US3615511A - Surface developer with heterocyclic mercaptan for use on internal image emulsion - Google Patents
Surface developer with heterocyclic mercaptan for use on internal image emulsion Download PDFInfo
- Publication number
- US3615511A US3615511A US731275A US3615511DA US3615511A US 3615511 A US3615511 A US 3615511A US 731275 A US731275 A US 731275A US 3615511D A US3615511D A US 3615511DA US 3615511 A US3615511 A US 3615511A
- Authority
- US
- United States
- Prior art keywords
- silver
- complexing agent
- process according
- mercaptoimidazole
- groups
- 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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims description 11
- 239000000839 emulsion Substances 0.000 title description 32
- 125000000623 heterocyclic group Chemical group 0.000 title 1
- 229910052709 silver Inorganic materials 0.000 claims abstract description 97
- 239000004332 silver Substances 0.000 claims abstract description 97
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000008139 complexing agent Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 47
- -1 silver halide Chemical class 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical group SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 8
- 238000004061 bleaching Methods 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 claims description 6
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 5
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 claims description 5
- QPOZGXKWWKLJDK-UHFFFAOYSA-N 6-nitro-3h-1,3-benzothiazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2NC(=S)SC2=C1 QPOZGXKWWKLJDK-UHFFFAOYSA-N 0.000 claims description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 claims description 4
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 claims description 4
- MFXKJBZEEFHOQH-UHFFFAOYSA-N 5-methyl-1,3-oxazolidine-2-thione Chemical compound CC1CNC(=S)O1 MFXKJBZEEFHOQH-UHFFFAOYSA-N 0.000 claims description 4
- 125000005462 imide group Chemical group 0.000 claims description 4
- VKONPNAILGGMSR-UHFFFAOYSA-N 2-(2-sulfanylidene-3h-1,3-thiazol-4-yl)acetic acid Chemical compound OC(=O)CC1=CSC(=S)N1 VKONPNAILGGMSR-UHFFFAOYSA-N 0.000 claims description 3
- YPXQSGWOGQPLQO-UHFFFAOYSA-N 5-nitro-1,3-dihydrobenzimidazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2N=C(S)NC2=C1 YPXQSGWOGQPLQO-UHFFFAOYSA-N 0.000 claims description 3
- BXDMTLVCACMNJO-UHFFFAOYSA-N 5-amino-1,3-dihydrobenzimidazole-2-thione Chemical compound NC1=CC=C2NC(S)=NC2=C1 BXDMTLVCACMNJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000003918 potentiometric titration Methods 0.000 claims description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims 4
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims 4
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims 2
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 claims 2
- XUEDGYZCOWRRAP-UHFFFAOYSA-N 4-phenyl-3-sulfanyl-2h-tetrazole Chemical compound SN1NN=CN1C1=CC=CC=C1 XUEDGYZCOWRRAP-UHFFFAOYSA-N 0.000 claims 2
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 claims 2
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims 2
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 claims 2
- 239000007844 bleaching agent Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- 239000000523 sample Substances 0.000 description 9
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 108700024661 strong silver Proteins 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ZNZJQJLLXWDANB-UHFFFAOYSA-N 1-benzofuran-2-thiol Chemical compound C1=CC=C2OC(S)=CC2=C1 ZNZJQJLLXWDANB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QSAOYVQFHWVHQT-UHFFFAOYSA-N 2-nitrosulfanyl-1H-benzimidazole Chemical compound [N+](=O)([O-])SC1=NC2=C(N1)C=CC=C2 QSAOYVQFHWVHQT-UHFFFAOYSA-N 0.000 description 1
- VZVSYSWIOYRZHL-UHFFFAOYSA-N 4-nitro-1,3-dihydrobenzimidazole-2-thione Chemical compound [O-][N+](=O)C1=CC=CC2=C1NC(=S)N2 VZVSYSWIOYRZHL-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241001446467 Mama Species 0.000 description 1
- 101000829705 Methanopyrus kandleri (strain AV19 / DSM 6324 / JCM 9639 / NBRC 100938) Thermosome subunit Proteins 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241001115903 Raphus cucullatus Species 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
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000013625 clathrin-independent carrier Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 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
- 229920003169 water-soluble 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
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/49—Print-out and photodevelopable emulsions
-
- 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
- G03C5/30—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
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
Definitions
- the developing or stabilizing compositions of this invention contain low concentrations of a silver complexing agent.
- photographic compositions are stabilized or developed with a process comprising a bleach bath followed by a surface type developer.
- direct-print materials containing either photodeveloped images or nonphotodeveloped latent images can be processed to provide permanent image records.
- This invention relates to processes and compositions for developing or stabilizing image records in photographic materials.
- this invention relates to novel processes for developing or stabilizing image records in directprint, photographic materials.
- this invention relates to novel processes comprising bleaching and then developing or stabilizing image records in direct-print -material.
- this invention relates to a means by which both latent images and photodeveloped images can be made into stable, permanent image records.
- direct-print compositions which have been imagewise exposed are processed in a surface developer containing selective silver complexing agent, fixed and washed.
- direct-print records which have been imagewise exposed are photodeveloped to a discernible image and then processed in a surface developer containing a selective silver complexing agent, fixed and washed.
- direct-print compositions which have been imagewise exposed are bleached and then processed in a surface developer containing a selective silver complexing agent, fixed and washed.
- direct-print compositions which have been imagewise exposed are photodeveloped, bleached, processed in a surface developer containing a selective silver complexing agent, fixed and washed.
- the selective silver complexing agents of this invention contain two characteristic groups which provide the unique properties in the surface developers.
- the silver complexing agents contain at least one group which is capable of forming a normal covalent bond with silver.
- Typical complexing agents contain groups capable of forming the covalent bonds such as -S-Ag, N-Ag and the like.
- the preferred complexing agents contain imide groups mercaptan groups (SI-l) and the like or tautomers thereof.
- the complexing agents also contain at least one secondary bonding group which does not generally form a covalent bond with silver under the conditions generally encountered in photographic emulsions and photographic developing solutions. Bonds of this type are sometimes referred to as 1r bonds in the atomic configuration of the ion complex formation.
- Typical groups in the silver complexing agents of this invention which can be classified as'secondary bonding groups are or carbon-carbon double bond groupsythese groups can occur for example as part of a hertocyclic ring system as in 2-mercaptoimidazole or in an alkyl side chain as in l-allyl-2-thiourea, (2) aromatic substituents; typical compounds of this type are benzo or phenyl derivatives, (3) donor atoms containing 2 nonbonding electron pairs; typical preferred groups of this type are S-S and the like.
- the silver complexing agents of this invention can be additionally characterized as compounds which are soluble in water at 70F. in'concentration of at least l0' and preferably 10 moles per liter and wherein said compounds are capable of forming a silver ion complex in a ratio of at least 10 silver ion to 10 complexing agent on a molar basis in the presence of an equal molar or excess of silver ion as measured by potentiometric titration.
- the silver complexing agents of this invention are incorporated in the developing solutions in lower concentrations than normally used for antifoggant purposes.
- the developing solution is used directly after imagewise exposure or photodevelopment it is critical to maintain the concentration level of the silver complexing agent at levels below 2X10 moles per liter of solution and preferably below 1.5Xl0 moles per liter of developing solution.
