US3420664A - Dehydrodithizone and mercaptotetrazolium salts as silver halide photographic antifoggants and stabilizers - Google Patents
Dehydrodithizone and mercaptotetrazolium salts as silver halide photographic antifoggants and stabilizers Download PDFInfo
- Publication number
- US3420664A US3420664A US517976A US3420664DA US3420664A US 3420664 A US3420664 A US 3420664A US 517976 A US517976 A US 517976A US 3420664D A US3420664D A US 3420664DA US 3420664 A US3420664 A US 3420664A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- emulsion
- dehydrodithizone
- fog
- salts
- 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
- -1 silver halide Chemical class 0.000 title description 36
- 239000003381 stabilizer Substances 0.000 title description 28
- 229910052709 silver Inorganic materials 0.000 title description 26
- 239000004332 silver Substances 0.000 title description 26
- GWJXGGNBNZFXMM-UHFFFAOYSA-N 1,3-bis(phenylimino)thiourea Chemical compound C=1C=CC=CC=1N=NC(=S)N=NC1=CC=CC=C1 GWJXGGNBNZFXMM-UHFFFAOYSA-N 0.000 title description 15
- DIGCWYGXBRVXIW-UHFFFAOYSA-O 1-sulfanyl-2H-tetrazol-1-ium Chemical class S[NH+]1N=NN=C1 DIGCWYGXBRVXIW-UHFFFAOYSA-O 0.000 title 1
- 239000000839 emulsion Substances 0.000 description 49
- 150000001875 compounds Chemical class 0.000 description 32
- 150000004694 iodide salts Chemical class 0.000 description 17
- 150000001649 bromium compounds Chemical class 0.000 description 16
- 150000001805 chlorine compounds Chemical class 0.000 description 16
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000005070 ripening Effects 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 description 1
- INKFOHXDPJTOJP-UHFFFAOYSA-N 5-methylsulfanyl-2,3-diphenyl-1H-tetrazol-1-ium iodide Chemical compound [I-].CSC1=NN(N([NH2+]1)C1=CC=CC=C1)C1=CC=CC=C1 INKFOHXDPJTOJP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-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
- 239000011354 acetal resin Substances 0.000 description 1
- WDLUEZJSSHTKAP-UHFFFAOYSA-N acetaldehyde;1,1-diethoxyethane Chemical compound CC=O.CCOC(C)OCC WDLUEZJSSHTKAP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- UCNMSHWTBMDEPY-UHFFFAOYSA-L disodium benzene-1,4-diol carbonate Chemical compound C([O-])([O-])=O.[Na+].C1(O)=CC=C(O)C=C1.[Na+] UCNMSHWTBMDEPY-UHFFFAOYSA-L 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 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 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- 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
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
- G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
Definitions
- ABSTRACT OF THE DESCLOSURE Stabilizer and antifogging compounds for use in silver halide photography include dehydrodithizone and chloride, bromide and iodide salts for S-alkyl m.ercapto-2,3- diaryltetrazole, 5-alkyl-mercapto-2,3 dialkyltetrazole, 5-carboXyalkylmercapto-2,3-diaryltetrazole and 5-carboxyalkylmercapto-Z,3-dialkyltetrazole compounds.
- This invention relates in general tophotography and in particular to the provision of novel stabilizing compounds for use in connection with the preparation and/ or processing of photographic silver halide emulsions.
- fog As used in the photographic art connotes that portion of the density obtained upon development which arises by virtue of factors other than the photographic exposure.
- the fog may be attributable to a number of influences including for example, excessive ripening of the emulsion, prolonged storage of the film and especially under conditions of elevated temperature and/ or humidity, as well as by prolonged development of the exposed emulsion and the like.
- the fog may be of two types, namely, yellow fog and chemical (gray) fog.
- the yellow fog sometimes referred to as colored or dichroic fog, is essentially a colloidal deposit of silver, the color intensity and general appearance of which are determined by the minute particle size and degree of subdivision.
- the fog is chiefly yellow in color and is most apparent in the lighter portions of the negative. The color may vary, however, and the colloidal silver particles may, for example, appear green by reflected light and yellow or red by transmitted light.
