EP0358037A2 - Method for processing a colour-photographic material - Google Patents
Method for processing a colour-photographic material Download PDFInfo
- Publication number
- EP0358037A2 EP0358037A2 EP89115447A EP89115447A EP0358037A2 EP 0358037 A2 EP0358037 A2 EP 0358037A2 EP 89115447 A EP89115447 A EP 89115447A EP 89115447 A EP89115447 A EP 89115447A EP 0358037 A2 EP0358037 A2 EP 0358037A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleach
- fixing
- solution
- acid
- developer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000012545 processing Methods 0.000 title claims abstract description 12
- -1 silver halide Chemical class 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004061 bleaching Methods 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 230000008929 regeneration Effects 0.000 claims abstract description 7
- 238000011069 regeneration method Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 125000004429 atom Chemical group 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 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 claims description 3
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 3
- 229940045105 silver iodide Drugs 0.000 claims description 3
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- 125000004442 acylamino group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 239000007844 bleaching agent Substances 0.000 abstract description 10
- 239000002244 precipitate Substances 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 235000002639 sodium chloride Nutrition 0.000 description 20
- 239000010410 layer Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 238000011161 development Methods 0.000 description 9
- 230000018109 developmental process Effects 0.000 description 9
- 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 8
- 239000008139 complexing agent Substances 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 150000004682 monohydrates Chemical class 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003585 thioureas Chemical class 0.000 description 4
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 3
- GTOOAPLRWMOITA-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methylanilino)ethyl hydrogen sulfate Chemical compound OS(=O)(=O)OCCN(CC)C1=CC=C(N)C(C)=C1 GTOOAPLRWMOITA-UHFFFAOYSA-N 0.000 description 3
- VFNOFXXKKALBEP-UHFFFAOYSA-N 4-(3,4-dimethyl-5-oxo-4h-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1C(C)C(C)=NN1C1=CC=C(S(O)(=O)=O)C=C1 VFNOFXXKKALBEP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- PJAOJNOBFQOBGE-UHFFFAOYSA-L azanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(2+) Chemical compound [NH4+].[Fe+2].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O PJAOJNOBFQOBGE-UHFFFAOYSA-L 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- QVLXDGDLLZYJAM-UHFFFAOYSA-N 2,5-dioctylbenzene-1,4-diol Chemical compound CCCCCCCCC1=CC(O)=C(CCCCCCCC)C=C1O QVLXDGDLLZYJAM-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- XXAXVMUWHZHZMJ-UHFFFAOYSA-N Chymopapain Chemical compound OC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- SHAAJFLFXFNNSF-UHFFFAOYSA-L disodium;acetic acid;cyclohexane-1,1-diamine;diacetate Chemical compound [Na+].[Na+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O.NC1(N)CCCCC1 SHAAJFLFXFNNSF-UHFFFAOYSA-L 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 238000003860 storage Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- SUVZGLSQFGNBQI-UHFFFAOYSA-N 2,5-bis(sulfanyl)hexanedioic acid Chemical compound OC(=O)C(S)CCC(S)C(O)=O SUVZGLSQFGNBQI-UHFFFAOYSA-N 0.000 description 1
- PDHFSBXFZGYBIP-UHFFFAOYSA-N 2-[2-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical compound OCCSCCSCCO PDHFSBXFZGYBIP-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
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical compound C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- QTFFUUQJZHEORK-UHFFFAOYSA-N 5,6-dihydroxybenzene-1,2,4-trisulfonic acid Chemical compound OC1=C(O)C(S(O)(=O)=O)=C(S(O)(=O)=O)C=C1S(O)(=O)=O QTFFUUQJZHEORK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ISWQCIVKKSOKNN-UHFFFAOYSA-L Tiron Chemical compound [Na+].[Na+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O ISWQCIVKKSOKNN-UHFFFAOYSA-L 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- PGYRJIWGRQEVMB-UHFFFAOYSA-N [Fe+3].C(C)(=O)ON(CCN(OC(C)=O)OC(C)=O)OC(C)=O Chemical compound [Fe+3].C(C)(=O)ON(CCN(OC(C)=O)OC(C)=O)OC(C)=O PGYRJIWGRQEVMB-UHFFFAOYSA-N 0.000 description 1
- CUMZMPIJUWXMLU-UHFFFAOYSA-N [Na].[Na].C=CC Chemical group [Na].[Na].C=CC CUMZMPIJUWXMLU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 description 1
- LRSAWRZHGQQHBJ-UHFFFAOYSA-N acetic acid;benzene-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NC1=CC=CC=C1N LRSAWRZHGQQHBJ-UHFFFAOYSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical class CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JINBYESILADKFW-UHFFFAOYSA-N aminomalonic acid Chemical compound OC(=O)C(N)C(O)=O JINBYESILADKFW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- VTYVIFFJJXAHTG-UHFFFAOYSA-M azanium;sodium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [NH4+].[Na+].[O-]S([O-])(=O)=S VTYVIFFJJXAHTG-UHFFFAOYSA-M 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- DGJMPUGMZIKDRO-UHFFFAOYSA-N cyanoacetamide Chemical class NC(=O)CC#N DGJMPUGMZIKDRO-UHFFFAOYSA-N 0.000 description 1
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DRTCFOYIJNCGCX-UHFFFAOYSA-N ethene;iron(3+) Chemical group [Fe+3].C=C DRTCFOYIJNCGCX-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical class CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229940083761 high-ceiling diuretics pyrazolone derivative Drugs 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- WMBCUXKYKVTJRF-UHFFFAOYSA-N n-methyl-1-(oxan-4-yl)methanamine Chemical compound CNCC1CCOCC1 WMBCUXKYKVTJRF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical class NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 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
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- QWSDEEQHECGZSL-UHFFFAOYSA-M sodium;acetaldehyde;hydrogen sulfite Chemical compound [Na+].CC=O.OS([O-])=O QWSDEEQHECGZSL-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 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
- 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 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
Definitions
- the invention relates to a method for processing an exposed, color-photographic, light-sensitive silver halide material by developing, bleach-fixing, washing or stabilizing and drying, the use of compounds coupling to colorless reaction products in the bleach-fixing solution to prevent the precipitation of poorly soluble residues.
- the developer solution used in the process according to the invention is free of benzyl alcohol; the pH value of the bleach-fix solution, which contains certain bleach accelerators, is ⁇ 7.
- the basic stages of processing color photosensitive materials generally include a color development stage and a silver removal stage. At Reversal materials are followed by an upstream black / white development and a second exposure.
- the silver produced during development is oxidized with a bleaching agent and dissolved with a fixing agent.
- the removal of the silver can be carried out in two stages with a bleaching bath and a fixing bath or in one stage with a bleach-fixing bath.
- the bleaching process is predominantly carried out using an iron (III) ion complex salt (for example aminopolycarboxylic acid iron (III) complex salt, in particular iron (III) ethylene diamine tetraacetate complex salt).
- iron (III) ion complex salt for example aminopolycarboxylic acid iron (III) complex salt, in particular iron (III) ethylene diamine tetraacetate complex salt.
- Iodoso compounds, persulfates, cobalt (III) ion complex salts and cerium IV ion complex salts are also suitable.
- iron (III) ion complex salts have a comparatively low oxidizing power. There was therefore a need to increase the bleaching power of the bleach-fixing solution containing an iron (III) ion complex salt as a bleaching agent.
- bleach accelerators examples include thiourea derivatives (JP-OS 8506/70, US Pat. No. 3,706,561), selenourea derivatives (JP-OS 280/71), mercapto compounds with a five-membered ring (GB-PS 1 138 842), thiazole derivatives and thiadiazole derivatives ( CH-PS 336 257).
- EP-A-0 270 217 describes a processing method in which the developer solution is free of benzyl alcohol and the pH of the bleach-fixing solution, which contains an iron (III) complex salt and a bleach accelerator, is between 3 and 6.8.
- the bleaching agent oxidizes the developer substance.
- the resulting water-insoluble developer oxidation products make a significant contribution to the contamination of the bleach-fix bath.
- the object of the invention was now to develop a method in which the poorly soluble precipitates are avoided.
- Another task was to develop a process that would have a bleach-fix time of less than 1 min. allowed.
