US3576633A - Photographic process and compositions - Google Patents
Photographic process and compositions Download PDFInfo
- Publication number
- US3576633A US3576633A US649119A US3576633DA US3576633A US 3576633 A US3576633 A US 3576633A US 649119 A US649119 A US 649119A US 3576633D A US3576633D A US 3576633DA US 3576633 A US3576633 A US 3576633A
- Authority
- US
- United States
- Prior art keywords
- solution
- mercapto
- developer
- photographic
- propanol
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title abstract description 49
- 238000000034 method Methods 0.000 title abstract description 41
- -1 SILVER HALIDE Chemical class 0.000 abstract description 58
- 229910052709 silver Inorganic materials 0.000 abstract description 31
- 239000004332 silver Substances 0.000 abstract description 31
- CARFETJZUQORNQ-UHFFFAOYSA-N 1h-pyrrole-2-thiol Chemical compound SC1=CC=CN1 CARFETJZUQORNQ-UHFFFAOYSA-N 0.000 abstract description 24
- 239000000243 solution Substances 0.000 description 67
- 239000003795 chemical substances by application Substances 0.000 description 26
- 239000000839 emulsion Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000012545 processing Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000011161 development Methods 0.000 description 15
- 125000003396 thiol group Chemical group [H]S* 0.000 description 13
- 229960005335 propanol Drugs 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 238000004061 bleaching Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 150000001412 amines Chemical group 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 3
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012260 resinous material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 150000004867 thiadiazoles Chemical group 0.000 description 2
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 2
- 229940103494 thiosalicylic acid Drugs 0.000 description 2
- 229950000329 thiouracil Drugs 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 229940086542 triethylamine Drugs 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- DBCKMJVEAUXWJJ-UHFFFAOYSA-N 2,3-dichlorobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Cl)=C1Cl DBCKMJVEAUXWJJ-UHFFFAOYSA-N 0.000 description 1
- JHKKTXXMAQLGJB-UHFFFAOYSA-N 2-(methylamino)phenol Chemical class CNC1=CC=CC=C1O JHKKTXXMAQLGJB-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 229940013085 2-diethylaminoethanol Drugs 0.000 description 1
- PHNGKIFUTBFGAG-UHFFFAOYSA-N 2-ethoxybenzene-1,4-diol Chemical compound CCOC1=CC(O)=CC=C1O PHNGKIFUTBFGAG-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- DMPODMBXLRMZSP-UHFFFAOYSA-N 3-(dibutylamino)propan-1-ol Chemical compound CCCCN(CCCC)CCCO DMPODMBXLRMZSP-UHFFFAOYSA-N 0.000 description 1
- WKCYFSZDBICRKL-UHFFFAOYSA-N 3-(diethylamino)propan-1-ol Chemical compound CCN(CC)CCCO WKCYFSZDBICRKL-UHFFFAOYSA-N 0.000 description 1
- QCMHUGYTOGXZIW-UHFFFAOYSA-N 3-(dimethylamino)propane-1,2-diol Chemical compound CN(C)CC(O)CO QCMHUGYTOGXZIW-UHFFFAOYSA-N 0.000 description 1
- SJSJAWHHGDPBOC-UHFFFAOYSA-N 4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(C)CN1C1=CC=CC=C1 SJSJAWHHGDPBOC-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- OUZCWDMJTKYHCA-UHFFFAOYSA-N 5-methyl-1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound CC1=NNC(S)=N1 OUZCWDMJTKYHCA-UHFFFAOYSA-N 0.000 description 1
- FOHWXVBZGSVUGO-UHFFFAOYSA-N 5-phenyl-3h-1,3,4-oxadiazole-2-thione Chemical compound O1C(S)=NN=C1C1=CC=CC=C1 FOHWXVBZGSVUGO-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical class NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- BXJGUBZTZWCMEX-UHFFFAOYSA-N dimethylhydroquinone Natural products CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 229940113083 morpholine Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N p-hydroxyphenylamine Natural products NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000004328 sodium tetraborate Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000004963 sulfonylalkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/50—Reversal development; Contact processes
Definitions
- the present invention is directed to photographic processes and compositions.
- this invention relates to a reversal process employing a silver halide developing agent and an aminoalkanol with a mercapto azole antifoggant.
- the invention is directed to a process for improved development in the first development step in a reversal process, especially a black-and-white reversal process.
- an object of the present invention to provide a means for reversal processing of a silver halide emulsion which results in increased photographic speed and lower minimum density.
- Another object of the invention is to provide an improved developer composition to decrease minimum density and provide increased speed of a photographic element.
- the present invention comprises a photographic silver halide developer composition, particularly useful in reversal processing of a photographic element, comprising a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant.
- Example 1 demonstrates that when one or both of the aminoalkanol and mercapto azole antifoggant are absent, the desired combination of increased gamma and maximum density without increased minimum density is not produced.
- Example 15 illustrates that neither an antifoggant, such as benzotriazole, containing no mercapto function or group, nor an antifoggant, such as thiosalicylic acid, containing no azole moiety provide the desired combination of results.
- One embodiment of the invention comprises a photographic silver halide developer composition, especially an aqueous developer solution, suitable for reversal processing, comprising a silver halide developing agent, an aminoalkanol of the formula:
- a developer composition found especially suitable for reversal processing comprises an aqueous solution of a polyhydroxybenzene developing agent, l-amino-Z-propanol and 1-phenyl-S-mercaptotetrazole.
- Another embodiment of the invention comprises, in a photographic process for developing a latent image in a photographic silver halide emulsion with a developer composition, the improvement of employing a developer composition containing a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant.
- a preferred embodiment of the invention comprises, in a photographic reversal process for developing a latent image, the improvement comprising developing said latent image with a composition comprising a silver halide developing agent, an amino-alkanol and a mercapto azole antifoggant.
- a reversal process for developing a latent image in an exposed photographic silver halide emulsion comprising developing an image in a developer composition comprising a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant, bleaching the resulting silver image and developing a positive image.
- the emulsion after the first development step is typically re-exposed before subsequent processing or is re-exposed during the second development step.
- a so-called fogging developer is employed as the second developer composition.
- the use of the term fogging developer refers to a composition containing a component such as thiourea which sulfides the silver halide, or a developer containing strong reducing agents such as hydrazine or potassium borohydride.
- Suitable aminoalkanols within the scope of the invention are those having at least one hydroxy alkyl radical and includes those compounds having one, two or more hydroxy radicals. These include compounds within the formula:
- R is a hydroxyalkyl radical such as one containing up to about 10 carbon atoms, typically a hydroxy lower alkyl radical, for example, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyisobutyl, dihydroxypropyl, dihydroxybutyl and the like, which provide an amino lower alkanol
- R and R are each selected from the group consisting of hydrogen atoms and alkyl radicals, such as those containing up to about 10 carbon atoms, typically lower alkyl radicals, such as methyl, ethyl, propyl, butyl, isobutyl and isopropyl radicals.
