US3137577A - Process for increasing the sensitivity of photographic silver halide emulsion - Google Patents
Process for increasing the sensitivity of photographic silver halide emulsion Download PDFInfo
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- US3137577A US3137577A US258122A US25812263A US3137577A US 3137577 A US3137577 A US 3137577A US 258122 A US258122 A US 258122A US 25812263 A US25812263 A US 25812263A US 3137577 A US3137577 A US 3137577A
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- silver halide
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- 239000000839 emulsion Substances 0.000 title claims description 47
- 229910052709 silver Inorganic materials 0.000 title claims description 20
- 239000004332 silver Substances 0.000 title claims description 20
- -1 silver halide Chemical class 0.000 title claims description 20
- 230000035945 sensitivity Effects 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 11
- 229940100892 mercury compound Drugs 0.000 claims description 11
- 150000002731 mercury compounds Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 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 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- VMNRZYKMPOZISX-UHFFFAOYSA-M COC(C[Hg]O)Cc1cccc2cc(C(O)=O)c(=O)oc12 Chemical compound COC(C[Hg]O)Cc1cccc2cc(C(O)=O)c(=O)oc12 VMNRZYKMPOZISX-UHFFFAOYSA-M 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [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
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229940056910 silver sulfide Drugs 0.000 description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-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
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 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
- HXMRAWVFMYZQMG-UHFFFAOYSA-N 1,1,3-triethylthiourea Chemical compound CCNC(=S)N(CC)CC HXMRAWVFMYZQMG-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
- DEBZQUFVQZPPLC-UHFFFAOYSA-N 2h-chromene-3-carboxylic acid Chemical compound C1=CC=C2OCC(C(=O)O)=CC2=C1 DEBZQUFVQZPPLC-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
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003378 silver Chemical class 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
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
-
- 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
Definitions
- This invention relates to photographic materials and particularly to light-sensitive silver halide emulsion having improved sensitivity.
- Such chemical sensitizers are believed to form, on the surface of the silver halide, minute amounts of silver sulfide or of silver or of gold, and these processes are capable of increasing the sensitivity of developing-out emulsions by very large factors.
- novel and effective chemical sensitizing method which does not belong to any of the above-mentioned chemical sensitizing methods, but increases the sensitivity of the silver halide photographic emulsion without presenting any increase of fog, and at the same time even improves the stability of the said emulsion on tropical aging.
- novel sensitizers of our invention may be used together with labile sulfur compounds, reducing agents and/or gold compounds, thereby we can further increase the sensitivity of the emulsion.
- novel sensitizers of our invention can be used to sensitize photographic silver halide emulsions containing no sensitizers.
- R is an alkyl group having from 1 to 3 carbon atoms, and ripening the said emulsion.
- one object of our invention is to increase the sensitivity of the light-sensitive photographic emulsion without increasing fog.
- Another object is to provide photographic emulsion containing the novel sensitizers. Other objects will become apparent from the following description of our invention.
- Inorganic and organic mercury compounds have been known hitherto as additives having stabilizing action, which, when added in minute quantity to a finished silver halide photographic emulsion, reduce its fog without appreciably affecting the sensitivity of the sensitive material, and further maintain the sensitivity and fog of the said silver halide emulsion at or close to initial optimum values under keeping conditions of high temperature and high humidity.
- stabilizing action which, when added in minute quantity to a finished silver halide photographic emulsion, reduce its fog without appreciably affecting the sensitivity of the sensitive material, and further maintain the sensitivity and fog of the said silver halide emulsion at or close to initial optimum values under keeping conditions of high temperature and high humidity.
- organo-rnercury compounds represented by the above general formula and used according to the present invention have never been described to be used as additives for photographic emulsion in any patents or literatures.
- the organo-mercury compounds are added to the photographic emulsion at any stage of preparing the said emulsion, particularly before and during chemical ripen-' ing, while the organo-mercury compounds disclosed in the above-mentioned patents are added to the finished photographic emulsion before coating, to act as anti.- foggants and stabilizers.
- the organo-mercury compounds of our invention are dissolved in water or other solvents which have no harmful effects upon the emulsion, and generally solvents which are miscible with water are to be preferred.
