JPS63226645A - Bleach-fixing solution having superior suitability to rapid processing - Google Patents
Bleach-fixing solution having superior suitability to rapid processingInfo
- Publication number
- JPS63226645A JPS63226645A JP25505387A JP25505387A JPS63226645A JP S63226645 A JPS63226645 A JP S63226645A JP 25505387 A JP25505387 A JP 25505387A JP 25505387 A JP25505387 A JP 25505387A JP S63226645 A JPS63226645 A JP S63226645A
- Authority
- JP
- Japan
- Prior art keywords
- bleach
- fixing
- solution
- present
- soln
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000012545 processing Methods 0.000 title claims abstract description 24
- -1 silver halide Chemical class 0.000 claims abstract description 33
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- 239000004332 silver Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 7
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000004061 bleaching Methods 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 10
- 238000001556 precipitation Methods 0.000 abstract description 5
- 229910052946 acanthite Inorganic materials 0.000 abstract description 3
- 229940056910 silver sulfide Drugs 0.000 abstract description 3
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 101100277337 Arabidopsis thaliana DDM1 gene Proteins 0.000 abstract 1
- 101150113676 chr1 gene Proteins 0.000 abstract 1
- 230000002950 deficient Effects 0.000 abstract 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 87
- 238000002474 experimental method Methods 0.000 description 21
- 239000000839 emulsion Substances 0.000 description 16
- 239000007844 bleaching agent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000011161 development Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- SRPOMGSPELCIGZ-UHFFFAOYSA-N disulfino carbonate Chemical class OS(=O)OC(=O)OS(O)=O SRPOMGSPELCIGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 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
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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
- 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- PMIIFNFHVJSOAN-UHFFFAOYSA-N acetic acid;thorium Chemical compound [Th].CC(O)=O PMIIFNFHVJSOAN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 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
- 230000005540 biological transmission Effects 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
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-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
- 230000002349 favourable effect Effects 0.000 description 1
- 229960005102 foscarnet Drugs 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 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
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 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
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 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
- 238000002834 transmittance Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は漂白定着液に関し、詳しくはｌＷｅ用感光感光
材料用して迅速処理化を達成できる漂白定着液に関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a bleach-fix solution, and more particularly to a bleach-fix solution that can be used for IWe light-sensitive materials and achieve rapid processing.
［発明の背１１
現在、高感度高沃臭化銀乳剤を用いた撮影用感光材料の
脱銀処理は漂白工程と定着工程が別々に行われている。[Background of the Invention 11 Currently, in the desilvering treatment of photographic light-sensitive materials using high-sensitivity silver iodobromide emulsions, a bleaching step and a fixing step are performed separately.
本発明者等は上記１影用感光材料の脱銀処理の簡略化お
よび迅速化を図るため、漂白と定着を一浴で処理する漂
白定着処理化を検討してきた。In order to simplify and speed up the desilvering process of the above-mentioned one-shade light-sensitive material, the present inventors have investigated a bleach-fixing process in which bleaching and fixing are performed in one bath.
その検討の中で、上記漂白定着液としては、液保存性お
よび得られる色素画像の復色不良の発生等の観点から従
来からｐＨが高い領域で使用することが有利であるとさ
れ、その高ＤＨ領域で優れたｇｌｉｉ能力を有する漂白
剤を探索した結果、本発明者等は種々の７ミノポリ力ル
ボン液鉄錯体の中でもジエチレ゛ントリアミン五酢酸第
２鉄錯塩（ＤＴＰＡ −Ｆｅ錯塩）が脱銀速度、得られ
る色素画像の復色性および漂白定着液の経時保存性を満
足できるものとして提案してきた。（特開昭６０−１３
４２３８号、同 ６０ｉ３０７３８号、同 Ｇｏ−１３
６７４４＠等）
上記ＤＴＰＡ−ＦＥｉ錯塩は、ｐＨが＾イ領域、具体的
には約１）Ｈ７〜９という範囲で上記の如くの特性を満
足できるものであるが、ががるｐＨ領域ではアンモニア
ガスが発生し易く、狭い空白で現像処理を行う際には作
業環境上好ましくない点を有していた。ざらに、感光材
料を長期にわたり処理した際の経時において、漂白定着
液中に第１鉄イオンの蓄積に起因すると考えられる脱銀
能力の低下と復色不良が発生することがわがってきた。During the study, it was found that it is advantageous to use the above bleach-fix solution in a high pH range from the viewpoint of solution storage stability and the occurrence of poor color recovery of the obtained dye image. As a result of searching for bleaching agents with excellent glii ability in the DH region, the present inventors found that among various 7-minopolycarbon liquid iron complexes, diethylenetriaminepentaacetic acid ferric complex salt (DTPA-Fe complex salt) was effective for desilvering. It has been proposed to be satisfactory in terms of speed, recoloring properties of the dye image obtained, and storage stability of the bleach-fix solution over time. (Unexamined Japanese Patent Publication No. 60-13
No. 4238, No. 60i30738, Go-13
6744@, etc.) The above DTPA-FEi complex salt can satisfy the above characteristics in the pH range of ﾾﾆ, specifically in the range of about 1)H7 to 9, but in the pH range of about 1), ammonia Gas is easily generated, which is disadvantageous in terms of the working environment when developing processing is carried out in a narrow space. In general, it has been found that when photographic materials are processed over a long period of time, desilvering ability decreases and color restoration failure occurs, which is thought to be caused by the accumulation of ferrous ions in the bleach-fix solution.
上記の欠点について詳細に検討を加えた結果、第１鉄イ
オンの蓄積は、漂白定着液のＤＨに大きく依存し、さら
に一定のｐＨ以上では処理した際の経時において、通常
漂白剤として用いられているアミノポリカルボン酸鉄錯
塩に共通して起こる問題点であることがわかった。As a result of a detailed study of the above drawbacks, we found that the accumulation of ferrous ions is highly dependent on the DH of the bleach-fix solution, and that above a certain pH, the amount of ferrous ions that are normally used as a bleaching agent increases over time during processing. This problem was found to be common to iron complex salts of aminopolycarboxylic acids.
本発明者等は、さらに検討を続けた結果、特定の低いｐ
Ｈ域でかつ特定のアミノポリカルボン酸鉄錯塩を用いる
ことにより、上記第１鉄イオンの蓄積に起因すると考え
られる脱銀能力の低下と復色不良が同時に解決され、か
つアンモニアガスの発生も解消されることを見い出した
。As a result of further investigation, the present inventors discovered that a specific low p
By using a specific aminopolycarboxylic acid iron complex in the H range, the decrease in desilvering ability and poor color restoration, which are thought to be caused by the accumulation of ferrous ions, can be solved at the same time, and the generation of ammonia gas can also be solved. I found out that it can be done.
また、該漂白定着液の実用化に際して、特定のポリビニ
ルピロリドンを用いることにより、上記問題点の改良効
果に悪影響を与えることなく、経時保存時における硫化
銀等の沈澱発生を遅延させ、さらに漂白定着液が低補充
化９８理される際に発生しやすい未露光部漂白スティン
を６改良できることを見い出し本発明を為すに至ったも
のである。In addition, when putting the bleach-fixing solution into practical use, by using a specific polyvinylpyrrolidone, it is possible to delay the occurrence of precipitation of silver sulfide etc. during storage over time without adversely affecting the improvement effect of the above problems, and to further improve the bleach-fixing solution. The inventors have discovered that it is possible to improve the unexposed area bleaching stain that tends to occur when the liquid is treated at a low replenishment rate, and has thus arrived at the present invention.