- Suitable aminoalkanols which can be referred to as hydroxyalkyl amines, include:
- mercapto azole antifoggants employed in the practice of this invention include those antifoggants which contain at least one mercapto function or group and at least one azole moiety.
- Suitable antifoggants can be represented wherein Z represents the atoms necessary to complete a 5 or 6 member heterocyclic ring, such as pyrimidine, triazine, tetrazole, triazole, imidazole, diazole, oxadiazole or thiadiazole ring; and SX represents a mercapto function, n being a whole number, typically a number from 1 to about 3, any free bonds being satisfied by hydrogen atoms.
- X is a cation which includes hydrogen, an alkali metal, e.g., sodium or potassium, ammonium or an organic amine residue of such amines as triethyl amine, trietanol amine, morpholine and the like.
- Mercapto tetrazole antifoggants are especially suitable in the practice of this invention and include those of the formula:
- R is an aliphatic or aromatic radical containing up to about 30 carbon atoms and SX is a mercapto function.
- X of the mercapto function or group is a cation including a hydrogen atom or, for example, an alkali metal such as sodium, potassium, ammonium or an organic amine residue of such amines as triethyl amine, triethanol amine, morpholine and the like.
- S-mercapto tetrazole as employed herein, is intended to cover compounds in which the mercapto function is in any of these forms.
- R can be a hydrocarbon or nonhydrocarbon and includes alkyl or aryl radicals which can contain atoms or groups other than carbon and hydrogen.
- Suitable atoms or groups which can be present in R together with hydrogen and carbon include, for example, alkoxy, phenoxy, halogen, cyano, amino, substituted amino, sulfo, sulfamyl, substituted sulfamyl, sulfonylphenyl, sulfonylalkyl, fluosulfonyl, sulfonamidophenyl, sulfonamidoalkyl, carboxy, carboxylate, carbam- 4 yl, carbamylphenyl, carbamyalkyl, carbonylphenyl and similar groups.
- Mercapto azole antifoggants within the scope of the invention include:
- thiobarbituric acid and thiouracil mercapto-substituted oxadiazoles or thiadiazoles such as:
- any of the silver halide developing agents can be employed in the practice of this invention.
- Suitable developing agents which can be employed are polyhydroxybenzenes, e.g., hydroquinone developing agents such as hydroquinone, alkyl substituted hydroquinones as exemplified by t butylhydroquinone, methylhydroquinone, dimethylhydroquinone; catechol and pyrogallol; chloro substituted hydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxy substituted hydroquinones such as methoxy or ethoxy hydroquinone; aminophenol developing agents such as 2,4-diaminophenols and methylaminophenols; ascorbic acid; pyrazolidone developing agents such as 1-phenyl-3-pyrazolidone, including those described in British Pat. 930,572; and acyl derivatives of p-aminophenol such as disclosed in British Pat. 1,045,303.
- Such developing agents can be
- Concentrations of the silver halide developing agent can vary over a wide range. Suitable concentrations in a developer composition will be determined based on other components, the desired image and other factors which can be determined by those skilled in the art. A typical concentration is about 2 to about 50 grams of developing agent per liter of processing solution.
- the concentration of the aminoalkanol in solution is typically at least about 2 grams per liter up to about grams per liter of processing solution. Good results are often obtained with concentrations in the range of about 10 grams to about 50 grams per liter of processing solution.
- the concentration of azole compound in solution is tyipcally in the range of about 0.02 gram per liter to about 0.5 gram per liter of solution.
- the pH ranges which are suitable for the purposes of the invention can vary and include those typically employed in processing photographic elements.
- the pH is usually above about 7, for instance, about 10 to about 13.
- Ordinary development activators can be employed with the above compositions and processes. These include the typical alkalis employed for activating developers, such as alkali metal hydroxides, typically sodium hydroxide, as well as other alkaline materials such as borax and alkali metal carbonates. These can be employed in any concentration which is effective for activating the development.
- alkali metal hydroxides typically sodium hydroxide
- other alkaline materials such as borax and alkali metal carbonates.
- Suitable photographic addenda include, e.g., hardeners, such as alum or those set out in British Pat. 974,317; buffers which maintain the desired pH level including various sulfonamides and boraxes; coating aids; plasticizers; speed-increasing addenda, such as quaternary ammonium salts and alkylene oxide polymers such as polyethylene glycols; and stabilizing agents such as sodium sulfite.
- photographic emulsions employed in the practice of the invention can be sensitized using any of the wellknown techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, noble metal and/or gold compounds.
- the photographic elements can also contain spectral sensitizing dyes such as described, for example, in U.S. Pats. 2,526,632 and 2,503,776.
- Spectral sensitizers which can be used include cyanines, merocyanines, styryls and hemicyanines.
- the photographic elements processed according to the invention typically contain an emulsion layer comprising any of the known hydrophilic water permeable binding materials suitable for photographic purposes. These include, for example, gelatin, cellulose derivatives, polymerized vinyl compounds, water insoluble polymers of acrylates and methacrylates, as well as mixtures of such binding agents.
- the photosensitive coatings which are processed according to the invention can be coated on a wide variety of supports.
- Typical supports include cellulose ester films, polyvinyl acetal films, polyethylene terephthalate films and related films and resinous materials as well as glass, paper, metals and the like.
- Paper supports which are coated with resinous materials such as polyethylene, polypropylene, ethylene-butene copolymers and the like can also be employed.
- silver salts can be used as the sensitive salt in the elements processed according to the invention. These include silver halides such as silver iodide, silver bromide, silver chloride, silver bromoiodide, silver chloroiodide and the like.
- Various silver halide fixing agents or solvents can also be employed in combination with the developer compositions and processes of the invention. These include alkali metal thiosulfates, such as sodium thiosulfate and thiocyanates such as ammonium thiocyanate.
- the photographic elements processed according to the invention can typically be bleached or converted to a light insensitive silver salt which is water soluble following a first development step.
- Suitable compositions for carrying outer this bleaching are known and include potassium dichromate and sulfuric acid bleaching compositions.
- compositions of the invention containing the silver halide developer, aminoalkanol, and mercapto azole antifoggant can be employed in the first black-and-white development step in a color reversal process.
- Such color reversal processes usually comprise treating the exposed photographic element in a black-and-white development step, re-exposure of the element, a color development step, then bleaching and fixing the resulting image.
- a typical color reversal process is disclosed, for example, in U.S. Pat. 2,944,900.
- sucrose and/or other sugars have increased the stability of such compositions.
- sucrose and/or other sugars added to ascorbic acid developers such as developers containing ascorbic acid with a 1 phenyl 3 pyrazolidone developing agent, greatly increases the stability of these developers. This is applicable especially to monobaths containing an alkaline material, ascorbic acid and a mercapto fixing agent, such as thioglycerol.
- Sucrose and/ or other sugars accordingly can be added to compositions of the present invention.
- temperatures which are normally employed in reversal processing are suitable for the purposes of the invention. Processing can be carried out at ambient temperatures such as between about 20 and about 30 C. or
- temperatures such as those above about 50 C., e.g., about 50 C. to about C. Suitable temperatures can be determined by those skilled in the art.