- the concentrations of the silver complexing agent for this embodiment are maintained between about 10 moles to about 2Xl0 moles per liter about 1X10 moles to about 1 5X10 moles per liter.
- the concentration of the silver complexing agent can be generally'from about l0" moles to about 4X10" moles and preferably from about 10" moles to not more than 2.5)(10 moles i solution. If the concentrations of the silver complexing agent exceed the above concentrations, the density of the developed image is greatly reduced.
- direct-print compositions are stabilized ordeveloped by contacting said compositions with -a bleach bath and then contacting said compositions withthe developing solutions containing the silver complexing agentsXHowever, the bleach bath will also provide some improvements in image properties in directprint emulsions when said bleach bath is followed with other developing solutions.
- Typical compounds which can be characterized by the above tests and are effective in the developing baths of this invention are Z-mercaptothiazole, Z-mercapto benzothiazole, 2- mercapto-6-nitrobenzothiazole, 4-carboxymethyl-4- thiazoline-Z-thione, thiazolidine-Z-thione, irnidazole, 2- benzimidazoletliiol, 5-amino-Z-benzimidazolethiol, 2-mercaptoimidazole, l-methyl-2-mercaptoimidazole, Z-mercaptopyrimidine, dithiourazole, o-aminobenzenethiol, o-mercapto-benzoic acid, l-phenyl-2-mercaptotetrazole, l-phenyl-2- thiourea, S-nitrobenzimidazolethiol, 6-amino-2-mercaptobenzothiozole, 2-benzoxazolethiol
- the silver halide emulsions which can be processed according to this invention contain small amounts of compounds which have the characteristics of the above silver complexing agents. This is often the case with directprint materials wherein halogen acceptors of this type are used in the compositions.
- the halogen acceptor concentration which is utilized to provide optimum image characteristics in a direct-print emulsion upon photodevelopemnt is generally too low to successfully provide the necessary image properties in a surface developer when permanizing the image record.
- the image record in direct-print emulsions containing these compounds as halogen acceptors are greatly improved by the use of the indicated concentrations of the silver complexing agent in the surface developer baths according to this invention.
- the bleach baths which can be used in certain preferred embodiments of this invention include baths containing oxidizing agents such as, for example, those disclosed in The Journal of Photographic Science, Vol. 9, 1961, pp. 217-222.
- oxidizing agent concentrations of baths used in this invention is from about onegram/liter to about 100gram/liter and preferably from about 5 grams to about 50 grams per liter.
- the developing bath comprises any of the conventional developing agents used for surfaces development of photographic records.
- Typical developing agents include hydroquinone, ascorbic acid, l-hydroxy-Z-methylaminobenzene, catechol, pyrogallol, l-phenyl-3-pyrazolidone, para-hydroxyphenyl-aminoacetic acid, t-butyl-hydroquinone, 4-methyl-4-hydroxymenthyl- 1 -phenyl-3-pyrazolidone and the like.
- the developing baths of this invention are substantially free of strong silver halide solvents or fixing agents such as water soluble thiocyanates and thiosulfates such as potassium thiocyanate and sodium thiosulfate.
- strong silver halide solvents such as water soluble thiocyanates and thiosulfates such as potassium thiocyanate and sodium thiosulfate.
- the silver halide compositions which can be stabilized or developed according to this invention are those which are internally sensitive to electromagnetic radiation, i.e., light, X- rays, electrons, etc.
- Suitable silver halides include internally sensitive silver bromide, silver bromoiodide, silver chlorobromide, silver chlorobromoiodide, and the like.
- the preferred emulsions are those wherein the silver halide is predominately silver bromide.
- preferred emulsions according to this invention have higher internal sensitivity than surface sensitivity.
- Typical suitable emulsions are disclosed in Davey et al., U.S. Pat. No. 2,592,250 issued Apr. 8, 1952; U.S. Pat. No.
- internal image emulsions can be used in the invention, such having silver halide grains wherein a predominant amount of the sensitivity is internal to the grains.
- Such internal image emulsions are those which, when measured according to normal photographic techniques by coating a test portion of the emulsion on a transparent support, exposing to a light intensity scale having a fixed time between 1X10" and 10 second, bleaching 5 minutes in a 0.3 percent potassium ferricyanide solution at 65 F., and then developing in Developer Z below (an "intemal-type developer), have a sensitivity measured at a density of 0.1 above fog, greater than the sensitivity of an identical test portion which has been exposed in the same way and developed for 6 minutes at 68 F. in Developer X below (a surface-type" developer).
- the direct-print emulsions which can be stabilized in accordance with this invention generally contain halogen acceptors, for example, nitrogen containing halogen acceptors such as those disclosed in McBride, U.S. Pat. No. 3,287,137 and McBride, U.S. Pat. No. 3,271,157.
- halogen acceptors for example, nitrogen containing halogen acceptors such as those disclosed in McBride, U.S. Pat. No. 3,287,137 and McBride, U.S. Pat. No. 3,271,157.
- watersoluble halides to the silver halide emulsion after its precipitation but before it is coated. More generally, about 1 to about 50 mole percent, and preferably about 1 to about 10 mole percent of water soluble halide based on the silver halide in the emulsion is used.
- the stabilizing or developing baths of this invention can also be used to treat other silver halide systems, such as developing out system, etc., if desired to maintain or improve image proparties in said systems.
- colloids can be used as vehicles or binding agents in preparing the silver halide emulsions of this invention.
- Satisfactory colloids which can be used for this purpose include any of the hydrophilic colloids generally employed in the photographic field including, for example, gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins such as polyvinyl compounds, including polyvinyl alcohol derivatives, acrylamide polymers and the like.
- the vehicle or binding agent can also contain hydrophobic colloids such as dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials. Suitable compounds of this type include water-soluble polymers of alkyl acrylates or methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, and the like.
- Typical supports for photographic elements of the invention include glass, metal, paper, polyolefin-coated paper, cellulose nitrate film, cellulose acetate film, polystyrene film,
- polyester films such as polyethylene terephthalate film, heat resistant polymeric films such as high temperature polyester, polyimide, polycarbonate films, and the like.
- the essential ingredients of the stabilizing compositions according to the invention namely the developing agents, the selective silver complexing agent and in some embodiments,
- the bleach can be prepackaged in a kit, diluted, concentrated, or in powder form and can be either mixed together or packaged individually for use in the systems of this invention.
- the respective compositions are generally prepackaged in- EXAMPLE 2 Samples of direct-print silver. halide emulsions prepared according to example I] of Kitze, Belgian Pat. No. 689,515 issued Jan. [3, i967, are imagewise exposed to a step tablet on dividually and can be readily added to aqueous alkaline solu- 5 a sensitometer b ex f l0 tion or water to from th necessary baths.
- kits prepared for making stabilizing composiphotodeveglo b ex gq z es s subsequently tions comprising the essential ingredients of this invention are illumination g 2 L d f i efci'of fluorescent contemplated to be within the scope of-this invention.
- th b k ens o t e area and r 0 e ac ground area are shown ln-table l.
- the invention can be further illustrated by the following ex- 0 f am lcs 0 the p isamples is processed as a con- P trol sample in Developer B for 60 seconds, then stopped for 10 seconds, fixed for 5 minutes and washed for 5 minutes.
