US2449836A - Photographic silver halide emulsions - Google Patents
Photographic silver halide emulsions Download PDFInfo
- Publication number
- US2449836A US2449836A US592057A US59205745A US2449836A US 2449836 A US2449836 A US 2449836A US 592057 A US592057 A US 592057A US 59205745 A US59205745 A US 59205745A US 2449836 A US2449836 A US 2449836A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- silver
- emulsion
- emulsions
- photographic
- 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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
Definitions
- This invention relates to photographic silver halide emulsions of improved stability. More particularly it relates to photographic silver halide emulsions and emulsion layers which contain small amounts of lower monoalkylaminomonohydroxybenzenes.
- Photographic elements deteriorate upon aging and ordinarily should be used within a year or two after manufacture if one is to obtain satisfactory results. This means that photographic elements should be used within such period in order to obtain good results.
- the deterioration of photographic elements upon aging generally results in a chemical fog which aflects the sensitivity and developability thereof.
- the formation of this fog is accelerated by the advance of time and temperature.
- Many proposals for controlling chemical fog have been made and while some are meritorious they involve the use of chemicals which are not always readily available. Others while improving the stability of emulsion layers decrease the sensitivi-ty.
- An object of this invention is to provide photographic silver halide emulsions of satisfactory stability.
- a further object is to provide such emulsions without deleteriously affecting their sensitivity to light.
- a related object is to provide photographic films, plates, and paperswith silver halide emulsion layers which remain stable for long periods of time in hot climates.
- Another object is to provide a simple and economical means for stabilizing silver halide emulsion layers. Still other objects will be apparent from the following description of the invention.
- the above objects are accomplished by incorporating with a colloid-silver halide emulsion a small amount of a lower monoalkylaminomonohydroxybenzene.
- the alkyl group attached to. the amino nitrogen atom may contain from 1 to 2 atoms.
- the monoalkylamino monohydroxybenzenes may be used in the form of the base or in the form of an addition salt, e. g., the hydrochloride or sulfate.
- the salts are preferred because of their stability and increased solubility in water.
- the above compounds may be added at various stages during the manufacture of colloid silver halide emulsions or dispersions r emulsion layers but are preferably added to the emulsions prior to coating.
- the alkylaminohydroxybenzene compounds may be added to an aqueous colloid solution, such as gelatin, and mixed with a colloid silver halide emulsion or the colloid solutions may be used as a substratum coating the alkylaminohydroxybenzenes with the emulsion layers would be to bathe a silver halide emulsion layer with an aqueous solution containing such compounds.
- colloid silver halide emulsions essentially composed of silver bromide and especially those containing small amounts, e. g., 0.5 to: 10% of silver iodide may be effectively stabilized by the addition of from 0.0015 to 0.03 gram of a lower monoalkylaminomonohydroxybenzene per grams 'of silver halide.
- the compounds when used in these small amounts do not exhibit any discernible developing action upon exposed silver salts when elements containing the same are immersedin an alkaline solution, e. g., caustic soda solution of 1 per cent strength.
- alkaline sulfite e. g., sodium sulfite, potassium sulfite, ammonium sulfite, etc., for instance, about 10' to 50 times that of the alkylaminohydroxybenzene compound are desirable in the emulsions because:
- the compounds do reduce the general or chemical fog to a marked extent and increase the stability of the emulsion layers upon aging.
- Suitable additional compounds include N-methyl-paraaminophenol hydrochloride, N-ethyl-para-aminophenol sulfate, N ethyl para aminophenol, N methyl-para-aminophenol, N-methyl para-- aminophenol hydrochloride.
- emulsion components may be used in conjunction with the. monoalkylaminomonohydroxybenzenes.
- color formers, hardeners, sensitizing dyes, wetting agents, fog inhibitors, and the like may be'present in the emulsion in addition to the silver salts and the monoalkylaminomonohydroxybenzenes
- General emulsion sensitizers, such as sodium sulfite may advantageously be used with such compounds.
- a suitable emulsion may contain in addition to the gelatin, silver iodide and silver bromide, small amounts of thymol, alkali sulfite, alcohol, a cyanine dye, a soluble bromide, saponin, and alum.
- Colloid binding agents other than gelatin may be used in the emulsions and emulsion layers.
- Suitable additional hydrophilic colloids include albumin, polyglycuronic acid, hydrophilic cellulose derivatives, e. g., ethers and carboxylic acid esters, vinyl alcohol polymers and interpolymers and polyamides. These colloids may be substituted in whole or in part for the gelatin.
