US3544336A - Phosphate antifoggants for photographic emulsions - Google Patents
Phosphate antifoggants for photographic emulsions Download PDFInfo
- Publication number
- US3544336A US3544336A US628829A US3544336DA US3544336A US 3544336 A US3544336 A US 3544336A US 628829 A US628829 A US 628829A US 3544336D A US3544336D A US 3544336DA US 3544336 A US3544336 A US 3544336A
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- US
- United States
- Prior art keywords
- phosphate
- silver
- silver halide
- antifoggants
- emulsion
- 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
- 239000000839 emulsion Substances 0.000 title description 57
- 229910019142 PO4 Inorganic materials 0.000 title description 46
- 239000010452 phosphate Substances 0.000 title description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 33
- -1 silver halide Chemical class 0.000 description 54
- 229910052709 silver Inorganic materials 0.000 description 49
- 239000004332 silver Substances 0.000 description 49
- 235000021317 phosphate Nutrition 0.000 description 45
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 9
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920002678 cellulose Chemical class 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NMPAICLYKOKXAP-UHFFFAOYSA-N (2-chlorophenyl) diphenyl phosphate Chemical compound ClC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 NMPAICLYKOKXAP-UHFFFAOYSA-N 0.000 description 1
- 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
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-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
- PNDJPSHYIFYPHP-UHFFFAOYSA-N 4,4-diphenylbutyl dihydrogen phosphate Chemical compound C=1C=CC=CC=1C(CCCOP(O)(=O)O)C1=CC=CC=C1 PNDJPSHYIFYPHP-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-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
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-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
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-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
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001541 aziridines Chemical class 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
- 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
- 239000011248 coating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 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
- 150000002344 gold compounds Chemical class 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 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
- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 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
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ZOPCDOGRWDSSDQ-UHFFFAOYSA-N trinonyl phosphate Chemical compound CCCCCCCCCOP(=O)(OCCCCCCCCC)OCCCCCCCCC ZOPCDOGRWDSSDQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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 new and improved antifoggants for photographic elements and to photographic silver halide emulsions containing said antifoggants therein.
- development fog has been reduced by prior art methods of processing exposed silver halide material in the presence of compounds which restrict development of unexposed silver halide.
- Such compounds can be incorporated in the silver halide emulsion or in the processing solutions for developing such silver halide emulsions.
- emulsion antifoggants Although a large number of emulsion antifoggants have been used in the prior art, many of these compounds cause undesirable losses in emulsion speed and contrast while others lack adequate compatibility with the emulsion gelatin.
- the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion there is incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion, from about 0.1 to about 5.0 grams, preferably from about 0.5 to about 1.0 gram, per mole of silver in the emulsion of an aryl phosphate, an alkyl phosphate, 3, mixed aryl-alkyl phosphate or mixtures thereof.
- the phosphate may be added to the emulsion or coated onto the element either as an alcoholic solution or in the form of a fine dispersion in gelatin. Use of the phosphate compound results in control of excessive fog formed on forced development of the silver halide emulsion.
- R R and R may each be the same or different radicals and are alkyl radicals having up to 10 carbon atoms or mononuclear aryl radicals, either or both of which may or may not be substituted.
- alkyl radicals having up to 10 carbon atoms or mononuclear aryl radicals, either or both of which may or may not be substituted.
- examples of such radicals include phenyl, cresyl, ethyl, butyl, 2-ethylhexyl, etc.
- phosphates falling within the formula include trinonyl phosphate, trioctyl phosphate, chlorophenyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, dicresylmethyl phosphate, diphenylbutyl phosphate, etc.
- the silver halide emulsion of a photographic element containing the antifoggants of this invention can contain conventional addenda such as gelatin plasticizers, coating aids, anti-foggants such as the azaindines and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bi-sulfate), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
- aldehyde hardeners e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bi-sulfate), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.
- sensitizing dyes useful in sensitizing such emulsions are described, for example, in US. Pats. 2,526,632 of Brooker and
- Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
- Developing agents can also be incorporated into the silver halide emulsion if desired or can be contained in a separate underlayer.
- 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 halide emulsion layer of a photographic element containing the antifoggants 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 antifoggants of the invention can be coated on a wide variety of supports.
- Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthalate) 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, ethylenebutene copolymers and the like can also be employed.
- the speed of photographic emulsions containing the antifoggants of the invention can be further increased by including in the emulsions a variety of hydrophilic colloids such as carboxymethyl protein of the type described in US. 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 US. 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 antifoggants of the instant invention can also contain speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers. Frequently, useful effects can be obtained by adding the aforementioned speedincreasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emuls1ons.
- speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers.
- Photographic elements containing the antifoggants of the invention can be used in various kinds of photographic systems. In addition to being useful in X-ray and other nonoptically sensitized systems they can also be used in orthochromatic, panchromatic and infrared sensitive systems.
- the sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.
- Silver halide emulsions containing the antifoggants of the invention can be used in color photography for example emulsions containing color-forming couplers or a second layer, while the two layers are inclose proximity to one another.
- the antifoggants of the invention could also be utilized by incorporating them into a photographic developer, since image formation would still take place in the presence of the antifoggants and they would still perform their antifoggant function.
- Triphenyl phosphate is added as a one percent alcoholic solution in an amount of 0.5 gram per silver mole to a panchromatically sensitized, medium-speed silver bromoiodide (3.1 mole percent iodide) emulsion.
- This emulsion and a control are coated on a polyethylene terephthalate support at a silver coverage of 474 milligrams per square foot, exposed on an intensity scale sensitometer and developed in Kodak D-19 developer with the following results:
- emulsions to be developed by solutions containing couplers or other color-generating materials emulsions of the mixed-packet type such as described in US. Pat. 2,698,794 of Godowsky issued Jan. 4, 1955; in silver dyebleach systems; and emulsions of the mixed-grain type such as described in US. Pat. 2,592,243 of Carroll and Hanson issued Apr. 8, 1952.
- Silver halide emulsions containing the antifoggants of the invention can be sensitized using any of the wellknown techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/or gold compounds.
- the emulsions am also be sensitized with salts of noble metals of Group VIII of the Periodic Table which have an atomic weight greater than 100.
- Kodak D-19 developer employed in this example has the following composition:
- Silver halide emulsions containing the antifoggants 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 undeveloped silver halide and precipitating it on a silver Triphenyl and tricresyl phosphates are added to emulsions, coated and tested as described in Example 1 with the following results:
- Examples 8 and 9 illustrate that optimum results are obtained at concentrations of about 5 grams or below of phosphate in the photographic emulsion. While higher Fos.timeindeveloper amounts of phosphate may be utilized to control fog,
- Example 5 12 24 36 5 they have a tendency to decrease the speed obtained. min. in. mm mm EXAMPLE 3 Control 0. 03 0.22 0.38 0. 65 Control plus triphenyl phosphate 0.03 0. 04 0.16 0.30
- the process of Example 5 1s repeated substltutmg cellulose acetate for the polyethylene terephthalate support
- the Kodak DK-SO developer used in this example has and using the amounts of triphenyl phosphate indicated the following composition: below with the following results:
- EXAMPLE 9 EXAMPLE 5 The process of Example 8 is repeated substituting poly- Tl-iphenyl phosphate at 5 gram per mole f silver i ethylene terephthalate for the cellulose acetate support added to a high speed panchromatically sensitized, silver Wlth the followmg results: bromoiodide (6.5 mole percent iodide) emulsion. This emulsion and a control are coated on a polyethylene terephthalate support at a coverage of 515 milligrams silver Time in per square foot. They are developed 1n Kodak D-19 8 mm 36 min developer with the following results: Phosphate,
- Example 5 The process of Example 5 is repeated substituting cel- 45 lulose acetate for the polyethylene terephthalate support
- the invention has been described in considerand usmg the phosphates indlcated below w1th the folable detail with reference to certain embodiments therelowing results: of, it will be understood that variations and modifica- Tlme in developer 8min. 24min. 36 min. Phosphate,
- a photographic silver halide emulsion containing from about 0.1 to about 5.0 grams per mole of-silver in said silver halide emulsion of an aryl phosphate, an alkyl phosphate, a mixed aryl-alkyl phosphate or mixtures thereof.
- a photographic element comprising a support coated with a silver halide emulsion, said element containing from about 0.1 to about 5.0 grams per mole of silver in said silver halide emulsion of an aryl phosphate, an alkyl phosphate, a mixed aryl-al-kyl phosphate or mixtures thereof.
- phosphate has the formula wherein R R and R may each be an alkyl radical having up to 10 carbon atoms or a mononuclear aryl radical.
