US3507658A - Thio and dithiocinnamic acids as antifoggants and stabilizers - Google Patents
Thio and dithiocinnamic acids as antifoggants and stabilizers Download PDFInfo
- Publication number
- US3507658A US3507658A US621427A US3507658DA US3507658A US 3507658 A US3507658 A US 3507658A US 621427 A US621427 A US 621427A US 3507658D A US3507658D A US 3507658DA US 3507658 A US3507658 A US 3507658A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- silver halide
- light
- dithiocinnamic
- fog
- 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
- 239000003381 stabilizer Substances 0.000 title description 28
- 239000002253 acid Substances 0.000 title description 15
- 150000007513 acids Chemical class 0.000 title description 5
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 title description 3
- 239000000839 emulsion Substances 0.000 description 53
- 229910052709 silver Inorganic materials 0.000 description 29
- 239000004332 silver Substances 0.000 description 29
- -1 silver halide Chemical class 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 125000004434 sulfur atom Chemical group 0.000 description 8
- 230000005070 ripening Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NAEHAPZYAHRUTE-UHFFFAOYSA-N 3-phenyl-2-sulfanylprop-2-enoic acid Chemical class OC(=O)C(S)=CC1=CC=CC=C1 NAEHAPZYAHRUTE-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
- 239000000203 mixture Substances 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- DTQQMICZMZQKHG-UHFFFAOYSA-N 3-(3-sulfanylphenyl)prop-2-enoic acid Chemical compound OC(=O)C=CC1=CC=CC(S)=C1 DTQQMICZMZQKHG-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction 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
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SLKXZKKNPSNVQO-ZZXKWVIFSA-N (e)-3-(4-sulfanylphenyl)prop-2-enoic acid Chemical compound OC(=O)\C=C\C1=CC=C(S)C=C1 SLKXZKKNPSNVQO-ZZXKWVIFSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- PDXIRRHBYATHAH-UHFFFAOYSA-N 3-(2-sulfanylphenyl)prop-2-enoic acid Chemical compound OC(=O)C=CC1=CC=CC=C1S PDXIRRHBYATHAH-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 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
- 230000000996 additive effect Effects 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 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
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 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
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 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
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 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
- 239000002904 solvent Substances 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
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920002554 vinyl 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
- G03C1/06—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
-
- 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
Definitions
- This invention relates in general to photography and in particular to the provision of novel antifogging and 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 sensitizing 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 stepsof pretreating or developing the emulsion is effected in the presence of a novel stabilizing compound to be more fully described hereinafter.
- X represents a member of the group consisting of a hydrogen atom and a sulfur atom and n represents a whole positive integrer having a value of from 1 through 2, inclusive with the proviso that when X is a hydrogen atom the value of n is equal to l and X is a sulfur atom the value of n is equal to 2.
- thiocinnamic and dithiocinnamic acids of the class described above which find immediate and practical utility in accomplishing the objects of the present invention, include for example the following:
- the antifoggant may conveniently be incorporated into the silver halide emulsion as a ripening final or as a coating final.
- Ripening finals are added during the ripening or the sensitivity increasing stage of the emulsion making process, whereas coatin finals are added to the silver halide emulsion just prior to the coating of the emulsion on a suitable support, such as, for example, paper, glass or film.
- antifoggants can be made before, during, or after the addition of the soluble silver salt to the soluble halide in the presence of a suitable carrier or colloid, such as gelatin, polyvinyl alcohol, solubilized casein, albumin and the like.
- a suitable carrier or colloid such as gelatin, polyvinyl alcohol, solubilized casein, albumin and the like.
- the amount of antifogging agent employed as additives to the light-sensitive emulsions varies from about 0.1 to about 50 milligrams of antifoggant per 0.6 mole of silver halide.
- antifogging agents When the antifogging agents are employed as ripening finals it has been found advantageous to employ them in amounts in the range of from about 0.1 to about 25 milligrams per 0.6 mole of silver halide, whereas when the antifogging agents are employed in coating finals, it has been found advantageous to employ amounts in the range of from about 0.5 to about 50 milligrams of antifoggant per 0.6 mole of silver halide. Obviously, the development of optimum characteristics within the ranges set forth above will depend, in part, upon the type of emulsion employed and can be readily determined in each case.