- the ima e record EXAMPLE 1 g densities obtained for this pro are shown m 2 L-.. strips of a direct-print silver halide emulsion prepared according to example Id of McBride US. Pat. No. 3,287,l36 are DEVELOPER B imagewise exposed to a step tablet on a sensitometer by exposing for 10'' second to a high intensity Xenon light.
- the respec- 1 tive samples are subsequently photodeveloped by exposing to r i 8-" 250 foot-candles of daylight fluorescent illumination for g ming: 3" seconds to produce a negative image with about 0.4 density Sodium carbonate so discrimination Potassium bromide 2
- Developer A described below, for 60 seconds, then stopped in acetic acid for l0 seconds, fixed for 2 minutes in sodium thiosulfate solution and Several additional'nonphotodeveloped and photodeveloped washed for 5 minutes in running water.
- samples are processes in Developer B containingvthe concen- A second sample is processed by the above procedure trations of selective silver complexing agents indicated in table wherein Developer A additionally contains 0.1 g./l. ofl -phenl.
- the densities of the image area obtained upon development yl-S-mercaptoterazole. 30 are recorded in table I.
- a bleach bath is preferably used when processing a directprint emulsion prior to processing in the developer containing selective silver complexing agents.
- a control sample is processed in Developer A for 2 minutes, Sodium Sfllfiw 500 fixcd for 5 minutes and washed in running water.
- a second odlum carbonate 80.0 g. sample of the above emulsion IS processed in Developer C acpomsium bmmidc 2,0 I cording to the same processing procedure.
- the combination of the bleach bath and the developer con- The normal surface developer produced a negative image taining the selective silver complexing agents produces lower with high background density; while the bleach process folminimum density with better image discrimination than the lowed by the developer containing the selective silver comdeveloper containing the selective silver complexing agents plexing agent greatly reduced the background and maintained alone or the bleach followed b the conventional surface equivalent image discrimination.
- the resulting image developer. produced by the bleach process followed by the developer containing the selective silver complexing agent provides :1 TABLE ll record which is much more discernible to the eye as the image density is on a percentage basis much darker than the A background density.
- sample A of a similar emulsion is prepared by the same procedure with the addition of Samples of direct-print silver halide emulsions prepare l5g./mole of silver of Z-mercaptoimidazole incorporated in ng l0 example 4 0f KaTlSOn, gi 705.036 the emulsion coating. Samples of the respective coatings are sued Nov.
- Nmethyl-para-amlnophenul 4.5 g. DEVELOPER F mas Sodium sulfite 50.0 g. Hydroquinnne 9.0 g. I Sodium carbonate 80.0 g. yl'p p 8 Potassium bromide 2.0 g. Hydwqumonc sw m I m" Sodium sulfite 45.0 g. Sodium carbonate 80.0 g.
- the selective silver complexing agent utilized in the emulsion shows an improvement in discrimination over the process without agent present.
- the addition of the selective silver complexing agent in the developer in addition to the use of the same or a similar compound in the emulsion coating shows an additional improvement in the image discrimination obtained after processing.
- a process for developing and stabilizing image records in an internal image silver halide compositions which has been imagewise exposed comprising contacting said silver halide composition with a surface developingsolution, said solution comprising a developing agent and from moles/liter to about 2X10 moles/liter of a silver complexing agent, said complexing agent containing at least one group capable of forming covalent bonds with silver said group selected from mercaptan groups, imide groups, or tautometers thereof and at least one secondary bonding group capable of forming pibonds, said secondary bonding group consisting of I l 1 i groups.
- a process according to claim 2 wherein said silver complexing agent is 2-mercaptoimidaz'ole.
- said silver complexing agent is selected from the group consisting of 2-mercaptothiazole, Z-mercapto benzothiazole, 2-mercapto-6- nitrobenzothiazole, 4-carboxymethyl-4-thiazoline-2-thione, thiazolidine-Z-thione, imidazole, 2-benzimidazolethiol, 5- amino-2-benzimidazolethiol, Z-mercaptoimidazole, l-methyl- Z-mercaptoimidazole, 2-mercaptcpyrimidine, dithiourazole,
- o-aminobenzenethiol o-mercaptobenzoic acid, l-phenyl-2- mercaptotetrazole, l-phenyl-2thiourea, 5- nitrobenzimidazolethiol, 6-amino-Z-mercaptobenzothiozole, 2-benzoxolethiol, 5-methyl-2-oxazolidinethione, 4- aminophenyl-disulfide and l-allyl-2-thiourea.
- a process according to claim 4 wherein said silver complexing agent is selected for the group consisting of l-allyl-2- thiourea, Z-mercaptoimidazole, dithiourazole, and l-phenyl- Smercaptotetrazole.
- a process according to claim 4 wherein said silver complexing agent is 2-mercaptoimidazole, in a concentration of from lXlO to about l.5 l0 moles/liter.
- a process for stabilizing image records in light developable internal image silver halide compositions which have been imagewise exposed and photodeveloped to produce a visible image therein comprising (1) contacting said silver halide composition with a silver halide bleaching solution, and then (2) contacting said silver halide with a surface developing solution comprising a developing agent and from about l0 to about 4X10 moles/liter of a silver complexing agent comprising at least one group capable of forming covalent bonds with silver, said groups selected from mercaptan groups, imide groups, or tautomers thereof and at least one secondary bonding group capable of forming pi-bonds, said secondary bonding group consisting of groups.
- said silver complexing agent is selected from a group consisting of 2-mercaptothiazole, Z-mercapto benzothiazole, 2-mercapto-6- nitrobenzthiazole, 4-carboxymcthyl-4-thiazoline-2-thione, thiazolidine-Z-thione, imidazole, 2-benzimidazolethiol, 5- amino-2benzimidasolethiol, 2-mercaptoimidazole, l-methyl- 2-mercaptoimidazole, Z-mercaptopyrimidine, dithiourazole, o-aminobenzenethiol, o-mercaptobenzoic acid, l-phenyl-2- mercaptotetrazole, l-phenyl-Z-thiourea, 5 nitrobenzimidazolethiol, o-amino-2-mercaptobenzothiozole, 2-benzoxazolethiol, 5-methyl-2-oxazolinethione
- said silver complexing agent is selected from the group consisting of l-allyl- 2thiourea, Zmercaptoimidazole, dithiourazole, and l-phenyl- S-mercaptotetrazole.
- bleaching solution comprises potassium dichromate
- silver complexing agent comprises Z-mercaptoimidazole
- a process according to claim 7 wherein said groups capable of forming covalent bonds with silver consists of mercaptan groups.
- a process according to claim 7 wherein said silver complexing agent is Z-mercaptoimidazole.
- said silver complexing agent is compound which is soluble in water in a concentration of at least 10" moles/liter at 70 F. and wherein said compound is capable of forming a silver complex having a ratio of at least 1 silver ion to 1 silver complexing agent in a molar basis in the presence of excess silver ions as measured by potentiometn'c titration.
- Claim 1 line 5 "10 should read O line 6, "2x1 0 should read --2x
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Abstract
Processes and compositions for developing or stabilizing image records in photographic, internal image, silver halide compositions. In one aspect, the developing or stabilizing compositions of this invention contain low concentrations of a silver complexing agent. In another aspect, photographic compositions are stabilized or developed with a process comprising a bleach bath followed by a surface type developer. In a preferred embodiment direct-print materials containing either photodeveloped images or nonphotodeveloped latent images can be processed to provide permanent image records.