Description
United States Patent 3,544,336 PHOSPHATE ANTIFOGGANTS FOR PHOTOGRAPHIC EMULSIONS Kirby M. Milton, Rochester, N. assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey N0 Drawing. Filed Apr. 6, 1967, Ser. No. 628,829 Int. Cl. G03c N34 US. Cl. 96-109 16 Claims ABSTRACT OF THE DISCLOSURE A photographic silver halide emulsion or photographic element containing as an antifoggant an aryl, alkyl or mixed alkyl-aryl phosphate.
BACKGROUND OF THE INVENTION Field of the invention This invention relates to new and improved antifoggants for photographic elements and to photographic silver halide emulsions containing said antifoggants therein.
Description of the prior art During development of a silver halide emulsion, small amounts of unexposed silver halide are reduced to metallic silver. This reduction of unexposed silver halide produces an objectionable background fog.
It is often desirable to use developers of high activity to develop photographic films. In addition, certain films such as aerographic and color negative films are often developed for long times even in developers of high activity in order to obtain more information or speed. Kodak D-19 Developer-a high sulfite, high-bromide, Elon-hydroquinone developeris typical of such developers used with black-and-white emulsions whereas paraphenylene diamine-type developers are used with color films. In the past, such developers have often given rise to excessive fog at long development times with certain spectrally sensitized emulsions.
Development fog has been reduced by prior art methods of processing exposed silver halide material in the presence of compounds which restrict development of unexposed silver halide. Such compounds can be incorporated in the silver halide emulsion or in the processing solutions for developing such silver halide emulsions. Although a large number of emulsion antifoggants have been used in the prior art, many of these compounds cause undesirable losses in emulsion speed and contrast while others lack adequate compatibility with the emulsion gelatin.
SUMMARY OF THE INVENTION According to this invention, there is incorporated into the silver halide emulsion of a photographic element or in a layer contiguous to the silver halide emulsion, from about 0.1 to about 5.0 grams, preferably from about 0.5 to about 1.0 gram, per mole of silver in the emulsion of an aryl phosphate, an alkyl phosphate, 3, mixed aryl-alkyl phosphate or mixtures thereof. The phosphate may be added to the emulsion or coated onto the element either as an alcoholic solution or in the form of a fine dispersion in gelatin. Use of the phosphate compound results in control of excessive fog formed on forced development of the silver halide emulsion.
ice
DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred fog stabilizing compounds of this invention have the formula wherein R R and R may each be the same or different radicals and are alkyl radicals having up to 10 carbon atoms or mononuclear aryl radicals, either or both of which may or may not be substituted. Examples of such radicals include phenyl, cresyl, ethyl, butyl, 2-ethylhexyl, etc. Examples of phosphates falling within the formula include trinonyl phosphate, trioctyl phosphate, chlorophenyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, dicresylmethyl phosphate, diphenylbutyl phosphate, etc.
The silver halide emulsion of a photographic element containing the antifoggants of this invention can contain conventional addenda such as gelatin plasticizers, coating aids, anti-foggants such as the azaindines and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bi-sulfate), maleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides. sensitizing dyes useful in sensitizing such emulsions are described, for example, in US. Pats. 2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, 1950. Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines. Developing agents can also be incorporated into the silver halide emulsion if desired or can be contained in a separate underlayer. 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 halide emulsion layer of a photographic element containing the antifoggants 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. 6, 1962; and 3,220,844 of Houck, Smith and Yudelson issued Nov. 30, 1965; and include the water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
The silver halide emulsion of a photographic element containing the antifoggants of the invention can be coated on a wide variety of supports. Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthalate) 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, ethylenebutene copolymers and the like can also be employed.
The speed of photographic emulsions containing the antifoggants of the invention can be further increased by including in the emulsions a variety of hydrophilic colloids such as carboxymethyl protein of the type described in US. 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 antifoggants of the instant invention can also contain speed-increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers. Frequently, useful effects can be obtained by adding the aforementioned speedincreasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emuls1ons.
Photographic elements containing the antifoggants of the invention can be used in various kinds of photographic systems. In addition to being useful in X-ray and other nonoptically sensitized systems they can also be used in orthochromatic, panchromatic and infrared sensitive systems. The sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.
Silver halide emulsions containing the antifoggants of the invention can be used in color photography for example emulsions containing color-forming couplers or a second layer, while the two layers are inclose proximity to one another.
While it is preferred to utilize the antifoggants of the invention by incorporating them directly into a photographic element, the antifoggants could also be utilized by incorporating them into a photographic developer, since image formation would still take place in the presence of the antifoggants and they would still perform their antifoggant function.
