EP0334317A2 - Composition for processing silver halide color photographic light-sensitive material - Google Patents
Composition for processing silver halide color photographic light-sensitive material Download PDFInfo
- Publication number
- EP0334317A2 EP0334317A2 EP89105128A EP89105128A EP0334317A2 EP 0334317 A2 EP0334317 A2 EP 0334317A2 EP 89105128 A EP89105128 A EP 89105128A EP 89105128 A EP89105128 A EP 89105128A EP 0334317 A2 EP0334317 A2 EP 0334317A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- acid
- bleaching
- mol
- ammonium
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 39
- 239000004332 silver Substances 0.000 title claims abstract description 39
- -1 silver halide Chemical class 0.000 title claims abstract description 39
- 238000012545 processing Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000004061 bleaching Methods 0.000 claims abstract description 74
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 22
- 150000001768 cations Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000004436 sodium atom Chemical group 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 66
- 239000002131 composite material Substances 0.000 description 46
- 239000000839 emulsion Substances 0.000 description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 25
- 239000010410 layer Substances 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000002253 acid Substances 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 19
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 16
- 230000001235 sensitizing effect Effects 0.000 description 15
- 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 14
- 108010010803 Gelatin Proteins 0.000 description 14
- 229920000159 gelatin Polymers 0.000 description 14
- 239000008273 gelatin Substances 0.000 description 14
- 235000019322 gelatine Nutrition 0.000 description 14
- 235000011852 gelatine desserts Nutrition 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- 230000000087 stabilizing effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 229910021612 Silver iodide Inorganic materials 0.000 description 9
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 9
- 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 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 229960001484 edetic acid Drugs 0.000 description 8
- 229940045105 silver iodide Drugs 0.000 description 8
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 7
- 239000007844 bleaching agent Substances 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000004682 monohydrates Chemical class 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002894 organic compounds Chemical group 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 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 2
- NWPKEYHUZKMWKJ-UHFFFAOYSA-N 1-ethoxy-4-nitrobenzene Chemical compound CCOC1=CC=C([N+]([O-])=O)C=C1 NWPKEYHUZKMWKJ-UHFFFAOYSA-N 0.000 description 2
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- DUHQIGLHYXLKAE-UHFFFAOYSA-N 3,3-dimethylglutaric acid Chemical compound OC(=O)CC(C)(C)CC(O)=O DUHQIGLHYXLKAE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 101000767534 Arabidopsis thaliana Chorismate mutase 2 Proteins 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QIAFMBKCNZACKA-UHFFFAOYSA-N N-benzoylglycine Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1 QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 description 2
- 101000986989 Naja kaouthia Acidic phospholipase A2 CM-II Proteins 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- LJOODBDWMQKMFB-UHFFFAOYSA-N cyclohexylacetic acid Chemical compound OC(=O)CC1CCCCC1 LJOODBDWMQKMFB-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229960004011 methenamine Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- 229940048102 triphosphoric acid Drugs 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NDNUANOUGZGEPO-QMMMGPOBSA-N (+)-coniine Chemical compound CCC[C@H]1CCCCN1 NDNUANOUGZGEPO-QMMMGPOBSA-N 0.000 description 1
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- 229930016881 coniine Natural products 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- CCQPAEQGAVNNIA-UHFFFAOYSA-N cyclobutane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCC1 CCQPAEQGAVNNIA-UHFFFAOYSA-N 0.000 description 1
- SUSAGCZZQKACKE-UHFFFAOYSA-N cyclobutane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC1C(O)=O SUSAGCZZQKACKE-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- YZFOGXKZTWZVFN-UHFFFAOYSA-N cyclopentane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1 YZFOGXKZTWZVFN-UHFFFAOYSA-N 0.000 description 1
- FDKLLWKMYAMLIF-UHFFFAOYSA-N cyclopropane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CC1 FDKLLWKMYAMLIF-UHFFFAOYSA-N 0.000 description 1
- RLWFMZKPPHHHCB-UHFFFAOYSA-N cyclopropane-1,2-dicarboxylate;hydron Chemical compound OC(=O)C1CC1C(O)=O RLWFMZKPPHHHCB-UHFFFAOYSA-N 0.000 description 1
- 229960001270 d- tartaric acid Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229950010030 dl-alanine Drugs 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- QWLISCJHYITNQF-UHFFFAOYSA-N n-methoxy-1-phenylmethanamine Chemical compound CONCC1=CC=CC=C1 QWLISCJHYITNQF-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- ILUJQPXNXACGAN-UHFFFAOYSA-N ortho-methoxybenzoic acid Natural products COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000004848 polyfunctional curative Substances 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
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- NDNUANOUGZGEPO-UHFFFAOYSA-N rac-coniine Natural products CCCC1CCCCN1 NDNUANOUGZGEPO-UHFFFAOYSA-N 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
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 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 composition for processing a silver halide color photographic light-sensitive material and, more particularly, to a composition for processing a silver halide color photographic light-sensitive material which can be rapidly processed and excellent in long term stable preservability.
- Such desilvering treatment is carried out in the following steps, namely, a step of converting metal silver once into silver halide through a treatment with a bleaching solution containing halogen ions and an oxidizer, and another successive step of removing silver halide produced by the bleaching treatment and silver halide remaining undeveloped through a treatment with a fixing solution containing a silver halide solvent.
- a silver halide color photographic light-sensitive material has been bleached with a bleaching agent such as a compound of hexancyanoferrate, ferric chloride, ferric complex salts of organic acids or the like.
- a bleaching agent such as a compound of hexancyanoferrate, ferric chloride, ferric complex salts of organic acids or the like.
- Hexacyanoferrate and ferric chloride each are excellent bleaching agents, because they have a strong bleaching capability, a high bleaching speed, i.e., a high oxidizing speed, and a sufficient capability of making a leuco compound that is an intermediate of a dye color-recurred.
- hexacyanoferrate itself is a cyan-type compound, and there may be some instances where free cyan ions may be produced from the aqueous solution thereof by photo-dissociation. In the case of the disposal of waste, it is, therefore, necessary to make the waste completely pollution-free.
- Bleaching solutions using ferric chloride have the disadvantages that metals constituting a processor containing such bleaching solution are seriously corroded away by the strong corrosive action thereof and that iron hydroxide is produced in a washing step following a bleaching step so that the so-called stains are produced on a light-sensitive material.
- Ferric complex salts of organic acids are known as a bleaching agent having less environmental problems and more ready to carry out a recovering process as compared to ferric chloride.
- ferric complex salt of ethylenediamine-tetraacetic acid is popularly put to practical use, because of its excellent bleaching capability and stability.
- kits are available in both of the solid powder type and the so-called liquid type in which the solution is concentrated in advance.
- the latter type is preferable from the viewpoint of a simplified dossolving labor.
- the already known liquid type kits include, for example, those for developers, bleacher, fixers, bleach-fixers, stabilizers and so forth.
- these kits still have a problem remaining unsolved on how to concentrate their solutions without decomposition
- the above-mentioned bleacher or bleach-fixer has a problem that the crystallization and deposition or deposition in the course of storage.
- of popular ammonium halides such as ammonium bromide are produced in low temperature storage.
- Another object of the invention is to provide a light-sensitive material bleacher having neither precipitate produced in storage nor color recurring deterioration.
- a further object of the invention is to provide a composition of a light-sensitive material bleacher excellent in storage stability.
- Still further object of the invention is to provide a composition of a light-sensitive material bleacher having neither precipitate produced in storage nor color recurring deterioration.
- a bleaching solution composition comprising a substance capable of bleaching, wherein said composition comprises a ferric complex of a compound represented by the following Formula A, which has bleaching capability, in an amount of not less than 40 wt% of the total amount of said substance contained in said composition and pH of said composition is in the range of from 2.0 to 6.0: wherein A1, A2, A3 and A4 each may be the same with or the different from each other and they represent each CH2OH-, -COOM or -PO3M1M2 in which M, M1 and M2 each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group; X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
- Formula A which has bleaching capability
- the above-mentioned objects of the invention can be accomplished in the case that the above-mentioned composition should contain ferric complex salt represented by Formula A in an amount of not less than 0.3 mol per one liter and not less than 50 mol% of the cation of the salts contained therein should comprise ammonium and, further, the pH value of the composition should be within the range of from 2.0 to 5.5; and
- the substituted or unsubstituted alkylene groups each having 3 to 6 carbon atoms, represented by X include, for example, a group of propylene, butylene, trimethylene, tetramethylene, pentamethylene or the like.
- the substituents thereof include, for example, a hydroxyl group.
- Preferable compounds represented by the foregoing Formula A will typically be given below.
- ammonium salts of ferric complex thereof may preferably be used from the viewpoint of the effects of the objects of the invention.
- (A-1), (A-2), (A-4) and (A-7) may more preferably be used in the invention and, inter alia, (A-1).
- the invention will be more effective when a ferric complex of a compound represented by the foregoing Formula A contains in an amount of not less than 0.3 mol per liter of a bleaching solution, more preferably within the range of from 0.3 to 2 mol per liter and, further preferably, from 0.35 to 1 mol per liter.
- any compound known as a bleaching agent may generally be used.
- ferric aminopolycarboxylate complexes such as ferric ethylenediaminetetraacetate complex, ferric diethylenetriaminepentaacetate complex, ferric 1,2-cyclohexanediaminetetraacetate complex, ferric glycoletherdiaminetetraacetate complex.
- the compound represented by the foregoing Formula [A] should be contained in an amount of not less than 40 wt%, preferably, not less than 45 wt% and, more preferably, not less than 50 wt%, to the total amount of a substance having bleaching capability. If it is contained in an amount of not less than 50 wt%, the effects of the invention can suffi strictlyciently be displayed.