［発明の目的１
従って、本発明の第１の目的は撮影用写真感光材料の迅
速処理を可能にした漂白定着液を提供するとにある。第
２の目的は、アンモニアガスの発生がなく、作業環境上
好ましい漂白定着液の提供にある。さらにまた第３の目
的は、経時保存時でも沈澱の発生が遅延され安定した漂
白定着性能が得られる漂白定着液の提供にある。第４の
目的は、低補充化処理する際の感光材料未露光部の漂白
スティンが改良された漂白定着液の掟倶にある。[Object of the Invention 1 Accordingly, the first object of the present invention is to provide a bleach-fix solution that enables rapid processing of photographic light-sensitive materials. The second object is to provide a bleach-fix solution that does not generate ammonia gas and is favorable in terms of working environment. Furthermore, a third object is to provide a bleach-fixing solution that retards the formation of precipitates and provides stable bleach-fixing performance even during storage over time. A fourth object is to provide a bleach-fixing solution that has improved bleach staining of unexposed areas of a photosensitive material during low replenishment processing.
［発明の構成］
本発明の上記目的はＢ影用ハロゲン化銀写真感光材料を
漂白定着りる処理液において、該液のｐＨが３．０〜６
．８の範囲にあり、かつ下記一般式［Ｉ］で示される化
合物を配位子とする第２鉄銘塩を含有し、さらに分子構
造中にピロリドン核単位を有する重合体を含有する漂白
定着液により達成された。[Structure of the Invention] The above object of the present invention is to provide a processing solution for bleaching and fixing silver halide photographic materials for B shadows, the pH of which is 3.0 to 6.
．． 8 and which contains a ferric salt having a compound represented by the following general formula [I] as a ligand, and further contains a polymer having a pyrrolidone core unit in its molecular structure. achieved by.
一般式［Ｉ］
（式中、Ｒ１は水素原子または低級アルキル基を表わし
、ｎｌ 、Ｒ２およびＲ３はそれぞれＯ〜３の整数を表
わ乃。但し、ｎｌ 、Ｒ２およびＲ３の合計は２乃至４
の整数であり、
数の総和は３以上である。）
［発明の具体的構成］
本発明の漂白定着液には、一般式［Ｉ］で示される化合
物を配位子とする第２鉄錯塩が用いられる。General formula [I] (In the formula, R1 represents a hydrogen atom or a lower alkyl group, and nl, R2 and R3 each represent an integer of O to 3. However, the total of nl, R2 and R3 is 2 to 4.
is an integer, and the sum of the numbers is 3 or more. ) [Specific Structure of the Invention] The bleach-fix solution of the present invention uses a ferric complex salt having a compound represented by the general formula [I] as a ligand.
一般式［Ｉ］において、Ｒ１としては好ましくは水素原
子である。また、
数の総和の通も好ましくは３である。In general formula [I], R1 is preferably a hydrogen atom. Also, the sum of the numbers is preferably 3.
以下、一般式ＣＩ］で示される化合物の好まし例示化合
物
Ｉ−１
上記一般式［Ｉ］で示される化合物を配位子とする第２
鉄錯塩（以下、本発明の第２鉄錯塩という）は、フリー
の酸（水素塩）としても用いられるが、対塩としてナト
リウム塩、カリウム塩、リチウム塩等のアルカリ金属塩
、もしくはアンモニウム塩、または水溶性アミン塩、例
えばトリエタノールアミン塩等としても用いることがで
きる。Hereinafter, preferred exemplary compound I-1 of the compound represented by the general formula [CI]] A second compound having the compound represented by the above general formula [I] as a ligand
The iron complex salt (hereinafter referred to as the ferric complex salt of the present invention) is also used as a free acid (hydrogen salt), but as a counter salt, it may be an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, Alternatively, it can also be used as a water-soluble amine salt, such as a triethanolamine salt.
好ましくはカリウム塩、ナトリウム塩及びアンモニウム
塩が使われる。これらの本発明の第２鉄錯塩は少なくと
も１種用いればよいが、２種以上を併用することもでき
る。ざらに本発明外の第２鉄錯塩と併用とすることもで
きる。Preferably potassium, sodium and ammonium salts are used. At least one type of these ferric complex salts of the present invention may be used, but two or more types can also be used in combination. It can also be used in combination with ferric complex salts other than those of the present invention.
上記例示の本発明の第２鉄錯塩の中では好ましくは、例
示化合物（１−１＞、（Ｉ−２）、ｆｆｉよび（Ｉ−３
）を配位子として用いる。第２鉄錯塩である。さらに、
例示化合物Ｎｏ、（Ｉ−１）、（Ｉ−２）および（Ｉ−
３）の中でも溶解性の点から（Ｉ−１）、（１−２）を
用いることが特に好ましく、本発明の目的の効果等積々
の点を鑑みると、（Ｉ−１）を用いることが本発明にお
いて最も好ましい。Among the above-exemplified ferric complex salts of the present invention, exemplary compounds (1-1>, (I-2), ffi and (I-3) are preferred.
) is used as a ligand. It is a ferric complex salt. moreover,
Exemplary compound No., (I-1), (I-2) and (I-
Among 3), it is particularly preferable to use (I-1) and (1-2) from the viewpoint of solubility, and from the viewpoint of the effects of the present invention, it is preferable to use (I-1). is most preferred in the present invention.
本発明の第２鉄錯塩は、本発明の漂白定着液生木発明の
効果を得る量であればいかなる量でも用いられるが、第
２鉄錯塩濃度が高くなりすぎると、漂白定着液の保存性
が劣化し、一方、第２鉄錯塩の濃度が低すぎると脱銀性
能と復色性能が劣化する。従って通常０．０２〜１．３
０モル／２の範囲で用いることが好ましく、０．１０〜
１．２０モル／ｌの範囲で用いることがより好ましい。The ferric complex salt of the present invention may be used in any amount as long as the effect of the invention of the bleach-fix solution of the present invention can be obtained, but if the concentration of the ferric complex salt becomes too high, the shelf life of the bleach-fix solution may be On the other hand, if the concentration of the ferric complex salt is too low, the desilvering performance and color recovery performance will deteriorate. Therefore, usually 0.02 to 1.3
It is preferable to use it in the range of 0 mol/2, and from 0.10 to
It is more preferable to use it within the range of 1.20 mol/l.
特に０．２０〜０．８０モル／ｌの範囲で用いると本発
明の効果を良好に奏し好ましい。In particular, it is preferable to use it in a range of 0.20 to 0.80 mol/l because the effects of the present invention can be achieved well.
本発明の漂白定着液は、ＩＩＨ３，０未満では亜硫酸ガ
ス発生のため、またｐｌ−１６，８より高ければ本発明
の効果が不充分のため、そのＩ）Ｈ範囲はｐＨ３，０〜
６．８であり、このＩ）Ｈ領域であればいかなるＤＨで
も用いることができるが脱銀性と復色性の他に、各種鉄
塩の低温時の溶解性、亜１ｉＩＲイオンより発生する亜
硫酸ガス臭気を考えるとＩ）８４．０〜６．７で用いる
ことが好ましく、特に１）８５．０〜６．５で用いるこ
とが最も好ましい。The bleach-fix solution of the present invention has an I)H range of pH 3.0 to
6.8, and any DH in this I)H region can be used, but in addition to desilvering and recoloring properties, the solubility of various iron salts at low temperatures, and the sulfite generated from 1iIR ions Considering gas odor, it is preferable to use I) 84.0 to 6.7, and most preferably 1) 85.0 to 6.5.
漂白定着液にポリビニルビＯリドンを長期保存時の漂白
刃の維持の目的で用いることは、従来より、例えば特公
昭５０−３８９３７号等で知られてきている。しかしな
がら、これら公知例を含め、従来より漂白定着液の漂白
剤として多用してきたエチレンジアミン四酢酸第２鉄錯
塩は酸性領域で用いる際には、とりわけ銀量の多い高感
度撮影用感光材料は復色不良の故障を生じやすい欠点を
有していた。しかるに、本発明では、特定の７ミノボリ
カルボン酸第２鉄錯塩とポリビニルとロリドンと組合せ
て ｐＨ３〜６．８の漂白定着液に用いる際に、驚くべ
きことに復色不良の欠点もなく、かつ漂白定着液独特の
硫化銀の沈、澱発生を抑え、ざらに前記本発明の目的の
効果を奏することを見い出し本発明をなすに至ったもの
である。The use of polyvinyl bi-O-lidone in a bleach-fix solution for the purpose of maintaining bleaching blades during long-term storage has been known, for example, from Japanese Patent Publication No. 38937/1983. However, when ferric complex salts of ethylenediaminetetraacetic acid, which have been frequently used as bleaching agents in bleach-fix solutions, including these known examples, are used in acidic regions, they cannot be used to restore color, especially for high-speed photographic materials containing a large amount of silver. It had the disadvantage of being prone to malfunctions. However, in the present invention, when a specific 7-minoboricarboxylic acid ferric complex salt is used in combination with polyvinyl and lolidone in a bleach-fix solution having a pH of 3 to 6.8, surprisingly there is no drawback of poor color recovery. Furthermore, it was discovered that the precipitation of silver sulfide and the formation of sludge, which are unique to bleach-fix solutions, can be suppressed, and the desired effects of the invention described above can be achieved, and the present invention has been completed.