- the invention relates to a method for processing imagewise exposed color photographic silver halide material which comprises at least three light-sensitive silver halide emulsion layers of different spectral sensitivity on a layer support, to which a cyan coupler, a magenta coupler and a yellow coupler are assigned, by developing, bleach-fixing, washing or stabilizing and drying, the aqueous developer solution is free of benzyl alcohol, the pH value of the bleach-fixing solution which contains an iron (III) complex salt is ⁇ 7 and the bleach-fixing solution is a compound of the general formula (I) wherein Z the atoms required to complete an optionally further substituted heterocyclic ring, and R1 is hydrogen, an alkali atom mean, characterized in that the bleach-fixing solution contains a coupler with an activated methylene group in which a hydrogen is replaced by alkyl, cycloalkyl, aryl or aralkyl and reacts with the oxidation product of the color developer to form colorless reaction products.
- Suitable compounds for the process according to the invention are, for example
- colorless coupling pyrazolones of the general formula II are suitable: in which mean: R2, R3 alkyl, alkoxy, aryl, carboxyl, carboxyalkyl, R4 halogen, -CN, -CF3, acylamino, sulfamoyl, alkylsulfamyl, -SO3H, carboxy, carboxyalkyl n 0-3.
- the pH of the bleach-fixing solution is 4.0-6.9, preferably 4.7-6.2.
- the bleaching fixation is preferably completed in a period of between 10 and 45 seconds.
- the temperatures suitable for the bleach-fixing according to the invention are in a range from 20 to 40 ° C., preferably between 33 and 38 ° C.
- the amount of the compounds of formula I in the bleach-fixing bath varies depending on the kind of the processing solution, the kind of the photographic material to be processed, the processing temperature, the time required to carry out the desired processing, etc. However, an amount is 0.1-10 g per liter of bleach-fix bath, with 0.5 to 3 g / l being preferred. In general, the best range is determined by simple preliminary tests.
- the compound to be used according to the invention can be added directly to the bleach-fix bath or introduced through an upstream conditioning bath.
- the compounds coupling to colorless reaction products are present in the bleach-fixing bath in concentrations of 0.1 to 30 g / l, preferably 1 to 10 g / l.
- the regeneration rate of the bleach-fix solution is 50 to 110 ml per m2 of photographic material.
- Suitable iron (III) ion complex salts are complexes of iron (III) ions and a chelating agent such as an aminopolycarboxylic acid or a salt thereof, in particular an alkali metal salt or ammonium salt.
- Typical examples of chelating agents are ethylenediaminetetraacetic acid; Disodium ethylenediaminetetraacetate; Diammonium ethylenediaminetetraacetate; Tetra (trimethylammonium) ethylenediaminetetraacetate; Tetrapotassium ethylenediaminetetraacetate; Tetrasodium ethylenediaminetetraacetate; trisodium ethylenediaminetetraacetate; Diethylenetriaminepentaacetic acid; Pentasodium diethylenetriaminepentaacetate; Ethylenediamine-N- (ß-hydroxyethyl) -N, N ′, N′-triacetic acid; Trisodium ethylenediamine-N- ( ⁇ -hydroxyethyl) -N, N ′, N′-triacetate; Triammonium ethylenediamine-N- ( ⁇ -hydroxyethyl) -N, N ′, N′-triacetate; Propyl
- the iron (III) ion complex salt can be used in the form of the complex salt or prepared in situ in the bleach-fix bath. Suitable cations are alkali cations and ammonium; the latter is preferred.
- the bleach-fixing solution of the present invention may contain rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and the like in addition to the bleaching agents.
- rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and the like in addition to the bleaching agents.
- additives which have a pH buffering action such as inorganic acids, organic acids or the salts thereof, which are known for use in conventional bleach-fixing solutions (for example boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid , Phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.) can be added.
- inorganic acids, organic acids or the salts thereof which are known for use in conventional bleach-fixing solutions
- conventional bleach-fixing solutions for example boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid , Phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
- customary fixing agents ie water-soluble agents which dissolve silver halide, such as thiosulfate (for example sodium thiosulfate, Ammonium thiosulfate, ammonium sodium thiosulfate, potassium thiosulfate, etc.); Thiocyanates (e.g. sodium thiocyanate; ammonium thiocyanate; potassium thiocyanate, etc.); Thioether compounds (e.g. ethylene bisthioglycolic acid, 3,6-dithia-1,8-octanediol, etc.); and thioureas can be used alone or in a combination of two or more.
- special bleach-fixing agents containing a combination of a fixing agent and a large amount of a halide compound such as potassium iodide can also be used.
- the ferric ion complex salt is usually present in an amount of 0.1 to 1 mol / l.
- the amount of the fixing agent is generally 0.2 to 4 mol per liter of the bleach-fixing solution.
- Bleach-fix solutions can also contain preservatives such as sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, aldehyde-bisulfite adducts (e.g. acetaldehyde sodium bisulfite adduct), etc.
- sulfites e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.
- hydroxylamine hydrazine
- aldehyde-bisulfite adducts e.g. acetaldehyde sodium bisulfite adduct
- various optical brighteners, defoamers, surfactants, organic solvents (e.g. methanol) and known bleach-fix accelerating agents e.g. polyamine compounds (US Pat. No. 3,578,457), thioureas (US Pat.
- the substances used in the development process according to the invention are p-phenylenediamines and in particular N, N-dialkyl-p-phenylenediamines, in which the alkyl groups and the aromatic nucleus are substituted or unsubstituted.
- N, N-diethyl-p-phenylenediamine hydrochloride 4-N, N-diethyl-2-methylphenylenediamine hydrochloride, 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate monohydrate, 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate and 4-N, N-diethyl-2,2'-methanesulfonylaminoethylphenylenediamine hydrochloride.
- the color developer preferably contains complexing agents in an effective amount for complexing iron ions and complexing agents in an effective amount for complexing calcium ions, both functions also being able to be performed by a single substance.
- the developer is particularly suitable for rapid processing with a development time of, for example, 45 seconds, the development being followed by bleaching fixation and washing or stabilization.
- the developer contains no benzyl alcohol.
- the color developer is essentially free of bromide. This means that the bromide ion can contain a concentration that is sensitometrically ineffective. This amount of bromide ions does not need to be added to the fresh developer, but can develop during the development process from the material to be developed. Their amount should be limited to less than 30 mg / l.
- the color developer according to the invention preferably contains chloride ions, in particular in an amount of 1 to 5 g / l.
- Suitable complexing agents for complexing calcium ions are, for example, aminopolycarboxylic acids, which are well known per se.
- aminopolycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), 1,3-diamino-2-hydroxypropyltetraacetic acid, diethylenetriaminepentaacetic acid, N, N'-bis- (2-hydroxybenzyl) -ethylenediamine-N, N'-diesiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid,
- calcium complexing agents are polyphosphates, phosphonic acids, aminopolyphosphonic acids and hydrolyzed polymaleic anhydride, e.g. Sodium hexametaphosphate, 1-hydroxyethane-1,1-diphosphonic acid, aminotrismethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid. 1-hydroxyethane-1,1-diphosphonic acid also acts as an iron complexing agent.
- iron complexing agents are, for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid and 3,4,5-trihydroxybenzoic acid.
- the iron complexing agent is used in amounts of about 0.02 to about 0.2 moles per mole of developer substance.
- the developer used in the process according to the invention is in particular an aqueous alkaline solution which has a pH above 7, in particular from 9 to 13.
- known buffer substances such as alkali carbonates and alkali phosphates are used.
- antioxidants are e.g. Hydroxylamine and diethylhydroxylamine and sulfites, such as preferably used in an amount up to 5 g / l.
- Optical brighteners e.g. Polyalkylene glycols, surfactants, stabilizers, e.g. heterocyclic mercapto compounds or nitrobenzimidazole and means for adjusting the desired pH.
- the silver halide emulsion layers of the color photographic recording material which is subjected to the processing method according to the invention be preferably consist of 80-100 mol% of silver chloride, 0-20 mol% of silver bromide and 0-2 mol% of silver iodide. 95-100 mol% of silver chloride, 0-5 mol% of silver bromide and 0-1 mol% of silver iodide are particularly preferred.
- the layer containing the cyan coupler is usually red, that which contains the magenta coupler is usually green and that which contains the yellow coupler is usually blue sensitized.
- the ready-to-use solutions can be prepared from the individual components or from so-called concentration, the individual components being dissolved in the concentrates in a much higher concentration.
- the concentrates are adjusted so that a so-called regenerator can be produced from them, ie a solution that has somewhat higher concentrations of the individual components than the ready-to-use solution, on the one hand, by further dilution and addition of a starter, preferably KCl, gives a ready-to-use solution and on the other hand, a developer solution in use is constantly added in order to replace the chemicals consumed during development or which have been dragged out of the developer solution by overflow or by the developed material.
