US3804629A - Process for the production of a stain-resistant photographic silver halide emulsion - Google Patents
Process for the production of a stain-resistant photographic silver halide emulsion Download PDFInfo
- Publication number
- US3804629A US3804629A US00286291A US28629172A US3804629A US 3804629 A US3804629 A US 3804629A US 00286291 A US00286291 A US 00286291A US 28629172 A US28629172 A US 28629172A US 3804629 A US3804629 A US 3804629A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- silver
- silver halide
- chloride
- halide 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
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
- G03C1/015—Apparatus or processes for the preparation of emulsions
-
- 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
Definitions
- Photographically active dust such as abrasion dust from metal contaminates the light-sensitive silver halide emulsion layer in spite of all precautions.
- the metal particles or their compounds or other photographically active substances dissolve in the photographic layers, auxiliary layers or supports with varying degrees of rapidity.
- the dissolved products diffuse in the layers and are liable to cause considerable harm to the photographic properties, e.g. by exerting a sensitizing or desensitizing effect.
- the well-known black or white patchiness is then found in the light-sensitive photographic materials after they have been processed in photographic baths in the usual manner.
- a similar harmful effect may also be caused by impurities e.g. in the raw material used for the production of the paper support.
- impurities e.g. in the raw material used for the production of the paper support.
- black or white patchiness is found in the material after development, especially if the material is stored under conditions of elevated temperature and moisture.
- a process for the production of a photographic silver halide emulsion comprising the steps of precipitation of the silver halide in the presence of a protective colloid, physical ripening, washing of the ripened emulsion to remove the soluble salts and chemical ripening has now been found in which a gelatin emulsion containing essentially only silver chloride is added to the physically ripened and washed emulsion before it is chemically ripened, or the silver chloride which is to be added is produced in the physically ripened and washed silver halide emulsion by precipitation by the addition of alkali metal chloride and silver nitrate solutions.
- the method according to the invention results in the formation of silver chloride hillocks on the silver halide grains of the original emulsion. These hillocks surprisingly produce excellent resistance to the formation of stains by particles of dirt. These silver chloride hillocks on the particles of the original silver halide emulsions, which is preferably a silver bromide emulsion, are clearly visible under an electron microscope.
- the concentration of silver chloride produced in the original silver halide emulsion either by the addition of a silver chloride emulsion or by precipitation may vary within wide limits.
- the optimum quantity can be determined by tests well known in the art. Quantities of from 2 to 10 mol of silver chloride, based on the total quantity of silver halide in the physically ripened and washed emulsion have generally been found to effect sufficient stabilization for practical purposes.
- the silver halides used for the emulsion which is to be stabilized may be silver chloride, silver bromide or mixtures of these if derived with a silver iodide content of up to 10
- the silver halides are dispersed in the usual hydrophilic binders, e.g. in proteins, preferably gelatin, carboxyrnethyl-cellulose, polyvinyl alcohol, polyvinyl pyrrolidone or alginic acid and its derivatives such as salts, esters or amides.
- the emulsions may be chemically ripened in the usual manner and treated with the usual additives.
- the emulsion may be optically sensitized with cyanines rhodacyanines or merocyanines, e.g. as described in The Cyanine Dyes and related Compounds by F. M. HAMER, published by Intersci-' ence Publishers (1964). i
- the emulsions may be chemically sensitized in the usual manner, e.g. with reducing agents such as tin(ll) salts, polyamines such as diethyltriamine or sulfur compounds as described in U.S. Pat. specification No. 1,574,944. Salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum or gold may also be added as chemical sensitizers, as described in the publication by R. KOSLOWSKY in Z. Wiss. Phot. 46, 65 72 (1951).
- the emulsions may also contain polyalkylene oxides as chemical sensitizers and in particular polyethylene oxides and derivatives thereof.
- the emulsions may be stabilized against spontaneous fogging by the addition of the usual stabilizers such as organic mercury compounds or mercury salts, e.g. mercury triazole compounds, simple mercury salts or mercury double salts.
- stabilizers are in particular azaindenes, e.g. tetraor pentaazaindenes and particularly those which are hydr 'oxyl substituted or amino substituted, as described in the publication by BIRR in Z. Wiss. Phot. 47, 2 58 (1952).
- Heterocyclic mercapto compounds such as l-phenyl-S-mercaptotetrazole, quaternary benzothiazole derivatives and benzotriazoles may also be used.
- the emulsion is hardened in the usual manner, e.g. with aldehydes such as formaldehyde, dialdehydes or halo substituted aldehydes which contain a carboxyl group, e.g. mucochloric acid or mucobromic acid, or diketones or sulfonic acid esters such as methanesulfonic acid esters.
- aldehydes such as formaldehyde, dialdehydes or halo substituted aldehydes which contain a carboxyl group, e.g. mucochloric acid or mucobromic acid, or diketones or sulfonic acid esters such as methanesulfonic acid esters.
- the emulsions prepared in accordance with the invention may be used for various photographic materials. They are particularly suitable for silver halide emulsion layers used for photographic copying materials mounted on a paper support but they may also be used for X-ray films, unsensitized emulsions, orthochromatically or panchromatically sensitized emulsions or emulsions which are sensitive to the infra-red region of the spectrum.
- the emulsions may be used in materials for the silver saltdiffusion process, in color photographic materials and also in photographic materials for the silver dye bleaching process.
- EXAMPLE 1 A silver bromide emulsion containing 14 mols of silver chloride and 1 mol of silver iodide is prepared in the usual manner by precipitation in the presence of gelatin.
- the emulsion is flocculated after physical ripening and the soluble salts resulting from precipitation are removed by washing with water.
- the silver halide is then melted at pH 5.5 with the addition of gelatin and water.
- the emulsion then contains 55 g of silver halide per kg and 220 g of gelatin per kg. It is then ripened to the required sensitivity at 53 C.
- optical sensitizer 10 ml of a 0.1 aqueous solution of optical sensitizer of the following formula:
- the emulsion is applied to a baryta-coated paper support to which a layer of gelatin containing iron dust has been applied to test the effectiveness of the process according to the invention.
- the emulsion is uniformly exposed and developed in a developer of the following composition:
- the sample obtained after processing is uniformly black. It has numerous white patches which can be attributed to the harmful effect of the iron dust.
- an emulsion is prepared by the same method except that, after washing and before chemical ripening, 20 ml of a aqueous sodium chloride solution and 83 ml ofa 5 aqueous silver nitrate solution are added. When precipitation takes place, hillocks of silver chloride are formed on the grains of the original emulsion. The quantity of silver chloride produced by precipitation is 8.3 mols of silver chloride based on the amount of silver halide in the original emulsion. The emulsion is then chemically ripened and processed as described above.
- the developed and fixed sample is practically free from stains.
- practically no white stains are formed even if the sample has been stored in an air conditioning cupboard at C and 40 atmospheric humidity for 2 days before processing.
- the formation of stains is increased under these conditions.
- EXAMPLE 2 A silver bromide emulsion containing 4.8 mols of silver chloride and 1.5 mols of silver iodide is prepared in the usual manner by precipitation in the presence of gelatin as protective colloid.
- the emulsion It is physically ripened and the emulsion is flocculated and the soluble salts are removed by washing.
- the silver halide is then redispersed by the addition of gelatin and water at pH 5.5.
- the emulsion then contains 55 g of silver halide and 160 g of gelatin per kg.
- the emulsion is then divided into two portions. 4 ml of a 10 sodium chloride solution and 17 ml of a 5 aqueous silver nitrate solution are added to one portion.
- the quantity of silver chloride produced, which forms hillocks on the grains of the original silver bromide emulsion, is 1.7 mols based on the amount of original emulsion.
- Example 1 The material is processed in the same way as de scribed in Example 1.
- EXAMPLE 3 The procedure is the same as that described in Example l, but instead of adding sodium chloride solution and silver nitrate solution to the physically ripened and washed emulsion, a previously prepared silver chloride gelatin emulsion is added.
- Example 1 The subsequent treatment is the same as described in Example 1. Examination of the sample shows equally good results to those obtained in Example I.
- Equally effective stabilization and prevention of the formation of white stains is achieved if instead of the 6 times the equimolar quantity of chloride ions is present when the silver chloride emulsion is added or the silver chloride is formed by precipitation.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2144127A DE2144127C3 (de) | 1971-09-03 | 1971-09-03 | Verfahren zur Herstellung einer photographischen Silberhalogenidemulsion |
Publications (1)
Publication Number | Publication Date |
---|---|
US3804629A true US3804629A (en) | 1974-04-16 |
Family
ID=5818554
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00286291A Expired - Lifetime US3804629A (en) | 1971-09-03 | 1972-09-05 | Process for the production of a stain-resistant photographic silver halide emulsion |
Country Status (5)
Country | Link |
---|---|
US (1) | US3804629A (fr) |
BE (1) | BE787868A (fr) |
DE (1) | DE2144127C3 (fr) |
FR (1) | FR2151106B3 (fr) |
GB (1) | GB1377407A (fr) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS511116A (ja) * | 1974-06-21 | 1976-01-07 | Mitsubishi Paper Mills Ltd | Harogenkaginshashinnyuzaino seizoho |
US4094684A (en) * | 1977-02-18 | 1978-06-13 | Eastman Kodak Company | Photographic emulsions and elements containing agel crystals forming epitaxial junctions with AgI crystals |
US4142900A (en) * | 1977-02-18 | 1979-03-06 | Eastman Kodak Company | Converted-halide photographic emulsions and elements having composite silver halide crystals |
US4435501A (en) | 1981-11-12 | 1984-03-06 | Eastman Kodak Company | Controlled site epitaxial sensitization |
US4463087A (en) * | 1982-12-20 | 1984-07-31 | Eastman Kodak Company | Controlled site epitaxial sensitization of limited iodide silver halide emulsions |
US4643966A (en) * | 1985-09-03 | 1987-02-17 | Eastman Kodak Company | Emulsions and photographic elements containing ruffled silver halide grains |
EP0215612A2 (fr) | 1985-09-03 | 1987-03-25 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Emulsions photographiques à l'halogénure d'argent avec des grains à faces |
EP0793139A1 (fr) * | 1996-02-21 | 1997-09-03 | Imation Corp. | Matériaux photographiques avec ton de l'image amélioré |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0019917B1 (fr) * | 1979-06-01 | 1983-09-21 | Konica Corporation | Emulsion photographique avec des cristaux d'halogénure d'argent composés et épitaxiaux, émulsion iodo-bromure et procédé de préparation |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3600180A (en) * | 1968-11-04 | 1971-08-17 | Eastman Kodak Co | Method of making a blend of fogged,direct positive silver halide emulsions of different grain sizes |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1214083B (de) * | 1964-08-14 | 1966-04-07 | Agfa Gevaert Ag | Lichtempfindliches photographisches Material mit mindestens einer lichtempfindlichen Silbersalzemulsionsschicht |
-
0
- BE BE787868D patent/BE787868A/fr unknown
-
1971
- 1971-09-03 DE DE2144127A patent/DE2144127C3/de not_active Expired
-
1972
- 1972-08-30 GB GB4013672A patent/GB1377407A/en not_active Expired
- 1972-09-01 FR FR7231182A patent/FR2151106B3/fr not_active Expired
- 1972-09-05 US US00286291A patent/US3804629A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3600180A (en) * | 1968-11-04 | 1971-08-17 | Eastman Kodak Co | Method of making a blend of fogged,direct positive silver halide emulsions of different grain sizes |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS511116A (ja) * | 1974-06-21 | 1976-01-07 | Mitsubishi Paper Mills Ltd | Harogenkaginshashinnyuzaino seizoho |
JPS5725825B2 (fr) * | 1974-06-21 | 1982-06-01 | ||
US4094684A (en) * | 1977-02-18 | 1978-06-13 | Eastman Kodak Company | Photographic emulsions and elements containing agel crystals forming epitaxial junctions with AgI crystals |
US4142900A (en) * | 1977-02-18 | 1979-03-06 | Eastman Kodak Company | