US3282700A - Chemical sensitization of photographic silver halide emulsions with magnesium metal powder - Google Patents
Chemical sensitization of photographic silver halide emulsions with magnesium metal powder Download PDFInfo
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- US3282700A US3282700A US338634A US33863464A US3282700A US 3282700 A US3282700 A US 3282700A US 338634 A US338634 A US 338634A US 33863464 A US33863464 A US 33863464A US 3282700 A US3282700 A US 3282700A
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- silver halide
- emulsion
- emulsions
- magnesium metal
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- 239000000839 emulsion Substances 0.000 title claims description 59
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 35
- -1 silver halide Chemical class 0.000 title claims description 27
- 229910052709 silver Inorganic materials 0.000 title claims description 25
- 239000004332 silver Substances 0.000 title claims description 25
- 206010070834 Sensitisation Diseases 0.000 title description 10
- 230000008313 sensitization Effects 0.000 title description 10
- 239000000843 powder Substances 0.000 title description 8
- 239000000126 substance Substances 0.000 title description 4
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 238000010348 incorporation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002344 gold compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-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
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-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
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical group CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 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
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- 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
- G03C1/08—Sensitivity-increasing substances
-
- 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
Definitions
- This invention relates to photography, and more particularly, to the manufacture of photographic silver halide emulsions which have been chemically sensitized by treatment with magnesium metal.
- the sensitivity of photographic silver halide emulsions can be increased by a number of different methods, other than by optical or spectral sensitization which results in a speed increase in a given region of the spectrum, as contrasted with a sensitivity increase in the region of the spectrum to which the silver halide emulsion already has inherent sensitivity.
- One of the more common methods of sensitizing emulsions is with a labile sulfur compound, this form of sensitization being known as sulfur sensitization.
- Still a difierent type of sensitization is by treatment with a gold compound, or some other noble metal.
- sensitization is known as reduction sensitiziation, wherein the silver halide emulsion is treated with a reducing compound, such as stannous chloride or thiourea dioxide, for example.
- a reducing compound such as stannous chloride or thiourea dioxide
- Other types of sensitization are also known as hereinafter explained.
- the magnesium metal can be added to the emulsions in the form of a finely-divided powder, preferably having a particle size within the range of about 50 to 400 microns.
- the amount of magnesium metal added can be varied, depending upon the presence or absence of other sensitization, silver halide content, inherent sensitivity of the emulsion, etc. In general, we have found that from about 0.5 to 10.0 grams of magnesium metal per mole of silver halide is adequate to accomplish the results desired.
- the emulsion Prior to coating, the emulsion should generally be filtered, for example,'through glass wool or some other inert material, to remove excess magnesium metal.
- photographic emulsions used in practicing our invention are of the developing-out type.
- the emulsions can be chemically sensitized, e.g., by digestion with naturally active getalin, or sulfur compounds can be added such as those described in Sheppard U.S. Patent 1,574,944, issued March 2, 1926, Sheppard et al. U.S. Patent 1,623,499, issued April 5, 1927, and Sheppard et al. U.S. Patent 2,410,689, issued November 5, 1946.
- the emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium, and platinum.
- the noble metals such as ruthenium, rhodium, palladium, iridium, and platinum.
- Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium ehloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, issued August 31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245, issued August 28, 1951 and 2,566,263, issued August 28, 1951.
- the emulsions can also be chemically sensitized with gold salts as described in Waller et al. U.S. Patent 2,399,- 083, issued April 23, 1946, and Damschroder et al. U.S. Patent 2,642,361, issued June 16, 1953.
- Suitable compounds are potassium chloroaurite, potassium aurithiocyaice nate, potassium chloroaurate, auric trichloride and 2- aurosulfobenzothiazole methochloride.
- the emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932, etc.
- the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. Patent 2,728,663, issued December 27, 1955; Carroll and Murray U.S. Patent 2,728,664, issued December 27, 1955; and Leubner and Murray U.S. Patent 2,728,665, issued December 27, 1955; or with gold salts as described in Damschroder U.S. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers U.S. Patent 2,597,915, issued May 27, 1952; the triazoles of Heimbach and Kelly U.S. Patent 2,444,608, issued July 6, 1948; the azaindenes of Heimbach and Kelly U.S.