- Cations of both ferric aminopolycarboxylate complex of the foregoing bleaching agent and the salts of additives such as those given below are usually comprised of alkali metal ion, ammonium ion and hydrogen ion.
- the composition of the invention contains not less than 50 mol% of ammonium ion, it means that a proportion of ammonium ion to alkali metal ion is not less than 50 mol%.
- the composition of the invention contains, preferably, not less than 70 mol%, more preferably, not less than 90 mol% and, preferably in particular, 100 mol%, of ammonium ion.
- the above-mentioned ferric aminopolycarboxylic acid complex salt is preferred to contain free aminopolycarboxylic acid not having an iron ligand in a proportion of not more than 20 mol% and, more preferably, not more than 10 mol% to the ferric aminopolycarboxylic acid complex salt.
- Compounds preferably added to the composition of a bleaching solution of the invention include, for example, a haliode and a pH buffer.
- halides include, for example, halogen ion releasing compounds such as ammonium bromide, sodium bromide, potassium bromide, ammonium chloride, ammonium iodide and so forth.
- pH buffers preferably applicable to the invention include, for example, the compounds represented by the following Formulas I through III and inorganic compounds each containing at least one nitrogen atom, phosphorus atom or boron atom.
- B-COOH wherein B represents an organic compound group or a hydrogen atom.
- B2, B3 and B4 each represent a hydrogen atom or an organic compound group, provided that at least one of B2, B3 and B4 is an organic compound group.
- Typical compounds represented by Formula I include, for example, fatty acid compounds and cyclic structured acid compounds.
- Such fatty acid compounds include, preferably, formic acid, acetic acid, acrylic acid, adipic acid, acetylenedicarboxylic acid, acetoacetic acid, isopropylmalonic acid, azelaic acid, isocrotonic acid, isobutylic acid, itaconic acid, isovaleric acid, ethylmalonic acid, caproic acid, valeric acid, citric acid, glycolic acid, aconitic acid, glutaric acid, 3,3-dimethylglutaric acid, crotonic acid, chlorofumaric acid.
- ⁇ -chloropropionic acid gluconic acid, glyceric acid, ⁇ -chloropropionic acid, succinic acid, cyanoacetic acid, diethylacetic acid, diethylmalonic acid, dichloracetic acid, citraconic acid, dimethylmalonic acid, oxalic acid, d-tartaric acid, meso-tartaric acid, trichloro- lactic acid, tricarballylic acid, trimethylacetic acid, lactic acid, vinylacetic acid, pimelic acid, pyrotartaric acid, racemic acid, fumaric acid, propionic acid, propylmalonic acid, maleic acid, malonic acid, mesaconic acid, methylmalonic acid, monochloroacetic acid, n-lactic acid, malic acid, aspartic acid, Dl-alanine, glutamic acid, 3,3-dimethylglutaric acid and so forth.
- cyclic-structured acids include, preferably, ascorbic acid, atropic acid, allocinnamic acid, benzoic acid, isophthalic acid, oxybenzoic acid (m-, p-), chlorobenzoic acid (o-, m-, p-), chlorophenylacetic acid (0-, m-, p-), cinnamic acid, salicylic acid, dioxybenzoic acid (2,3, 2,4, 2,5, 2,6, 3,4, 3,5), cyclobutane-1,1-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid (trans-, cis-), cyclopropane-1,1-dicarboxylic acid, cyclopropane-1,2-dicarboxylic acid (trans, cis), cyclo hexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid (trans, cis), cyclo
- additional examples of the preferable compounds represented by Formula I include, typically, glycine, N-(2-acetamido)iminodiacetic acid, N-(2-acetamido)aminoethanesulfonic acid, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, 2-(N-morpholino)ethanesulfonic acid, 3-(N-morpholino)-2-hydroxypropanesulfonic acid, piperazine-N,N′-bis(2-ethanesulfonic acid), ethylenediaminediacetic acid, ethylenediamine-2-propionic acid, N-hydroxyethylenediamine-N,N′,N′-triacetic acid, and so forth.
- Typical examples of the compounds represented by Formula II include, preferably, amine compounds such as isoamylamine, isobutylamine, isopropylamine, ethylamine, ethylenediamine, diisoamylamine, diisobutylamine, diethylamine, dipropylamine, dimethylamine, tetramethylenediamine, triethylamine, trimethylamine, trimethylenediamine, butylamine, sec-butylamine, tert-butylamine, propylamine, pentamethylenediamine, hexamethylenetetramine, quinoline, o-toluidine, aminobenzenesulfonic acid (o-, m-, p-), N-methylbenzylamine, o-methylbenzylamine, m-methylbenzylamine, p-methylbenzylamine, 2-methylpiperidine, N-methoxybenzylamine, o-methoxybenzylamine
- preferable inorganic acid compounds include, typically, nitrous acid, phosphorous acid, hypophosphorous acid, boric acid, triphosphoric acid, metatriphosphoric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, polymetaphosphoric acid, and so forth.
- the typical compounds represented by Formula III include, for example, nitrilotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), aminomethylphosphonic acid-N,N-diacetic acid, 2-phosphonoethyliminodiacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, and so forth.
- the other additives which may be added to the constituents of the bleaching solution of the invention include, for example, defoaming agents, rust preventives such as nitrate and so forth, activators, antimolds, bleaching accelerators, and so forth.
- the bleaching solutions of the invention may be used in the form of a concentrated composition which is defined to be more condensed than a bleaching solution in such a state that it is stored in a bleaching solution preparation kit.
- the concentrated composition of bleaching solution consist of a single solution or a set of separate parts such as a set of two or three separate liquid parts, a set of one liquid part and one powder part, or the like.
- the concentrated composition of the invention means one of the separate parts described above, that is a concentrated one containing ferric aminopolycarboxylic acid complex salt.
- a bleaching solution is prepared by mixing the concentrated compositions of a bleaching solution of the invention together and/or diluting the compositions with water.
- prepared bleaching solution can be used for processing ordinary type light-sensitive materials.
- the pH of the bleaching solution of the invention is in the range of 2.0 to 6.0, preferably 2.5 to 5.5 and, more preferably, 2.5 to 5.0.
- a halide such as ammonium bromide. It is also allowed to add various types of fluorescent whitening agents and defoaming agents or surface active agents and antimolds.
- compositions (2) through (8) the proportions of ferric 1,3-propanediaminetetraacetic acid complex salts to the whole bleaching component were equivalent to 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt% and 60 wt%, respectively.
- Table-2 shows the results obtained by using Fe(III) ammonium 2-hydroxy-1,3-propanediaminetetraacetate, monohydrate, in place of Fe(III) ammonium 1,3-propanediaminetetraacetate, monohydrate and
- Table-3 shows the results obtained by using Fe(III) ammonium 1,4-butanediaminetetraacetate, monohydrate, instead.
- o mark indicates that no crystal deposition was found at all; ⁇ mark indicates that some crystal-like matters were found; and x mark indicates that crystal depositions were apparently found. The more x marks are, the more the depositions are serious.
- Example-4 The same composites as used in Example-1 were put into a polyethylene container and allowed to stand at 50°C for two weeks. After then, the concentration of the ferrous complex salt of the composite was quantitatively measured with o-phenanthroline method. The results thereof are shown in Table-4
- Table-4 shows the results obtained by using Fe(III) ammonium 2-hydroxy-1,3-propanediaminetetraacetate, monohydrate in place of Fe(III) ammonium 1,3-propanediaminetetraacetate, monohydrate, and Table-6 shows the results obtained by using Fe(III) ammonium 1,4-butanediaminetetraacetate, monohydrate.
- Example-1 Each of the same composites as in Example-1 was added by 50 g of sodium acetate as a buffer and the pH values thereof each were adjusted to be within the range of 1.8 to 7.5 as shown in Table-7.
- the resulted composites were named (1′) to (8′), respectively.
- the composites (1′) to (8′) and (1) to (8) were put into polyethylene conctainers and allowed to stand at 25°C for one month, respectively. After then, the pH variation of each composite was examined.
- Example-1 Each of the same composites as in Example-1 of which pH had been adjusted to be within the range of 1.8 to 7.5 was allowed to stand at 50°C for two weeks. After then, 500 ml of each of the resulted composites was diluted to make one liter and the pH thereof was adjusted to be 6.0, so that the bleaching solutions were prepared, respectively.
- an antihalation layer and a gelatin layer were coated on a triacetate film base. Further theron, 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 were coated so as to make the total amount of silver contents thereof to be 62 mg per 100cm2.
- the above-mentioned emulsion layers each were comprised of silver iodobromide containing silver iodide in a proportion of about 4.8 mol%.
- the blue-sensitive silver halide emulsion layer was added by ⁇ -(4-nitrophenoxy)- ⁇ -pivalyl-5-[ ⁇ -(2,4-di-t-aminophenoxy)butylamido]-2-chloroacetoanilide as a yellow coupler;
- the green-sensitive silver halide emulsion layer was added by 1-(2,4,6-trichlorophenyl)-3- ⁇ [ ⁇ -(2,4-di-t-amylphenoxy)-acetoamido]benzamido)-3-pyrazolone and 1-(2,4,6-trichlorophenyl)-3- ⁇ [ ⁇ -(2, 4-di-t-amylphenoxy)-acetoamido]benzamido ⁇ -4-(4-methoxyphenylazo)-5-pyrazolone each as magenta couplers;
- the red-sensitive silver halide emulsion layer was added by the following (C-1) as a cyan
- every amount of components which are to be added to a silver halide photographic light-sensitive material will be indicated in terms of gram per square meter, and every amount of silver or colloidal silver will be indicated in terms of silver contents, unless otherwise expressly stated.