- the sensitizer can be dissolved in solvents such as water, methanol, etc., and added to the emulsion in this form.
- the particular quantity of the organo-mercury compound used in a given emulsion can vary, depending upon the effect desired, degree of ripening, silver content of the emulsion, etc.
- the amount used is also dependent upon the particular stage at which the sensitizer is added during the preparation of theemulsion. Although we found that from about 0.05 mg. to about 5.0 mg. of the sensitizer per mole of silver halide is quite adequate to accomplish the desired sensitization of many of the common photographic silver halide emulsions, these limits are merely illustrative.
- sensitized emulsions of our invention can be used in the preparation of color photographs. This may be accomplished either by using photographic emulsions containing color-forming compounds or couplers which are well-known in the art, or by the use of photographic emulsions which are developed in color developers containing color-forming compounds or couplers also well-known in the art.
- Example 1 A high-speed negative-type gelatino-silver iodo-bromide photographic emulsion, in which the silver halide consists of 5.0 mole percent silver iodide and 95.0 mole percent silver bromide, is divided into several portions.
- One portion is retained as a control and the quantities of mercumallylic acid indicated in the following table are added to the other portions.
- To each portions respectively containing 1 mole of silver halide, are then added 10.0 g. of an active type gelatin which is considered to contain natural sulfur sensitizers and 1.0 mg. of HAuCl -4H O and 80 mg. of KSCN dissolved together in an aqueous solution, and the emulsions are ripened at 50 C. for 60 minutes under stirring.
- Example 2 To a washed full ammoniacal gelatino silver iodo-bromide photographic emulsion containing 1 mole of silver halide, in which the silver halide consists of 2.2 mole percent Agl and 97.8 mole percent of AgBr, there is added 1.2 cc. of a 0.01% methanolic solution of triethylthiourea, 5.0 cc. of a 0.01% aqueous solution of HAuCL; 4H O admixed with 4.0 cc. of a 0.1 N aqueous solution of NH SCN, and thereafter the emulsion is ripened for 40 minutes at 50 C.
- the emulsion is further ripened for l5 minutes at 50 C.
- the emulsion thus obtained is added under stirring at 35 C., 0.3 g. of 4-hydroxy-6-methyl-1,3,3a,7-tetraza indene, 0.2 g. of chrome alum and 0.2 g. of saponin, and then the mixture is coated on cellulose triacetate film and dried in the usual manner to produce a thin emulsion.
- a process for increasing the sensitivity of photographic silver halide emulsion which comprises, adding to said emulsion at least one mercury compound IEPI'Q sented by the general formula:
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
United States Patent Ofi ice 3,137,577 -Patented June 16, 1964 3,137,577 PROCESS FOR INCREASING THE SENSITIVITY OF PHOTGGHIC SILVER HALIDE EMULSRON Yoshio Miura, Fumihiko Nishio, and Akira Kurnai, Ka-
nagawa-ken, Japan, assignors to Fuji Photo Film Co., Ltd, Kanagawa-ken, Japan, a corporation of Japan No Drawing. Filed Feb. 13, 1963, Ser. No. 258,122 Claims priority, application Japan May 23, 1962 3 Claims. (Cl. 96108) This invention relates to photographic materials and particularly to light-sensitive silver halide emulsion having improved sensitivity.
In the preparation of a light-sensitive silver halide photographic emulsion, various methods have been known as so-called chemical sensitization to increase its sensitivity.
For example, it is well-known to increase the sensitivity of photographic emulsion by addition of sulfur C0111- pounds such as allylthiourea, sodium thiosulfate, etc., which contain labile sulfur atoms and capable of reacting with silver salts to form silver sulfide (compounds of these types are also naturally present in gelation), or with reducing agents such as stannous chloride and hydrazine derivatives, or with salts of gold such as aurous thiocyanate, or with combinations of two or more of the aforementioned compounds generally known as chemical sensitizers. (See P. Glafkides, Chimie Photographique, Paul Montel, Paris (1957), p. 297 and p. 301.)
Such chemical sensitizers are believed to form, on the surface of the silver halide, minute amounts of silver sulfide or of silver or of gold, and these processes are capable of increasing the sensitivity of developing-out emulsions by very large factors.
