fixing solutions according to this invention, in other words, the bleach-fixing solutions having the pH ranging between 3.0 and 6.8, containing a ferric complex salt having a ligand comprising a compound represented by General Formula (I), and further containing a ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas of General Formulas (IV) to (VII) can have a good desilvering performance particularly even after storage with time, can favorably prevent color reproduction inferiority from being occurred, and can have good shelf stability. In addition, the bleach-fixing solutions of this invention had no ammoniacal odor at all.
- Using bleach-fixing solutions Nos. 19-1 to 19-10, Nos. 20-1 to 20-10 and Nos. 21-1 to 21-10 employed in Experiment 1 of Example 9, the experiments same as in Experiment 2 of Example 9 were repeated. Here, however, the proportion of the two types of ferric complex salts used in combination was not changed, but the concentration of the ferric complex salt was varied as shown in Table 18, and the pH was adjusted to 5.0. Results obtained are shown together in Table 18.
- As will be clear from Table 18, among the bleach-fixing solutions of this invention, particularly those having the content of bleaching agent in the range of 0.02 mol/lit. to 1.30 mol/lit., preferably 0.10 to 1.20 mol/lit., and more preferably 0.20 to 0.8 mol/lit., are seen to be good bleach-fixing solutions that can have high desilvering and color reproduction performances and may not be sulfidized for a long period even if they are stored with time.
- Using bleach-fixing solutions Nos. 17-1, 19-4, 20-4 and 21-4 used in Experiment 1 of Example 9, the experiments same as in Experiment 1 of Example 9 were repeated. Here, however, the concentration of the ferric complex salt was controlled as shown in Table 19 below, and the pH of the bleach-fixing solutions was adjusted to 6.0.
- After storage with time, evaluation on the desilvering performance was carried out in the same manner as in Experiment 1 of Example 9. Results obtained are shown in Table 19.
- The samples having been processed were also subjected to bleaching and fixing according to the CNK-4 standard processing (color negative processing by Konishiroku Photo Industry Co., Ltd.), and, after the residual silver was perfectly removed by carrying out bleaching and fixing, transmission density of magenta dyes was measured. The value obtained was designated as DR1. Next, after color developing was carried out in the same manner as in Experiment 1 of Example 9, the transmission density of magenta dyes of the samples subjected to bleaching and fixing according to the CNK-4 standard processing was measured, and the resulting value was designated as DR2. The difference between DR1 and DR2 was determined (ΔDR) to evaluate the magenta stain. Results obtained are shown together in Table 19.
- As will be clear from Table 19, in the comparative bleach-fixing solutions, the addition of KI can make small the magenta stain, but the desilvering performance is greatly lowered. However, in the bleach-fixing solutions of this invention, not only the addition of KI can suppress the magenta stain to a lower level, but also the desilvering performance is only slightly lowered to obtain good results.
- Bleach-fixing solutions Nos. 17-21 to 17-26 and Nos. 19-31 to 19-36 were prepared in the same manner as in Experiment 1 of Example 9 except that, in bleach-fixing solutions No. 17-1 and No. 19-1 prepared in Experiment 1 of Example 9, the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 20 below.
- Using the bleach-fixing solutions thus obtained, evaluation was carried out in the same manner as in Experiment 2 of Example 9 except that the bleach-fixing time 4 minutes 20 seconds in Experiment 1 was set to 3 minutes 15 seconds.
-
- As will be clear from Table 20, in the case the bleach accelerator is added, the bleach-fixing solutions of this invention can maintain good effect in any of the desilvering performance, color reproduction performance and shelf stability even when stored, even if the bleach-fixing time is shortened. In contrast thereto, the bleach-fixing solutions outside this invention, which can be effective for any of the performances observed immediately after the solutions were prepared, result in further deterioration of the desilvering performance, color reproduction performance and shelf stability when they are stored.