以下、本発明の漂白定着液中に含有される分子構造中に
ピロリドン核単位を有する重合体く以下、本発明のビニ
ルピロリドン重合体という）について説明する。Hereinafter, the polymer having a pyrrolidone core unit in the molecular structure contained in the bleach-fix solution of the present invention (hereinafter referred to as the vinylpyrrolidone polymer of the present invention) will be explained.
本発明のビニルピロリドン重合体は、ビニルビロリドン
単独のホモポリマーであっても、他の共重合し得る単量
体とのコポリマーであってもよいが、重合体として水溶
性であることが必要である。The vinyl pyrrolidone polymer of the present invention may be a homopolymer of vinyl pyrrolidone alone or a copolymer with other copolymerizable monomers, but it is necessary that the polymer is water-soluble. .
上記ビニルピロリドンと共重合し得る他の単量体として
は、例えばビニルエステル、アクリル酸エステル、メタ
クリル酸エステル、アクリル酸、メタクリル酸、スチレ
ン等が代表的で、ビニルエステルとしては例えば酢酸ビ
ニル、プロピオン酸ビニル、酪酸ビニル等が挙げられ、
アクリル系のエステルとしては、例えばメチルエステル
、エチルエステル、ブチルエステル、２−エチルヘキシ
ルエステル等が挙げられ、これらの共重合体である場合
、共重合比としては、ビニルピロリドンに対して５〜１
００モル％の範囲で用いられることが好ましい。Typical examples of other monomers that can be copolymerized with the vinyl pyrrolidone include vinyl esters, acrylic esters, methacrylic esters, acrylic acid, methacrylic acid, and styrene. Examples of vinyl esters include vinyl acetate and propionic esters. Examples include vinyl acid, vinyl butyrate, etc.
Examples of acrylic esters include methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, etc. In the case of copolymers of these, the copolymerization ratio is 5 to 1 to vinylpyrrolidone.
It is preferably used in a range of 0.00 mol%.
また、本発明のビニルピロリドン重合体は平均分子量は
特に限定されないが好ましくは５００〜８００、０００
であり、より好ましくは２，０００〜４００．０００で
ある。Furthermore, the average molecular weight of the vinylpyrrolidone polymer of the present invention is not particularly limited, but is preferably 500 to 800,000.
and more preferably 2,000 to 400,000.
重合体の平均分子量を求める方法は通常の方法に従って
行うことができ、例えば以下の如くで求められる。The average molecular weight of a polymer can be determined by a conventional method, for example, as follows.
正確に重合体基１８１１，０００りを秤量し、１００１
ｊ２のメスフラスコにとり蒸溜水を加えて１％の水溶液
を調整債、該水溶液と溶媒である水との粘度をそれぞれ
測定する。粘度の測定にはウベローデ型毛管粘度計を利
用した。測定溶液を入れた該粘度計をサーモスフ１〜内
に懸垂せしめ３０分間２０℃±０゜０１℃保持し、溶液
が２つのゲージ間を流れるのに要する時間を測定し、数
回平均値な求め次式に示す関係より、相対粘度を算出し
た。Accurately weigh 1,811,000 grams of polymer base,
A 1% aqueous solution was prepared by adding distilled water to a volumetric flask, and the viscosity of the aqueous solution and water as a solvent was measured. An Ubbelohde capillary viscometer was used to measure the viscosity. The viscometer containing the measurement solution was suspended in a thermos valve 1 and kept at 20°C ± 0°C for 30 minutes, and the time required for the solution to flow between the two gauges was measured, and the average value was calculated several times. The relative viscosity was calculated from the relationship shown in the following equation.
溶液の流動時間
１η「ｅｌ讃
溶媒の流ｖＪ待時
間対粘度よりフィケンヂャーの等式の
（Ｐｈｙｓｉｋａｌｉｓｃｈｅ Ｕ、 ｔｅｃｈｎｏ
ｌｏｇｉｓｃｈｅＰｒｊｒｕｎｇｓｖｅｒｒａｈｒｅｎ
’ ｒｊｉｒ １ａｃｋｅ ｕｎｄ １ｈｒｅＲｏｈ
ｓｔｏＮｅ、１９５３ Ｅ ｄｉｔ、、参照）ニ従っＴ
Ｋｉｉを求め、通常の方法でに値より平均分子量を求め
る。From the flow time of the solution 1η "el, the flow of the solvent vJ, the waiting time vs. the viscosity, the Fikenger equation (Physikalische U, techno
logischeprjrungsverrahren
'rjir 1acke and 1hreRoh
stoNe, 1953 Edit,, see)
Kii is determined, and the average molecular weight is determined from the value in the usual manner.
以下、本発明に用いられるビニルとロリドン重合体の代
表的具体例を示すが、これらに限定されるものではない
。Typical examples of vinyl and lolidone polymers used in the present invention are shown below, but the invention is not limited thereto.
例示化合物
（１）ポリビニルピロリドン（平均分子量約４０．００
０ ）
（２）ポリビニルピロリドン（平均分子量約９，０００
）
（３）ポリビニルピロリドン（平均分子量約１６，００
０）
（４）ビニルピロリドン−酢酸ビニル共重合体（共重合
モル比７：３）
（平均分子ｆｉ ４，０００）
（５）ビニルピロリドン−メチルアクリレート共重合体
（共重合モル比７：３）（平均分子量１，０００
）
（６）ビニルピロリドン−エチルアクリレート共重合体
（共重合モル比７：３）（平均分子量２５，００
０）
（７）ピニルピロリドンーブブルアクリレート共重合体
（共重合モル比７：３）（平均分子１ｉ ７，０
００）
（８）ビニルピロリドン−２−二［ブ・ルヘキシルアク
リレーＩ・共重合体
（共重合モル比７：３）
（平均分子量１８，０００）
（９）ビニルビロリドンースナレン共重合体く共重合モ
ル比に３）
（平均分子量２０．０００ ）
上記本発明のビニルピロリドン重合体の添加覆は、重合
体のｆＩ！類、重合度等により異なるが、概ね本発明の
漂白定着液１２当たり０．１ｇ〜１００ｇが好ましく、
より好丈しくは０，２〜５０ｇであり、ざらに好ましく
は０．３〜２０ｇであり、特に好ましくは０．５〜１０
ｇである。Exemplary compound (1) Polyvinylpyrrolidone (average molecular weight approximately 40.00
0) (2) Polyvinylpyrrolidone (average molecular weight approximately 9,000
) (3) Polyvinylpyrrolidone (average molecular weight approximately 16,00
0) (4) Vinylpyrrolidone-vinyl acetate copolymer (copolymerization molar ratio 7:3) (average molecular fi 4,000) (5) Vinylpyrrolidone-methyl acrylate copolymer (copolymerization molar ratio 7:3) (Average molecular weight 1,000
) (6) Vinylpyrrolidone-ethyl acrylate copolymer (copolymerization molar ratio 7:3) (average molecular weight 25,00
0) (7) Pinylpyrrolidone-bubbly acrylate copolymer (copolymerization molar ratio 7:3) (average molecular 1i 7,0
00) (8) Vinylpyrrolidone-2-di[bu-ruhexyl acrylate I/copolymer (copolymerization molar ratio 7:3) (average molecular weight 18,000) (9) Vinylpyrrolidone-snarene copolymer (Average molecular weight: 20.000) Addition of the vinylpyrrolidone polymer of the present invention increases the fI of the polymer! Although it varies depending on the species, degree of polymerization, etc., it is generally preferably 0.1 g to 100 g per 12 of the bleach-fixing solution of the present invention.