The invention can be further illustrated by the following examples or preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention,
EXAMPLE 1 Triphenyl phosphate is added as a one percent alcoholic solution in an amount of 0.5 gram per silver mole to a panchromatically sensitized, medium-speed silver bromoiodide (3.1 mole percent iodide) emulsion. This emulsion and a control are coated on a polyethylene terephthalate support at a silver coverage of 474 milligrams per square foot, exposed on an intensity scale sensitometer and developed in Kodak D-19 developer with the following results:
emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed-packet type such as described in US. Pat. 2,698,794 of Godowsky issued Jan. 4, 1955; in silver dyebleach systems; and emulsions of the mixed-grain type such as described in US. Pat. 2,592,243 of Carroll and Hanson issued Apr. 8, 1952.
Silver halide emulsions containing the antifoggants of the invention can be sensitized using any of the wellknown techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/or gold compounds. The emulsions am also be sensitized with salts of noble metals of Group VIII of the Periodic Table which have an atomic weight greater than 100.
Kodak D-19 developer employed in this example has the following composition:
Water to make 1 liter.
EXAMPLE 2 Coatings similar to those in Example 1 are made on a cellulose triacetate support. They are similarly evaluated with the following results:
Silver halide emulsions containing the antifoggants 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 undeveloped silver halide and precipitating it on a silver Triphenyl and tricresyl phosphates are added to emulsions, coated and tested as described in Example 1 with the following results:
Relative speed, time in PhosI/flfiate, Fog, time in developer- Developer S V81 8 mole a min. 20 min. 36 min. 3 min. 20 min. 36 min.
Control 0. 13 0. 67 1.46 100 174 174 Control plus Triphenyl phosphate 0. 5 0. 08 0. 42 0. 97 82 155 166 Do 1. 0 0. 07 0. 35 0. 83 78 143 166 0.5 0. 0s 0. 45 1.09 91 166 166 1. 0 0. 06 0. 39 0. 93 87 155 166 layer in close proximity to the original silver halide emulsion layer. Such processes are described in US. Pats. EXAMPLE 4 2,352,014 of Rott issued June 20, 1944; 2,543,181 of Land issued Feb. 27, 1951; and 3,020,155 of Yackel, Yutzy, Foster and Rasch issued Feb. 6, 1962. 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 silver per square foot. They are developed in Kodak DKO developer with the following results:
Examples 8 and 9 illustrate that optimum results are obtained at concentrations of about 5 grams or below of phosphate in the photographic emulsion. While higher Fos.timeindeveloper amounts of phosphate may be utilized to control fog,
5 12 24 36 5 they have a tendency to decrease the speed obtained. min. in. mm mm EXAMPLE 3 Control 0. 03 0.22 0.38 0. 65 Control plus triphenyl phosphate 0.03 0. 04 0.16 0.30 The process of Example 5 1s repeated substltutmg cellulose acetate for the polyethylene terephthalate support The Kodak DK-SO developer used in this example has and using the amounts of triphenyl phosphate indicated the following composition: below with the following results:
Grams N-methyl-p-aminophenol sulfate 2.5 Hvdroquinone 2.5
Tlmeln develo er S0d1um sulfite, des1ccated 30.0 p Sodium metaborate 10.0 Phosphate 3mm Potassium bromide 0.5 g. per Relative Relative Water to make 1 liter. silver mole speed Fog speed Fog Samples of the films of this example are also developed 5; 115 50 in Kodak Dl9 developer with the following results: p e v phosphate 0. 5 100 0.22 126 0. 40 Do 1.0 95 0.20 115 0.34 2.0 87 0.18 100 0. 2s Fog, time in developer- 4. 0 83 0. 16 91 0. 24 8.0 83 0.12 87 0.13 5 12 24 36 16.0 30 0.12 87 0.16 min. min. min. min.