- Layer-1 An antihalation layer, HC-1 Black colloidal silver ... 0.20 UV absorbent, UV-1 ... 0.20 Colored coupler, CC-1 ... 0.05 Colored coupler, CM-2 ... 0.05 High boiling solvent, Oil-1 ... 0.20 Gelatin ... 1.4
- Layer-2 An interlayer, IL-1 UV absorbent, UV-1 ... 0.01 High boiling solvent, Oil-1 ... 0.01 Gelatin ... 1.4
- Layer-3 A low-speed red-sensitive emulsion layer, RL Silver iodobromide emulsion, EM-1 ... 1.2 Silver iodobromide emulsion, Em-2 ... 0.6 Sensitizing dye, S-1 ...
- Layer-10 A low-speed blue-sensitive emulsion layer, BL Silver iodobromide emulsion, Em-1 ... 0.25 Silver iodobromide emulsion, Em-2 ... 0.25 Sensitizing dye, S-10 ... 7.0x10 ⁇ 4 mol/mol of silver Yellow coupler, Y-1 ... 0.6 Yellow coupler, Y-2 ... 0.12 DIR compound, D-2 ... 0.01 High boiling solvent, Oil-3 ... 0.15 Gelatin ... 1.0
- Layer-11 A high-speed blue-sensitive emulsion layer, BH Silver iodobromide emulsion, Em-4 ... 0.50 Silver iodobromide emulsion, Em-1 ...
- the first protective layer Pro-1 Finely grained silver iodobromide emulsion, having an average grain size of 0.08 ⁇ m and an AgI content of 2mol% ... 0.4 UV absorbent, UV-1 ... 0.10 UV absorbent, UV-2 ... 0.05 High boiling solvent, Oil-1 ... 0.1 High boiling solvent, Oil-4 ... 0.1 Formalin scavenger, HS-1 ...
- Coating assistant Su-2 dispersing assistant Su-3, layer hardening agents H-1 and H-2, antiseptic agent DI-1, stabilizing agent Stab-1 and antifogging agents AF-1 and AF-2.
- Em-1, Em-3 and Em-4 are octahedral silver iodobromide emulsions each having a multilayered structure, which may be prepared by referring to Japanese Patent O.P.I Publication Nos. 60-138538/1985 and 61-245151/1986.
- the average ration of grain sizes to grain thickness thereof is 1.0 and the broardness of grain distribution thereof are 14%, 10%, 12% and 12%, respectively.
- compositions of the processing solutions each used in this example were as follows.
- the bleaching step was carried out for 4 minutes in the case of using a bleaching solution containing a ferric complex salt of ethylenediaminetetraacetic acid and for 40 seconds in the case of using a bleaching solution containing a ferric complex salt of (A-1).
- the red transmission densities of their maximum density areas were measured with a photoelectrodensitometer, PDA-65A manufactured by Konica Corporation. Then, after the materials were dipped into an aqueous 5% potassium ferricyanide solution for three minutes and dried, the same measurement was made again.
- the first measured density was regarded as a relative value of 100 and the density increase, i.e., color recurring, obtained in the second measurement was expressed by a percentage relatively. The results thereof are shown in Table-10.
- Table-10 shows the degree of change of a cyan dye to a leuco dye wherein, the less the values are, the more the results are preferable.
- Table-10 (Color recurring percentage, %) (Bleaching agent) pH Ratio of ammonium ion (mol%) Aminopolycarboxylic acid 0 30 50 70 90 100 Ethylenediaminetetraacetic acid 1.0 2 2 2 2 2 1.5 2 2 2 2 2 2 2 2.0 2 2 2 2 2 2 2 2 2 2.5 2 2 2 2 2 2 3.0 2 2 2 2 2 2 2 2 4.0 2 2 2 2 2 2 2 2 2 5.0 2 2 2 2 2 2 2 2 5.5 2 2 2 2 2 2 2 2 6.0 2 2 2 2 2 2 2 2 2 6.5 2 2 2 2 2 2 2 7.5 2 2 2 2 2 2 2 Not stored 2 2 2 2 2 2 2 (A-1) 1.0 2 2 2 2 2 2 1.5 2 2 2 2 2 2 2.0 2 2 2 2 2 2 2 2 2.5 2 2 2 2 2 3.0 8 6 3 3 2 2
- the pH value of its concentrated composite should preferably be not lower than 6.5, while, in the case of using the ferric complex of (A-1) of the invention, of which the pH value is 2.0 to 5.5 which is within the range specified in the invention and the ratio of ammonium ions to cations is not lower than 50%, such ferric complex of (A-1) of the invention can be excellently preferable to use, because it does not produce any precipitate and displays a good color recurring property.
- Example-5 In the concentrated composites I and II of the bleaching solution of Example-5, the amounts of ethylenediaminetetraacetic acid and (A-1) and the pH of the concentrated composites were changed as shown in Table-11. The same storage was carried out as in Example-5 and then the appearance of the solution was observed and the experiment of the color recurring property was carried out. The results thereof are shown in Table-11 and Table -12, respectively. Those not stored were also tested for the comparison purpose, similar to those of Example-5.
- the bleaching solution of the invention containing ammonium ion as the cation of concentrated composite II should be excellently preferable, when the solution contains ferric complex salt of a compound represented by Formula A in an amount of 0.3 mol per liter and the pH thereof is within the range of 2.0 to 5.5.
- the concentrated composites of each bleaching solution were prepared in the same manner as in the concentrated composite II of the bleaching solution of Example-5, except that aminopolycarboxylic acid and the ferric ammonium salt thereof were changed to those shown in Table-13 and the pH value of the solutions were changed to 1.5, 3.0 and 6.5, respectively.
- the resulted solutions were subjected to the experiments and evaluated.
- the pH of the part not containing ferric complex salt of organic acid should preferably be within the range of 4 to 7.
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Abstract
A bleaching solution composition for processing a silver halide color photographic light-sensitive material comprising a substance capable of bleaching is disclosed, said composition comprising a ferric complex of a compound represented by the following Formula A, which has bleaching capability, in an amount of not less than 40 wt% of the total amount of said substance contained in said composition and pH of said composition is in the range of from 2.0 to 6.0:
Description
- This invention relates to a composition for processing a silver halide color photographic light-sensitive material and, more particularly, to a composition for processing a silver halide color photographic light-sensitive material which can be rapidly processed and excellent in long term stable preservability.
- To obtain a color photographic image, it is essential to carry out the so-called desilvering treatment in which a metal silver produced together with a dye image obtained in a color developing step is removed from a silver halide color photographic light-sensitive material.
- Generally, such desilvering treatment is carried out in the following steps, namely, a step of converting metal silver once into silver halide through a treatment with a bleaching solution containing halogen ions and an oxidizer, and another successive step of removing silver halide produced by the bleaching treatment and silver halide remaining undeveloped through a treatment with a fixing solution containing a silver halide solvent.
- Heretofore, following a color developing step, a silver halide color photographic light-sensitive material has been bleached with a bleaching agent such as a compound of hexancyanoferrate, ferric chloride, ferric complex salts of organic acids or the like.
- Hexacyanoferrate and ferric chloride each are excellent bleaching agents, because they have a strong bleaching capability, a high bleaching speed, i.e., a high oxidizing speed, and a sufficient capability of making a leuco compound that is an intermediate of a dye color-recurred. However, hexacyanoferrate itself is a cyan-type compound, and there may be some instances where free cyan ions may be produced from the aqueous solution thereof by photo-dissociation. In the case of the disposal of waste, it is, therefore, necessary to make the waste completely pollution-free.
- Bleaching solutions using ferric chloride have the disadvantages that metals constituting a processor containing such bleaching solution are seriously corroded away by the strong corrosive action thereof and that iron hydroxide is produced in a washing step following a bleaching step so that the so-called stains are produced on a light-sensitive material.
- Ferric complex salts of organic acids are known as a bleaching agent having less environmental problems and more ready to carry out a recovering process as compared to ferric chloride. Inter alia, ferric complex salt of ethylenediamine-tetraacetic acid is popularly put to practical use, because of its excellent bleaching capability and stability.
- In recent years, a rapid processing system is demanded more than ever along with the popularization of color photography and, in parallel with the demands for the rapid processing system, the simplification of processing control system is also demanded as most photofinishers are getting decentralized to the so-called 'mini-labs', including in-store photofinishers, who are being on the rise now. An answer to the above-mentioned demands is to simplify the labor of dissolving processing chemicals. For example, there is the so-clled processing chemical kit usually preparedy by mixing in advance its processing chemical components together each in a prescribed amount. Such kit may be ready to use when simply adding water to the mixture of the chemicals to make a uniform solution before using. The above-mentioned kits are available in both of the solid powder type and the so-called liquid type in which the solution is concentrated in advance. The latter type is preferable from the viewpoint of a simplified dossolving labor. The already known liquid type kits include, for example, those for developers, bleacher, fixers, bleach-fixers, stabilizers and so forth. However, these kits still have a problem remaining unsolved on how to concentrate their solutions without decomposition
- For example, the above-mentioned bleacher or bleach-fixer has a problem that the crystallization and deposition or deposition in the course of storage. of popular ammonium halides such as ammonium bromide are produced in low temperature storage.
- It is an object of the invention to provide a light-sensitive material bleacher which is excellent both in rapid processability and in storage stability.
- Another object of the invention is to provide a light-sensitive material bleacher having neither precipitate produced in storage nor color recurring deterioration.
- A further object of the invention is to provide a composition of a light-sensitive material bleacher excellent in storage stability.
- Still further object of the invention is to provide a composition of a light-sensitive material bleacher having neither precipitate produced in storage nor color recurring deterioration.