- Chloride ions usually do not need to be added except for the freshly prepared developer, since chloride ions are released from the photographic material by the development.
- color photographic material can be completely bleached in less than 45 seconds with a low regeneration rate of 50-100 ml / m2 of photographic material.
- a mixture of a color developer solution and a low-sulfite bleach-fix bath is prepared that does not contain a white coupler.
- Composition of the color developer solution water 800 ml Ethylenediaminetetraacetic acid (EDTA) 3.0 g 4,5-dihydroxy-1,3-benzenedisulfonic acid, 0.3 g Disodium salt 2.0 g Sodium chloride 8.0 g Triethanolamine 5.0 ml N, N-diethyl-hydroxylamine, 85% by weight 5.0 g 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate monohydrate (CD3) Potassium carbonate 25.0 g fill up to 1 liter with water; pH 10
- Composition of the bleach-fix bath water 800 ml Ammonia solution, 25% by weight 3 ml 3-mercapto-1,2,4-triazole 1 g Sodium sulfite, si
- 250 ml of developer solution are added to 250 ml of bleach-fix bath with stirring.
- the pH is adjusted to pH 6.5 with acetic acid.
- An open beaker is used with the dimensions: Height 120 mm, Diameter 100 mm, Filling volume 500 ml mixture, Room temperature about 22 ° C.
- a mixture is prepared as in the comparative experiment, but containing 3,4-dimethyl-1- (4-sulfophenyl) -5-pyrazolone.
- composition of the color developer solution as a comparison test
- Composition of the bleach-fix bath water 800 ml Ammonia solution 25% by weight 3 ml 3-mercapto-1,2,4-triazole 1 g 3,4-dimethyl-1- (4-sulfophenyl) -5-pyrazolone 5 g Sodium sulfite, sicc. 2 g Ammonium thiosulfate 100 g Ammonium-iron-ethylenediaminetetraacetic acid 50 g make up to 1 liter with water. pH adjustment to pH 4.8 with acetic acid.
- the mixture is prepared and stored as in the comparative experiment.
- the residual silver-free bleach fixation using the method according to the invention is demonstrated within 45 seconds.
- a color photographic recording material which is suitable for the processing method according to the invention was produced by applying the following layers in the order given to a layer support on paper coated on both sides with polyethylene.
- the quantities given relate to 1 m2.
- the corresponding amounts of AgNO3 are given.
- 1st layer (substrate layer): 0.2 g gelatin 2nd layer (blue-sensitive layer): blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 ⁇ m) from 0.63 g AgNO3 with 1.38 g gelatin 0.95 g Yellow coupler Y 0.2 g White coupler W 0.29 g Tricresyl phosphate (CPM) 3rd layer (protective layer) 1.1 g gelatin 0.06 g 2,5-dioctyl hydroquinone 0.06 g Dibutyl phthalate (DBP) 4th layer (green-sensitive layer) green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 ⁇ m) from 0.45 g AgNO3 with) 1.08 g gelatin 0.41 g Purple coupler M 0.16 g Ethyl ⁇ - (3-t-butyl
- a step wedge is exposed on the photographic material described above and processed as follows: Color developer 45 s 35 ° C Bleach-fixer 45 s 25 ° C Watering 90 s 25 ° C Drying
- the individual processing baths had the following composition: Color developer water 800 ml Ethylenediaminetetraacetic acid (EDTA) 3.0 g 4,5-dihydroxy-1,3-benzenedisulfonic acid, disodium salt 0.3 g Sodium chloride 2.0 g Triethanolamine 8.0 g N, N-diethyl-hydroxylamine, 85% by weight 5.0 ml 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate monohydrate (CD3) 5.0 g Potassium carbonate 25.0 g fill up to 1 liter with water; pH 10 Bleach-fixer water 800 ml Ammonia solution, 25% by weight 5 ml 3-mercapto-1,2,4-triazole 1 g 3,4-dimethyl-1- (4-sulfophenyl) -5-pyrazolone 5 g Sodium sulfite, sicc.
- the exposed step wedge of the photographic material which was then processed as described above, was examined for residual silver in the image blackness using an infrared silver detector PM 8030 from Photo-Matic, Denmark.
- the processed sample contains no residual silver.
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Abstract
Mit einem Verfahren zur Verarbeitung von bildmäßig belichtetem farbfotografischem Silberhalogenidmaterial, durch Entwickeln, Bleichfixieren, Wässern oder Stabilisieren und Trocknen, wobei die wäßrige Entwicklerlösung benzylalkoholfrei ist, der pH-Wert der Bleichfixierlösung, die ein Eisen-(III)-Ionenkomplexsalz als Bleichmittel enthält, < 7 ist, die Bleichfixierlösung eine Verbindung der allgemeinen Formel I <IMAGE> worin Z die zur Vervollständigung eines gegebenenfalls weiter substituierten heterocyclischen Rings erforderlichen Atome und R¹ Wasserstoff, ein Alkaliatom bedeuten und einen Kuppler mit einer aktivierten Methylengruppe enthält, bei dem ein Wasserstoff durch Alkyl, Cycloalkyl, Cycloalkyl, Aryl oder Aralkyl ersetzt ist und mit dem Oxydationsprodukt des Farbentwicklers unter Bildung farbloser Reaktionsprodukte reagiert, wird eine restsilberfreie Bleichung bei niedriger Regenerierrate des Bleichfixierbades erreicht, ohne daß wasserunlösliche Ausfällungen auftreten.Using a process for processing imagewise exposed silver halide color photographic material, by developing, bleach-fixing, washing or stabilizing and drying, the aqueous developer solution being free of benzyl alcohol, the pH of the bleach-fixing solution containing an iron (III) ion complex salt as bleaching agent, < 7, the bleach-fixing solution is a compound of the general formula I <IMAGE> in which Z denotes the atoms required to complete an optionally further substituted heterocyclic ring and R 1 is hydrogen, an alkali atom and contains a coupler with an activated methylene group in which a hydrogen is substituted by alkyl, Cycloalkyl, cycloalkyl, aryl or aralkyl is replaced and reacts with the oxidation product of the color developer to form colorless reaction products, a residual silver-free bleaching is achieved at a low regeneration rate of the bleach-fixing bath without water-insoluble precipitates occurring en.
Description
Die Erfindung betrifft ein Verfahren zur Verarbeitung eines belichteten, farbfotografischen, lichtempfindlichen Silberhalogenidmaterials durch Entwickeln, Bleichfixieren, Wässern oder Stabilisieren und Trocknen, wobei unter Verwendung von zu farblosen Reaktionsprodukten kuppelnden Verbindungen in der Bleichfixierlösung die Ausfällung von schwerlöslichen Rückständen vermieden wird.The invention relates to a method for processing an exposed, color-photographic, light-sensitive silver halide material by developing, bleach-fixing, washing or stabilizing and drying, the use of compounds coupling to colorless reaction products in the bleach-fixing solution to prevent the precipitation of poorly soluble residues.
Die bei dem erfindungsgemäßen Verfahren verwendete Entwicklerlösung ist benzylalkoholfrei; der pH-Wert der Bleichfixierlösung, die bestimmte Bleichbeschleuniger enthält, ist < 7.The developer solution used in the process according to the invention is free of benzyl alcohol; the pH value of the bleach-fix solution, which contains certain bleach accelerators, is <7.
Die grundlegenden Stufen der Verarbeitung von lichtempfindlichen Farbmaterialien umfassen allgemein eine Farbentwicklungsstufe und eine Silber-Entfernungsstufe. Bei Umkehrmaterialien kommen noch eine vorgeschaltete Schwarz/Weiß-Entwicklung und eine Zweitbelichtung hinzu.The basic stages of processing color photosensitive materials generally include a color development stage and a silver removal stage. At Reversal materials are followed by an upstream black / white development and a second exposure.
In der letzten Stufe wird das bei der Entwicklung erzeugte Silber mit einem Bleichmittel oxidiert und mit einem Fixiermittel gelöst.In the last stage, the silver produced during development is oxidized with a bleaching agent and dissolved with a fixing agent.
Die Entfernung des Silbers kann zweistufig mit einem Bleichbad und einem Fixierbad oder einstufig mit einem Bleich-Fixier-Bad durchgeführt werden.The removal of the silver can be carried out in two stages with a bleaching bath and a fixing bath or in one stage with a bleach-fixing bath.
