JPH04190349A - Processing of silver halogenide color photosensitive material - Google Patents
Processing of silver halogenide color photosensitive materialInfo
- Publication number
- JPH04190349A JPH04190349A JP32205890A JP32205890A JPH04190349A JP H04190349 A JPH04190349 A JP H04190349A JP 32205890 A JP32205890 A JP 32205890A JP 32205890 A JP32205890 A JP 32205890A JP H04190349 A JPH04190349 A JP H04190349A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- acid
- hydrogen atom
- color
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000012545 processing Methods 0.000 title claims abstract description 41
- 229910052709 silver Inorganic materials 0.000 title claims description 52
- 239000004332 silver Substances 0.000 title claims description 52
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 12
- -1 chlorine ions Chemical class 0.000 claims abstract description 61
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 21
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 34
- 229910001868 water Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000011282 treatment Methods 0.000 claims description 16
- 238000011161 development Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 14
- 125000003277 amino group Chemical group 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 230000006641 stabilisation Effects 0.000 claims description 6
- 238000011105 stabilization Methods 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 62
- 239000000839 emulsion Substances 0.000 description 54
- 239000007788 liquid Substances 0.000 description 54
- 239000000243 solution Substances 0.000 description 44
- 239000000975 dye Substances 0.000 description 39
- 239000003795 chemical substances by application Substances 0.000 description 27
- 235000002639 sodium chloride Nutrition 0.000 description 26
- 239000003381 stabilizer Substances 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 19
- 239000002253 acid Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 230000018109 developmental process Effects 0.000 description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 14
- 108010010803 Gelatin Proteins 0.000 description 13
- 229920000159 gelatin Polymers 0.000 description 13
- 239000008273 gelatin Substances 0.000 description 13
- 235000019322 gelatine Nutrition 0.000 description 13
- 235000011852 gelatine desserts Nutrition 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000003755 preservative agent Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- 239000002738 chelating agent Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 230000001235 sensitizing effect Effects 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000004061 bleaching Methods 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
- 238000009826 distribution Methods 0.000 description 6
- 229960003330 pentetic acid Drugs 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000002429 hydrazines Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 101100221809 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cpd-7 gene Proteins 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 4
- 150000004989 p-phenylenediamines Chemical class 0.000 description 4
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical compound OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 239000012463 white pigment Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000002443 hydroxylamines Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 125000000565 sulfonamide group Chemical group 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-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
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 2
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 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
- 229940126062 Compound A Drugs 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 241000282887 Suidae Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 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
- OTZKODYMSSYHRQ-UHFFFAOYSA-N acetic acid;azane;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid Chemical compound N.CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O OTZKODYMSSYHRQ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 239000002585 base 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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229960005102 foscarnet Drugs 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- LTHCIVZEQZAFPI-UHFFFAOYSA-N ethane-1,2-diamine;2-(2-hydroxyphenyl)acetic acid Chemical compound NCCN.OC(=O)CC1=CC=CC=C1O LTHCIVZEQZAFPI-UHFFFAOYSA-N 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical class O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WTNULKDCIHSVKN-UHFFFAOYSA-N imidazo[1,2-a]pyridin-2-ol Chemical compound C1=CC=CC2=NC(O)=CN21 WTNULKDCIHSVKN-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002545 isoxazoles Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical class [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical class N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-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
- ZJEFVRRDAORHKG-UHFFFAOYSA-M potassium;2-hydroxy-5-sulfobenzoate Chemical compound [K+].OC1=CC=C(S(O)(=O)=O)C=C1C([O-])=O ZJEFVRRDAORHKG-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 125000001500 prolyl group Chemical class [H]N1C([H])(C(=O)[*])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- GGOZGYRTNQBSSA-UHFFFAOYSA-N pyridine-2,3-diol Chemical class OC1=CC=CN=C1O GGOZGYRTNQBSSA-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Chemical class 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- RILRIYCWJQJNTJ-UHFFFAOYSA-M sodium;3-carboxy-4-hydroxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(S([O-])(=O)=O)=CC=C1O RILRIYCWJQJNTJ-UHFFFAOYSA-M 0.000 description 1
- QHFDHWJHIAVELW-UHFFFAOYSA-M sodium;4,6-dioxo-1h-1,3,5-triazin-2-olate Chemical class [Na+].[O-]C1=NC(=O)NC(=O)N1 QHFDHWJHIAVELW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 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
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 description 1
- 235000010296 thiabendazole Nutrition 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- QGVNJRROSLYGKF-UHFFFAOYSA-N thiobarbital Chemical compound CCC1(CC)C(=O)NC(=S)NC1=O QGVNJRROSLYGKF-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 125000002987 valine group Chemical class [H]N([H])C([H])(C(*)=O)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はハロゲン化銀カラー写真感光材の処理方法に関
し、特に、連続処理時やカラー現像液の経時劣化に伴う
写真特性の変動(特に最大濃度、Dmax )を小さく
し、同時に、処理タンクや感光材料の汚れを改良した処
理方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic materials, in particular changes in photographic properties (especially the maximum The present invention relates to a processing method that reduces contamination (density, Dmax) and at the same time reduces staining of processing tanks and photosensitive materials.
(従来の技術)
ハロゲン化銀カラー写真感光材料の処理方法において、
処理時間の短縮化や補充液量の低減は、昨今の仕上がり
納期の短縮化や地球規模での環境問題に答える意味でも
益々重要な課題となりつつある。このようなニーズに対
して、国際公開特許WO37104534号や特開昭6
1−70552号には高塩化銀乳剤を用いた迅速処理や
低補充処理の技術が開示されている。確かに高塩化銀乳
剤を用いた場合には、迅速化や低補充化がより容易に達
成できようになることは事実であるが、同時に新たな問
題が発生することとなった。即ち、現像時間の短縮化に
伴い、現像時間内に銀現像が十分に纒了しないうちに次
の脱銀工程へ進む場合がある。(Prior Art) In a method for processing silver halide color photographic materials,
Shortening processing time and reducing the amount of replenisher are becoming increasingly important issues in terms of shortening the current delivery time and responding to global environmental issues. In response to these needs, International Publication Patent No. WO37104534 and Japanese Patent Application Laid-Open No. 6
No. 1-70552 discloses a technique for rapid processing and low replenishment processing using a high silver chloride emulsion. It is true that when a high silver chloride emulsion is used, speeding up and low replenishment can be achieved more easily, but at the same time new problems have arisen. That is, as the development time is shortened, the next desilvering step may proceed before the silver development is sufficiently completed within the development time.
(発明が解決しようとする課題)
此の場合には現像条件の微細な変化や、現像液組成の微
妙な違いにより、写真特性が変動し易(なり、とりわけ
、最大濃度の変動が顕著に現れることが判明した。さら
に、従来から現像液の保恒剤として用いられていた亜硫
酸塩は、発色濃度に影響を与えるため、その使用量は極
力少なくすることが好ましいが、亜硫酸塩を低減すると
カラー現像主薬の酸化物であるクールが発生し易くなり
、感光材料や処理機の不所望な汚染の原因となる。(Problem to be solved by the invention) In this case, photographic properties tend to fluctuate due to minute changes in developing conditions or subtle differences in developer composition. In addition, sulfites, which have traditionally been used as preservatives in developing solutions, affect the color density, so it is preferable to use as little as possible; Cool, which is an oxide of the developing agent, is likely to be generated, causing undesirable contamination of photosensitive materials and processing equipment.
更には、処理タンク内での現像主薬に起因した析出物が
発生し易くなり、汚れやキズ等の原因となる。したがっ
て、このような問題点の解決法が待ち望まれていた。Furthermore, precipitates caused by the developing agent in the processing tank are likely to occur, causing stains, scratches, and the like. Therefore, a solution to these problems has been awaited.
他方、カラー現像液に各種高分子を添加する技術は古く
から知られている。例えば、特公昭46−41676号
及び同5(1−21250号にはセルロース類を添加す
る技術、同47−20743号にはピロリドン類を添加
する技術、同58−16179号にはポリマーを添加す
る技術が開示されている。これらは、主に現像主薬の液
中での析出防止を目的にしたもので、本発明の効果に関
しては開示されておらず、また単に上記化合物を添加し
ても、本発明の目的を十分に達成することは出来なかっ
た。On the other hand, techniques for adding various polymers to color developers have been known for a long time. For example, Japanese Patent Publication Nos. 46-41676 and 5 (1-21250) use a technology to add cellulose, Japanese Patent Publication No. 47-20743 uses a technique to add pyrrolidones, and Japanese Patent Publication No. 58-16179 uses a technology to add polymers. These techniques are mainly aimed at preventing precipitation of a developing agent in a solution, and do not disclose the effects of the present invention, and even if the above compound is simply added, The object of the present invention could not be fully achieved.
また、界面活性剤をカラー現像液に添加する技術として
は特開昭62−234161号や同62−42155号
に記載されている。しかしながら前者の界面活性剤は本
発明の目的においては、効果は十分でなく、また、後者
においては、本発明の問題点には全く言及されておらず
、更に、後者の系においては、効果は不十分であった。Further, a technique for adding a surfactant to a color developer is described in JP-A-62-234161 and JP-A-62-42155. However, the former surfactant is not sufficiently effective for the purpose of the present invention, the latter does not mention the problems of the present invention at all, and furthermore, the latter system has no sufficient effect. It was insufficient.
また、リサーチ・デスクロジャー16986号には、ノ
ニオン系の界面活性剤を添加することで、増感色素の洗
い出しを促進し、残色を低減する技術が開示されている
が、本発明の問題点には全く言及されておらず、本発明
の系においては効果は不十分であった。Furthermore, Research Disclosure No. 16986 discloses a technique for promoting washout of sensitizing dyes and reducing residual color by adding a nonionic surfactant; however, there are problems with the present invention. was not mentioned at all, and the effect was insufficient in the system of the present invention.
従って、本発明の課題は、連続処理時やカラー現像液の
経時劣化に伴う写真特性の変動(特に、最大濃度の変化
)を小さくし、同時に、処理タンクや感光材料の汚れを
改良し、更に、タンク内の析出物の発生(特に、気液界
面での析出物の成長)を防止することにある。Therefore, an object of the present invention is to reduce fluctuations in photographic properties (particularly changes in maximum density) that occur during continuous processing or due to deterioration of color developers over time, and at the same time, to improve staining of processing tanks and photosensitive materials. The objective is to prevent the generation of precipitates in the tank (especially the growth of precipitates at the gas-liquid interface).
(課題を達成するための手段)
本発明の課題は以下の技術を実施することにより、効果
的に達成できることを見出した。(Means for Achieving the Objects) It has been found that the objects of the present invention can be effectively achieved by implementing the following techniques.
(1)ハロゲン化銀カラー写真感光材料をカラー現像の
後に脱銀処理し、続いて水洗及び/又は安定化処理を行
なう処理方法に於いて、上記カラー現像液が0.04モ
ル/p以上の塩素イオンと、4X10−5〜2X10−
’モル/Pの臭素イオンを含有し、且つ、下記一般式(
I)又は(II)で表される化合物の少なくとも一種を
含有することを特徴とするハロゲン化銀カラー写真感光
材料の処理方法。(1) In a processing method in which a silver halide color photographic light-sensitive material is desilvered after color development, followed by water washing and/or stabilization treatment, the color developer contains 0.04 mol/p or more. Chlorine ion and 4X10-5 to 2X10-
'mol/P of bromide ions, and has the following general formula (
A method for processing a silver halide color photographic material, which comprises at least one of the compounds represented by I) or (II).
一般式(I)
式中、R,、R,、R,及びR4は各々水素原子、アル
キル基もしくはアルケニル基を表す。nは1〜3の整数
を表し、Mは水素原子もしくは対カチオンを表す。General Formula (I) In the formula, R, , R, , R, and R4 each represent a hydrogen atom, an alkyl group, or an alkenyl group. n represents an integer of 1 to 3, and M represents a hydrogen atom or a counter cation.
一般式(It)
A−(X)、−B
式中、Aはアルキル基、アルコキシ基、フェニル基、フ
ェノキシ基を表す。Xは下記の構造を表す。General formula (It) A-(X), -B In the formula, A represents an alkyl group, an alkoxy group, a phenyl group, or a phenoxy group. X represents the following structure.
−(CH2)p−(C)I)、−(CIIZ)、 −0
−p、q、rは各々0.1.2または3の整数を表し全
て同時に0となることは無い。Yは−OHまたはメチル
基を表す。又、Xは上記構造式で表される異なった構造
を複数個有しても良い。-(CH2)p-(C)I), -(CIIZ), -0
-p, q, and r each represent an integer of 0.1.2 or 3, and cannot all be 0 at the same time. Y represents -OH or a methyl group. Further, X may have a plurality of different structures represented by the above structural formula.
mは2以上の整数を表す。m represents an integer of 2 or more.
Bは水素原子、アルキル基、アリール基または−so、
zを表す。Zは水素原子、またはカチオンを表す。B is a hydrogen atom, an alkyl group, an aryl group or -so,
represents z. Z represents a hydrogen atom or a cation.
(2)上記ハロゲン化銀カラー写真感光材料の塗布銀量
が0.75g/m”以下であることを特徴とする上記第
(1)項記載のハロゲン化銀カラー写真感光材料の処理
方法。(2) The method for processing a silver halide color photographic material according to item (1) above, wherein the amount of coated silver in the silver halide color photographic material is 0.75 g/m'' or less.
(3)上記カラー現像液が実質的に亜硫酸イオンを含を
しないことを特徴とする上記第(1)項記載のハロゲン
化銀カラー写真感光材料の処理方法。(3) The method for processing a silver halide color photographic material according to item (1) above, wherein the color developer does not substantially contain sulfite ions.
このように、本発明の如く、特定濃度のノ\ロゲンと前
述の化合物を併用することによって写真特性の変動の抑
制だけでなく、処理タンク内の析出物の発生、成長を著
しく抑制しえたことはまったく予想外のことである。こ
こで析出物とは、液中に溶解度の点で析出ないし晶出す
るものではなく、カラー現像液(特に、疲労した液)が
空気とタンクの部材(例えば壁面、浮きブタなどの合成
樹脂からなる部材〕と接触する付近にて発生するもので
あり、液中のものとはまったく異なる。この現象は、特
にタンクのコーナ一部分や浮きブタなどの狭くなった個
所によく発生する。Thus, as in the present invention, by using a specific concentration of nologen in combination with the above-mentioned compound, it was possible to not only suppress fluctuations in photographic properties but also to significantly suppress the generation and growth of precipitates in the processing tank. is completely unexpected. Here, precipitates do not precipitate or crystallize in the solution due to their solubility, but rather the color developer (particularly a tired solution) is caused by air and tank components (e.g. walls, floating pigs, etc.) from synthetic resins. This phenomenon occurs in the vicinity of contact with other parts, and is completely different from what occurs in liquid. This phenomenon often occurs particularly in narrow areas such as the corners of tanks and floating pigs.
上記写真特性の変動に関しては、塗布銀量が、0.75
g/m2以下の感光材料に於いてその効果が顕著であり
、また、亜硫酸イオンが実質的に含有しない現像液にて
、特に顕著である。また、汚れや析出防止に関しては、
亜硫酸イオンの存在しない現像液において特に効果的で
ある。Regarding the variation in photographic properties mentioned above, the amount of coated silver is 0.75
The effect is remarkable in light-sensitive materials of g/m2 or less, and is especially remarkable in developing solutions containing substantially no sulfite ions. In addition, regarding prevention of stains and precipitation,
It is particularly effective in developing solutions that do not contain sulfite ions.