Description
United States Patent Inventor Roger M. Cole Rochester, N.Y. Appl. No. 731,275 Filed May 22, 1968 Patented Oct. 26, 1971 Assignee Eastman Kodak Company Rochester, N.Y.
SURFACE DEVELOPER WITH IIETEROCYCLIC MERCAPTAN FOR USE ON INTERNAL IMAGE EMULSION 13 Claims, No Drawings U.S. Cl 96/61, 96/108, 96/63, 96/66.5 Int. Cl G03c 5/38 Field of Search 96/108, 61, 63, 66.5, 66
References Cited UNITED STATES PATENTS 3,335,009 8/1967 Rasch et al. 96/61 3,241,971 3/1966 Kitze 96/108X 3,396,017 8/1968 Baconetal. 3,418,124 12/1968 Hunt Primary Examiner-Norman G. Torchin Assistant Examiner-Won H. Louie, J r. Att0rneysW. 11.1. Kline, G. E. Battist and B. D. Wiese ABSTRACT: Processes and compositions for developing or stabilizing image records in photographic, internal image, silver halide compositions. In one aspect, the developing or stabilizing compositions of this invention contain low concentrations of a silver complexing agent. In another aspect, photographic compositions are stabilized or developed with a process comprising a bleach bath followed by a surface type developer. In a preferred embodiment direct-print materials containing either photodeveloped images or nonphotodeveloped latent images can be processed to provide permanent image records.
SURFACE DEVELOPER WITII I-IETEROCY CLIC MERCAPTAN FOR USE ON INTERNAL IMAGE EMULSION This invention relates to processes and compositions for developing or stabilizing image records in photographic materials. In one aspect this invention relates to novel processes for developing or stabilizing image records in directprint, photographic materials. In another aspect, this invention relates to novel processes comprising bleaching and then developing or stabilizing image records in direct-print -material. In still another aspect, this invention relates to a means by which both latent images and photodeveloped images can be made into stable, permanent image records.
It is often desirable to permanize (i.e., to make permanent archival quality records) the image records in printout or direct-print compositions. Many printout and direct-print compositions produce high background density when the image records are subjected to conventional developers. The increase in background fog is especially a problem when photodeveloped direct-print records are stabilized or developed in conventional developers; in this instance photolytic silver is generally formed in both the image and background areas of the record. Moreover, single developing or stabilizing compositions known in the present art generally can not be successfully used to provide good stable image properties in both nonphotodeveloped and photodeveloped direct-print compositions. Therefore, improved means to obtain good stabilized records in printout or direct-print emulsions would be desirable.
It is an object of this invention to provide new means for stabilizing or developing internal image silver halide photographic compositions.
It is another object of this invention to provide new means for stabilizing or developing direct-print and printout photographic compositions.
It is another object of this invention to provide a means for producing a uniform image in a direct-print record which has been photodeveloped over only a portion of the record area.
It is another object of this invention to provide novel compositions for developing or stabilizing photographic compositions. 7
These and other objects of the invention have been accomplished by processing internal image silver halide materials in a surface developer containing low concentrations of a selective silver complexing agent and a silver halide developing agent. The surface developer is substantially free of strong silver halide solvents such as thiocy'anates, hypo, etc. It is quite unexpected that low concentration of the selective silver complexing agents would provide improved development properties in this system since higher concentrations of the same compounds do not exhibit the same improvements in the development characteristics of the system. It is even more unexpected that this system can be used to permanize good images in both nonphotodeveloped and photodeveloped direct-print compositions.
In one embodiment, direct-print compositions which have been imagewise exposed are processed in a surface developer containing selective silver complexing agent, fixed and washed.
In another embodiment, direct-print records which have been imagewise exposed are photodeveloped to a discernible image and then processed in a surface developer containing a selective silver complexing agent, fixed and washed.
In another embodiment, direct-print compositions which have been imagewise exposed are bleached and then processed in a surface developer containing a selective silver complexing agent, fixed and washed.
In still another embodiment, direct-print compositions which have been imagewise exposed are photodeveloped, bleached, processed in a surface developer containing a selective silver complexing agent, fixed and washed.
The selective silver complexing agents of this invention contain two characteristic groups which provide the unique properties in the surface developers. The silver complexing agents contain at least one group which is capable of forming a normal covalent bond with silver. Typical complexing agents contain groups capable of forming the covalent bonds such as -S-Ag, N-Ag and the like. The preferred complexing agents contain imide groups mercaptan groups (SI-l) and the like or tautomers thereof. The complexing agents also contain at least one secondary bonding group which does not generally form a covalent bond with silver under the conditions generally encountered in photographic emulsions and photographic developing solutions. Bonds of this type are sometimes referred to as 1r bonds in the atomic configuration of the ion complex formation. Typical groups in the silver complexing agents of this invention which can be classified as'secondary bonding groups are or carbon-carbon double bond groupsythese groups can occur for example as part of a hertocyclic ring system as in 2-mercaptoimidazole or in an alkyl side chain as in l-allyl-2-thiourea, (2) aromatic substituents; typical compounds of this type are benzo or phenyl derivatives, (3) donor atoms containing 2 nonbonding electron pairs; typical preferred groups of this type are S-S and the like. I
The silver complexing agents of this invention can be additionally characterized as compounds which are soluble in water at 70F. in'concentration of at least l0' and preferably 10 moles per liter and wherein said compounds are capable of forming a silver ion complex in a ratio of at least 10 silver ion to 10 complexing agent on a molar basis in the presence of an equal molar or excess of silver ion as measured by potentiometric titration.
The silver complexing agents of this invention are incorporated in the developing solutions in lower concentrations than normally used for antifoggant purposes. In embodiments wherein the developing solution is used directly after imagewise exposure or photodevelopment it is critical to maintain the concentration level of the silver complexing agent at levels below 2X10 moles per liter of solution and preferably below 1.5Xl0 moles per liter of developing solution. The concentrations of the silver complexing agent for this embodiment are maintained between about 10 moles to about 2Xl0 moles per liter about 1X10 moles to about 1 5X10 moles per liter. In embodiments where a bleach bath is used prior to the developing bath the concentration of the silver complexing agent can be generally'from about l0" moles to about 4X10" moles and preferably from about 10" moles to not more than 2.5)(10 moles i solution. If the concentrations of the silver complexing agent exceed the above concentrations, the density of the developed image is greatly reduced.