- the emulsions may also contain speed increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued February 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; or the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955; or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437, issued May 12, 1959; as well as the thiop-olymers of Graham and Sagal U.S. Patent 3,046,129, issued July 24, 1962, and the Dann and Chechak U.S. Patent 3,046,134, issued July 24, 1962.
- the addenda which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other nonoptically sensitized emulsions they may also be used in orthochromatic, panchromatic, and infrared sensitive emulsions. They may be added to the emulsion before or after any sensitizing dyes which are used.
- Various silver salts may 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 agents may be used in emulsions intended for 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 mixed-packet type, such as described in Godowsky U.S. Patent 2,698,794, issued January 4, 1955; or emulsions of the mixed-grain type, such as described in Carroll and Hanson U.S. Patent 2,592,243, issued April 8, 1952.
- These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silver halide crystals, such as those described in Davey and Knott U.S. Patent 2,592,250, issued April 8, 1952.
- our photographic emulsions can employ any of the conventional silver halide dispersing agents, such as gelatin, albumin, hydrolyzed polyvinyl acetate, hydrolyzed cellulose ester, etc.
- the magnesium metal used in our invention can be added at various stages during the preparation of the emulsion, but we have found that particularly useful results can be obtained when the magnesium metal is added shortly before coating and after conventional finishing operations, which are designed to produce optimum sensitivity in the emulsion.
- the emulsion is then advantageously filtered as described above and coated in the conventional manner.
- Example 1 To 317 g. (0.1 mole) of a fine-grain gelatino-silverbromoiodide emulsion which had been sensitized with a gold compound as described in U.S. Patent 2,399,983, and sulfur sensitized as described in U.S. Patent 1,574,- 944 was added 0.10 g. of powdered magnesium metal having an average particle size of about 200 microns.
- the gelatin content of the emulsion was 24.5 grams, and it was stirred to insure distribution of the powdered magnesium throughout the emulsion.
- the emulsion was then filtered through ordinary glass wool, coated on conventional cellulose acetate film support and dried. The coated film was then exposed in the conventionl manner on an Eastman type Ib sensitometer (intensity scale) and processed for 5 minutes in an MQ developer having the following composition:
- the film was then fixed, washed and dried inthe usual manner.
- a similar coating was prepared without treatment with magnesium metal and coated and processed as described above. Increased speed was exhibited by the treated emulsion in comparison to the untreated.
- Some chemical fog is produced by the strong chemical action of the powdered magnesium and it has been found that this fog can be materially reduced by incorporating an antifoggant into the emulsion prior to treatment with the magnesium metal.
- an antifoggant is 4-hydroxy-6-methyl-1,3,3a,7- tetraazaindene.
- Example 2 TABLE A Coating Mg. Powder Antifoggant Relative Gamma Fog number (g./Ag mole) (gJAg mole) speed a Control Control 2.30 0.16 b 0.1 0.0 2.30 0.20 1.0 0.0 151 2.22 0.32 0.1 4.0 2.10 0.10 1.0 4.0 159 2.20 0.16
- Example 3 Coating Addenda Relative Gamrna Fog number speed a Control 100 2.46 0.18 b Aluminum powder (0.1) 102 2.28 0.18 e Magnesiumpowder (0.1) 174 2.14 0.45
- the sensitization provided by the magnesium powder of our invention can be effected, as shown in the above examples, by merely mixing the magnesium powder intimately with the silver halide emulsion.
- the time of contact between the magnesium powder and the emulsion can be varied considerably, depending upon temperature, size of silver halide grains, silver-colloid ratio, etc. In general, it is necessary to mix the emulsion and the powder together only for a minute or two before removing unreacted powder by filtration or other suitable means. If desired, the emulsioncan be slightly warmed to diminish the contact time, although there is ordinarily no advantage in warming the emulsion. In general, we have found that the mixing can be performed quite effectively at ambient or room temperatures.
