JPS63276051A - Method for processing silver halide color photographic sensitive material with which defective color reproduction is suppressed and stable photographic performance is obtained - Google Patents
Method for processing silver halide color photographic sensitive material with which defective color reproduction is suppressed and stable photographic performance is obtainedInfo
- Publication number
- JPS63276051A JPS63276051A JP11221387A JP11221387A JPS63276051A JP S63276051 A JPS63276051 A JP S63276051A JP 11221387 A JP11221387 A JP 11221387A JP 11221387 A JP11221387 A JP 11221387A JP S63276051 A JPS63276051 A JP S63276051A
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- salt
- silver halide
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000012545 processing Methods 0.000 title claims abstract description 42
- -1 silver halide Chemical class 0.000 title claims description 78
- 229910052709 silver Inorganic materials 0.000 title claims description 54
- 239000004332 silver Substances 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 42
- 230000002950 deficient Effects 0.000 title description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 77
- 239000007844 bleaching agent Substances 0.000 claims abstract description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 10
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 10
- 239000000872 buffer Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 46
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000011161 development Methods 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 abstract description 2
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 62
- 239000002253 acid Substances 0.000 description 44
- 239000010410 layer Substances 0.000 description 41
- 238000004061 bleaching Methods 0.000 description 40
- 239000000839 emulsion Substances 0.000 description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 22
- 239000000975 dye Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 230000018109 developmental process Effects 0.000 description 17
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 16
- 108010010803 Gelatin Proteins 0.000 description 16
- 229920000159 gelatin Polymers 0.000 description 16
- 239000008273 gelatin Substances 0.000 description 16
- 235000019322 gelatine Nutrition 0.000 description 16
- 235000011852 gelatine desserts Nutrition 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 14
- 238000011084 recovery Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000002738 chelating agent Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- 125000000623 heterocyclic group Chemical group 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 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 9
- 238000005406 washing Methods 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003672 processing method Methods 0.000 description 6
- 239000008280 blood Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 229910001447 ferric ion Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 229960003330 pentetic acid Drugs 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000004149 thio group Chemical group *S* 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 101000619542 Homo sapiens E3 ubiquitin-protein ligase parkin Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- MKBUQYWFFBCMFG-UHFFFAOYSA-N acetic acid propane-1,1-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CCC(N)N MKBUQYWFFBCMFG-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 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
- 150000002366 halogen compounds Chemical class 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 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
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 102000045222 parkin Human genes 0.000 description 2
- 125000005499 phosphonyl group Chemical group 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003413 spiro compounds Chemical group 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- COKIOUWMXONTKQ-UHFFFAOYSA-N 1-phosphonopropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)P(O)(O)=O COKIOUWMXONTKQ-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- JKRNNIGZNCVVHA-UHFFFAOYSA-N 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;trimethylazanium Chemical compound C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JKRNNIGZNCVVHA-UHFFFAOYSA-N 0.000 description 1
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- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 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
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- JZBRFIUYUGTUGG-UHFFFAOYSA-J tetrapotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JZBRFIUYUGTUGG-UHFFFAOYSA-J 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- KWINHMKYYFEPRI-UHFFFAOYSA-J tetrasodium propane-1,2-diamine tetraacetate Chemical compound C(C)(=O)[O-].[Na+].[Na+].[Na+].[Na+].C(C(C)N)N.C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] KWINHMKYYFEPRI-UHFFFAOYSA-J 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003548 thiazolidines Chemical class 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はハロゲン化銀カラー写真感光材料の処理方法に
関し、詳しくは高感度、高銀量のハロゲン化銀カラー写
真感光材料に適用してシアン色素のロイコ化を抑えて復
色不良が改善され、さらにマゼンタスティンの発生が防
止され安定した写真性能が得られるハロゲン化銀カラー
写真感光材料の処理方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for processing silver halide color photographic materials, and more specifically, it is applied to a silver halide color photographic material with high sensitivity and a high silver content. The present invention relates to a method for processing a silver halide color photographic light-sensitive material, which suppresses leuco formation, improves poor color recovery, prevents the occurrence of magentastin, and provides stable photographic performance.
［発明の背ｌ１ｌ
一般にカラー感光材料の処理の基本工程は発色現像工程
と脱銀工程である。発色現像工程では発色現像主薬によ
り、露光されたハロゲン化銀が還元されて銀を生ずると
ともに、酸化された発色現像工程は発色剤（カプラー）
と反応して色素画像を与える。次の脱銀工程においては
、酸化剤（漂白剤と通称する）の作用により、発色現像
工程で生じた銀が酸化され、しかるのち、定着剤と通称
される銀イオンの錯化剤によって溶解される。この脱銀
工程を経ることによって、カラー感光材料には色素画像
のみができあがる。[Background of the Invention In general, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. In the color development process, the exposed silver halide is reduced by a color developing agent to produce silver, and the oxidized color development process produces a color former (coupler).
reacts with the dye to give a dye image. In the next desilvering step, the silver produced in the color development step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved by a silver ion complexing agent, commonly called a fixing agent. Ru. By going through this desilvering step, only a dye image is created on the color photosensitive material.
以上の脱銀工程は、漂白剤を含む漂白浴と定着剤を含む
定着浴との２浴にて行なわれる場合と、漂白剤と定着剤
を共存せしめた漂白定着浴により１浴で行なわれる場合
、さらにそれらの浴を組合せた場合とがある。The above desilvering process is carried out in two baths, a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, or in one bath using a bleach-fixing bath containing both a bleaching agent and a fixing agent. , and even a combination of these baths.
実際の現像処理は、上記の基本工程のほかに、画像の写
真的、物理的品質を保つため、あるいは画像の保存性を
良くするため等の種々の補助的工程を含んでいる。例え
ば硬膜浴、停止浴、画像安定浴、水洗浴などである。In addition to the above-mentioned basic steps, actual development processing includes various auxiliary steps to maintain the photographic and physical quality of the image or to improve the storage stability of the image. Examples include a hardening bath, a stop bath, an image stabilization bath, and a water washing bath.
一般に漂白剤として、赤血塩、重クロム酸塩、塩化第２
鉄、アミノポリカルボン酸第２鉄錯塩、アミノポリホス
ホン酸第２鉄錯塩、過硫酸塩などが知られている。Commonly used bleaching agents include red blood salt, dichromate, and ferric chloride.
Iron, aminopolycarboxylic acid ferric complex salts, aminopolyphosphonic acid ferric complex salts, persulfates, and the like are known.
しかしながら、赤血塩、重クロム酸塩には、シアン化合
物、６価クロムに関する公害上の問題があり、その使用
には特別な処理設備を要する。また塩化第２鉄には、そ
の後の水洗工程での水酸化鉄の生成やスティン発生の問
題があり実用工種々の障害がある。過硫酸塩については
、その漂白作用が非常に弱く、著しく長い漂白時間を要
する欠点がある。これについては、漂白促進剤の併用に
より、漂白作用を高める方法も提案されているが、過硫
酸塩自体に消防法上危険物の規制があり貯蔵工種々の措
置を要するなど一般には実用しにくい欠点がある。However, red blood salt and dichromate have pollution problems related to cyanide compounds and hexavalent chromium, and their use requires special treatment equipment. Furthermore, ferric chloride has various problems in practical use, such as the generation of iron hydroxide and staining during the subsequent washing process. Persulfates have the disadvantage that their bleaching action is very weak and that they require a significantly long bleaching time. Regarding this, a method has been proposed to increase the bleaching effect by using a bleach accelerator in combination, but persulfate itself is regulated as a dangerous substance under the Fire Service Act, and various storage measures are required, making it difficult to put it into practical use. There are drawbacks.
これに対し、アミノポリカルボン酸第２鉄Ｒ塩（代表的
なものとしｔエチレンジアミンテトラ酢酸第２鉄錯塩）
は、上記の漂白剤が有する公害上の問題も少なぐ、貯蔵
上の問題点もないことから、現在量も広く実用化されて
いる漂白剤である。In contrast, aminopolycarboxylic acid ferric R salt (typically ethylenediaminetetraacetic acid ferric complex salt)
is a bleaching agent that is currently in widespread practical use because it has fewer pollution problems and no storage problems that the above-mentioned bleaching agents have.
しかしながら、アミノポリカルボン酸第２鉄錯塩の漂白
刃は必ずしも十分とは言えず、これを漂白剤として用い
た処理液では、塩臭化銀乳剤を主体とした低感度のハロ
ゲン化銀カラー写真感光材料を漂白もしくは漂白定着処
理する場合には、一応所望の目的を達成することができ
るが、塩奥沃化銀あるいは沃臭化銀乳剤を主体とする高
感度のカラー写真感光材料、特に、高銀量乳剤を用いる
撮影用カラー反転感光材料、撮影用カラーネガ感光材料
を処理する場合には脱銀不良を生じたり、漂白するのに
長時間を要するという欠点を有していた。However, the bleaching edge of the ferric aminopolycarboxylic acid complex salt is not necessarily sufficient, and processing solutions using this as a bleaching agent cannot be used with low-sensitivity silver halide color photography based on silver chlorobromide emulsions. If the material is bleached or bleach-fixed, it is possible to achieve the desired purpose, but high-sensitivity color photographic materials based on silver iodide or silver iodobromide emulsions, especially those with a high silver content, When processing color reversal light-sensitive materials for photography and color negative light-sensitive materials for photography using emulsions, there have been disadvantages in that desilvering failure occurs and bleaching takes a long time.
例えば、撮影用カラーネガ感光材料をアミノポリカルボ
ン酸第２鉄錯塩を用いて漂白処理する場合においては少
なくとも４分以上の漂白時間を要しており、また、脱銀
のためには漂白処理に続いて少なくとも３分以上の定着
液による処理が必要であり、漂白時間を短くしようとし
た場合、前記したような脱銀不良や復色不良が発生する
という問題もあり漂白時間を長くせざるを得なかった。For example, when bleaching color negative photosensitive materials for photography using a ferric aminopolycarboxylic acid complex salt, a bleaching time of at least 4 minutes is required, and desilvering requires subsequent bleaching. It is necessary to process with a fixing solution for at least 3 minutes or more, and if you try to shorten the bleaching time, you will have the problem of poor desilvering and poor recoloring as described above, so you have no choice but to lengthen the bleaching time. There wasn't.
従ってこのような長時間を要する脱銀処理に対して所要
時間の短縮が強く望まれていた。Therefore, it has been strongly desired to shorten the time required for such a long desilvering process.
漂白時間を短縮し、脱銀性能を高める方法としては漂白
液のＥＩＨを低くする方法、漂白剤の濃度を高くする方
法、更には米国特許第３，８９３，８５８号、特開昭５
３−９５６３１号公報、同５３−１４１６２３号公報記
載のメルカプト化合物、同５３−９５６３０号公報記載
のジスルフィド結合を有する化合物、特公昭５３−９８
５４号公報記載のチアゾリジン誘導体、特開昭５３−９
４９２７号記載のイソチオ尿素誘導体等に代表される漂
白促進剤を漂白液又は前浴に添加する方法が知られてい
る。しかしながら、漂白液のｐＨを低くする方法は漂白
速度は改良されても復色不良が生じやすい欠点があり、
漂白剤の濃度を高くした場合も鉄錯塩の析出の問題から
多量に添加できず前記と同様の欠点が生じやすい。又、
漂白促進剤を添加する方法は銀と難溶性の銀錯体を形成
しやすいこと、更に溶解性も悪く、仮に使用した場合で
も復色性が十分ではないという欠点がある。Methods for shortening bleaching time and improving desilvering performance include methods such as lowering the EIH of the bleaching solution, increasing the concentration of the bleaching agent, and methods such as U.S. Patent No. 3,893,858 and JP-A-5
3-95631, mercapto compounds described in 53-141623, compounds having a disulfide bond described in 53-95630, Japanese Patent Publication No. 53-98
Thiazolidine derivatives described in Publication No. 54, JP-A-53-9
A method is known in which a bleaching accelerator, typified by the isothiourea derivatives described in No. 4927, is added to the bleaching solution or pre-bath. However, although the method of lowering the pH of the bleaching solution improves the bleaching speed, it has the disadvantage that it tends to cause poor color recovery.
Even when the concentration of bleaching agent is increased, a large amount cannot be added due to the problem of precipitation of iron complex salts, and the same drawbacks as mentioned above are likely to occur. or,
The method of adding a bleaching accelerator has the disadvantage that it tends to form a poorly soluble silver complex with silver, has poor solubility, and even if it is used, the color recovery is not sufficient.
従って前記した様に漂白時間を長時間とらざるを得なか
った。Therefore, as mentioned above, the bleaching time had to be long.
脱銀工程を迅速化する手段としては、ドイツ特許第８６
６．６０５号に記載のアミノポリカルボン酸第２鉄錯塩
と定着剤であるチオ硫酸塩を１浴中に含有せしめた漂白
定着液で処理することが知られている。As a means to speed up the desilvering process, German Patent No. 86
It is known to process with a bleach-fix solution containing a ferric aminopolycarboxylic acid complex salt described in No. 6.605 and a thiosulfate as a fixing agent in one bath.
しかしながら、上記漂白定着液においては、アミノポリ
カルボン酸第２鉄錯塩の酸化力がもともと弱い上に、共
存する保恒剤である亜硫酸塩や定着剤であるチオ硫酸塩
が還元剤であるために、アミノポリカルボン酸第２鉄錯
塩の酸化力を更に弱める働きを有し、結果的に脱銀性能
を低下せしめるばかりでなく、発色現像で形成されたシ
アン色素をロイコ色素に変化させ易く、かつロイコ色素
を顕色化する能力にも乏しく復色不良という色再現上の
重大な欠かんを引き起す問題点を有していた。However, in the above bleach-fix solution, the oxidizing power of the ferric aminopolycarboxylic acid complex is inherently weak, and the coexisting preservative sulfite and fixing agent thiosulfate are reducing agents. , has the function of further weakening the oxidizing power of the ferric aminopolycarboxylic acid complex salt, and as a result not only reduces the desilvering performance, but also easily converts the cyan dye formed by color development into a leuco dye, and It also lacks the ability to develop leuco dyes and has the problem of poor color reproduction, which causes a serious deficiency in color reproduction.