Die Bleichverarbeitung wird überwiegend unter Verwendung eines Eisen-(III)-Ionenkomplexsalzes (zum Beispiel Aminopolycarbonsäure-Eisen-(III)-Komplexsalz, insbesondere Eisen-(III)-ethylendiamintetraacetat-Komplexsalz) durchgeführt. Auch Iodosoverbindungen, Persulfate, Kobalt-(III)-Ionenkomplexsalze sowie Cer-IV-Ionenkomplexsalze sind geeignet.The bleaching process is predominantly carried out using an iron (III) ion complex salt (for example aminopolycarboxylic acid iron (III) complex salt, in particular iron (III) ethylene diamine tetraacetate complex salt). Iodoso compounds, persulfates, cobalt (III) ion complex salts and cerium IV ion complex salts are also suitable.
Jedoch weisen Eisen-(III)-Ionenkomplexsalze eine vergleichsweise geringe Oxidationskraft auf. Es bestand daher ein Bedürfnis, die Bleichkraft der Bleich-Fixier-Lösung, die als Bleichmittel ein Eisen-(III)-Ionenkomplexsalz enthält, zu erhöhen.However, iron (III) ion complex salts have a comparatively low oxidizing power. There was therefore a need to increase the bleaching power of the bleach-fixing solution containing an iron (III) ion complex salt as a bleaching agent.
Um die Bleichkraft einer Bleich-Fixier-Lösung, die ein Eisen-(III)-Ionenkomplexsalz wie Eisen-(III)-ethylendiamin tetraacetat als Bleichmittel enthält, zu erhöhen wurde vorgeschlagen, verschiedene Bleichbeschleuniger dem Verarbeitungsbad zuzusetzen.In order to increase the bleaching power of a bleach-fix solution which contains an iron (III) ion complex salt such as iron (III) ethylenediamine tetraacetate as a bleaching agent, it has been proposed to add various bleaching accelerators to the processing bath.
Beispiele für solche Bleichbeschleuniger umfassen Thioharnstoffderivate, (JP-OS 8506/70, US-PS 3 706 561), Selenoharnstoffderivate (JP-OS 280/71), Mercaptoverbindungen mit fünfgliedrigem Ring (GB-PS 1 138 842), Thiazolderivate und Thiadiazolderivate (CH-PS 336 257).Examples of such bleach accelerators include thiourea derivatives (JP-OS 8506/70, US Pat. No. 3,706,561), selenourea derivatives (JP-OS 280/71), mercapto compounds with a five-membered ring (GB-PS 1 138 842), thiazole derivatives and thiadiazole derivatives ( CH-PS 336 257).
In EP-A-0 270 217 wird ein Verarbeitungsverfahren beschrieben, bei dem die Entwicklerlösung benzylalkoholfrei ist und der pH-Wert der Bleichfixierlösung, die ein Eisen(III)-Komplexsalz und einen Bleichbeschleuniger enthält, zwischen 3 und 6,8 liegt.EP-A-0 270 217 describes a processing method in which the developer solution is free of benzyl alcohol and the pH of the bleach-fixing solution, which contains an iron (III) complex salt and a bleach accelerator, is between 3 and 6.8.
Bei Anwendung dieses Verfahrens bei gleichzeitig niedriger Regenerierquote der Bleichfixierbäder, die aus verfahrensökonomischen und finanziellen Gründen angestrebt wird, kommt es jedoch zur Ausfällung schwerlöslicher Rückstände. Bei niedriger Regenerierquote enthalten solche Bleichfixierbäder insbesondere bei längeren Arbeitspausen nur noch wenig Sulfit.When this process is used with a low regeneration rate of the bleach-fix baths, which is sought for procedural and financial reasons, however, poorly soluble residues are precipitated. With a low regeneration rate, such bleach-fix baths contain only a little sulfite, especially during longer breaks.
Wird unter diesen Bedingungen Entwickler durch das fotografische Material in das Bleichfixierbad eingeschleppt, so kommt es zur Oxidation der Entwicklersubstanz durch das Bleichmittel. Die hierdurch entstandenen wasserunlöslichen Entwickleroxidationsprodukte tragen in erheblichem Ausmaß an der Verunreinigung des Bleichfixierbades bei.If developer is introduced into the bleach-fixing bath through the photographic material under these conditions, the bleaching agent oxidizes the developer substance. The resulting water-insoluble developer oxidation products make a significant contribution to the contamination of the bleach-fix bath.
Ein weiterer Nachteil des oben beschriebenen Verfahrens ist die lange Bleichfixierdauer von 1 min. 30 sec.Another disadvantage of the process described above is the long bleach-fixing time of 1 min. 30 sec.
Aufgabe der Erfindung war es nun, ein Verfahren zu entwickeln, bei dem die schwerlöslichen Ausfällungen vermieden werden.The object of the invention was now to develop a method in which the poorly soluble precipitates are avoided.
Eine weitere Aufgabe war die Entwicklung eines Verfahrens, welches eine Bleichfixierzeit von weniger als 1 min. erlaubt.Another task was to develop a process that would have a bleach-fix time of less than 1 min. allowed.
Gegenstand der Erfindung ist ein Verfahren zur Verarbeitung von bildmäßig belichtetem farbfotografischem Silberhalogenidmaterial, welches auf einem Schichtträger mindestens drei lichtempfindliche Silberhalogenidemulsionsschichten unterschiedlicher Spektralempfindlichkeit, denen ein Blaugrünkuppler, ein Purpurkuppler und ein Gelbkuppler zugeordnet ist, durch Entwickeln, Bleichfixieren, Wässern oder Stabilisieren und Trocknen, wobei die wäßrige Entwicklerlösung benzylalkoholfrei ist, der pH-Wert der Bleichfixierlösung, die ein Eisen-(III)-Komplexsalz enthält, < 7 ist und die Bleichfixierlösung eine Verbindung der allgemeinen Formel (I)
Z die zur Vervollständigung eines gegebenenfalls weiter substituierten heterocyclischen Rings erforderlichen Atome, und
R¹ Wasserstoff, ein Alkaliatom
bedeuten, enthält, dadurch gekennzeichnet, daß die Bleichfixierlösung einen Kuppler mit einer aktivierten Methylengruppe enthält, bei der ein Wasserstoff durch Alkyl, Cycloalkyl, Aryl oder Aralkyl ersetzt ist und mit dem Oxydationsprodukt des Farbentwicklers unter Bildung farbloser Reaktionsprodukte reagiert.The invention relates to a method for processing imagewise exposed color photographic silver halide material which comprises at least three light-sensitive silver halide emulsion layers of different spectral sensitivity on a layer support, to which a cyan coupler, a magenta coupler and a yellow coupler are assigned, by developing, bleach-fixing, washing or stabilizing and drying, the aqueous developer solution is free of benzyl alcohol, the pH value of the bleach-fixing solution which contains an iron (III) complex salt is <7 and the bleach-fixing solution is a compound of the general formula (I)
Z the atoms required to complete an optionally further substituted heterocyclic ring, and
R¹ is hydrogen, an alkali atom
mean, characterized in that the bleach-fixing solution contains a coupler with an activated methylene group in which a hydrogen is replaced by alkyl, cycloalkyl, aryl or aralkyl and reacts with the oxidation product of the color developer to form colorless reaction products.
Verbindungen gemäß Formel I sind in DE-PS 1 290 912 beschrieben.Compounds according to formula I are described in DE-PS 1 290 912.
Geeignete Verbindungen für das erfindungsgemäße Verfahren sind z.B.
Als farblos kuppelnde Komponenten können Verbindungen vom Typ der Pyrazolone, Benzoyl- und Acetessigester, Benzoyl- und Acetessigsäureanilide, Cyanacetylverbindungen und Cyanacetamide verwendet werden, bei denen ein Wasserstoffatom der aktivierten Methylengruppe durch Alkyl, Aryl oder Aralkyl ersetzt ist.Compounds of the pyrazolone type, benzoyl and acetoacetic esters, Benzoyl- and acetoacetic anilides, cyanoacetyl compounds and cyanoacetamides are used in which a hydrogen atom of the activated methylene group is replaced by alkyl, aryl or aralkyl.
Die in Frage kommenden Benzoyl- und Acetessigesterverbindungen werden analog der in Can.J.Chem, 31, S. 1025 (1953), gegebenen Vorschrift hergestellt.The benzoyl and acetoacetic ester compounds in question are prepared analogously to the instructions given in Can.J. Chem. 31, p. 1025 (1953).