Control 0.06 0.11 0.55 0. 04 25 Control plus triphenyl phosphate 0.06 0.07 0. 20 0.36
EXAMPLE 9 EXAMPLE 5 The process of Example 8 is repeated substituting poly- Tl-iphenyl phosphate at 5 gram per mole f silver i ethylene terephthalate for the cellulose acetate support added to a high speed panchromatically sensitized, silver Wlth the followmg results: bromoiodide (6.5 mole percent iodide) emulsion. This emulsion and a control are coated on a polyethylene terephthalate support at a coverage of 515 milligrams silver Time in per square foot. They are developed 1n Kodak D-19 8 mm 36 min developer with the following results: Phosphate,
g. per Relative Relative Fog timein developer silver mole speed Fog speed Fog Control 100 0. 129 0. s2 5 Control plus tri- 40 pheuyl phosphate 0.5 105 0.29 115 0.54 Control 0.01 0.01 0.21 0.42 D 5 2g 3; 333 Control plus tnphenyl phosphate 0.03 0. 08 0.15 0.23 40 76 Q15 80 Q22 8.0 73 0.12 30 0.16 16.0 69 0.12 76 0.16 EXAMPLE 6 The process of Example 5 is repeated substituting cel- 45 lulose acetate for the polyethylene terephthalate support Although the invention has been described in considerand usmg the phosphates indlcated below w1th the folable detail with reference to certain embodiments therelowing results: of, it will be understood that variations and modifica- Tlme in developer 8min. 24min. 36 min. Phosphate,
g. per Relative Relative Relative silver mole speed Fog speed Fog speed Fog (nnh'nl 0.03 155 0.09 170 0.23 Control plus triphenyl phosphate 1.0 94 0.03 148 0.08 170 0.18 Control plus tributyl phosphate 1.0 97 0.03 155 0. 08 174 0.19 Control plus tri(2-ethy1hexyl) phosphate 1.0 0.02 159 0.09 182 0.21
EXAMPLE7 tions can be effected without departing from the spirit The process of Example 5 is repeated using the phos and scope of the invention as described hereinabove and as defined in the appended claims. phates mdlcated below with the followmg results.
Timeindeveloper 8min. 24min. 36 min. Phosphate,
g. per Relative Relative Relative silver mole speed Fog speed Fog speed Fog Conn-01- 100 0.04 151 0.14 166 0.33 Control plus tributyl phosphate 1.0 91 0.02 155 0.10 162 0.24 Control plus tn(2'ethy1l1exyl) phosphate. 1.0 95 0.03 148 0.12 162 0.29
I claim:
1. A photographic silver halide emulsion containing from about 0.1 to about 5.0 grams per mole of-silver in said silver halide emulsion of an aryl phosphate, an alkyl phosphate, a mixed aryl-alkyl phosphate or mixtures thereof.
2. The emulsion of claim 1 wherein said phosphate has the formula wherein R R and R may each be an alkyl radical having up to carbon atoms or a mononuclear aryl radical.
3. The emulsion of claim 1 wherein said phosphate is present in an amount of from about 0.5 gram to about 1.0 gram per mole of silver in said silver halide emulsion.
4. The emulsion of claim 1 wherein said phosphate is triphenyl phosphate.
5. The emulsion of claim 1 wherein said phosphate is tricresyl phosphate.
6. The emulsion of claim 1 wherein said phosphate is tributyl phosphate.
7. The emulsion of claim 1 wherein said phosphate is tri(Z-ethylhexyl) phosphate.
8. A photographic element comprising a support coated with a silver halide emulsion, said element containing from about 0.1 to about 5.0 grams per mole of silver in said silver halide emulsion of an aryl phosphate, an alkyl phosphate, a mixed aryl-al-kyl phosphate or mixtures thereof.
i 9. The photographic element of claim 8 wherein said phosphate has the formula wherein R R and R may each be an alkyl radical having up to 10 carbon atoms or a mononuclear aryl radical.
10. The photographic element of claim 8 wherein said phosphate ispresent in a layer contiguous to said silver halide emulsion.
11. The photographic element of claim 8 wherein said phosphate is present in said silver halide emulsion.
12. The photographic element of claim 8 wherein said phosphate is present in an amount of from about 0.5 to about 1.0 gram per mole of silver in said silver halide emulsion.
13. The photographic element of claim 8 wherein said phosphate is triphenyl phosphate. 7 l
14. The photographic element of claim 8 wherein said phosphate is tricresyl phosphate.
15. The photographic element of claim 8 wherein said phosphate is tributyl phosphate.
16. The photographic element of claim 8 wherein said phosphate is tri(Z-ethylhexyl) phosphate.
References Cited UNITED STATES PATENTS 3,057,721 10/ 1962 Cowdan et a1 96-109 X OTHER REFERENCES Abstract of Gevaert Photo-Producten patent Belg. 609,497 in Chemical Abstracts vol. 58, p. 7542 G, 1963.