Claims (16)
- A bleach-fix solution for processing a light-sensitive silver halide photographic material for photographing, wherein said solution has a pH ranging from between 3.0 to 6.8, contains a ferric complex salt having a ligand comprising a compound represented by the Formulas I-1 and I-2 shown below, and further contains at least one of;(i) at least one of the compounds represented respectively by General Formula (II) and General Formula (III) shown below;(ii) a water-soluble polymer having a unit of pyrrolidone nucleus in the molecular structure; and(iii) a ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII),
General Formula (III):
General Formula (IV):
General Formula (V):
General Formula (VI):
General Formula (VII): - The bleach-fixing solution according to Claim 1, wherein the solution has the pH value ranging between 4.0 and 6.7.
- The bleach-fixing solution according to Claim 3, wherein the solution has the pH value ranging between 5.0 and 6.5.
- The bleach-fixing solution according to Claim 1, wherein the ferric complex salt is contained in the range of 0.02 to 1.30 mol/lit.
- The bleach-fixing solution according to Claim 1, wherein the sulfite is ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium hydrogensulfite or sodium metabisulfite.
- The bleach-fixing solution according to Claim 1, wherein the alkyl group represented by R₂ and R₃ of General Formula (II) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- The bleach-fixing solution according to Claim 1, wherein the alkyl group represented by R₄ and R₅ of General Formula (III) is an alkyl group having 1 to 2 carbon atoms and n represents an integer of 1 to 4.
- The bleach-fixing solution according to Claim 1, wherein the compound selected from the compounds of General Formula (II) and (III) is contained in an amount of 0.01 to 2 mol/lit.
- The bleach-fixing solution according to Claim 1, wherein the polymer having a unit of a pyrrolidone nucleus has an average molecular weight of 500 to 800,000.
- The bleach-fixing solution according to Claim 1, wherein the polymer having a unit of a pyrrolidone nucleus is contained in an amount of 0.1 to 100 g per one liter of the bleach-fixing solution.
- The bleach-fixing solution according to Claim 1, wherein, when the bleach-fixing solution contains the polymer having a unit of a pyrrolidone nucleus, the bleach-fixing solution further contains a sulfite or sulfite releasable compound in an amount of 1 x 10⁻¹ mol/lit.
- The bleach-fixing solution according to Claim 1, wherein the ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) is contained in an amount of 1 to 95 mol % based on the total amount of said ferric complex salt and the ferric complex salt having a ligand comprising a compound represented by General Formula (I).
- The bleach-fixing solution according to Claim 1, the ferric complex salt having a ligand comprising the compound represented by General Formula (I) and that having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII) is contained in the range of 0.02 to 1.30 mol/lit. in the total amount of them.
- The bleach-fixing solution according to Claim 1, wherein the bleach-fixing solution further contains at least one bleaching accelerator selected from the compounds represented by General Formulas (A-I) to A-IV) shown below:
General Formula (A-I):
General Formula (A-II):
or a heterocyclic residual group with a valence of n₁ (including those condensed with an unsaturated ring of 5 or 6 members); and X represents =S, =O or =NRʺ; where, R and Rʹ each have the same meaning as R₂ and R₃, Xʹ have the same meaning as X; Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic group, an alkyl group or
Rʺ represents a hydrogen atom an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residual group (including those condensed with an unsaturated ring of 5 or 6 members) or an amino group; and n₁ to n₆ and m₁ to m₅ each represent an integer of 1 to 6; B represents an alkylene group having 1 to 6 carbon atoms; Y represents -N〈 or -CH〈, R₄ and R₅ each have the same meaning as R₂ and R₃, provided that R₄ and R₅ each may represent -B-SZ, or R and Rʹ, R₂ and R₃, and R₄ and R₅ each may combine to form a ring; the compound represented by General Formula (A-II) may include compounds of enol form and salts thereof,
General Formula (A-III):
General Formula (IV): - The bleach-fixing solution according to Claim 14, wherein the bleaching accelerator is contained in an amount of 0.01 to 100 g per liter of the bleach-fixing solution.