- The objects of the invention can be accomplished with a bleaching solution composition comprising a substance capable of bleaching, wherein said composition comprises a ferric complex of a compound represented by the following Formula A, which has bleaching capability, in an amount of not less than 40 wt% of the total amount of said substance contained in said composition and pH of said composition is in the range of from 2.0 to 6.0:
- Further, the above-mentioned objects of the invention can be accomplished in the case that the above-mentioned composition should contain ferric complex salt represented by Formula A in an amount of not less than 0.3 mol per one liter and not less than 50 mol% of the cation of the salts contained therein should comprise ammonium and, further, the pH value of the composition should be within the range of from 2.0 to 5.5; and
- Next, the compounds each represented by Formula A will be detailed.
- The substituted or unsubstituted alkylene groups each having 3 to 6 carbon atoms, represented by X, include, for example, a group of propylene, butylene, trimethylene, tetramethylene, pentamethylene or the like. The substituents thereof include, for example, a hydroxyl group. Preferable compounds represented by the foregoing Formula A will typically be given below.
- Besides the above-given examples of the compounds (A-1) through (A-8), those of sodium salt, potassium salt or ammonium salt may also be used arbitrarily.
- Among those, ammonium salts of ferric complex thereof may preferably be used from the viewpoint of the effects of the objects of the invention.
- Especially among the examples of the above-given compounds, (A-1), (A-2), (A-4) and (A-7) may more preferably be used in the invention and, inter alia, (A-1).
- The invention will be more effective when a ferric complex of a compound represented by the foregoing Formula A contains in an amount of not less than 0.3 mol per liter of a bleaching solution, more preferably within the range of from 0.3 to 2 mol per liter and, further preferably, from 0.35 to 1 mol per liter.
- As for a substance having bleaching capability which is other than those represented by Formula A, any compound known as a bleaching agent may generally be used. From the viewpoints of economy and less bleach-fog, it is preferable to use ferric aminopolycarboxylate complexes such as ferric ethylenediaminetetraacetate complex, ferric diethylenetriaminepentaacetate complex, ferric 1,2-cyclohexanediaminetetraacetate complex, ferric glycoletherdiaminetetraacetate complex.
- The compound represented by the foregoing Formula [A] should be contained in an amount of not less than 40 wt%, preferably, not less than 45 wt% and, more preferably, not less than 50 wt%, to the total amount of a substance having bleaching capability. If it is contained in an amount of not less than 50 wt%, the effects of the invention can sufficiently be displayed.
- Cations of both ferric aminopolycarboxylate complex of the foregoing bleaching agent and the salts of additives such as those given below are usually comprised of alkali metal ion, ammonium ion and hydrogen ion. In the case that the composition of the invention contains not less than 50 mol% of ammonium ion, it means that a proportion of ammonium ion to alkali metal ion is not less than 50 mol%. The composition of the invention contains, preferably, not less than 70 mol%, more preferably, not less than 90 mol% and, preferably in particular, 100 mol%, of ammonium ion.
- The above-mentioned ferric aminopolycarboxylic acid complex salt is preferred to contain free aminopolycarboxylic acid not having an iron ligand in a proportion of not more than 20 mol% and, more preferably, not more than 10 mol% to the ferric aminopolycarboxylic acid complex salt.
- It is another preferable method that two or more kinds of different aminopolycarboxylic acids are used in the above-mentioned free aminopolycarboxylic acid and ferric aminopolycarboxylic acid complex salt.
- Compounds preferably added to the composition of a bleaching solution of the invention include, for example, a haliode and a pH buffer. Such halides include, for example, halogen ion releasing compounds such as ammonium bromide, sodium bromide, potassium bromide, ammonium chloride, ammonium iodide and so forth.
- Such pH buffers preferably applicable to the invention include, for example, the compounds represented by the following Formulas I through III and inorganic compounds each containing at least one nitrogen atom, phosphorus atom or boron atom.
- B-COOH
wherein B represents an organic compound group or a hydrogen atom. - B₁-PO₃H₂
wherein B₁ is synonymous with the above-given B. -
- Typical compounds represented by Formula I include, for example, fatty acid compounds and cyclic structured acid compounds.
- Such fatty acid compounds include, preferably, formic acid, acetic acid, acrylic acid, adipic acid, acetylenedicarboxylic acid, acetoacetic acid, isopropylmalonic acid, azelaic acid, isocrotonic acid, isobutylic acid, itaconic acid, isovaleric acid, ethylmalonic acid, caproic acid, valeric acid, citric acid, glycolic acid, aconitic acid, glutaric acid, 3,3-dimethylglutaric acid, crotonic acid, chlorofumaric acid. α-chloropropionic acid, gluconic acid, glyceric acid, β-chloropropionic acid, succinic acid, cyanoacetic acid, diethylacetic acid, diethylmalonic acid, dichloracetic acid, citraconic acid, dimethylmalonic acid, oxalic acid, d-tartaric acid, meso-tartaric acid, trichloro- lactic acid, tricarballylic acid, trimethylacetic acid, lactic acid, vinylacetic acid, pimelic acid, pyrotartaric acid, racemic acid, fumaric acid, propionic acid, propylmalonic acid, maleic acid, malonic acid, mesaconic acid, methylmalonic acid, monochloroacetic acid, n-lactic acid, malic acid, aspartic acid, Dl-alanine, glutamic acid, 3,3-dimethylglutaric acid and so forth.
- The examples of the foregoing cyclic-structured acids include, preferably, ascorbic acid, atropic acid, allocinnamic acid, benzoic acid, isophthalic acid, oxybenzoic acid (m-, p-), chlorobenzoic acid (o-, m-, p-), chlorophenylacetic acid (0-, m-, p-), cinnamic acid, salicylic acid, dioxybenzoic acid (2,3, 2,4, 2,5, 2,6, 3,4, 3,5), cyclobutane-1,1-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid (trans-, cis-), cyclopropane-1,1-dicarboxylic acid, cyclopropane-1,2-dicarboxylic acid (trans, cis), cyclo hexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid (trans, cis-), cyclohexylacetic acid, cyclopentane-1,1-dicarboxylic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrophenoldiphenylic acid, sulfanilic acid, terephthalic acid, toluic acid (o-, m-, p-), naphthoic acid (α-, β-), nicotinic acid, nitroanisole (o-, m-, p-), nitrobenzoic acid, nitrophenylacetic acid (o-, m-, p-), p-nitrophenetole, p-nitrophenetole, uric acid, hippuric acid, barbituric acid, violuric acid, phenylacetic acid, phthalic acid, fluorobenzoic acid (o-, m-, p-), picorinic acid, bromobenzoic acid (o-, m-, p-), hexahydrobenzoic acid, benzilic acid, dl-mandelic acid, mesitylenic acid, methoxybenzoic acid (o-, m-, p-), methoxycinnamic acid (o-, m-, p-), p-methoxyphenylacetic acid, gallic acid, aminobenzoic acid (o-, m-, p-), and so forth.
- Besides the above, additional examples of the preferable compounds represented by Formula I include, typically, glycine, N-(2-acetamido)iminodiacetic acid, N-(2-acetamido)aminoethanesulfonic acid, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane, 2-(N-morpholino)ethanesulfonic acid, 3-(N-morpholino)-2-hydroxypropanesulfonic acid, piperazine-N,N′-bis(2-ethanesulfonic acid), ethylenediaminediacetic acid, ethylenediamine-2-propionic acid, N-hydroxyethylenediamine-N,N′,N′-triacetic acid, and so forth.
- Typical examples of the compounds represented by Formula II include, preferably, amine compounds such as isoamylamine, isobutylamine, isopropylamine, ethylamine, ethylenediamine, diisoamylamine, diisobutylamine, diethylamine, dipropylamine, dimethylamine, tetramethylenediamine, triethylamine, trimethylamine, trimethylenediamine, butylamine, sec-butylamine, tert-butylamine, propylamine, pentamethylenediamine, hexamethylenetetramine, quinoline, o-toluidine, aminobenzenesulfonic acid (o-, m-, p-), N-methylbenzylamine, o-methylbenzylamine, m-methylbenzylamine, p-methylbenzylamine, 2-methylpiperidine, N-methoxybenzylamine, o-methoxybenzylamine, m-methoxybenzylamine, p-methoxybenzylmine, benzylamine, coniine, diethylbenzylamine, cyclohexylamine, piperazine, and so forth.
- The examples of preferable inorganic acid compounds include, typically, nitrous acid, phosphorous acid, hypophosphorous acid, boric acid, triphosphoric acid, metatriphosphoric acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, polymetaphosphoric acid, and so forth.
- The typical compounds represented by Formula III include, for example, nitrilotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), aminomethylphosphonic acid-N,N-diacetic acid, 2-phosphonoethyliminodiacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, and so forth.
- Besides the above compounds, the other additives which may be added to the constituents of the bleaching solution of the invention include, for example, defoaming agents, rust preventives such as nitrate and so forth, activators, antimolds, bleaching accelerators, and so forth.
- The bleaching solutions of the invention may be used in the form of a concentrated composition which is defined to be more condensed than a bleaching solution in such a state that it is stored in a bleaching solution preparation kit.
- The concentrated composition of bleaching solution consist of a single solution or a set of separate parts such as a set of two or three separate liquid parts, a set of one liquid part and one powder part, or the like.
- The concentrated composition of the invention means one of the separate parts described above, that is a concentrated one containing ferric aminopolycarboxylic acid complex salt. In the case of a set of two liquid parts in particular, it is preferred to adjust the pH of the other concentrated part than that of the invention to be within the range of 4 to 7 so as to prevent the precipitation when mixing the parts together.
- A bleaching solution is prepared by mixing the concentrated compositions of a bleaching solution of the invention together and/or diluting the compositions with water. Thus prepared bleaching solution can be used for processing ordinary type light-sensitive materials.
- Next, some series of preferable processing steps will be given below.