- 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 efiectively 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 prebath.
- 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 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 2,289,776; polyvinyl alcohol and gelling compound as described in U.S. Patent 2,249,537; polyvinyl acetaldehyde acetal resins and partially hydrolyzed acetate resins 4 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 2,289,776
- 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.
- EXAMPLE I A silver halide emulsion in gelatin containing 2% silver iodide and 98% silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating, finals were added such as sensitizing dyes and hardening agents. A 0.1% solution of mercaptocinnamic acid 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 coated on a suitable cellulose ester base and dried. Samples of these film coatings were then exposed in a Type 1B Sensitometer and developed in a developer of the following composition:
- CH CHCOOH
- X represents a member of the group consisting of a hydrogen atom and a sulfur atom
- n represents a Whole positive integer having a value of from 1 through 2, inclusive with the proviso that when X is a hydrogen atom the value of n is equal to 1 and when X is a sulfur atom the value of n is equal to 2.
- a light-sensitive photographic material comprising a base and a light-sensitive silver halide emulsion, said light-sensitive material containing as an antifoggant and stabilizer, a stabilizing amount of a compound of the following structural formula:
- a light-sensitive photographic material according to claim 8 wherein said antifoggant and stabilizer compound is present in said light-sensitive silver halide emulsion layer.
- a process of treating an exposed silver halide emulsion which comprises developing said emulsion in the presence of a stabilizing amount of a compound of the following structural formula:
- X represents a member of the group consisting of a hydrogen atom and a sulfur atom and n represents a whole positive integer having a value of from 1 through 2, inclusive with the proviso that when X is a hydrogen atom the value of n is equal to 1 and when X is a sulfur atom the value of n is equal to 2.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62142767A | 1967-03-08 | 1967-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3507658A true US3507658A (en) | 1970-04-21 |
Family
ID=24490141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US621427A Expired - Lifetime US3507658A (en) | 1967-03-08 | 1967-03-08 | Thio and dithiocinnamic acids as antifoggants and stabilizers |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3507658A (en, 2012) |
| BE (1) | BE711801A (en, 2012) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4336321A (en) * | 1980-02-07 | 1982-06-22 | Mitsubishi Paper Mills, Ltd. | Silver halide photographic materials |
| US4740438A (en) * | 1986-12-10 | 1988-04-26 | Eastman Kodak Company | Organic disulfides as image dye stabilizers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3226232A (en) * | 1963-05-16 | 1965-12-28 | Gen Aniline & Film Corp | Fog reduction in silver halide emulsions with a diphenyldisulfide dicarboxylic acid |
| US3244522A (en) * | 1962-09-26 | 1966-04-05 | Gen Aniline & Film Corp | Fog reduction in photographic silver halide emulsions |
-
1967
- 1967-03-08 US US621427A patent/US3507658A/en not_active Expired - Lifetime
-
1968
- 1968-03-07 BE BE711801D patent/BE711801A/xx unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3244522A (en) * | 1962-09-26 | 1966-04-05 | Gen Aniline & Film Corp | Fog reduction in photographic silver halide emulsions |
| US3226232A (en) * | 1963-05-16 | 1965-12-28 | Gen Aniline & Film Corp | Fog reduction in silver halide emulsions with a diphenyldisulfide dicarboxylic acid |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4336321A (en) * | 1980-02-07 | 1982-06-22 | Mitsubishi Paper Mills, Ltd. | Silver halide photographic materials |
| US4740438A (en) * | 1986-12-10 | 1988-04-26 | Eastman Kodak Company | Organic disulfides as image dye stabilizers |
| EP0271322A3 (en) * | 1986-12-10 | 1989-02-01 | Eastman Kodak Company | Organic disulfides as image dye stabilizers |
| JP2633878B2 (ja) | 1986-12-10 | 1997-07-23 | イーストマン コダック カンパニー | 安定剤化合物を含有する写真材料 |
Also Published As
| Publication number | Publication date |
|---|---|
| BE711801A (en, 2012) | 1968-07-15 |
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