- the so-called chemical fog or gray fog
- such fog may be caused by the nucleation of silver on or in the silver halide grains due to inadvertent exposure, excessive ripening of the emulsion, storage of the film under severe conditions of temperature and/or humidity, etc.
- Fog may also be caused by exposure to chemicals, for example, hydrogen sulfide and other reactive sulphur compounds, hydrogen peroxide vapors and strongly reducing materials such as those present in the developer solution.
- the fog will usually manifest itself as a spurious density extant over the entire area of the sensitive coating and typically, is substantially nonuniform.
- the antifogging and stabilization characteristics of light-sensitive silver halide emulsions can be synergistically modified to advantage by the utilization of a particular class of chemical compounds in connection with the preparation and/or processing of such emulsions.
- a primary object of the present invention resides in the provision of improved antifogging and stabilizer compounds in which the foregoing and related disadvantages are eliminated or at least mitigated to a substantial degree.
- Another object of the present invention resides in the provision of light-sensitive silver halide emulsions containing a compound which stabilizes the emulsion against fogging while exhibiting little, if any, tendency to reduce the speed or contrast of such emulsions.
- a further object of the present invention resides in the provision of light-sensitive silver halide emulsions and photographic elements prepared therewith containing an antifogging compound which is substantially devoid of any tendency to reduce the sensitivity of the emulsion to light of longer wave length due to the presence of one or more sensiizing dyes.
- a still further object of the present invention resides in the provision of a process for the treatment of an exposed photographic silver halide emulsion wherein at least one of the steps of pretreating or developing the emulsion is effected in the presence of a novel stabilizing compound to be more fully described hereinafter.
- a light-sensitive photographic element e.g., silver halide emulsion
- developing solution and/or pretreatment solution of a compound selected from the group consisting of (a) S-alkylmercapto-Z,3-diaryltetrazolium salts, (b) 5-alkylmercapto-Z,3-dialkyltetrazolium salts, (c) 5-carboxyalkylmercapto-Z,3-diaryltetrazolium salts, (d) S-carboxyalkylmercapto-Z,3-dialkyltetrazolium salts and (e) dehydrodithizone.
- R, R and R represent alkyl, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, undecyl, dodecyl, etc., and preferably lower alkyl of 1 to 4 carbon atoms; aryl, e.
- R represents lower alkylene, branch or straight chained, substituted or unsubstituted, e.g., methylene, ethylene, isobutylene, etc.
- X represents an anion such as a halide atom, e.g., chloride, bromide or iodide
- M represents hydrogen or a watersolubilizing cation such as alkali metal, e.g., sodium, potassium, etc.; ammonium, substituted ammonium, etc.
- dehydrodithizone as reported in the literature is capable of several formulistic definitions. In this connection specific reference is made to J.A.C.S., vol. 83, p. 5023. Despite the fact that several theories are postulated in explanation of the validity of a given structural representation, it is nevertheless manifest that the term dehydrodithizone connotes a specific species of tetrazolium salts.
- ripening finals are added during the ripening or sensitivity increasing stage of the emulsion making process. Such additions may be effected before, during or after the decomposition of the soluble silver salt such as silver nitrate by means of a soluble halide such as potassium bromide, sodium chloride or the like in the presence of a suitable colloid carrier such as gelatin, polyvinyl alcohol, solubilized casein albumen or the like.
- a suitable colloid carrier such as gelatin, polyvinyl alcohol, solubilized casein albumen or the like.
- Coating finals are added to the emulsion just prior to coating on a suitable support such as glass, paper or film at a time when the emulsion has nearly attained its maximum sensitivity.
- novel stabilizers of the present invention may be incorporated in a layer adjacent to the sensitized layer such as an anti-abrasion layer.
- the stabilizing compound may be utilized in concentrations varying over a relatively wide range; for example, when added to the light-sensitive silver halide emulsion layer as a ripening final, it is found that optimum realization of results provided herein are assured with stabilizer concentrations ranging from as low as .02 milligram up to about 500 milligrams per 0.6 mole of silver halide.
- the concentration selected within the aforestated range will depend to a large extent on the type of emulsion employed and thus it is advisable to determine the optimum concentration from case to case. If added during the emulsion preparation stage, stabilizer concentrations on the order of approximately one-tenth of those employed when adding the stabilizer as a coating final are found to be quite suitable.