- (1) Color developing - bleaching - fixing - washing,
- (2) Color developing - bleaching - fixing - washing - stabilizing,
- (3) Color developing - bleaching - fixing - stabilizing,
- (4) Color developing - bleaching - fixing - first stabilizing - second stabilizing,
- (5) Color developing - bleaching - bleach-fixing - washing,
- (6) Color developing - bleaching - bleach-fixing - washing - stabilizing,
- (7) Color developing - bleaching - bleach-fixing - stabilizing,
- (8) Color developing - bleaching - bleach-fixing - first stabilizing - second stabilizing
- The pH of the bleaching solution of the invention is in the range of 2.0 to 6.0, preferably 2.5 to 5.5 and, more preferably, 2.5 to 5.0.
- Further, it is usual to add a halide such as ammonium bromide. It is also allowed to add various types of fluorescent whitening agents and defoaming agents or surface active agents and antimolds.
- Now, some examples of the invention will be detailed below. It is, however, to be understood that the invention shall not be limited thereto.
- The combinations of the following ferric organic acid complex salts each and ammonium bromide were dissolved in water in the following proportions and the pH values of the resulted solutions each were adjusted to be within the range of 1.8 to 7.5 as shown in Table-1, respectively. Each of the resulted solutions was put separately into a polyethylene container and allowed to stand at 5°C for one month. After then, the crystal deposition of each composite, i.e., each processing kit, was examined.
-
- In the compositions (2) through (8), the proportions of ferric 1,3-propanediaminetetraacetic acid complex salts to the whole bleaching component were equivalent to 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt% and 60 wt%, respectively.
- Table-2 shows the results obtained by using Fe(III) ammonium 2-hydroxy-1,3-propanediaminetetraacetate, monohydrate, in place of Fe(III) ammonium 1,3-propanediaminetetraacetate, monohydrate and Table-3 shows the results obtained by using Fe(III) ammonium 1,4-butanediaminetetraacetate, monohydrate, instead.
Table-1 Composite No. pH of Composites 1.8 2.0 2.5 3.0 4.0 5.0 5.5 6.0 6.5 7.5 (1) xx xx xx xx xx xx xx xx xx xx (2) xx xx xx xx xx xx xx xx xx xx (3) x x x x x x x x xx xx (4) x Δ Δ Δ Δ Δ Δ Δ x xx (5) x Δ Δ o o o Δ Δ x x (6) x Δ o o o o Δ Δ x x (7) x Δ o o o o o Δ x x (8) x Δ o o o o o Δ x x Table-2 Composite No. pH of Composites 1.8 2.0 2.5 3.0 4.0 5.0 5.5 6.0 6.5 7.5 (1) xx xx xx xx xx xx xx xx xx xx (2) xx xx xx xx xx xx xx xx xx xxx (3) xx xx xx x x x xx x xx xx (4) xx x x Δ Δ Δ Δ Δ x x (5) x Δ Δ Δ Δ o o Δ x x (6) x Δ Δ o o o o Δ x x (7) x Δ o o o o Δ Δ x x (8) x Δ o o o o Δ Δ x x Table-3 Composite No. pH of Composites 1.8 2.0 2.5 3.0 4.0 5.0 5.5 6.0 6.5 7.5 (1) xx xx xx xx xx xx xx xx xx xx (2) xx xx xx xx xx xx xx xx xx xx (3) xx xx x x x x x xx x xx (4) x x Δ Δ Δ Δ Δ x x x (5) x Δ Δ Δ o o Δ Δ x x (6) x Δ Δ o o o Δ Δ x x (7) x Δ o o o o o Δ x x (8) x Δ o o o o o Δ x x - In the above-given tables, o mark indicates that no crystal deposition was found at all; Δ mark indicates that some crystal-like matters were found; and x mark indicates that crystal depositions were apparently found. The more x marks are, the more the depositions are serious.
- The same composites as used in Example-1 were put into a polyethylene container and allowed to stand at 50°C for two weeks. After then, the concentration of the ferrous complex salt of the composite was quantitatively measured with o-phenanthroline method. The results thereof are shown in Table-4
- The numerical values shown in the table each express the production ratios of ferrous complex salts. pH was adjusted to be within the range of 2.0 to 10.0 as shown in Table-4. Table-5 shows the results obtained by using Fe(III) ammonium 2-hydroxy-1,3-propanediaminetetraacetate, monohydrate in place of Fe(III) ammonium 1,3-propanediaminetetraacetate, monohydrate, and Table-6 shows the results obtained by using Fe(III) ammonium 1,4-butanediaminetetraacetate, monohydrate.
Table-4 Composite No. pH of Composites 2.0 4.0 6.0 8.0 10.0 (1) 5.2 5.5 5.3 7.1 23.0 (2) 5.4 5.3 5.8 12.1 32.4 (3) 6.0 5.9 6.7 12.3 39.6 (4) 5.9 5.8 6.4 15.6 53.3 (5) 6.1 6.3 7.0 18.2 60.9 (6) 6.1 6.4 6.9 21.0 65.1 (7) 5.8 6.0 7.1 20.4 72.5 (8) 6.6 6.5 7.0 23.6 75.5 Table-5 Composite No. pH of Composites 2.0 4.0 6.0 8.0 10.0 (1) 5.2 5.5 5.3 7.1 23.0 (2) 6.0 5.9 6.3 15.0 39.2 (3) 6.3 6.5 7.0 21.4 48.7 (4) 6.1 6.6 6.8 22.9 50.6 (5) 6.5 6.8 7.1 21.8 63.3 (6) 6.7 6.7 7.1 25.0 75.7 (7) 6.8 6.9 7.2 25.3 80.3 (8) 7.0 7.2 8.0 24.9 81.4 Table-6 Composite No. pH of Composites 2.0 4.0 6.0 8.0 10.0 (1) 5.2 5.5 5.3 7.1 23.0 (2) 5.2 5.8 5.7 10.0 36.6 (3) 6.4 6.2 7.0 18.3 38.4 (4) 6.2 6.0 6.5 20.9 40.3 (5) 6.5 6.7 6.9 23.1 53.6 (6) 6.5 6.6 6.8 33.4 62.1 (7) 6.9 6.8 7.0 38.8 73.2 (8) 7.3 7.4 7.4 50.2 73.0 - It can be found from the results shown in the above tables that the bleaching solutions of the invention do not produce many ferrous complex salts but displays excellent storage stability.
- Each of the same composites as in Example-1 was added by 50 g of sodium acetate as a buffer and the pH values thereof each were adjusted to be within the range of 1.8 to 7.5 as shown in Table-7. The resulted composites were named (1′) to (8′), respectively. The composites (1′) to (8′) and (1) to (8) were put into polyethylene conctainers and allowed to stand at 25°C for one month, respectively. After then, the pH variation of each composite was examined.
- The results thereof are shown in Table-7.
Table-7 Composite No. pH of Composites 1.8 2.0 2.5 3.0 4.0 5.0 5.5 6.0 6.5 7.5 (1) xx xx x x Δ Δ Δ o o o (1′) xx x Δ Δ o o o o o o (2) xx xx x x x x Δ Δ o Δ (2′) xx x Δ Δ o o o o o o (3) xx xx xx x x x Δ Δ Δ Δ (3′) xx x Δ Δ Δ o o o o o (4) xx xx x x x x Δ Δ Δ Δ (4′) xx x Δ Δ Δ o o o o o (5) xx xx x x x x Δ Δ Δ Δ (5′) xx x Δ Δ Δ o o o o o (6) xx xx x x x x x Δ Δ Δ (6′) xx x Δ Δ Δ Δ o o o o (7) xx xx x x x x x Δ Δ Δ (7′) xx x Δ Δ Δ Δ o o o o (8) xx xx x x x x x x Δ Δ (8′) xx x Δ Δ Δ Δ Δ o o o In the above table, mark o indicates a pH variation of not more than ±0.2; mark Δ indicates that within the range of ±0.2 to ±0.4; mark x indicates that within the range of ±0.4 to ±0.6; and mark xx indicates that of not less than 0.6. - It can be found from the above table that the bleaching solutions of the invention has a few pH variations even after they are stored and an excellent storage stability.
- The same results were obtained even when sodium phosphate was used in place of sodium acetate
- Each of the same composites as in Example-1 of which pH had been adjusted to be within the range of 1.8 to 7.5 was allowed to stand at 50°C for two weeks. After then, 500 ml of each of the resulted composites was diluted to make one liter and the pH thereof was adjusted to be 6.0, so that the bleaching solutions were prepared, respectively.
- Using these bleaching solutions and light-sensitive material samples shown below already exposed to light through a wedge, the following processing steps were carried out. After each sample was processed, silver residues in the maximum density area of the sample were measured by fluorescent X-ray method.
- The results thereof are shown in Table-8.
[Processing steps] Time Temperature Color developing 3min15sec. 38°C Bleaching 45sec. 38°C Fixing 3min15sec. 35°C Washing 3min. 30 to 34°C Stabilizing 1min20sec. 30 to34°C Drying - The following color developer, fixer and stabilizer were used.
[Color developer] Potassium carbonate 30.0 g Sodium sulfite 2.0 g Hydroxylamine sulfate 2.0 g Potassium bromide 1.2 g Sodium hydroxide 3.4 g 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate 4.6 g Add water to make 1 liter Adjust pH with sodium hydroxide and a 50% sulfuric acid solution to be pH10.1 - On a triacetate film base, an antihalation layer and a gelatin layer were coated. Further theron, 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 were coated so as to make the total amount of silver contents thereof to be 62 mg per 100cm². The above-mentioned emulsion layers each were comprised of silver iodobromide containing silver iodide in a proportion of about 4.8 mol%. In this preparation, the blue-sensitive silver halide emulsion layer was added by α-(4-nitrophenoxy)-α-pivalyl-5-[γ-(2,4-di-t-aminophenoxy)butylamido]-2-chloroacetoanilide as a yellow coupler; the green-sensitive silver halide emulsion layer was added by 1-(2,4,6-trichlorophenyl)-3-{[α-(2,4-di-t-amylphenoxy)-acetoamido]benzamido)-3-pyrazolone and 1-(2,4,6-trichlorophenyl)-3-{ [α-(2, 4-di-t-amylphenoxy)-acetoamido]benzamido}-4-(4-methoxyphenylazo)-5-pyrazolone each as magenta couplers; the red-sensitive silver halide emulsion layer was added by the following (C-1) as a cyan coupler; and each emulsion layer was further added by ordinary type additives such as a sensitizing dye, a hardener and so forth in an ordinary method.