More preferably 0.2 to 50 g, more preferably 0.3 to 20 g, particularly preferably 0.5 to 10 g
It is g.
本発明のビニルピロリドン重合体の漂白定着液への添加
方法は、例えば粉末のまま直接添加してもよいし、水等
の溶媒に溶解して添加してもよい。The vinyl pyrrolidone polymer of the present invention may be added directly to the bleach-fix solution, for example, by directly adding it as a powder, or by dissolving it in a solvent such as water.
本発明では、前記本発明のビニルピロリドン重合体とと
もに亜硫酸塩又は亜硫酸放出化合物（例えば、特公昭５
／ｌ−３８８９５号明細ｌ中のカルボニル重亜硫酸塩付
加物等）を併用する際に漂白定着液の経時保存性がより
改良されるために、本発明においてはより好ましく用い
られる。In the present invention, a sulfite or a sulfite-releasing compound (for example,
It is more preferably used in the present invention because the storage stability of the bleach-fixing solution over time is further improved when used in combination with carbonyl bisulfite adducts (such as carbonyl bisulfite adducts in Patent No. 1-38895).
本発明では、亜硫酸塩又は亜硫酸放出化合物を本発明の
漂白定着液１２当り１ Ｘ １０−３モル以上含有する
のが好ましく、より好ましくは０，０２モル以上２．０
モル以下、であり、さらにより好ましくは０．０５モル
以上１．３モル以下、最も好ましくは０．０９モル以上
０．９モル以下で使用される。In the present invention, the content of the sulfite or sulfite-releasing compound is preferably 1.times.10@-3 mol or more per 12 of the bleach-fix solution of the present invention, more preferably 0.02 mol or more and 2.0 mol or more.
It is used in an amount of 0.05 mol or more and 1.3 mol or less, most preferably 0.09 mol or more and 0.9 mol or less.
上記亜硫酸塩としては、亜［ｉ１アンモニウム、亜硫酸
ナトリウム、亜硫酸カリウム、亜硫酸水素ナトリウム、
亜硫酸水素カリウム、メタ重亜硫酸ナトリウム等があげ
られる。The above-mentioned sulfites include [i1 ammonium nitrite, sodium sulfite, potassium sulfite, sodium hydrogen sulfite,
Examples include potassium hydrogen sulfite and sodium metabisulfite.
本発明の漂白定着液に含ませるハロゲン化銀定着剤とし
ては通常の定着処理に用いられるようなハロゲン化銀と
反応して水溶性の錯塩を形成する化合物、例えばチオ硫
酸カリウム、チオ硫酸ナトリウム、チオ硫酸アンモニウ
ムの如きチオ硫酸塩、チオシアン酸カリウム、チオシア
ン酸ナトリウム、チオシアン酸アンモニウムの如きチオ
シアン酸塩、チオ尿素、チオエーテル、高濃度の臭化物
、ヨウ化物等がその代表的なものである。これらの定着
剤は５９／１以上、好ましくは５０（ｌｌ／１以上、よ
り好ましくは７０ａ／１以上溶解できる範囲の量で使用
できる。The silver halide fixing agent to be included in the bleach-fixing solution of the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount within the range of dissolving 59/1 or more, preferably 50 (1/1 or more), more preferably 70 (1/1) or more.
本発明の漂白定着液は、種々の添加剤を含むことができ
る。添加剤としては、特にアルカリハライドまたはアン
モニウムハライド、例えば臭化カリウム、臭化ナトリウ
ム、塩化ナトリウム、臭化アンモニウム、沃化カリウム
、沃化ナトリウム、沃化アンモニウム等を含有させるこ
とが望ましい。The bleach-fix solution of the present invention can contain various additives. As additives, it is particularly desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like.
本発明の漂白定着液には硼酸、硼砂、水酸化ナトリウム
、′水酸化カリウム、炭酸ナトリウム、炭酸カリウム、
重炭酸ナトリウム、重炭酸カリウム、酢酸、酢酸ナトリ
ウム、水酸化アンモニウム等の各種の塩からなるｐＨＩ
衝剤を単独であるいは２種以上組合せて含有せしめるこ
とができる。ざらにまた、各種の蛍光増白剤や消泡剤あ
るいは界面活性剤や防ぽい剤を含有せしめることもでき
る。The bleach-fix solution of the present invention includes boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
pHI consisting of various salts such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
Shocking agents can be contained alone or in combination of two or more. The powder may also contain various optical brighteners, antifoaming agents, surfactants, and antifoaming agents.
またアセチルアセトン、ホスホノカルボン酸、ポリリン
酸、有機ホスホン酸、オキシカルボン酸、ポリカルボン
酸、ジカルボン酸及びアミツボリカ゛ ルボン酸等の
有機キレート剤あるいは二ｌ−０アルコール、硝酸塩等
の安定剤、アルカノールアミン等の可溶化剤、有機アミ
ン等のスティン防止剤、その他の添加物や、メタノール
、ジメチルホルムアミド、ジメチルスルホキシド等の有
機溶媒を適宜含有せしめることができる。In addition, organic chelating agents such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid, and amitobilicarboxylic acid, stabilizers such as dil-0 alcohol, nitrate, alkanolamine, etc. A solubilizing agent, an anti-stinting agent such as an organic amine, other additives, and an organic solvent such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be appropriately contained.
本発明の漂白定着液には漂白促進剤を用いることが好ま
しく、例えば特願昭６０−１６０９４３号等に記載され
る化合物を用いることができ、下記一般式［Ａ〜工〕〜
［Ａ −ＩＶ ］に示される化合物を用いることが本発
明の効果を良好に奏し好ましい。It is preferable to use a bleaching accelerator in the bleach-fixing solution of the present invention, and for example, compounds described in Japanese Patent Application No. 160943/1988 can be used, and the following general formulas [A~E]~
It is preferable to use the compounds shown in [A-IV] because the effects of the present invention can be achieved well.
一般式［Ａ−Ｉ］
式中、Ｑｌは含窒素へテロ環（５〜６員の不飽和環また
は飽和環が縮合しているものも含む）を形成するに必要
な原子群を表わし、Ｒ１は水素原またはアルキル基を表
わす。但し、Ｑ′はＱｌ と同義である。General formula [A-I] In the formula, Ql represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed), and R1 represents a hydrogen atom or an alkyl group. However, Q' has the same meaning as Ql.
一般式［Ａ−Ｉ［］
式中、Ｒ２およびＲ３はそれぞれ水素原子、炭素原子数
１〜６のアルキル基、ヒドロキシ基、カルボキシ基、ア
ミノ基、炭素原子数１〜３のアシル基、アリール基また
はアルケニル基を表わす。General formula [A-I[] In the formula, R2 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, or an aryl group. Or represents an alkenyl group.