In a preferred embodiment of this invention, direct-print compositions are stabilized ordeveloped by contacting said compositions with -a bleach bath and then contacting said compositions withthe developing solutions containing the silver complexing agentsXHowever, the bleach bath will also provide some improvements in image properties in directprint emulsions when said bleach bath is followed with other developing solutions. I
Typical compounds which can be characterized by the above tests and are effective in the developing baths of this invention are Z-mercaptothiazole, Z-mercapto benzothiazole, 2- mercapto-6-nitrobenzothiazole, 4-carboxymethyl-4- thiazoline-Z-thione, thiazolidine-Z-thione, irnidazole, 2- benzimidazoletliiol, 5-amino-Z-benzimidazolethiol, 2-mercaptoimidazole, l-methyl-2-mercaptoimidazole, Z-mercaptopyrimidine, dithiourazole, o-aminobenzenethiol, o-mercapto-benzoic acid, l-phenyl-2-mercaptotetrazole, l-phenyl-2- thiourea, S-nitrobenzimidazolethiol, 6-amino-2-mercaptobenzothiozole, 2-benzoxazolethiol, 5 -methyl-2-oxazolidinethione, 4-aminophenyldisulfide and l-allyl-2-thiourea.
ln some instances the silver halide emulsions which can be processed according to this invention contain small amounts of compounds which have the characteristics of the above silver complexing agents. This is often the case with directprint materials wherein halogen acceptors of this type are used in the compositions. However, the halogen acceptor concentration which is utilized to provide optimum image characteristics in a direct-print emulsion upon photodevelopemnt is generally too low to successfully provide the necessary image properties in a surface developer when permanizing the image record. The image record in direct-print emulsions containing these compounds as halogen acceptors are greatly improved by the use of the indicated concentrations of the silver complexing agent in the surface developer baths according to this invention.
The bleach baths which can be used in certain preferred embodiments of this invention include baths containing oxidizing agents such as, for example, those disclosed in The Journal of Photographic Science, Vol. 9, 1961, pp. 217-222. Generally the oxidizing agent concentrations of baths used in this invention is from about onegram/liter to about 100gram/liter and preferably from about 5 grams to about 50 grams per liter.
The developing bath comprises any of the conventional developing agents used for surfaces development of photographic records. Typical developing agents include hydroquinone, ascorbic acid, l-hydroxy-Z-methylaminobenzene, catechol, pyrogallol, l-phenyl-3-pyrazolidone, para-hydroxyphenyl-aminoacetic acid, t-butyl-hydroquinone, 4-methyl-4-hydroxymenthyl- 1 -phenyl-3-pyrazolidone and the like.
It is understood that the developing baths of this invention are substantially free of strong silver halide solvents or fixing agents such as water soluble thiocyanates and thiosulfates such as potassium thiocyanate and sodium thiosulfate. The presence of such strong silver halide solvents destroys the equilibrium balance necessary to obtain good results by the process of this invention.
The silver halide compositions which can be stabilized or developed according to this invention are those which are internally sensitive to electromagnetic radiation, i.e., light, X- rays, electrons, etc. Suitable silver halides include internally sensitive silver bromide, silver bromoiodide, silver chlorobromide, silver chlorobromoiodide, and the like. The preferred emulsions are those wherein the silver halide is predominately silver bromide. In a typical embodiment preferred emulsions according to this invention have higher internal sensitivity than surface sensitivity. Typical suitable emulsions are disclosed in Davey et al., U.S. Pat. No. 2,592,250 issued Apr. 8, 1952; U.S. Pat. No. 3,206,316; Porter et al., U.S. Pat. No. 3,206,313 Glafkides, Photographic Chemistry, Vol. 1, pp. 31-32, Fountain Press, London; McBride, U.S. Pat. No. 3,271,157 issued Sept. 6, 1966, McBride U.S. Pat. No. 3,287,137 issued Nov. 22, 1966, and Hunt, Photographic Science and Engineering, Vol. 5, No. 2, Mar.-Apr., l96l, pp. 104-108.
The so-called "internal image emulsions can be used in the invention, such having silver halide grains wherein a predominant amount of the sensitivity is internal to the grains. Such internal image emulsions are those which, when measured according to normal photographic techniques by coating a test portion of the emulsion on a transparent support, exposing to a light intensity scale having a fixed time between 1X10" and 10 second, bleaching 5 minutes in a 0.3 percent potassium ferricyanide solution at 65 F., and then developing in Developer Z below (an "intemal-type developer), have a sensitivity measured at a density of 0.1 above fog, greater than the sensitivity of an identical test portion which has been exposed in the same way and developed for 6 minutes at 68 F. in Developer X below (a surface-type" developer).
Water to make 1 liter The direct-print emulsions which can be stabilized in accordance with this invention generally contain halogen acceptors, for example, nitrogen containing halogen acceptors such as those disclosed in McBride, U.S. Pat. No. 3,287,137 and McBride, U.S. Pat. No. 3,271,157.
In certain preferred emulsions to be stabilized or developed by the methods of this invention, it is desirable to add watersoluble halides to the silver halide emulsion after its precipitation but before it is coated. More generally, about 1 to about 50 mole percent, and preferably about 1 to about 10 mole percent of water soluble halide based on the silver halide in the emulsion is used.
The stabilizing or developing baths of this invention can also be used to treat other silver halide systems, such as developing out system, etc., if desired to maintain or improve image proparties in said systems.
Various colloids can be used as vehicles or binding agents in preparing the silver halide emulsions of this invention. Satisfactory colloids which can be used for this purpose include any of the hydrophilic colloids generally employed in the photographic field including, for example, gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins such as polyvinyl compounds, including polyvinyl alcohol derivatives, acrylamide polymers and the like. In addition to the above hydrophilic colloids, the vehicle or binding agent can also contain hydrophobic colloids such as dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials. Suitable compounds of this type include water-soluble polymers of alkyl acrylates or methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, and the like.
The above-described emulsions of the invention can be coated on a wide variety of supports in accordance with usual practice. Typical supports for photographic elements of the invention include glass, metal, paper, polyolefin-coated paper, cellulose nitrate film, cellulose acetate film, polystyrene film,
polyester films such as polyethylene terephthalate film, heat resistant polymeric films such as high temperature polyester, polyimide, polycarbonate films, and the like.
The essential ingredients of the stabilizing compositions according to the invention, namely the developing agents, the selective silver complexing agent and in some embodiments,
the bleach, can be prepackaged in a kit, diluted, concentrated, or in powder form and can be either mixed together or packaged individually for use in the systems of this invention. The respective compositions are generally prepackaged in- EXAMPLE 2 Samples of direct-print silver. halide emulsions prepared according to example I] of Kitze, Belgian Pat. No. 689,515 issued Jan. [3, i967, are imagewise exposed to a step tablet on dividually and can be readily added to aqueous alkaline solu- 5 a sensitometer b ex f l0 tion or water to from th necessary baths. Therefore it is unxenon Ii ht i mg 9 to a derstood that kits prepared for making stabilizing composiphotodeveglo b ex gq z es s subsequently tions comprising the essential ingredients of this invention are illumination g 2 L d f i efci'of fluorescent contemplated to be within the scope of-this invention. th b k ens"), o t e area and r 0 e ac ground area are shown ln-table l. The invention can be further illustrated by the following ex- 0 f am lcs 0 the p isamples is processed as a con- P trol sample in Developer B for 60 seconds, then stopped for 10 seconds, fixed for 5 minutes and washed for 5 minutes. The ima e record EXAMPLE 1 g densities obtained for this pro are shown m 2 L-.. Strips of a direct-print silver halide emulsion prepared according to example Id of McBride US. Pat. No. 3,287,l36 are DEVELOPER B imagewise exposed to a step tablet on a sensitometer by exposing for 10'' second to a high intensity Xenon light. The respec- 1 tive samples are subsequently photodeveloped by exposing to r i 8-" 250 foot-candles of daylight fluorescent illumination for g ming: 3" seconds to produce a negative image with about 0.4 density Sodium carbonate so discrimination Potassium bromide 2 One of the samples is processed in Developer A., described below, for 60 seconds, then stopped in acetic acid for l0 seconds, fixed for 2 minutes in sodium thiosulfate solution and Several additional'nonphotodeveloped and photodeveloped washed for 5 minutes in running water. samples are processes in Developer B containingvthe concen- A second sample is processed by the above procedure trations of selective silver complexing agents indicated in table wherein Developer A additionally contains 0.1 g./l. ofl -phenl. The densities of the image area obtained upon development yl-S-mercaptoterazole. 30 are recorded in table I.