Farblos kuppelnde Pyrazolonderivate sind in DE-AS 1 155 675 beschrieben.Colorless coupling pyrazolone derivatives are described in DE-AS 1 155 675.
Geeignet sind folgende farblos kuppelnde Pyrazolone der allgemeinen Formel II:
R², R³ Alkyl, Alkoxy, Aryl, Carboxyl, Carboxyalkyl,
R⁴ Halogen, -CN, -CF₃, Acylamino, Sulfamoyl, Alkylsulfamyl, -SO₃H, Carboxy, Carboxyalkyl
n 0-3.The following colorless coupling pyrazolones of the general formula II are suitable:
R², R³ alkyl, alkoxy, aryl, carboxyl, carboxyalkyl,
R⁴ halogen, -CN, -CF₃, acylamino, sulfamoyl, alkylsulfamyl, -SO₃H, carboxy, carboxyalkyl
n 0-3.
Beispielhaft seien folgende bevorzugte Verbindungen genannt:
Der pH-Wert der Bleichfixierlösung beträgt 4,0 - 6,9, vorzugsweise 4,7-6,2.The pH of the bleach-fixing solution is 4.0-6.9, preferably 4.7-6.2.
Die Bleichfixierung ist bevorzugt in einem Zeitraum zwischen 10 und 45 sec abgeschlossen.The bleaching fixation is preferably completed in a period of between 10 and 45 seconds.
Die für die erfindungsgemäße Bleichfixierung geeigneten Temperaturen liegen in einem Bereich von 20 bis 40°C, vorzugsweise zwischen 33 und 38°C.The temperatures suitable for the bleach-fixing according to the invention are in a range from 20 to 40 ° C., preferably between 33 and 38 ° C.
Die Menge der Verbindungen gemäß Formel I in dem Bleichfixierbad variiert je nach der Art der Verarbeitungslösung, der Art des zu verarbeitenden photographischen Materials, der Verarbeitungstemperatur, der zur Durchführung der gewünschten Verarbeitung benötigten Zeit, usw. Jedoch ist eine Menge von 0,1-10 g pro Liter Bleichfixierbad geeignet, wobei 0,5 bis 3 g/l bevorzugt sind. Im allgemeinen wird der jeweils beste Bereich durch einfache Vorversuche bestimmt. Die erfindungsgemäß zu verwendende Verbindung kann dem Bleichfixierbad direkt zugesetzt oder durch ein vorgeschaltetes Conditionierbad eingebracht werden.The amount of the compounds of formula I in the bleach-fixing bath varies depending on the kind of the processing solution, the kind of the photographic material to be processed, the processing temperature, the time required to carry out the desired processing, etc. However, an amount is 0.1-10 g per liter of bleach-fix bath, with 0.5 to 3 g / l being preferred. In general, the best range is determined by simple preliminary tests. The compound to be used according to the invention can be added directly to the bleach-fix bath or introduced through an upstream conditioning bath.
Die zu farblosen Reaktionsprodukten kuppelnden Verbindungen sind in Konzentrationen von 0,1 bis 30 g/l, vorzugsweise von 1 bis 10 g/l, im Bleichfixierbad enthalten.The compounds coupling to colorless reaction products are present in the bleach-fixing bath in concentrations of 0.1 to 30 g / l, preferably 1 to 10 g / l.
Die Regenerierrate der Bleichfixierlösung beträgt 50 bis 110 ml pro m² fotografisches Materials.The regeneration rate of the bleach-fix solution is 50 to 110 ml per m² of photographic material.
Als Eisen-(III)-Ionenkomplexsalze eignen sich Komplexe von Eisen-(III)-Ionen und einem chelatbildenden Mittel wie einer Aminopolycarbonsäure oder einem Salz davon, insbesondere einem Alkalimetallsalz oder Ammoniumsalz.Suitable iron (III) ion complex salts are complexes of iron (III) ions and a chelating agent such as an aminopolycarboxylic acid or a salt thereof, in particular an alkali metal salt or ammonium salt.
Typische Beispiele chelatbildender Mittel sind Ethylendiamintetraessigsäure; Dinatriumethylendiamintetraacetat; Diammoniumethylendiamintetraacetat; Tetra(trimethylammonium)-ethylendiamintetraacetat; Tetrakaliumethylendiamintetraacetat; Tetranatriumethylendiamintetraacetat;Trinatriumethylendiamintetraacetat; Diethylentriaminpentaessigsäure; Pentanatriumdiethylentriaminpentaacetat; Ethylendiamin-N-(ß-hydroxyethyl)-N,N′,N′-triessigsäure; Trinatrium ethylendiamin-N-(ß-hydroxyethyl)-N,N′,N′-triacetat; Triammoniumethylendiamin-N-(ß-hydroxyethyl)-N,N′,N′-triacetat; Propylendiamintetraessigsäure; Dinatriumpropylendiamintetraacetat; Nitrilotriessigsäure; Trinatriumnitrilotriacetat; Cyclohexandiamintetraessigsäure; Dinatriumcyclohexandiamintetraacetat; Nitrilotriessigsäure; Trinatriumnitrilotriacetat; Cyclohexandiamintetraessigsäure; Dinatriumcyclohexandiamintetraacetat; Iminodiessigsäure; Dihydroxyethylglycin; Ethylether-diamin tetraessigsäure; Glykoletherdiamintetraessigsäure; Ethylendiamintetrapropionsäure; Phenylendiamintetraessigsäure.Typical examples of chelating agents are ethylenediaminetetraacetic acid; Disodium ethylenediaminetetraacetate; Diammonium ethylenediaminetetraacetate; Tetra (trimethylammonium) ethylenediaminetetraacetate; Tetrapotassium ethylenediaminetetraacetate; Tetrasodium ethylenediaminetetraacetate; trisodium ethylenediaminetetraacetate; Diethylenetriaminepentaacetic acid; Pentasodium diethylenetriaminepentaacetate; Ethylenediamine-N- (ß-hydroxyethyl) -N, N ′, N′-triacetic acid; Trisodium ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetate; Triammonium ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetate; Propylenediaminetetraacetic acid; Disodium propylene diamine tetraacetate; Nitrilotriacetic acid; Trisodium nitrilotriacetate; Cyclohexanediamine tetraacetic acid; Disodium cyclohexanediamine tetraacetate; Nitrilotriacetic acid; Trisodium nitrilotriacetate; Cyclohexanediamine tetraacetic acid; Disodium cyclohexanediamine tetraacetate; Iminodiacetic acid; Dihydroxyethylglycine; Ethyl ether diamine tetraacetic acid; Glycol ether diamine tetraacetic acid; Ethylenediaminetetrapropionic acid; Phenylenediaminetetraacetic acid.
Das Eisen(III)-Ionenkomplexsalz kann in der Form des Komplexsalzes verwendet oder in situ in dem Bleichfixierbad hergestellt werden. Geeignete Kationen sind Alkalikationen und Ammonium; letzteres ist bevorzugt.The iron (III) ion complex salt can be used in the form of the complex salt or prepared in situ in the bleach-fix bath. Suitable cations are alkali cations and ammonium; the latter is preferred.
Die erfindungsgemäße Bleichfixierlösung kann rehalogenierende Mittel wie Bromide (z.B. Kaliumbromid, Natriumbromid, Ammoniumbromid, usw.), Chloride (z.B. Kaliumchlorid, Natriumchlorid, Ammoniumchlorid, usw.) und dergleichen zusätzlich zu den Bleichmitteln enthalten. Darüber hinaus können Zusätze, die eine pH-Pufferwirkung haben, wie anorganische Säuren, organische Säuren oder die Salze davon, die zur Verwendung in üblichen Bleichfixierlösungen bekannt sind (z.B. Borsäure, Borax, Natriummetaborat, Essigsäure, Natriumacetat, Natriumcarbonat, Kaliumcarbonat, Phosphorige-Säure, Phosphorsäure, Natriumphosphat, Zitronensäure, Natriumzitrat, Weinsäure, usw.) zugesetzt werden.The bleach-fixing solution of the present invention may contain rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide, etc.), chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride, etc.) and the like in addition to the bleaching agents. In addition, additives which have a pH buffering action, such as inorganic acids, organic acids or the salts thereof, which are known for use in conventional bleach-fixing solutions (for example boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid , Phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.) can be added.
