US3539350A - Photographic elements and emulsions stabilized against thermal fog - Google Patents
Photographic elements and emulsions stabilized against thermal fog Download PDFInfo
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- US3539350A US3539350A US650211A US3539350DA US3539350A US 3539350 A US3539350 A US 3539350A US 650211 A US650211 A US 650211A US 3539350D A US3539350D A US 3539350DA US 3539350 A US3539350 A US 3539350A
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- Prior art keywords
- silver halide
- silver
- emulsion
- photographic
- fog
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- Expired - Lifetime
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- 239000000839 emulsion Substances 0.000 title description 63
- 229910052709 silver Inorganic materials 0.000 description 60
- 239000004332 silver Substances 0.000 description 60
- -1 silver halide Chemical class 0.000 description 49
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 47
- 239000003381 stabilizer Substances 0.000 description 30
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011975 tartaric acid Substances 0.000 description 6
- 229960001367 tartaric acid Drugs 0.000 description 6
- 235000002906 tartaric acid Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- 150000001875 compounds Chemical class 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
- 239000000123 paper Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920002678 cellulose Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002344 gold compounds Chemical class 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011885 synergistic combination Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-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
- 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
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 244000186140 Asperula odorata Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000008526 Galium odoratum Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-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
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- YGZZDQOCTFVBFC-UHFFFAOYSA-L disodium;1,5-dihydroxypentane-1,5-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C(O)CCCC(O)S([O-])(=O)=O YGZZDQOCTFVBFC-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- JGEMYUOFGVHXKV-OWOJBTEDSA-N fumaraldehyde Chemical compound O=C\C=C\C=O JGEMYUOFGVHXKV-OWOJBTEDSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 229910052725 zinc Chemical class 0.000 description 1
- 239000011701 zinc Chemical class 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
Definitions
- This invention relates to photographic materials, their preparation and use.
- One aspect of the invention relates to new and improved stabilizers against thermal fog for photographic elements.
- Another aspect of the invention relates to photographic silver halide emulsions containing the stabilizers therein.
- U.S. Fat. 2.839,405 of Jones issued June 7, 1958 discloses various emulsion stabilizers such as the watersoluble inorganic acid salts of cadmium, cobalt, manganese and zinc. While these fog inhibitors are effective at temperatures which are ordinarily encountered, these and other prior art emulsion stabilizers will not stabilize an emulsion for very long when the emulsion is heated to 100 C. It would be desirable to have an emulsion stabilizer which would protect a photographic emulsion exposed to temperatures over 100 C. A photographic element with great heat resistance could be commercially used in airplanes to record all the characteristics of the flight and could be kept intact even though the airplane has crashed and the photographic element has been heated for a long time.
- a fogstabilizing amount of cadmium chloride and an acid selected from the group consisting of citric acid, tartaric acid or mixtures thereof is incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion.
- This particular emulsionstabilizer combination is a synergistic stabilizer combination as will be shown by the examples hereinafter.
- the emulsion stabilizers of this invention may be incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion, in any amount which will stabilize the silver halide emulsion against thermal fog.
- a concentration of the cadmium chloride in an amount of from about 10 to about grams per mole of silver in the silver halide emulsion and a concentration of the acid in an amount of from about 5 to about 55 grams per mole of silver in the silver halide emulsion can be used with good results.
- the cadmium chloride is employed in a concentration of from about 12 to about 60 grams per mole of silver in the silver halide emulsion and the acid is employed in a concentration of from about 7 to about 20 grams per mole of silver in the silver halide emulsion.
- the preparation of photographic silver halide emulsions such as are suitably stabilized with the emulsion stabilizers of this invention typically involves three separate operations:
- the emulsion stabilizers of the invention can be added to the emulsion before this final digestion or after ripening or it can be added immediately prior to the coating step.
- the silver halide emulsion of a photographic element containing the stabilizers of this invention can contain conventional addenda such as gelatin plasticizers, coating aids, and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis- (sodium bisulfite), maleic dialdehyde, aziridines, dioxane, derivatives and oxypolysaccharides.
- Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
- Sensitizing dyes useful in sensitizing such emulsions are described, for example, in US. Pat. 2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, 1950.
- Developing agents can also be incorporated into the silver halide emulsion if desired or can be contained in a contiguous layer.
- Various silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
- the silver halides used can be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images inside the silver halide crystals such as described in US. Pat. 2,592,250 of Davey and Knott issued Apr. 8, 1952.
- the silver halide emulsion layer of a photographic element containing the stabilizers of the invention can contain any of the hydrophilic, water-permeable binding materials suitable for this purpose. Suitable materials include gelatin, colloidal albumin, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc. Mixtures of these binding agents can also be used.