上記現象はさらに感光材料を長期にわたり連続処理した
際の経時において顕著に表れる。The above phenomenon becomes even more noticeable over time when a photosensitive material is continuously processed over a long period of time.
本発明者等は上記問題点について検討を重ねた結果、上
記復色不良は、脱銀工程の漂白、液又は漂白定着液中に
漂白剤としてアミノポリカルボン酸第２鉄錯塩およびア
ミノポリホスホン酸の第２鉄錯塩を用いる場合共通して
発生する問題であり、特にアミノポリカルボン酸または
アミノポリホスホン酸の第２鉄錯塩が酸化剤として作用
した結果、自身が還元されて生成するアミノポリカルボ
ン酸またはアミノポリホスホン酸の第１鉄錯塩（鑵イオ
ン）が処理液あるいは感材中に蓄積してくることにより
特に大きな問題となることがわかってきた。As a result of repeated studies on the above-mentioned problems, the present inventors have found that the above-mentioned poor color restoration is caused by the use of aminopolycarboxylic acid ferric complex salts and aminopolyphosphonic acid as bleaching agents in the bleaching solution or bleach-fixing solution in the desilvering step. This is a common problem when using ferric complex salts of aminopolycarboxylic acid or aminopolyphosphonic acid, especially when the ferric complex salt of aminopolycarboxylic acid or aminopolyphosphonic acid acts as an oxidizing agent, resulting in reduction of the aminopolycarbonate itself. It has been found that the accumulation of ferrous complex salts (ferrous ions) of acids or aminopolyphosphonic acids in processing solutions or sensitive materials poses a particularly serious problem.
また、上記第１鉄錯イオンの蓄積は漂白液又は漂白定着
液のＥＩＨにも依存し、高１）Ｈ程第１鉄錯イオンの生
成が起り易くなることが判明した。さらに、第１鉄錯イ
オンの生成はアミノポリカルボン酸またはアミノポリホ
スホン酸の第２鉄錯塩自身の分解により起る現象に加え
て、漂白定着液を用いた場合、漂白定着液中に保恒剤と
して含有する亜硫酸塩によっても第２鉄錯塩が還元され
第１鉄錯イオンが生成し、また別には高銀量の感光材料
を処理することにより銀を酸化し、第２鉄錯塩自身が還
元され第１鉄諸イオンとなり処理中の写真感光材料の塗
膜中に第１鉄錫イオンが高い濃度で存在し、シアン色素
をロイコ化することが判明した。It has also been found that the accumulation of ferrous complex ions depends on the EIH of the bleach solution or bleach-fix solution, and the higher the 1)H, the more likely the formation of ferrous complex ions occurs. Furthermore, the formation of ferrous complex ions occurs not only due to the decomposition of the ferric complex salt of aminopolycarboxylic acid or aminopolyphosphonic acid itself, but also when a bleach-fix solution is used. The sulfite contained as an agent also reduces the ferric complex salt to produce ferrous complex ions.Also, by processing a photosensitive material with a high amount of silver, silver is oxidized, and the ferric complex salt itself is reduced and ferrous complex ions are produced. It has been found that ferrous tin ions are present at high concentrations in the coating film of photographic light-sensitive materials during processing as ferrous ions, and leucoize cyan dyes.
このシアン色素のロイコ化による復色不良は、高感度、
高銀量タイプの膜厚が１３μ−以上の写真感光材料にお
いて特に顕著であった。Poor color restoration due to leucoization of this cyan dye is caused by high sensitivity,
This was particularly noticeable in photographic materials with a high silver content type having a film thickness of 13 μm or more.
上記第１鉄諸イオンが漂白液又は漂白定着、液中に高い
濃度で蓄積していると、漂白反応で生じた写真感光材料
塗膜中の第１鉄錯イオンは塗膜外への拡散が著しく抑え
られロイコ色素の生成を増大させ、復色不良を大きくす
るものと考えられる。If the ferrous ions mentioned above accumulate at a high concentration in the bleaching solution or bleach-fixing solution, the ferrous complex ions in the photographic light-sensitive material coating produced by the bleaching reaction will not diffuse out of the coating. It is thought that this significantly suppresses the production of leuco dye and increases the defective color recovery.
一般に上記アミノポリカルボン酸またはアミノポリホス
ホン酸の第１鉄錯イオンを酸化して第２鉄諸イオンに賦
活せしめるには、処理液中に空気を吹き込んで酸化する
エアレーションと呼ばれる方法が良く知られている。Generally, in order to oxidize the ferrous complex ions of the aminopolycarboxylic acid or aminopolyphosphonic acid and activate them to ferric ions, a method called aeration, in which air is blown into the treatment liquid to oxidize it, is well known. ing.
しかしながら、この方法は保恒剤である亜硫酸をも酸化
してしまうため、カラーベーパー等の処理の如く処理量
が比較的多く液の更新率が高い場合には危険はないが、
カラーネガの如く処理量が比較的少ない場合には液の酸
化が進み過ぎてしまい保恒剤である亜硫酸が酸化されチ
オ硫酸塩が分解し硫黄（硫化物）を析出し沈澱が生じる
重大な故障を引き、起してしまう危険がある。However, this method also oxidizes sulfurous acid, which is a preservative, so it is not dangerous when the amount of treatment is relatively large and the renewal rate of the solution is high, such as when processing color vapor.
When the amount of processing is relatively small, such as when processing color negatives, the oxidation of the liquid may proceed too much, causing the sulfurous acid preservative to oxidize, decomposing thiosulfate, and precipitating sulfur (sulfide), resulting in a serious malfunction. There is a danger of it being pulled and woken up.
それ故に、第１鉄錯イオンがある程度存在しても復色不
良を引き起さない方法が強（求められている。Therefore, there is a strong need for a method that does not cause poor color restoration even if ferrous complex ions are present to some extent.
また、上記復色不良は漂白液又は漂白定着液の１）Ｈを
高めることで改良されることも知られているが米国特許
第３，７７３，５１０号明ｌ１に記載の如く、漂白液又
は漂白定着液の吐を高めると逆に漂白刃を弱めるばかり
か、チオＷｌ酸アンモニウムや第２鉄アンモニウム塩の
アンモニウムが揮発し易くなり臭気が環境を汚染すると
いうことがら復色不良のために漂白液又は漂白定着液の
Ｅ）Ｈを高めることは実現不可能である。It is also known that the above-mentioned poor color restoration can be improved by increasing 1)H of the bleach solution or bleach-fix solution, but as described in U.S. Pat. No. 3,773,510, Increasing the output of the bleach-fixing solution not only weakens the bleaching blade, but also makes it easier for ammonium thioWlate and ferric ammonium salts to volatilize, causing odor to pollute the environment. It is not feasible to increase the E)H of the solution or bleach-fix solution.
また、米国特許第３，１８９，４５２号明ｌ１ＩＩには
、漂白、定着後に赤血塩漂白液を使用しロイコ色素を酸
化してシアン色素に戻す方法が開示されている。Further, US Pat. No. 3,189,452, No. 11II, discloses a method in which after bleaching and fixing, a red blood salt bleaching solution is used to oxidize a leuco dye and return it to a cyan dye.
しかしながら、赤血塩の使用には前記し、た公害上の問
題があり実用化するには極めて困難な赤血塩回収操作を
ともなうという欠点がある。However, the use of red blood salt has the above-mentioned pollution problems and is disadvantageous in that it involves a red blood salt recovery operation that is extremely difficult to put into practical use.
本発明者等は、脱銀工程に漂白剤として特定の化合物、
即ち特定のアミノポリカルボン酸またはアミノポリホス
ホン酸の第２鉄錯塩を使用し、かつ前記脱銀工程後、ｐ
Ｈ８，０以上のアルカリ浴で処理することにより、上記
公害等の問題もなく、脱銀性能にも優れ、ざらに復色不
良が改良されることを見い出した。The present inventors used a specific compound as a bleaching agent in the desilvering process,
That is, using a specific ferric complex salt of aminopolycarboxylic acid or aminopolyphosphonic acid, and after the desilvering step, p
It has been found that by treating with an alkaline bath of H8.0 or higher, there is no problem such as the above-mentioned pollution, the desilvering performance is excellent, and defective color recovery is significantly improved.
しかしながら、上記特に復色不良が改良される方法を実
用化するために種々検討を加えた結果、脱銀工程後、ｐ
）ｌ ８．０以上のアルカリ浴で処理するとマゼンタス
ティンの発生が大きくなってくることがわかった。この
マゼンタスティンの発生は、感光材料の処理量が少なく
脱銀工程の定着能を有する処理浴に含有される保恒剤の
量が少なくなった場合、さらに顕在化してくる。However, as a result of various studies in order to put into practical use the above-mentioned method that particularly improves the defective color recovery, it was found that after the desilvering process, p.
) It was found that the generation of magentastin increases when treated with an alkaline bath of 8.0 or higher. The occurrence of magentastin becomes more noticeable when the amount of photosensitive material processed is small and the amount of preservative contained in the processing bath having fixing ability in the desilvering step is reduced.
本発明者等は上記問題を解決するためにさらに検討を加
えた結果、特定のマゼンタカプラーを含有した感光材料
を脱銀工程後、ｐＨ８，０以上のアルカリ浴で処理する
ことにより、前記復色不良改良効果等に悪影響を与える
ことなくマゼンタスティンの発生を良好に防止できるこ
とを見い出し本発明を為すに到ったものである。As a result of further studies to solve the above problem, the inventors of the present invention discovered that the above-mentioned color restoration is possible by treating a photosensitive material containing a specific magenta coupler with an alkaline bath having a pH of 8.0 or higher after the desilvering process. The present invention was developed based on the discovery that the occurrence of magentastin can be satisfactorily prevented without adversely affecting the defect improvement effect.
−［発明の目的］
従って、本発明の目的は、カラー写真感光材料、特に高
感度高銀量タイプの高膜厚を有するハロゲン化銀カラー
写真感光材料の処理においてもシアン色素のロイコ化の
起り難くかつマゼンタスティンの発生も抑えられる処理
方法を提供するにある。- [Object of the Invention] Therefore, the object of the present invention is to prevent leucoization of cyan dyes even in the processing of color photographic materials, especially high-sensitivity, high-silver-content type silver halide color photographic materials having a high film thickness. It is an object of the present invention to provide a processing method that can also suppress the occurrence of magentastin.
［発明の構成］
本発明の上記目的は、露光されたハロゲン化銀カラー写
真感光材料を発色現像処理した後、少なくとも脱銀工程
を含む処理を施すハロゲン化銀カラー写真感光材料の処
理方法において、前記感光材料が下記一般式［Ｍ−Ｉ
］で示されるマゼンタカブ、ラーを含有し、前記脱銀工
程に漂白剤として下記一般式［Ｉ］および一般式［ＩＩ
］で示される化合物から選ばれる少なくとも１つの化合
物の第２鉄鉗塩を使用し、かつ脱銀工程後、ｐＨ８，０
以上のアルカリ浴で処理するハロゲン化銀カラー写真感
光材料の処理方法により達成されることを見い出した。[Structure of the Invention] The above-mentioned object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, in which the exposed silver halide color photographic light-sensitive material is subjected to a process including at least a desilvering step after color development processing. The photosensitive material has the following general formula [M-I
], and the following general formula [I] and general formula [II] are used as a bleaching agent in the desilvering step.
] using a ferric salt of at least one compound selected from the compounds shown in
It has been found that the present invention can be achieved by the above method for processing silver halide color photographic materials in an alkaline bath.
一般式［Ｍ−Ｉ ］
［式中、２は含窒素複素環を形成するに必要な非金属原
子群を表し、該２により形成される環は置換基を有して
もよい。×は水素原子又は発色現像主薬の酸化体との反
応により離脱し得る基を表す。またＲは水素原子又は置
換基を表す。］一般式［Ｉ］
一般式［Ｉ［］
１式中、Ｌはアルキレン基、シクａアルキレン基、フェ
ニレン基、−Ｌａ −０−Ｌａ −０−Ｌａ −または
−Ｌｓ−Ｚ−Ｌｓ−を表す。ここで２は、１１〜Ｌ１３
はそれぞれアルキレン基を表す。Ｒ１〜Ｒ＋＋はそれぞ
れ水素原子、水酸基、カルボン酸基（その塩を含む）ま
たはホスホン酸基１基（その塩を含む）を表す。但し、
Ｒ１〜Ｒ＋のうちの少なくとも２つはカルボン酸基（そ
の塩を含む）またはホスホン酸基（その塩を含む）であ
り、またＲ５−Ｒ７のうちの少なくとも１つはカルボン
酸基（その塩を含む）またはホスホン酸基（その塩を含
む）である。］
さらに好ましい態様として、■上記アルカリ浴に鉄イオ
ンとのキレート安定度定数（ｆｆｉＯＱＫＭＡ＞が６以
上であるキレート剤を含有、■上記アルカリ浴に、該浴
１１１当たりＩ Ｘ １０−３モル以上のアミノポリカ
ルボン酸第２鉄錯塩を含有、■上記アルカリ浴に酸化剤
を含有、することにより前記目的がさらに効率的に達成
されるものである。General formula [M-I] [wherein 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent. × represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula [I] General formula [I [] In formula 1, L represents an alkylene group, a cycloalkylene group, a phenylene group, -La -0-La -0-La - or -Ls-Z-Ls- . Here, 2 is 11 to L13
each represents an alkylene group. R1 to R++ each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including salts thereof), or one phosphonic acid group (including salts thereof). however,
At least two of R1 to R+ are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R5 to R7 is a carboxylic acid group (including salts thereof). ) or a phosphonic acid group (including its salts). ] As a further preferred embodiment, (1) the alkaline bath contains a chelating agent having a chelate stability constant (ffiOQKMA> of 6 or more) with iron ions; (2) the alkaline bath contains at least 10-3 mol of I By containing a ferric aminopolycarboxylic acid complex salt and (2) containing an oxidizing agent in the alkaline bath, the above object can be achieved more efficiently.