Table-8 Composite No. pH of Composites 1.8 2.0 2.5 3.0 4.0 5.0 5.5 6.0 6.5 7.5 (1) 19.0 18.4 17.9 17.3 17.5 17.3 17.5 17.4 17.4 17.6 (2) 11.5 10.8 10.6 10.7 10.7 10.9 10.7 10.7 10.8 15.0 (3) 9.9 9.4 9.5 9.4 9.4 9.5 9.5 9.5 9.6 10.1 (4) 3.6 2.4 2.4 2.5 2.3 2.3 2.4 2.4 3.4 8.3 (5) 3.4 1.6 1.7 1.5 1.5 1.6 1.6 1.6 2.5 7.6 (6) 2.7 1.0 1.0 0.8 0.9 0.8 0.8 0.8 2.3 7.4 (7) 2.7 1.0 0.9 0.8 0.8 0.8 0.9 0.9 1.9 6.2 (8) 2.6 0.9 0.9 0.8 0.8 0.9 0.8 0.9 1.7 6.3 Numerical values in the above table represent mg of silver per 100 cm². - It can be found from the table that the bleaching solutions of the invention have a high bleaching capability and an excellent storage stability.
- In the concentrated compositions I and II of the following, aminopolycarboxylic acids were replaced by those shown in Table-9 and the pH values were changed to those within the range of 1.0 to 7.5. The proportion of ammonium ion was changed as shown in Table-9 by mixing concentrated composition I, i.e., sodium ion, and concentrated composition II, i.e., ammonium ion, each having different cation, and the mixture thereof was put into a 100 ml capacity sample bottle. The bottle was stoppered tightly and stored in a 50°C- thermostat chamber for three days. The appearance of the resulted matter was observed by three inspectors. Table-9 shows the observation results.
Concentrated composition I of bleachin solution Ferric sodium salt of aminopolycarboxylate (Refer to Table-9) 0.8 mol Aminopolycarboxylic acid (Refer to Table-9) 0.01 mol Sodium nitrate 20 g Sodium bromide 50 g Add water to make 1 liter Adjust pH with glacial acetic acid and NaCO₃ to be that shown in Table-9 Concentrated composition II of bleaching solution Ferric ammonium aminopolycarboxylate (Refer to Table-9) 0.8 mol Aminopolycarboxylic acid (Refer to Table-9) 0.01 mol Ammonium nitrate 20 g Ammonium bromide 50 g Add water to make 1 liter Adjust pH with glacial acetic acid and aqueous ammonia to be that shown in Table-9 - Next, using the concentrated solution after it was stored in the 100ml-capacity sample bottle, a color film was prepared personally and was then processed with the processing solutions in the processing steps as described below. On the other hand, as the comparisons to the above-mentioned concentrated compositions of the stored bleaching solution, the other non-stored bleaching solutions each were processed after adding a concentrated composition in an amount calculated out from the contents of the foregoing concentrated compositions.
- In this example, every amount of components which are to be added to a silver halide photographic light-sensitive material will be indicated in terms of gram per square meter, and every amount of silver or colloidal silver will be indicated in terms of silver contents, unless otherwise expressly stated.
- Onto a triacetyl cellulose film support, the layers having the following compositions were provided in order from the support, so that Sample-1 of a multilayered color photographic light-sensitive material was prepared.
-
Layer-1 : An antihalation layer, HC-1 Black colloidal silver ... 0.20 UV absorbent, UV-1 ... 0.20 Colored coupler, CC-1 ... 0.05 Colored coupler, CM-2 ... 0.05 High boiling solvent, Oil-1 ... 0.20 Gelatin ... 1.4 Layer-2 : An interlayer, IL-1 UV absorbent, UV-1 ... 0.01 High boiling solvent, Oil-1 ... 0.01 Gelatin ... 1.4 Layer-3 : A low-speed red-sensitive emulsion layer, RL Silver iodobromide emulsion, EM-1 ... 1.2 Silver iodobromide emulsion, Em-2 ... 0.6 Sensitizing dye, S-1 ... 3.0x10⁻⁴ mol/mol of silver Sensitizing dye, S-2 ... 2.5x10⁻⁴ mol/mol of silver Sensitizing dye, S-3 ... 0.6x10⁻⁴ mol/mol of silver Cyan coupler, C-4 ... 1.2 Cyan coupler, C-2 ... 0.06 Colored cyan coupler, CC-1 ... 0.05 DIR compound, D-1 ... 0.002 High boiling solvent, Oil-1 ... 0.5 Gelatin ... 1.4 Layer-4 : A high-speed red-sensitive emulsion layer, RH Silver iodobromide emulsion, Em-3 ... 2.0 Sensitizing dye, S-1 ... 2.0x10⁻⁴ mol/mol of silver Sensitizing dye, S-2 ... 2.0x10⁻⁴ mol/mol of silver Sensitizing dye, S-3 ... 0.1x10⁻⁴ mol/mol of silver Cyan coupler, C-1 ... 0.15 Cyan coupler, C-2 ... 0.018 Cyan coupler, C-3 ... 1.15 Colored cyan coupler, CC-1 ... 0.015 DIR compound, D-2 ... 0.05 High boiling solvent, Oil-1 ... 0.5 Gelatin ... 1.4 Layer 5 : An interlayer, IL-2 Gelatin ... 0.5 Layer-6 : A low-speed green-sensitive emulsion layer, GL Silver iodobromide emulsion, Em-1 ... 1.0 Sensitizing dye, S-4 ... 5.0x10⁻⁴ mol/mol of silver Sensitizing dye, S-5 ... 1.0x10⁻⁴ mol/mol of silver Magenta coupler, M-1 ... 0.5 Colored magenta coupler, CM-1 ... 0.05 DIR compound, D-2 ... 0.015 DIR compound, D-4 ... 0.020 High boiling solvent, Oil-2 ... 0.5 Gelatin ... 1.0 Layer-7 : An interlayer, IL-3 Gelatin ... 0.8 High boiling solvent, Oil-1 ... 0.2 Layer-8 : A high-speed green-sensitive emulsion layer, GH Silver iodobromide emulsion Em-3 ... 1.3 Sensitizing dye, S-6 ... 1.5x10⁻⁴ mol/mol of silver Sensitizing dye, S-7 ... 2.5x10⁻⁴ mol/mol of silver Sensitizing dye, S-8 ... 0.5x10⁻⁴ mol/mol of silver Magenta coupler, M-2 ... 0.06 Magenta coupler, M-3 ... 0.18 Colored magenta coupler, CM-2 ... 0.05 DIR compound, D-3 ... 0.01 High boiling solvent, Oil-3 ... 0.5 Gelatin ... 1.0 Layer-9 : A yellow filter layer, YC Yellow colloidal silver ... 0.1 Color contamination preventive, SC-1 ... 0.1 High boiling solvent, Oil-3 ... 0.1 Gelatin ... 0.8 Layer-10: A low-speed blue-sensitive emulsion layer, BL Silver iodobromide emulsion, Em-1 ... 0.25 Silver iodobromide emulsion, Em-2 ... 0.25 Sensitizing dye, S-10 ... 7.0x10⁻⁴ mol/mol of silver Yellow coupler, Y-1 ... 0.6 Yellow coupler, Y-2 ... 0.12 DIR compound, D-2 ... 0.01 High boiling solvent, Oil-3 ... 0.15 Gelatin ... 1.0 Layer-11: A high-speed blue-sensitive emulsion layer, BH Silver iodobromide emulsion, Em-4 ... 0.50 Silver iodobromide emulsion, Em-1 ... 0.20 Sensitizing dye, S-9 ... 1.0x10⁻⁴ mol/mol of silver Sensitizing dye, S-10 ... 3.0x10⁻⁴ mol/mol of silver Yellow coupler, Y-1 ... 0.36 Yellow coupler, Y-2 ... 0.06 High boiling solvent, Oil-3 ... 0.07 Gelatin ... 1.1 Layer-12: The first protective layer, Pro-1 Finely grained silver iodobromide emulsion, having an average grain size of 0.08µm and an AgI content of 2mol% ... 0.4 UV absorbent, UV-1 ... 0.10 UV absorbent, UV-2 ... 0.05 High boiling solvent, Oil-1 ... 0.1 High boiling solvent, Oil-4 ... 0.1 Formalin scavenger, HS-1 ... 0.5 Formalin scavenger, HS-2 ... 0.2 Gelatin ... 1.0 Layer13: The second protective layer, Pro-2 Surfactant, Su-1 ... 0.005 Alkali-soluble matting agent, having an average particle size of 2µm ... 0.10 Cyan dye, AIC-1 ... 0.005 Magenta dye, AIM-1 ... 0.01 Lubricant, WAX-1 ... 0.04 Gelatin ... 0.8 - Besides the above, the following additives were added to each of the layers. Coating assistant Su-2, dispersing assistant Su-3, layer hardening agents H-1 and H-2, antiseptic agent DI-1, stabilizing agent Stab-1 and antifogging agents AF-1 and AF-2.