Bei Verwendung in einem Bleichfixierbad können übliche Fixiermittel, d.h. wasserlösliche, Silberhalogenid auflösende Mittel, wie Thiosulfat (z.B. Natriumthiosulfat, Ammoniumthiosulfat, Ammoniumnatriumthiosulfat, Kaliumthiosulfat, usw.); Thiocyanate (z.B. Natriumthiocyanat; Ammoniumthiocyanat; Kaliumthiocyanat, usw.); Thioetherverbindungen (z.B. Ethylenbisthioglykolsäure, 3,6-Dithia-1,8-octandiol, usw.); und Thioharnstoffe allein oder in einer Kombination von zwei oder mehreren verwendet werden. Zusätzlich können spezielle Bleich-Fixier-Mittel, die eine Kombination eines Fixiermittels und eine große Menge einer Halogenidverbindung wie Kaliumjodid enthalten, ebenfalls verwendet werden.When used in a bleach-fixing bath, customary fixing agents, ie water-soluble agents which dissolve silver halide, such as thiosulfate (for example sodium thiosulfate, Ammonium thiosulfate, ammonium sodium thiosulfate, potassium thiosulfate, etc.); Thiocyanates (e.g. sodium thiocyanate; ammonium thiocyanate; potassium thiocyanate, etc.); Thioether compounds (e.g. ethylene bisthioglycolic acid, 3,6-dithia-1,8-octanediol, etc.); and thioureas can be used alone or in a combination of two or more. In addition, special bleach-fixing agents containing a combination of a fixing agent and a large amount of a halide compound such as potassium iodide can also be used.
In der Bleichfixierbad-Zusammensetzung ist das Eisen(III)-ionenkomplexsalz üblicherweise in einer Menge von 0,1 bis 1 Mol/l vorhanden. Die Menge des Fixiermittels beträgt im allgemeinen 0,2 bis 4 Mol pro Liter der Bleichfixierlösung.In the bleach-fixing bath composition, the ferric ion complex salt is usually present in an amount of 0.1 to 1 mol / l. The amount of the fixing agent is generally 0.2 to 4 mol per liter of the bleach-fixing solution.
Bleichfixierlösungen können darüber hinaus konservierende Mittel wie Sulfite (z.B. Natriumsulfit, Kaliumsulfit, Ammoniumsulfit, usw.), Hydroxylamin, Hydrazin, Aldehyd-Bisulfit-Addukte (z.B. Acetaldehydnatriumbisulfitaddukt), usw. enthalten. Darüber hinaus können verschiedene optische Aufheller, Entschäumungsmittel, oberflächenaktive Mittel, organische Lösungsmittel (z.B. Methanol) und bekannte Bleich-Fixier-Beschleunigungsmittel, z.B. Polyaminverbindungen (US-PS 3 578 457), Thioharnstoffe (US-PS 3 617 283), Iodide (DE-PS 1 127 715), Polyethylenoxide (DE-PS 966 410) und andere Thioharnstoffe verwendet werden.Bleach-fix solutions can also contain preservatives such as sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, aldehyde-bisulfite adducts (e.g. acetaldehyde sodium bisulfite adduct), etc. In addition, various optical brighteners, defoamers, surfactants, organic solvents (e.g. methanol) and known bleach-fix accelerating agents, e.g. polyamine compounds (US Pat. No. 3,578,457), thioureas (US Pat. No. 3,617,283), iodides (DE -PS 1 127 715), polyethylene oxides (DE-PS 966 410) and other thioureas can be used.
Die in dem erfindungsgemäßen Verfahren bei der Entwicklung verwendeten Substanzen sind p-Phenylendiamine und insbesondere N,N-Dialkyl-p-phenylendiamine, in denen die Alkylgruppen und der aromatische Kern substituiert oder unsubstituiert sind. Beispiele solche Verbindungen sind N,N-Diethyl-p-phenylendiamin-hydrochlorid, 4-N,N-Diethyl-2-methylphenylendiamin-hydrochlorid, 4-(N-Ethyl-N-2-methansulfonylaminoethyl)-2-methylphenylendiaminsesquisulfatmonohydrat, 4-(N-Ethyl-N-2-hydroxyethyl)-2-methylphenylendiaminsulfat und 4-N,N-Diethyl-2,2′-methansulfonylaminoethylphenylendiamin-hydrochlorid.The substances used in the development process according to the invention are p-phenylenediamines and in particular N, N-dialkyl-p-phenylenediamines, in which the alkyl groups and the aromatic nucleus are substituted or unsubstituted. Examples of such compounds are N, N-diethyl-p-phenylenediamine hydrochloride, 4-N, N-diethyl-2-methylphenylenediamine hydrochloride, 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate monohydrate, 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate and 4-N, N-diethyl-2,2'-methanesulfonylaminoethylphenylenediamine hydrochloride.
Vorzugsweise enthält der Farbentwickler Komplexierungsmittel in wirksamer Menge zur Komplexierung von Eisenionen und Komplexierungsmittel in wirksamer Menge zur Komplexierung von Kalziumionen, wobei beide Funktionen auch durch eine einzige Substanz wahrgenommen werden kann. Der Entwickler ist insbesondere für eine Schnellverarbeitung mit beispielsweise 45 Sekunden Entwicklungszeit geeignet, wobei sich an die Entwicklung eine Bleichfixierung und eine Wäsche oder eine Stabilisierung anschließen. Der Entwickler enthält erfindungsgemäß keinen Benzylalkohol.The color developer preferably contains complexing agents in an effective amount for complexing iron ions and complexing agents in an effective amount for complexing calcium ions, both functions also being able to be performed by a single substance. The developer is particularly suitable for rapid processing with a development time of, for example, 45 seconds, the development being followed by bleaching fixation and washing or stabilization. According to the invention, the developer contains no benzyl alcohol.
Der Farbentwickler ist im wesentlichen bromidfrei. Das bedeutet, daß der Bromidionen in einer Konzentration enthalten kann, die sensitometrisch unwirksam ist. Diese Bromidionenmenge braucht nicht dem frischen Entwickler zugegeben werden, sondern kann sich während des Entwick lungsvorganges aus dem zu entwickelnden Material herauslösen. Ihre Menge sollte auf weniger als 30 mg/l begrenzt sein.The color developer is essentially free of bromide. This means that the bromide ion can contain a concentration that is sensitometrically ineffective. This amount of bromide ions does not need to be added to the fresh developer, but can develop during the development process from the material to be developed. Their amount should be limited to less than 30 mg / l.
Vorzugsweise enthält der erfindungsgemäße Farbentwickler Chloridionen, insbesondere in einer Menge von 1 bis 5 g/l.The color developer according to the invention preferably contains chloride ions, in particular in an amount of 1 to 5 g / l.
Geeignete Komplexbildner zur Komplexierung von Kalziumionen sind beispielsweise Aminopolycarbonsäuren, die an sich gut bekannt sind. Typische Beispiele für solche Aminopolycarbonsäuren sind Nitrilotriessigsäure, Ethylendiamintetraessigsäure (EDTA), 1,3-Diamino-2-hydroxypropyltetraessigsäure, Diethylentriaminpentaessigsäure, N,N′-Bis-(2-hydroxybenzyl)-ethylendiamin-N,N′-diessigsäure, Hydroxyethylethylendiamintriessigsäure, Cyclohexandiaminotetraessigsäure und Aminomalonsäure.Suitable complexing agents for complexing calcium ions are, for example, aminopolycarboxylic acids, which are well known per se. Typical examples of such aminopolycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), 1,3-diamino-2-hydroxypropyltetraacetic acid, diethylenetriaminepentaacetic acid, N, N'-bis- (2-hydroxybenzyl) -ethylenediamine-N, N'-diesiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetamic acid, hydroxyethylenediaminodiacetate, and aminomalonic acid.
Weitere Kalziumkomplexbildner sind Polyphosphate, Phosphonsäuren, Aminopolyphosphonsäuren und hydrolisiertes Polymaleinsäureanhydrid, z.B. Natriumhexametaphosphat, 1-Hydroxyethan-1,1-diphosphonsäure, Aminotrismethylenphosphonsäure, Ethylendiamintetramethylenphosphonsäure. 1-Hydroxyethan-1,1-diphosphonsäure wirkt auch als Eisenkomplexbildner.Other calcium complexing agents are polyphosphates, phosphonic acids, aminopolyphosphonic acids and hydrolyzed polymaleic anhydride, e.g. Sodium hexametaphosphate, 1-hydroxyethane-1,1-diphosphonic acid, aminotrismethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid. 1-hydroxyethane-1,1-diphosphonic acid also acts as an iron complexing agent.