［発明の具体的構成］
本発明は、一般式［Ｍ−ＩＦで示される特定のマゼンタ
カプラーを含有した感光材料を、脱銀工程に漂白剤とし
て一般式［ＩＦおよび一般式［Ｉ［］で示される化合物
から選ばれる少なくとも１つの化合物の第２鉄錯塩（以
下、本発明の化合物の第２鉄錯塩という）を用いて脱銀
処理した後ＥＩＨ８，０以上のアルカリ浴で処理するこ
とにより、マゼンタスティンの発生を良好に防止すると
共に、ハロゲン化銀カラー写真感光材料のゼラチン塗膜
中に生成して吸着し蓄積している本発明の化合物の第１
鉄錯イオンを脱着させ、上記ゼラチン塗膜系外に早く拡
散させ、アルカリ性雰囲気にすることでシアン色素の顕
色を著しく早め復色不良を改良するものである。[Specific Structure of the Invention] The present invention provides that a photosensitive material containing a specific magenta coupler represented by the general formula [M-IF] is used as a bleaching agent in the desilvering process by using a bleaching agent of the general formula [IF and the general formula [I]]. By desilvering using a ferric complex salt of at least one compound selected from the compounds shown (hereinafter referred to as ferric complex salt of the compound of the present invention) and then treating with an alkaline bath of EIH 8.0 or higher, The first compound of the present invention that satisfactorily prevents the generation of magentastin, and also forms, adsorbs and accumulates in the gelatin coating of silver halide color photographic light-sensitive materials.
By desorbing iron complex ions and quickly diffusing them out of the gelatin coating system to create an alkaline atmosphere, the color development of the cyan dye is significantly accelerated and defective color recovery is improved.
本発明の処理方法において、発色現像工程後に施される
脱銀処理は、漂白剤として本発明の化合物の第２鉄鎖塩
を使用するものであればいかなる工程をもとりうるが、
本発明を適用して好シしい代表的脱銀工程例は以下の如
き処理である。In the processing method of the present invention, the desilvering treatment performed after the color development step can be any process as long as it uses the ferric chain salt of the compound of the present invention as a bleaching agent.
A typical example of a preferable desilvering process to which the present invention is applied is the following treatment.
［１］漂白一定着
［２１漂白定着
［３］漂白−漂白定着
［４］漂白−漂白定着一定着
［５］漂漂白定着−漂白一定着
［６１定肴−漂白−漂白定着
上記脱銀工程において、漂白および漂白定着処理浴、即
ち漂白能を有する処理液には、漂白剤として本発明の化
合物の第２鉄錯塩が用いられる。[1] Bleach-fix [21 Bleach-fix] [3] Bleach-bleach-fix [4] Bleach-bleach-fix [5] Bleach-fix - Bleach-fix [61 Fix] In the above desilvering step A ferric complex salt of the compound of the present invention is used as a bleaching agent in bleaching and bleach-fixing processing baths, that is, processing solutions having bleaching ability.
本発明の化合物は以下の一般式［ＩＦおよび一般式［Ｉ
Ｆで示される化合物から選ばれる少なくとも１つの化合
物である。The compounds of the present invention have the following general formulas [IF and general formulas [I
It is at least one compound selected from the compounds represented by F.
一般式［ＩＦ
一般式［ＩＩ］
［式中、Ｌはアルキレン基、シクロアルキレン基、フェ
ニレン基、−Ｌａ −０−Ｌｅａ −０−Ｌａ −また
は−Ｌｓ−Ｚ−Ｌｓ−を表す。ここで２は、１１Ｒ１１
し１〜Ｌ１３はそれぞれアルキレン基を表す。’Ｒ＋〜
Ｒ１１はそれぞれ水素原子、水酸基、カルボン酸基（そ
の塩を含む）またはホスホン酸基（その塩を含む）を表
す。但し、Ｒ１〜Ｒ＋のうちの少なくとも２つはカルボ
ン酸基（その塩を含む）またはホスホン酸基（その塩を
含む）であり、またＲ５−Ｒ７のうちの少なくとも１つ
はカルボン酸基（その塩を含む）またはホスホン酸基（
その塩を含む）である。］
本発明の漂白能を有する処理液に用いられる本発明の化
合物の第２鉄錯塩は、第２鉄イオン（Ｆｅ ３ ” ）
と本発明の化合物との錯体である。General Formula [IF General Formula [II] [Wherein, L represents an alkylene group, a cycloalkylene group, a phenylene group, -La -0-Lea -0-La - or -Ls-Z-Ls-. Here, 2 is 11R11 and 1 to L13 each represent an alkylene group. 'R+～
R11 each represents a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphonic acid group (including its salts). However, at least two of R1 to R+ are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R5 to R7 is a carboxylic acid group (including salts thereof). salts) or phosphonic acid groups (
(including its salt). ] The ferric complex salt of the compound of the present invention used in the treatment solution having bleaching ability of the present invention contains ferric ion (Fe 3 '')
and the compound of the present invention.
以下に本発明の化合物の代表的具体例を示すＡ−１エチ
レンジアミンテトラ酢酸
Ａ−２エチレンジアミンテトラ酢酸ジナトリウム塩
Ａ−３・エチレンジアミンテトラ酢酸ジアンモニウム塩
Ａ−４エチレンジアミンテトラ酢酸テトラ（トリメチル
アンモニウム）塩
Ａ−５エチレンジアミンテトラ酢酸テトラカリウム塩
Ａ−６エチレンジアミンテトラ酢酸テトラナトリウム塩
Ａ−７エチレンジアミンテトラ酢酸トリナトリウム塩
Ａ−８ジエチレントリアミンペンタ酢酸アンモニウム塩
Ａ−９ジエチレントリアミンペンタ酢酸ペンタナトリウ
ム塩
Ａ −１０エチレンジアミン−Ｎ−（β−オキシエチル
）−Ｎ、Ｎ’ 、Ｎ’ −トリ酢酸Ａ−１１エチレンジ
アミン−Ｎ−（β−オキシエチル）−Ｎ、Ｎ’ 、Ｎ’
−トリ酢酸トリナトリウム塩
Ａ−１２エチレンジアミン−Ｎ−（β−オキシエチル）
−Ｎ、Ｎ’ 、Ｎ’ −トリ酢酸トリアンモニウム塩
Ａ−１３プロピレンジアミンテトラ酢酸アンモニウム塩
Ａ−１４プロピレンジアミンテトラ酢酸ジナトリウム塩
Ａ−１５ニトリロトリ酢酸
Ａ−１６ニトリロトリ酢酸トリナトリウム塩Ａ−１７シ
クロヘキサンジアミンテトラ酢酸Ａ−１８シクロヘキサ
ンジアミンテトラ酢酸ジナトリウム塩
Ａ−１９イミノジ酢酸
Ａ−２０ジヒドロキシエチルグリシン
Ａ−２１エチルエーテルジアミンテトラ酢酸Ａ−２２グ
リコールエーテルジアミンテトラ酢酸
八−２３エチレンジアミンテトラプロピオン酸Ａ−２４
１，２−ジアミノプロパンテトラ酢酸アンモニウム塩
Ａ−２５１，２−ジアミノプロパンテトラ酢酸ナトリウ
ム塩
Ａ−２６ヒドロキシイミノジ酢酸アンモニウム塩
Ａ−２１ヒドロキシイミノジ酢酸ナトリウム塩Ａ−２８
トリエチレンテトラミンヘキサ酢酸Ａ−２９１，３−ジ
アミノプロパン−２−オール−テトラ酢酸
Ａ−３０フェニレンジアミンテトラ・酢酸Ａ−３１ニト
リロトリプロピオン酸
Ａ−３２エチレンジアミンテトラメチレンホスホン酸
Ａ−３３ジエチレントリアミンペンタメチレンホスホン
酸
Ａ−３４シクロヘサンジアミンテトラメチレンホスホン
酸
Ａ−３５ニトリロトリメチレンホスホン酸Ａ−３６イミ
ノジメチレンホスホン酸
これらの化合物の中では、アミノポリカルボン酸類が好
ましく、特に、Ａ−１〜Ａ−３、Ａ−８、Ａ−１３、Ａ
−１４、Ａ−１７〜Ａ−１９、Ａ−２２、八−２４〜Ａ
−２７が好ましい。Typical specific examples of the compounds of the present invention are shown below A-1 Ethylenediaminetetraacetic acid A-2 Ethylenediaminetetraacetic acid disodium salt A-3 Ethylenediaminetetraacetic acid diammonium salt A-4 Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt A-5 Ethylenediaminetetraacetic acid tetrapotassium salt A-6 Ethylenediaminetetraacetic acid tetrasodium salt A-7 Ethylenediaminetetraacetic acid trisodium salt A-8 Diethylenetriaminepentaacetic acid ammonium salt A-9 Diethylenetriaminepentaacetic acid pentasodium salt A-10 Ethylenediamine-N -(β-oxyethyl)-N, N', N' -Triacetic acid A-11 ethylenediamine-N-(β-oxyethyl)-N, N', N'
-Triacetic acid trisodium salt A-12 ethylenediamine-N-(β-oxyethyl)
-N, N', N' - Triammonium triacetate salt A-13 Propylene diamine tetraacetic acid ammonium salt A-14 Propylene diamine tetraacetic acid disodium salt A-15 Nitrilotriacetic acid A-16 Nitrilotriacetic acid trisodium salt A-17 Cyclohexane Diaminetetraacetic acid A-18 Cyclohexanediaminetetraacetic acid disodium salt A-19 Iminodiacetic acid A-20 Dihydroxyethylglycine A-21 Ethyl ether diamine tetraacetic acid A-22 Glycol ether diamine tetraacetic acid octa-23 Ethylenediamine tetrapropionic acid A-24
1,2-Diaminopropane tetraacetic acid ammonium salt A-25 1,2-diaminopropane tetraacetic acid sodium salt A-26 Hydroxyiminodiacetic acid ammonium salt A-21 Hydroxyiminodiacetic acid sodium salt A-28
Triethylenetetraminehexaacetic acid A-291,3-Diaminopropan-2-ol-tetraacetic acid A-30Phenylenediaminetetraacetic acid A-31Nitrilotripropionic acid A-32Ethylenediaminetetramethylenephosphonic acid A-33Diethylenetriaminepentamethylenephosphonic acid A-34 Cyclohesanediamine tetramethylene phosphonic acid A-35 Nitrilotrimethylene phosphonic acid A-36 Iminodimethylene phosphonic acid Among these compounds, aminopolycarboxylic acids are preferred, especially A-1 to A-3, A-3 -8, A-13, A
-14, A-17 to A-19, A-22, 8-24 to A
-27 is preferred.
本発明に用いられる本発明の化合物の第２鉄錯塩は、錯
塩の形で使用してもよいし、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鉄などと本発明の化合物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。錯塩の形で使用す
る場合は、１種類の錯塩を用いてもよいし、又２種類以
上の錯塩を用いてもよい。一方、第２鉄塩と本発明の化
合物を用いて溶液中で錯塩を形成する場合は第２鉄塩を
１種類又は２種類以上使用してもよい。更に本発明の化
合物を１種類又は２種類以上使用してもよい。また、い
ずれの場合にも、本発明の化合物を第２鉄イオン鑵塩を
形成する以上に過剰に用いてもよい。The ferric complex salt of the compound of the present invention used in the present invention may be used in the form of a complex salt, or may be a ferric salt, such as ferric sulfate.
Ferric ion complex salts may be formed in solution using the compounds of the present invention with iron, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and the like. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and the compound of the present invention, one or more types of ferric salts may be used. Furthermore, one type or two or more types of compounds of the present invention may be used. Also, in any case, the compound of the present invention may be used in excess of the amount required to form the ferric ion salt.
また上記の第２鉄イオン錯体を含む漂白能を有する液に
は鉄以外のコバルト、銅、ニッケル等の金属イオン錯塩
が入っていてもよい。Further, the bleaching solution containing the ferric ion complex described above may contain a complex salt of a metal ion other than iron, such as cobalt, copper, or nickel.
本発明の漂白能を有する液において、上記本発明の化合
物の第２鉄錯塩は、漂白能を有する液１２当たり、０．
０５〜２モルが好ましく、より好ましくは０．１〜１．
０モル、特に好ましくは０，２〜０．６モルの範囲であ
る。In the liquid having bleaching ability of the present invention, the ferric complex salt of the compound of the present invention is contained in an amount of 0.0% per 12 liquid having bleaching ability.
The amount is preferably 0.5 to 2 mol, more preferably 0.1 to 1.0 mol.
0 mol, particularly preferably in the range from 0.2 to 0.6 mol.
本発明の脱銀工程において、漂白液を用いる場合、漂白
液には前記漂白剤としての本発明の化合物の第２鉄ｌｉ
塩の他にｔｉ酸、硼砂、メタ硼酸、水酸化ナトリウム、
水酸化カリウム、炭酸ナトリウム、炭酸カリウム、重炭
酸ナトリウム、重炭酸カリウム、酢酸、酢酸ナトリウム
、水酸化アンモニウム等の各種の塩からなるｐＨ！ｌ！
ｉｌｉ剤、臭化カリウム、塩化水素酸、臭化水素酸、臭
化リチウム、臭化ナトリウム、臭化アンモニウム、沃化
カリウム、沃化ナトリウム、沃化アンモニウム等のハロ
ゲン化合物等通常漂白液に用いることが公知の添加剤を
任意に含有することができる。In the desilvering step of the present invention, when a bleaching solution is used, the bleaching solution contains ferric lithium of the compound of the present invention as the bleaching agent.
In addition to salt, ti acid, borax, metaboric acid, sodium hydroxide,
pH consisting of various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide! l!
Illuminating agents, halogen compounds such as potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. Can be used in normal bleaching solutions. may optionally contain known additives.
本発明の漂白液のｐＨは４．０〜８，０の範囲が好まし
く、より好ましくは５．０〜６．５である。The pH of the bleaching solution of the present invention is preferably in the range of 4.0 to 8.0, more preferably 5.0 to 6.5.