以下、本発明の詳細について説明する。The details of the present invention will be explained below.
−綴代(+)において、R1、R2、R3及びR6はそ
れぞれ同しでも異なってもよく、水素原子、置換・無置
換のアルキル基、アルコキシ基もしくはアルケニル基を
表す。アルキル基及びアルコキシ基、アルケニル基の炭
素数は1〜20、好ましくは2〜10である。また置換
基としては、ヒドロキシル基、ハロゲン原子、シアノ基
、アミン基(アルキル基で置換されても良い)、炭素数
1〜4のアルコキシ基、スルホン酸、カルボン酸、アシ
ルアミノ基、スルホンアミド基、カルボニルアミド基等
を表す。特に、炭素数1〜4のアルキル基の場合が最も
好ましい。Mは水素原子もしくは対カチオンを表し、対
カチオンの例としてはアンモニウム、アルカリ金属類、
アルカリ土類類が好ましい。nは1〜3の整数を表し、
特に1又は2の場合が好ましい。- In the margin (+), R1, R2, R3 and R6 may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkenyl group. The alkyl group, alkoxy group, and alkenyl group have 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms. Substituents include hydroxyl group, halogen atom, cyano group, amine group (which may be substituted with an alkyl group), alkoxy group having 1 to 4 carbon atoms, sulfonic acid, carboxylic acid, acylamino group, sulfonamide group, Represents a carbonylamide group, etc. In particular, an alkyl group having 1 to 4 carbon atoms is most preferred. M represents a hydrogen atom or a counter cation, examples of counter cations include ammonium, alkali metals,
Alkaline earths are preferred. n represents an integer from 1 to 3,
In particular, the case of 1 or 2 is preferable.
次に、−綴代([1)においては、Aは置換、無置換の
アルキル基、アルコキシ基、フェニル基、フェノキシ基
、アミノ基を表す。アルキル基やアルコキシ基の炭素数
は1〜100好ましくは5〜40である。また、アルキ
ル基やアルコキン基の置換基は一般式(1)の置換基と
同しである。また、アミノ基、フェニル基やフェノキン
基の置換基としては、炭素数1〜100のアルキル基や
アルコキシ基、その他の置換基として、ヒドロキシル基
、ハロゲン原子、シアノ基、アミノ基 (アルキル基で
置換されても良い)、炭素数1〜4のアルコキシ基、ス
ルホン酸、カルボン酸、アシルアミノ基、スルホンアミ
ド基、カルポニルアミド基等を挙げることが出来る。Next, in -Tsuriyo ([1), A represents a substituted or unsubstituted alkyl group, alkoxy group, phenyl group, phenoxy group, or amino group. The alkyl group or alkoxy group has 1 to 100 carbon atoms, preferably 5 to 40 carbon atoms. Further, the substituents of the alkyl group and the alkokene group are the same as the substituents of general formula (1). In addition, substituents for amino groups, phenyl groups, and fenoquine groups include alkyl groups and alkoxy groups having 1 to 100 carbon atoms, and other substituents include hydroxyl groups, halogen atoms, cyano groups, and amino groups (substituted with alkyl groups). ), an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid, a carboxylic acid, an acylamino group, a sulfonamide group, a carponylamide group, and the like.
p、q、及びrは各々0.1.2.3の整数を表し、三
者が同時に0となることは無い。特に、qとrはOで、
ρが2又は3で有る場合が好ましい。Yは−OH又はメ
チル基を表し、特に−CH基の場合が好ましい。mは2
以上の整数を表し、好ましくは2〜100、最も好まし
くは3〜50である。Bは水素原子、置換、無置換のア
ルキル基、アリール基、及び−3○、Zを表す。アルキ
ル基としては炭素数1〜50が好ましく更には1〜20
が好ましい。アルキル基の置換基としては−Ic式(1
)に示したものと同じである。また、アリール基の置換
基としては、アルキル基、ヒドロキシル基、ハロゲン原
子、シアノ基、アミン基(アルキルで置換されても良い
)、炭素数1〜4のアルコキシ基、スルホン酸、カルボ
ン酸、アシルアミノ基、スルホンアミド基、カルボニル
アミド基等を挙げることができる。p, q, and r each represent an integer of 0.1.2.3, and all three are never 0 at the same time. In particular, q and r are O,
It is preferable that ρ is 2 or 3. Y represents -OH or a methyl group, particularly preferably a -CH group. m is 2
It represents an integer of the above, preferably 2 to 100, most preferably 3 to 50. B represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, and -3○, Z. The alkyl group preferably has 1 to 50 carbon atoms, more preferably 1 to 20 carbon atoms.
is preferred. As a substituent for the alkyl group, -Ic formula (1
). Substituents for the aryl group include alkyl groups, hydroxyl groups, halogen atoms, cyano groups, amine groups (which may be substituted with alkyl), alkoxy groups having 1 to 4 carbon atoms, sulfonic acids, carboxylic acids, acylamino group, sulfonamide group, carbonylamide group, etc.
Zは水素原子又は対カチオンを表し、対カチオンの例は
一般式(1)のMと同じである。Z represents a hydrogen atom or a counter cation, and examples of the counter cation are the same as M in general formula (1).
Xは上記構造式で示された異なった構造を複数個打して
もよいが、特に、エチレンオキサイドを繰り返し単位に
有する構造が最も好ましい。Although X may have a plurality of different structures shown in the above structural formula, a structure having ethylene oxide as a repeating unit is most preferable.
以下に一般式(1)及び(n)で示される化合物の具体
例を示すが、これらに限定されるものではない。Specific examples of compounds represented by general formulas (1) and (n) are shown below, but the invention is not limited thereto.
1 1 C11(CHt)zCH(CH3)
1
■−4
I−7゜
CHs Cll3
0(Jl :I
!
I−13
0COC3)l、。1 1 C11(CHt)zCH(CH3)
1 ■-4 I-7°CHs Cll3 0 (Jl:I! I-13 0COC3)l,.
■−15
I−1
I−3
CIH90÷CH□CH20−h、H
C1aH3+0+ CtLzCt(zOhn)Il−6
Cz+HjffO←CH2C)120h、HC16H3
−0÷CH2CH20)−TT+CH2CHz C)1
20 h tlCH
CH
■−10
C,H,C00(’CH,CI(20h、!(l−11
CHJO+CI+□CI(20hCH。■-15 I-1 I-3 CIH90÷CH□CH20-h, H C1aH3+0+ CtLzCt(zOhn)Il-6 Cz+HjffO←CH2C) 120h, HC16H3
-0÷CH2CH20)-TT+CH2CHz C)1
20 h tlCH CH ■-10 C,H,C00('CH,CI(20h,!(l-11 CHJO+CI+□CI(20hCH.
J−12
■−13
C11)12ffcf)O+C1hCHC)120hl
+CH
■−14
+10(−CH、CH□O’h(CHC)I20h(C
H2CH20hHCH。J-12 ■-13 C11) 12ffcf) O+C1hCHC) 120hl
+CH ■-14 +10(-CH, CH□O'h(CHC) I20h(C
H2CH20hHCH.
■−15
■−16
■−17
NaO+SO+cHzCH20hoSOsNa■−18
(CHzCI(20r、 H
■
Cl2H+5N4CHzCL0六Hp+q=5CHCO
O−
本発明に於ける一般式(I)及び(II)で表される化
合物は市販品にて入手することができるかその他、特公
昭4.1−8401.US−2739891、同350
2473、同3026202、特開昭48−43924
、同46−79185、同50−46133、英国特許
1022878、US−3437598、同37233
41等の明細書に記載の方法に準じて合成することもて
きる。■-15 ■-16 ■-17 NaO+SO+cHzCH20hoSOsNa■-18 (CHzCI(20r, H ■ Cl2H+5N4CHzCL06Hp+q=5CHCO
O- Are the compounds represented by general formulas (I) and (II) in the present invention available commercially? US-2739891, US-350
2473, 3026202, JP-A-48-43924
, 46-79185, 50-46133, British Patent 1022878, US-3437598, 37233
It can also be synthesized according to the method described in the specification of No. 41 et al.
本発明に於ける一般式(I)及びCII)で表される化
合物の添加量は、カラー現像液Ilあたり001g〜I
Og好ましくは0.05g〜5gであり、前記化合物が
感光材料から溶出し、蓄積して上記濃度になっても良い
し、あらかじめ、現像液中に添加されていても良いが、
後者の方法か一定の効果を持続するうえで好ましい。In the present invention, the addition amount of the compound represented by the general formula (I) and CII) is 0.001 g to 1.0 g per color developer Il.
Og is preferably 0.05 g to 5 g, and the compound may be eluted from the photosensitive material and accumulated to reach the above concentration, or it may be added to the developer in advance.
The latter method is preferable in terms of maintaining a certain effect.
°次に本発明に使用するカラー現像液について説明する
。Next, the color developer used in the present invention will be explained.
本発明に使用されるカラー現像液中には、公知の芳香族
第一級アミンカラー現像主薬を含有する。The color developer used in the present invention contains a known aromatic primary amine color developing agent.
好ましい例はp−フェニレンジアミン誘導体であり、代
表例を以下に示すがこれらに限定されるものではない。Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.
D−IN、N−ジエチル−p−フェニレンジアミン
D−22−アミノ−5−ジエチルアミノトルエン
D−32−アミノ−5−(N−エチル−N−ラウリルア
ミノ)トルエン
D−44−(N−エチル−N−(β−ヒドロキシエチル
)アミノコアニリン
D−52−メチル−4−〔N−エチル−N−〔β−ヒド
ロキシエチル〕アミノ〕アニリン
D−64−アミノ−3−メチル−N−エチル−N−Cβ
−(メタンスルホンアミド)エチルシーアニリン
D−7N−(2−アミノ−5−ジエチルアミノフェニル
エチル)メタンスルホンアミドD−8N、N−ジメチル
−p−フェニレンジアミン
D−94−アミノ−3−メチル−N−エチル−N−メト
キシエチルアニリン
D−104−アミノ−3−メチル−N−エチル−N−β
−エトキシエチルアニリン
D−114−アミノ−3−メチル−N−エチル−N−β
−ブトキシエチルアニリン
上記p−フェニレンジアミン誘導体のうち特に好ましく
は4−アミノ−3−メチル−N−エチル−N=〔β−(
メタンスルホンアミド)エチルシーアニリン(例示化合
物D−6)である。D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-[β-hydroxyethyl]amino]aniline D-64-amino-3-methyl-N-ethyl-N -Cβ
-(methanesulfonamide)ethylcyaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N=[β-(
methanesulfonamido)ethylcyaniline (exemplified compound D-6).
また、これらのp−フェニレンジアミン誘導体と硫酸塩
、塩酸塩、亜硫酸塩、p−トルエンスルホン酸塩などの
塩であってもよい。該芳香族第−級アミン現像主薬の使
用量は現像液11当り好ましくは約0.1g〜約20g
1より好ましくは約0.5g〜約10gの濃度である。Further, salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates may be used with these p-phenylenediamine derivatives. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per developer solution 11.
1 and more preferably from about 0.5 g to about 10 g.
本発明の実施にあたっては、実質的にベンジルアルコー
ルを含有しない現像液を使用することが好ましい。ここ
で実質的に含有しないとは、好ましくは2 m l /
1以下、更に好ましくは0.5 m A’/l以下の
ベンジルアルコール濃度であり、最も好ましくは、ベン
ジルアルコールを全く含有しないことである。In practicing the present invention, it is preferred to use a developer solution that is substantially free of benzyl alcohol. Here, "substantially not containing" preferably means 2 ml/
The concentration of benzyl alcohol is less than 1, more preferably less than 0.5 mA'/l, and most preferably no benzyl alcohol is contained at all.
本発明に用いられる現像液は、亜硫酸イオンを実質的に
含有しないことがより好ましい。亜硫酸イオンは、現像
主薬の保恒剤としての機能と同時に、ハロゲン化銀溶解
作用及び現像主薬酸化体と反応し、色素形成効率を低下
させる作用を有する。It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.
このような作用が、連続処理に伴う写真特性の変動の増
大の原因の1つと推定される。ここで実質的に含有しな
いとは、好ましくは3.0X10−”モル/l以下の亜
硫酸イオン濃度であり、最も好ましくは亜硫酸イオンを
全く含有しないことであ但し、本発明においては、使用
液に調液する前に現像主薬が濃縮されている処理剤キッ
トの酸化防止に用いられるごく少量の亜硫酸イオンは除
外される。Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0 x 10-" mol/l or less, most preferably not containing sulfite ions at all. However, in the present invention, the liquid used Excludes the very small amount of sulfite ions used to prevent oxidation in processing agent kits in which the developing agent is concentrated before preparation.
本発明に用いられる現像液は亜硫酸イオンを実質的に含
有しないことが好ましいが、さらにヒドロキシルアミン
を実質的に含有しないことがより好ましい。これは、ヒ
ドロキシルアミンが現像液の保恒剤としての機能と同時
に自身が銀現像活性を持ち、ヒドロキシルアミンの濃度
の変動が写真特性に大きく影響すると考えられるためで
ある。The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.
ここでいうヒドロキシルアミンを実質的に含有しないと
は、好ましくは5.0X10−’モル/l以下のヒドロ
キシルアミン濃度であり、最も好ましくはヒドロキシル
アミンを全く含有しないことである。The term "substantially free of hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0 x 10-' mol/l or less, and most preferably no hydroxylamine at all.
本発明に用いられる現像液は、前記ヒドロキシルアミン
や亜硫酸イオンに替えて有機保恒剤を含有することがよ
り好ましい。It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.
ここで有機保恒剤とは、カラー写真感光材料の処理液へ
添加することで、芳香族第一級アミンカラー現像主薬の
劣化速度を減じる有機化合物全般を指す。即ち、カラー
現像主薬の空気などによる酸化を防止する機能を有する
有機化合物類であるが、中でも、ヒドロキシルアミン誘
導体(ヒドロキシルアミンを除く。以下同様)、ヒドロ
キサム酸類、ヒドラジン類、ヒドラジド類、フェノール
類、α−ヒドロキシケトン類、α−アミノケトン類、糖
類、モノアミン類、ジアミン類、ポリアミン類、四級ア
ンモニウム塩類、ニトロキシラジカル類、アルコール類
、オキシム類、ジアミド化合物類、縮環式アミン類など
が特に有効な有機保恒剤である。これらは、特開昭63
−4235号、同63−30845号、同63−216
47号、同63−44655号、同63−53551号
、同63−43140号、同63−56654号、同6
3−58346号、同63−43138号、同63−1
46041号、同63−44657号、同63−446
56号、米国特許第3,615゜503号、同2,49
4,903号、特開昭52−143020号、特公昭4
8−30496号などに開示されている。The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, Especially α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines, etc. It is an effective organic preservative. These are JP-A-63
-4235, 63-30845, 63-216
No. 47, No. 63-44655, No. 63-53551, No. 63-43140, No. 63-56654, No. 6
No. 3-58346, No. 63-43138, No. 63-1
No. 46041, No. 63-44657, No. 63-446
No. 56, U.S. Patent No. 3,615゜503, U.S. Patent No. 2,49
No. 4,903, JP-A-52-143020, Special Publication No. 4, 1973
No. 8-30496 and the like.