- the time of development with the compositions of the invention can vary between a second up to several minutes or more, depending on the desired image and processing conditions.
- the desired optimum time can be determined based on the element to be processed, temperatures of processing, various addenda present in the processing compositions and the like.
- the components of the developer composition can be stored in individual containers, for instance in plastic packets or bottles as part of a kit, before processing is to be carried out.
- the silver halide developer accordingly, can comprise a combination for use in an aqueous developer solution of a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant.
- EXAMPLE 1 This example is a comparative example demonstrating reversal processing of a photographic element with (A) A developer composition containing a developing agent without an aminoalkanol and without an antifoggant,
- a film containing a fine-grained, low speed silver bromoiodide gelatino photographic emulsion is exposed imagewise and divided into four equal strips, (A), (B), (C) and (D). Each part is processed at 55 C. for 5 seconds in three successive solutions with agitation.
- the first solution is a developer solution, the second a bleach solution and the third a fogging developer solution.
- Strip (A) is treated in a first developer solution having the following composition:
- Strip (D) is also treated in the same manner as strip (A) with the exception that 30 cc. of l-amino-Z-propanol and 0.1 gram of l-phenyl-5-mercaptotetrazole is added to each liter of the first developer solution.
- EXAMPLE 2 This example illustrates the use of l-amino-2-propanol at varying concentrations with 1-phenyl-5-mercaptotetrazole in reversal processing employing first and second developer solutions which are alike.
- a film containing a fine-grained, low speed silver bromoiodide gelatino photographic emulsion is exposed imagewise to light.
- the resulting exposed emulsion is hand processed at 55 C. for 5 seconds in three successive solutions with agitation.
- the first solution is a developer solution having the following composition:
- the second solution is a bleach solution having the following composition:
- the third solution is a developer solution having the same composition as the first solution above.
- the emulsion is re-exposed by photoflood illumination during treatment in the third solution.
- control-no aminoalkanol 100 1. 3 0. 42 10 cc. per liter 150 2. 1 0. 23 30 cc. per liter 280 2.6 0. 22 50 cc. per liter 1, 300 2. 3 0.26
- EXAMPLE 3 This example illustrates the use of l-amino-Z-propanol at varying concentrations with l-phenyl 5 mercaptotetrazole in reversal processing employing a fogging developer as a second developer without an exposure step after the first developer
- a film containing a fine-grained, low speed silver bromoiodide gelatino photographic emulsion is exposed imagewise to light.
- the resulting exposed emulsion is hand processed at 55 C. for 5 seconds in three successive solutions with agitation as in Example 2 with the excep- 8 tion that the following solution is employed as the third solution:
- EXAMPLE 5 The procedure set out in Example 4 is repeated with the exception that 10 cc. per liter of solution of 3-aminol-propanol is added to the first developer solution in place of 2-diethylaminoethanol.
- EXAMPLE 6 The procedure set out in Example 4 is repeated with the exception that 10 cc. per liter of solution of 2-amino- 2-methyl 1 propanol is added to the first developer solution in place of Z-diethylaminoethanol.
- EXAMPLE 7 The procedure set out in Example 4 is repeated with the exception that 10 cc. per liter of solution of 3-diethylamino-l-propanol is added to the first developer solution in place of Z-diethylaminoethanol.
- EXAMPLE 8 The procedure set out in Example 4 is repeated with the exception that 10 cc. per liter of solution of 3-di-nbutylamino-l-propanol is added to the first developer solution in place of Z-diethylaminoethanol. Only part of the 3-di-n-butylamino-l-propanol is soluble in the solution at this concentration.
- a film containing a fine-grained, low speed silver bromoiodide gelatino photographic emulsion is exposed imagewise. It is then processed for seconds in each of three successive processing solutions at 55 C.
- the first solution is a developer solution having the following composition:
- the second soluition is a bleach solution having the following composition:
- Example 10 EXAMPLE 10 The procedure set out in Example 9 is repeated with the exception that 0.1 gram per liter of solution of thiobarbituric acid of the formula /g: C H2 is employed in place of 2-thiouracil. The results are set out in Table V in following Example 13.
- EXAMPLE 13 The procedure set out in Example 9 is repeated with the exception that 0.05 gram per liter of solution of Potassium dichromate grams 25.0 1 phenyl 5 mercaptotetrazole is employed in place of Sulfuric acid (conc.) cc 32.0 2-thiourac1l. Water to make 1 liter. The results are set out in Table V.
- the third solution is a fogging developer having the following composition:
- a control is also employed in which no aminoalkanol or mercapto azole compounds are used in the developer solutions.
- a second control is employed in which l-amino- 2-propanol is used in the first developer solution in the absence of a mercapto azole compound.
- EXAMPLE 14 1 1 EXAMPLE 15 1-amino-2-propanol ml. 30.0 N-methyl-p-aminophenol (Elon) grams 0.6 Sodium sulfite 50.0 Hydroquinone do 20.0 Potassium bromide do 8.0 Sodium hydroxide d 20.0
- the second solution is a bleach solution having the following composition:
- the third solution is a fogging developer solution having the following composition:
- Strip (A) is treated with the addition of 0.1 gram of 1-phenyl-S-mercaptotetrazole to the first developer solution.
- Strip (B) is treated in the same manner as strip (A) with the exception that 0.5 gram of thiosalicylic acid (a known mercapto antifoggant, but not a mercapto azole antifoggant) is added to the first developer solution in place of l-phenyl-S-mercaptotetrazole.
- thiosalicylic acid a known mercapto antifoggant, but not a mercapto azole antifoggant
- Strip (C) is treated in the same manner as strip (A) with the exception that 5 grams of benzotriazole (a known azole antifoggant, not containing a mercapto group) is added to the first developer solution in place of 1-phenyl-5-mercaptotetrazole.
- benzotriazole a known azole antifoggant, not containing a mercapto group
- a reversal process for developing a latent image in an exposed photographic silver halide emulsion compriing developing said latent image with a composition comprising a silver halide developing agent, an amino lower alkanol and a mercapto azole antifoggant; bleaching the resulting silver image; and developing a positive image in said emulsion.
- aminoalkanol is an aminoalkanol of the formula:
- Z represents the atoms necessary to complete a 5 or 6 member heterocyclic ring
- SX represents a mercapto function wherein X is a cation and n is a whole number from 1 to about 3.
- a process as in claim 1 wherein said aminoalkanol is l-amino-2-propanol.
- a process as in claim 1 also comprising carrying out said developing at temperatures above about 50 C.
- a reversal process for developing a latent image in an exposed photographic silver halide emulsion comprising developing said latent image in an aqueous solution comprising a hydroquinone developing agent, about 30 cc. per liter of said solution of l-amino-2-propanol and about 0.02 gram to about 0.5 gram per liter of said solution of 1-phenyl-S-mercaptotetrazole at a temperature above about 50 C.; bleaching the resulting image; and developnig a positive image in said emulsion.