- a photographic silver halide emulsion which has been chemically sensitized by incorporating therein magnesium metal powder, followed by filtration to remove unreacted magnesium particles.
- a photographic silver halide developing-out emulsion which has been chemically sensitized with a gold sensitizer and sulfur sensitized, said emulsion having been treated by incorporating therein magnesium powder, followed by filtration to remove unreacted magnesium particles.
- a photographic gelatino-silver-bromoiodide emulsion which has been chemically sensitized with a gold sensitizer and sulfur sensitized, said emulsion having been treated by incorporating therein magnesium powder, followed by filtration to remove unreacted magnesium particles.
- a photographic silver halide which has been chemi- 20 cally sensitized by incorporating therein magnesium metal having a particle size between about 50 and 400 microns,
- magnesium powder varying between about 0.5 and 10 grams per mole of silver halide, followed by filtration to remove unreacted magnesium particles.
- a method of chemically sensitizing photographic silver halide emulsion comprising adding to an aqueous suspension of said emulsion a small amount of magnesium metal powder, intimately admixing said powdered magnesium metal with said emulsion, followed by filtration to remove substantially all unreacted magnesium powdered particles.
- a photographic silver halide emulsion which has been chemically sensitized by the incorporation of powdered magnesium, said emulsion being substantially free of unreacted powdered magnesium.
Description
United States Patent CHEMICAL SENSITIZATION OF PHOTO-GRAPHIC SILVER HALIDE EMULSIONS WITH MAGNESI- UM METAL POWDER John Figueras, Jr., and Charles A. Goffe, both of Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Jan. 20, 1964, Ser. No. 338,634
7 Claims. (Cl. 96-108) This invention relates to photography, and more particularly, to the manufacture of photographic silver halide emulsions which have been chemically sensitized by treatment with magnesium metal.
It is known that the sensitivity of photographic silver halide emulsions can be increased by a number of different methods, other than by optical or spectral sensitization which results in a speed increase in a given region of the spectrum, as contrasted with a sensitivity increase in the region of the spectrum to which the silver halide emulsion already has inherent sensitivity. One of the more common methods of sensitizing emulsions is with a labile sulfur compound, this form of sensitization being known as sulfur sensitization. Still a difierent type of sensitization is by treatment with a gold compound, or some other noble metal. Still another form of sensitization is known as reduction sensitiziation, wherein the silver halide emulsion is treated with a reducing compound, such as stannous chloride or thiourea dioxide, for example. Other types of sensitization are also known as hereinafter explained.
We have found a novel method of increasing the sensitivity of photographic silver halide emulsions by treating the liquid emulsions with magnesium metal. The magnesium metal can be added to the emulsions in the form of a finely-divided powder, preferably having a particle size within the range of about 50 to 400 microns. The amount of magnesium metal added can be varied, depending upon the presence or absence of other sensitization, silver halide content, inherent sensitivity of the emulsion, etc. In general, we have found that from about 0.5 to 10.0 grams of magnesium metal per mole of silver halide is adequate to accomplish the results desired. Prior to coating, the emulsion should generally be filtered, for example,'through glass wool or some other inert material, to remove excess magnesium metal.
The photographic emulsions used in practicing our invention are of the developing-out type.
The emulsions can be chemically sensitized, e.g., by digestion with naturally active getalin, or sulfur compounds can be added such as those described in Sheppard U.S. Patent 1,574,944, issued March 2, 1926, Sheppard et al. U.S. Patent 1,623,499, issued April 5, 1927, and Sheppard et al. U.S. Patent 2,410,689, issued November 5, 1946.
The emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium, and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium ehloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, issued August 31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245, issued August 28, 1951 and 2,566,263, issued August 28, 1951.
The emulsions can also be chemically sensitized with gold salts as described in Waller et al. U.S. Patent 2,399,- 083, issued April 23, 1946, and Damschroder et al. U.S. Patent 2,642,361, issued June 16, 1953. Suitable compounds are potassium chloroaurite, potassium aurithiocyaice nate, potassium chloroaurate, auric trichloride and 2- aurosulfobenzothiazole methochloride.
The emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932, etc.
The emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. Patent 2,728,663, issued December 27, 1955; Carroll and Murray U.S. Patent 2,728,664, issued December 27, 1955; and Leubner and Murray U.S. Patent 2,728,665, issued December 27, 1955; or with gold salts as described in Damschroder U.S. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers U.S. Patent 2,597,915, issued May 27, 1952; the triazoles of Heimbach and Kelly U.S. Patent 2,444,608, issued July 6, 1948; the azaindenes of Heimbach and Kelly U.S. Patents 2,444,605 and 2,444,- 606, issued July 6, 1948; Heimbach U.S. Patents 2,444,- 607, issued July 6, 1948 and 2,450,397, issued September 28, 1948; Heimbach and Clark U.S. Patent 2,444,609, issued July 6, 1948; Allen and Reynolds U.S. Patents 2,713,541, issued July 19, 1955 and 2,743,181, issued April 24, 1956; Carroll and Beach U.S. Patent 2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent 2,735,769, issued February 21, 1956; Reynolds and Sagal U.S. Patent 2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164, issued November 27, 1956, and those disclosed by Birr in Z. wiss. Phot., vol. 47, 1952, pages 2-28; the disulfides of Kodak Belgian Patent 569,317, issued July 31, 1958; the quaternary benzothiazolium compounds of Brooker and Stand U.S. Patent 2,131,038, issued September 27, 1938 or the polymethylene bis-benzothiazolium salts of Allen and Wilson U.S. Patent 2,694,716, issued November 16, 1954; the zinc and cadmium salts of Jones U.S. Patent 2,839,405, issued June 17, 1958; and the carboxymethylmercapto compounds of Murray, Reynolds and Van Allan U.S. Patent 2,819,965, issued January 14, 1958.
The emulsions may also contain speed increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued February 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; or the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955; or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437, issued May 12, 1959; as well as the thiop-olymers of Graham and Sagal U.S. Patent 3,046,129, issued July 24, 1962, and the Dann and Chechak U.S. Patent 3,046,134, issued July 24, 1962.
The addenda which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other nonoptically sensitized emulsions they may also be used in orthochromatic, panchromatic, and infrared sensitive emulsions. They may be added to the emulsion before or after any sensitizing dyes which are used. Various silver salts may 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 agents may be used in emulsions intended for 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 mixed-packet type, such as described in Godowsky U.S. Patent 2,698,794, issued January 4, 1955; or emulsions of the mixed-grain type, such as described in Carroll and Hanson U.S. Patent 2,592,243, issued April 8, 1952. These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silver halide crystals, such as those described in Davey and Knott U.S. Patent 2,592,250, issued April 8, 1952.
These may also be used in emulsions intended for use in diffusion transfer processes which utilize the undeveloped silver halide in the nonimage areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer. Such processes are described in Rott U.S. Patent 2,352,014, issued June 20, 1944, and Land U.S. Patents 2,584,029, issued January 29, 1952; 2,698,236, issued December 28, 1954 and 2,543,181, issued February 27, 1951; and Yackel et al. U.S. Patent 3,020,155, issued February 6, 1962. They may also be used in color transfer processes which utilize the diffusion transfer of an image-wise 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. Color processes of this type are described in Land U.S. Patents 2,559,643, issued July 10, 1951 and 2,698,798, issued January 4, 1955; Land and Rogers Belgian Patents 554,933 and 554,934, granted August 12, 1957; International Polaroid Belgian Patents 554,212, granted July 16, 1957 and 554- 935, granted August 12, 1957; Yutzy U.S. Patent 2,756,- 142, granted July 24, 1956 and Whitmore and Mader U.S. patent application Serial No. 734,141, filed May 9, 1958 (now abandoned). They may also be used in emulsions intended for use in a monobath process such as described in Haist et a1. U.S. Patent 2,875,048, issued February 24, 1959, and in web-type processes, such as the one described in Tregillus et al. U.S. patent application Serial No. 835,473, filed August 24, 1959, now U.S. Patent No. 3,179,517.
In general, our photographic emulsions can employ any of the conventional silver halide dispersing agents, such as gelatin, albumin, hydrolyzed polyvinyl acetate, hydrolyzed cellulose ester, etc.