その他保恒剤として、特開昭57−44148号及び同
57−53749号に記載の各種金属類、特開昭59−
180588号記載のサリチル酸類、特開昭54−35
32号記載のアルカノールアミン類、特開昭56−94
349号記載のポリエチレンイミン類、米国特許第3,
746,544号等記載の芳香族ポリヒドロキシ化合物
等を必要に応じて含有しても良い。特にトリエタノール
アミンのようなアルカノールアミン類、ジエチルヒドロ
キシルアミンのようなジアルキルヒドロキシルアミン、
ヒドラジン誘導体あるいは芳香族ポリヒドロキシ化合物
の添加が好ましい。Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
If necessary, aromatic polyhydroxy compounds described in No. 746,544 and the like may be contained. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine,
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added.
前記の有機保恒剤のなかでもヒドロキシルアミン誘導体
やヒドラジン誘導体(ヒドラジン類やヒドラジド類)が
特に好ましく、その詳細については、特願昭62−25
5270号、同63−9713号、同63−9714号
、同63−11300号などに記載されている。Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
It is described in No. 5270, No. 63-9713, No. 63-9714, No. 63-11300, etc.
また前記のヒドロキシルアミン誘導体またはヒドラジン
誘導体とアミン類を併用して使用することが、カラー現
像液の安定性の向上、しいては連続処理時の安定性向上
の点てより好ましい。Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.
前記のアミン類としては、特開昭63−239447号
に記載されたような環状アミン類や特開昭63−128
340号に記載されたようなアミン類やその他特願昭6
3−9713号や同63−11300号に記載されたよ
うなアミン類が挙げられる。Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-128.
Amines such as those described in No. 340 and other patent applications filed in 1983
Examples include amines such as those described in No. 3-9713 and No. 63-11300.
本発明に使用されるカラー現像液は、好ましくはpH9
〜12、より好ましくは9〜11.0であり、そのカラ
ー現像液には、その他に既知の現像液成分の化合物を含
ませることができる。The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.
上記pHを保持するためには、各種緩衝剤を用いるのが
好ましい。緩衝剤としては、炭酸塩、リン酸塩、ホウ酸
塩、四ホウ酸塩、ヒドロキシ安息香酸塩、グリンル塩、
N、 N−ジメチルグリジン塩、ロインン塩、ノルロイ
シン塩、グアニン塩、3.4−ジヒドロキシフェニルア
ラニン塩、アラニン塩、アミノ酪酸塩、2−アミノ−2
−メチル−1,3−プロパンジオール塩、バリン塩、プ
ロリン塩、トリスヒドロキンアミノメタン塩、リジン塩
などを用いることができる。特に炭酸塩、リン酸塩、四
ホウ酸塩、ヒドロキン安息香酸塩は、溶解性、pH9,
0以上の高pH領域での緩衝能に優れ、カラー現像液に
添加しても写真性能面への悪影響(カブリなど)がなく
、安価であるとった利点を有し、これらの緩衝剤を用い
ることが特に好ましい。In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonates, phosphates, borates, tetraborates, hydroxybenzoates, Grindle salts,
N, N-dimethylglydine salt, loin salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2
-Methyl-1,3-propanediol salt, valine salt, proline salt, trishydroquine aminomethane salt, lysine salt, etc. can be used. In particular, carbonate, phosphate, tetraborate, and hydroquine benzoate are soluble, pH 9,
These buffers have the advantage of having excellent buffering ability in the high pH range of 0 or more, having no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and being inexpensive. It is particularly preferable.
これらの緩衝剤の具体例としては、炭酸ナトリウム、炭
酸カリウム、重炭酸ナトリウム、重炭酸カリウム、リン
酸三ナトリウム、リン酸三カリウム、リン酸二ナトリウ
ム、リン酸二カリウム、ホウ酸テトリウム、ホウ酸カリ
ウム、四ホウ酸ナトリウム(ホウ砂)、四ホウ酸カリウ
ム、0−ヒドロキシ安息香酸ナトリウム(サリチル酸ナ
トリウム)、o−ヒドロキシ安息香酸カリウム、5−ス
ルホ−2−ヒドロキシ安息香酸ナトリウム(5−スルホ
サリチル酸ナトリウム)、5−スルホ−2=ヒドロキシ
安息香酸カリウム(5−スルホサリチル酸カリウム)な
どを挙げることができる。しかしながら本発明は、これ
らの化合物に限定されるものではない。Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, tetrium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), potassium 5-sulfo-2=hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.
該緩衝剤のカラー現像液への添加量は、01−1モル/
f!以上であることが好ましく、特に0. 1モル/l
〜0.4モル/lであることが好ましい。The amount of the buffer added to the color developer is 01-1 mol/
f! It is preferable that it is more than 0. 1 mol/l
It is preferable that it is 0.4 mol/l.
その他、カラー現像液中にはカルシウムやマグネシウム
の沈澱防止剤として、あるいはカラー現像液の安定性向
上のために、各種キレート剤を用いることができる。例
えば、ニトリロ三酢酸、ジエチレントリアミン五酢酸、
エチレンジアミン四酢酸、N、 N、 N−1−リメチ
レンホスホン酸、エチレンジアミン−N、N、N’ 、
N’−テトラメチレンスルホン酸、トランスシロヘキサ
ンジアミン四酢酸、1,2−ジアミノプロパン4酢酸、
グリコールエーテルジアミン四酢酸、エチレンジアミン
オルトヒドロキシフェニル酢酸、2−ホスホノブタン−
1,2,1−1−リカルボン酸、1−ヒドロキシエチリ
デン−1,1−ジホスホン酸、N。In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N, N, N-1-rimethylenephosphonic acid, ethylenediamine-N, N, N',
N'-tetramethylene sulfonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid,
Glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-
1,2,1-1-licarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N.
N′−ビス(2−ヒドロキンベンジル)エチレンジアミ
ンーN、 N’−ジ酢酸等が挙げられる。Examples include N'-bis(2-hydroquinbenzyl)ethylenediamine-N,N'-diacetic acid.
これらのキレート剤は必要に応じて2種以上併用しても
良い。Two or more of these chelating agents may be used in combination, if necessary.
これらのキレート剤の添加量はカラー現像液中の金属イ
オンを封鎖するのに充分な量であれば良い。例えばl、
f+当り0.1g/l0g程度である。These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example l,
It is about 0.1 g/l0g per f+.
カラー現像液には、必要により任意の現像促進剤を添加
できる。Any development accelerator can be added to the color developer if necessary.
現像促進剤としては、特公昭37−16088号、同3
7−5987号、同38−7826号、同44−123
80号、同45−9019号及び米国特許第3,813
,247号等に表わされるチオエーテル系化合物、特開
昭52−49829号及び同50−15554号に表わ
されるp−フェニレンジアミン系化合物、特開昭50−
137726号、特公昭44−30074号、特開昭5
6−156826号及び同52−43429号等に表わ
される4級アンモニウム塩類、米国特許第2.494,
903号、同3,128,182号、同4,230,7
96号、同3,253,919・号、特公昭41−11
431号、米国特許第2゜482.546号、同2,5
96,926号及び同3,582,346号等に記載の
アミン系化合物、特公昭37−16’088号、同42
−25201号、米国特許第3,128,183号、特
公昭41−11431号、同42−23f183号及び
米国特許第3.532,501号等に表わされるポリア
ルキレンオキサイド、その他1−フェニルー3−ピラゾ
リドン類、イミダゾール類、等を必要に応じて添加する
ことができる。As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
6-156826 and 52-43429, etc., U.S. Patent No. 2.494,
No. 903, No. 3,128,182, No. 4,230,7
No. 96, No. 3,253,919, Special Publication No. 41-11
No. 431, U.S. Patent No. 2.482.546, U.S. Pat.
96,926 and 3,582,346, etc., Japanese Patent Publication No. 37-16'088, 42
-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23f183, and U.S. Patent No. 3,532,501, etc., and other 1-phenyl-3- Pyrazolidones, imidazoles, etc. can be added as necessary.
本発明においては、必要に応じて、任意のカブリ防止剤
を添加できる。カブリ防止剤としては、塩化ナトリウム
、臭化カリウム、沃化カリウムの如きアルカリ金属ハロ
ゲン化物及び有機カブリ防止剤が使用できる。有機カブ
リ防止剤としては、例えばベンゾトリアゾール、6−ニ
トロインインダゾール、5−ニトロインインダゾール、
5〜メチルベンゾトリアゾール、5−ニトロペンゾトリ
アヅール、5−クロローヘンゾトリアヅール、2−チア
ヅリルーヘンズイミダヅール、2−チアプリルメチルー
ヘンズイミダゾール、インダゾール、ヒドロキシアザイ
ンドリジン、アデニンの如き含窒素へテロ環化合物を代
表例としてあげることができる。In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitroindazole, 5-nitroindazole,
5-methylbenzotriazole, 5-nitropenzotriazole, 5-chlorohenzotriazole, 2-thiazuryl-henzimidazole, 2-thiaprylmethyl-henzimidazole, indazole, hydroxyazaindolizine, A typical example is a nitrogen-containing heterocyclic compound such as adenine.
特に本発明においては、写真特性の変動の低減及び析出
物の成長抑制の目的で、塩素イオンを0゜04モル/l
以上、好ましくは0.045〜0゜15モル/P金含有
る必要がある。In particular, in the present invention, for the purpose of reducing fluctuations in photographic properties and suppressing the growth of precipitates, chloride ions are added at 0.04 mol/l.
As mentioned above, it is necessary to preferably contain 0.045 to 0.15 mol/P of gold.
更に本発明においては、同様の目的で臭素イオンを4
X 10−5〜2.0XIO−’モル/p、好ましくは
5X10−″〜lXl0−’モル/l含有する必要があ
る。Furthermore, in the present invention, bromine ions are added to 4 for the same purpose.
It is necessary to contain X 10-5 to 2.0XIO-' mol/p, preferably 5X10-'' to 1X10-' mol/l.
これらの範囲外になると上記の目的の点で好ましくない
。If it is outside these ranges, it is not preferable for the above purpose.
ここで塩素イオン及び臭素イオンは現像液中に直接添加
されてもよく、現像処理中に感光材料から現像ン夜にン
容出してもよい。Here, chloride ions and bromine ions may be added directly to the developer, or may be removed from the light-sensitive material during the development process.
カラー現像液に直接添加される場合、塩素イオン供給物
質として、塩化ナトリウム、塩化カリウム、塩化アンモ
ニウム、塩化リチウム、塩化ニッケル、塩化マグネシウ
ム、塩化マンガン、塩化カルシウム、塩化カドミウムが
挙げられるが、そのうち好ましいものは塩化ナト1ノウ
ム、塩化カリウムである。When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. is sodium chloride, potassium chloride.
また、現像液中に添加されている蛍光増白剤がら供給さ
れてもよい。Alternatively, the optical brightener added to the developer may be supplied.
臭素イオンの供給物質として、臭素ナトリウム、臭化カ
リウム、臭化アンモニウム、臭化リチウム、臭化カルシ
ウム、臭化マグネシウム、臭化マンガン、臭化ニッケル
、臭化カドミウム、臭化セリウム、臭化タリウムが挙げ
られるが、そのうち好ましいものは臭化カリウム、臭化
ナトリウムである。Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, and thallium bromide are used as bromide ion supply materials. Among these, preferred are potassium bromide and sodium bromide.
現像処理中に感光材料から溶出する場合、塩素イオンや
臭素イオンは共に乳剤から供給されてもよく、乳剤以外
から供給されても良い。When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.
本発明に適用されうるカラー現像液には、蛍光増白剤を
含有するのが好ましい。蛍光増白剤としては、4,4′
−ジアミノ−2,2′−ジスルホスチルベン系化合物が
好ましい。添加量は0〜5g/l好ましくは0.1g〜
4 g/I!である。The color developer applicable to the present invention preferably contains an optical brightener. As an optical brightener, 4,4'
-Diamino-2,2'-disulfostilbene compounds are preferred. Addition amount is 0 to 5 g/l, preferably 0.1 g to
4 g/I! It is.
又、必要に応じてアルモルスルホン酸、アリ−ルスルホ
ン酸、脂肪族カルボン酸、芳香族カルボン酸等の各種界
面活性剤を添加しても良い。Further, various surfactants such as almolsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, etc. may be added as necessary.
本発明に適用されうるカラー現像液の処理温度は20〜
50°C好ましくは30〜40°Cである。The processing temperature of the color developer that can be applied to the present invention is 20~
50°C, preferably 30-40°C.
処理時間は20秒〜5分好ましくは30秒〜2分である
。補充量は少ない方が好ましいが、感光材料1d当たり
20〜600rrlが適当であり、好ましくは50〜3
00mj!である。更に好ましくは60rl! 〜20
0ml、最も好ましくは60−〜150mfである。The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but 20 to 600 rrl is appropriate per 1 d of photosensitive material, preferably 50 to 3 rrl.
00mj! It is. More preferably 60rl! ~20
0ml, most preferably 60-150mf.
次に本発明に適用されうる脱銀工程について説明する。Next, a desilvering process that can be applied to the present invention will be explained.
脱銀工程は、一般には、漂白工程一定着工程、定着工程
−漂白定着工程、漂白工程−漂白定着工程、漂白定着工
程等いかなる工程を用いても良い。The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.
以下に本発明に適用されうる漂白液、漂白定着液及び定
着液を説明する。The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below.
漂白液又は漂白定着液において用いられる漂白剤として
は、いかなる漂白剤も用いることができるが、翁に鉄(
I)の有機錯塩(例えばエチレンジアミン四酢酸、ジエ
チレントリアミン五酢酸などのアミノポリカルボン酸類
、アミノポリホスホン酸、ホスホノカルボン酸および有
機ホスホン酸などの錯塩)もしくはクエン酸、酒石酸、
リンゴ酸などの有機酸:過硫酸塩;過酸化水素などが好
ましい。As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but iron (
I) organic complex salts (for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or citric acid, tartaric acid,
Organic acids such as malic acid: persulfates; hydrogen peroxide, etc. are preferred.
これらのうち、鉄(III)の有機錯塩は迅速処理と環
境汚染防止の観点から特に好ましい。鉄CI[l)の有
機錯塩を形成するために有用なアミノポリカルボン酸、
アミノポリホスホン酸、もしくは有機ホスホン酸または
それらの塩を列挙すると、エチレンジアミン四酢酸、ジ
エチレントリアミン五酢酸、1,3−ジアミノプロパン
四酢酸、プロピレンジアミン四酢酸、ニトリロ三酢酸、
シクロヘキサンジアミン四酢酸、メチルイミノニ酢酸、
イミノニ酢酸、グリコールエーテルジアミン四酢酸、な
どを挙げることができる。これらの化合物はナトリウム
、カリウム、チリウム又はアンモニウム塩のいずれでも
良い。これらの化合物の中で、エチレンジアミン四酢酸
、ジエチレントリアミン五酢酸、シクロヘキサンジアミ
ン四酢酸、1,3−ジアミノプロパン四酢酸、メチルイ
ミノニ酢酸の鉄(III)錯塩が漂白刃が高いことから
好ましい。Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids useful for forming organic complex salts of iron CI[l],
Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, iron(III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.