Abstract
PHOTOGRAPHIC COMPOSITIONS AND PROCESSES EMPLOYING A SILVER HALIDE DEVELOPER, AN AMINOALKANOL AND A MERCAPTO AZOLE ANTIFOGGANT.
Description
United States Patent Office 3,576,633 Patented Apr. 27, 1971 3,576,633 PHOTOGRAPHIC PROCESS AND COMPOSITIONS Richard W. Henn and Bernadette D. Mack, Rochester,
N.Y1.\,I trgssignors to Eastman Kodak Company, Rochester, No Drawing. Filed June 27, 1967, Ser. No. 649,119 Int. Cl. G03c 5/30, 5 /50 U.S. Cl. 96-665 7 Claims ABSTRACT OF THE DISCLOSURE Photographic compositions and processes employing a silver halide developer, an aminoalkanol and amercapto azole antifoggant.
The present invention is directed to photographic processes and compositions. In a particular aspect, this invention relates to a reversal process employing a silver halide developing agent and an aminoalkanol with a mercapto azole antifoggant.
In another aspect, the invention is directed to a process for improved development in the first development step in a reversal process, especially a black-and-white reversal process.
It has been well known to develop positive photographic images by a conventional two-step negative-positive process. Another widely used procedure is the known reversal process in which the positive is obtained from an exposed silver halide emulsion in three main steps. The exposed silver halide emulsion is first developed to a negative image, then the silver formed during the first development step is bleached or converted to a light-insensitive silver salt which is water soluble. The remaining silver halide is then developed to a positive image in a second development step. The latter development step can be carried out in a developer without a re-exposure or in a developer following or during re-exposure.
While reversal processes are well known, they have been subject to certain shortcomings such as low contrast in the resulting image, loss in photographic speed, and relatively high minimum density.
It is, accordingly, an object of the present invention to provide a means for reversal processing of a silver halide emulsion which results in increased photographic speed and lower minimum density.
Another object of the invention is to provide an improved developer composition to decrease minimum density and provide increased speed of a photographic element.
These and other objects and advantages of the invention will be apparent from the following description.
The present invention comprises a photographic silver halide developer composition, particularly useful in reversal processing of a photographic element, comprising a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant.
It was completely unexpected to find that the use of this developer composition, especially in a reversal process, results in decreased minimum density as well as increased photographic speed and contrast of the element processed. Thus, in a developer solution the presence of a mercapto azole antifoggant generally produces a moderate increase in maximum density and gamma, but this is accompanied by a substantial loss in photographic speed. In contrast, when an aminoalkanol, as described herein, is present in the developer with the mercapto azole antifoggant, an unexpected increase in gamma and maximum density as well as an expected increase in photographic speed with a lowering of minimum density is achieved. The advantages of the combination are demonstrated in the following examples. Example 1 demonstrates that when one or both of the aminoalkanol and mercapto azole antifoggant are absent, the desired combination of increased gamma and maximum density without increased minimum density is not produced. Example 15 illustrates that neither an antifoggant, such as benzotriazole, containing no mercapto function or group, nor an antifoggant, such as thiosalicylic acid, containing no azole moiety provide the desired combination of results.
One embodiment of the invention comprises a photographic silver halide developer composition, especially an aqueous developer solution, suitable for reversal processing, comprising a silver halide developing agent, an aminoalkanol of the formula:
R2 R1N/ wherein R is a hydroxyalkyl radical, and R and R are each selected from the group consisting of hydrogen atoms and alkyl radicals; and a mercapto azole of the wherein Z represents the atoms necessary to complete a 5 or 6 membered heterocyclic ring and SX represents a mercapto function or group wherein X is a cation, including hydrogen, and n is a whole number from 1 to 3. A developer composition found especially suitable for reversal processing comprises an aqueous solution of a polyhydroxybenzene developing agent, l-amino-Z-propanol and 1-phenyl-S-mercaptotetrazole.
Another embodiment of the invention comprises, in a photographic process for developing a latent image in a photographic silver halide emulsion with a developer composition, the improvement of employing a developer composition containing a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant.
A preferred embodiment of the invention comprises, in a photographic reversal process for developing a latent image, the improvement comprising developing said latent image with a composition comprising a silver halide developing agent, an amino-alkanol and a mercapto azole antifoggant. According to this embodiment, a reversal process for developing a latent image in an exposed photographic silver halide emulsion is provided comprising developing an image in a developer composition comprising a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant, bleaching the resulting silver image and developing a positive image.
The emulsion after the first development step is typically re-exposed before subsequent processing or is re-exposed during the second development step. However, it is not necessary to carry out a re-exposure step after the first development step of a black-and-White reversal process if a so-called fogging developer is employed as the second developer composition. The use of the term fogging developer refers to a composition containing a component such as thiourea which sulfides the silver halide, or a developer containing strong reducing agents such as hydrazine or potassium borohydride.
Suitable aminoalkanols within the scope of the invention are those having at least one hydroxy alkyl radical and includes those compounds having one, two or more hydroxy radicals. These include compounds within the formula:
wherein R is a hydroxyalkyl radical such as one containing up to about 10 carbon atoms, typically a hydroxy lower alkyl radical, for example, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyisobutyl, dihydroxypropyl, dihydroxybutyl and the like, which provide an amino lower alkanol, and R and R are each selected from the group consisting of hydrogen atoms and alkyl radicals, such as those containing up to about 10 carbon atoms, typically lower alkyl radicals, such as methyl, ethyl, propyl, butyl, isobutyl and isopropyl radicals.
Suitable aminoalkanols, which can be referred to as hydroxyalkyl amines, include:
1-amino-2-propanol 2-diethylaminoethanol 3-amino-l-propanol Z-amino-Z-methyl-l-propanol 3-diethylamino-l-propanol 3-di-n-butylamino-l-propanol 2-amino-2-mthyl-1,3-propanediol 3-dimethylamino-1,2-propanediol The mercapto azole antifoggants employed in the practice of this invention include those antifoggants which contain at least one mercapto function or group and at least one azole moiety. Suitable antifoggants can be represented wherein Z represents the atoms necessary to complete a 5 or 6 member heterocyclic ring, such as pyrimidine, triazine, tetrazole, triazole, imidazole, diazole, oxadiazole or thiadiazole ring; and SX represents a mercapto function, n being a whole number, typically a number from 1 to about 3, any free bonds being satisfied by hydrogen atoms. In mercapto function or group, X is a cation which includes hydrogen, an alkali metal, e.g., sodium or potassium, ammonium or an organic amine residue of such amines as triethyl amine, trietanol amine, morpholine and the like.