TABLE I Non-phtdvlpd Phtdvlpd Concendensity density tration, Y Y Developer Silver complexing agent g.ll. Bkgrnd Image Bkgrnd Image None None 0.38 o. 68 None 0.14 1. 24 0.56 0.411 D 2-mereaptoimldazole 0.1 0.12 L18 0. 52 0.85 Dodo 0.01 D0. 2-thiouraciL 0. 1 0. l4 1. 21 0. 64 0, 111 Do. .do. 0. 01 0.15 1. 21 0. as n. 64 Do FQP i 3; i3 2 8; $5 3 D0 Dlthiwmole 0% 3: l3 i133 8:33 8:23 0.1 0.16 1. 22 0. 62 0. so ZMm-mmma Z-thiwwm acid 0911i 3153 {3% 3123 3:43 z am 3313 i 31 3 22 32?,
DEVELOPER A The above data demonstrates that good image densities can be obtained with either photodeveloped or I I nonphotodeveloped direct-print samples which are processed I '"1"" 6 with surface developers containing low concentrations of Sodium lsoascorbale 40 g- Potassium bromide l g. sllver comp|exu1g n Kodulk 40 8- 4 methyl-l-phenyl-3-pyrosolidone l g. When the Z-mercaptormrdazole as used in the developer is will" "take I replaced with imidazole, l-allyl-2-thiorea or o-mercaptobenzoic acid similar improvements in photographic properties are obtained. Background Image Sample Density Density 1 Developer A 0.48 0.46 A Develo er A l-phenyl- EXAMPLE 3 S-mercaplotetrazole 0.67 l.0l
A bleach bath is preferably used when processing a directprint emulsion prior to processing in the developer containing selective silver complexing agents.
A direct-print silver halide emulsion prepared according to example 111 of McBride US. Pat. No. 3,287,136 is imagewise exposed on a .sensitometer using a 10 second flash with a high intensity Xenon lamp. The sample is then photodevelQPed by exposing it to 250 loot-candles of daylight =fluorescent illumination for 2 minutes.
A control sample is processed in Developer A for 2 minutes, Sodium Sfllfiw 500 fixcd for 5 minutes and washed in running water. A second odlum carbonate 80.0 g. sample of the above emulsion IS processed in Developer C acpomsium bmmidc 2,0 I cording to the same processing procedure. Z-mercaptoimidazole 0| 8.
5 Water to l liter DEVELOPER C A photodeveloped sample is prepared as above and then Water 800 ml bathed in an oxidizing bath (Bleach B) for l minute, then -"1= x -P l 6 8- l0 Processed in an identical manner as the control. The density l data obtained is shown in Table III. Potassium bromide l g. Kodak Balanced Alkali 40 s- 4-methyl-phenyl-S-pyrazolidone l-g. BLEACH B l-phenyl-5-mercaptotetrazole 0.l g. water to make 1 liter Potassium dichromale 20 g.
H=10 0 Sulfuric acid (cone) 4 ml.
Water to l liter Additional samples prepared by the above procedure are TABLE 1 treated with an oxidizing bath, Bleach A, for 2 minutes, then processed in a manner similar to the control sample.
Transmission Densities BLEACH A Bleach Dev Background Image None D 0.72 l.l2 Potassium dichromate 7.5 g. None E 065 L22 Sulfuric acid (cone) 5.0 ml. B D 0.l2 0.22 Water to l liter B E 0.25 0.66
The combination of the bleach bath and the developer con- The normal surface developer produced a negative image taining the selective silver complexing agents produces lower with high background density; while the bleach process folminimum density with better image discrimination than the lowed by the developer containing the selective silver comdeveloper containing the selective silver complexing agents plexing agent greatly reduced the background and maintained alone or the bleach followed b the conventional surface equivalent image discrimination. The resulting image developer. produced by the bleach process followed by the developer containing the selective silver complexing agent provides :1 TABLE ll record which is much more discernible to the eye as the image density is on a percentage basis much darker than the A background density. Similar results are obtained when l-allyl- Reflection Densitifi 2-thiourea, imidazole, dithiourazole, and l-phenyl-Z-thiourea Backgmmd are utilized in Developer E in place of the Z-mcrcaptoimidazole. None A 0.55 0.48 None c 0.51 0.09 EXAMPLE 5 A A 0.47 0.30 A C A control direct-print emulsion is prepared according to example Ia of Kitze, Belgian Pat. No. 689.515, issued Jan. l3. Examplglt I967. Another sample (sample A) ofa similar emulsion is prepared by the same procedure with the addition of Samples of direct-print silver halide emulsions prepare l5g./mole of silver of Z-mercaptoimidazole incorporated in ng l0 example 4 0f KaTlSOn, gi 705.036 the emulsion coating. Samples of the respective coatings are sued Nov. I4, 1967 (which containsa urazole halogen accepexposed for l0 second to a high intensity Xenon lamp tor) are imagewise exposed to a step tablet on a sensitometer through a 0 to 3.0 neutral density step tablet on a sensitomeby exposing for 10" second with a high intensity Xenon light. ter. The images are then photodeveloped with 245 foot-can- The respective samples are subsequently photodeveloped by dles of daylight fluorescent light for 30 seconds. The respecexposing to 50 foot-candles of daylight fluorescent illuminative photodeveloped samples are solution processed at 70 F. tion for 5 minutes. One of the photodeveloped samples is in the following solutions as indicated in table IV. processed as a control sample in Developer D for l minute, fixed for 30 seconds and washed in running water. Another Bleach A 30 seconds sample is processed for the same duration in Developer E.
Potassium dichromale 20 gJl. DEVELOPER D Sulfuric Acid (cone) 4 l.
Nmethyl-para-amlnophenul 4.5 g. DEVELOPER F mamas Sodium sulfite 50.0 g. Hydroquinnne 9.0 g. I Sodium carbonate 80.0 g. yl'p p 8 Potassium bromide 2.0 g. Hydwqumonc sw m I m" Sodium sulfite 45.0 g. Sodium carbonate 80.0 g.
Potassium romide I!) g Water to l liter DEVELOPER E Sodium thiosull'ute l40.0 60 seconds Sodium sulfite I50 g. Nmeih lurll-amino henol 4.5 g. Water In 1 liter Wash Running Water 2 minutes Additional samples are processed by the above procedure except Developer G was substituted for Developer F on the procedure. Developer G is identical in all respects to Developer F with the addition of 0.075 g./l. of Z-mercaptoimidazole.
The densities obtained in the respective photographic samples are reported in table lV below.
The selective silver complexing agent utilized in the emulsion shows an improvement in discrimination over the process without agent present. Moreover, the addition of the selective silver complexing agent in the developer in addition to the use of the same or a similar compound in the emulsion coating shows an additional improvement in the image discrimination obtained after processing.