The process of chemical sensitization, however, generally presents some increases of fog, and moreover reaches a definite limit beyond which further addition of sensitizer, or of further ripening with the sensitizer present, merely increases the fog of the photographic emulsion with constant or decreasing sensitivity.
It is also well-known in the art that there is, at the present time, a practical limit to the advantages which can be obtained by the addition of such compounds without presenting deleterious effects such as instability on tropical aging.
We have now found a novel and effective chemical sensitizing method which does not belong to any of the above-mentioned chemical sensitizing methods, but increases the sensitivity of the silver halide photographic emulsion without presenting any increase of fog, and at the same time even improves the stability of the said emulsion on tropical aging. Moreover the novel sensitizers of our invention may be used together with labile sulfur compounds, reducing agents and/or gold compounds, thereby we can further increase the sensitivity of the emulsion.
However, the novel sensitizers of our invention can be used to sensitize photographic silver halide emulsions containing no sensitizers.
According to our invention, we have found that the sensitivity of an ordinary photographic silver halide emulsion can be increased by incorporating therein at least one organo-mercury compound having the following general formula:
COOH
wherein R is an alkyl group having from 1 to 3 carbon atoms, and ripening the said emulsion.
Therefore one object of our invention is to increase the sensitivity of the light-sensitive photographic emulsion without increasing fog.
Another object is to provide photographic emulsion containing the novel sensitizers. Other objects will become apparent from the following description of our invention.
Among examples of the compounds corresponding to the above general formula is 8-(3'-hydroxymercuri-2'- methoxy propyl) 2 oxo 1,2H benzopyran 3 carboxylic acid, which is conventionally named mercumallylic acid (see The Merck Index, 7th edition, p. 649 (1960); and US. Patent 2,667,422).
Inorganic and organic mercury compounds have been known hitherto as additives having stabilizing action, which, when added in minute quantity to a finished silver halide photographic emulsion, reduce its fog without appreciably affecting the sensitivity of the sensitive material, and further maintain the sensitivity and fog of the said silver halide emulsion at or close to initial optimum values under keeping conditions of high temperature and high humidity. (See' e.g. US. Patents 2,728,663- 2,728,667, 2,732,502, 2,751,299, etc.)
The. organo-rnercury compounds represented by the above general formula and used according to the present invention, however, have never been described to be used as additives for photographic emulsion in any patents or literatures. Furthermore, according to the present invention, the organo-mercury compounds are added to the photographic emulsion at any stage of preparing the said emulsion, particularly before and during chemical ripen-' ing, while the organo-mercury compounds disclosed in the above-mentioned patents are added to the finished photographic emulsion before coating, to act as anti.- foggants and stabilizers.
The organo-mercury compounds of our invention are dissolved in water or other solvents which have no harmful effects upon the emulsion, and generally solvents which are miscible with water are to be preferred. In a preferred embodiment, the sensitizer can be dissolved in solvents such as water, methanol, etc., and added to the emulsion in this form.
The particular quantity of the organo-mercury compound used in a given emulsion can vary, depending upon the effect desired, degree of ripening, silver content of the emulsion, etc. The amount used is also dependent upon the particular stage at which the sensitizer is added during the preparation of theemulsion. Although we found that from about 0.05 mg. to about 5.0 mg. of the sensitizer per mole of silver halide is quite adequate to accomplish the desired sensitization of many of the common photographic silver halide emulsions, these limits are merely illustrative.
As supports on which the photographic emulsion prepared according to our present invention is to be coated ordinary supports for photographic emulsion such as glass, cellulose triacetate film base, polyethylene terephthalate film base, barytaged paper, etc. are used.
In addition, the sensitized emulsions of our invention can be used in the preparation of color photographs. This may be accomplished either by using photographic emulsions containing color-forming compounds or couplers which are well-known in the art, or by the use of photographic emulsions which are developed in color developers containing color-forming compounds or couplers also well-known in the art.
The following examples will further illustrate the invention, but it is to be understood that it is not limited thereto.
Example 1 A high-speed negative-type gelatino-silver iodo-bromide photographic emulsion, in which the silver halide consists of 5.0 mole percent silver iodide and 95.0 mole percent silver bromide, is divided into several portions.