The magnesium metal used in our invention can be added at various stages during the preparation of the emulsion, but we have found that particularly useful results can be obtained when the magnesium metal is added shortly before coating and after conventional finishing operations, which are designed to produce optimum sensitivity in the emulsion. The emulsion is then advantageously filtered as described above and coated in the conventional manner.
The following examples will serve to illustrate more fully the manner of practicing our invention.
Example 1 To 317 g. (0.1 mole) of a fine-grain gelatino-silverbromoiodide emulsion which had been sensitized with a gold compound as described in U.S. Patent 2,399,983, and sulfur sensitized as described in U.S. Patent 1,574,- 944 was added 0.10 g. of powdered magnesium metal having an average particle size of about 200 microns. The gelatin content of the emulsion was 24.5 grams, and it was stirred to insure distribution of the powdered magnesium throughout the emulsion. The emulsion was then filtered through ordinary glass wool, coated on conventional cellulose acetate film support and dried. The coated film was then exposed in the conventionl manner on an Eastman type Ib sensitometer (intensity scale) and processed for 5 minutes in an MQ developer having the following composition:
Water, about 125 F. (50 C.) ccs 500 N-methyl-p-aminophenol sulfate grams 2.5 Sodium sulfite, desiccated do 30.0 Hydroquinone do 2.5 Sodium metaborate do 10.0 Potassium bromide do 0.5
Water to make 1.0 liter.
The film Was then fixed, washed and dried inthe usual manner. A similar coating was prepared without treatment with magnesium metal and coated and processed as described above. Increased speed was exhibited by the treated emulsion in comparison to the untreated.
Some chemical fog is produced by the strong chemical action of the powdered magnesium and it has been found that this fog can be materially reduced by incorporating an antifoggant into the emulsion prior to treatment with the magnesium metal. One of the more useful antifog- .gants for this purpose is 4-hydroxy-6-methyl-1,3,3a,7- tetraazaindene.
Example 2 TABLE A Coating Mg. Powder Antifoggant Relative Gamma Fog number (g./Ag mole) (gJAg mole) speed a Control Control 2.30 0.16 b 0.1 0.0 2.30 0.20 1.0 0.0 151 2.22 0.32 0.1 4.0 2.10 0.10 1.0 4.0 159 2.20 0.16
Example 3 Coating Addenda Relative Gamrna Fog number speed a Control 100 2.46 0.18 b Aluminum powder (0.1) 102 2.28 0.18 e Magnesiumpowder (0.1) 174 2.14 0.45
The sensitization provided by the magnesium powder of our invention can be effected, as shown in the above examples, by merely mixing the magnesium powder intimately with the silver halide emulsion. The time of contact between the magnesium powder and the emulsion can be varied considerably, depending upon temperature, size of silver halide grains, silver-colloid ratio, etc. In general, it is necessary to mix the emulsion and the powder together only for a minute or two before removing unreacted powder by filtration or other suitable means. If desired, the emulsioncan be slightly warmed to diminish the contact time, although there is ordinarily no advantage in warming the emulsion. In general, we have found that the mixing can be performed quite effectively at ambient or room temperatures.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. A photographic silver halide emulsion which has been chemically sensitized by incorporating therein magnesium metal powder, followed by filtration to remove unreacted magnesium particles.
2. A photographic silver halide developing-out emulsion which has been chemically sensitized with a gold sensitizer and sulfur sensitized, said emulsion having been treated by incorporating therein magnesium powder, followed by filtration to remove unreacted magnesium particles.
3. A photographic gelatino-silver-bromoiodide emulsion which has been chemically sensitized with a gold sensitizer and sulfur sensitized, said emulsion having been treated by incorporating therein magnesium powder, followed by filtration to remove unreacted magnesium particles.
4. A photographic silver halide which has been chemi- 20 cally sensitized by incorporating therein magnesium metal having a particle size between about 50 and 400 microns,
followed by filtration to remove unreacted magnesium particle size between 50 and 400 microns, the amount of said magnesium powder varying between about 0.5 and 10 grams per mole of silver halide, followed by filtration to remove unreacted magnesium particles.