The invention has been described in considerable detail with reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and in the appended claims.
I claim:
1. A process for developing and stabilizing image records in an internal image silver halide compositions which has been imagewise exposed comprising contacting said silver halide composition with a surface developingsolution, said solution comprising a developing agent and from moles/liter to about 2X10 moles/liter of a silver complexing agent, said complexing agent containing at least one group capable of forming covalent bonds with silver said group selected from mercaptan groups, imide groups, or tautometers thereof and at least one secondary bonding group capable of forming pibonds, said secondary bonding group consisting of I l 1 i groups.
2. A process according to claim 1 wherein said groups capable of forming covalent bonds with silver consist of mercaptan groups.
3. A process according to claim 2 wherein said silver complexing agent is 2-mercaptoimidaz'ole.
4. A process according to claim I wherein said silver complexing agent is selected from the group consisting of 2-mercaptothiazole, Z-mercapto benzothiazole, 2-mercapto-6- nitrobenzothiazole, 4-carboxymethyl-4-thiazoline-2-thione, thiazolidine-Z-thione, imidazole, 2-benzimidazolethiol, 5- amino-2-benzimidazolethiol, Z-mercaptoimidazole, l-methyl- Z-mercaptoimidazole, 2-mercaptcpyrimidine, dithiourazole,
o-aminobenzenethiol, o-mercaptobenzoic acid, l-phenyl-2- mercaptotetrazole, l-phenyl-2thiourea, 5- nitrobenzimidazolethiol, 6-amino-Z-mercaptobenzothiozole, 2-benzoxolethiol, 5-methyl-2-oxazolidinethione, 4- aminophenyl-disulfide and l-allyl-2-thiourea.
5. A process according to claim 4 wherein said silver complexing agent is selected for the group consisting of l-allyl-2- thiourea, Z-mercaptoimidazole, dithiourazole, and l-phenyl- Smercaptotetrazole. 3
6; A process according to claim 4 wherein said silver complexing agent is 2-mercaptoimidazole, in a concentration of from lXlO to about l.5 l0 moles/liter.
7. A process for stabilizing image records in light developable internal image silver halide compositions which have been imagewise exposed and photodeveloped to produce a visible image therein, said process comprising (1) contacting said silver halide composition with a silver halide bleaching solution, and then (2) contacting said silver halide with a surface developing solution comprising a developing agent and from about l0 to about 4X10 moles/liter of a silver complexing agent comprising at least one group capable of forming covalent bonds with silver, said groups selected from mercaptan groups, imide groups, or tautomers thereof and at least one secondary bonding group capable of forming pi-bonds, said secondary bonding group consisting of groups.
8. A process according to claim 7 wherein said silver complexing agent is selected from a group consisting of 2-mercaptothiazole, Z-mercapto benzothiazole, 2-mercapto-6- nitrobenzthiazole, 4-carboxymcthyl-4-thiazoline-2-thione, thiazolidine-Z-thione, imidazole, 2-benzimidazolethiol, 5- amino-2benzimidasolethiol, 2-mercaptoimidazole, l-methyl- 2-mercaptoimidazole, Z-mercaptopyrimidine, dithiourazole, o-aminobenzenethiol, o-mercaptobenzoic acid, l-phenyl-2- mercaptotetrazole, l-phenyl-Z-thiourea, 5 nitrobenzimidazolethiol, o-amino-2-mercaptobenzothiozole, 2-benzoxazolethiol, 5-methyl-2-oxazolinethione, 4- aminophenyl-disulfide and l-allyl- 2-thiourea.
9. A process according to claim 7 wherein said silver complexing agent is selected from the group consisting of l-allyl- 2thiourea, Zmercaptoimidazole, dithiourazole, and l-phenyl- S-mercaptotetrazole.
10. A process according to claim 7 wherein said bleaching solution comprises potassium dichromate, and said silver complexing agent comprises Z-mercaptoimidazole.
11. A process according to claim 7 wherein said groups capable of forming covalent bonds with silver consists of mercaptan groups.
12. A process according to claim 7 wherein said silver complexing agent is Z-mercaptoimidazole.
13. A process according to claim 7 wherein said silver complexing agent is compound which is soluble in water in a concentration of at least 10" moles/liter at 70 F. and wherein said compound is capable of forming a silver complex having a ratio of at least 1 silver ion to 1 silver complexing agent in a molar basis in the presence of excess silver ions as measured by potentiometn'c titration.
* t t i gggr UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 5,5 1 Dated October 26, 'l 971 Inventor(s) Roger M. Cole It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column line 60, after the word "containing" please insert -a--. Column 2, line 28, "hertooyclic" should read heterooyolic--; line L D, "10 should read 1 O line In, 10 should read ---|o line a2, "10" should read line L3,}, "10" should read 1 line 52,
"2X1 0 should read ZXI O line 53, "1 .5xlO should read l .5211 O line 55, "1 0 should read O line 56, "2X1 0 should read 2Xl O line 56, after "liter" insert the words and preferably from---; line 56,
"1 X1 0 should read 1 X1 O f line 57, "1 .5X1O13" should read -1 .Sxl O line 59, "1 O should read 1 O line 60, after "moles" please insert per liter-; line 60,
"hxl 0 should read Lpcl O' line 60, "10 should read O)+---; line 61 "2.5261 0 should read -2.5x| O line 61 "10" should read per liter- Column 3, line 19,
" photodevelopemnt" should read -photodevel0pment; line 36, "comprises" should read can comprise-. Column L line 1 'lxi 0 should read 1 x! O line 2, "10" should read --i line hl "1 should read --.I line 61 "watersoluble" should read waterinsoluble--. Column 5, line 6,
"from" should read --form---; line 19, "10 should read ---i O""'--; line 30, "meroaptoterazole" should read mercapi;otetrazole-; line 56, "pyrosolidone" should read pyrozolidone; line 63, "O.) B" should be listed directly under the heading; Baokground Density-; line 67, "mercaptotetraazole" should read -meroaptotetrazole---.
Page of 2. L. .J
P040510 UNITED STATES PATENT OFFICE (5 6g) CERTIFICATE OF CORRECTION Patent No 3: 1 Dated October 26 1 97 PAGE 2 Inventor(s) Roger M. Cole It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 6, line 2, "Example 11 should read --Example 1 a---; line 5, "1 0 4-" should read O line 72, "10 should read O Column 7, line 13, "1 should be inserted n 1 belmeeilL mgghg l pge y llne 55, 10 should read --I 0 --;/line 58, table" should read -Table-; line 73, 1L 0.0g" should read -2J 0.0g-. Claim 1 line 5, "10 should read O line 6, "2x1 0 should read --2x| O Claim 6, line 3, "1X1O1LL" should read --I XI O line 3, *1 .5X1O1 should read 1 .Sxi 0 Claim 7, line 8, "10 should read --l O line 8, "M610 should read. ---l xl O Claim 9, line 3, should be inserted between -2 thiourea-; line 3, should be inserted between -2 meroaptoimidazole--; Claim 1 3, line 3, "10 should read "-10- Column 3. line 2.2,
"record" should read --reoords---.
Page 2 of 2.
Signed and sealed this 9th day of May 1972.
(SEAL) Attest: EDWARD M.FLE'ICHER,JR. ROBERT GOTTSCHALK J Attesting Officer Commissioner of Patents
Claims (12)
- 2. A process according to claim 1 wherein said groups capable of forming covalent bonds with silver consist of mercaptan groups.
- 3. A process according to claim 2 wherein said silver complexing agent is 2-mercaptoimidazole.
- 4. A process according to claim 1 wherein said silver complexing agent is selected from the group consisting of 2-mercaptothiazole, 2-mercapto benzothiazole, 2-mercapto-6-nitrobenzothiazole, 4-carboxymethyl-4-thiazoline-2-thione, thiazolidine-2-thione, imidazole, 2-benzimidazolethiol, 5-amino-2-benzimidazolethiol, 2-mercaptoimidazole, 1-methyl-2-mercaptoimidazole, 2-mercaptopyrimidine, dithiourazole, o-aminobenzenethiol, o-mercaptobenzoic acid, 1-phenyl-2-mercaptotetrazole, 1-phenyl-2-thiourea, 5-nitrobenzimidazolethiol, 6-amino-2-mercaptobenzothiozole, 2-benzoxazolethiol, 5-methyl-2-oxazolidinethione, 4-Aminophenyl-disulfide and 1-allyl-2-thiourea.
- 5. A process according to claim 4 wherein said silver complexing agent is selected for the group consisting of 1-allyl-2-thiourea, 2-mercaptoimidazole, dithiourazole, and 1-phenyl-5mercaptotetrazole.
- 6. A process according to claim 4 wherein said silver complexing agent is 2-mercaptoimidazole, in a concentration of from 1 X 10 4 to about 1.5 X 10 3 moles/liter.
- 7. A process for stabilizing image records in light developable internal image silver halide compositions which have been imagewise exposed and photodeveloped to produce a visible image therein, said process comprising (1) contacting said silver halide composition with a silver halide bleaching solution, and then (2) contacting said silver halide with a surface developing solution comprising a developing agent and from about 10 5 to about 4 X 10 3 moles/liter of a silver complexing agent comprising at least one group capable of forming covalent bonds with silver, said groups selected from mercaptan groups, imide groups, or tautomers thereof and at least one secondary bonding group capable of forming pi-bonds, said secondary bonding group consisting of groups.
- 8. A process according to claim 7 wherein said silver complexing agent is selected from a group consisting of 2-mercaptothiazole, 2-mercapto benzothiazole, 2-mercapto-6-nitrobenzthiazole, 4-carboxymethyl-4-thiazoline-2-thione, thiazolidine-2-thione, imidazole, 2-benzimidazolethiol, 5-amino-2benzimidasolethiol, 2-mercaptoimidazole, 1-methyl-2-mercaptoimidazole, 2-mercaptopyrimidine, dithiourazole, o-aminobenzenethiol, o-mercaptobenzoic acid, 1-phenyl-2-mercaptotetrazole, 1-phenyl-2-thiourea, 5-nitrobenzimidazolethiol, 6-amino-2-mercaptobenzothiozole, 2-benzoxazolethiol, 5-methyl-2-oxazolidinethione, 4-aminophenyl-disulfide and 1-allyl- 2-thiourea.
- 9. A process according to claim 7 wherein said silver complexing agent is selected from the group consisting of 1-allyl-2thiourea, 2mercaptoimidazole, dithiourazole, and 1-phenyl-5-mercaptotetrazole.
- 10. A process according to claim 7 wherein said bleaching solution comprises potassium dichromate, and said silver complexing agent comprises 2-mercaptoimidazole.
- 11. A process according to claim 7 wherein said groups capable of forming covalent bonds with silver consists of mercaptan groups.
- 12. A process according to claim 7 wherein said silver complexing agent is 2-mercaptoimidazole.
- 13. A process according to claim 7 wherein said silver complexing agent is compound which is soluble in water in a concentration of at least 10 5 moles/liter at 70* F. and wherein said compound is capable of forming a silver complex having a ratio of at least 1 silver ion to 1 silver complexing agent in a molar basis in the presence of excess silver ions as measured by potentiometric titration.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US73127568A | 1968-05-22 | 1968-05-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3615511A true US3615511A (en) | 1971-10-26 |
Family
ID=24938827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US731275A Expired - Lifetime US3615511A (en) | 1968-05-22 | 1968-05-22 | Surface developer with heterocyclic mercaptan for use on internal image emulsion |
Country Status (5)
Country | Link |
---|---|
US (1) | US3615511A (en) |
BE (1) | BE733492A (en) |
DE (1) | DE1923824A1 (en) |
FR (1) | FR2009092A1 (en) |
GB (1) | GB1275074A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852071A (en) * | 1971-11-09 | 1974-12-03 | Fuji Photo Film Co Ltd | Process of producing positive images |
DE2518015A1 (en) * | 1974-04-23 | 1975-11-13 | Polaroid Corp | PHOTOGRAPHIC DEVELOPERS, PROCESSES AND RECORDING MATERIALS |
US4126459A (en) * | 1976-05-14 | 1978-11-21 | Polaroid Corporation | Thioether substituted silver halide solvents |
US4211562A (en) * | 1974-04-23 | 1980-07-08 | Polaroid Corporation | Photographic compositions with silver halide solvents containing thioether groups |
US5998110A (en) * | 1996-12-11 | 1999-12-07 | Ferrania S.P.A. | Photographic silver halide developer composition and process for forming photographic silver images |
EP1191395A1 (en) * | 2000-08-21 | 2002-03-27 | Eastman Kodak Company | Ascorbic acid developing compositions and methods of use |
-
1968
- 1968-05-22 US US731275A patent/US3615511A/en not_active Expired - Lifetime
-
1969
- 1969-05-09 DE DE19691923824 patent/DE1923824A1/en active Pending
- 1969-05-21 FR FR6916527A patent/FR2009092A1/fr not_active Withdrawn
- 1969-05-22 BE BE733492A patent/BE733492A/fr unknown
- 1969-05-22 GB GB26150/69A patent/GB1275074A/en not_active Expired
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852071A (en) * | 1971-11-09 | 1974-12-03 | Fuji Photo Film Co Ltd | Process of producing positive images |
DE2518015A1 (en) * | 1974-04-23 | 1975-11-13 | Polaroid Corp | PHOTOGRAPHIC DEVELOPERS, PROCESSES AND RECORDING MATERIALS |
US4211562A (en) * | 1974-04-23 | 1980-07-08 | Polaroid Corporation | Photographic compositions with silver halide solvents containing thioether groups |
US4126459A (en) * | 1976-05-14 | 1978-11-21 | Polaroid Corporation | Thioether substituted silver halide solvents |
US5998110A (en) * | 1996-12-11 | 1999-12-07 | Ferrania S.P.A. | Photographic silver halide developer composition and process for forming photographic silver images |
EP1191395A1 (en) * | 2000-08-21 | 2002-03-27 | Eastman Kodak Company | Ascorbic acid developing compositions and methods of use |
Also Published As
Publication number | Publication date |
---|---|
FR2009092A1 (en) | 1970-01-30 |
BE733492A (en) | 1969-07-31 |
DE1923824A1 (en) | 1969-12-11 |
GB1275074A (en) | 1972-05-24 |
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