- the binding agents for the emulsion layer of the photographic element can also contain dispersed polymerized vinyl compounds. Such compounds are disclosed, for example, in US. Pats. 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of White issued July 6, 1965; 3,062,674 of Houck, Smith and Yudelson issued Nov.
- the silver halide emulsion of a photographic element containing the stabilizers of the invention can be used on a wide variety of supports.
- Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthaate) film and related films or resinous materials as well as glass, paper, metal and the like.
- Supports such as paper which are coated with a-olefin polymers, particularly polymers of a-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylene-butene copolymers and the like can also be employed.
- the speed of the photographic emulsions containing the stabilizers of the invention can be further enhanced by including in the emulsions a variety of hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Pat. 3,011,890 of Gates, Jr., Miller and Koller issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. 635,206 of Koller and Russell issued Jan. 23, 1962.
- hydrophilic colloids such as carboxymethyl protein of the type described in U.S. Pat. 3,011,890 of Gates, Jr., Miller and Koller issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. 635,206 of Koller and Russell issued Jan. 23, 1962.
- Photographic emulsions containing the stabilizers of the invention can also contain speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers. Frequently, usefui effects can be obtained by adding the aforementioned speedincreasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emulsions.
- speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers.
- Photographic elements containing the stabilizers of the instant invention can be used in various kinds of photographic systems. In addition to being useful in X-ray and other non-optically sensitized systems, they can also be used in orthochromatic, panchromatic and infrared sen sitive systems.
- the sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.
- Silver halide emulsions containing the stabilizers of the invention can be used in color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixedpacket type such as described in U.S. Pat. 2,698,794 of Godowsky issued Jan. 4, 1955; in silver dye-bleach systerns; and emulsions of the mixed-grain type such as described in U.S. Pat. 2,592,243 of Carroll and Hanson issued Apr. 8, 1952.
- the emulsions can also be used in diffusion transfer color processes which utilize a diffusion transfer of an imagewise distribution of developer, coupler or dye, from a light-sensitive layer to a second layer, while the two layers are in close proximity to one another.
- Silver halide emulsions containing the stabilizers of the invention can be processed in stabilization processes such as the ones described in U.S. Pat. 2,614,927 of Broughton and Woodward issued Oct. 21, 1952, and as described in the article Stabilization Processing of Films and Papers by H. D. Russell, E. C. Yackel and J. S. Bruce in PSA Journal, Photographic Science and Technique, volume 16B, October 1950.
- the stabilizers of this invention can be incorporated to advantage during manufacture in silver halide emulsions representing the variations described above. Moreover, fog control in binderless silver halide films prepared by vapor deposition of silver halide on a suitable support can be achieved by coating the stabilizing agents of the invention over the vapor deposited layer of silver halide.
- Example 1 A coarse-grain, ammonical, gelatinosilver bromoiodide emulsion is prepared containing about 99 mole percent bromide and 1 mole percent iodide. The emulsion is sensitized with conventional sulfur and gold compounds and then a portion of it coated on a baryta paper support (250 grams baryta per square decimeter) at a silver coverage of about 40 milligrams per square decimeter and a gelatin coverage of about 80 milligrams per square decimeter. Similar portions of the emulsion are coated in the same manner containing the stabilizers listed in the following table. The coated elements are then exposed on an intensity scale sensitometer and enclosed in an impervious package of a composite aluminum-polyethylene sheet.
- the invention can be sensitized using any of the well- 60 known techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/ or gold compounds.
- the emulsions can also be sensitized with salts of noble metals of Group VH1 of the Periodic Table which have an atomic weight greater than 100.
- Silver halide emulsions containing the stabilizers of the invention can be used in diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the 7 undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
- diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the 7 undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
- Such processes are described in U.S. Pats. 2,352,014 of Rott issued June 20, 1944; 2,543,181 of Water at 125 F.500 cc. N-methyl-p-aminophenol sulfate2 grams Sodium sulfite (desiccated)--72 grams Hydroquinone8 grams Sodium carbonate (monohydrated)56 grams Potassium bromide4 grams Land issued Feb
- the stabilizer combination of the invention is a synergistic combination in providing protection for the longest period of time.
- Example 4 Although a cellulose triacetate film support undergoes deformation at 100 C., it is still possible to study changes of characteristics of an emulsion coated on such a support. To illustrate, an emulsion similar to that of Example 1 is prepared and the various stabilizers listed in the following table are added. The various samples are then coated on a cellulose triacetate support, 0.2 millimeter thick, at the same coverage as in Example 1 and then processed in the same manner as in Example 1 with the following results:
- a composition comprising a photographic silver halide emulsion containing a fog-stabilizing amount of cadmium chloride and an acid selected from the group consisting of citric acid, tartaric acid or mixtures thereof.