- Em-1: A monodisperse type silver iodobromide emulsion containing low silver iodide on the surface thereof having an average grain size of 0.46µm and an average silver iodide content of 7.5 mol%,
- Em-2: A monodisperse type silver iodobromide emulsion having a uniform compositions having an average grain size of 0.32 µm and an average silver iodide content of 2.0 mol%,
- Em-3: A monodisperse type silver iodobromide emulsion containing low silver iodide on the surface thereof having an average grain size of 0.78µm and an average silver iodide content of 6.0 mol%, and
- Em-4: A monidisperse type silver iodobromide emulsion containing low silver iodide on the surface thereof having an average grain size of 0.95µm and an average silver iodide content of 8.0 mol%
- Em-1, Em-3 and Em-4 are octahedral silver iodobromide emulsions each having a multilayered structure, which may be prepared by referring to Japanese Patent O.P.I Publication Nos. 60-138538/1985 and 61-245151/1986.
-
- Thus prepared light-sensitive materials were exposed to white light through a wedge and then processed in the following processing steps.
<Development process> Processing step Processing time Processing temperature Number of tanks Color developing 3min.15sec. 38°C 1 Bleaching See Note-1 38°C 1 Fixing 1min.15sec. 38°C 1 Stabilizing 1min. 38°C 3 (Cascade) Drying 60sec. 40 to 80°C - Note-1: Bleaching time was determined by the results of the preliminary experiments of the foregoing light-sensitive materials, because a period of time necessary for completiing a bleaching step depends on the kinds and adding amounts of aminopolycarboxylic acids. - The compositions of the processing solutions each used in this example were as follows.
[Color developing solution] Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 4 g Sodium bromide 1.3 g Potassium iodide 1.2 g Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate 4.8 g Potassium hydroxide 1.2 g Add water to make 1 liter Adjust pH with potassium hydroxide or a 50% sulfuric acid solution to be pH10.06 [Bleaching solution] Concentrated composition after stored (See Table-9) 300 ml Ammonium bromide 140 g Ammonium acetate 80 g Imidazole 5 g Add water to make 1 liter Adjust pH with aqueous ammonia or glacial acetic acid to be pH5.0 [Fixing solution] Ammonium thiosulfate 250 g Ammonium sulfite 30 g Disodium ethylenediaminetetraacetate 0.5 g Sodium carbonate 10 g The foregoing bleaching solution 100 ml Add water to make 1 liter Adjust pH with acetic acid or aqueous ammonia to be pH7.0 [Stabilizing solution] Aqueous 37% formaldehyde solution 2 ml 5-chloro-2-methyl-4-isothiazoline-3-one 0.05 g Emulgen 810 1 ml Formaldehyde-sodium bisulfite adduct 2 g Add water to make 1 liter Adjust pH with aqueous ammonia and a 50% sulfuric acid solution to be pH7.0 - The bleaching step was carried out for 4 minutes in the case of using a bleaching solution containing a ferric complex salt of ethylenediaminetetraacetic acid and for 40 seconds in the case of using a bleaching solution containing a ferric complex salt of (A-1).
- After the light-sensitive materials were processed, the red transmission densities of their maximum density areas were measured with a photoelectrodensitometer, PDA-65A manufactured by Konica Corporation. Then, after the materials were dipped into an aqueous 5% potassium ferricyanide solution for three minutes and dried, the same measurement was made again. The first measured density was regarded as a relative value of 100 and the density increase, i.e., color recurring, obtained in the second measurement was expressed by a percentage relatively. The results thereof are shown in Table-10.
- Table-10 shows the degree of change of a cyan dye to a leuco dye wherein, the less the values are, the more the results are preferable.
Table-10 (Color recurring percentage, %) (Bleaching agent) pH Ratio of ammonium ion (mol%) Aminopolycarboxylic acid 0 30 50 70 90 100 Ethylenediaminetetraacetic acid 1.0 2 2 2 2 2 2 1.5 2 2 2 2 2 2 2.0 2 2 2 2 2 2 2.5 2 2 2 2 2 2 3.0 2 2 2 2 2 2 4.0 2 2 2 2 2 2 5.0 2 2 2 2 2 2 5.5 2 2 2 2 2 2 6.0 2 2 2 2 2 2 6.5 2 2 2 2 2 2 7.5 2 2 2 2 2 2 Not stored 2 2 2 2 2 2 (A-1) 1.0 2 2 2 2 2 2 1.5 2 2 2 2 2 2 2.0 2 2 2 2 2 2 2.5 2 2 2 2 2 2 3.0 8 6 3 3 2 2 4.0 10 6 4 3 2 2 5.0 11 7 4 4 3 2 5.5 12 9 5 4 4 3 6.0 15 14 14 13 13 12 6.5 22 21 22 21 21 21 7.5 25 26 26 27 27 28 Not stored 2 2 2 2 2 2 - As are obvious from Table-9 and Table-10, it is found that, in the case of using ethylenediamine tetraacetic acid, the pH value of its concentrated composite should preferably be not lower than 6.5, while, in the case of using the ferric complex of (A-1) of the invention, of which the pH value is 2.0 to 5.5 which is within the range specified in the invention and the ratio of ammonium ions to cations is not lower than 50%, such ferric complex of (A-1) of the invention can be excellently preferable to use, because it does not produce any precipitate and displays a good color recurring property.
- In the concentrated composites I and II of the bleaching solution of Example-5, the amounts of ethylenediaminetetraacetic acid and (A-1) and the pH of the concentrated composites were changed as shown in Table-11. The same storage was carried out as in Example-5 and then the appearance of the solution was observed and the experiment of the color recurring property was carried out. The results thereof are shown in Table-11 and Table -12, respectively. Those not stored were also tested for the comparison purpose, similar to those of Example-5.
Table-11 (Appearance of solution) Concentrated composite A-1 mol/liter EDTA* mol/liter pH of Concentrated composite 1.5 2.5 4.0 5.5 6.5 I (Sodium ion) 0.2 - + - - - - 0.3 - ++ - - - - 0.35 - +++ + - - - 1.0 - +++ ++ ++ ++ - 2.0 - +++ +++ +++ +++ - 0.4 0.6 +++ + + + - 0.5 0.5 +++ + + + - 0.6 0.3 +++ + + + - II (Ammonium ion) 0.2 - + - - - - 0.3 - +++ - - - - 0.35 - +++ - - - - 1.0 - +++ - - - - 2.0 - +++ ++ ++ ++ - 0.4 0.6 +++ - - - - 0.5 0.5 +++ - - - - 0.6 0.3 +++ - - - - 0.8 - +++ - - - - 0.8 0.2 +++ - - - - 0.8 0.4 +++ - - - - * EDTA: Ethylenediaminetetraacetic acid Table-12 (Color recurring property, %) Concentrated composite A-1 mol/liter EDTA* mol/liter pH of Concentrated composite Non-stored (For comparison) Bleaching time 1.5 2.5 4.0 5.5 6.5 I (Sodium ion) 0.2 - 2 2 2 3 16 2 3min. 0.3 - 2 4 5 6 17 2 2min. 0.35 - 2 6 8 10 19 2 1min.30sec. 1.0 - 2 7 10 12 22 2 45sec. 2.0 - 2 7 9 11 18 2 30sec. 0.4 0.6 2 4 4 5 13 2 1min.50sec. 0.5 0.5 2 6 7 9 17 2 60sec. 0.6 0.3 2 7 8 10 17 2 50sec. II (Ammonium ion) 0.2 - 2 2 2 3 16 2 3min. 0.3 - 2 2 2 3 17 2 2min. 0.35 - 2 2 2 3 19 2 1min.30sec. 1.0 - 2 2 2 3 21 2 45sec. 2.0 - 2 2 2 3 18 2 30sec. 0.4 0.6 2 2 2 3 12 2 1min.50sec. 0.5 0.5 2 2 2 3 14 2 60sec. 0.6 0.3 2 2 2 3 16 2 50sec. 0.8 - 2 2 2 3 21 2 45sec. 0.8 0.2 2 2 2 3 18 2 45sec. 0.8 0.4 2 2 2 3 16 2 45sec. * EDTA = Ethylenediaminetetraacetic acid - As are obvious from Table-11 and Table-12. it is found that the bleaching solution of the invention containing ammonium ion as the cation of concentrated composite II should be excellently preferable, when the solution contains ferric complex salt of a compound represented by Formula A in an amount of 0.3 mol per liter and the pH thereof is within the range of 2.0 to 5.5.
- The concentrated composites of each bleaching solution were prepared in the same manner as in the concentrated composite II of the bleaching solution of Example-5, except that aminopolycarboxylic acid and the ferric ammonium salt thereof were changed to those shown in Table-13 and the pH value of the solutions were changed to 1.5, 3.0 and 6.5, respectively. The resulted solutions were subjected to the experiments and evaluated.
- The bleaching step thereof was carried out for 6 minutes so as to satisfactorily bleach the samples. The results thereof are shown in Table-13.
Table-13 Chelating agent of ferric complex of organic acid Appearance of solution Color recurring (%) pH of concentrated composite pH of concentrated composite 1.5 3.0 6.5 1.5 3.0 6.5 EDTA* +++ +++ - 2 2 2 (A - 1) +++ - - 2 2 21 (A - 2) +++ - - 2 3 20 (A - 3) +++ - - 2 4 19 (A - 4) +++ - - 2 3 15 (A - 5) +++ - - 2 4 27 (A - 7) +++ - - 2 3 18 * EDTA = Ethylenediaminetetraacetic acid - As is obvious from Table-13, it is found that the invention can be effective when using not only a ferric complex of the compound (A-1) but also those of the compounds (A-2), (A-3), (A-4), (A-5) and (A-7) each represented by Formula A.