Weitere Eisenkomplexbildner sind z.B. 4,5-Dihydroxy-1,3-benzoldisulfonsäure, 5,6-Dihydroxy-1,2,4-benzoltrisulfonsäure und 3,4,5-Trihydroxybenzoesäure.Other iron complexing agents are, for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid and 3,4,5-trihydroxybenzoic acid.
Für die Komplexierung des Kalziums werden bevorzugt etwa 0,2 bis etwa 1,8 Mol eines Kalziumplexbildners pro Mol Entwicklersubstanz eingesetzt.About 0.2 to about 1.8 moles of a calcium complexing agent per mole of developer substance are preferably used for complexing the calcium.
Der Eisenkomplexbildner wird in Mengen von etwa 0,02 bis etwa 0,2 Mol pro Mol Entwicklersubstanz angewendet.The iron complexing agent is used in amounts of about 0.02 to about 0.2 moles per mole of developer substance.
Der in dem erfindungsgemäßen Verfahren verwendete Entwickler ist insbesondere eine wäßrige alkalische Lösung, die einen pH-Wert oberhalb 7, insbesondere von 9 bis 13 aufweist. Um diesen pH-Wert einzustellen, werden an sich bekannte Puffersubstanzen verwendet wie Alkalicarbonate und Alkaliphosphate.The developer used in the process according to the invention is in particular an aqueous alkaline solution which has a pH above 7, in particular from 9 to 13. In order to set this pH, known buffer substances such as alkali carbonates and alkali phosphates are used.
Weiterhin kann es zweckmäßig sein, den Entwicklerlösungen Weißtöner und Oxidationsschutzsubstanzen zuzusetzen. Geeignete Oxidationsschutzmittel sind z.B. Hydroxylamin und Diethylhydroxylamin sowie Sulfite, wie vorzugsweise in einer Menge bis zu 5 g/l eingesetzt werden.It may also be expedient to add whiteners and antioxidants to the developer solutions. Suitable antioxidants are e.g. Hydroxylamine and diethylhydroxylamine and sulfites, such as preferably used in an amount up to 5 g / l.
Als weitere Bestandteile kommen optische Aufheller, Gleitmittel, z.B. Polyalkylenglykole, Tenside, Stabilisatoren, z.B. heterocyclische Mercaptoverbindungen oder Nitrobenzimidazol und Mittel zur Einstellung des gewünschten pH-Wertes in Frage.Optical brighteners, lubricants, e.g. Polyalkylene glycols, surfactants, stabilizers, e.g. heterocyclic mercapto compounds or nitrobenzimidazole and means for adjusting the desired pH.
Die Silberhalogenidemulsionsschichten des farbfotografischen Aufzeichnungsmaterials, welches dem erfindungsgemäßen Verarbeitungsverfahren unterworfen wird, be stehen vorzugsweise aus 80 - 100 Mol-% Silberchlorid, 0 - 20 Mol-% Silberbromid und 0 - 2 Mol-% Silberiodid. Besonders bevorzugt sind 95 - 100 Mol-% Silberchlorid, 0 - 5 Mol-% Silberbromid und 0 - 1 Mol-% Silberiodid.The silver halide emulsion layers of the color photographic recording material which is subjected to the processing method according to the invention be preferably consist of 80-100 mol% of silver chloride, 0-20 mol% of silver bromide and 0-2 mol% of silver iodide. 95-100 mol% of silver chloride, 0-5 mol% of silver bromide and 0-1 mol% of silver iodide are particularly preferred.
Die Schicht, die den Blaugrünkuppler enthält, ist üblicherweise rot, die, die den Purpurkuppler enthält, üblicherweise grün und die, die den Gelbkuppler enthält, üblicherweise blau sensibilisiert.The layer containing the cyan coupler is usually red, that which contains the magenta coupler is usually green and that which contains the yellow coupler is usually blue sensitized.
Die gebrauchsfertigen Lösungen können aus den einzelnen Bestandteilen oder aus sogenannten Konzentration hergestellt werden, wobei in den Konzentraten die einzelnen Bestandteile wesentlich höher konzentriert gelöst werden. Die Konzentrate sind so eingestellt, daß sich aus ihnen ein sogenannter Regenerator herstellen läßt, d.h. eine Lösung, die etwas höhere Konzentrationen an den einzelnen Bestandteilen als die gebrauchsfertige Lösung aufweist, einerseits durch weiteres Verdünnen und Zugabe eines Starters, vorzugsweise KCl eine gebrauchsfertige Lösung ergibt und andererseits ständig einer in Gebrauch befindlichen Entwicklerlösung zugesetzt wird, um die beim Entwickeln verbrauchten oder aus der Entwicklerlösung durch Überlauf oder durch das entwickelte Material ausgeschleppten Chemikalien zu ersetzen. Chloridionen brauchen dabei üblicherweise nicht zugesetzt werden außer beim frisch angesetzten Entwickler, da Chloridionen aus dem fotografischen Material durch die Entwicklung freigesetzt werden.The ready-to-use solutions can be prepared from the individual components or from so-called concentration, the individual components being dissolved in the concentrates in a much higher concentration. The concentrates are adjusted so that a so-called regenerator can be produced from them, ie a solution that has somewhat higher concentrations of the individual components than the ready-to-use solution, on the one hand, by further dilution and addition of a starter, preferably KCl, gives a ready-to-use solution and on the other hand, a developer solution in use is constantly added in order to replace the chemicals consumed during development or which have been dragged out of the developer solution by overflow or by the developed material. Chloride ions usually do not need to be added except for the freshly prepared developer, since chloride ions are released from the photographic material by the development.
Bei dem erfindungsgemäßen Verfahren treten im Bleichfixierbad keine schwerlöslichen Ausfällungen auf. Darüberhinaus gelingt es, farbfotografisches Material in weniger als 45 sec. vollständig bei geringer Regenerierquote von 50 - 100 ml/m² fotografischen Materials zu bleichen.In the process according to the invention, there are no poorly soluble precipitates in the bleach-fixing bath. In addition, color photographic material can be completely bleached in less than 45 seconds with a low regeneration rate of 50-100 ml / m² of photographic material.
In diesem Beispiel wird die Wirkungsweise von Weißkupplern vom Typ 4-substituierter Pyrazolone in einem Modellversuch gezeigt, der die Praxissituation unter definierten Bedingungen simuliert.In this example, the mode of action of white couplers of the 4-substituted pyrazolone type is shown in a model experiment that simulates the practical situation under defined conditions.
Es wird eine Mischung aus einer Farbentwicklerlösung und einem sulfitarmen Bleichfixierbad hergestellt, das keinen Weißkuppler enthält.
250 ml Entwicklerlösung werden unter Rühren zu 250 ml Bleichfixierbad gegeben.250 ml of developer solution are added to 250 ml of bleach-fix bath with stirring.
Die pH-Einstellung erfolgt mit Essigsäure auf pH 6,5.The pH is adjusted to pH 6.5 with acetic acid.
Es wird ein offenes Becherglas verwendet mit den Maßen:
Höhe 120 mm,
Durchmesser 100 mm,
Füllvolumen 500 ml Mischung,
Raumtemperatur ca. 22°C.An open beaker is used with the dimensions:
Height 120 mm,
Diameter 100 mm,
Filling volume 500 ml mixture,
Room temperature about 22 ° C.
Es wird wie im Vergleichsversuch eine Mischung hergestellt, die jedoch 3,4-Dimethyl-1-(4-sulfophenyl)-5-pyrazolon enthält.A mixture is prepared as in the comparative experiment, but containing 3,4-dimethyl-1- (4-sulfophenyl) -5-pyrazolone.
Zusammensetzung der Farbentwicklerlösung: wie Vergleichsversuch
Herstellung und Lagerung der Mischung erfolgt wie im Vergleichsversuch.The mixture is prepared and stored as in the comparative experiment.
Ergebnis: Während der Lagerung bilden sich innerhalb weniger Tage in der Mischung des Vergleichsversuchs an der Oberfläche und im Verdunstungsbereich wasserunlösliche blau bis braun gefärbte Ausfällungen.
Die Mischung mit erfindungsgemäßer Zusammensetzung des Bleichfixierbades zeigt diese Ausfällungen nicht.Result: During storage, water-insoluble blue to brown-colored precipitates form in the mixture of the comparative test on the surface and in the evaporation area.