Ａは
又はｎ１１ｉ１［ｉのへテＯ環残基（５〜６員の不飽和
環が縮合しているものも含む）を表わし、Ｘはｍ５１−
〇または−ＮＲ＃を表わす。ここで、ＲおよびＲ′はそ
れぞれＲ２Ｊ５よびＲ３と同義、Ｘ′はＸと同義、Ｚは
水素原子、アルカリ金ｆｉ ＩＶ、子、アンモニウム基
、アミムＬ含窒素ヘテロ環残基、アルキル基、または
原子を表わし、Ｒ＃は水素原子、炭素原子数１〜６のア
ルキル基、シクロアルキル基、アリール基、ヘテロ環残
基（５〜６員の不飽和環が縮合しているものも含む）ま
たはアミン基を表わし、０１〜ｎｓｉよび１１〜１５は
それぞれ１〜６の整数を表わす。Ｂは炭素原子数１〜６
のフルキレン基を表わし、Ｙは−Ｎくまたは−ＣＨぐを
表わし、Ｒ４およびＲ５はそれぞれＲ２！３よびＲ３と
同義である。但し、Ｒ４およびＲ５はそれぞれ−Ｂ−８
Ｚを表わしてもよく、またＲ２とＲ３、ＲとＲ’ 、Ｒ
４とＲ５はそれぞれ結合して環を形成してもよい。A represents a hetero-O ring residue of or n11i1[i (including those in which 5- to 6-membered unsaturated rings are fused), and X is m51-
Represents 〇 or -NR#. Here, R and R' are synonymous with R2J5 and R3, respectively, X' is synonymous with R# represents an atom, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are fused), or It represents an amine group, and 01 to nsi and 11 to 15 each represent an integer of 1 to 6. B has 1 to 6 carbon atoms
represents a fullkylene group, Y represents -N or -CH, and R4 and R5 have the same meanings as R2!3 and R3, respectively. However, R4 and R5 are each -B-8
Z may also be represented, and R2 and R3, R and R', R
4 and R5 may each be combined to form a ring.
なお、該式で表わされる化合物はエノール化体、および
その塩も含む。Note that the compound represented by the formula also includes enolated products and salts thereof.
一般式［Ａ−ＩＩＩ］
ｔ（７
式中、Ｒ６およびＲ７はそれぞれ水素原子、炭素原子数
１〜６のアルキル基、ヒトＯキシ基、カルボキシ基、ア
ミノ基、炭素原子数１〜３のアシル基、アリール基、ア
ルケニル基または−Ｂ１−８−Ｚ＋ を表わｙ。但し、
ＲＧとＲ７は結合して環を形成してもよい。Ｙｌは Ｎ
−または、ＣＨ−を表わし、Ｂ１は炭素原子数１〜６の
アルキレン基を表わし、ｚｌは水素原子、アルカリ金属
原子、アンモニウム基、アミノ基、含窒素へテＯ環残基
または
の整数を表わす。］
一般式［Ａ −ＩＶ ］
（Ｇ’ ）ｚ
式中、Ａｒは２価のアリール基またはアリール基とＭ素
原子および／もしくはアルキレン基とを組みあわせた２
価の有機基を表わし、Ｂ２およびＢ３はそれぞれ低級ア
ルキレン基を表わし、Ｒ８、ＲＢ、ＲｈｏおよびＲｔ＋
はそれぞれヒドロキシ置換低級アルキル基を表わし、×
およびｙはそれぞれ０または１を表わす。Ｇ′はアニオ
ンを表わし、２は０，１または２を表わす。General formula [A-III] t(7 In the formula, R6 and R7 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a human Ooxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms) y represents a group, an aryl group, an alkenyl group, or -B1-8-Z+.However,
RG and R7 may be combined to form a ring. Yl is N
- or represents CH-, B1 represents an alkylene group having 1 to 6 carbon atoms, and zl represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heteO ring residue, or an integer of . ] General formula [A-IV] (G')z In the formula, Ar is a divalent aryl group or 2 which is a combination of an aryl group and an M elementary atom and/or an alkylene group.
B2 and B3 each represent a lower alkylene group, R8, RB, Rho and Rt+
each represents a hydroxy-substituted lower alkyl group, ×
and y represent 0 or 1, respectively. G' represents an anion, and 2 represents 0, 1 or 2.
以下、本発明に好ましく用いられる漂白促進剤の具体例
を示す。Specific examples of bleach accelerators preferably used in the present invention are shown below.
例示化合物 （Ａ−１） （Ａ−２）（Ａ−３） （Ａ−４） （Ａ−５） （Ａ−６） （Ａ−７） Ｈ，Ｎ−Ｃ５ＮＨＮＨＣ３−ＮＨ。Exemplary compound (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) H,N-C5NHNHC3-NH.
（Ａ−９）
漂白促進剤の添加屋は本発明の漂白定着液１１当り約０
．０１〜１００（ｌの範囲で用いるのが好ましく、さら
に、０．０５〜５０ｏが好ましく、特に好ましくは０．
０５〜１５（Ｉである。(A-9) The bleach accelerator additive is about 0 per 11 of the bleach-fix solution of the present invention.
．． It is preferably used in the range of 0.01 to 100 (L), more preferably 0.05 to 50O, particularly preferably 0.0L.
05-15 (I.
近年、公害負荷低減及び処理液コストの低減の目的か、
ら低補充化が行なわれるが、本発明の漂白定着液も低補
充化に適用して好ましい。この時、本発明の漂白定着液
中にヨウ素イオンの蓄積が起こることが予想される。従
来、ヨウ素イオンの蓄積は、脱銀速度の低下をもたらす
ことが知られているが、本発明の漂白定着液では、ヨウ
素イオンの蓄積によっても脱銀性が実質的に低下しない
ばかりか、驚くべきことに、発色現像処理後水洗工程等
洗浄工程を経ることなく、漂白定着液に浸漬される場合
にも未露光部の濃度上昇（いわゆるカブリ）がほとんど
起こらないことが明らかとなった。In recent years, the purpose of reducing pollution load and processing liquid cost,
Although low replenishment is carried out, the bleach-fixing solution of the present invention is also preferably applied to low replenishment. At this time, it is expected that iodine ions will accumulate in the bleach-fix solution of the present invention. Conventionally, it has been known that the accumulation of iodine ions causes a decrease in the desilvering rate, but in the bleach-fix solution of the present invention, not only does the accumulation of iodine ions not substantially reduce the desilvering performance, but surprisingly Interestingly, it has become clear that even when the film is immersed in a bleach-fix solution without going through a washing process such as a water washing process after color development, there is almost no increase in density in the unexposed area (so-called fog).
この時ヨウ素イオンは漂白定着液にｏ、 ｏｏｏｓモル
／１以上含有することが好ましく、より好ましくは、漂
白定着液に０．００１モル／１以上含有することが好ま
しい。At this time, it is preferable that the bleach-fix solution contains iodine ions in an amount of 0.001 mol/1 or more, more preferably 0.001 mol/1 or more.
本発明の漂白定着液による処理時間は特に限定はないが
処理時間の短縮のため１ｏ分以下で処理することが好ま
しく、特に本発明では７分以下の迅速処理が可能である
。The processing time with the bleach-fix solution of the present invention is not particularly limited, but in order to shorten the processing time, it is preferable to perform the processing in 10 minutes or less, and in particular, the present invention allows rapid processing in 7 minutes or less.
本発明の漂白定着液の温度は８０℃以下で使用されるが
、望ましくは５５℃以下、最も好ましくは４５℃以下で
使用される。又蒸発等を抑えて使用するのが望ましい。The bleach-fix solution of the present invention is used at a temperature of 80°C or lower, preferably 55°C or lower, most preferably 45°C or lower. It is also desirable to use it while suppressing evaporation.
上記本発明の漂白定着液は、ｉ影用ハロゲン化銀写真感
光材料であればいかなるハロゲン化銀写真感光材料でも
適用できる。具体的に好ましくは沃化銀含有率が０．５
モル％以上、ざらに好ましくは１モル％以上含有する高
感度沃臭化銀乳剤を用いた感光材料であることが好まし
い。The above-mentioned bleach-fix solution of the present invention can be applied to any silver halide photographic material as long as it is an i-shadow silver halide photographic material. Specifically, the silver iodide content is preferably 0.5.
A photosensitive material using a high-sensitivity silver iodobromide emulsion containing at least mol %, preferably at least 1 mol % is preferable.
本発明の漂白定着液は、上記撮影用ハロゲン化銀写真感
光材料を発色現像後、直ちに漂白定着する処理液として
用いてもよいし、発色現像後、水洗又はリンス又は停止
等の処理を行った後の漂白定着処理液として用いてもよ
く、さらに発色現像後に前定着処理を行った後の漂白定
着処理液として用いてもよい。また、本発明の漂白定着
液による処理の後、水洗処理し、その後安定化処理して
もよいし、水洗処理工程を省略もしくは水洗水９を極端
に低減する特開昭５７−８５４３号に記載の多段向流安
定化処理技術や、特開昭５８−１４８３４号公報に記載
されているような水洗代替処理液による処理技術に適用
することもできる。□また、発色現象、漂白定着、水洗
等の工程の他に硬膜、中和、黒白現象、反転、少岱水洗
工程等、必要に応じて各種の補助工程が付加されてもよ
い。The bleach-fixing solution of the present invention may be used as a processing solution for bleaching and fixing the silver halide photographic light-sensitive material for photography immediately after color development, or it may be used as a processing solution for washing, rinsing, stopping, etc. after color development. It may be used as a subsequent bleach-fixing treatment solution, or may be used as a bleach-fixing treatment solution after pre-fixing treatment is performed after color development. Furthermore, after the treatment with the bleach-fixing solution of the present invention, washing with water and subsequent stabilization may be performed, or the washing process may be omitted or the amount of washing water 9 is extremely reduced as described in JP-A No. 57-8543. The present invention can also be applied to the multi-stage countercurrent stabilization treatment technology described in JP-A-58-14834, and the treatment technology using a washing alternative treatment liquid as described in Japanese Patent Laid-Open No. 14834/1983. □Furthermore, in addition to the steps of color development, bleach-fixing, washing with water, various auxiliary steps such as hardening, neutralization, black-and-white phenomenon, reversal, and washing with water may be added as necessary.
本発明に適用できる撮影用ハロゲン化銀乳剤は、常法に
より化学増感することができ、増感色素を用いて、所望
の波長域に光学的に増感できる。The photographic silver halide emulsion applicable to the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.
ハロゲン化銀乳剤には、カブリ防止剤、安定剤等を加え
ることができる。該乳剤のバインダーとしては、ゼラチ
ンを用いるのが有利である。Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.
乳剤層、その他の親水性コロイド層は、硬膜することが
でき、又、可塑剤、水不溶性又は難溶性合成ポリマーの
分散物（ラテックス）を含有させることができる。The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.
カラー写真用感光材料の乳剤層には、カプラーが用いら
れる。A coupler is used in the emulsion layer of a light-sensitive material for color photography.
更に色補正の効果を有しているカラードカプラー、競合
カプラー及び現像主薬の酸化体とのカップリングによっ
て現像促進剤、漂白促進剤、現像剤、ハロゲン化銀溶剤
、調色剤、硬膜剤、カブリ剤、カブリ防止剤、化学増感
剤、分光増感剤、及び減感剤のような写真的に有用なフ
ラグメントを放出する化合物が用いることができる。Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.
感光材料には、フィルタ一層、ハレーション防止層、イ
ラジェーション防止層等の補助層を設けることができる
。これらの層中及び／又は乳剤層中には現像処理中に感
光材料から流出するかもしくは漂白される染料が含有さ
せられてもよい。The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.
感光材料には、マット剤、滑剤、画像安定剤、界面活性
剤、色カブリ防止剤、現像促進剤、現像遅延剤や漂白促
進剤を添加できる。A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.
支持体としては、ポリエチレン等をラミネートした紙、
ポリエチレンテレフタレートフィルム、バライタ紙、三
酢ｒｔルロース等を用いることができる。As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, tri-vinegar rt-lulose, etc. can be used.
［実施例］
以下、実施例によって本発明の詳細な説明するが、これ
により本発明の実施悪様が限定されるものではない。[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the mode of implementation of the present invention is not limited thereby.
実施例−１
（実験１）
トリアセテートフィルムベース上にハレーション防止層
及びゼラチン層を設けこの上に赤感性ハロゲン化銀乳剤
層、緑感性ハロゲン化銀乳剤層、黄色コロイド銀を含有
するフィルタ一層及び青感性ハロゲン化銀乳剤層を総体
の銀量が１００ｃｆ当り９０ｍＣｌになるよう塗布した
。上記のプＬ剤層は沃化銀のモル％が約４，１％の沃臭
化銀であり。この際、青感性ハロゲン化銀乳剤層にはイ
エローカプラーとして下記（Ｙ−１）、緑感性ハロゲン
化銀乳剤層には、マゼンタカプラーとして下記（〜１−
１）、赤感性ハロゲン化銀乳剤層にはシアンカプラーと
して下記（Ｃ−１）を用い、各乳剤層にはそれぞれ増感
色素、硬膜剤及び延展割等通常の添加剤を加えた。この
ようにして得られたハロゲン化銀カラーネガ感光材料を
試料として用いた。Example-1 (Experiment 1) An antihalation layer and a gelatin layer were provided on a triacetate film base, and on top of this, 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. A sensitive silver halide emulsion layer was coated to give a total silver content of 90 mCl/100 cf. The above-mentioned pre-L agent layer is made of silver iodobromide with a molar percentage of silver iodide of approximately 4.1%. At this time, the following yellow coupler (Y-1) is used in the blue-sensitive silver halide emulsion layer, and the following magenta coupler (~1-1) is used in the green-sensitive silver halide emulsion layer.
1) The following (C-1) was used as a cyan coupler in the red-sensitive silver halide emulsion layer, and ordinary additives such as a sensitizing dye, a hardening agent, and a spreading agent were added to each emulsion layer. The silver halide color negative light-sensitive material thus obtained was used as a sample.
イエローカプラー（Ｙ−１）
マゼンタカプラー（Ｍ−１）
シアンカプラー（Ｃ−１）
この試料をピースに裁断し、常法に従って模型露光を与
えたものを用い、次の工程に従ってピース用処理装置を
用いて処理（以下、手現処理と称する）を行った。Yellow coupler (Y-1) Magenta coupler (M-1) Cyan coupler (C-1) This sample was cut into pieces and subjected to model exposure according to a conventional method. Processing (hereinafter referred to as manual processing) was performed using the following methods.
処理工程 処理温度（”Ｃ）槽数 処理時間１発色現
像 ３７．８ １１ ３分１５秒２漂白定
看 ３７．８ １槽 ４分２０秒３水 洗
３０〜３４ ２槽 ４分２０秒４安 定
３０〜３４ １槽 ２分１０秒５乾 燥
発色現像液、漂白定着液及び安定液は以下のものを使用
した。Processing process Processing temperature ("C) Number of tanks Processing time 1 Color development 37.8 11 3 minutes 15 seconds 2 Bleach 37.8 1 tank 4 minutes 20 seconds 3 Washing 30-34 2 tanks 4 minutes 20 seconds 4 An Constant 30-34 1 tank 2 minutes 10 seconds 5 drying The following dry color developing solution, bleach-fixing solution and stabilizing solution were used.
［発色現像液］
炭酸カリウム ３０ Ｑ炭酸
水素ナトリウム ２．５ｇ亜硫酸カリ
ウム ５．０ｇ臭化ナトリウム
１．２ｇ沃化カリウム
２Ｉ１ｇヒトＯキシアミン硫酸塩
２．５ｇ塩化ナトリウム
０．６ｇジエチレントリアミン五酸酢
酸トリウム ２．０ｇＮ−エチ
ル−Ｎ−β−ヒドロ
キシエチル−３−メチル−４−
アミノアニリン硫酸塩 ４．５ｇ水酸化カ
リウム １．２ｇ水を加えて１にに
仕上げ、水酸化ナトリウム又は２０％Ｉｉｉ！酸を用い
てｐＨ１０，０６に調整した。[Color developer] Potassium carbonate 30 Q Sodium bicarbonate 2.5 g Potassium sulfite 5.0 g Sodium bromide
1.2g potassium iodide
2I1g Human O-xyamine sulfate
2.5g sodium chloride
0.6g diethylenetriaminepentate thorium acetate 2.0g N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate 4.5g potassium hydroxide 1.2g Add water to make up to 1, and dilute with water Sodium oxide or 20% III! The pH was adjusted to 10.06 using acid.