本発明の脱銀工程に漂白定着液を用いる場合、漂白定着
液には前記漂白液に添加し得る化合物の他、ハロゲン化
銀定着剤として通常の定着処理に用いられるようなハロ
ゲン化銀と反応して水溶性の錯塩を形成する化合物、例
えばチオ硫酸カリウム、チオ硫酸ナトリウム、チオ硫酸
アンモニウムの如きチオ硫酸塩、チオシアン酸カリウム
、チオシアン酸ナトリウム、チオシアン酸アンモニウム
の如きチオシアン酸塩、チオ尿素、チオエーテル、高濃
度の臭化物、ヨウ化物等が用いられる。これらの定着剤
は５ａ／１以上、好ましくは５０ｇ／１以上、より好ま
しくは７０ａ／／１以上溶解できる範囲の量で使用でき
る。When a bleach-fix solution is used in the desilvering step of the present invention, the bleach-fix solution contains compounds that can be added to the bleach solution, as well as silver halide fixing agents that react with silver halide that is used in normal fixing processing. compounds which form water-soluble complex salts, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate; thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate; thioureas; thioethers; High concentrations of bromide, iodide, etc. are used. These fixing agents can be used in an amount within the range of dissolving 5a/1 or more, preferably 50g/1 or more, more preferably 70a/1 or more.
さらにまた、各種の蛍光増白剤や消泡剤あるいは界面活
性剤や防ばい剤を含有せしめることもできる。またヒド
ロキシルアミン、ヒドラジン、亜硫酸塩、異性重亜硫酸
塩、アルデヒドやケトン化合物の重亜硫酸付加物等の保
恒剤、アセチルアセトン、ホスホノカルボン酸、ポリリ
ン酸、有機ホスホン酸、オキシカルボン酸、ポリカルボ
ン酸、ジカルボン酸及びアミノポリカルボン酸等の有機
キレート剤あるいはニトロアルコール、硝酸塩等の安定
剤、アルカノールアミン等の可溶化剤、有機アミン等の
スティン防止剤、その他の添加剤や、メタノール、ジメ
チルホルムアミド、ジメチルスルホキシド等の有機溶媒
等を適宜含有せしめることができる。Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. Also, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, and polycarboxylic acids. , organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, methanol, dimethylformamide, An organic solvent such as dimethyl sulfoxide can be appropriately contained.
本発明の漂白定着液のＩ）Ｈは、３．０〜９．８の範囲
が好ましく、より好ましくは５，６〜８．５、特に好ま
しくは６．０〜８．３である。I)H of the bleach-fix solution of the present invention is preferably in the range of 3.0 to 9.8, more preferably 5.6 to 8.5, particularly preferably 6.0 to 8.3.
本発明の脱銀工程に定着液を用いる場合、定着液には、
ハロゲン化銀定着剤として上記漂白定着液に述べたチオ
硫酸塩、チオシアン酸塩等の定着剤が含有される。When using a fixing solution in the desilvering step of the present invention, the fixing solution includes:
As a silver halide fixing agent, a fixing agent such as thiosulfate or thiocyanate mentioned in the above-mentioned bleach-fixing solution is contained.
また定着剤の保恒剤として、ヒドロキシルアミン、ヒド
ラジン、亜硫酸塩、異性重亜硫酸塩、アルデヒドやケト
ン化合物の重亜硫酸付加物等の保恒剤、さらに漂白液で
述べた各種ｐＨＩ衝剤、ハロゲン化合物等通常定着液に
用いられる公知の添加剤を含有することができる。In addition, as preservatives for fixing agents, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, and various pHI buffers and halogen compounds as mentioned for bleaching solutions can also be used. It may contain known additives commonly used in fixers.
定着液のｐＨは、５．０〜８．５の範囲が好ましく、よ
り好ましくは６．０〜８．０である。The pH of the fixer is preferably in the range of 5.0 to 8.5, more preferably 6.0 to 8.0.
上記脱銀処理工程において、漂白浴に漂白補充液を添加
した結果漂白浴から流出する使用済の漂白浴オーバーフ
ロー液、および定着浴に定着補充液を添加した結果定着
浴から流出する使用済の定着浴オーバーフロー液のそれ
ぞれ一部または全部を漂白定着浴に導入することができ
る。その場合、漂白、定看両浴からのオーバーフロー液
が効果的に再利用され、脱銀性能にも悪影響を与えず、
補充液総議の低減も可能であり好ましい態様である。In the above desilvering process, the used bleach bath overflow solution flows out from the bleach bath as a result of adding bleach replenisher to the bleach bath, and the used fixer flows out from the fixer bath as a result of adding fixer replenisher to the fixing bath. A respective part or all of the bath overflow liquid can be introduced into the bleach-fixing bath. In that case, the overflow liquid from both the bleaching and constant cleaning baths can be effectively reused, without adversely affecting the desilvering performance.
It is also possible to reduce the total amount of replenisher, which is a preferred embodiment.
本発明において、上記脱銀処理されたハロゲン化銀カラ
ー写真感光材料はｐｉ−１８，０以上で且つ緩衝剤を含
有するアルカリ浴で処理される。ここで、アルカリ浴で
処理するに際し、脱銀処理後連続的にアルカリ浴による
処理をするのは勿論、アルカリ浴処理前に、水洗、リン
ス、さらに特開昭５７−８５４３号等に記載の水洗水量
を極端に低減する水洗代替安定化処理等を施してもよい
。コスト等を考慮すると脱−銀処理後連続的にアルカリ
浴処理するのが好ましい。In the present invention, the desilvered silver halide color photographic light-sensitive material is treated in an alkaline bath having pi-18.0 or more and containing a buffer. When processing in an alkaline bath, it is of course necessary to carry out continuous alkaline bath treatment after desilvering treatment, as well as water washing, rinsing, and further water washing as described in JP-A No. 57-8543 etc. A stabilization treatment as an alternative to washing may be performed to extremely reduce the amount of water. Considering costs and the like, it is preferable to carry out continuous alkaline bath treatment after desilvering treatment.
以下、本発明のｐＨ８，０以上で且つ緩衝剤を含有する
アルカリ処理液（以下単に本発明のアルカリ浴という）
について説明する。Hereinafter, the alkaline treatment solution of the present invention having a pH of 8.0 or more and containing a buffer (hereinafter simply referred to as the alkaline bath of the present invention)
I will explain about it.
本発明のアルカリ浴に用いられる緩衝剤は、ｐＨ８，０
以上の水溶液中で安定な緩衝効果を有するものであれば
いかなる化合物でも用いられるが、具体的には例えば炭
酸ナトリウム、重炭酸ナトリウム、炭酸カリウム、重炭
酸カリウム、炭酸アンモニウム、重炭酸アンモニウム、
硼酸、硼砂、メタ硼酸ナトリウム、燐酸ナトリウム、燐
酸カリウム、第１燐酸ナトリウム等の無機塩類、エタノ
ールアミン、エチレンジアミン、メチルアミン、トリメ
チルアミン、プロピルアミン等のアミン類、ヒドロキシ
フェニル、Ｏイシン、グリシン、アラニン、アスパラギ
ン酸、γ−アミノブチル酢酸等のアミノ酸類、スルホサ
リチル酸、ピペラジン、グアニジン等の各種有機化合物
が挙げられ、これらを単独または組み合わせて用いるこ
とができる。The buffer used in the alkaline bath of the present invention has a pH of 8.0.
Any compound can be used as long as it has a stable buffering effect in the above aqueous solution, but specific examples include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate,
Boric acid, borax, sodium metaborate, sodium phosphate, potassium phosphate, inorganic salts such as monobasic sodium phosphate, amines such as ethanolamine, ethylenediamine, methylamine, trimethylamine, propylamine, hydroxyphenyl, Oisine, glycine, alanine, Examples include amino acids such as aspartic acid and γ-aminobutylacetic acid, and various organic compounds such as sulfosalicylic acid, piperazine, and guanidine, and these can be used alone or in combination.
本発明に用いられるａｍ剤として、コスト、本発明の復
色不良改良効果、長期に亘る連続使用におけるｆｌＨ維
持効果、さらに他の写真性能への悪影響等を考慮すると
炭酸ナトリウム、炭酸カリウム、重炭酸カリウム、硼酸
、硼砂、メタ硼酸ナトリウム、リン酸ナトリウム、リン
酸カリウム、第１リン酸ナトリウム、スルホサリチル酸
等が好ましく用いられる。Considering the cost, the effect of improving poor color restoration of the present invention, the effect of maintaining flH during long-term continuous use, and the adverse effects on other photographic performance, the am agents used in the present invention include sodium carbonate, potassium carbonate, and bicarbonate. Potassium, boric acid, borax, sodium metaborate, sodium phosphate, potassium phosphate, monobasic sodium phosphate, sulfosalicylic acid, and the like are preferably used.
本発明のアルカリ浴における上記緩衝剤の使用器は、ア
ルカリ浴のｐＨ１用いる緩衝剤の種類等によって大きく
異なり、あまりに多量に用いると処理済感光材料の画像
に汚れが発生したり、少■では緩衝効果が小さい等の問
題も発生するので、アルカリ浴の条件によって決められ
るものであるが、目安としてアルカリ浴１２当たり０．
２〜５０ Ｑの範囲で用いることが好ましく、より好ま
しくは０．５〜３０ Ｑである。The use of the above-mentioned buffer in the alkaline bath of the present invention varies greatly depending on the pH of the alkaline bath. Problems such as low effectiveness may occur, so this is determined by the conditions of the alkaline bath, but as a guideline, 0.0.
It is preferably used in a range of 2 to 50 Q, more preferably 0.5 to 30 Q.
本発明においてアルカリ浴処理は一槽または多槽で問題
なく使用することができるが、好ましくは１槽〜２槽で
ある。In the present invention, alkaline bath treatment can be used in one bath or in multiple baths without any problem, but preferably in one to two baths.
また、本発明のアルカリ浴は、従来知られている他の写
真用処理浴と同様の用いられ方、具体的には補充液を充
分に供給してもよいが、公害等を考慮して補充量を最小
限にすることが好ましい。In addition, the alkaline bath of the present invention may be used in the same manner as other conventionally known photographic processing baths, and specifically, a sufficient amount of replenisher may be supplied; Preferably, the amount is minimized.
前浴からアルカリ浴への写真用処理液の持ち込み量は感
光材料の種類、自動現像機の搬送速度、搬送方式、感光
材料表面のスクイズ方式等により異なるが、本発明にお
いては、処理する感光材料の単位面積当たりを基準とし
て、通常持ち込み凶は２５ｔＮ／ｆ〜１５０ｄ／１’で
あることが好ましく、この持ち込み量に対する本発明の
効果がより顕著である補充量は５０ｉＮ／ｆ〜３．０１
！、／ｆの範囲にあり、特に効果が顕著な補充量は１０
０ｉＮ／１〜９５０ｍ１２／ｆの範囲にある。The amount of photographic processing solution brought into the alkaline bath from the prebath varies depending on the type of photosensitive material, the conveyance speed of the automatic processor, the conveyance method, the method of squeezing the surface of the photosensitive material, etc., but in the present invention, Based on the unit area of
! , /f, and the most effective replenishment amount is 10
It is in the range of 0iN/1 to 950m12/f.
上記本発明のアルカリ浴には、鉄イオンとのキレート安
定度定数ｉｏｇＫＭＡ）が６以上であるキレート剤を含
有させることにより、本発明の効果、具体的には復色不
良の改良を更に効果的に達成することができる。また、
アルカリ浴に持ち込まれた可溶性鉄塩の水酸化物生成を
防止する効果も有する。By containing a chelating agent having a chelate stability constant iogKMA) of 6 or more with iron ions in the alkaline bath of the present invention, the effects of the present invention, specifically, the improvement of poor color restoration can be further effectively improved. can be achieved. Also,
It also has the effect of preventing hydroxide formation of soluble iron salts brought into the alkaline bath.
ここにキレート安定度定数とは、Ｌ、Ｇ。Here, the chelate stability constants are L and G.
３ｉｌｌ 、 ｅｎ、 Ａ、 Ｅ、 Ｍａｒｔｅｌｌ著
、“５ｔａｂｉｌｉｔｙＣＯｎＳｔａｎｔＳ ｏｆ
Ｍｅｔａｌ−ｉｏｎ Ｃ０１ｐｌｅＸｅＳ”。3ill, en, A. E. Martell, “5tabilityCONStantSof
Metal-ion C01pleXeS”.
Ｔｈｅ Ｃｈｅｍｉｃａｌ ５ｏｃｉｅｔｙ、 Ｌｏ
ｎｄｏｎ （１９６４）、Ｓ、 Ｃｈａｂｅｒｅｋ
、 Ａ、 Ｅ、 Ｍａｒｔｅｌｌ著。The Chemical 5ociety, Lo
ndon (1964), Chaberek, S.
, by A. E. Martell.
“Ｑｒｇａｎｉｃ ５ｅＱｔｌｅＳｔｅｒｉｎ！Ｉｆ
ＡＯｅｎｔＳ”、Ｗｉｌｅｙ（１９５９）等により一
般に知られた定数を意味する。“Qrganic 5eQtleSterin!If
AOentS", a constant generally known by Wiley (1959) and others.
本発明において鉄イオンに対するキレート安定度定数が
６以上であるキレート剤としては、有機カルボン酸キレ
ート剤、有機アミノポリカルボン酸、有機リン酸キレー
ト剤、無機リン酸キレート剤、ポリヒドロキシ化合物等
が挙げられる。尚上記鉄イオンとは第２鉄イオン（Ｆｅ
３ ” ）および第１鉄イオン（Ｆｅ ２ ” ）の
両者を意味する。In the present invention, examples of the chelating agent having a chelate stability constant of 6 or more for iron ions include organic carboxylic acid chelating agents, organic aminopolycarboxylic acids, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. It will be done. Note that the iron ion mentioned above refers to ferric ion (Fe
3 ”) and ferrous ion (Fe 2 ”).