- the invention has many advantages.
- a gelatino-silver iodobromide emulsion containing from 0.0015 to 0.03 gram of N-alkyl-paraaminophenol having from 1 to 2 carbon atoms in the alkyl group per 100 grams of silver halide.
- a gelatino-silver iodobromide emulsion layer containing from 0.0015 to 0.03 gram of N-methylpara-aminophenol sulfate per 100 grams of silver halide.
- a gelatino-silver iodobromide emulsion layer containing from 0.0015 to 0.03 gram of N-methylpara-aminophenol sulfate and a small amount of an alkaline sulfite per 100 grams of silver halide.
- a photographic element bearing at least one hydrophilic colloid-silver iodobromide emulsion layer which contains 0.0015 to 0.03 gram of a lower monoalkylaminomonohydroxybenzene per 100 grams of silver halide.
- a photographic element bearing at least one hydrophilic colloid-silver bromide emulsion layer which contains 0.0015 to 0.03 gram of N-alkylaminomonohydroxybenzene having from 1 to 2 carbon atoms in the alkyl group per 100 grams of silver halide.
- a photographic element bearing at least one gelatino-silver iodobromide emulsion layer which contains 0.0015 to 0.03 gram of N-methyl-paraaminophenol sulfate per 100 grams of silve halide.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Sept. 21, 1 948 PHOTOGRAPHIC SILVER HALIDE EMULSION S Ralph Kingsley Blake, Parlin, N. J., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del, a corporation of Delaware No Drawing. Application May 4, 1945, Serial No. 592,057
8 Claims.
This invention relates to photographic silver halide emulsions of improved stability. More particularly it relates to photographic silver halide emulsions and emulsion layers which contain small amounts of lower monoalkylaminomonohydroxybenzenes.
Photographic elements deteriorate upon aging and ordinarily should be used within a year or two after manufacture if one is to obtain satisfactory results. This means that photographic elements should be used within such period in order to obtain good results. The deterioration of photographic elements upon aging generally results in a chemical fog which aflects the sensitivity and developability thereof. The formation of this fog is accelerated by the advance of time and temperature. Many proposals for controlling chemical fog have been made and while some are meritorious they involve the use of chemicals which are not always readily available. Others while improving the stability of emulsion layers decrease the sensitivi-ty.
An object of this invention is to provide photographic silver halide emulsions of satisfactory stability. A further object is to provide such emulsions without deleteriously affecting their sensitivity to light. A related object is to provide photographic films, plates, and paperswith silver halide emulsion layers which remain stable for long periods of time in hot climates. Another obiect is to provide a simple and economical means for stabilizing silver halide emulsion layers. Still other objects will be apparent from the following description of the invention.
The above objects are accomplished by incorporating with a colloid-silver halide emulsion a small amount of a lower monoalkylaminomonohydroxybenzene. The alkyl group attached to. the amino nitrogen atom may contain from 1 to 2 atoms. The monoalkylamino monohydroxybenzenes may be used in the form of the base or in the form of an addition salt, e. g., the hydrochloride or sulfate. The salts are preferred because of their stability and increased solubility in water.
The above compounds may be added at various stages during the manufacture of colloid silver halide emulsions or dispersions r emulsion layers but are preferably added to the emulsions prior to coating. The alkylaminohydroxybenzene compounds may be added to an aqueous colloid solution, such as gelatin, and mixed with a colloid silver halide emulsion or the colloid solutions may be used as a substratum coating the alkylaminohydroxybenzenes with the emulsion layers would be to bathe a silver halide emulsion layer with an aqueous solution containing such compounds.
To be more specific, colloid silver halide emulsions essentially composed of silver bromide and especially those containing small amounts, e. g., 0.5 to: 10% of silver iodide may be effectively stabilized by the addition of from 0.0015 to 0.03 gram of a lower monoalkylaminomonohydroxybenzene per grams 'of silver halide. The compounds when used in these small amounts do not exhibit any discernible developing action upon exposed silver salts when elements containing the same are immersedin an alkaline solution, e. g., caustic soda solution of 1 per cent strength. Small amounts of alkaline sulfite, e. g., sodium sulfite, potassium sulfite, ammonium sulfite, etc., for instance, about 10' to 50 times that of the alkylaminohydroxybenzene compound are desirable in the emulsions because:
it prevents a possible loss in speed. The compounds, however, do reduce the general or chemical fog to a marked extent and increase the stability of the emulsion layers upon aging. The
compounds do not have any significant effect upon the sensitivity of the emulsionlayersand have a. fog inhibiting action.