6. A method of chemically sensitizing photographic silver halide emulsion comprising adding to an aqueous suspension of said emulsion a small amount of magnesium metal powder, intimately admixing said powdered magnesium metal with said emulsion, followed by filtration to remove substantially all unreacted magnesium powdered particles.
7. A photographic silver halide emulsion which has been chemically sensitized by the incorporation of powdered magnesium, said emulsion being substantially free of unreacted powdered magnesium.
References Cited by the Examiner UNITED STATES PATENTS 1,791 ,053 2/ 1931 Cooley 96-94 2,642,361 6/1953 Damschroder et al. 96108 3,189,454 9/1965 Luckey et a1 9666 FOREIGN PATENTS 135,038 11/ 1949 Australia.
NORMAN G. TORCHIN, Primary Examiner.
J. H. RAUBITSCHEK, Assistant Examiner.
Claims (1)
- 7. A PHOTOGRAPHIC SILVER HALIDE EMULSION WHICH HAS BEEN CHEMICALLY SENSITIZED BY THE INCORPORATION OF POWDERED MAGNESIUM, SAID EMULSION BEING SUBSTANTIALLY FREE OF UNREACTED POWERED MAGNESIUM.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US338634A US3282700A (en) | 1964-01-20 | 1964-01-20 | Chemical sensitization of photographic silver halide emulsions with magnesium metal powder |
FR2280A FR1426437A (en) | 1964-01-20 | 1965-01-18 | Process for the chemical sensitization of a photographic emulsion and novel silver halide emulsion obtained by this process |
GB2530/65A GB1091342A (en) | 1964-01-20 | 1965-01-20 | Method of preparing photographic silver halide emulsions and emulsions prepared thereby |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US338634A US3282700A (en) | 1964-01-20 | 1964-01-20 | Chemical sensitization of photographic silver halide emulsions with magnesium metal powder |
Publications (1)
Publication Number | Publication Date |
---|---|
US3282700A true US3282700A (en) | 1966-11-01 |
Family
ID=23325484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US338634A Expired - Lifetime US3282700A (en) | 1964-01-20 | 1964-01-20 | Chemical sensitization of photographic silver halide emulsions with magnesium metal powder |
Country Status (3)
Country | Link |
---|---|
US (1) | US3282700A (en) |
FR (1) | FR1426437A (en) |
GB (1) | GB1091342A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3531289A (en) * | 1966-12-02 | 1970-09-29 | Eastman Kodak Co | Silver halide photographic emulsions improved by new precipitation methods |
US3975199A (en) * | 1973-12-18 | 1976-08-17 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1791053A (en) * | 1928-06-07 | 1931-02-03 | Austin o | |
US2642361A (en) * | 1949-07-20 | 1953-06-16 | Eastman Kodak Co | Photographic silver halide emulsions sensitized with water-insoluble gold compounds |
US3189454A (en) * | 1961-10-16 | 1965-06-15 | Eastman Kodak Co | Method of photographic development and fixing |
-
1964
- 1964-01-20 US US338634A patent/US3282700A/en not_active Expired - Lifetime
-
1965
- 1965-01-18 FR FR2280A patent/FR1426437A/en not_active Expired
- 1965-01-20 GB GB2530/65A patent/GB1091342A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1791053A (en) * | 1928-06-07 | 1931-02-03 | Austin o | |
US2642361A (en) * | 1949-07-20 | 1953-06-16 | Eastman Kodak Co | Photographic silver halide emulsions sensitized with water-insoluble gold compounds |
US3189454A (en) * | 1961-10-16 | 1965-06-15 | Eastman Kodak Co | Method of photographic development and fixing |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3531289A (en) * | 1966-12-02 | 1970-09-29 | Eastman Kodak Co | Silver halide photographic emulsions improved by new precipitation methods |
US3975199A (en) * | 1973-12-18 | 1976-08-17 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
Also Published As
Publication number | Publication date |
---|---|
FR1426437A (en) | 1966-01-28 |
GB1091342A (en) | 1967-11-15 |
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