本発明において鉄イオンとのキレート安定度定数が６以
上であるキレート剤の具体的化合物例としては、下記化
合物が挙げられるが、これらに限定されるものではない
。即ちエチレンジアミンジオルトヒドロキシフェニル酢
酸、ジアミノプロパン四酢酸、ニトリロ三酢酸、ヒドロ
キシエチルエチレンジアミン三酢酸、ジヒドロキシエチ
ルグリシン、エチレンジアミンニ酢酸、エチレンジアミ
ンニブロビオン酸、イミノニ酢酸、ジエチレントリアミ
ン五酢酸、ヒト０キシエチルイミノ二酢酸、ジアミノプ
ロパノール四酢酸、トランスシクロヘキサンジアミン四
酢酸、エチレンジアミン四酢酸、グリコールエーテルジ
アミン四酢酸、エチレンジアミンテトラキスメチレンホ
スホン酸、ニトリロトリメチレンホスホン酸、１−ヒド
ロキシエチリデン−１，１−ジホスホン酸、１．１−ジ
ホスホンエタン−２−カルボン酸、２−ホスホノブタン
−１，２，４−トリカルボン酸、１−ヒドロキシ−１−
ホスホノプロパン−１，２，３−トリカルボン酸、カテ
コール−３，５−ジスルホン酸、ビロリン酸ナトリウム
、テトラポリリン酸ナトリウム、ヘキサメタリン酸ナト
リウムが挙げられ、特に好ましくは、ジアミノプロパン
四酢酸、ジエチレントリアミン五酢酸、ヒト０キシエチ
ルイミノ二酢酸、ジアミノプロパノール西酢酸、エチレ
ンジアミン四酢酸やこれらの塩である。In the present invention, specific examples of compounds of chelating agents having a chelate stability constant of 6 or more with iron ions include the following compounds, but are not limited thereto. Namely, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenibrobionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, human oxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonic acid Ethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-
Examples include phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium birophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, and particularly preferred are diaminopropanetetraacetic acid and diethylenetriaminepentaacetic acid. , human oxyethyliminodiacetic acid, diaminopropanol diacetic acid, ethylenediaminetetraacetic acid, and salts thereof.
本発明において用いられる上記キレート剤の使用量はア
ルカリ浴１１１当たり、０．０１〜５０ｇ、好ましくは
０．０５〜２０ｇの範囲で良好な結果が得られる。Good results can be obtained when the amount of the chelating agent used in the present invention ranges from 0.01 to 50 g, preferably from 0.05 to 20 g, per 111 alkaline baths.
本発明においてはアルカリ浴に前記キレート剤と鉄イオ
ンとの錯塩、即ち鉄錯塩を含有せしめることは復色不良
を改良する点で極めて好ましいことである。特に好まし
い化合物としてはエチレンジアミンテトラ酢酸第２鉄ナ
トリウム塩、ジエチレントリアミン五酢酸第２鉄ナトリ
ウム塩、プロピレンジアミン四酢酸第２鉄ナトリウム塩
、１゜２−ジアミノプロパン四酢酸第２鉄ナトリウム塩
等が挙げられ、添加量としてはアルカリ浴１１当たり０
．５〜３０Ｇであり、特に好ましくは２〜１５ｏである
。In the present invention, it is extremely preferable for the alkaline bath to contain a complex salt of the chelating agent and iron ions, that is, an iron complex salt, from the viewpoint of improving color restoration defects. Particularly preferred compounds include ferric sodium salt of ethylenediaminetetraacetic acid, ferric sodium salt of diethylenetriaminepentaacetic acid, ferric sodium salt of propylenediaminetetraacetic acid, and ferric sodium salt of 1゜2-diaminopropanetetraacetic acid. , the amount added is 0 per 11 alkaline baths.
．． It is 5 to 30G, particularly preferably 2 to 15o.
本発明においては、前記漂白能を有する液のオーバーフ
ロー液をアルカリ液に流し込み、アルカリ浴１更当たり
Ｉ Ｘ １０−３モル以上の濃度でアミノポリカルボン
酸第２鉄諸塩を存在せしめることにより、ざらに復色不
良を良好に防止できる。In the present invention, by pouring the overflow liquid of the liquid having bleaching ability into an alkaline liquid and making the aminopolycarboxylic acid ferric salts exist at a concentration of I x 10 -3 mol or more per alkaline bath, Poor color recovery can be effectively prevented.
また、本発明のアルカリ浴に酸化剤として、例えば過酸
化水素、過炭酸ナトリウム、過硼酸ナトリウム、過硫酸
カリウム、過硫酸アンモニウム、塩素酸ナトリウム、次
亜塩素酸ナトリウム、臭素酸カリウム、臭素酸アンモニ
ウム、臭素酸ナトリウム等を含有させることにより、さ
らに復色不良を良好に防止することができる。酸化剤の
添加量として好ましくはｏ、 ｏｉｇ〜３０Ｑ／Ｉｔで
ある。Further, as an oxidizing agent in the alkaline bath of the present invention, for example, hydrogen peroxide, sodium percarbonate, sodium perborate, potassium persulfate, ammonium persulfate, sodium chlorate, sodium hypochlorite, potassium bromate, ammonium bromate, By containing sodium bromate or the like, poor recoloring can be better prevented. The amount of the oxidizing agent added is preferably o, oig to 30Q/It.
本発明の処理方法においては、上記アルカリ浴処理で終
ってもよいしさらに、水洗処理もしくは実質的に水洗水
を用いない安定化処理液で処理してもよい。In the treatment method of the present invention, the above-mentioned alkaline bath treatment may be completed, and further treatment may be performed with water washing treatment or with a stabilizing treatment liquid that does not substantially use washing water.
本発明において、アルカリ浴の後の処理として好ましく
は後者の実質的に水洗水を用いない安定化処理である。In the present invention, the latter stabilization treatment that substantially does not use washing water is preferred as the treatment after the alkaline bath.
安定液の成分は基本的には水のみでもよいが、種々の化
合物を添加することもでき、本発明に好ましく使用でき
る化合物としては、ホルマリン、界面活性剤、アンモニ
１クム塩、キレート剤及び金属塩がある。The stabilizer may basically consist of only water, but various compounds may also be added. Compounds that can be preferably used in the present invention include formalin, surfactants, ammonium cum salts, chelating agents, and metals. There is salt.
本発明の前記アルカリ浴または安定液において必要に・
応じて防黴剤が用いられる。用いられる防黴剤は、ヒド
ロキシ安息香酸系化合物、フェノール系化合物、チアゾ
ール系化合物、ピリジン系化合物、グアニジン系化合物
、カーバメイト系化合物、モルホリン系化合物、四級ホ
スホニウム系化合物、四級アンモニウム系化合物、尿素
系化合物、イソオキサゾール系化合物、ブＯパノールア
ミン系化合物、スルファミド誘導体、アミノ酸系化合物
、トリアジン系化合物及びベンゾトリアゾール系化合物
である。In the alkaline bath or stabilizing solution of the present invention, necessary
Antifungal agents are used accordingly. The antifungal agents used include hydroxybenzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, quaternary ammonium compounds, and urea. compounds, isoxazole-based compounds, buOpanolamine-based compounds, sulfamide derivatives, amino acid-based compounds, triazine-based compounds, and benzotriazole-based compounds.
本発明の処理方法においては、発色現像、脱銀処理およ
び本発明に係るアル、カリ浴処理等の工程の他に硬膜、
中和、黒白現像、反転、少量水洗工程等、必要に応じて
各種の補助工程が一付加されてもよい。In the processing method of the present invention, in addition to steps such as color development, desilvering treatment, and alkali bath treatment according to the present invention, hardening film,
Various auxiliary processes may be added as necessary, such as neutralization, black and white development, reversal, and washing with a small amount of water.
本発明の処理方法に用いられるハロゲン化銀カラー写真
感光材料には一般式［Ｍ−ＩＩで示されるマゼンタカプ
ラーを含有する。The silver halide color photographic light-sensitive material used in the processing method of the present invention contains a magenta coupler represented by the general formula [M-II].
以下−１本発明に係るマゼンタカプラーについて説明す
る。Below-1, the magenta coupler according to the present invention will be explained.
本発明に係る前記一般式［Ｍ−ＩＩ
一般式［Ｍ−ＩＩ
で表されるマゼンタカプラーにおいて、Ｚは含窒素複素
環を形成するに必要な非金属原子群を表し、該２により
形成される環は置換基を有してもよい。In the magenta coupler represented by the general formula [M-II] according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and The ring may have a substituent.
Ｘは水素原子又は発色現像主薬の酸化体との反応により
離脱しうる基を表す。X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.
またＲは水素原子又は置換基を表す。Moreover, R represents a hydrogen atom or a substituent.
Ｒの表す置換基としては特に制限はないが、代表的には
、アルキル、アリール、アニリノ、アシルアミノ、スル
ホンアミド、アルキルチオ、アリールチオ、アルケニル
、シクロアルキル等の各基が挙げられるが、この他にハ
ロゲン原子及びシクロアルケニル、アルキニル、複素環
、スルホニル、スルフィニル、ホスホニル、アシル、カ
ルバモイル、スルフ７モイル、シアノ、アルコキシ、ア
リールオキシ、複素環オキシ、シロキシ、アシルオキシ
、カルバモイルオキシ、アミノ、アルキルアミノ、イミ
ド、ウレイド、スルファモイルアミノ、アルコキシカル
ボニルアミノ、アリールオキシカルボニルアミノ、アル
コキシカルボニル、アリールオキシカルボニル、複素環
チオの各基、ならびにスピロ化合物残基、有橋炭化水素
化合物残基等も挙げられる。The substituent represented by R is not particularly limited, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl, but in addition to these, halogen Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulf7moyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido , sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.
Ｒで表されるアルキル基としては、炭素数１〜３２のも
のが好ましく、直鎖でも分岐でもよい。The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.
Ｒで表されるアリール基としては、フェニル基が好まし
い。The aryl group represented by R is preferably a phenyl group.
Ｒで表されるアシルアミノ基としては、アルキルカルボ
ニルアミＬＬアリールカルボニルアミノ基等が挙げられ
る。Examples of the acylamino group represented by R include alkylcarbonylamino LL arylcarbonylamino groups.
Ｒで表されるスルホンアミド基としては、アルキルスル
ホニルアミノ基、アリールスルホニルアミノ基等が挙げ
られる。Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.
Ｒで表されるアルキルチオ基、アリールチオ基における
アルキル成分、アリール成分は上記Ｒで表されるアルキ
ル基、アリール基が挙げられる。Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.
Ｒで表されるアルケニル基としては、炭素数２〜３２の
もの、シクロアルキル基としては炭素数３〜１２、特に
５〜７のものが好ましく、アルケニル基は直鎖でも分岐
でもよい。The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.
Ｒで表されるシクロアルケニル基としては、炭素数３〜
１２、特に５〜７のものが好ましい。The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.
Ｒで表されるスルホニル基としてはアルキルスルホニル
基、アリールスルホニル基等；スルフィニル基としては
アルキルスルフィニル基、アリールスルフィニル基等：
ホスホニル基としてはアルキルホスホニル基、アルコキ
シホスホニル基、アリールオキシホスホニル基、アリー
ルホスホニル基等ニ
アシル基としてはアルキルカルボニル基、アリールカル
ボニル基等；
カルバモイル基としてはアルキルカルバモイル基、アリ
ールカルバモイル基等：
スルファモイル基としてはアルキルスルファモイル基、
アリールスルファモイル基等ニアシルオキシ基としては
アルキルカルボニルオキシ基、アリールカルボニルオキ
シ基等：カルバモイルオキシ基としてはアルキルカルバ
モイルオキシ基、アリールカルバモイルオキシ基等：
ウレイド基としてはアルキルウレイド基、アリールウレ
イド基等；
スルファモイルアミノ基としてはアルキルスルファモイ
ルアミノ基、アリールスルファモイルアミノ基等；
複素環基としては５〜７員のものが好ましく、具体的に
は２−フリル基、２−チェニル基、２−ピリミジニル基
、２−ベンゾチアゾリル基等；複素環オキシ基としては
５〜７員の複素環を有するものが好ましく、例えば３，
４．５．６−テトラヒドロビラニル−２−オキシ基、１
−フェニルテトラゾール−５−オキシ基等：
複素環チオ基としては、５〜７員の複素環チオ基が好ま
しく、例えば２−ピリジルチオ基、２−ベンゾチアゾリ
ルチオ基、２．４−ジフェノキシ−１，３，５−トリア
ゾール−６一チオ基等：シロキシ基としてはトリメチル
シロキシ基、トリエチルシロキシ基、ジメチルブチルシ
ロキシ基等；
イミド基としてはコハク酸イミド基、３−ヘプタデシル
コハク酸イミド基、フタルイミド基、グルタルイミド基
等；
スピロ化合物残基としてはスピロ［３，３］へブタン−
１−イル等；
有橋炭化水素化合物残基としてはビシクＯ［２゜２．１
１へブタン−１−イル、トリシクロ［３゜３．１．１３
）７］デカン−１−イル、７，７−シメチルービシクロ
［２，２，１］へブタン−１−イル等が挙げられる。Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc. Niacyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups include alkylsulfamoyl groups,
Niacyloxy groups such as arylsulfamoyl groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; As the heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-chenyl group , 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, such as 3,
4.5.6-tetrahydrobilanyl-2-oxy group, 1
-Phenyltetrazole-5-oxy group, etc.: The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1 , 3,5-triazole-6 monothio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group. group, glutarimide group, etc.; as a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; as a bridged hydrocarbon compound residue, bisic O [2°2.1
1 hebutan-1-yl, tricyclo[3゜3.1.13
)7] Decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.
Ｘの表す発色現像主薬の酸化体との反応により離脱しう
る基としては、例えばハロゲン原子（塩素原子、臭素原
子、弗素原子等）及びアルコキシ、アリールオキシ、複
素環オキシ、アシルオキシ、スルホニルオキシ、アルコ
キシカルボニルオキシ、アリールオキシカルボニル、ア
ルキルオキザリルオキシ、アルコキシオキザリルオキシ
、アルキルチオ、アリールチオ、複素環チオ、アルキル
オキシチオカルボニルチオ、アシルアミノ、スルホンア
ミド、Ｎ原子で結合した含窒素複素環、アルキルオキシ
カルボニルアミノ
ニルアミノ
（Ｒ１′は前記Ｒと同義であり、Ｚ′は前記２と同義で
あり、Ｒ２’及びＲ３’ は水素原子、アリール基、ア
ルキル基又は複素環基を表す。）等の各基が挙げられる
が、好ましくはハロゲン原子、特に塩素原子である。Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino Each group such as nylamino (R1' has the same meaning as R, Z' has the same meaning as 2, and R2' and R3' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) Preferably, it is a halogen atom, especially a chlorine atom.
また２又は２′により形成される含窒素複素環としては
、ピラゾール環、イミダゾール環、トリアゾール環又は
テトラゾール環等が挙げられ、前記環が有りでもよい置
換基としては前記Ｒについて述ぺたものが挙げられる。Examples of the nitrogen-containing heterocycle formed by 2 or 2' include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the substituent that the ring may have include those mentioned above for R. It will be done.