これらの第2鉄イオン錯塩は錯塩の形で使用しても良い
し、第2鉄塩、例えば硫酸第2鉄、塩化第2鉄、硝酸第
2鉄、硫酸第2鉄アンモニウム、燐酸第2鉄などとアミ
ノポリカルボン酸、アミノポリホスホン酸、ホスホノカ
ルボン酸などのキレート剤とを用いて溶液中で第2鉄イ
オン錯塩を形成させてもよい。また、キレート剤を第2
鉄イオン錯塩を形成する以上に過剰に用いてもよい。鉄
錯体のなかでもアミノポリカルボン酸鉄錯体が好ましく
、その添加量は0.01〜1. 0モル/l、好ましく
は0.05〜0.50モル/lである。These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. In addition, a chelating agent can be used as a second
It may be used in excess to form an iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1. 0 mol/l, preferably 0.05 to 0.50 mol/l.
漂白液、漂白定着液及び/またはこれらの前浴には、漂
白促進剤として種々の化合物を用いることができる。例
えば、米国特許箱3. 893. 858号明細書、ド
イツ特許第1,290,812号明細書、特開昭53−
95630号公報、リサーチディスクロージャー第17
129号(1978年7月号)に記載のメルカプト基ま
たはジスルフィド結合を有する化合物や、特公昭45−
8506号、特開昭52−20832号、同53−32
735号、米国特許3,706,561号等に記載のチ
オ尿素系化合物、あるいは沃素、臭素イオン等のハロゲ
ン化物が漂白刃に優れる点で好ましい。Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, US Patent Box 3. 893. Specification No. 858, German Patent No. 1,290,812, Japanese Unexamined Patent Publication No. 1983-
Publication No. 95630, Research Disclosure No. 17
129 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 8506, JP-A-52-20832, JP-A No. 53-32
Thiourea compounds described in No. 735, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.
その他、本発明に適用されうる漂白液又は漂白定着液に
は、臭化物(例えば、臭化カリウム、臭化ナトリウム、
臭化アンモニウム)または塩化物(例えば、塩化カリウ
ム、塩化ナトリウム、塩化アンモニウム)または沃化物
(例えば、沃化アンモニウム)等の再ハロゲン化剤を含
むことができる。必要に応じ硼砂、メタ硼酸ナトリウム
、酢酸、酢酸ナトリウム、炭酸ナトリウム、炭酸カリウ
ム、亜燐酸、燐酸、燐酸ナトリウム、クエン酸、クエン
酸ナトリウム、酒石酸などのpH緩衝能を有する1種類
以上の無機酸、有機酸およびこれらのアルカリ金属また
はアンモニウム塩または、硝酸アンモニウム、グアニジ
ンなどの腐蝕防止剤などを添加することができる。In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, one or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.
漂白定着液又は定着液に使用される定着剤は、公知の定
着剤、即ちチオ硫酸ナトリウム、チオ硫酸アンモニウム
などのチオ硫酸塩、チオシアン酸ナトリウム、チオンア
ン酸アンモニウムなどのチオシアン酸塩;エチレンビス
チオグリコール酸、3.6−シチアー1. 8−オクタ
ンジオールなどのチオエーテル化合物およびチオ尿素類
などの水溶性のハロゲン化銀溶解剤であり、これらを1
種あるいは2種以上混合して使用することができる。The fixing agent used in the bleach-fixing solution or the fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thioanate; ethylene bisthioglycolic acid. , 3.6-Sythia 1. It is a water-soluble silver halide solubilizing agent such as thioether compounds such as 8-octanediol and thioureas.
A species or a mixture of two or more kinds can be used.
また、特開昭55−155354号に記載された定着剤
と多量の沃化カリウムの如きハロゲン化物などの組み合
わせからなる特殊な漂白定着液等も用いることができる
。本発明においては、チオ硫酸塩特にチオ硫酸アンモニ
ウム塩の使用が好ましい。11あたりの定着剤の量は、
0.3〜2モルが好ましく、更に好ましくは0. 5〜
1.0モルの範囲である。漂白定着液又は定着液のpH
領域は、3〜lOが好ましく、更には5〜9が特に好ま
しい。It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per 11 is
The amount is preferably 0.3 to 2 mol, more preferably 0.3 to 2 mol. 5~
The range is 1.0 mol. pH of bleach-fix solution or fix solution
The range is preferably from 3 to 10, more preferably from 5 to 9.
又、漂白定着液には、その他各種の蛍光増白剤や消泡剤
あるいは界面活性剤、ポリビニルピロリドン、メタノー
ル等の有機溶媒を含有させることができる。Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.
漂白定着液や定着液は、保恒剤として亜硫酸塩(例えば
、亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸アンモニ
ウム、など)、重亜硫酸塩(例えば、重亜硫酸アンモニ
ウム、重亜硫酸ナトリウム、重亜硫酸カリウム、など)
、メタ重亜硫酸塩(例えば、メタ重亜硫酸カリウム、メ
タ重亜硫酸ナトリウム、メタ重亜硫酸アンモニウム、な
ど)等の亜硫酸イオン放出化合物を含有するのが好まし
い。Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).
これらの化合物は亜硫酸イオンに換算して約0゜02〜
0.05モル/l含有させることが好ましく、更に好ま
しくは0.04〜0.40モル/lである。These compounds have a concentration of approximately 0°02~ in terms of sulfite ions.
The content is preferably 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.
保恒剤としては、亜硫酸塩の添加が一般的であるが、そ
の他、アスコルビン酸や、カルボニル重亜硫酸付加物、
あるいは、カルボニル化合物等を添加しても良い。Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.
、 更には緩衝剤、蛍光増白剤、キレート剤、消泡剤、
防カビ剤等を必要に応じて添加しても良い。In addition, buffering agents, optical brighteners, chelating agents, antifoaming agents,
A fungicide or the like may be added as necessary.
定着又は漂白定着等の脱銀処理後、水洗及び/又は安定
化処理をするのが一般的である。After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.
水洗工程での水洗水量は、感光材料の特性(例えばカプ
ラー等使用素材による)や用途、水洗水温、水洗タンク
の数(段数)、向流、順流等の補充方式、その他種々の
条件によって広範囲に設定し得る。このうち、多段向流
方式における水洗タンク数と水量の関係は、ジャーナル
・オン・ザ・ソサエティ・オン・モーション・ピクチャ
ー・アンド・テレヴィジョン・エンジニアズ(Jour
nalof the 5ociety of Moti
on Picture andTelevision
Engineers)第64巻、p、248〜253
(1955年5月号)に記載の方法で、もとめること
ができる。通常多段向流方式における段数は2〜6が好
ましく、特に2〜4が好ましい。The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal on the Society on Motion Picture and Television Engineers.
nalof the 5ociety of Moti
on Picture and Television
Engineers) Volume 64, p. 248-253
(May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.
多段向流方式によれば、水洗水量を大巾に減少でき、例
えば感光材料1−当たり0.51〜11以下が可能であ
り、本発明の効果が顕著であるが、タンク内での水の滞
留時間増加により、バクテリアが繁殖し、生成した浮遊
物か感光材料に付着する等の問題が生じる。この様な問
題の解決策として、特開昭62−288838号に記載
のカルシワム、マグネシウムを低減させる方法を、極め
て有効に用いることができる。また、特開昭57−85
42号に記載のインチアゾロン化合物やサイアベンダゾ
ール類、同61−120145号に記載の塩素化イソチ
アヌール酸ナトリウム等の塩素系殺菌剤、特開昭61−
267761号に記載のベンゾトリアゾール、銅イオン
その他堀口博著「防菌防黴の化学J (1986年)
三共出版、衛生技術金線「微生物の滅菌、殺菌、防黴技
術」(1982年)工業技術台、日本防菌防黴学金線[
防菌防黴剤事典J (1986年)、に記載の殺菌剤
を用いることもできる。According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.51 to 11 or less per 1 - of photosensitive material, and the effect of the present invention is remarkable. The increased residence time causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-85
Inthiazolone compounds and thiabendazoles described in No. 42, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 61-120145, JP-A No. 61-1986
Benzotriazole, copper ion, etc. described in No. 267761, Hiroshi Horiguchi, “Chemistry of antibacterial and antifungal J (1986)
Sankyo Publishing, Hygiene Technology Gold Wire "Sterilization, Disinfection, and Anti-Mold Technology of Microorganisms" (1982) Industrial Technology Center, Japan Antibacterial and Anti-Mold Science Gold Wire [
The fungicides described in Dictionary of Antibacterial and Antifungal Agents J (1986) can also be used.
更に、水洗水には、水切り剤として界面活性剤や、硬水
軟化剤としてEDTAに代表されるキレート剤を用いる
ことができる。Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.
以上の水洗工程に続くか、又は水洗工程を経ずに直接安
定液で処理することも出来る。安定液には、画像安定化
機能を有する化合物が添加され、例えばホルマリンに代
表されるアルデヒド化合物や、色素安定化に適した膜p
Hに調整するための緩衝剤や、アンモニウム化合物があ
げられる。又、液中でのバクテリアの繁殖防止や処理後
の感光材料に防黴性を付与するため、前記した各種殺菌
剤や防黴剤を用いることができる。The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.
更に、界面活性剤、蛍光増白剤、硬膜剤を加えることも
できる。本発明の感光材料の処理において、安定化が水
洗工程を経ることなく直接行われる場合、特開昭57−
8543号、同58−14834号、同60−2203
45号等に記載の公知の方法を、すべて用いることがで
きる。Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step,
No. 8543, No. 58-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.
その他、1−ヒドロキシエチリデン−1,■−ジホスホ
ン酸、エチレンジアミン四メチレンホスホン酸等のキレ
ート剤、マグネシウムやビスマス化合物を用いることも
好ましい態様である。In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,■-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.
脱銀処理後用いられる水洗液または安定化液としていわ
ゆるリンス液も同様に用いられる。A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.
水洗工程又は安定化工程の好ましいpHは4〜lOであ
り、更に好ましくは5〜8である。温度は感光材料の用
途・特性等で種々設定し得るが、一般には15〜45°
C好ましくは20〜40°Cである。時間は任意に設定
できるか短かい方か処理時間の低減の見地から望ましい
。好ましくは15秒〜1分45秒更に好ましくは30秒
〜1分30秒である。補充量は、少ない方がランニング
コスト、排出量減、取扱い性等の観点で好ましい。The preferred pH of the water washing step or stabilization step is 4-10, more preferably 5-8. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45 degrees.
C is preferably 20 to 40°C. It is preferable to set the time arbitrarily or to shorten it from the viewpoint of reducing processing time. Preferably it is 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.
具体的な好ましい補充量は、感光材料、単位面積あたり
前浴からの持込み量の0.5〜50倍、好ましくは3倍
〜40倍である。または感光材料lイ当り11以下、好
ましくは500ml以下である。また補充は連続的に行
っても間欠的に行ってもよい。A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Alternatively, the amount is 11 or less, preferably 500ml or less per liter of light-sensitive material. Further, replenishment may be performed continuously or intermittently.
水洗及び/又は安定化工程に用いた液は、更に、前工程
に用いることもできる。この例として多段向流方式によ
って削減して水洗水のオーバーフローを、その前浴の漂
白定着浴に流入させ、漂白定着浴には濃縮液を補充して
、廃液量を減らすことがあげられる。The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by using a multi-stage counter-current system to allow the overflow of the wash water to flow into the bleach-fix bath, which is a pre-bath, and to replenish the bleach-fix bath with concentrated liquid.
本発明のカラー写真感光材料は、支持体上に青感性ハロ
ゲン化銀乳剤層、緑感性ハロゲン化銀乳剤層および赤感
性ハロゲン化銀乳剤層を少なくとも一層ずつ塗設して構
成することができる。一般のカラー印画紙では、支持体
上に前出の順で塗設されているのが普通であるが、これ
と異なる順序であっても良い。これ等の感光性乳剤層に
は、それぞれの波長域に怒度を有するハロゲン化銀乳剤
と、感光する光と補色の関係にある色素−すなわち青に
対するイエロー、緑に対するマゼンタそして赤に対する
シアン−を形成する所謂カラーカプラーを含有させるこ
とで減色法の色再現を行うことができる。The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. These light-sensitive emulsion layers contain a silver halide emulsion with intensity in each wavelength range, and dyes that are complementary colors to the light to which the light is exposed - yellow for blue, magenta for green, and cyan for red. By incorporating a so-called color coupler to form, subtractive color reproduction can be performed.
本発明に用いるハロゲン化銀乳剤に含まれるノ\ロゲン
化銀粒子の平均粒子サイズ(粒子の投影面積と等価な円
の直径を以て粒子サイズとし、その数平均をとったもの
)は、0.1μ〜2μが好ましく、単分散性のハロゲン
化銀乳剤が好ましい。The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken) is 0.1μ. ~2μ is preferred, and monodisperse silver halide emulsions are preferred.
本発明に好ましく用いられるr単分散性のハロゲン化銀
粒子」とは、電子顕微鏡写真により乳剤を観察したとき
に各々のハロゲン化銀粒子の形状が均一に見え、粒子サ
イズが揃っていて、かつ粒径分布の標準偏差Sと平均粒
径〒との比S/rが0.20以下のものを示し、好まし
くは、0.15以下である。ここにおいて、粒径分布の
標準偏差Sは次式に従って求められる。Monodisperse silver halide grains preferably used in the present invention are those in which the shape of each silver halide grain appears uniform when the emulsion is observed using an electron microscope, and the grain size is uniform. The ratio S/r of the standard deviation S of the particle size distribution to the average particle size 〒 is 0.20 or less, preferably 0.15 or less. Here, the standard deviation S of the particle size distribution is determined according to the following formula.
またここで言う平均粒径は下は、球状のハロゲン化銀粒
子の場合、その直径、また立方体や球状以外の形状の粒
子の場合は、その投影像を周面積の円像に換算したとき
の直径の平均値であって、個々のその粒径がriであり
、その数がniである時、下記の式によって下が定義さ
れたものである。In addition, the average grain size referred to here refers to the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted into a circular image of the circumferential area in the case of grains with shapes other than cubic or spherical. The average value of the diameter is defined by the following formula, where the individual particle size is ri and the number is ni.
Σn1ri
Σni
なお、上記の粒子径は、上記の目的のために当該技術分
野において一般に用いられる各種の方法によってこれを
測定することかできる。代表的な“方法としては、ラブ
ランドの「粒子径分析表J A。Σn1ri Σni The above particle diameter can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's Particle Size Analysis Table JA.
S、T、M、 ンンポジウム・オン・ライト・マイク
ロスコピー1955年、94〜122頁または「写真プ
ロセスの理論」 ミースおよびジェームズ共著、第3版
、マクミラン社発行(1966年)の第2章に記載され
ている。この粒子径は、粒子の投影面積か直径近似値を
使ってこれを測定することができる。粒子が実質的に均
一形状である場合は、粒径分布は直径か投影面積として
かなり正確にこれを表わすことができる。S, T, M, Symposium on Light Microscopy 1955, pp. 94-122 or in chapter 2 of ``Theory of the Photographic Process'' by Mies and James, 3rd edition, published by Macmillan (1966) has been done. The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.