NORMAN G. TORCHIN, Primary Examiner R. E. FICHTER, Assistant Examiner
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US62882967A | 1967-04-06 | 1967-04-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3544336A true US3544336A (en) | 1970-12-01 |
Family
ID=24520479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US628829A Expired - Lifetime US3544336A (en) | 1967-04-06 | 1967-04-06 | Phosphate antifoggants for photographic emulsions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3544336A (en) |
| BE (1) | BE712877A (en) |
| FR (1) | FR1557552A (en) |
| GB (1) | GB1217051A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4326022A (en) * | 1979-12-07 | 1982-04-20 | Konishiroku Photo Industry Co., Ltd. | Photographic material containing a high boiling solvent |
| US4353979A (en) * | 1979-07-25 | 1982-10-12 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic materials |
| US4980275A (en) * | 1988-04-13 | 1990-12-25 | Eastman Kodak Company | Photographic material and process comprising a dye stabilizer |
| US6696237B1 (en) * | 1999-10-26 | 2004-02-24 | Fuji Photo Film Co., Ltd. | Photothermographic material |
| US20040115572A1 (en) * | 2002-12-03 | 2004-06-17 | Yoshihisa Tsukada | Photothermographic material |
| US20040126722A1 (en) * | 2000-10-26 | 2004-07-01 | Yasuhiro Yoshioka | Photothermographic material |
| US6783927B2 (en) * | 2000-07-07 | 2004-08-31 | Fuji Photo Film, Co., Ltd. | Photothermographic material |
| US20060199115A1 (en) * | 2001-01-30 | 2006-09-07 | Hajime Nakagawa | Photothermographic material and image forming method |
| US20060204908A1 (en) * | 2002-12-03 | 2006-09-14 | Hajime Nakagawa | Photothermographic material |
| US20070099132A1 (en) * | 2000-09-18 | 2007-05-03 | Hajime Nakagawa | Photothermographic material |
| US20070122755A1 (en) * | 1999-10-26 | 2007-05-31 | Yasuhiro Yoshioka | Heat developable photosensitive material including a combination of specified reducing agents |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3057721A (en) * | 1959-12-28 | 1962-10-09 | Eastman Kodak Co | Photographic colloid transfer process |
-
1967
- 1967-04-06 US US628829A patent/US3544336A/en not_active Expired - Lifetime
-
1968
- 1968-03-28 BE BE712877D patent/BE712877A/xx unknown
- 1968-03-29 FR FR1557552D patent/FR1557552A/fr not_active Expired
- 1968-04-05 GB GB06416/68A patent/GB1217051A/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3057721A (en) * | 1959-12-28 | 1962-10-09 | Eastman Kodak Co | Photographic colloid transfer process |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4353979A (en) * | 1979-07-25 | 1982-10-12 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic materials |
| US4326022A (en) * | 1979-12-07 | 1982-04-20 | Konishiroku Photo Industry Co., Ltd. | Photographic material containing a high boiling solvent |
| US4980275A (en) * | 1988-04-13 | 1990-12-25 | Eastman Kodak Company | Photographic material and process comprising a dye stabilizer |
| US6696237B1 (en) * | 1999-10-26 | 2004-02-24 | Fuji Photo Film Co., Ltd. | Photothermographic material |
| US20040038163A1 (en) * | 1999-10-26 | 2004-02-26 | Fuji Photo Film Co., Ltd. | Photothermographic material |
| US20070122755A1 (en) * | 1999-10-26 | 2007-05-31 | Yasuhiro Yoshioka | Heat developable photosensitive material including a combination of specified reducing agents |
| US6783927B2 (en) * | 2000-07-07 | 2004-08-31 | Fuji Photo Film, Co., Ltd. | Photothermographic material |
| US20070099132A1 (en) * | 2000-09-18 | 2007-05-03 | Hajime Nakagawa | Photothermographic material |
| US20040126722A1 (en) * | 2000-10-26 | 2004-07-01 | Yasuhiro Yoshioka | Photothermographic material |
| US20070134603A9 (en) * | 2000-10-26 | 2007-06-14 | Yasuhiro Yoshioka | Photothermographic material |
| US20060199115A1 (en) * | 2001-01-30 | 2006-09-07 | Hajime Nakagawa | Photothermographic material and image forming method |
| US20060204908A1 (en) * | 2002-12-03 | 2006-09-14 | Hajime Nakagawa | Photothermographic material |
| US20040115572A1 (en) * | 2002-12-03 | 2004-06-17 | Yoshihisa Tsukada | Photothermographic material |
| US7381520B2 (en) | 2002-12-03 | 2008-06-03 | Fujifilm Corporation | Photothermographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1557552A (en) | 1969-02-14 |
| BE712877A (en) | 1968-07-31 |
| GB1217051A (en) | 1970-12-23 |
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