一ａ式ＣＭ− Ｉ ］で表されるものは更に具体的には
例えば下記一般式［Ｍ−Ｉｔ］〜［ Ｍ − Ｖｌ ］
により表わされる。More specifically, those represented by the formula 1a CM-I] are, for example, the following general formulas [M-It] to [M-Vl]
It is represented by
［Ｍ−Ｉｔ ］
［Ｍ−１１１１
［Ｍ−ＩＶＩ
［Ｍ−Ｖｌ
［Ｍ−ＶＩＥ
一般式［Ｍ−Ｖｌ］
前記一般式［Ｍ−Ｉ１１〜［Ｍ−■］においてＲ１−Ｒ
ａ及びＸは前記Ｒ及びＸと同義である。[M-It] [M-1111 [M-IVI [M-Vl [M-VIE General formula [M-Vl]] In the general formula [M-I11 to [M-■], R1-R
a and X have the same meanings as R and X above.
又、一般式［Ｍ−ＩＩの中でも好ましいのは、下記一般
式［Ｍ−■］で表されるものである。゛−一般式Ｍ−■
］
式中Ｒ１，Ｘ及びｚｌは一般式［Ｍ−１１におけるＲ、
Ｘ及び２と同義である。Also, preferred among the general formulas [M-II] are those represented by the following general formula [M-■].゛-General formula M-■
] In the formula, R1, X and zl are the general formula [R in M-11,
It has the same meaning as X and 2.
前記一般式［Ｍ−［１〜〔Ｍ−■〕で表されるマゼンタ
カプラーの中で特に好ましいものは一般式［Ｍ−１［］
で表されるマゼンタカプラーである。Among the magenta couplers represented by the general formulas [M-[1 to [M-■]], particularly preferred ones are those represented by the general formula [M-1[]
It is a magenta coupler represented by .
一般式［Ｍ−１１における２により形成される環及び一
般式［Ｍ−■］におけるｚｌにより形成される環が有し
てもよい置換基、並びに一般式％式％
ては下記一般式［Ｍ−ＩＸ］で表されるものが好ましい
。The substituents that the ring formed by 2 in general formula [M-11 and the ring formed by zl in general formula [M-■] may have, and the general formula % formula % and the following general formula [M -IX] is preferred.
一般式［Ｍ−ＩＸ］
Ｒ’ −３０２−Ｒ２
式中Ｒ１はアルキレン基を、Ｒ２はアルキル基、シクロ
アルキル基又はアリール基を表す。General formula [M-IX] R' -302-R2 In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group.
Ｒ１で示されるアルキレン基は好ましくは直鎖部分の炭
素数が２以上、より好ましくは３ないし６であり、直鎖
１分岐を問わない。The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the straight chain has one branch or not.
Ｒ２で示されるシクロアルキル基としては５〜６農のも
のが好ましい。The cycloalkyl group represented by R2 is preferably a 5-6 cycloalkyl group.
又、ＷＡ画像形成に用いる場合、前記複素環上の置換基
Ｒ及びＲ１として最も好ましいものは、下記一般式［Ｍ
−Ｘｌにより表されるものである。Further, when used for WA image formation, the most preferable substituents R and R1 on the heterocycle are those represented by the following general formula [M
-Xl.
一般式ＣＭ−Ｘ］
Ｒｈｏ−Ｃ−
式中Ｒｓ、Ｒ１ｏ及びＲｔｌはそれぞれ前記Ｒと同義で
ある。General Formula CM-X] Rho-C- In the formula, Rs, R1o and Rtl each have the same meaning as R above.
又、前記Ｒｓ、Ｒ１ｏ及びＲｎの中の２つ例えばＲ９と
Ｒｈｏは結合して飽和又は不飽和の環（例えばシクロア
ルカン、シクロアルケン、複素環）を形成してもよく、
更に族環にＲ１１が結合して有橋炭化水素化合物残基を
構成してもよい。Also, two of the Rs, R1o and Rn, for example R9 and Rho, may be combined to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocycle),
Furthermore, R11 may be bonded to the group ring to constitute a bridged hydrocarbon compound residue.
一般式［Ｍ−Ｘｌの中でも好ましいものは、（ｉ）Ｒｓ
〜Ｒ１１の中の少なくとも２つがアルキル基の場合、（
ｉりＲｓ〜Ｒｎの中の１つ例えばＲ＋＋が水素原子であ
って、他の２つＲ９とＲｈｏが結合して根元炭素原子と
共にシクロアルキルを形成する場合、である。Among the general formulas [M-Xl, preferred are (i) Rs
When at least two of ~R11 are alkyl groups, (
This is the case when one of Rs to Rn, for example, R++, is a hydrogen atom, and the other two, R9 and Rho, combine to form a cycloalkyl together with the root carbon atom.
更に（＋ ＞の中でも好ましいのは、Ｒ９〜Ｒ＋１の中
の２つがアルキル基であって、他の１つが水素原子又は
アルキル基の場合である。Furthermore, among (+>), it is preferable that two of R9 to R+1 are alkyl groups and the other one is a hydrogen atom or an alkyl group.
又、陰画像形成に用いる場合、前記複素環上の置換基Ｒ
及びＲ１として最も好ましいのは、下記一般式ＣＭ−Ｘ
ＩＩにより表わされるものである。In addition, when used for negative image formation, the substituent R on the heterocycle
The most preferred as R1 is the following general formula CM-X
II.
一般式［Ｍ−ＸＩＩ Ｒ１２〜〇Ｈ２一 式中Ｒ１２は前記Ｒと同義である。General formula [M-XII R12~〇H2- In the formula, R12 has the same meaning as R above.
Ｒ１２として好ましいのは、水素原子又はアルキル基で
ある。Preferred as R12 is a hydrogen atom or an alkyl group.
以下に本発明に係る化合物の代表的具体例を示す。Typical specific examples of the compounds according to the present invention are shown below.
ＣＨ。CH.
ＣＨｓ
（）・ｒｌ−テｔｔノ
ＣＨり
Ｉ、 ｎ ３ Ｎ ｒ１５１Ｊ ２ シ＋ ｓ Ｎ
２ ｓ１Ｎ−バーへ
Ｃ１２Ｍ ２ ｓ
以上の本発明に係るマゼンタカプラーの代表的具体例の
他に、本発明に係るマゼンタカプラーの具体例としては
特願昭６１−９７９１号明＠書の第６６頁〜１２２頁に
記載されている化合物の中で、Ｎｏ。CHs ()・rl-tttノCHriI, n 3 N r151J 2 C+ s N
2 s1N-bar to C12M 2 s In addition to the above-described representative examples of the magenta coupler according to the present invention, examples of the magenta coupler according to the present invention are described on page 66 of Japanese Patent Application No. 61-9791 Mei@. Among the compounds described on pages 122 to 122, No.
１〜４．６．８〜１７．１９〜２４．２６〜４３゜４５
〜５９．６１〜１０４． １０６〜１２１． １２３〜
１６２、 １６４〜２２３で示される化合物を挙げるこ
とができる。1~4.6.8~17.19~24.26~43°45
~59.61~104. 106-121. 123～
162, 164-223 can be mentioned.
又、前記カプラーはジャーナル・オブ・ザ・ケミカル・
ソサイアティ（Ｊｏｕｒｎａｌ ｏｆ ｔｈｅＣｈｅｍ
ｉｃａｌ ５ｏｃｔｅｔｙ）、パーキン（ｐａｒｋｉｎ
） １（１９７７） 、 ２０４７〜２０５２、米国
特許第３，７２５，０６７号、−特開昭５９−９９４３
７号、同５８−４２０４５号、同５９−１６２５４８号
、同５９−１７１９５６号、同６Ｇ−３３５５２号、同
６Ｇ−４３６５９号、同６０−１７２９８２号及び同６
Ｇ−１９０７７９号等を参考にして合成することができ
る。Also, the coupler is described in the Journal of the Chemical
Society (Journal of the Chem)
ical 5 octety), parkin (parkin)
) 1 (1977), 2047-2052, U.S. Patent No. 3,725,067, - JP-A-59-9943
No. 7, No. 58-42045, No. 59-162548, No. 59-171956, No. 6G-33552, No. 6G-43659, No. 60-172982, and No. 6
It can be synthesized by referring to No. G-190779 and the like.
本発明のカプラーは通常へ〇ゲン化銀１モル当りｌＸ１
Ｇ−３モル〜１モル、好ましくは１Ｘ１０−２モル〜８
Ｘ１Ｇ”モルの範囲で用いることができる。The coupler of the present invention is usually
G-3 mole to 1 mole, preferably 1X10-2 mole to 8
It can be used in the range of X1G'' moles.
又、本発明のカプラーは他の種類のマゼンタカブラーと
併用することもできる。The coupler of the present invention can also be used in combination with other types of magenta couplers.
本発明の処理方法に適用される一般式［Ｍ−王１で示さ
れるマゼンタカプラーを含有するハロゲン化銀カラー写
真感光材料は、基本的にその種類に制限はないが、本発
明に用いて特に有効であるのは、ハロゲン化銀乳剤層の
少なくとも一層に沃化銀を０．５モル％以上、好ましく
は３〜１０モル％の範囲で含有するハロゲン化銀粒子を
有する高感度写真感光材料である。また、支持体上のハ
ロゲン化銀乳剤層を有する側の全写真構成層の乾燥膜厚
の総和が１３μｍ以上、好ましくは１５μｌ〜２８μｍ
、さらに好ましくは１７μＩＩｌ〜２４μｍにある感光
材料であり、さらに支持体上に塗布銀層が２０ ｍ＋３
／ １００Ｃ１’以上、好ましくは３０Ｉｌ（＋／１０
０ｃｆ〜８０１０／ １００ｃｆ、さらに好ましくは４
０ｎｉｇ／ １００ｃｆ〜７０１０／ １ｏｏｃｒの高
銀ｍ写真感光材料である。The silver halide color photographic light-sensitive material containing a magenta coupler represented by the general formula [M-King 1] applied to the processing method of the present invention is basically not limited in type, but is particularly suitable for use in the present invention. It is effective for high-sensitivity photographic materials having silver halide grains containing silver iodide in at least 0.5 mol% or more, preferably in the range of 3 to 10 mol%, in at least one of the silver halide emulsion layers. be. Further, the total dry film thickness of all the photographic constituent layers on the side having the silver halide emulsion layer on the support is 13 μm or more, preferably 15 μl to 28 μm.
, more preferably a photosensitive material having a thickness of 17 μII to 24 μm, and furthermore a coated silver layer on the support having a thickness of 20 m+3
/100C1' or more, preferably 30Il(+/10
0cf~8010/100cf, more preferably 4
It is a high silver m photographic light-sensitive material of 0 nig/100 cf to 7010/1 oocr.
本発明に適用できるハロゲン化銀カラー写真感光材料の
ハロゲン化銀乳剤は、常法により化学増感することがで
き、増感色素を用いて、所望の波長域に光学的に増感で
きる。The silver halide emulsion of the silver halide color photographic light-sensitive material applicable to the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.
ハロゲン化銀乳剤には、カブリ防止剤、安定剤等を加え
ることができる。該乳剤のバインダーとしては、ゼラチ
ンを用いるのが有利である。Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.
乳剤層、その他の親水性コロイド層は、硬膜することが
でき、又、可塑剤、水不溶性又は難溶性合成ポリマーの
分散物（ラテックス）を含有させることができる。The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.
フルカラー写真用感光材料の乳剤層には、前記本発明に
係るマゼンタカプラーの他、従来知られる任意のシアン
カプラーおよびイエローカプラーが用いられる。In addition to the magenta coupler according to the present invention, any conventionally known cyan coupler and yellow coupler may be used in the emulsion layer of the full-color photographic light-sensitive material.
更に色補正の効果を有しているカラードカプラー、競合
カプラー及び現像主薬の酸化体とのカップリングによっ
て現像促進剤、漂白促進剤、現像剤、ハロゲン化銀溶剤
、調色剤、硬膜剤、カブリ剤、カブリ防止剤、化学増感
剤、分光増感剤、及び減感剤のような写真的に有用なフ
ラグメントを放出する化合物が用いることができる。Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.
感光材料には、フィルタ一層、ハレーション防止層、イ
ラジェーション防止層等の補助層を設けることができる
。これらの層中及び／又は乳剤層中には現像処理中に感
光材料から流出するかもしくは漂白される染料が含有さ
せられてもよい。The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.
感光材料には、マット剤、滑剤、画像安定剤、界面活性
剤、色カプリ防止剤、現像促進剤、現像遅延剤や漂白促
進剤を添加できる。A matting agent, a lubricant, an image stabilizer, a surfactant, an anti-color capri agent, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.
支持体としては、ポリエチレン等をラミネートした紙、
ポリエチレンテレフタレートフィルム、バライタ紙、三
酢酸セルロース等を用いることができる。As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.
〔実施例］
以下、実施例によって本発明の詳細な説明するが、これ
により本発明の実施態様が限定されるものではない。[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereby.
実施例−１
当業界で高感度ハロゲン化銀カラー写真感光材料に対し
て採用される届構成に倣い、各種の補助層を介在させな
がら、支持体の方から黒色コロイド銀ハレーション防止
層、赤感光性ハロゲン化銀乳剤層、緑感光性ハロゲン化
銀乳剤層及び青感光性ハロゲン化銀乳剤層とし、該青感
光性ハロゲン化銀乳剤層の最外側に単分散高感度ハロゲ
ン化銀乳剤層を配し、試料Ｎ０１１を作製した。但し塗
布銀１ ハ５５ ｍ（Ｊ／ １００ｃｆ、乾燥膜厚は２
３μｍとしｌこ 。Example 1 Following the structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials, a black colloidal silver antihalation layer, a red-sensitive colloidal silver antihalation layer, and a red light-sensitive layer were coated from the support side with various auxiliary layers interposed. a green-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and a monodisperse high-sensitivity silver halide emulsion layer is disposed on the outermost side of the blue-sensitive silver halide emulsion layer. Then, sample N011 was prepared. However, coating silver 1 is 55 m (J/100 cf, dry film thickness is 2
3 μm.