- the stabilizer compounds contemplated herein can be applied in a variety of ways to impart stability to photographic elements. As previously mentioned, they may be included as a constituent of the emulsion layer, of a surface layer over the emulsion or alternatively, over the base or support.
- inventions of the present invention contemplate the addition of such compounds to at least one of the developing, fixing, washing, drying, etc. solutions utilized in the processing of the exposed emulsion.
- the stabilizer when utilized in the Washing step the stabilizer can be applied to the otherwise finished photographic element by immersing same in an alcohol, e.g., methanol or alcohol-water solution in the case of the free acid derivatives while the salt derivatives may be employed effectively as simple water solutions.
- the improvements provided by the present invention are particularly manifest according to procedures whereby development is effected in the presence of said stabilizer compounds.
- This would be the case should the stabilizer be included in the light-sensitive photographic element, the developing solution and/or suitable developer pre-bath.
- the stabilizers of the present invention are preferably employed in concentrations ranging from about 1 to about 50 milligrams per liter of solution, with a range of about 5 milligrams to about 20 milligrams per liter being particularly preferred.
- the stabilizers may also be used in non-sensitized emulsions, X-ray emulsions, paper emulsions, color emulsions and the like. If used with sensitizing dyes, they may be added'to the emulsion before or after dye addition. Moreover, the present stabilizers may also be employed in conjunction with other known antifoggants and stabilizers, reduction stabilizers, metal and noble metal sensitizers or in combination with other additive agents and the like.
- the stabilizer may also be employed in gelatin or other water-permeable colloids including polyamides or a mixture of gelatin with a polyamide as described in U.S. Patent 2,289,775; polyvinyl alcohol and gelling compound as described in U.S. Patent 2,249,537; polyvinyl acetaldehyde acetal resins and partially hydrolyzed acetate resins described in U.S. Patents 1,939,422 and 2,036,092; cellulose derivatives, e.g., cellulose nitrate, cellulose acetate, and the lower fatty acid esters of cellulose including sample and mixed esters and ethers of cellulose and the like.
- polyamides or a mixture of gelatin with a polyamide as described in U.S. Patent 2,289,775
- polyvinyl alcohol and gelling compound as described in U.S. Patent 2,249,537
- a solution of the stabilizer in a suitable solvent such as water, alcohol, dimethyl formamide or alcohol-water mixture adjusted to a neutral or slightly alkaline pH, i.e. about 7.5 to 10, is made up and the solution mixed with the emulsion at any convenient stage during its preparation, but preferably during ripening or just prior to coating.
- any of the aforedescribed compounds may be utilized to advantage in the practice of the present invention, particularly beneficial results are obtained and especially with regard to the suppression of fog which would otherwise result from film storage under severe conditions of humidity and temperature with the 1,3-diphenyl derivatives.
- such compounds there may be mentioned without limitation the following:
- a silver halide emulsion in gelatin containing 2% silver iodide and 98% silver bromide is prepared in conventional manner and brought up to its maximum light sensitivity. It is then readied for coating; finals are added such as sensitizing dyes and hardening agents. Approximately 6 cc. of a 0.01% solution of S-methylmercapto- 2,3-diphenyltetrazolium iodide was added to the emulsion as an antifoggant and stabilizer. The emulsion samples contained about 0.6 mole of silver halide. The so prepared emulsion samples were then coated on a suitable cellulose ester base and dried. Samples of these film coatings were then exposed in a Type IB sensitometer and developed in a developer of the following composition:
- the developer composition may be any of those conventionally employed in the development of exposed silver halide emulsions and accordingly, may be of the hydroquinone type, i.e., those which contain hydroquinone, potassium meta'bisulfite and potassium bromide, or they may be of the metol-hydroquinone type, i.e., those which contain p-methylaminophenol, sodium sulfite, sodium bisulfite, hydroquinone sodium carbonate, and potassium bromide.
- the developer composition may be of the so-called borax type, i.e., those which contain p-methylaminophenol, sodium sulfite, hydroquinone borax and potassium bromide.
- novel stabilizers of the present invention may be employed singly or in admixtures comprising two or more of such compounds. Again, optimum combinations thereof can be readily ascertained in a particular instance by routine laboratory experimentation.