One portion is retained as a control and the quantities of mercumallylic acid indicated in the following table are added to the other portions. To each portions, respectively containing 1 mole of silver halide, are then added 10.0 g. of an active type gelatin which is considered to contain natural sulfur sensitizers and 1.0 mg. of HAuCl -4H O and 80 mg. of KSCN dissolved together in an aqueous solution, and the emulsions are ripened at 50 C. for 60 minutes under stirring.
Thereafter, 30 mg. of 1,l'-diethyl-2,2-cyanine iodide, 0.45 g. of chrome alum, and 0.12 g. of saponin are added to the emulsions and the mixtures are coated on cellulose triacetate film base and dried.
These films are exposed on an intensity scale sensitometer to 5,400 K. illumination for 1 second and developed at 20 C. in a developing solution of the following composition:
(3. N-methyl-p-aminophenol sulfate 2.0 Hydroquinone 5.0 Sodium sulfite (anhydrous) 100.0 Borax 2.0 Water to 1.0 litre.
The result is shown in the following table.
Relative sensitivity Gamma Fog Gamma (control) 0.04
Example 2 To a washed full ammoniacal gelatino silver iodo-bromide photographic emulsion containing 1 mole of silver halide, in which the silver halide consists of 2.2 mole percent Agl and 97.8 mole percent of AgBr, there is added 1.2 cc. of a 0.01% methanolic solution of triethylthiourea, 5.0 cc. of a 0.01% aqueous solution of HAuCL; 4H O admixed with 4.0 cc. of a 0.1 N aqueous solution of NH SCN, and thereafter the emulsion is ripened for 40 minutes at 50 C.
To one-half of the ripened emulsion. is added 8 cc. of a 0.001% methanolic solution of 8-(3'-hydroX ymercuri-2'- ethoxypropyl)-2oxo1,2H-benzopyran-3-carboxylic acid,
and thereafter the emulsion is further ripened for l5 minutes at 50 C.
The emulsion thus obtained is added under stirring at 35 C., 0.3 g. of 4-hydroxy-6-methyl-1,3,3a,7-tetraza indene, 0.2 g. of chrome alum and 0.2 g. of saponin, and then the mixture is coated on cellulose triacetate film and dried in the usual manner to produce a thin emulsion.
layer (12 microns).
The other half of the emulsion is handled in like manner except that the solution of the mercury compound is omitted. 4
These two films are exposed on an intensity scale sensitometer to 5400 K. illumination and developed for 4 minutes at 20 C. in a solution of the following composition:
\Vhat we claim is:
1. A process for increasing the sensitivity of photographic silver halide emulsion which comprises, adding to said emulsion at least one mercury compound IEPI'Q sented by the general formula:
(1)12 HO -HgCHrCH-$Ha --COOH wherein R is an alkyl group having from 1 to 3 carbon atoms, and ripening said emulsion.
2. A process according to claim 1, wherein a labile sulfur compound, in addition to said mercury compound, is added to said emulsion.
3. A process according to claim 1, wherein a labile sulfur compound and a gold compound, in addition to said mercury compound, are added to said emulsion.
No references cited,
Claims (1)
1. A PROCESS FOR INCREASING THE SENSITIVITY OF PHOTOGRAPHIC SILVER HALIDE EMULSION WHICH COMPRISES, ADDING TO SAID EMULSION AT LEAST ONE MERCURY COMPOUND REPRESENTED BY THE GENERAL FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2037962 | 1962-05-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3137577A true US3137577A (en) | 1964-06-16 |
Family
ID=12025395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US258122A Expired - Lifetime US3137577A (en) | 1962-05-23 | 1963-02-13 | Process for increasing the sensitivity of photographic silver halide emulsion |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3137577A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3420668A (en) * | 1964-06-29 | 1969-01-07 | Fuji Photo Film Co Ltd | (n - phenyl - p - toluenesulfonamido)alkyl mercury compounds as silver halide emulsion sensitizers |
-
1963
- 1963-02-13 US US258122A patent/US3137577A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3420668A (en) * | 1964-06-29 | 1969-01-07 | Fuji Photo Film Co Ltd | (n - phenyl - p - toluenesulfonamido)alkyl mercury compounds as silver halide emulsion sensitizers |
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