The invention will be further illustrated but is not intended to be limited by the following examples. The parts are by weight.
To portions of a gelatinoesilver halide emulsion containing. 6.8 per cent molar silver iodide and 93.2 per cent molar silver bromide and a small amount of sodium sulfite were added the N-methyl-para-aminophenol sulfate grams 0.8 Hydroquinone do- 1.0 Sodium sulfite (anhydrous) do 900 Borax do 3.0 Potassium bromide do 0.1
Water to "liters; 1
for 7 minutes at 68 F. with the results listed in the following table:
Fresh-film tested fresh Room-film held approximately 1 week at room temperature after coating before testing O venfllm held approximately 1 week at 120 F. after coating before testing EXPERIMENT No. 1
N'-methylpara-amino- Film Relative phenol sulfate Age Speed Gamma Fog Fresh. 528 75 13 Control Rcom 400 71 16 Ovenm. 264 65 .33 Fresh. 493 79 10 0.0025 g Room... 400 73 .06
ven. 325 74 15 Fresh. 493 76 07 00050 g Room 400 76 07 Oven 303 71 .15
EXPERIMENT N0. 2
N-methyl-para-amino- Film Relative phenol sulfate Age Speed Gamma Tog Fresh 400 78 14 Control Room 373 78 10 Oven 214 70 31 Fresh 400 78 12 0.0050 g Room 373 78 10 Oven 283 71 21 Fresh 373 78 12 0.0067 g Room 303 75 .09 Oven 264 72 15 Fresh 373 .76 12 0.0083 g Room 325 .76 09 Oven 283 78 15 Similar results were obtained without the sulfite with an insignificant loss in speed.
In place of the particular monoalkylaminomonohydroxybenzene compound described in the above experiments there may be substituted various other salts coming within this class. Suitable additional compounds include N-methyl-paraaminophenol hydrochloride, N-ethyl-para-aminophenol sulfate, N ethyl para aminophenol, N methyl-para-aminophenol, N-methyl para-- aminophenol hydrochloride.
Various emulsion components may be used in conjunction with the. monoalkylaminomonohydroxybenzenes. For example, color formers, hardeners, sensitizing dyes, wetting agents, fog inhibitors, and the like may be'present in the emulsion in addition to the silver salts and the monoalkylaminomonohydroxybenzenes, General emulsion sensitizers, such as sodium sulfite, may advantageously be used with such compounds. A suitable emulsion, for example, may contain in addition to the gelatin, silver iodide and silver bromide, small amounts of thymol, alkali sulfite, alcohol, a cyanine dye, a soluble bromide, saponin, and alum.
Colloid binding agents other than gelatin may be used in the emulsions and emulsion layers. Suitable additional hydrophilic colloids include albumin, polyglycuronic acid, hydrophilic cellulose derivatives, e. g., ethers and carboxylic acid esters, vinyl alcohol polymers and interpolymers and polyamides. These colloids may be substituted in whole or in part for the gelatin.-
The invention has many advantages.
It provides a means for obtaining stable emulsions and emulsion layers in a simple and economical manner. Another advantage resides in the fact that photographic elements containing such emulsions are readily obtained without any significant loss in sensitivity. A further advantage resides in the fact that the novel elements have good stability in hot climates.
As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims. J
What I claim is: y
l. A colloid silver bromide emulsion containing from 0.0015 to 0.03 gram of N-alkylaminomonohydroxybenzene having from 1 to 2 carbon atoms in the alkyl radical per grams of silver halide.
2. A gelatino-silver iodobromide emulsion containing from 0.0015 to 0.03 gram of N-alkyl-paraaminophenol having from 1 to 2 carbon atoms in the alkyl group per 100 grams of silver halide.
3. A gelatino-silver iodobromide emulsion layer containing from 0.0015 to 0.03 gram of N-methylpara-aminophenol sulfate per 100 grams of silver halide.
4. A gelatino-silver iodobromide emulsion layer containing from 0.0015 to 0.03 gram of N-methylpara-aminophenol sulfate and a small amount of an alkaline sulfite per 100 grams of silver halide.
5. A photographic element bearing at least one hydrophilic colloid-silver iodobromide emulsion layer which contains 0.0015 to 0.03 gram of a lower monoalkylaminomonohydroxybenzene per 100 grams of silver halide.
6. A photographic element bearing at least one hydrophilic colloid-silver bromide emulsion layer which contains 0.0015 to 0.03 gram of N-alkylaminomonohydroxybenzene having from 1 to 2 carbon atoms in the alkyl group per 100 grams of silver halide.
7. A photographic element bearing at least one hydrophilic colloid-silver iodobromide emulsion layer which contains 0.0015 to 0.03 gram of N-alkyl-para-aminophenol having from 1 to 2 carbon atoms in the alkyl group per 100 grams of silver halide.
8. A photographic element bearing at least one gelatino-silver iodobromide emulsion layer which contains 0.0015 to 0.03 gram of N-methyl-paraaminophenol sulfate per 100 grams of silve halide.
, RALPH KINGSLEY BLAKE.
, REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Great Britain 1898
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US592057A US2449836A (en) | 1945-05-04 | 1945-05-04 | Photographic silver halide emulsions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US592057A US2449836A (en) | 1945-05-04 | 1945-05-04 | Photographic silver halide emulsions |
Publications (1)
Publication Number | Publication Date |
---|---|
US2449836A true US2449836A (en) | 1948-09-21 |
Family
ID=24369103
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US592057A Expired - Lifetime US2449836A (en) | 1945-05-04 | 1945-05-04 | Photographic silver halide emulsions |
Country Status (1)
Country | Link |
---|---|
US (1) | US2449836A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB189811420A (en) * | 1898-05-19 | 1899-04-29 | Pierre Mercier | Improvements in the Preparation of Argentiferous Sensitive Surfaces for Photographic Purposes. |
US956567A (en) * | 1908-04-24 | 1910-05-03 | William Hay Caldwell | Sensitized surface or film for photographic purposes. |
US1109514A (en) * | 1913-12-23 | 1914-09-01 | Raymond Edwin Crowther | Photographic sensitive plates and the like. |
US2313529A (en) * | 1941-08-09 | 1943-03-09 | Eastman Kodak Co | Fog inhibitor for photographic emulsions |
-
1945
- 1945-05-04 US US592057A patent/US2449836A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB189811420A (en) * | 1898-05-19 | 1899-04-29 | Pierre Mercier | Improvements in the Preparation of Argentiferous Sensitive Surfaces for Photographic Purposes. |
US956567A (en) * | 1908-04-24 | 1910-05-03 | William Hay Caldwell | Sensitized surface or film for photographic purposes. |
US1109514A (en) * | 1913-12-23 | 1914-09-01 | Raymond Edwin Crowther | Photographic sensitive plates and the like. |
US2313529A (en) * | 1941-08-09 | 1943-03-09 | Eastman Kodak Co | Fog inhibitor for photographic emulsions |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2566245A (en) | Complex compounds of the platinum group as photographic fog inhibitors | |
US2592368A (en) | Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent | |
DE1281845B (en) | Silver halide photographic emulsion | |
US2419974A (en) | Silver halide emulsions containing water-insoluble hydrazine derivatives | |
US2983609A (en) | Chemical sensitization of photographic emulsions | |
US3447925A (en) | Anti-fogging and anti-plumming disulfide compound for use in silver halide photographs | |
US3499761A (en) | Silver halide emulsions containing alkyl esters of benzimidazole carbamic acid antifogging agents | |
US2983610A (en) | Sensitization of photographic emulsions | |
US3477852A (en) | Direct-positive silver halide emulsion resistant to kink-marking desensitization | |
US2666700A (en) | Process of preparing a light sensitive silver halide emulsion | |
US2339309A (en) | Photographic reducing composition and process | |
US2552229A (en) | Fog inhibitors for photographic emulsions | |
US2449836A (en) | Photographic silver halide emulsions | |
US3420664A (en) | Dehydrodithizone and mercaptotetrazolium salts as silver halide photographic antifoggants and stabilizers | |
US4040839A (en) | Direct-positive process utilizing a supersensitized silver halide emulsion | |
US1930140A (en) | Acid hardening fixing bath | |
US3420667A (en) | Substituted quinones and dimine quinones as silver halide sensitizers | |
US3396022A (en) | Quinone stabilizers and antifoggants for silver halide emulsions | |
US4145218A (en) | Process for developing light-sensitive silver halide photographic materials | |
US3173790A (en) | Silver halide emusions containing polyoxyalkylene sensitizers | |
US3161515A (en) | Stabilized light-sensitive silver halide emulsions | |
US4299913A (en) | Photographic reversal process without second exposure | |
US3573915A (en) | Photographic silver halide emulsions containing nitrosubstituted or unisubstituted cinnamic acid or cinnamaldehyde | |
JPH037090B2 (en) | ||
US2552230A (en) | Fog inhibitors for photographic emulsions |