- a process of treating an exposed silver halide emulsion which comprises developing said emulsion in the presence of an antifoggant and stabilizer comprising a compound selected from the group consisting of (a) dehydrodithizone, (b) 5-alkylmercapto-2,3-diaryltetrazoliurn chlorides, bromides and iodides, (c) S-alkylmercapto- 2,3-dialkyltetrazolium chlorides, bromides and iodides, (d) S-carboxyalkylmercapto-2,3-diaryltetrazolium chlorides, bromides and iodides, (e) S-carboxyalkylmercapto- 2,3-dialkyltetrazolium chlorides, bromides and iodides and (f) the alkali metal, ammonium and substituted ammonium salts of the carboxy compounds of (d) and (e).
- said antifoggant and stabilizer compound comprises S-methylmercapto-2,3-diphenyltetrazolium iodide.
- a process according to claim 1 wherein said antifoggant and stabilizer compound comprises dehydrodithizone.
- An aqueous developer solution containing a silver halide photographic developing agent and an antifoggant and stabilizer comprising a compound selected from the group consisting of (a) dehydrodithizone, (b) 5-alkylmercapto-2,3 -diaryltetrazolium chlorides, bromides and iodides, (c) 5-alkylrnercapto-2,3-dialky1tetrazolium chlorides, bromides and iodides, (d) S-carboxyalkylmercapto- 2,3-diaryltetrazolium chlorides, bromides and iodides, (e) 5-carboxyalkylmercapto-Z,3-dia1kyltetrazolium chlorides, bromides and iodides and (f) the alkali metal, ammonium and substituted ammonium salts of the carboxy compounds of (d) and (e).
- a light-sensitive silver halide emulsion containing an antifoggant and stabilizer comprising a compound selected from the group consisting of (a) dehydrodithizone, (b) 5-alkylmercapto-Z,3-diaryltetrazolium chlorides, bromides and iodides, (c) 5-alky1mercapto-2,3-dialkyltetrazolium chlorides, bromides and iodides, (d) S-carboxyalkylmercapto 2,3 diaryltetrazolium chlorides, bromides and iodides, (e) 5-carboxyalkylmercapt0-2,3-dialkyltetrazolium chlorides, bromides and iodides and (f) the alkali metal, ammonium and substituted ammonium salts of the carboxy compounds of (d) and (e).
- a light-sensitive photographic material comprising a base and a light-sensitive silver halide emulsion, said lightsensitive material containing an antifoggant and stabilizer comprising a compound selected from the group consisting of (a) dehydrodithizone, (b) 5-alkylmer capto-2,3-diaryltetrazolium chlorides, bromides and iodides, (c) 5-alkylmercapto-2,3-dialkyltetrazolium chlorides, bromides and iodides, (d) S-carboxyalkylrnercapto-2,3-diaryltetrazolium chlorides, bromides and iodides, (e) 5-carboXya1kylmercapto-2,3-dialkyltetrazolium chlorides, bromides and iodides and (f) the alkali metal, ammonium and substituted ammonium salts of the carboxy compounds of (d) and (e).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51797666A | 1966-01-03 | 1966-01-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3420664A true US3420664A (en) | 1969-01-07 |
Family
ID=24062015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US517976A Expired - Lifetime US3420664A (en) | 1966-01-03 | 1966-01-03 | Dehydrodithizone and mercaptotetrazolium salts as silver halide photographic antifoggants and stabilizers |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3420664A (en)) |
| BE (1) | BE691942A (en)) |
| DE (1) | DE1547920A1 (en)) |
| FR (1) | FR1507069A (en)) |
| GB (1) | GB1174907A (en)) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2422069A1 (de) * | 1973-05-07 | 1974-12-05 | Minnesota Mining & Mfg | Tetrazolium-c-oxybetainverbindungen und ihre verwendung als schleierverhuetungsmittel |
| US4009029A (en) * | 1973-06-05 | 1977-02-22 | Eastman Kodak Company | Cyanoethyl-containing blocked development restrainers |