- Concentrated solution of ammonium bromide, ammonium acetate and imidazole, which are components other than ones in the bleaching solution used in Example-5 was prepared as the extra parts in concentration ratios and pH values shown in Table-14. The resulted solution was stored in 50°C thermostat tanks for three days. On the other hand, another bleaching solution was prepared by using the non-stored concentrated composite II having a pH of 3.0 which is the same as in Example-5. Each of the bleaching solution were subjected to the same experiment as in Example-5 so as to evaluate their color recurring properties. The results thereof are shown in Table-14.
Table-14 Concentration ratio pH of concentrated composite 2.0 3.0 4.0 5.5 7.0 8.0 700 ml/liter 38 25 3 2 1 13 300 ml/liter 40 26 3 2 1 14 - From the results shown in Table-14 above, it is found that, in the case of a bleaching solution in two liquid parts of concentrated composites, the pH of the part not containing ferric complex salt of organic acid should preferably be within the range of 4 to 7.
- The following bleaching solutions each having a single liquid part of concentrated composites were subjected to the same experiment and evaluation as in Example-5.
- The single liquid part of each bleaching solution was diluted double. The results thereof are shown in Table-15.
Bleaching solution having a single liquid concentrated composite III Ferric sodium salt of Exemplified compound (A-1) 0.8mol Compound shown in Table-15 See Table-15 Sodium bromide 150 g Add water to make 900 ml Adjust pH with acetic acid and NaCO₃ to pH4.8 Further add water to make 1 liter Bleaching solution having a single liquid concentrated composite IV Ferric ammonium salt of Exemplified compound (A-1) 0.8mol Compound shown in Table-15 See Table-15 Sodium bromide 150 g Add water to make 900 ml Adjust pH with acetic acid and NaCO₃ to pH4.8 Further add water to make 1 liter Table-15 No. Compound added Amount added mol/l Apparance of solution Color recurring Concentrated composite Concentrated composite III IV III IV 1 None - + - 4 2 2 Citric acid 0.5 ++ - 11 2 3 Succinic acid 0.5 ++ - 10 2 4 Salicylic acid 0.5 ++ - 12 2 5 Phthalic acid 0.5 ++ - 10 2 6 Triethylamine 0.5 ++ - 9 2 7 Hexamethylene tetramine 0.5 ++ - 8 2 8 Nitrous acid 0.5 ++ - 10 2 9 Triphosphoric acid 0.5 ++ - 10 2 10 Acetic acid 0.5 + - 5 2 11 ditto 1.0 ++ - 7 2 12 ditto 1.5 ++ - 10 2 13 ditto 2.0 ++ - 12 2 14 Sulfuric acid 0.5 ++ + 4 2 15 Ethyl alcohol 0.5 + - 4 2 16 Ethylene glycol 0.5 + - 4 2 17 Tetramethyl ammonium chloride 0.5 ++ ++ 31 20 In Table-15 above, Compounds No. 2 through No. 15 should be preferable for preventing bleach-fog. - As is obvious from the results shown in Table-15, it is found that, in the case that a concentrated composite contains one of the compounds No. 2 through No. 13, precipitates are liable to be produced, however, the invention has effectively worked against such precipitation production. It is also found that the invention was extremely effective in color recurring when any of the compounds No. 2 through No. 13 was contained.
Claims (9)
1. A bleaching solution composition for processing a silver halide color photographic light-sensitive material, comprising a substance capable of bleaching, wherein said composition comprises a ferric complex of a compound represented by the following Formula A, which has bleaching capability, in an amount of not less than 40 wt% of the total amount of said substance contained in said composition and pH of said composition is in the range of from 2.0 to 6.0:
wherein A₁, A₂, A₃ and A₄ each may be the same or different from each other and represent CH₂OH-, -COOM or -PO₃M₁M₂ in which M, M₁ and M₂ each represent a hydrogen atom, a sodium atom, potassium atom or an ammonium group; X represents a substituted or an unsubstituted alkylene group having 3 to 6 carbon atoms.
2. The composition of claim 1, wherein said composition comprises said ferric complex in an amount of not less than 45 wt% of the total amount of said substance in said composition.
3. The composition of claim 1, wherein said composition comprises said ferric complex in an amount of not less than 50 wt% of the total amount of said substance in said composition.
4. The composition of claim 1, wherein pH of said composition is in the range of from 2.0 to 5.5.
5. The composition of claim 1, wherein pH of said composition is in the range of from 2.5 to 5.5.
6. The composition of claim 1, wherein pH of said composition is in the range of from 2.5 to 5.0.
7. The composition of claim 1, wherein said composition is comprised of not less than 50 mol% of an ammonium cation to the total cation.
8. A bleaching solution composition for processing a silver halide color photographic light-sensitive material, comprising a substance capable of bleaching, wherein said composition comprises not less than 0.3 mol per liter of a ferric complex of a compound represented by the following Formula A and not less than 50 mol% of an ammonium cation to the total cation contained in said composition and pH of said composition is in the range of from 2.0 to 6.0:
wherein A₁, A₂, A₃ and A₄ each may be the same or different from each other and represent CH₂OH-, -COOM or -PO₃M₁M₂ in which M, M₁ and M₂ each represent a hydrogen atom, a sodium atom, potassium atom or an ammonium group; X represents a substituted or an unsubstituted alkylene group having 3 to 6 carbon atoms.
9. The composition of claim 8, wherein pH of said composition is in the range of from 2.0 to 5.5.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP71266/88 | 1988-03-25 | ||
JP63071266A JP2686952B2 (en) | 1988-03-25 | 1988-03-25 | Concentrating composition of bleaching solution for silver halide color photographic light-sensitive material |
JP7126588A JPH01244453A (en) | 1988-03-25 | 1988-03-25 | Composition for silver halide color photographic sensitive material |
JP71265/88 | 1988-03-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0334317A2 true EP0334317A2 (en) | 1989-09-27 |
EP0334317A3 EP0334317A3 (en) | 1990-05-30 |
Family
ID=26412391
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89105128A Withdrawn EP0334317A3 (en) | 1988-03-25 | 1989-03-22 | Composition for processing silver halide color photographic light-sensitive material |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP0334317A3 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0450293A2 (en) * | 1990-02-21 | 1991-10-09 | Konica Corporation | Bleaching solution for light-sensitive silver halide color photographic material and processing method using the same |
US5064750A (en) * | 1988-08-05 | 1991-11-12 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material |
EP0652476A1 (en) * | 1993-11-05 | 1995-05-10 | Agfa-Gevaert AG | Bleaching agent |
EP0344470B1 (en) * | 1988-04-28 | 1995-08-02 | Fuji Photo Film Co., Ltd. | Bleach-fixing solution concentrate composition and method for processing silver halide color photographic materials |
EP1308778A1 (en) * | 2001-10-30 | 2003-05-07 | Eastman Kodak Company | Odorless photographic bleach-fixing composition and method of use |
EP1403705A2 (en) * | 2002-09-27 | 2004-03-31 | Eastman Kodak Company | Odorless photographic bleaching composition and color photographic processing |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3518257A1 (en) * | 1984-05-21 | 1985-11-21 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | METHOD FOR PROCESSING A LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIAL |
EP0293729A1 (en) * | 1987-05-25 | 1988-12-07 | Konica Corporation | Composition containing ferric complex salt |
EP0329088A2 (en) * | 1988-02-15 | 1989-08-23 | Konica Corporation | Processing method and bleaching solution for silver halide color photographic light-sensitive materials |
-
1989
- 1989-03-22 EP EP89105128A patent/EP0334317A3/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3518257A1 (en) * | 1984-05-21 | 1985-11-21 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | METHOD FOR PROCESSING A LIGHT-SENSITIVE COLOR PHOTOGRAPHIC MATERIAL |
EP0293729A1 (en) * | 1987-05-25 | 1988-12-07 | Konica Corporation | Composition containing ferric complex salt |
EP0329088A2 (en) * | 1988-02-15 | 1989-08-23 | Konica Corporation | Processing method and bleaching solution for silver halide color photographic light-sensitive materials |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0344470B1 (en) * | 1988-04-28 | 1995-08-02 | Fuji Photo Film Co., Ltd. | Bleach-fixing solution concentrate composition and method for processing silver halide color photographic materials |
US5064750A (en) * | 1988-08-05 | 1991-11-12 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material |
EP0450293A2 (en) * | 1990-02-21 | 1991-10-09 | Konica Corporation | Bleaching solution for light-sensitive silver halide color photographic material and processing method using the same |
EP0450293A3 (en) * | 1990-02-21 | 1993-02-10 | Konica Corporation | Bleaching solution for light-sensitive silver halide color photographic material and processing method using the same |
EP0652476A1 (en) * | 1993-11-05 | 1995-05-10 | Agfa-Gevaert AG | Bleaching agent |
US5565138A (en) * | 1993-11-05 | 1996-10-15 | Agfa Ag | Bleach |
EP1308778A1 (en) * | 2001-10-30 | 2003-05-07 | Eastman Kodak Company | Odorless photographic bleach-fixing composition and method of use |
US6727051B2 (en) | 2001-10-30 | 2004-04-27 | Eastman Kodak Company | Odorless photographic bleach-fixing composition and method of use |
EP1403705A2 (en) * | 2002-09-27 | 2004-03-31 | Eastman Kodak Company | Odorless photographic bleaching composition and color photographic processing |
EP1403705A3 (en) * | 2002-09-27 | 2004-04-21 | Eastman Kodak Company | Odorless photographic bleaching composition and color photographic processing |
US6828084B2 (en) | 2002-09-27 | 2004-12-07 | Eastman Kodak Company | Odorless photographic bleaching composition and color photographic processing |
Also Published As
Publication number | Publication date |
---|---|
EP0334317A3 (en) | 1990-05-30 |
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