粒径分布の関係は「写真乳剤におけるセンシトメトリー
分布と粒径分布との間の経験的関係」ザ・フォトグラフ
ィックジャーナル、LXXIX巻、(1949年)33
0〜338頁のトリベリとスミスの論文に記載される方
法で、これを決めることができる。The relationship between grain size distribution is described in "Empirical relationship between sensitometric distribution and grain size distribution in photographic emulsions," The Photographic Journal, Vol. LXXIX, (1949) 33.
This can be determined by the method described in the article by Trivelli and Smith, pages 0-338.
本発明のハロゲン化銀カラー写真感光材料の塗布銀量は
、感光材料lボ当り、0.3g〜1.5g好ましくは0
.4g〜0.75gである。The amount of coated silver in the silver halide color photographic light-sensitive material of the present invention is preferably 0.3 to 1.5 g per liter of light-sensitive material.
.. 4g to 0.75g.
本発明に用いるハロゲン化銀乳剤は、その乳剤粒子形成
もしくは物理熟成の過程において種々の多価金属イオン
不純物を導入することができる。Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.
使用する化合物の例としては、カドミウム、亜鉛、鉛、
銅、タリウムなどの塩、あるいは第■族元素である鉄、
ルテニウム、ロジウム、パラジウム、オスミウム、イリ
ジウム、白金などの塩もしくは錯塩を挙げることができ
る。特に上記第■族元素は好ましく用いることができる
。これ等の化合物の添加量は目的に応じて広範囲にわた
るがハロゲン化銀に対して10−g〜lO−1モルが好
ましい。Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 10 g to 1 O mole relative to silver halide.
本発明に用いられるハロゲン化銀乳剤は、通常化学増感
および分光増感を施される。The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.
本発明に用いられるハロゲン化銀としては、塩化銀、臭
化銀、(沃)塩臭化銀、沃臭化銀などを用いることがで
きるが、特に迅速処理の目的には沃化銀を実質的に含ま
ない塩化銀含を率が90モル%以上、更には95%以上
、特に98%以上の塩臭化銀または塩化銀乳剤の使用が
好ましい。As the silver halide used in the present invention, silver chloride, silver bromide, silver (iod)chlorobromide, silver iodobromide, etc. can be used, but especially for the purpose of rapid processing, silver iodide can be used substantially. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content of 90 mol % or more, more 95 % or more, particularly 98 mol % or more.
本発明に係わる感光材料には、画像のシャープネス等を
向上させる目的で親水性コロイド層に、欧州特許EP0
,337.49OA2号の第27〜76頁に記載の、処
理により脱色可能な染料(なかでもオキソノール系染料
)を咳感材の680 nmに於ける光学反射濃度が0.
70以上になるように添加したり、支持体の耐水性樹脂
層中に2〜4価のアルコール類(例えばトリメチロール
エタン)等で表面処理された酸化チタンを12重量%以
上(より好ましくは14重量%以上)含有させるのが好
ましい。In the photosensitive material according to the present invention, a hydrophilic colloid layer is incorporated into a hydrophilic colloid layer for the purpose of improving image sharpness, etc.
, No. 337.49OA2, pages 27 to 76, dyes that can be decolorized by treatment (especially oxonol dyes) are used to produce a cough-sensitive material whose optical reflection density at 680 nm is 0.
70 or more, or 12% by weight or more (more preferably 14 (wt% or more) is preferably contained.
また、本発明に係わる感光材料には、カプラーと共に欧
州特許EP0,277.589A2号に記載のような色
像保存性改良化合物を使用するのが好ましい。Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277.589A2 together with a coupler.
特にビラヅロアゾールカプラーとの併用が好ましい。Particularly preferred is the combination with a viladuroazole coupler.
即ち、発色現像処理後に残存する芳香族アミン系現像主
薬と化学結合して、化学的に不活性でかつ実質的に無色
の化合物を生成する化合物(F)および/または発色現
像処理後に残存する芳香族アミン系発色現像主薬の酸化
体と化学結合して、化学的に不活性でかつ実質的に無色
の化合物を生成する化合物(G)を同時または単独に用
いることが、例えば処理後の保存における膜中残存発色
現像主薬ないしその酸化体とカプラーの反応による発色
色素生成によるスティン発生その他の副作用を防止する
上で好ましい。That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.
また、本発明に係わる感光材料には、親水性コロイド層
中に繁殖して画像を劣化させる各種の黴や細菌を防ぐた
めに、特開昭63−271247号に記載のような防黴
剤を添加するのが好ましい。Furthermore, in order to prevent various types of mold and bacteria that propagate in the hydrophilic colloid layer and cause image deterioration, the light-sensitive material according to the present invention contains an anti-mold agent as described in JP-A No. 63-271247. It is preferable to do so.
また、本発明に係わる感光材料に用いられる支持体とし
ては、デイスプレィ用に白色ポリエステル系支持体また
は白色顔料を含む層がハロゲン化銀乳剤層を有する側の
支持体上に設けられた支持体を用いてもよい、更に鮮鋭
性を改良するために、アンチハレーション層を支持体の
ハロゲン化1!乳剤層塗布側または裏面に塗設するのが
好ましい。The support used in the photosensitive material according to the present invention may be a white polyester support for display or a support in which a layer containing a white pigment is provided on the support on the side having a silver halide emulsion layer. To further improve sharpness, an antihalation layer may be used to halogenate the support! It is preferable to coat the emulsion layer coating side or the back side.
特に反射光でも透過光でもデイスプレィが観賞できるよ
うに、支持体の透過濃度を0.35〜0゜8の範囲に設
定するのが好ましい。In particular, it is preferable to set the transmission density of the support in the range of 0.35 to 0.8° so that the display can be viewed in both reflected light and transmitted light.
本発明に係わる感光材料は可視光で露光されても赤外光
で露光されてもよい、露光方法としては低照度露光でも
高照度短時間露光でもよく、特に後者の場合には一画素
光りの露光時間が10−4秒より短いレーザー走査露光
方式が好ましい。The photosensitive material according to the present invention may be exposed to visible light or infrared light, and the exposure method may be low-light exposure or high-light short-time exposure, and especially in the latter case, it is possible to expose the photosensitive material to visible light or infrared light. A laser scanning exposure method in which the exposure time is shorter than 10 −4 seconds is preferred.
また、露光に際して、米国特許第4,880.726号
に記載のバンド・ストップフィルターを用いるのが好ま
しい、これによって光混色が取り除かれ、色再現性が著
しく向上する。Further, during exposure, it is preferable to use a band stop filter as described in US Pat. No. 4,880.726, which eliminates light color mixture and significantly improves color reproducibility.
露光清心の感光材料は惧用の白黒またはカラー現像処理
が施されうるが、カラー感材の場合には迅速処理の目的
からカラー現像の後、漂白定着処理するのが好ましい、
特に前記高塩化銀乳剤が用いられる場合には、漂白定着
液のPHは脱線促進等の目的から約6.5以下が好まし
く、更に約6以下が好ましい。Light-sensitive materials with a simple exposure can be subjected to black-and-white or color development processing, but in the case of color light-sensitive materials, for the purpose of rapid processing, it is preferable to carry out bleach-fixing processing after color development.
In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of promoting delineation.
本発明に係わる感光材料に通用されるハロゲン化銀乳剤
やその他の素材(添加剤など)および写真構成層C層配
置など)、並びにこの感材を処理するために適用される
処理法や処理用添加剤としては、下記の特許公報、特に
欧州特許EP0,355.66OA2号(特願平1−1
07011号)に記載されているものが好ましく用いら
れる。Silver halide emulsions and other materials (additives, etc.) used in the photosensitive material of the present invention, arrangement of photographic constituent layer C layer, etc.), and processing methods and processing materials applied to process this sensitive material. As additives, the following patent publications, especially European Patent EP 0,355.66OA2 (Japanese Patent Application Hei 1-1)
07011) are preferably used.
また、シアンカプラーとして、特開平2−33144号
に記載のジフェニルイミダゾール系シアンカプラーの他
に、欧州特許EP0,333;1B!iAZ号に記載の
3−ヒドロキシピリジン系シアンカプラー(なかでも具
体例として列挙されたカプラー(42)の4当量カプラ
ーに塩素離脱基をもたせて2当量化したものや、カプラ
ー(6)や(9)が特に好ましい)や特開昭64−32
260号に記載された環状活性メチレン系シアンカプラ
ー(なかでも具体例として列挙されたカプラー例3.8
.34′が特に好ましい)の使用も好ましい。Furthermore, as a cyan coupler, in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, European Patent EP 0,333; 1B! 3-hydroxypyridine-based cyan couplers described in No. ) is particularly preferred) and JP-A-64-32
Cyclic active methylene cyan couplers described in No. 260 (especially coupler examples 3.8 listed as specific examples)
.. 34' is particularly preferred).
本発明の感材における膨潤率〔(25°C,H,0中で
の平衡膨潤膜厚−25℃、55%RHでの乾燥全膜厚/
25℃、55%RHでの乾燥全膜厚)x100]は50
〜200%が好ましく、70〜150%がより好ましい
。膨潤率が上記数値よりはすれると写真性の変動を受は
易くなる。Swelling rate of the photosensitive material of the present invention [(equilibrium swelling film thickness at 25°C, H, 0 - dry total film thickness at 25°C, 55% RH/
Total dry film thickness at 25°C and 55% RH) x 100] is 50
-200% is preferable, and 70-150% is more preferable. If the swelling ratio falls below the above-mentioned value, the photographic properties will be more susceptible to fluctuations.
さらに、本発明の感材における膨潤速度は、発色現像液
中(38°C)において飽和膨潤膜厚の90%に到達す
るまでの時間の各を膨潤速度T’yAと定義したときに
、THが15秒以下であるのが好ましい。より好ましく
はT’Aは9秒以下である。Further, the swelling speed of the photosensitive material of the present invention is determined by TH is preferably 15 seconds or less. More preferably, T'A is 9 seconds or less.
その他、本発明の感光材料には、各種染料を添加するこ
とができる。In addition, various dyes can be added to the photographic material of the present invention.
これらの染料は単独で用いても複数を併用して用いても
よい。またこれら染料の添加層には特に制限はなく、最
下層の感光層と支持体との間の層、感光層、中間層、保
護層、保護層と最上層の感光層の間の層などに添加でき
る。These dyes may be used alone or in combination. There are no particular restrictions on the layer to which these dyes are added, such as the layer between the bottom photosensitive layer and the support, the photosensitive layer, the intermediate layer, the protective layer, the layer between the protective layer and the top photosensitive layer, etc. Can be added.
これらの染料の添加法としては、従来の方法を適用でき
、例えば、水やメタノールなどのアルコール類に溶解し
て添加できる。Conventional methods can be used to add these dyes; for example, they can be added after being dissolved in water or an alcohol such as methanol.
前記の染料の添加量としては、下記の塗布量を一つの目
安とすることができる。The following coating amount can be used as a guideline for the amount of the dye added.
シアン染料 ;20■/醒〜100■/醒(最も好まし
い量)
マゼンタ染料:0〜50■/m′(好ましい量)0〜1
0■/イ(最も好ましい量)
イエロー染料:0〜30■/ホ(好ましいI)5〜20
■/m′(最も好ましい量)
前記の層に添加される染料は、感光材料の塗布から乾燥
までの間に全層に拡散する形で存在させるほうが、特定
の層に固定させる方法よりも本発明の効果を顕著なもの
とし、また特定の層を設けることによる製造コスト上昇
を防止する観点からも好ましい。Cyan dye: 20 μ/m to 100 μ/m (most preferred amount) Magenta dye: 0 to 50 μ/m′ (preferred amount) 0 to 1
0 ■/I (most preferred amount) Yellow dye: 0 to 30 ■/E (preferred I) 5 to 20
■/m' (Most preferable amount) It is better to have the dye added to the layer in the form of diffusion throughout the entire layer from coating to drying than to fix it in a specific layer. This is preferable from the viewpoint of making the effects of the invention more noticeable and also from the viewpoint of preventing an increase in manufacturing costs due to the provision of a specific layer.
本発明で使用できる染料は、例えば英国特許第506.
385号、同1,177.429号、同1.311,8
84号、同1,338,799号、同1,385,37
1号、同1,467.214号、同1,433,102
号、同1. 553. 516号、特開昭48−85,
130号、同49−114.420号、同52−117
,123号、同55−161,233号、同59−11
1,640号、特公昭39−22,069号、同43−
13.168号、同62−273527号、米国特許第
3,247,127号、同3. 469. 985号、
同4,078,933号等に記載されたピラゾロン核や
バルビッール酸核を有するオキソノール染料、米国特許
第2,533,472号、同3,379.533号、英
国特許第1. 278゜621号等記載されたその他の
オキソノール染料、英国特許第575,691号、同6
80,631号、同599,623号、同786,90
7号、同907,125号、同1,045,609号、
米国特許第4,255.326号、特開昭59−211
.043号等に記載されたアゾ染料、特開昭50−10
0,116号、同54−118,247号、英国特許第
2,014,598号、同750.031号等に記載さ
れたアゾメチン染料、米国特許第2,865,752号
に記載されたアントラキノン染料、米国特許第2. 5
38. 009号、同2,688,541号、同2,5
38゜008号、英国特許第584,609号、同l。Dyes that can be used in the present invention include, for example, British Patent No. 506.
No. 385, No. 1,177.429, No. 1.311,8
No. 84, No. 1,338,799, No. 1,385,37
No. 1, No. 1,467.214, No. 1,433,102
No. 1. 553. No. 516, JP-A-48-85,
No. 130, No. 49-114.420, No. 52-117
, No. 123, No. 55-161, 233, No. 59-11
No. 1,640, Special Publication No. 39-22,069, No. 43-
No. 13.168, No. 62-273527, U.S. Patent No. 3,247,127, No. 3. 469. No. 985,
oxonol dyes having a pyrazolone nucleus or barbylic acid nucleus described in US Pat. No. 4,078,933, U.S. Pat. No. 2,533,472, US Pat. 278゜621, etc., British Patent Nos. 575,691 and 6
No. 80,631, No. 599,623, No. 786,90
No. 7, No. 907,125, No. 1,045,609,
U.S. Patent No. 4,255.326, JP 59-211
.. Azo dye described in No. 043, etc., JP-A-50-10
Azomethine dyes described in U.S. Pat. Dye, U.S. Pat. No. 2. 5
38. No. 009, No. 2,688,541, No. 2,5
No. 38°008, British Patent No. 584,609, ibid.