〔漂白定着液］
表１に示す有ｉ酸の第２鉄
アンモニウム錯塩 ０．２７モルチオ硫酸
アンモニウム（７０％、溶液） ３００ｄ亜硫酸ア
ンモニウム １０ Ｑ例示化合物（２
） １．００銀粉末
２．０ ！Ｉ＋水を加えて全量を１
２とし、酢酸とアンモニア水でｐＨを表１に示す様に調
整した。[Bleach-fix solution] Ferric ammonium complex salt of i acid shown in Table 1 0.27 mol ammonium thiosulfate (70%, solution) 300d ammonium sulfite 10 Q exemplified compound (2
) 1.00 silver powder
2.0! Add I + water to bring the total volume to 1
2, and the pH was adjusted as shown in Table 1 using acetic acid and aqueous ammonia.
［安定液］
ホルマリン（３７％水溶液） ２−コニダツ
クス（小西六写真工業社［） ５ｔ１２水を加えて１
ｉとした。[Stabilizing solution] Formalin (37% aqueous solution) 2-Konidax (Konishi Roku Photo Industry Co., Ltd.) Add 5t12 water and 1
It was set as i.
表 １
表 １ （続き）
上記処理後の漂白定着液を開口比率１０ｃｆ／１（一般
の自動現像機に相当する開口条件であり、１２の漂白定
着液に対して、１０Ｃｆの空気接触面積を有している事
を意味する。）で、３８℃、１週間の経時保存し、保存
後の漂白定着液を用いて上記処理を再び行なった。処理
後のフィルム試料（漂白定着液の経時保存前後のそれぞ
れ）の最高濃度部の残留銀量（１ｇ／ｄｆ）を蛍光Ｘ線
法により、測定し、さらに、シアン色素濃度をサクラ光
電濃度計ＰＤＡ−６５（小西六写真工業ｆｔｌ製）を用
いて復色率を測定した。Table 1 Table 1 (Continued) The bleach-fix solution after the above treatment was mixed with an aperture ratio of 10 cf/1 (an opening condition equivalent to that of a general automatic processor, with an air contact area of 10 Cf for 12 bleach-fix solutions). ) at 38° C. for one week, and the above treatment was performed again using the bleach-fix solution after storage. The amount of residual silver (1 g/df) in the highest density part of the film sample after processing (before and after storage of the bleach-fix solution over time) was measured using a fluorescent X-ray method, and the cyan dye density was measured using a Sakura photoelectric densitometer PDA. -65 (manufactured by Konishiroku Photo Industry FTL) to measure the color recovery rate.
結果をまとめて表２に示す。The results are summarized in Table 2.
上記表２より、本発明に係りる有礪酸第２鉄錯塩を用い
て、０１−４３．０〜６．８の領域の漂白定着液を使用
する際には、経時保存の如何にかかわらず、残留銀も少
なく、かつ復色率も良好であることが判る。特に、ｐＨ
−＋が４．０〜６．７の時がより良好で、ｐＨが５．Ｏ
〜６．５の際にとりわけ特に良好であることが判る。From Table 2 above, when using the ferric silicic acid complex salt according to the present invention and a bleach-fixing solution in the range of 01-43.0 to 6.8, regardless of how it is stored over time, It can be seen that there is little residual silver and that the color restoration rate is also good. In particular, pH
It is better when -+ is 4.0 to 6.7, and pH is 5. O
˜6.5, it turns out to be particularly good.
しかるに、比較のＤ丁ＰＡを有礪渡として用いた比較の
漂白定着液によればｐＨ７〜８で経時保存前は脱銀性能
及び復色性能は極めて良好であるが、１週間の保存後に
は不充分なる性能となってしまう。ざらに、ＥＤＴＡは
、経時保存の如何にかかわらず、脱銀性能及び復色性能
が不充分なものであることが判る。However, according to a comparative bleach-fixing solution using comparative D-cho PA as a buffer, the desilvering performance and recoloring performance were extremely good at pH 7 to 8 before storage over time, but after storage for one week, This results in insufficient performance. In general, it can be seen that EDTA has insufficient desilvering performance and color restoring performance regardless of how long it has been stored.
（実験°２）
前記（実験１）で用いた漂白定着液Ｎ ｏ、 ３の例示
化合物（２）を下記表３に示す様に、未添加のもの、例
示Ｎｏ、（１）、（３）、（５）それぞれ変更して、ざ
らにｐＨを６．０として漂白定着液Ｎｏ、６−１〜６−
５を調製した。該漂白定着液を用いた実験１の感材を処
理し、得られた処理後の漂白定着液を実験１と同様に経
時保存し、この経時保存漂白定着液を用いて、脱銀性能
及び復色性能を実験１と同様に測定し表３に併せて示し
た。(Experiment ° 2) As shown in Table 3 below, the exemplified compound (2) of the bleach-fix solution No. 3 used in the above (Experiment 1) was added, as shown in Table 3 below. , (5) Bleach-fix solution Nos. 6-1 to 6- with the pH roughly adjusted to 6.0.
5 was prepared. The photosensitive material of Experiment 1 using the bleach-fix solution was processed, and the bleach-fix solution obtained after treatment was stored over time in the same manner as in Experiment 1. Using this bleach-fix solution stored over time, desilvering performance and recovery were evaluated. Color performance was measured in the same manner as in Experiment 1 and is also shown in Table 3.
また１週間保存後、さらに開口比率を１０倍にして保存
をつづけ沈澱の発生が生じるまでの日数を目視にて観察
した。After one week of storage, the opening ratio was further increased to 10 times, storage was continued, and the number of days until precipitation occurred was visually observed.
以上の結果をまとめて表３に示す。The above results are summarized in Table 3.
上記表３Ｊ：す、明らかな様に、本発明に係わるビニル
ピロリドン重合体を使用することにより、沈澱発生まで
の日数を大巾に伸ばすだけでなく、残留銀ｍ及び復色性
もより良好となることが判る。Table 3J above: As is clear, by using the vinylpyrrolidone polymer according to the present invention, not only the number of days until precipitation occurs can be greatly extended, but also the residual silver m and color reversibility are also better. It turns out that it will happen.
なお、（実験２）の実験Ｎ０１１〜５５で用いた例示化
合物（５）の代わりに、それぞれ（７）、（８）、（９
）、（４）を用いた以外は（実験２）と同じ実験を行な
ったところく実験２）のＮ０９１−５５とほぼ同じ結果
を得た。In addition, instead of the exemplified compound (5) used in Experiments N011 to 55 of (Experiment 2), (7), (8), and (9) were used, respectively.
), (4) were used, but the same experiment as in (Experiment 2) was conducted, and almost the same results as in Experiment 2) were obtained for N091-55.
以上の実験１６３よび実験２の結果より、本発明の漂白
定着液、即ち ｐＨが３．０〜６．８の範囲で一般式［
Ｉ］で示される化合物を配位子とする第２鉄銘塩を含有
し、さらに本発明のポリビニルピロリドンを含有する漂
白定着処理液は、特に経時保存後においても優れた脱銀
性能を有し、復色不良の発生も良好に防止され、さらに
保存安定性も良好であることがわかる。なＪ５、本発明
の漂白定着液はアンモニア臭は全くないものであった。From the results of Experiment 163 and Experiment 2 above, it was found that the bleach-fixing solution of the present invention, that is, the pH range of 3.0 to 6.8, has the general formula [
A bleach-fixing solution containing a ferric salt having the compound represented by [I] as a ligand and further containing the polyvinylpyrrolidone of the present invention has excellent desilvering performance especially after storage over time. It can be seen that the occurrence of poor color restoration was well prevented, and the storage stability was also good. J5, the bleach-fix solution of the present invention had no ammonia odor at all.
実施例−２
実施例−１の実験１と同様に漂白定着液を経時保存させ
た。ただし、ここでは漂白定着液中の亜硫酸アンモニウ
ムの濃度を１２０ ／ｌ、漂白剤の種類を表４に記載し
た如くとし、漂白剤の濃度を表４の如く変化させた。ま
た漂白定着液のｐＨを６．０とした。Example 2 A bleach-fix solution was stored over time in the same manner as in Experiment 1 of Example 1. However, here, the concentration of ammonium sulfite in the bleach-fix solution was 120/l, the type of bleaching agent was as shown in Table 4, and the concentration of the bleaching agent was varied as shown in Table 4. Further, the pH of the bleach-fix solution was set to 6.0.