- A method for processing a processing a light-sensitive silver halide photographic material for photographing, which comprises carrying out the processing by using a bleach-fixing solution having a pH ranging between 3.0 to 6.8, containing a ferric complex salt having a ligand comprising a compound represented by the Formulas I-1 and I-2 shown below, and further containing at least one of;(i) at least one of the compounds represented respectively by General Formula (II) and General Formula (III) shown below;(ii) a water-soluble polymer having a unit of pyrrolidone nucleus in the molecular structure; and(iii) a ferric complex salt having a ligand comprising at least one compound selected from the compounds represented respectively by General Formulas (IV) to (VII),
General Formula (III):
General Formula (IV):
General Formula (V):
General Formula (VI):
General Formula (VII):
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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JP240061/86 | 1986-10-08 | ||
JP24006186 | 1986-10-08 | ||
JP24175086 | 1986-10-11 | ||
JP241749/86 | 1986-10-11 | ||
JP24174986 | 1986-10-11 | ||
JP241750/86 | 1986-10-11 |
Publications (3)
Publication Number | Publication Date |
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EP0270217A2 EP0270217A2 (en) | 1988-06-08 |
EP0270217A3 EP0270217A3 (en) | 1989-03-22 |
EP0270217B1 true EP0270217B1 (en) | 1993-08-04 |
Family
ID=27332768
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19870308819 Expired - Lifetime EP0270217B1 (en) | 1986-10-08 | 1987-10-06 | Bleach-fixing solution having good processing performance and method for processing light-sensitive material using the same |
Country Status (2)
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EP (1) | EP0270217B1 (en) |
DE (1) | DE3786895D1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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DE69031376T2 (en) * | 1989-11-16 | 1998-01-08 | Fuji Photo Film Co Ltd | Process for processing a silver halide photographic material and fixing composition |
DE69129161T2 (en) * | 1990-01-24 | 1998-07-30 | Fuji Photo Film Co Ltd | Color development composition and processing method using the same |
JP2873850B2 (en) * | 1990-02-21 | 1999-03-24 | コニカ株式会社 | Processing method of silver halide color photographic light-sensitive material |
EP0468325B1 (en) * | 1990-07-27 | 1995-11-22 | Agfa-Gevaert AG | Bleach bath |
DE4031757A1 (en) * | 1990-10-06 | 1992-04-09 | Agfa Gevaert Ag | bleach |
DE69224867T2 (en) * | 1991-07-26 | 1998-09-17 | Konishiroku Photo Ind | Bleaching solution for color photographic processes |
US5582958A (en) * | 1995-01-10 | 1996-12-10 | Eastman Kodak Company | Photographic bleaching composition and processing method using ternary iron carboxylate complexes as bleaching agents |
US5541041A (en) * | 1995-04-17 | 1996-07-30 | Eastman Kodak Company | Stabilized peroxide bleaching solutions containing multiple chelating ligands and their use for processing of photographic elements |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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BE758333A (en) * | 1969-11-03 | 1971-04-01 | Eastman Kodak Co | NEW PHOTOGRAPHIC COMPOSITION OF |
JPS6024463B2 (en) * | 1977-05-06 | 1985-06-13 | コニカ株式会社 | Processing methods for silver halide photographic materials |
JPS5814834A (en) * | 1981-07-21 | 1983-01-27 | Konishiroku Photo Ind Co Ltd | Method for stabilizing silver halide color photosensitive material |
US4552834A (en) * | 1984-08-06 | 1985-11-12 | Eastman Kodak Company | Enhanced bleaching of photographic elements containing silver halide and adsorbed dye |
US4707434A (en) * | 1984-08-20 | 1987-11-17 | Konishiroku Photo Industry Co., Ltd. | Color image forming method comprising processing with a bleach-fixing solution |
-
1987
- 1987-10-06 EP EP19870308819 patent/EP0270217B1/en not_active Expired - Lifetime
- 1987-10-06 DE DE8787308819T patent/DE3786895D1/en not_active Expired - Lifetime
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EP0270217A3 (en) | 1989-03-22 |
EP0270217A2 (en) | 1988-06-08 |
DE3786895D1 (en) | 1993-09-09 |
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