210.252号、特開昭50−40,625号、同5
1−3,623号、同51−10,927号、同54−
118,247号、特公昭4’8−3,286号、同5
9−37,303号等に記載されたアゾメチン染料、特
公昭28−3,082号、同44−16.594号、同
59−28,898号等に記載されたスチリル染料、英
国特許第446.583号、同1,335,422号、
特開昭59−228,250号等に記載されたトリアリ
ールメタン染料、英国特許第1. 075. 65.3
号、同1,153,341号、同1. 284. 73
0号、同1,475.228号、同1,542゜807
号等に記載されたメロシアニン染料、米国特許第2,8
43.486号、同3. 294. 539号等に記載
されたシアニン染料などが挙げられる。No. 210.252, JP-A No. 50-40,625, No. 5
No. 1-3,623, No. 51-10,927, No. 54-
No. 118,247, Special Publication No. 4'8-3,286, No. 5
Azomethine dyes described in Japanese Patent Publication No. 9-37,303, styryl dyes described in Japanese Patent Publication No. 28-3,082, Japanese Patent Publication No. 44-16.594, Japanese Patent Publication No. 59-28,898, etc., British Patent No. 446 .583, 1,335,422,
Triarylmethane dyes described in JP-A No. 59-228,250, etc., British Patent No. 1. 075. 65.3
No. 1,153,341, No. 1. 284. 73
No. 0, No. 1,475.228, No. 1,542°807
Merocyanine dyes described in US Patent Nos. 2 and 8
No. 43.486, 3. 294. Examples include cyanine dyes described in No. 539 and the like.
これらの中で、本発明で特に好ましく用いることのでき
る染料は以下の一般式(1)、(II)、(III)、
(IV)、(V)又は(VI)で表わされる染料である
。Among these, dyes that can be particularly preferably used in the present invention have the following general formulas (1), (II), (III),
It is a dye represented by (IV), (V) or (VI).
一般式(I)
式中、2..2.は各々同じでも異っていてもよく、複
素環を形成するのに必要な非金属原子群を表わし、L、
、L、、Ls、L、、Llはメチン基を表わし、nl+
n!は0又は1を表わし、M■は水素又はその他の1価
のカチオンを表わす。General formula (I) In the formula, 2. .. 2. may be the same or different and each represents a group of nonmetallic atoms necessary to form a heterocycle, L,
, L, , Ls, L, , Ll represent a methine group, nl+
n! represents 0 or 1, and M represents hydrogen or other monovalent cation.
一般式(II)
一般式(n)において、X、Yは同一または異なってい
てもよく、電子吸引性基を表わし、XとYが連結されて
環を形成してもよい。General Formula (II) In General Formula (n), X and Y may be the same or different, represent an electron-withdrawing group, and X and Y may be linked to form a ring.
R11、R12は同一または異なっていてもよく、水素
原子、ハロゲン原子、アルキル基、アルコキシ基、ヒド
ロキシ基、カルボキシル基、置換アミノ基、カルバモイ
ル基、スルファモイル基、アルコキシカルボニル基、ス
ルホ基を表わす。R11 and R12 may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, a substituted amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or a sulfo group.
R4s、R11は同一または異なっていてもよく、水素
原子、アルキル基、アルケニル基、アリール基、アシル
基、スルホニル基を表わし、R11、R11が連結され
て5〜6員環を形成してもよい。また、R41とR41
、RlfとR14がそれぞれ連結されて5〜6員環を形
成してもよい。R4s and R11 may be the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group, and R11 and R11 may be linked to form a 5- to 6-membered ring. . Also, R41 and R41
, Rlf and R14 may be respectively connected to form a 5- to 6-membered ring.
上記X、Y、R,いR+ t % R+ I % R+
tのうち、少なくとも1つは置換基としてスルホ基ま
たはカルボキシル基を有する。Above X, Y, R, R+ t % R+ I % R+
At least one of t has a sulfo group or a carboxyl group as a substituent.
L 11% L+t、Ll!は各々メチン基を表わす。L 11% L+t, Ll! each represents a methine group.
kはO又はlを表わす。k represents O or l.
一般式(I[[)
%式%
式中、A r + 、A r tは同じでも異っていて
も良く、アリール基又は複素環基を表わす。General formula (I[[)% formula% In the formula, A r + and A r t may be the same or different and represent an aryl group or a heterocyclic group.
一般式(IV)
式中、R”、R″、RoおよびR”は同一または、互い
に異なっていてもよく、水素原子、ヒドロキシ基、アル
コキシ基、アリールオキシ基、力R”は同一または互い
に異なっていてもよく、水素原子および少なくとも一つ
のスルホン酸基またはカルボキシル基をもつアルキル基
、アリール基)を表わす。General formula (IV) In the formula, R'', R'', Ro and R'' may be the same or different from each other, and hydrogen atoms, hydroxy groups, alkoxy groups, aryloxy groups, and the force R'' are the same or different from each other. represents an alkyl group or aryl group having a hydrogen atom and at least one sulfonic acid group or carboxyl group.
RStz R”s R”およびR”は同一または互いに
異なっていてもよく、水素原子、スルホン酸基、カルボ
キシル基又は少なくとも一つのスルホン酸基又はカルボ
キシル基をもつアルキル基又はアリ−ル基を表わす。RStz R"s R" and R" may be the same or different and represent a hydrogen atom, a sulfonic acid group, a carboxyl group, or an alkyl group or aryl group having at least one sulfonic acid group or carboxyl group.
一般式(V)
式中、LSL’ は置換または非置換のメチン基または
窒素原子を表わし、mは0.1.2または3を表わす。General formula (V) In the formula, LSL' represents a substituted or unsubstituted methine group or a nitrogen atom, and m represents 0.1.2 or 3.
Zはピラゾロン核、ヒドロキシピリドン核、バルビッー
ル酸核、チオバルビッール酸核、ジメドン核、インダン
−1,3−ジオン核、ロダニン核、チオヒダントイン核
、オキサゾリジン−4−オン−2−チオン核、ホモフタ
ルイミド核、ピリミジン−2,4−ジオン核、または1
. 2. 3. 4−テトラヒドロキノリン−2,4−
ジオン核を形成するに必要な非金属原子群を表わす。Z is pyrazolone nucleus, hydroxypyridone nucleus, barbituric acid nucleus, thiobarbital acid nucleus, dimedone nucleus, indan-1,3-dione nucleus, rhodanine nucleus, thiohydantoin nucleus, oxazolidin-4-one-2-thione nucleus, homophthalimide nucleus , pyrimidine-2,4-dione nucleus, or 1
.. 2. 3. 4-tetrahydroquinoline-2,4-
Represents a group of nonmetallic atoms necessary to form a diion nucleus.
Yはオキサゾール核、ベンゾオキサゾール核、ナフトオ
キサゾール核、チアゾール核、ベンゾチアゾール核、ナ
フトチアゾール核、ベンゾセレナゾール核、ピリジン核
、キノリン核、ベンゾイミダゾール核、ナフトイミダゾ
ール核、イミダゾキノキサリン核、インドレニン核、イ
ソオキサゾール核、ベンゾイソオキサゾール核、ナフト
イソオキサゾール核、またはアクリジン核を形成するに
必要な非金属原子群を表わし、ZおよびYは更に置換基
を有していてもよい。Y is an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a pyridine nucleus, a quinoline nucleus, a benzoimidazole nucleus, a naphthimidazole nucleus, an imidazoquinoxaline nucleus, an indolenine nucleus , represents a group of nonmetallic atoms necessary to form an isoxazole nucleus, a benzisoxazole nucleus, a naphthoisoxazole nucleus, or an acridine nucleus, and Z and Y may further have a substituent.
一般式(VI)
または
式中、RおよびR′ は互いに同一または異っていても
よく、置換または非置換のアルキル基を表わす。In the general formula (VI), R and R' may be the same or different and represent a substituted or unsubstituted alkyl group.
L、 、L、 、L、は互いに同一または異っていても
よく、置換または非置換のメチン基を表わし、mは0.
1.2または3を表わす。L, , L, , L, which may be the same or different from each other, represent a substituted or unsubstituted methine group, and m is 0.
1.2 or 3.
、zSz’ は互いに同一または異っていてもよく、置
換または非置換の複素5員環または複素6員環を形成す
るに必要な非金属原子群を表わし、!およびnはそれぞ
れ0または1である。, zSz' may be the same or different from each other and represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted 5-membered or 6-membered hetero ring, and ! and n are 0 or 1, respectively.
Xeはアニオンを表わす。pは1または2を表わし、化
合物が分子内塩を形成するときはpはlである。Xe represents an anion. p represents 1 or 2, and when the compound forms an inner salt, p is 1.
一般式(I)で表わされる染料のうち、特に好ましいも
のは下記−綴代(I−a)で表わさる染料である。Among the dyes represented by the general formula (I), particularly preferred are the dyes represented by the following formula (I-a).
一般式(I −a)
式中、R+ 、Rsは脂肪族基、芳香族基又はヘテロ環
基を表わし、Rt、R1は脂肪族基、芳香族基、 OR
* 、 C00Rs 、 NRi Ra、−CONR,
R,、−NR,C0NR,R,、−3o、R,、−〇O
R,、−NR,COR,、−NR,5o2R? 、シア
ノ基(ここに、R3、R,は水素原子、脂肪族基又は芳
香族基を表わし、R1は脂肪族基又は芳香族基を表わし
、R5とR6又はR6とR7は連結して5又は6員環を
形成していても良い。)を表わし、LllLtl’Ls
lLt、Ls及びn+ 、nt + Mのは一般式(I
)における定義と同義である。General formula (I-a) In the formula, R+ and Rs represent an aliphatic group, an aromatic group, or a heterocyclic group, and Rt and R1 are an aliphatic group, an aromatic group, and OR
*, C00Rs, NRiRa, -CONR,
R,, -NR,C0NR,R,, -3o,R,, -〇O
R,, -NR,COR,, -NR,5o2R? , a cyano group (herein, R3, R, represents a hydrogen atom, an aliphatic group, or an aromatic group, R1 represents an aliphatic group or an aromatic group, and R5 and R6 or R6 and R7 are connected to form 5 or may form a 6-membered ring), and LllLtl'Ls
lLt, Ls and n+, nt + M are represented by the general formula (I
) has the same meaning as the definition in ).
以下に一般式(I−a)で表わされる染料の例を示すが
、本発明はこれらに限定されるものではない。Examples of dyes represented by general formula (I-a) are shown below, but the present invention is not limited thereto.
本発明に用いられる一般式(1)〜(VI)で示される
染料としては、特開平1−297213号明細書第27
頁〜第103頁に記載されているものを用いることがで
きる。The dyes represented by the general formulas (1) to (VI) used in the present invention include those described in JP-A-1-297213 No. 27
Those described on pages 1 to 103 can be used.
本発明に用いられる染料は、現像から水洗までのいずれ
かの工程において、ハロゲン化銀写真感光材料から溶出
するかあるいは英国特許第506゜385号に記載され
ているように亜硫酸塩によって脱色される。The dye used in the present invention is eluted from the silver halide photographic material during any step from development to washing, or is decolorized by sulfite as described in British Patent No. 506.385. .
(実施例)
以下に本発明の実施例を具体的に示すが、本発明はこれ
らに限定されるものではない。(Examples) Examples of the present invention will be specifically shown below, but the present invention is not limited thereto.
実施例1
(支持体の調製)
写真用印画紙用LBKP (広葉樹晒、硫酸塩パルプ)
100%(秤量175 g / m %厚み約180μ
);白色原紙の表面に下記の組成の耐水性酸化チタンか
らなる白色顔料含有樹脂層を設け、以下に示す支持体を
えた。Example 1 (Preparation of support) LBKP for photographic paper (bleached hardwood, sulfate pulp)
100% (Weight 175 g/m % Thickness approx. 180μ
); A white pigment-containing resin layer made of water-resistant titanium oxide having the composition shown below was provided on the surface of a white base paper to obtain the support shown below.
支持体:
ポリエチレン組成部(密度0. 920 g/cc、メ
ルトインデックス(MI)5.0g/lo分)の90重
量部に、次のような表面処理したアナタース形酸化チタ
ン白色顔料lO重量部添加し、同様に混練した後、熔融
押し出しコーティングにより30μmの耐水性樹脂層を
えた。Support: To 90 parts by weight of polyethylene composition (density 0.920 g/cc, melt index (MI) 5.0 g/lo min), 10 parts by weight of anatase titanium oxide white pigment subjected to the following surface treatment was added. After kneading in the same manner, a 30 μm water-resistant resin layer was obtained by melt extrusion coating.
酸化チタン粉末を、2.4−ジヒドロキン−2−メチル
ペンタンのエタノール溶液に&aし加熱してエタノール
蒸散せしめて表面処理した酸化チタン白色顔料を得た。Titanium oxide powder was added to an ethanol solution of 2,4-dihydroquine-2-methylpentane and heated to evaporate the ethanol to obtain a surface-treated titanium oxide white pigment.
該アルコールは、酸化チタンに対して約1重量%相当粒
子表面に被覆した。The alcohol was coated on the particle surface in an amount equivalent to about 1% by weight based on titanium oxide.
白紙原紙のその裏面にポリエチレン組成物を用い耐水性
樹脂層を設けた。A water-resistant resin layer was provided on the back side of the blank base paper using a polyethylene composition.
以上のように作成した反射支持体の上にコロナ放電処理
をおこないゼラチン下塗層を設けた。この上に、以下に
示す層を塗布し多層カラー印画紙を作製した。塗布液は
下記のようにして作製した。A gelatin undercoat layer was provided on the reflective support prepared as described above by performing corona discharge treatment. On top of this, the following layers were applied to produce a multilayer color photographic paper. The coating liquid was prepared as follows.
第−層塗布液調製
イエローカプラー(Exy)19.1gおよび色像安定
剤(Cpd−1)4.4g及び色像安定剤(Cpd−7
)0.7gに酢酸エチル27.2ccおよび溶媒(So
lv−1)8.2gを加え溶解し、この溶液を10%ド
デシルベンゼンスルホン酸ナトリウム8ccを含む10
%ゼラチン水溶液185ccに乳化分散させた。一方で
下記に示す青感性増感色素を加えた後に硫黄増感を施し
た塩臭化銀乳剤(乳剤1、製法は後述)を調製した。19.1 g of yellow coupler (Exy), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-7)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
lv-1) 8.2g was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate containing 8cc.
% gelatin aqueous solution (185 cc). On the other hand, a silver chlorobromide emulsion (emulsion 1, the manufacturing method of which will be described later) was prepared by adding the blue-sensitive sensitizing dye shown below and then sulfur sensitization.
前記の乳化分散物とこの乳剤とを混合溶解し、以下に示
す組成となるように第一塗布液を調製した。第二層から
第七履用の塗布液も第−層塗布液と同様の方法で調製し
た。The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.
各層のセラチン硬化剤としては、1−オキシ−3,5−
ジクロロ−s−トリアジンナトリウム塩を用いた。各層
の乳剤は乳剤の形成時にヘキサクロロイリジウム(■)
カリウムを加えた。添加量は各層の乳剤とも大、小サイ
ズとも同じ量で銀1モルあたり青感性層用lXl0−’
モル、緑感性層用3X10−’モル、赤感性層用5 X
to−’モル用いた。The ceratin curing agent in each layer is 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used. The emulsion of each layer is hexachloroiridium (■) when forming the emulsion.
Added potassium. The amount added is the same for both large and small emulsions in each layer, and it is lXl0-' for the blue-sensitive layer per mole of silver.
mole, 3X10-' mole for green sensitive layer, 5X for red sensitive layer
to-' moles were used.
各層の分光増感色素として下記のものを用い、局在相形
酸の際のCR化合物とした。The following spectral sensitizing dyes were used as the spectral sensitizing dyes in each layer, and were used as CR compounds for localized phase acids.