層１・・・□硝酸銀を還元剤としてハイドロキノンを用
い還元して波長域４００〜７００ｎｍの光に高い吸収性
を示す黒色コロイド銀ｏ、ａｇをゼラチン３ｇにて分散
液を作りハレーション防止層を塗設した。Layer 1...□ Silver nitrate is reduced using hydroquinone as a reducing agent to make a dispersion of black colloidal silver o, ag, which exhibits high absorption in the wavelength range of 400 to 700 nm, in 3 g of gelatin and coated with an antihalation layer. Established.
層２・・・ゼラチンからなる中間層。Layer 2: Middle layer made of gelatin.
層３・・・１，５ｇの低感度赤感光性沃臭化銀乳剤（Ａ
ｇｌニアモル％）、１．６ｇのゼラチン並びに０．８５
（ｌの１−ヒドロキシ−４−（β−メトキシエチルアミ
ノカルボニルメトキシ
［δ−（２．４−ジー（−アミルフェノキシ）ブチル】
−２−ナフトアミド（以下、シアンカプラー（Ｃ−１）
と称す）、０．０３０ｇの１−ヒドロキシ−４−’［４
−（１−ヒドロキシ−８−アセトアミド−３，６−ジス
ルホ−２−ナフチルアゾ）フェノキシ］ −Ｎ−［δ−
（２，４−ジ−アミルフェノキシ）ブチル】−２−ナフ
トアミド・ジナトリウム（以下、カラードシアンカプラ
ー（ＣＧ−１）と称す）を溶解した０、４９のトリクレ
ジルホスフェート（以下、ＴＣＰと称す）を含有してい
る低感度赤感光性ハロゲン化銀乳剤層。Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (A
gl nia mole%), 1.6 g gelatin and 0.85
(1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy[δ-(2,4-di(-amylphenoxy)butyl)]
-2-naphthamide (hereinafter referred to as cyan coupler (C-1)
), 0.030 g of 1-hydroxy-4-'[4
-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy] -N-[δ-
(2,4-di-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CG-1)) dissolved in 0.49 tricresyl phosphate (hereinafter referred to as TCP). ) containing a low-sensitivity red-sensitive silver halide emulsion layer.
層４・・・１．１ｇの高感度赤感光性沃臭化銀乳剤（Ａ
ｌｌＩＳ６モル％）、１．２ｇのゼラチン並びに０．２
５（ｌのシアンカプラー（Ｃ−１）、０．０２０ｇのカ
ラードシアンカプラー（ＣＣ−１）を溶解した０、１７
ｇのＴＣＰを含有している高感度赤感光性ハロゲン化銀
乳剤層。Layer 4...1.1g of highly sensitive red-sensitive silver iodobromide emulsion (A
llIS6 mol%), 1.2 g gelatin and 0.2
5 (l of cyan coupler (C-1), 0.17 in which 0.020 g of colored cyan coupler (CC-1) was dissolved
A highly sensitive red-sensitive silver halide emulsion layer containing g of TCP.
層５・・・０．０７（＋の２．５−ジ−ｔ−オクチルハ
イドロキノン（以下、汚染防止剤（ＨＱ−１）と称す）
を溶解したＱ、０４Ｑのジブチルフタレート（以下、Ｄ
ＢＰと称す）及び１．２０のゼラチンを含有している中
間層。Layer 5...0.07 (+2.5-di-t-octylhydroquinone (hereinafter referred to as anti-fouling agent (HQ-1))
Q, 04Q dibutyl phthalate (hereinafter referred to as D
BP) and 1.20 gelatin.
層６・・・１．６ｇの低感度緑感光性沃臭化銀乳剤（Ａ
ｔ＋１：６モル％）、１．７ｇのゼラチン並びに０．３
２ｏの１− （２，４，６−ドリクロロフエニル）−３
−［３−（２，４−ジ−ｔ−アミルフェノキシアセトア
ミド）ベンゼンアミド］−５−ピラゾロン（以下、マゼ
ンタカプラー（Ｍ−１）と称す）、０．２０１；ｌの４
．４−メチレンビス−１１−（２，４，６−ドリクロル
フエニル）−３−［３−（２，４−ジー（−アミルフェ
ノキシアセトアミド）ベンゼンアミド］−５−ピラゾロ
ン（以下、マゼンタカプラー（Ｍ−２）と称す）、０．
０６６０の１−（２，４゜６−ドリクロロフエニル）−
４−（１−ナフチルアゾ）−３−（２−クロロ−５−オ
クタデセニルスクシンイミドアニリノ）−５−ピラゾロ
ン（以下、カラードマゼンタカプラー（ＣＭ−１）と称
す）の３種のカプラーを溶解した０、３９のＴＣＰを含
有している低感度緑感光性ハロゲン化銀乳剤層。Layer 6: 1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (A
t+1: 6 mol%), 1.7 g of gelatin and 0.3
2o 1-(2,4,6-dolichlorophenyl)-3
-[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0.201; 4
．． 4-methylenebis-11-(2,4,6-dolychlorophenyl)-3-[3-(2,4-di(-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M -2)), 0.
0660 1-(2,4゜6-dolichlorophenyl)-
Three types of couplers: 4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimideanilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)) were dissolved. A low-sensitivity green-sensitive silver halide emulsion layer containing 0.39 TCP.
層７・・・１．５ｇの＾感度緑感光性沃臭化銀乳剤（Ａ
ｔｌｌｌ：８モル％）、１．９ｇのゼラチン並びに０．
１０（ｌのマゼンタカプラー（Ｍ−１）、０、０７８（
ｌのマゼンタカプラー（Ｍ−２）、０、０４９ｇのカラ
ードマゼンタカプラー（ＣＭ−１）を溶解した０、 １
２（ＪのＴＣＰを含有している高感度緑感光性ハロゲン
化銀乳剤層。Layer 7: 1.5 g of green-sensitive silver iodobromide emulsion (A
8 mol %), 1.9 g of gelatin and 0.
10(l magenta coupler (M-1), 0,078(
1 of magenta coupler (M-2), 0.1 in which 0.049 g of colored magenta coupler (CM-1) was dissolved.
Highly sensitive green-sensitive silver halide emulsion layer containing TCP 2 (J).
層８・・・０．２０の黄色コロイド銀、０．２１Ｊの汚
染防止剤（ＨＱ−１）を溶解した０、 １１（ｌのＤＢ
Ｐ及び２．１ｇのゼラチンを含有するイエローフィルタ
一層。Layer 8...0.20 yellow colloidal silver, 0.11 (l DB) dissolved in 0.21 J stain inhibitor (HQ-1).
One layer of yellow filter containing P and 2.1 g gelatin.
層９・・・０．９５（ｌの低感度青感光性沃臭化銀乳剤
（Ａ（ＩＩニアモル％）、１．９９のゼラチン並びに１
、８４（ｌのα−［４−（１−ベンジル−２−〕〕ニ
ルルー３．５−ジオキソー１．２４−トリアジリジニル
）］−］９−ピバロイルー２−クロロー５ ［７−（２
，４−ジー側−アミルフェノキシ）ブタンアミド］アセ
トアニリド（以下、イエローカプラー（Ｙ−１）と称す
）を溶解した０、 ９３（ｌのＤＢＰを含有する低感度
青感光性ハロゲン化銀乳剤層。Layer 9...0.95 (l) of low-speed blue-sensitive silver iodobromide emulsion (A (II nmol%), 1.99 of gelatin and 1
, 84 (l of α-[4-(1-benzyl-2-]]nyl-3,5-dioxo-1,24-triaziridinyl)]-]9-pivaloyl-2-chloro5
, 4-G-side-amylphenoxy)butanamide]acetanilide (hereinafter referred to as yellow coupler (Y-1)) is dissolved therein.
層１０・・・１．２ｇの高感度単分散青感光性沃臭化銀
乳剤（ＡＩＪＩ；６モル％）、２．０ｇのゼラチン並び
にｏ、ｎｅｇのイエローカプラー（Ｙ−１）を溶解した
０、 ２３９のＤＢＰを含有する高感度青感光性ハロゲ
ン化銀乳剤層。Layer 10...1.2g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (AIJI; 6 mol%), 2.0g of gelatin, and o, neg yellow coupler (Y-1) dissolved in 0 , a highly sensitive blue-sensitive silver halide emulsion layer containing a DBP of 239.
ＩＩ １１−・・ゼラチンからなる第２保護層。II 11--Second protective layer made of gelatin.
１１１２・・・２．３ｇのゼラチンを含有する第１保護
層。1112...First protective layer containing 2.3 g of gelatin.
上記試料Ｎ００１において、層６および７のマゼンタカ
プラー（Ｍ−１）および（Ｍ−２＞を本発明の例示マゼ
ンタカプラー１．２，４．．１０゜１８．２０．２１，
２３，３１．３２．３７゜３９．４４．６１．６３．６
５および６８にそれぞれ代えた（等モル量）以外は同様
にして試料ＮＯ１２〜１８を作製した。In the above sample N001, the magenta couplers (M-1) and (M-2> of layers 6 and 7 were replaced with the exemplary magenta couplers of the present invention 1.2, 4..10°18.20.21,
23, 31.32.37゜39.44.61.63.6
Samples Nos. 12 to 18 were prepared in the same manner except that they were replaced with Nos. 5 and 68 (equimolar amounts).
これらの試料をピースに裁断し、常法に従って模型露光
を与えたものを用い、次の工程に従ってピース用処理装
置を用いて処理（以下、手現処理と称する）を行った。These samples were cut into pieces, subjected to model exposure according to a conventional method, and processed using a piece processing device according to the following steps (hereinafter referred to as hand processing).
処理工程 処理温度（’Ｃ） 槽数 処理時間１、発
色現像 ３７．８ １槽 ３分１５秒２、漂
白定着 ３７．８ １槽 ３分３０秒（但し
、漂白定着液のｐＨは下記の表−１の如くとした。）
３、アルカリ浴 ３０〜３４ ２槽 ３分３０秒
（但し、アルカリ浴のＩＩＨは下記表−１の如くとした
。）
４、安 定 ３０〜３４ １槽 ２分１０秒
５、乾 燥
発色現像液、漂白定着液、アルカリ浴液及び安定液は以
下のものを使用した。Processing process Processing temperature ('C) Number of tanks Processing time 1, color development 37.8 1 tank 3 minutes 15 seconds 2, bleach-fixing 37.8 1 tank 3 minutes 30 seconds (However, the pH of the bleach-fix solution is as shown in the table below. -1) 3. Alkaline bath 30-34 2 tanks 3 minutes 30 seconds (However, the IIH of the alkaline bath was as shown in Table-1 below.) 4. Stable 30-34 1 tank 2 minutes 10 seconds 5, drying The following color developing solution, bleach-fixing solution, alkaline bath solution and stabilizing solution were used.
［発色現像液］
亜硫酸カリウム ５・Ｏｇｌは２０
％硫酸を用いてｐＨ１０，０６に調整した。[Color developer] Potassium sulfite 5.Ogl is 20
The pH was adjusted to 10.06 using % sulfuric acid.
［漂白定着液］
さらに銀粉を加え、エチレンジアミンテトラ酢酸第２鉄
ジアンモニウム塩を還元し、エチレンジアミンテトラ酢
酸第１鉄ジアンモニウム塩が４゜生成するようにして再
びｐＨを表−１になるように調整した。[Bleach-fix solution] Further add silver powder to reduce the ferric diammonium salt of ethylenediaminetetraacetate to produce 4° of ferrous diammonium salt of ethylenediaminetetraacetate, and adjust the pH to Table 1 again. It was adjusted.
［アルカリ浴液］
［安定液１
表−１
上記に従って感光材料試料を処理し、処理後゛の試料に
おける最高ｌｌ１Ｉ部の残留銀１ （ｍｏ／ ｄｆ）を
蛍光ＸＩ！法により測定した。さらに、シアン色素濃度
をサクラ光電瀧度計ＰＤＡ−６５（小西六写真工業■製
）を用いて測定した後この値を用い、同じ試料を常法に
従い３％の赤面塩溶液にて空温で３分間処理した後のシ
アン色素濃度を１００とすることにより復色率を計算し
た。また、未露光部のマゼンタ色素濃度（Ｍ−スティン
）をＰＤＡ−６５で同様に測定した。[Alkaline bath solution] [Stabilizing solution 1 Table-1 A photosensitive material sample is processed according to the above, and residual silver 1 (mo/df) of the maximum 111 part in the sample after processing is determined by fluorescence XI! It was measured by the method. Furthermore, the cyan dye concentration was measured using a Sakura Photoelectric Water Meter PDA-65 (manufactured by Konishi Roku Photo Industries, Ltd.), and using this value, the same sample was incubated in a 3% blush salt solution at air temperature according to a conventional method. The color restoration rate was calculated by setting the cyan dye density after 3 minutes of processing to 100. Furthermore, the magenta dye density (M-stin) of the unexposed area was similarly measured using PDA-65.
結果をまとめて表−２に示ず。The results are not summarized in Table 2.
表−２
表 −２（続き）
表−２の結果から明らかなように、漂白定着液で脱銀処
理の後ｐＨ８，０以上のアルカリ浴で処理したものは脱
銀性およびシアン色素の復色不良が大幅に改良されてい
る。しかしながら、マゼンタカプラーとして本発明のカ
プラーを用いていない試料Ｎ０１１を処理した実験では
マゼンタスティンが発生している。これに対し本発明の
マゼンタカプラーを含有した試料Ｎ００２〜１８を脱銀
処理した後ｐＨ８，０以上のアルカリ浴で処理した実験
では、マゼンタスティンの発生も良好に抑えられ、脱銀
性に優れ復色不良も顕著に改良されている。Table 2 Table 2 (Continued) As is clear from the results in Table 2, those treated with an alkaline bath with a pH of 8.0 or higher after desilvering with a bleach-fix solution have improved desilvering properties and restoration of cyan dye. Defects have been greatly improved. However, in an experiment in which sample N011 was processed without using the coupler of the present invention as a magenta coupler, magentastin was generated. On the other hand, in an experiment in which samples Nos. 002 to 18 containing the magenta coupler of the present invention were desilvered and then treated in an alkaline bath with a pH of 8.0 or higher, the generation of magentastin was well suppressed and the recovery was excellent with excellent desilvering properties. Color defects have also been significantly improved.
実施例−２ 以下のアルカリ浴を調製した。Example-2 The following alkaline bath was prepared.