The mixture with the bleach-fixing bath composition according to the invention does not show these precipitates.
In diesem Beispiel wird die restsilberfreie Bleichfixierung unter Verwendung des erfindungsgemäßen Verfahrens innerhalb von 45 sec. demonstriert.In this example, the residual silver-free bleach fixation using the method according to the invention is demonstrated within 45 seconds.
Ein farbfotografisches Aufzeichnungsmaterial, welches für das erfindungsgemäßen Verarbeitungsverfahren geeignet ist, wurde hergestellt, indem auf einen Schichtträger auf beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO₃ angegeben.A color photographic recording material which is suitable for the processing method according to the invention was produced by applying the following layers in the order given to a layer support on paper coated on both sides with polyethylene. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.
1. Schicht (Substratschicht): 0,2 g Gelatine
2. Schicht (blauempfindliche Schicht): blauempfindliche Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,63 g AgNO₃ mit
1st layer (substrate layer): 0.2 g gelatin
2nd layer (blue-sensitive layer): blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g AgNO₃ with
Die verwendeten Komponenten haben folgende Formel:
Ein Stufenkeil wird auf das oben beschriebene fotografische Aufzeichnungsmaterial aufbelichtet und wie folgt verarbeitet:
Die einzelnen Verarbeitungsbäder hatten die folgende Zusammensetzung:
Der belichtete und anschließend wie oben beschrieben verarbeitete Stufenkeil des fotografischen Materials wurde mit einem Infrarot-Silberdetector PM 8030 der Fa. Photo-Matic, Denmark auf Restsilber in den Bildschwärzen untersucht.The exposed step wedge of the photographic material, which was then processed as described above, was examined for residual silver in the image blackness using an infrared silver detector PM 8030 from Photo-Matic, Denmark.
Die verarbeitete Probe enthält kein Restsilber.The processed sample contains no residual silver.
Claims (9)
Z die zur Vervollständigung eines gegebenenfalls weiter substituierten heterocyclischen Rings erforderlichen Atome, und
R¹ Wasserstoff, ein Alkaliatom
bedeuten, enthält, dadurch gekennzeichnet, daß die Bleichfixierlösung, einen Kuppler mit einer aktivierten Methylengruppe enthält, bei der ein Wasser stoff durch Alkyl, Cycloalkyl, Cycloalkyl, Aryl oder Aralkyl ersetzt ist und mit dem Oxydationsprodukt des Farbentwicklers unter Bildung farbloser Reaktionsprodukte reagiert.1. A method for processing imagewise exposed color photographic silver halide material which has at least three light-sensitive silver halide emulsion layers of different spectral sensitivity on a layer support, to which a cyan coupler, a magenta coupler and a yellow coupler are assigned, by developing, bleach-fixing, watering or stabilizing and drying, the aqueous developer solution being free from benzyl alcohol the pH of the bleach-fixing solution containing an iron (III) complex salt is <7 and the bleach-fixing solution is a compound of the general formula (I)
Z the atoms required to complete an optionally further substituted heterocyclic ring, and
R¹ is hydrogen, an alkali atom
mean, characterized in that the bleach-fixing solution contains a coupler with an activated methylene group, in which a water Substance is replaced by alkyl, cycloalkyl, cycloalkyl, aryl or aralkyl and reacts with the oxidation product of the color developer to form colorless reaction products.
R², R³ Alkyl, Alkoxy, Aryl, Carboxy, Carboxyalkyl,
R⁴ Halogen, -CN, -CF₃, Acylamino, Sulfamoyl, Alkylsulfamyl, -SO₃H, Carboxy, Carboxyalkyl
n 0-3,
bedeuten.2. The method according to claim 1, characterized in that the coupling compounds of the general formula (II) used in the bleach-fixing solution to form colorless reaction products.
R², R³ alkyl, alkoxy, aryl, carboxy, carboxyalkyl,
R⁴ halogen, -CN, -CF₃, acylamino, sulfamoyl, alkylsulfamyl, -SO₃H, carboxy, carboxyalkyl
n 0-3,
mean.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3830024 | 1988-09-03 | ||
| DE3830024A DE3830024A1 (en) | 1988-09-03 | 1988-09-03 | METHOD FOR PROCESSING A COLOR PHOTOGRAPHIC MATERIAL |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0358037A2 true EP0358037A2 (en) | 1990-03-14 |
| EP0358037A3 EP0358037A3 (en) | 1991-03-13 |
Family
ID=6362257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19890115447 Withdrawn EP0358037A3 (en) | 1988-09-03 | 1989-08-22 | Method for processing a colour-photographic material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4933264A (en) |
| EP (1) | EP0358037A3 (en) |
| JP (1) | JPH02109045A (en) |
| DE (1) | DE3830024A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0498950A1 (en) * | 1991-02-13 | 1992-08-19 | Agfa-Gevaert AG | Processing colour photographic recording materials |
| EP0564909A1 (en) * | 1992-04-06 | 1993-10-13 | Agfa-Gevaert AG | Process for the production of a photographic image |
| EP1315040A2 (en) * | 2001-10-30 | 2003-05-28 | Eastman Kodak Company | Method to reduce corrosivity of photographic processing effluent |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2670862B2 (en) * | 1989-07-25 | 1997-10-29 | 富士写真フイルム株式会社 | Processing method of silver halide photographic material |
| US5945262A (en) * | 1995-12-14 | 1999-08-31 | Agfa-Gevaert, N.B. | Correcting liquid for a silver imaged lithographic printing plate |
| US6790600B2 (en) | 2003-02-07 | 2004-09-14 | Eastman Kodak Company | Method of color photographic processing for color photographic papers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2998314A (en) * | 1956-09-18 | 1961-08-29 | Agfa Ag | Color photography |
| GB1132399A (en) * | 1966-07-25 | 1968-10-30 | Ilford Ltd | Photographic colour processing |
| DE2705974A1 (en) * | 1977-02-12 | 1978-08-17 | Agfa Gevaert Ag | METHOD FOR PRODUCING COLOR PHOTOGRAPHIC IMAGES USING NOVEL WHITE COUPLER SUBSTANCES |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780398A (en) * | 1986-08-28 | 1988-10-25 | Olin Hunt Specialty Products, Inc. | Bleaching composition and process for color photographic materials |
| DE3800681A1 (en) * | 1987-10-17 | 1989-04-27 | Agfa Gevaert Ag | WASP-FREE PHOTOGRAPHIC PROCESSING METHOD AND STABILIZING BATH USED FOR THIS METHOD |
-
1988
- 1988-09-03 DE DE3830024A patent/DE3830024A1/en not_active Withdrawn
-
1989
- 1989-08-18 US US07/395,549 patent/US4933264A/en not_active Expired - Fee Related
- 1989-08-22 EP EP19890115447 patent/EP0358037A3/en not_active Withdrawn
- 1989-09-02 JP JP1226399A patent/JPH02109045A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2998314A (en) * | 1956-09-18 | 1961-08-29 | Agfa Ag | Color photography |
| GB1132399A (en) * | 1966-07-25 | 1968-10-30 | Ilford Ltd | Photographic colour processing |
| DE2705974A1 (en) * | 1977-02-12 | 1978-08-17 | Agfa Gevaert Ag | METHOD FOR PRODUCING COLOR PHOTOGRAPHIC IMAGES USING NOVEL WHITE COUPLER SUBSTANCES |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0498950A1 (en) * | 1991-02-13 | 1992-08-19 | Agfa-Gevaert AG | Processing colour photographic recording materials |
| EP0564909A1 (en) * | 1992-04-06 | 1993-10-13 | Agfa-Gevaert AG | Process for the production of a photographic image |
| EP1315040A2 (en) * | 2001-10-30 | 2003-05-28 | Eastman Kodak Company | Method to reduce corrosivity of photographic processing effluent |
| EP1315040A3 (en) * | 2001-10-30 | 2003-08-06 | Eastman Kodak Company | Method to reduce corrosivity of photographic processing effluent |
| US6740477B2 (en) | 2001-10-30 | 2004-05-25 | Eastman Kodak Company | Method to reduce corrosivity of photographic processing effluent |
Also Published As
| Publication number | Publication date |
|---|---|
| US4933264A (en) | 1990-06-12 |
| EP0358037A3 (en) | 1991-03-13 |
| DE3830024A1 (en) | 1990-03-08 |
| JPH02109045A (en) | 1990-04-20 |
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