青感性乳剤層 (S−1)
(ハロゲン化銀1モル当たり、大サイズ乳剤に対しては
各々2.0X10−’モル)
緑感性乳剤層 (S−2)
(S−3)
赤感性乳剤層 (S−4)
C2H,I C,H,。Blue-sensitive emulsion layer (S-1) (2.0 x 10-' mol each for large size emulsions per mol of silver halide) Green-sensitive emulsion layer (S-2) (S-3) Red-sensitive emulsion layer (S-4) C2H,I C,H,.
赤感性乳剤層に対しては、下記の化合物をハロゲン化銀
1モル当たり2.6XlO−’モル添加した。To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6XlO-' mol per mol of silver halide.
また青感性乳剤層、緑感性乳剤層、赤感性乳剤層に対し
、1−(5−メチルウレイドフェニル)−5−メルカプ
トテトラゾールをそれぞれハロゲン化銀1モル当たりB
、5X10−’モル、7.7XIO−’モル、2.5X
10−”モル添加した。In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer per mole of silver halide.
, 5X10-'mol, 7.7XIO-'mol, 2.5X
10-" moles were added.
また、青感性乳剤層と緑感性乳剤層に対し、4−ヒドロ
キシ−6−メチル−1,3,3a、?−テトラザインデ
ンをそれぞれハロゲン化銀1モル当たり、lXl0−’
モルと2X10−’モル添加した。Also, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,? -tetrazaindene per mole of silver halide, respectively, lXl0-'
mol and 2X10-' mol were added.
イラジェーション防止のために乳剤層に下記の染料を添
加した。The following dyes were added to the emulsion layer to prevent irradiation.
青感層(イエロー染料) および 緑感層(マゼンタ染料) SO3Na Sot Na5、0mg/m シアン染料■ また防腐剤として下記の化合物を使用した。Blue sensitive layer (yellow dye) and Green-sensitive layer (magenta dye) SO3Na Sot Na5, 0mg/m cyan dye■ In addition, the following compound was used as a preservative.
(数字は塗布量) 000C,H。(The number is the amount of coating) 000C,H.
(25,0mg/m”) (50,Omvm’)
青感性乳剤B−1(第1表試料1の場合)(1液)
Hlo 1000ccNaC
A 5.5gゼラチン
32g(2液)
硫酸(IN) 24cc(3
液)
下記化合物A(1%) 3ccCH
8
CH。(25,0mg/m”) (50,Omvm')
Blue-sensitive emulsion B-1 (for sample 1 in Table 1) (1 liquid) Hlo 1000ccNaC
A 5.5g gelatin
32g (2 liquids) Sulfuric acid (IN) 24cc (3
Liquid) Compound A below (1%) 3ccCH
8 CH.
(4液)
NaC1! 1.7gH,
Oを加えて 200cc(5液)
A g N Os 5
gH,Oを加えて 200cc(6
液)
NaCj2 41.
3gKr I rCj!a(0,0OIX)
o、5ccH20を加えて
600cc(7液)
AgN○s 120g
H,Oを加えテロ 00 cc
(1液)を76℃に加熱し、(2液)と(3液)を添加
した。(4 liquids) NaC1! 1.7gH,
Add O to 200cc (5 liquids) A g N Os 5
Add gH and O to 200cc (6
liquid) NaCj2 41.
3gKr I rCj! a(0,0OIX)
o, add 5ccH20
600cc (7 liquids) AgN○s 120g
After adding H and O, 00 cc (liquid 1) was heated to 76°C, and liquid (liquid 2) and liquid (3) were added.
その後、(4液)と(5液)を10分分間中して同時添
加した。Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 10 minutes.
さらに10分後、(6液)と(7液)をlO分分間中し
て同時添加した。添加5分後、温度を下げ、脱塩した。After another 10 minutes, (liquid 6) and (liquid 7) were added simultaneously over 10 minutes. After 5 minutes of addition, the temperature was lowered and desalted.
水と分散ゼラチンを加えpHを6゜3に合わせて、平均
粒子サイズ1.1μm、変動係数(標準偏差を平均粒子
サイズで割った値:S/d)0.30の立方体塩化銀乳
剤を得た。Add water and dispersed gelatin to adjust the pH to 6°3 to obtain a cubic silver chloride emulsion with an average grain size of 1.1 μm and a coefficient of variation (standard deviation divided by average grain size: S/d) of 0.30. Ta.
この乳剤1.0kgに、青色用分光増感色素(S−1)
の0.6%溶液を26cc添加し、さらに、0.05μ
のAgBr超微粒子乳剤を、ホストAgC1’乳剤に対
して0.5モル%の比率で添加し、58°Cで10分間
混合熟成した。その後チオ硫酸ナトリウムを添加し、最
適に化学増感をほどこし安定剤(Stb−1)をlo−
1モル1モルAg添加した。To 1.0 kg of this emulsion, add blue spectral sensitizing dye (S-1).
Add 26cc of 0.6% solution of
The AgBr ultrafine grain emulsion was added at a ratio of 0.5 mol % to the host AgC1' emulsion, and mixed and aged at 58°C for 10 minutes. After that, sodium thiosulfate was added to optimally chemically sensitize the stabilizer (Stb-1).
1 mole of Ag was added.
次に(6液)と(7液)の添加時間を延長して、変動係
数の異なったB−2(25%)、B−3(20%)、B
−4(15%)、及びB−5(10%)の乳剤を各々作
成した。Next, by extending the addition time of (liquid 6) and (liquid 7), B-2 (25%), B-3 (20%), and B-2 with different coefficients of variation were added.
-4 (15%) and B-5 (10%) emulsions were prepared.
緑感性乳剤G−1(第1表試料1の場合)(8液)
Hr O1000m1
Na(13,3g
ゼラチン 32g(9液)
硫酸(IN) 24m1(1
0液)
化合物A(1%) 3mI!(1
1液)
N a Cl 11.00
gH,Oを加えて 200mj7(
12液)゛
AgNOl 32. OOg
H20を加え”’C200m1
(13液)
NaC144,OOg
K、 I r C1g(0,001N)
2.3 m lH2Oを加えて
560m1(14液)
AgNOl 128gH,
Oを加えて 560mj7(8液)を
52°Cに加熱し、(9液)と(10液)を添加した。Green-sensitive emulsion G-1 (for sample 1 in Table 1) (8 liquids) Hr O1000ml Na (13.3g Gelatin 32g (9 liquids) Sulfuric acid (IN) 24ml (1
0 liquid) Compound A (1%) 3mI! (1
1 liquid) N a Cl 11.00
Add gH, O and make 200mj7(
12 liquid) ゛AgNOl 32. OOg
Add H20"'C200ml (13 liquids) NaC144, OOg K, I r C1g (0,001N)
Add 2.3 ml H2O
560ml (14 liquids) AgNOl 128gH,
After adding O, 560mj7 (8 liquids) was heated to 52°C, and (9 liquids) and (10 liquids) were added.
その後、(11液)と(12液)を8分間費やして同時
添加した。さらに10分後、(13液)と(14液)を
15分分間中して同時添加した。Thereafter, (Liquid 11) and (Liquid 12) were added simultaneously over a period of 8 minutes. After another 10 minutes, (Liquid 13) and (Liquid 14) were added simultaneously over a period of 15 minutes.
この乳剤に増感色素(S−2)を、ハロゲン化銀1mo
f’当り4xlO−’moi’、 (S−3)を8×
10−′mo1添加し、後に下記の(15液)を10分
間にわたって添加し、添加5分後、温度を下げ脱塩した
。A sensitizing dye (S-2) was added to this emulsion in an amount of 1 mo of silver halide.
4xlO-'moi' per f', (S-3) 8x
10-'mo1 was added, and then the following (liquid 15) was added over 10 minutes, and 5 minutes after the addition, the temperature was lowered and desalted.
水と分散ゼラチンを加え、pHを6,2に合せて、
(15液)
KBr 5.60gH1O
を加えて 280m158°Cでチオ
硫酸ナトリウムを添加し、最適に化学増感を施し、平均
粒子サイズ0.48μm、変動係数(標準偏差を平均粒
子サイズで割った値; s/d)0.30の単分散立方
体塩化銀乳剤を得た。Add water and dispersed gelatin and adjust the pH to 6.2 (15 liquids) KBr 5.60gH1O
was added and sodium thiosulfate was added at 280 m at 158 °C to perform optimal chemical sensitization, with an average particle size of 0.48 μm and a coefficient of variation (standard deviation divided by average particle size; s/d) of 0.30. A monodisperse cubic silver chloride emulsion was obtained.
次に(11液)と(12液)及び(13液と14液)の
添加時間を延長して、変動係数の異なったG−2(25
%) 、G−3(20%)、G−4(15%)及びG−
5(10%)の乳剤を各々作成した。Next, the addition time of (liquid 11), (liquid 12) and (liquid 13 and 14) was extended, and G-2 (25
%), G-3 (20%), G-4 (15%) and G-
5 (10%) emulsions were each prepared.
赤感性乳剤は、緑感性乳剤の調製法において、使用する
増感色素を(S−4)に変更して、添加量をハロゲン化
銀1モル当り1.5X10−’モルとしたほかは、全く
同様にして調製した。The red-sensitive emulsion was prepared using the same method as the green-sensitive emulsion except that the sensitizing dye used was changed to (S-4) and the amount added was 1.5 x 10-' mol per mol of silver halide. Prepared in the same manner.
変動係数
R−130%
R−225%
R−320%
R−415%
R−510%
(層構成)
以下に各層の組成を示す。数字は塗布量(g/m′)を
表す。ハロゲン化銀乳剤は銀換算塗布量を第−層(青感
層)
前記塩臭化銀乳剤 0.30ゼラチン
1.86イエローカプラー
(ExY) 0.82色像安定剤(Cpd−
1) 0.19溶媒(Solv−1)
0.35色像安定剤(Cpd−7)、
0.06第二層(混色防止層)
ゼラチン 0.99混色防止
剤(Cpd−5) 0.08溶媒(Sol
v−1) 0.16溶媒(So I
v−4) 0. 08第五層(緑感N)
塩臭化銀乳剤((499%、平均粒子サイズ0゜5μ、
変動係数10%) 0.20ゼラチン
1.24マゼンクカブラ−(Ex
M) 0.20色像安定剤(Cpd−2)
0.03色像安定剤(Cp d−3)
0. 15色像安定剤(Cpd−4)
0.02色像安定剤(Cpd−9) 0.
02溶媒(Solv−2) 0.40第
四層(紫外線吸収層)
ゼラチン 1.58紫外線吸
収剤(UV−1) 0.47混色防止剤(C
pd−5) 0.05溶媒(Solv−5)
0.24第五層(赤感N)
塩臭化銀乳剤(C199,8%、平均粒子サイズ0.4
9μ、変動係数8%) 0.20ゼラチン
1.34シアンカプラー(ExC)
0.32色像安定剤(Cpd−6)
0.17/
/
/
色像安定剤(Cpd−7) 0.40色像安
定剤(Cpd−8) 0.04溶媒(So
Iv−6) 0. 15第六層(紫外
線吸収層)
ゼラチン 0.53紫外線吸
収剤(UV−1) 0. 16混色防止剤(
Cpd−5) o、02溶媒(Solv−5
) 0.08第七層(保護層)
ゼラチン 1.33ポリビニ
ルアルコールのアクリル変性共重合体(変性度17%)
0.17流動パラフイン
0.03(ExY)イエローカプラー
C,H。Variation coefficient R-130% R-225% R-320% R-415% R-510% (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m'). The silver halide emulsion is coated in terms of silver coating amount as follows: Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-
1) 0.19 solvent (Solv-1)
0.35 color image stabilizer (Cpd-7),
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Sol
v-1) 0.16 solvent (So I
v-4) 0. 08 Fifth layer (green feel N) Silver chlorobromide emulsion ((499%, average grain size 0°5μ,
Coefficient of variation 10%) 0.20 gelatin
1.24 Mazenku Kabura (Ex
M) 0.20 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cp d-3)
0. 15 color image stabilizer (Cpd-4)
0.02 Color image stabilizer (Cpd-9) 0.
02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (C
pd-5) 0.05 solvent (Solv-5)
0.24 Fifth layer (red feeling N) Silver chlorobromide emulsion (C199.8%, average grain size 0.4
9μ, coefficient of variation 8%) 0.20 gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-6)
0.17/ / / Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.04 Solvent (So
Iv-6) 0. 15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0. 16 Color mixing prevention agent (
Cpd-5) o, 02 solvent (Solv-5
) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)
0.17 liquid paraffin
0.03 (ExY) Yellow coupler C, H.
とのl:1混合物(モル比) (ExC) シアンカプラー し1 R=C,H,とC,)I。l:1 mixture (molar ratio) with (ExC) Cyan coupler 1 R=C, H, and C,)I.
と の各々重量で2:4:4の混合物 (Cpd−1)色像安定剤 (Cpd−2)色像安定剤 (Cpd−3)色像安定剤 (Cpd−4)色像安定剤 (Cpd−5)混色防止剤 (Cpd−6)色像安定剤 の2:4:4 温合物(重量比) (Cpd−7)色像安定剤 べCl(、−CH+ 置 (口pd−8’)色像安定剤 (Cpd−9)色像安定剤 (tlV−1)紫外線吸収剤 の4:2:4混合物(重量比ン (Solv−1)溶 媒 (Salv−2)溶 媒 の2:1混合物(容量比) (Solv−4)溶 媒 (Solv−5)溶 媒 C00C,Il、t 「 (CH2)。and a 2:4:4 mixture by weight of each (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing prevention agent (Cpd-6) Color image stabilizer 2:4:4 warm mixture (weight ratio) (Cpd-7) Color image stabilizer BeCl(, -CH+ Place (PD-8') Color image stabilizer (Cpd-9) Color image stabilizer (tlV-1) Ultraviolet absorber A 4:2:4 mixture (weight ratio) of (Solv-1) Solvent (Salv-2) Solvent A 2:1 mixture (by volume) of (Solv-4) Solvent (Solv-5) Solvent C00C, Il, t " (CH2).
COOC,lt、?
(Solv−6)溶 媒
の゛(95:5)混合物
以上のようにして得られた試料をくさび形ウェッジを通
して露光した後に、カラー現像液の添加剤と組成とを第
12表に示したように変更して、下記処理工程にて処理
した。COOC,lt? After exposing the sample thus obtained through a wedge-shaped wedge, the additives and composition of the color developer were as shown in Table 12. The following treatment steps were carried out after changing to:
処理工程 星−皮 峙−固
カラー現像 38℃ 45秒
漂白定着 30〜35℃ 45秒リンス■ 3
0〜35°0 20秒リンス■ 30〜35°0
20秒リンス■ 30〜35°0 20秒
乾 燥 70〜80’C60秒
用いた各処理液の組成は以下に示す通りである。Processing process Star - Leather Face - Solid color development 38℃ 45 seconds bleach fixing 30-35℃ 45 seconds rinse ■ 3
0~35°0 20 seconds rinse ■ 30~35°0
Rinse for 20 seconds 30-35°0 20 seconds Dry 70-80'C 60 seconds The compositions of each treatment solution used are as shown below.