経時保存後実施例−１の実験１と同様の評涌を行ない、
結果を表４に示した。After storage over time, the same evaluation as in Experiment 1 of Example-1 was carried out.
The results are shown in Table 4.
次にすべての漂白定着液を実施例−１の実験２と同様に
継続して保存し、硫化するまでの日数を測定し、結果を
表４に併せて示した。Next, all the bleach-fix solutions were continuously stored in the same manner as in Experiment 2 of Example-1, and the number of days until sulfurization was measured. The results are also shown in Table 4.
表４
表 ４ （絖き）
表４より明らかなように、本発明の漂白定着液の中でも
、特に漂白剤の含有量が０．０２モル／ｌ〜１．３０モ
ル／２、好ましくは０．１０〜１．２０モル／ｙ１ざら
に好ましくは０．２０〜０．８モル／ｌの範囲であれば
、経時保存しても脱銀及び復色能力は高くかつ硫化まで
の日数が長い良好な漂白定着液であることがわかる。Table 4 Table 4 (Screen) As is clear from Table 4, the bleach-fixing solution of the present invention particularly has a bleach content of 0.02 mol/l to 1.30 mol/2, preferably 0.02 mol/l to 1.30 mol/2. If it is in the range of 10 to 1.20 mol/y1, preferably 0.20 to 0.8 mol/l, the desilvering and restoring ability will be high even when stored over time, and the number of days until sulfurization will be long. It turns out to be a bleach-fix solution.
実施例−３
実施例−１の実験１と同様に漂白定着液を経時保存させ
た。ただし、ここでは漂白定着液として、実験１の漂白
定着液Ｎｏ、１−１の漂白剤及びその添加ｍを表５の如
くとし、漂白定着液中のＫｌの濃度を表５の如く変化さ
せ、さらに漂白定着液中のｐＨを６．０とした。Example 3 A bleach-fix solution was stored over time in the same manner as in Experiment 1 of Example 1. However, here, as the bleach-fix solution, the bleach-fix solution No. of Experiment 1, the bleaching agent of 1-1 and its addition m were as shown in Table 5, and the concentration of Kl in the bleach-fix solution was changed as shown in Table 5. Furthermore, the pH of the bleach-fix solution was set to 6.0.
経時保存後実施例−１の実１ｉＡ１と同様に脱銀能力の
評価を行ない結果を表５に記載した。After storage over time, the desilvering ability was evaluated in the same manner as in Example 1 iA1, and the results are shown in Table 5.
また処理後の試料を、ＣＮＫ−４基準処理（小西六写真
工業カラーネガ処理）に従って°漂白及び定着処理を施
こし残存銀を完全に除いた後に、マゼンタ色素の透過濃
度を測定してこの値をＤＧＩとした。次に実施例−１の
実験１と同様に発色現像を行った後、ＣＮＫ−４基準処
理に従って漂白及び定着処理した試料のマゼンタ色素の
透過濃度を測定し、この値をＤＧ２とした。ＤＧＩ
とＤｃ２の差を求める（ΔＤＧ）ことにより、マゼンタ
スティンを評価した。In addition, the processed sample was bleached and fixed according to CNK-4 standard processing (Konishi Roku Photo Industry Color Negative Processing) to completely remove residual silver, and then the transmission density of the magenta dye was measured and this value was calculated. It was designated as DGI. Next, color development was performed in the same manner as in Experiment 1 of Example-1, and then the transmittance density of the magenta dye of the sample subjected to bleaching and fixing according to the CNK-4 standard process was measured, and this value was designated as DG2. D.G.I.
Magentastin was evaluated by determining the difference between and Dc2 (ΔDG).
表５
表５から明らかなように、比較の漂白定着液では、Ｋｌ
の添加によってマゼンタスティンは小さくなるが脱銀能
力が大きく低下する。しかし本発明の漂白定着液では、
Ｋｌの添加によりマゼンタスティンが低く抑えられる一
方、脱銀能力の低下が小さく良好な結果が得られた。Table 5 As is clear from Table 5, in the comparative bleach-fix solution, Kl
By adding , the magentastin becomes smaller, but the desilvering ability is greatly reduced. However, in the bleach-fix solution of the present invention,
By adding Kl, the magentastin was suppressed to a low level, while the desilvering ability was little reduced, and good results were obtained.
実施Ｖ１４−４
実施例−１の実験１において調製した漂白定着液Ｎ０．
１−１および３−１において、ｐＨを６．０とし漂白促
進剤を下記表６に示す如くに添加した以外は同様にして
、漂白窓１液Ｎｏ、１−１１〜１−１６および３−３２
〜３−３７を調製した。Implementation V14-4 Bleach-fix solution No. 1 prepared in Experiment 1 of Example-1.
1-1 and 3-1, except that the pH was adjusted to 6.0 and the bleaching accelerator was added as shown in Table 6 below. 32
~3-37 was prepared.
得られた漂白定着液を用いて、実１Ｉ４１における漂白
定着時４分２０秒を３分１５秒とした以外は、実施例−
１の実験１労よび２と同様の評価を行った。Using the obtained bleach-fix solution, the procedure of Example-1 was changed from 4 minutes 20 seconds to 3 minutes 15 seconds during bleach-fixing in Example 1I41.
Evaluations similar to those in Experiments 1 and 2 were conducted.
結果を表６に示す。The results are shown in Table 6.
表６より、漂白促進剤を添加した時には本発明の漂白定
着液は保存によっても脱銀性、復色性および保存性のい
ずれも良好な効果を維持できるのに対して、本発明外の
漂白定着液は、調製直後の場合はいずれも効果があった
が、保存により脱銀性と復色性および保存性が更に劣化
することが明らかとなった。Table 6 shows that when a bleach accelerator is added, the bleach-fix solution of the present invention can maintain good effects in terms of desilvering properties, recoloring properties, and preservability even after storage, whereas bleaching solutions other than those of the present invention The fixing solutions were all effective immediately after preparation, but it became clear that the desilvering properties, recoloring properties, and preservability deteriorated further upon storage.
Claims (1)
において、該液のｐＨが３．０〜６．８の範囲にあり、
かつ下記一般式［ I ］で示される化合物を配位子とす
る第２鉄錯塩を含有し、さらに分子構造中にピロリドン
核単位を有する重合体を含有することを特徴とする漂白
定着液。 一般式［ I ］ ▲数式、化学式、表等があります▼ （式中、Ｒ＿１は水素原子または低級アルキル基を表わ
し、ｎ＿１、ｎ＿２およびｎ＿３はそれぞれ０〜３の整
数を表わす。但し、ｎ＿１、ｎ＿２およびｎ＿３の合計
は２乃至４の整数であり、 ▲数式、化学式、表等があります▼における炭素原子数
の総和は３以上である。）[Scope of Claims] A processing solution for bleaching and fixing silver halide photographic light-sensitive materials, the pH of which is in the range of 3.0 to 6.8;
A bleach-fixing solution comprising a ferric complex salt having a compound represented by the following general formula [I] as a ligand, and further comprising a polymer having a pyrrolidone core unit in its molecular structure. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a lower alkyl group, and n_1, n_2 and n_3 each represent an integer from 0 to 3. The sum of and n_3 is an integer from 2 to 4, and the total number of carbon atoms in ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is 3 or more.)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24174986 | 1986-10-11 | ||
| JP61-241749 | 1986-10-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63226645A true JPS63226645A (en) | 1988-09-21 |
Family
ID=17078964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25505387A Pending JPS63226645A (en) | 1986-10-11 | 1987-10-09 | Bleach-fixing solution having superior suitability to rapid processing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63226645A (en) |
-
1987
- 1987-10-09 JP JP25505387A patent/JPS63226645A/en active Pending
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