Mercapto tetrazole antifoggants are especially suitable in the practice of this invention and include those of the formula:
(III) NZN wherein R is an aliphatic or aromatic radical containing up to about 30 carbon atoms and SX is a mercapto function. As in structure H, X of the mercapto function or group is a cation including a hydrogen atom or, for example, an alkali metal such as sodium, potassium, ammonium or an organic amine residue of such amines as triethyl amine, triethanol amine, morpholine and the like. In addition, many of the mercapto tetrazoles within the scope of structure III can be in tautomeric form, for example, in the thione form, in which case the labile hydrogen atom in the mercapto function becomes bonded to the nitrogen atom and the group becomes a thiocarbonyl C=S) group. The term S-mercapto tetrazole, as employed herein, is intended to cover compounds in which the mercapto function is in any of these forms. R can be a hydrocarbon or nonhydrocarbon and includes alkyl or aryl radicals which can contain atoms or groups other than carbon and hydrogen. Suitable atoms or groups which can be present in R together with hydrogen and carbon include, for example, alkoxy, phenoxy, halogen, cyano, amino, substituted amino, sulfo, sulfamyl, substituted sulfamyl, sulfonylphenyl, sulfonylalkyl, fluosulfonyl, sulfonamidophenyl, sulfonamidoalkyl, carboxy, carboxylate, carbam- 4 yl, carbamylphenyl, carbamyalkyl, carbonylphenyl and similar groups.
Mercapto azole antifoggants within the scope of the invention include:
mercapto-substituted pyrimidines such as:
thiobarbituric acid and thiouracil, mercapto-substituted oxadiazoles or thiadiazoles such as:
S-phenyI-Z-mercapto-1,3,4-oxadiazole and 5-o-tolyl-2-mercapto-1,3,4-thiadiazole, mercapto triazines such as: 2,4,6-trimercapto-1,3,5-triazine, mercapto imidazoles such as: Z-mercapto-5-phenylimidazole, condensed imidazoles such as: Z-mercaptobenzimidazole, triazoles such as:
3,4,-diphenyl-5-mercapto-1,2,4-triazole and 3-mercapto-5-methyl-1,2,4-triazole, mercapto tetrazoles such as:
1-phenyl-5-mercaptotetrazole and 1- 3-capramido) phenyl-S-mercaptotetrazole.
Other compounds which are suitable are disclosed in Belgian Pat. 681,359.
Any of the silver halide developing agents can be employed in the practice of this invention. Suitable developing agents which can be employed are polyhydroxybenzenes, e.g., hydroquinone developing agents such as hydroquinone, alkyl substituted hydroquinones as exemplified by t butylhydroquinone, methylhydroquinone, dimethylhydroquinone; catechol and pyrogallol; chloro substituted hydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxy substituted hydroquinones such as methoxy or ethoxy hydroquinone; aminophenol developing agents such as 2,4-diaminophenols and methylaminophenols; ascorbic acid; pyrazolidone developing agents such as 1-phenyl-3-pyrazolidone, including those described in British Pat. 930,572; and acyl derivatives of p-aminophenol such as disclosed in British Pat. 1,045,303. Such developing agents can be used alone or in combination.
Concentrations of the silver halide developing agent can vary over a wide range. Suitable concentrations in a developer composition will be determined based on other components, the desired image and other factors which can be determined by those skilled in the art. A typical concentration is about 2 to about 50 grams of developing agent per liter of processing solution.
The concentration of the aminoalkanol in solution is typically at least about 2 grams per liter up to about grams per liter of processing solution. Good results are often obtained with concentrations in the range of about 10 grams to about 50 grams per liter of processing solution.
The concentration of azole compound in solution is tyipcally in the range of about 0.02 gram per liter to about 0.5 gram per liter of solution.
The pH ranges which are suitable for the purposes of the invention can vary and include those typically employed in processing photographic elements. The pH is usually above about 7, for instance, about 10 to about 13.
Ordinary development activators can be employed with the above compositions and processes. These include the typical alkalis employed for activating developers, such as alkali metal hydroxides, typically sodium hydroxide, as well as other alkaline materials such as borax and alkali metal carbonates. These can be employed in any concentration which is effective for activating the development.
Various photographic addenda, particularly those known to be beneficial in photographic compositions, can be employed in the compositions of the invention as well as in the photographic elements processed. The types of addenda and concentrations to be employed can be determined by those skilled in the art. Suitable photographic addenda include, e.g., hardeners, such as alum or those set out in British Pat. 974,317; buffers which maintain the desired pH level including various sulfonamides and boraxes; coating aids; plasticizers; speed-increasing addenda, such as quaternary ammonium salts and alkylene oxide polymers such as polyethylene glycols; and stabilizing agents such as sodium sulfite.
The photographic emulsions employed in the practice of the invention can be sensitized using any of the wellknown techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, noble metal and/or gold compounds.
The photographic elements can also contain spectral sensitizing dyes such as described, for example, in U.S. Pats. 2,526,632 and 2,503,776. Spectral sensitizers which can be used include cyanines, merocyanines, styryls and hemicyanines.
The photographic elements processed according to the invention typically contain an emulsion layer comprising any of the known hydrophilic water permeable binding materials suitable for photographic purposes. These include, for example, gelatin, cellulose derivatives, polymerized vinyl compounds, water insoluble polymers of acrylates and methacrylates, as well as mixtures of such binding agents.
The photosensitive coatings which are processed according to the invention can be coated on a wide variety of supports. Typical supports include cellulose ester films, polyvinyl acetal films, polyethylene terephthalate films and related films and resinous materials as well as glass, paper, metals and the like. Paper supports which are coated with resinous materials such as polyethylene, polypropylene, ethylene-butene copolymers and the like can also be employed.
Various silver salts can be used as the sensitive salt in the elements processed according to the invention. These include silver halides such as silver iodide, silver bromide, silver chloride, silver bromoiodide, silver chloroiodide and the like.
Various silver halide fixing agents or solvents can also be employed in combination with the developer compositions and processes of the invention. These include alkali metal thiosulfates, such as sodium thiosulfate and thiocyanates such as ammonium thiocyanate.
The photographic elements processed according to the invention can typically be bleached or converted to a light insensitive silver salt which is water soluble following a first development step. Suitable compositions for carrying outer this bleaching are known and include potassium dichromate and sulfuric acid bleaching compositions.
The compositions of the invention containing the silver halide developer, aminoalkanol, and mercapto azole antifoggant can be employed in the first black-and-white development step in a color reversal process. Such color reversal processes usually comprise treating the exposed photographic element in a black-and-white development step, re-exposure of the element, a color development step, then bleaching and fixing the resulting image. A typical color reversal process is disclosed, for example, in U.S. Pat. 2,944,900.
It has been found that the addition of sucrose and/or other sugars to developer compositions has increased the stability of such compositions. For instance, sucrose and/or other sugars added to ascorbic acid developers, such as developers containing ascorbic acid with a 1 phenyl 3 pyrazolidone developing agent, greatly increases the stability of these developers. This is applicable especially to monobaths containing an alkaline material, ascorbic acid and a mercapto fixing agent, such as thioglycerol. Sucrose and/ or other sugars accordingly can be added to compositions of the present invention.
The temperatures which are normally employed in reversal processing are suitable for the purposes of the invention. Processing can be carried out at ambient temperatures such as between about 20 and about 30 C. or
at elevated temperatures such as those above about 50 C., e.g., about 50 C. to about C. Suitable temperatures can be determined by those skilled in the art.