立之二里盈鹿 タンク液水
800mlニトリロ
−N、N、N−1リ
メチレンホスホン酸(40%) 8..5mj2添加
剤(第2表参照) 0.5g1−ヒドロキ
シエチリデン−
1,1−ジホスホン酸(60X) 1. Oml
!ジエチレントリアミン五酢酸 1.0g添加剤
第2表参照臭化カリウム
第2表参照塩化ナトリウム
第2表参照I・リエタノールアミン
8.0g塩化ナトリウム 1.
4g炭酸カリウム 258N
−エチル−N−(β−メタ
ンスルホンアミドエチル)
−3−メチル−4−アミノ
アニリン硫酸塩 5.0gジエチルヒ
ドロキシルアミン 5.5g蛍光増白剤(4,4
′−ジア
ミノ−スチルヘン系) 1.0g水を加
えて 1000 m1pH10,
05
1R足春丘
水 40
0 mlチオ硫酸アンモニウム(70%) 10
0Id亜硫酸ナトリウム 17g
エチレンジアミン四酢酸酢酸(Ill)アンモニウム
55gエチレンジアミン四酢酸
二
ナトリウム 5g水を加えて
1000dPH(25%)6.
0
二ノス撒
イオン交換水(カルシウム、マグネシウムは各々3 p
I)nl以下)
前記カラー現像液は、調液直後(新液)及び、1rビー
カーにて、35°C−カ月経時した後(経時液)の各り
にて処理され、新液処理時からの、マゼンタの感度低下
量” (△SG)、及び汚れを評価するため、イエロー
の最小濃度の変化(ΔDB 、i、 )を求めた。(本
初%J濃度0.8を示す露光点の濃度低下量)
結果を第−表に示した。Tatenojiri Eika tank liquid water
800ml Nitrilo-N,N,N-1 rimethylenephosphonic acid (40%) 8. .. 5mj2 additive (see table 2) 0.5g 1-hydroxyethylidene-1,1-diphosphonic acid (60X) 1. Oml
! Diethylenetriaminepentaacetic acid 1.0g additive
See Table 2 Potassium Bromide
See Table 2 Sodium chloride
See Table 2 I. Reethanolamine
8.0g sodium chloride 1.
4g potassium carbonate 258N
-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g diethylhydroxylamine 5.5g optical brightener (4,4
'-diamino-stilhen system) Add 1.0g water to 1000ml pH10,
05 1R Ashiharuokasui 40
0 ml ammonium thiosulfate (70%) 10
0Id Sodium Sulfite 17g
Ethylenediaminetetraacetic acid ammonium acetate (Ill)
55g disodium ethylenediaminetetraacetate Add 5g water to 1000dPH (25%)6.
0 Ninos sprinkled ion exchange water (calcium, magnesium 3 p each
I) nl or less) The color developing solution was treated immediately after preparation (new solution) and after aging at 35°C for a month in a 1R beaker (aged solution), and from the time of processing the new solution. In order to evaluate the magenta sensitivity reduction amount (△SG) and the stain, the change in yellow minimum density (∆DB, i, ) was determined. Amount of concentration decrease) The results are shown in Table 1.
第−表
第一表(続き)
(*印〜木発明)
本発明(N09〜23)においては、マゼンタの感度低
下や、スティンの上昇が著しく低減され、良好な写真特
性が得られた。更に本発明においては、ビーカーの液界
面付近での析出物の発生はほとんど無かった。Table 1 (Continued) (*marked ~ wood invention) In the present invention (N09-23), the decrease in magenta sensitivity and the increase in stain were significantly reduced, and good photographic characteristics were obtained. Furthermore, in the present invention, there was almost no occurrence of precipitates near the liquid interface in the beaker.
(実施例2)
実施例1の試料の塗布銀量を以下のように変更にして、
試料2−A、 B、 C,D、を作成した。(Example 2) The coated silver amount of the sample of Example 1 was changed as follows,
Samples 2-A, B, C, and D were created.
次に試料2Cを像様露光後、下記の処理工程にて、カラ
ー現像液のタンク容量の2倍補充するまで連続処理(ラ
ンニングテスト)を行なった。Next, after imagewise exposure of Sample 2C, continuous processing (running test) was performed in the following processing steps until twice the tank capacity of the color developer was replenished.
試料2Aから2Dは、くさび形ウェッジを通して露光し
た後に、ランニングテスト時と終了時に処理し、スター
ト時からの△Sc及び△Dlsinの変化を実施例1と
同様に求めた。Samples 2A to 2D were exposed through a wedge and then processed during and at the end of the running test, and changes in ΔSc and ΔDlsin from the start were determined in the same manner as in Example 1.
又、処理後の処理タンク壁面の析出物の有無を目視判断
した。In addition, the presence or absence of precipitates on the wall surface of the treatment tank after treatment was visually determined.
製U保 1度 朋 且X撒゛ム佼」ミ1bラー現像
38°C45秒 12m1 、17j2漂白定
着 30〜35°C45秒 60m1! Inリ
ンス■ 30〜35°c 20秒 −1042リン
ス■ 30〜35°C20秒 −10!リンス■ 3
0〜35’C20秒 −10fリンス■ 30〜35
°C30秒 200#+110f乾 燥 70〜80
°C60秒
*補充量は感光材料1ff12あたり
カラー現像液は以下のA−E5つの処方を用いて連続処
理を行なった。1 degree U-protection 1 degree, 38°C, 45 seconds, 12ml, 17j2 bleach fixing, 30-35°C, 45 seconds, 60ml! In rinse■ 30~35°C 20 seconds -1042 Rinse■ 30~35°C 20 seconds -10! Rinse ■ 3
0~35'C20 seconds -10f rinse■ 30~35
°C 30 seconds 200#+110f drying 70~80
°C for 60 seconds *The amount of replenishment was per 1ff12 of the photosensitive material.Continuous processing was carried out using the following five formulations of color developers A to E.
リンスは■→■→■→■の4タンク向流方式とした。The rinsing was done using a 4-tank countercurrent flow system: ■→■→■→■.
各処理液の組成は以下の通りである。The composition of each treatment liquid is as follows.
友旦二嬰像櫃人 叉l久撒 且り撒水
800d 8
00d1−ヒドロキシエチリデン
=1.1−ジホスホン酸
(60%) 1.0g ]、
Ogジエチレントリアミン五酢
酸 1.0g
1.0g二1−リロトリメチレンホス
ホン酸(40%) 7.0g 7.0g
臭化カリウム 2X10−’*ol −ト
リエタノールアミン 8.0g 12.0
g塩化ナトリウム 0.085mol
−炭酸カリウム 25g 25g
N=エチルーN−(β−メ
タンスルホンアミドエチ
ル)−3−メチル−4−
アミノアニリン硫酸塩 5.0g 11.0g
N、N−ビス(スルホエチ
ル)ヒドロキソルアミン
2 N a 5.5g
9.0g蛍光増白剤(讐1117EX 4゜
水を加えて 1000d 1000
idpH(25°c ) 10.05
10.75カラー現像液B
カラー現像液Aにタンク液、補充液とも亜硫酸ナトリウ
ムを0.8g/f添加したもの。Two statues of friends, two children, sprinkled with water
800d 8
00d1-hydroxyethylidene=1.1-diphosphonic acid (60%) 1.0g],
Og diethylenetriaminepentaacetic acid 1.0g
1.0g 21-lylotrimethylenephosphonic acid (40%) 7.0g 7.0g
Potassium bromide 2X10-'*ol -triethanolamine 8.0g 12.0
g Sodium chloride 0.085 mol
-Potassium carbonate 25g 25g
N=ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g 11.0g
N,N-bis(sulfoethyl)hydroxolamine 2 Na 5.5g
9.0g optical brightener (1117EX 4° Add water 1000d 1000
idpH (25°c) 10.05
10.75 Color developer B Color developer A with 0.8 g/f of sodium sulfite added to both tank liquid and replenisher.
カラー現像液C
カラー現像液Aにタンク液、補充液ともll−9を0.
2g/l添加したもの。Color developer C Add 0.0% ll-9 to color developer A for both tank liquid and replenisher.
Added 2g/l.
カラー現像液D
カラー現像液Bにタンク液、補充液ともll−9を0.
2g/n添加したもの。Color developer D Add 0.0% ll-9 to color developer B for both tank liquid and replenisher.
2g/n added.
カラー現像液E
カラー現像液Aにタンク液、補充液ともl−3を0.5
g/l添加したもの。Color developer E Add 0.5 l-3 to color developer A for both tank liquid and replenisher.
g/l added.
盈a定春撒 tノ文撒 液光撒水
400af 40
0dチオ硫酸アンモニウム
(70%) 100m 200m
ff亜硫酸ナトリウム 17g 34
gエチレンジアミン四酢酸鉄
(I[I)アンモニウム 55g 110
gエチレンジアミン四酢酸二
水を加え7 1000d 1000
dpH(25°C) 6.0
4.7ユl久斂(タンク液と補充液は同じ)
イオン交換水(カルシウム、マグネシウムは各々3pp
ffl以下)
結果を第3表に示した。Yinga Dingharu sprinkling T-nobun sprinkling Liquid light sprinkling
400af 40
0d Ammonium thiosulfate (70%) 100m 200m
ff Sodium sulfite 17g 34
g Ethylenediaminetetraacetic acid iron (I[I) ammonium 55g 110
g Add ethylenediaminetetraacetic acid dihydrate 7 1000d 1000
dpH (25°C) 6.0
4.7 liters Hisatoshi (tank fluid and refill fluid are the same) Ion exchange water (calcium and magnesium are 3pp each)
ffl or less) The results are shown in Table 3.
本発明は口印にて示した。The invention is indicated by a seal.
×;析出物は多い △:析出物は多少有り。×; There are many precipitates △: Some precipitates were present.
O;ネ斤出物は殆ど無い。O; There are almost no nematode materials.
本発明の処理液C,D、Eにおいては、最大濃度の変化
も小さく、また、汚れによる最小濃度の変化の小さい。In the treatment liquids C, D, and E of the present invention, the change in maximum concentration is small, and the change in minimum concentration due to dirt is also small.
特に亜硫酸塩を含有しない処理C及びEが優れている。In particular, treatments C and E, which do not contain sulfites, are excellent.
また、塗布銀量0.75g/l12以下の試料2−A及
び2−Bにおいて特に効果が顕著である。更に、本発明
の処理においては処理タンクの壁面への析出物も殆ど発
生しなかった。Moreover, the effect is particularly remarkable in samples 2-A and 2-B where the amount of coated silver is 0.75 g/l12 or less. Furthermore, in the treatment of the present invention, almost no deposits were generated on the walls of the treatment tank.
特許出願人 冨士写真フィルム株式会社平成9年に月(
7日
2、 発明の名称 ハロゲン化銀カラー写真感光材料
の処理方法
3、補正をする者
事件との関係 特許出願人
件 所 神奈川県南足柄市中沼210番地名 称(
520)富士写真フィルム株式会社連絡先 〒106東
京都港区西麻布2丁目26番30号富士写真7(3A株
式会社 東京本社
4、補正命令の日付 自発
上1
5、補正の対象 明細書
6、補正の内容
明細書の浄書(内容に変更なし)を提出致します。Patent applicant: Fuji Photo Film Co., Ltd.
7th, 2nd, Title of the invention Processing method for silver halide color photographic light-sensitive materials 3, Relationship to the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (
520) Fuji Photo Film Co., Ltd. Contact information Fuji Photo 7 2-26-30 Nishi-Azabu, Minato-ku, Tokyo 106 (3A Co., Ltd. Tokyo Head Office 4, Date of amendment order Voluntary 1 5. Subject of amendment Statement 6, Amendment We will submit an engraving of the detailed statement of contents (with no changes to the contents).
平成3年メ/月、L7!−日May/Monday, 1991, L7! -day
Claims (3)
後に脱銀処理し、続いて水洗及び/又は安定化処理を行
なう処理方法に於いて、上記カラー現像液が0.04モ
ル/l以上の塩素イオンと、4×10^−^5〜2×1
0^−^3モル/lの臭素イオンを含有し、且つ、下記
一般式( I )又は(II)で表される化合物の少なくと
も一種を含有することを特徴とするハロゲン化銀カラー
写真感光材料の処理方法。 一般式( I ) ▲数式、化学式、表等があります▼ (式中、R_1、R_2、R_3及びR_4は各々水素
原子、アルキル基、アルコキシ基もしくはアルケニル基
を表す。nは1〜3の整数を表し、Mは水素原子もしく
は対カチオンを表す。) 一般式(II) A−(X)_m−B (式中、Aはアルキル基、アルコキシ基、フェニル基、
フェノキシ基またはアミノ基を表す。Xは下記の構造を
表す。 ▲数式、化学式、表等があります▼ p、q、rは各々0、1、2または3の整数を表し全て
同時に0となることは無い。Yは−OHまたはメチル基
を表す。又、Xは上記構造式で表される異なった構造を
複数個有しても良い。 mは2以上の整数を表す。 Bは水素原子、アルキル基、アリール基または−SO_
3Zを表す。Zは水素原子、またはカチオンを表す。)(1) In a processing method in which a silver halide color photographic light-sensitive material is desilvered after color development, followed by water washing and/or stabilization treatment, the color developer contains 0.04 mol/l or more. Chlorine ion and 4 x 10^-^5 ~ 2 x 1
A silver halide color photographic light-sensitive material containing 0^-^3 mol/l of bromide ion and at least one kind of compound represented by the following general formula (I) or (II). processing method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, and R_4 each represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkenyl group. General formula (II) A-(X)_m-B (wherein A is an alkyl group, an alkoxy group, a phenyl group,
Represents a phenoxy group or an amino group. X represents the following structure. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ p, q, and r each represent an integer of 0, 1, 2, or 3, and they cannot all be 0 at the same time. Y represents -OH or a methyl group. Further, X may have a plurality of different structures represented by the above structural formula. m represents an integer of 2 or more. B is a hydrogen atom, an alkyl group, an aryl group, or -SO_
Represents 3Z. Z represents a hydrogen atom or a cation. )
が0.75g/m^2以下であることを特徴とする特許
請求の範囲第(1)項記載のハロゲン化銀カラー写真感
光材料の処理方法。(2) The silver halide color photographic light-sensitive material according to claim (1), wherein the silver halide color photographic light-sensitive material has a coated silver amount of 0.75 g/m^2 or less. Processing method.
しないことを特徴とする特許請求の範囲第(1)項記載
のハロゲン化銀カラー写真感光材料の処理方法。(3) The method for processing a silver halide color photographic light-sensitive material according to claim (1), wherein the color developer does not substantially contain sulfite ions.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32205890A JP2691474B2 (en) | 1990-11-26 | 1990-11-26 | Processing method of silver halide color photographic light-sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32205890A JP2691474B2 (en) | 1990-11-26 | 1990-11-26 | Processing method of silver halide color photographic light-sensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04190349A true JPH04190349A (en) | 1992-07-08 |
JP2691474B2 JP2691474B2 (en) | 1997-12-17 |
Family
ID=18139446
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5660972A (en) * | 1994-03-16 | 1997-08-26 | Mitsubishi Paper Mills Limited | Method for photographic development using a filter to inhibit occurrence of silver sludges |
-
1990
- 1990-11-26 JP JP32205890A patent/JP2691474B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5660972A (en) * | 1994-03-16 | 1997-08-26 | Mitsubishi Paper Mills Limited | Method for photographic development using a filter to inhibit occurrence of silver sludges |
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