- composition of claim 1 wherein said cadmium chloride is present in a concentration of from about 10 to about 150 grams per mole of silver in said silver halide emulsion and said acid is present in a concentration of from about to about 55 grams per mole of silver in said silver halide emulsion.
- composition of claim 2 wherein said acid is citric acid.
- composition of claim 2 wherein said acid is tartaric acid.
- a photographic element comprising a support coated with a silver halide layer, said element containing a fogstabilizing amount of cadmium chloride and an acid selected from the group consisting of citric acid, tartaric acid or mixtures thereof.
- Thermal fog stabilizers (grams per silver mole) 0 hrs. 1 hr. 2 hrs. 4 hrs. 5 hrs. 6 hrs.
- Citric acid (8.8) 0. 18 0. 17 0. 17
- the stabilizer combination of the invention is a synergistic combination and also point out the unobviousness of the invention in that acids other than citric and tartaric acid are not efiective, chlorides other than cadmium chloride are not effective and cadmium salts other than cadmium chloride are not efiective.
- Example 5 Coated elements similar to those of Example 4 are prepared but are not exposed before enclosing in the impervious package. Instead, the coated elements are heated for various times and then exposed on an intensity scale sensitometer, developed, washed and fixed as in Example 4 with the following results:
- Thermal tog stabilizers (grams Rel. Rel. per silver mole) speed Fog Hours speed Fog None 100 0. 18 1 100 0. CdCl (14) 126 0. 16 1 145 0. 24 Citric acid (8.8) 50 0. 18 4 100 0. 36 CdCla (14) plus citric acid (8.8). 71 0. 16 4 100 0. 2O CdClz (14) plus 2N Sulfuric acid (26 ml.) 112 0.16 2 159 0. 30 Citric acid (8.8) plus KCl (5.6) 0. 17 2 63 0.
- said silver halide layer comprises coarse grain silver bromoiodide, sensitized with sulfur or gold.
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- 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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR72203A FR1498513A (fr) | 1966-08-05 | 1966-08-05 | Nouvelles émulsions photographiques stabilisées contre le voile thermique et produits photographiques contenant ces nouvelles émulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3539350A true US3539350A (en) | 1970-11-10 |
Family
ID=8614935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US650211A Expired - Lifetime US3539350A (en) | 1966-08-05 | 1967-06-30 | Photographic elements and emulsions stabilized against thermal fog |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3539350A (mo) |
| BE (1) | BE700303A (mo) |
| DE (1) | DE1597532A1 (mo) |
| FR (1) | FR1498513A (mo) |
| GB (1) | GB1161264A (mo) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6078155A (en) * | 1999-01-18 | 2000-06-20 | Mitsubishi Denki Kabushiki Kaisha | Electric power steering circuit assembly |
| US20110200809A1 (en) * | 2010-02-12 | 2011-08-18 | Eastman Chemical Company | Sulfite softwood based cellulose triacetate for lcd films |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2042533C3 (de) * | 1970-08-27 | 1981-10-01 | Agfa-Gevaert Ag, 5090 Leverkusen | Verfahren zur Herstellung photographischer Silberhalogenidemulsionen |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2384663A (en) * | 1943-08-21 | 1945-09-11 | Eastman Kodak Co | Method of preventing aerial oxidation and color stain |
| US2839405A (en) * | 1955-03-08 | 1958-06-17 | Eastman Kodak Co | Inorganic salt antifoggants for photographic emulsions |
-
1966
- 1966-08-05 FR FR72203A patent/FR1498513A/fr not_active Expired
-
1967
- 1967-06-21 BE BE700303D patent/BE700303A/xx unknown
- 1967-06-30 US US650211A patent/US3539350A/en not_active Expired - Lifetime
- 1967-08-04 DE DE19671597532 patent/DE1597532A1/de active Pending
- 1967-08-07 GB GB36179/67A patent/GB1161264A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2384663A (en) * | 1943-08-21 | 1945-09-11 | Eastman Kodak Co | Method of preventing aerial oxidation and color stain |
| US2839405A (en) * | 1955-03-08 | 1958-06-17 | Eastman Kodak Co | Inorganic salt antifoggants for photographic emulsions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6078155A (en) * | 1999-01-18 | 2000-06-20 | Mitsubishi Denki Kabushiki Kaisha | Electric power steering circuit assembly |
| US20110200809A1 (en) * | 2010-02-12 | 2011-08-18 | Eastman Chemical Company | Sulfite softwood based cellulose triacetate for lcd films |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1498513A (fr) | 1967-10-20 |
| GB1161264A (en) | 1969-08-13 |
| DE1597532A1 (de) | 1970-06-04 |
| BE700303A (mo) | 1967-12-01 |
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