| DE2803178A1 (de) * | 1977-02-01 | 1978-08-03 | Konishiroku Photo Ind | Lichtempfindliches photographisches silberhalogenidaufzeichnungsmaterial |
| DE2803232A1 (de) * | 1977-01-27 | 1978-08-03 | Konishiroku Photo Ind | Lichtempfindliches photographisches silberhalogenid-aufzeichnungsmaterial und verfahren zu seiner entwicklung |
| US4175966A (en) * | 1975-08-02 | 1979-11-27 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof |
| US4268620A (en) * | 1977-01-31 | 1981-05-19 | Konishiroku Photo Industry Co., Ltd. | Method of processing of light-sensitive silver halide photographic material |
| US4416980A (en) * | 1977-01-28 | 1983-11-22 | Konishiroku Photo Industry Co., Ltd. | High-contrast light-sensitive silver halide photographic material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2981624A (en) * | 1957-06-05 | 1961-04-25 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsion |
| US3071465A (en) * | 1961-03-14 | 1963-01-01 | Gen Aniline & Film Corp | Fog reduction in silver halide emulsions by 2h-tetrazolium halides |
| US3311474A (en) * | 1962-08-31 | 1967-03-28 | Gevaert Photo Prod Nv | Photographic material |
| DE1240399B (de) * | 1963-12-17 | 1967-05-11 | Agfa Ag | Nicht spektral sensibilisierte Silberhalogenidemulsion mit nichtsensibilisierenden quaternaeren Cycloammoniumsalzen |
-
1966
- 1966-01-03 US US517976A patent/US3420664A/en not_active Expired - Lifetime
- 1966-12-20 GB GB56895/66A patent/GB1174907A/en not_active Expired
- 1966-12-21 DE DE19661547920 patent/DE1547920A1/de active Pending
- 1966-12-29 BE BE691942D patent/BE691942A/xx unknown
- 1966-12-30 FR FR89652A patent/FR1507069A/fr not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2981624A (en) * | 1957-06-05 | 1961-04-25 | Gen Aniline & Film Corp | Antifoggants and stabilizers for photographic silver halide emulsion |
| US3071465A (en) * | 1961-03-14 | 1963-01-01 | Gen Aniline & Film Corp | Fog reduction in silver halide emulsions by 2h-tetrazolium halides |
| US3311474A (en) * | 1962-08-31 | 1967-03-28 | Gevaert Photo Prod Nv | Photographic material |
| DE1240399B (de) * | 1963-12-17 | 1967-05-11 | Agfa Ag | Nicht spektral sensibilisierte Silberhalogenidemulsion mit nichtsensibilisierenden quaternaeren Cycloammoniumsalzen |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2422069A1 (de) * | 1973-05-07 | 1974-12-05 | Minnesota Mining & Mfg | Tetrazolium-c-oxybetainverbindungen und ihre verwendung als schleierverhuetungsmittel |
| US4009029A (en) * | 1973-06-05 | 1977-02-22 | Eastman Kodak Company | Cyanoethyl-containing blocked development restrainers |
| US4175966A (en) * | 1975-08-02 | 1979-11-27 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof |
| DE2803232A1 (de) * | 1977-01-27 | 1978-08-03 | Konishiroku Photo Ind | Lichtempfindliches photographisches silberhalogenid-aufzeichnungsmaterial und verfahren zu seiner entwicklung |
| US4211835A (en) * | 1977-01-27 | 1980-07-08 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic material and method of processing the same |
| US4416980A (en) * | 1977-01-28 | 1983-11-22 | Konishiroku Photo Industry Co., Ltd. | High-contrast light-sensitive silver halide photographic material |
| US4268620A (en) * | 1977-01-31 | 1981-05-19 | Konishiroku Photo Industry Co., Ltd. | Method of processing of light-sensitive silver halide photographic material |
| DE2803178A1 (de) * | 1977-02-01 | 1978-08-03 | Konishiroku Photo Ind | Lichtempfindliches photographisches silberhalogenidaufzeichnungsmaterial |
| US4221864A (en) * | 1977-02-01 | 1980-09-09 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic materials |
Also Published As
| Publication number | Publication date |
|---|---|
| BE691942A (en)) | 1967-05-29 |
| DE1547920A1 (de) | 1969-12-11 |
| FR1507069A (fr) | 1967-12-22 |
| GB1174907A (en) | 1969-12-17 |
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