［アルカリ浴液］
上記アルカリ浴を用いて、漂白定着液として実施例−１
のｐ）ｌ ６．５を用い、さらに実施例−１の感光材料
試料Ｎ０１１および２を用いた以外は、実施例−１の同
様の実験および評価を行った。[Alkaline bath solution] Example-1 as a bleach-fix solution using the above alkaline bath
Experiments and evaluations were conducted in the same manner as in Example-1, except that p)l of 6.5 was used and photosensitive material samples N011 and 2 of Example-1 were used.
さらにアルカリ浴については、開口面積１５ｃｆ（アル
カリ浴１２当たりの開口面積）のガラスビーカーに５０
℃で５日間、１０日間それぞれ保存した後、各保存アル
カリ浴を用いて上記と同様にして処理し、アルカリ浴経
時保存後の劣化を見た。Furthermore, regarding the alkaline bath, 50
After being stored at ℃ for 5 days and 10 days, each sample was treated in the same manner as above using each storage alkaline bath, and the deterioration after storage in the alkaline bath over time was observed.
結果を併せて表−３に示す。The results are also shown in Table 3.
表−３の結果から明らかなように、本発明外のマゼンタ
カプラーを含有した試料をｐＨａ、ｏ以上のアルカリ浴
で処理した実験・２−２〜２−５では経時後も復色不良
の改良効果があるがマゼンタスティンの発生も大きい。As is clear from the results in Table 3, in experiments 2-2 to 2-5 in which samples containing magenta couplers other than the present invention were treated in an alkaline bath with a pH of 0 or higher, poor color recovery was improved even after aging. Although it is effective, magentastin is generated a lot.
また、実験２−１では復色不良も大きくマゼンタスティ
ンも大きい。これに対し、本発明のマゼンタカプラーを
含有した試料をｐ）（８，０以上のアルカリ浴で処理し
た実験２−７〜２−１８では、経時後も復色不良の改良
効果も大きくマゼンタスティンも良好に抑えられている
。なお、実験２−１９の如くアルカリ浴に緩衝剤を含有
させない場合、アルカリ浴調製直後では復色不良の改良
効果およびマゼンタスティンの抑制効果は満足できるが
、経時と共に特に復色率が不充分となり安定した写真画
像が得られないことがわかる。Furthermore, in Experiment 2-1, the color recovery defect was large and the magenta tin was large. In contrast, in Experiments 2-7 to 2-18, in which samples containing the magenta coupler of the present invention were treated in an alkaline bath of p) In addition, when the alkaline bath does not contain a buffer as in Experiment 2-19, the effect of improving poor recoloring and suppressing magentastin is satisfactory immediately after preparing the alkaline bath, but as time passes, In particular, it can be seen that the color recovery rate is insufficient and a stable photographic image cannot be obtained.
実施例−３
実施例−１における処理工程、即ち１０発色現像、２．
漂白定着、３．アルカリ浴、４．安定の各処理工程を下
記表−４の如くの処理工程に代え表−４−２
上記処理工程で用いた処理液において、漂白定着液は実
施例−１におけるｐ）Ｉ ６．５のものを用い、アルカ
リ浴は同様にｐ）ｌ ＩＱ、Ｏのものを用いた。さらに
以下の漂白液および定着液以外のものは、実施例−１の
同様のものである。Example-3 Processing steps in Example-1, namely 10 color development, 2.
Bleach fixing, 3. Alkaline bath, 4. Each stable processing step was replaced with a processing step as shown in Table 4 below. Table 4-2 Among the processing solutions used in the above processing steps, the bleach-fix solution was one with p)I 6.5 in Example-1. The same alkaline bath was used as p)l IQ,O. Furthermore, the following components other than the bleaching solution and fixing solution were the same as those in Example-1.
［漂白液］
なお、実施例−１と同様銀粉を加え、エチレンジアミン
テトラ酢酸第２鉄ジアンモニウム塩を還元し、エチレン
ジアミンテトラ酢酸第１鉄ジアンモニウム塩が４５９に
なるようにした。[Bleaching Solution] As in Example 1, silver powder was added to reduce the ferric diammonium salt of ethylenediaminetetraacetate so that the ferrous diammonium salt of ethylenediaminetetraacetate became 459.
［定着液］
上記の処理工程以外は実施例−１と同様の実験を行い、
復色率、脱銀性およびマゼンタスティンを調べた。なお
、用いた感光材料試料は実施例−１のＮ０９１とＮ０９
２である。結果を表−５に示す表−５の結果から明らか
なように、脱銀処理を種々変化させても本発明のアルカ
リ浴処理を施すことにより復色不良が顕著に改良されて
いる。しかしながら本発明外のマゼンタカプラーを含有
した感光材料試料を用いた実験ではマゼンタスティンが
大きい。これに対し本発明のマゼンタカプラーを含有し
た試料では復色不良の改良効果を維持してマゼンタステ
ィンも良好に抑えられていることがわかる。[Fixer] An experiment similar to Example 1 was conducted except for the above processing steps,
The recoloring rate, desilvering property and magentastin were examined. The photosensitive material samples used were N091 and N09 of Example-1.
It is 2. The results are shown in Table 5. As is clear from the results in Table 5, even if the desilvering treatment was variously changed, poor color restoration was significantly improved by applying the alkali bath treatment of the present invention. However, in experiments using light-sensitive material samples containing magenta couplers other than those of the present invention, magentastin was large. On the other hand, it can be seen that in the sample containing the magenta coupler of the present invention, the effect of improving color restoration defects was maintained and magentastin was well suppressed.
実施例−４
上記実施例−１において、感光材料試料ＮＯ１２を用い
、漂白定着液のｌ）Ｈを６．５、アルカリ浴のｐｌ−１
１０，０とし、さらに漂白定着液中のアミノポリカルボ
ン酸としてエチレンジアミンテトラ酢酸第２鉄ジアンモ
ニウム塩に代えて下記表−６に示す有Ｉｌ！酸第２鉄錯
塩（一般式［Ｉ］、 ［Ｉ［］の化合物）を表−６に
示す濃度で用いた以外は実施例−１と同様にして実験を
行った。結果を併せて表−６に示す。Example-4 In Example-1 above, photosensitive material sample No. 12 was used, l)H of the bleach-fix solution was 6.5, and pl-1 of the alkaline bath.
10.0, and furthermore, in place of the ferric diammonium salt of ethylenediaminetetraacetic acid as the aminopolycarboxylic acid in the bleach-fix solution, Il! shown in Table 6 below was used. An experiment was conducted in the same manner as in Example 1, except that the acid ferric complex salt (compound of general formula [I], [I[]) was used at the concentration shown in Table 6. The results are also shown in Table 6.
表−６
表−６の結果から明らかなように、漂白定着液に用いる
漂白剤の種類および濃度を変化させても本発明の効果が
得られることがわかる。Table 6 As is clear from the results in Table 6, it can be seen that the effects of the present invention can be obtained even if the type and concentration of the bleach used in the bleach-fix solution are changed.
実施例−５
実施例−４の実験Ｎｏ、４−２において、さらに下記表
−７に示す添加剤をアルカリ浴１１中に１０９添加した
以外は同様にして実験を行った。Example 5 An experiment was conducted in the same manner as in Experiment No. 4-2 of Example 4, except that 10 9 of the additives shown in Table 7 below were added to the alkaline bath 11.
結果を併せて表−７に示す。The results are also shown in Table-7.
ｅ＠＠＠＠＠ｆＥ）＠＠＠＠＠０＠
表−７の結果から明らかなように、本発明の処理方法に
おいて、アルカリ浴に、鉄との安定度定数が６以上のキ
レート剤を含有させた場合、またアミノポリカルボン酸
第２鉄錯塩を一定濃度以上で含有させた場合、さらに酸
化剤を含有させた場合において、それぞれ本発明に係る
復色不良の改良効果がさらに顕著であることがわかる。e@@@@@@fE) @@@@@0@ As is clear from the results in Table 7, in the treatment method of the present invention, a chelating agent with a stability constant of 6 or more with iron is added to the alkaline bath. The improvement effect of poor color recovery according to the present invention is even more remarkable when the ferric aminopolycarboxylic acid complex salt is contained at a certain concentration or more, and when an oxidizing agent is further contained. I understand that.
実施例−６
実施例−１において、感光材料試料Ｎ００２を用いて、
感光材料の膜厚（膜厚変化はゼラチン量のみ変化させた
）および塗布銀量を変化させて下記表−８に示す感光材
料を用いた以外は処理Ｎ０１１−４と同様にして実験を
行った。但し、アルカリ浴を用いないものを比較として
実験した。結果を併せて表−８に示す。Example-6 In Example-1, using photosensitive material sample N002,
Experiments were conducted in the same manner as in Processing No. 011-4, except that the film thickness of the photosensitive material (only the amount of gelatin was changed to change the film thickness) and the amount of coated silver, and the photosensitive materials shown in Table 8 below were used. . However, for comparison, an experiment was conducted in which no alkaline bath was used. The results are also shown in Table-8.
表−８
表−８の結果から明らかなように、本発明の処理方法に
おいては、感光材料の膜厚、塗布銀量に大きく影響を受
けなく良好な復色不良及びマゼンタスティン改良の効果
が得られるのは膜厚１３μ−以上である。（膜厚１３μ
園以下では復色不良が小さいがマゼンタスティンは大き
い）膜厚１６μｍ以上の場合に特に大きな改良結果が得
られ、塗布銀」は多い程大きな改良効果が得られること
がわかる。Table 8 As is clear from the results in Table 8, the processing method of the present invention is not significantly affected by the film thickness of the light-sensitive material or the amount of coated silver, and is effective in improving color reproduction defects and magentastin. The film thickness is 13μ or more. (film thickness 13μ
It can be seen that a particularly large improvement result is obtained when the film thickness is 16 μm or more, and that the larger the amount of coated silver, the greater the improvement effect.
Claims (1)
処理した後、少なくとも脱銀工程を含む処理を施すハロ
ゲン化銀カラー写真感光材料の処理方法において、前記
感光材料が下記一般式［Ｍ− I ］で示されるマゼンタ
カプラーを含有し、前記脱銀工程に、漂白剤として下記
一般式［ I ］および一般式［II］で示される化合物か
ら選ばれる少なくとも１つの化合物の第２鉄錯塩を使用
し、かつ前記脱銀工程後、ｐＨ８．０以上で且つ緩衝剤
を含有するアルカリ浴で処理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［Ｍ− I ］ ▲数式、化学式、表等があります▼ ［式中、Ｚは含窒素複素環を形成するに必要な非金属原
子群を表し、該Ｚにより形成される環は置換基を有して
もよい。Ｘは水素原子又は発色現像主薬の酸化体との反
応により離脱し得る基を表す。またＲは水素原子又は置
換基を表す。］一般式［ I ］ ▲数式、化学式、表等があります▼ 一般式［II］ ▲数式、化学式、表等があります▼ ［式中、Ｌはアルキレン基、シクロアルキレン基、フェ
ニレン基、−Ｌ＿８−Ｏ−Ｌ＿８−Ｏ−Ｌ＿８−または
−Ｌ＿９−Ｚ−Ｌ＿９−を表す。ここでＺは、＞Ｎ−Ｌ
＿１＿０−Ｒ＿８、▲数式、化学式、表等があります▼
、 ＞Ｎ−Ｒ１＿０または▲数式、化学式、表等があります
▼を表す。 Ｌ＿１〜Ｌ＿１＿３はそれぞれアルキレン基を表す。Ｒ
＿１〜Ｒ＿１＿１はそれぞれ水素原子、水酸基、カルボ
ン酸基（その塩を含む）またはホスホン酸基（その塩を
含む）を表す。但し、Ｒ＿１〜Ｒ＿４のうちの少なくと
も２つはカルボン酸基（その塩を含む）またはホスホン
酸基（その塩を含む）であり、またＲ＿５〜Ｒ＿７のう
ちの少なくとも１つはカルボン酸基（その塩を含む）ま
たはホスホン酸基（その塩を含む）である。］[Scope of Claims] A method for processing a silver halide color photographic material, in which the exposed silver halide color photographic material is subjected to color development processing and then subjected to a treatment including at least a desilvering step, wherein the light-sensitive material is A second compound containing a magenta coupler represented by the formula [M-I] and at least one compound selected from the compounds represented by the following general formula [I] and general formula [II] is used as a bleaching agent in the desilvering step. 1. A method for processing a silver halide color photographic material, which uses an iron complex salt and, after the desilvering step, is treated with an alkaline bath having a pH of 8.0 or higher and containing a buffer. General formula [M-I] ▲ Numerical formulas, chemical formulas, tables, etc. It may have. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, L is an alkylene group, cycloalkylene group, phenylene group, -L_8- Represents O-L_8-O-L_8- or -L_9-Z-L_9-. Here Z is >NL
＿１＿０－R＿８、▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ＞N-R1_0 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. L_1 to L_1_3 each represent an alkylene group. R
_1 to R_1_1 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt), or a phosphonic acid group (including its salt). However, at least two of R_1 to R_4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R_5 to R_7 is a carboxylic acid group (including salts thereof). (including its salts) or a phosphonic acid group (including its salts). ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11221387A JPS63276051A (en) | 1987-05-08 | 1987-05-08 | Method for processing silver halide color photographic sensitive material with which defective color reproduction is suppressed and stable photographic performance is obtained |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11221387A JPS63276051A (en) | 1987-05-08 | 1987-05-08 | Method for processing silver halide color photographic sensitive material with which defective color reproduction is suppressed and stable photographic performance is obtained |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63276051A true JPS63276051A (en) | 1988-11-14 |
Family
ID=14581084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11221387A Pending JPS63276051A (en) | 1987-05-08 | 1987-05-08 | Method for processing silver halide color photographic sensitive material with which defective color reproduction is suppressed and stable photographic performance is obtained |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63276051A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0859276A1 (en) * | 1997-02-13 | 1998-08-19 | Eastman Kodak Company | Cyan dye recovery using ferric aminopolycarboxylic acid bleaching composition |
-
1987
- 1987-05-08 JP JP11221387A patent/JPS63276051A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0859276A1 (en) * | 1997-02-13 | 1998-08-19 | Eastman Kodak Company | Cyan dye recovery using ferric aminopolycarboxylic acid bleaching composition |
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