The time of development with the compositions of the invention can vary between a second up to several minutes or more, depending on the desired image and processing conditions. The desired optimum time can be determined based on the element to be processed, temperatures of processing, various addenda present in the processing compositions and the like.
The components of the developer composition can be stored in individual containers, for instance in plastic packets or bottles as part of a kit, before processing is to be carried out. The silver halide developer, accordingly, can comprise a combination for use in an aqueous developer solution of a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant.
The invention is further illustrated in the following examples:
EXAMPLE 1 This example is a comparative example demonstrating reversal processing of a photographic element with (A) A developer composition containing a developing agent without an aminoalkanol and without an antifoggant,
(B) A developer composition with a developing agent and an aminoalkanol without an antifoggant,
(C) A developer composition with a developing agent and an antifoggant without an aminoalkanol, and
(D) A developer composition with a developing agent, an aminoalkanol and a mercapto azole antifoggant.
This example demonstrates that when either the aminoalkanol or the mercapto azole antifoggant are absent from the developer composition, the desired combination of increased gamma and maximum density without in creased minimum density, is not achieved.
A film containing a fine-grained, low speed silver bromoiodide gelatino photographic emulsion is exposed imagewise and divided into four equal strips, (A), (B), (C) and (D). Each part is processed at 55 C. for 5 seconds in three successive solutions with agitation. The first solution is a developer solution, the second a bleach solution and the third a fogging developer solution.
Strip (A) is treated in a first developer solution having the following composition:
Grams N-methyl-p-aminophenol 0.6 Sodium sulfite 50.0 Hydroquinone 20.0 Potassium bromide 8.0 Sodium hydroxide 20.0
Water to make 1 liter.
It is then treated in a bleach solution having the following composition:
Grams Potassium dichromate 25.0 Sulfuric acid (conc.) 31.0
Water to make 1 liter.
Finally, it is treated in a fogging developer solution having the following composition:
Grams Thiourea 20.0 Sodium hydroxide "a 5.0 Sodium sulfate 50.0
Water to make 1 liter.
Strip (D) is also treated in the same manner as strip (A) with the exception that 30 cc. of l-amino-Z-propanol and 0.1 gram of l-phenyl-5-mercaptotetrazole is added to each liter of the first developer solution.
The results obtained for each of these strips is given in Table I, the relative speed being calculated at 0.1 above fog level.
TABLE I Relative Contrast Strip speed (gamma) Dmin. DmBX.
(A) Control(no aminoalkanol or antiioggant).-. 100 1. 15 0. 20 1. 58 (B) l-amino-Z-propanol 480 0.75 0.11 0.78 (C) 1-phenyl-5-mercaptotetrazole 80 1. 64. 0. 17 1. 72 (D) l-amino-Z-propanol and 1-phenyl-fi-mercaptotetrazole 360 3.24 0.13 1.71
EXAMPLE 2 This example illustrates the use of l-amino-2-propanol at varying concentrations with 1-phenyl-5-mercaptotetrazole in reversal processing employing first and second developer solutions which are alike.
A film containing a fine-grained, low speed silver bromoiodide gelatino photographic emulsion is exposed imagewise to light. The resulting exposed emulsion is hand processed at 55 C. for 5 seconds in three successive solutions with agitation. The first solution is a developer solution having the following composition:
Grams Sodium sulfite 65.00 Sodium bromide 6.92 Phenylmercaptotetrazole 0.12 Dimezone 1.00 Hydroquinone 40.00
Water to make 1 liter. Potassium hydroxide added until solution has pH 12.3. The second solution is a bleach solution having the following composition:
Grams Potassium dichromate 25.0 Sulfuric acid (conc.) 32.0
Water to make 1 liter.
The third solution is a developer solution having the same composition as the first solution above. The emulsion is re-exposed by photoflood illumination during treatment in the third solution.
The procedure is repeated with the exception that l-amino 2 propanol is added at rates of 10, 30 and 50 cc. per liter to both the first and last solutions. After drying the resulting developed emulsions have the following values shown in Table II for relative speed, determined at a density of 0.1 above fog, contrast and minimum density.
TABLE II Concentration of 1-amino-2- Relaitve Contrast propanol speed (gamma) Dmin.
(control-no aminoalkanol) 100 1. 3 0. 42 10 cc. per liter 150 2. 1 0. 23 30 cc. per liter 280 2.6 0. 22 50 cc. per liter 1, 300 2. 3 0.26
EXAMPLE 3 This example illustrates the use of l-amino-Z-propanol at varying concentrations with l-phenyl 5 mercaptotetrazole in reversal processing employing a fogging developer as a second developer without an exposure step after the first developer A film containing a fine-grained, low speed silver bromoiodide gelatino photographic emulsion is exposed imagewise to light. The resulting exposed emulsion is hand processed at 55 C. for 5 seconds in three successive solutions with agitation as in Example 2 with the excep- 8 tion that the following solution is employed as the third solution:
Grams Thiourea 20.0 Sodium hydroxide 5.0 Sodium sulfate 50.0
Water to make 1 liter.
The procedure is repeated with the addition of l-amino- 2-propanol at the rates of 10, 30 and 50- cc. per liter of solution to the first developer solution. After drying, the resulting developed emulsions have the following values shown in Table III:
TABLE III Concentration of l-amino-Z- Relative Contrast propanol Speed (gamma) D... in
0 (control-n0 aminoalkanol) 1. 6 O. 15 10 cc. per liter 240 2. 9 0. 14 30 cc. per liter 630 5. 0 0. 14 50 00. per liter 1, 600 3. 8 0. 14
EXAMPLE 4 Grams Thiourea 20.0 Sodium hydroxide 5.0 Sodium sulfate 50.0
Water to make 1 liter.
The results are set out in Table IV in following Example 8. A control is also employed wherein no aminoalkanol is employed in either developer solution.
EXAMPLE 5 The procedure set out in Example 4 is repeated with the exception that 10 cc. per liter of solution of 3-aminol-propanol is added to the first developer solution in place of 2-diethylaminoethanol.
The results are set out in Table IV in following Example 8.
EXAMPLE 6 The procedure set out in Example 4 is repeated with the exception that 10 cc. per liter of solution of 2-amino- 2-methyl 1 propanol is added to the first developer solution in place of Z-diethylaminoethanol.
The results are set out in Table IV in following Example 8.
EXAMPLE 7 The procedure set out in Example 4 is repeated with the exception that 10 cc. per liter of solution of 3-diethylamino-l-propanol is added to the first developer solution in place of Z-diethylaminoethanol.
The results are set out in Table IV in following Example 8.
EXAMPLE 8 The procedure set out in Example 4 is repeated with the exception that 10 cc. per liter of solution of 3-di-nbutylamino-l-propanol is added to the first developer solution in place of Z-diethylaminoethanol. Only part of the 3-di-n-butylamino-l-propanol is soluble in the solution at this concentration.
The results are set out in Table IV.
The results shown in Table IV for 3-di-n-butylaminol-propanol demonstrate that it is desirable to employ an amount of aminoalkanol which is completely soluble in the developer solution used.
EXAMPLE 9 This example demonstrates the use of l-amino-Z-propanel and Z-thiouracil in reversal processing:
A film containing a fine-grained, low speed silver bromoiodide gelatino photographic emulsion is exposed imagewise. It is then processed for seconds in each of three successive processing solutions at 55 C. The first solution is a developer solution having the following composition:
l-amino-Z-propanol cc 30.1 N-methyl-p-aminophenol (Elon) grams 0.6 Sodium sulfite do 50.0 Hydroquinone do 20.0 Potassium bromide do 8.0 Sodium hydroxide ..do 20.0 2-Thiouracil do 0.1
Water to make 1 liter.
The second soluition is a bleach solution having the following composition:
10 EXAMPLE 10 The procedure set out in Example 9 is repeated with the exception that 0.1 gram per liter of solution of thiobarbituric acid of the formula /g: C H2 is employed in place of 2-thiouracil. The results are set out in Table V in following Example 13.
EXAMPLE 11 The procedure set out in Example 9 is repeated with the exception that 0.1 gram per liter of solution of 2-benzimidazole thiol of the formula:
I C-SH HC is employed in place of 2-thiouracil. The results are set out in Table V in following Example 13.
EXAMPLE 12 The procedure set out in Example 9 is repeated with the exception that 0.05 gram per liter of solution of S-phenyl-Z-mercapto-1,3,4-oxadiazole of the formula:
0 -o CSH is employed in place a 2-thiouracil. The results are set out in Table V in following Example 13.
EXAMPLE 13 The procedure set out in Example 9 is repeated with the exception that 0.05 gram per liter of solution of Potassium dichromate grams 25.0 1 phenyl 5 mercaptotetrazole is employed in place of Sulfuric acid (conc.) cc 32.0 2-thiourac1l. Water to make 1 liter. The results are set out in Table V.
TABLE V Relative Contrast Example Number speed (gamma) Dmin- D Contro1No aminoalkanol or mercaptoazole 100 0.95 0. 19 l. 69 Contro11-a1;nino-2-propanol without mercapto azole 650 1. 2 0. 15 1. 11 9. l-amino-Z-propanol with 2-thiouracil. 400 1. 4 0. 16 1. 36 10. 1-amino-2-propanol with thiobarbitur 380 1. 3 0. 15 1. 41 11. 1-amino-2-propanol with 2-benzlmidazole thiol. 250 1.25 0. l6 1. 44 12. 1-amino-2-propanol with 5-phenyl-2-mercapto- 1,3,4-oxadiazole 200 1. 0. 18 1. 92 13. l-amino-Z-propanol with 1-phenyl-5-mercaptotetrazole 320 1. 8 0. 18 1. 9
The third solution is a fogging developer having the following composition:
Grams Thiourea 20.0 Sodium hydroxide 5.0 Sodium sulfate 50.0
Water to make 1 liter.
A control is also employed in which no aminoalkanol or mercapto azole compounds are used in the developer solutions. A second control is employed in which l-amino- 2-propanol is used in the first developer solution in the absence of a mercapto azole compound.
The results are set out in Table V in following Example 13.
The results in Table V demonstrate that the presence of the mercapto azole compounds with the aminoalkanol provides increased maximum density of the developed image while maintaining the desired increased relative speed and contrast or gamma.
EXAMPLE 14 1 1 EXAMPLE 15 1-amino-2-propanol ml. 30.0 N-methyl-p-aminophenol (Elon) grams 0.6 Sodium sulfite 50.0 Hydroquinone do 20.0 Potassium bromide do 8.0 Sodium hydroxide d 20.0
Water to make 1 liter.
The second solution is a bleach solution having the following composition:
Potassium dichromate grams 25.0 Sulfuric acid (conc.) cc. 32.0 Water to make 1 liter.
The third solution is a fogging developer solution having the following composition:
Grams Thiourea 20.0 Sodium hydroxide 5.0 Sodium sulfate 50.0
Water to make 1 liter.
Strip (A) is treated with the addition of 0.1 gram of 1-phenyl-S-mercaptotetrazole to the first developer solution.
Strip (B) is treated in the same manner as strip (A) with the exception that 0.5 gram of thiosalicylic acid (a known mercapto antifoggant, but not a mercapto azole antifoggant) is added to the first developer solution in place of l-phenyl-S-mercaptotetrazole.
Strip (C) is treated in the same manner as strip (A) with the exception that 5 grams of benzotriazole (a known azole antifoggant, not containing a mercapto group) is added to the first developer solution in place of 1-phenyl-5-mercaptotetrazole.
The results obtained for each of the strips is set out in Table VI, the relative speed being calculated at 0.1
The results in Table VI demonstrate that only strip (A) which was treated in a first developer solution containing l-amino-Z-propanol and l-phenyl-S-mercaptotetrazole provides the desired combination of relative speed, increased gamma, and increased maximum density.
Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected without departing from the spirit and scope of the invention as described herein above and as defined in the appended claims.
We claim:
1. A reversal process for developing a latent image in an exposed photographic silver halide emulsion compri ing developing said latent image with a composition comprising a silver halide developing agent, an amino lower alkanol and a mercapto azole antifoggant; bleaching the resulting silver image; and developing a positive image in said emulsion.
2. A process as in claim 1 wherein said aminoalkanol is an aminoalkanol of the formula:
RiN
formula:
( Z sx).
wherein Z represents the atoms necessary to complete a 5 or 6 member heterocyclic ring, and SX represents a mercapto function wherein X is a cation and n is a whole number from 1 to about 3.
3. A process as in claim 1 wherein said aminoalkanol is l-amino-2-propanol.
4. A process as in claim 1 wherein said mercapto azole is 1-phenyl-S-mercaptotetrazole.
5. A process as in claim 1 wherein said developing of a positive image, after said bleaching, is carried out with a composition which comprises a silver halide developing agent, an aminoalkanol and a mercapto azole antifoggant.
6. A process as in claim 1 also comprising carrying out said developing at temperatures above about 50 C.
7. A reversal process for developing a latent image in an exposed photographic silver halide emulsion comprising developing said latent image in an aqueous solution comprising a hydroquinone developing agent, about 30 cc. per liter of said solution of l-amino-2-propanol and about 0.02 gram to about 0.5 gram per liter of said solution of 1-phenyl-S-mercaptotetrazole at a temperature above about 50 C.; bleaching the resulting image; and developnig a positive image in said emulsion.
References Cited UNITED STATES PATENTS 3,335,009 8/1967 Rasch et a1. 9661 3,232,761 2/1966 Allen et al. 96-66 NORMAN G. TORCHIN, Primary Examiner E. C. KIMLIN, Assistant Examiner U.S. Cl. X.R. 96-59 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent: No. 3 576,633 Dated April 2'? 1971 Inventor(s) Richard W. Henn and Bernadette D. Mack It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In column 3 line 19 (page 5, line 12 of the application) "2-amino-2-mthyl-l,3-propanediol" should read 2-amino2methyll,3propanediol In column 3, line 39 (page 5, line 28 of the application) "trietanol" should read --triethanol--.
In column LL, line 56 (page 8, line 19 of the application), "tyipcally" should read ---typically---.
In column 6, line 58 (page 13, line 17 of the application), "31.0" should read 32.0--
In column 8, line 20 (page 16, line 19 of the application) "2.9" should read --l.9--.
In column 9, line 3L4. (page 19, line 6 of the application) "30.1" should read -30.0--.
In column 12, line 52 (last line of claim 16 in the application) "developnig" should read --developing- Signed and sealed this 16th day of November 1971 (SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Acting Commissioner of Patents
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US64911967A | 1967-06-27 | 1967-06-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3576633A true US3576633A (en) | 1971-04-27 |
Family
ID=24603544
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US649119A Expired - Lifetime US3576633A (en) | 1967-06-27 | 1967-06-27 | Photographic process and compositions |
Country Status (4)
Country | Link |
---|---|
US (1) | US3576633A (en) |
BE (1) | BE717136A (en) |
DE (1) | DE1772724A1 (en) |
GB (1) | GB1219315A (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3808003A (en) * | 1969-01-24 | 1974-04-30 | Fuji Photo Film Co Ltd | Photographic material development method |
US3839046A (en) * | 1972-10-12 | 1974-10-01 | Ilford Ltd | Process for the production of a photographic print |
US4030920A (en) * | 1976-04-12 | 1977-06-21 | Eastman Kodak Company | Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement |
US4172728A (en) * | 1977-12-16 | 1979-10-30 | E. I. Du Pont De Nemours And Company | High contrast continuous tone developer and process of use |
US4184875A (en) * | 1977-04-30 | 1980-01-22 | Agfa-Gevaert, A.G. | Photographic reversal process |
US4322493A (en) * | 1978-09-26 | 1982-03-30 | Fuji Photo Film Co., Ltd. | Reversal processing methods for black and white photographic light-sensitive materials |
US4362811A (en) * | 1978-12-11 | 1982-12-07 | Mitsubishi Paper Mills Ltd. | Processing solution composition for silver complex diffusion transfer process |
US4568634A (en) * | 1983-11-14 | 1986-02-04 | Fuji Photo Film Co., Ltd. | Processing composition for use in silver salt diffusion transfer containing alkali metal phosphate salt and aminoalcohol |
US4988603A (en) * | 1988-01-11 | 1991-01-29 | Konica Corporation | Method for the formation of high-contrast images using a developer comprising a hydrazine derivative |
US5063136A (en) * | 1989-05-18 | 1991-11-05 | Agfa-Gevaert, N.V. | Processing liquid for use in dtr-photography with two toners |
US5204212A (en) * | 1991-01-21 | 1993-04-20 | Agfa-Gevaert, N.V. | Processing liquid for the silver salt diffusion transfer process containing 3-(n,n-diethylamino)propane-1,2-diol |
US5340705A (en) * | 1989-05-18 | 1994-08-23 | Agfa-Gevaert, N.V. | Processing liquid for use in silver complex diffusion transfer processing |
US5811226A (en) * | 1996-03-14 | 1998-09-22 | Eastman Kodak Company | Method of processing a silver halide photographic element which reduces fog |
EP1182498A1 (en) * | 2000-08-21 | 2002-02-27 | Eastman Kodak Company | Ascorbic acid developing compositions containing sugar and methods of use |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS511426B1 (en) * | 1971-02-09 | 1976-01-17 | ||
IT1175017B (en) * | 1983-09-20 | 1987-07-01 | Minnesota Mining & Mfg | DEVELOPMENT COMPOSITIONS FOR PHOTOGRAPHIC MATERIALS WITH SILVER HALIDES |
-
1967
- 1967-06-27 US US649119A patent/US3576633A/en not_active Expired - Lifetime
-
1968
- 1968-06-25 BE BE717136D patent/BE717136A/xx unknown
- 1968-06-26 DE DE19681772724 patent/DE1772724A1/en active Pending
- 1968-06-26 GB GB30447/68A patent/GB1219315A/en not_active Expired
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3808003A (en) * | 1969-01-24 | 1974-04-30 | Fuji Photo Film Co Ltd | Photographic material development method |
US3839046A (en) * | 1972-10-12 | 1974-10-01 | Ilford Ltd | Process for the production of a photographic print |
US4030920A (en) * | 1976-04-12 | 1977-06-21 | Eastman Kodak Company | Processing compositions containing glycols for color transfer processes comprising direct positive silver halide developement |
US4184875A (en) * | 1977-04-30 | 1980-01-22 | Agfa-Gevaert, A.G. | Photographic reversal process |
US4172728A (en) * | 1977-12-16 | 1979-10-30 | E. I. Du Pont De Nemours And Company | High contrast continuous tone developer and process of use |
US4322493A (en) * | 1978-09-26 | 1982-03-30 | Fuji Photo Film Co., Ltd. | Reversal processing methods for black and white photographic light-sensitive materials |
US4362811A (en) * | 1978-12-11 | 1982-12-07 | Mitsubishi Paper Mills Ltd. | Processing solution composition for silver complex diffusion transfer process |
US4568634A (en) * | 1983-11-14 | 1986-02-04 | Fuji Photo Film Co., Ltd. | Processing composition for use in silver salt diffusion transfer containing alkali metal phosphate salt and aminoalcohol |
US4988603A (en) * | 1988-01-11 | 1991-01-29 | Konica Corporation | Method for the formation of high-contrast images using a developer comprising a hydrazine derivative |
US5063136A (en) * | 1989-05-18 | 1991-11-05 | Agfa-Gevaert, N.V. | Processing liquid for use in dtr-photography with two toners |
US5340705A (en) * | 1989-05-18 | 1994-08-23 | Agfa-Gevaert, N.V. | Processing liquid for use in silver complex diffusion transfer processing |
US5204212A (en) * | 1991-01-21 | 1993-04-20 | Agfa-Gevaert, N.V. | Processing liquid for the silver salt diffusion transfer process containing 3-(n,n-diethylamino)propane-1,2-diol |
US5811226A (en) * | 1996-03-14 | 1998-09-22 | Eastman Kodak Company | Method of processing a silver halide photographic element which reduces fog |
US5935771A (en) * | 1996-03-14 | 1999-08-10 | Eastman Kodak Company | Method of processing a silver halide photographic element which reduces fog |
EP1182498A1 (en) * | 2000-08-21 | 2002-02-27 | Eastman Kodak Company | Ascorbic acid developing compositions containing sugar and methods of use |
US6673528B2 (en) | 2000-08-21 | 2004-01-06 | Eastman Kodak Company | Ascorbic acid developing compositions containing sugar and methods of use |
Also Published As
Publication number | Publication date |
---|---|
GB1219315A (en) | 1971-01-13 |
BE717136A (en) | 1968-12-02 |
DE1772724A1 (en) | 1970-09-10 |
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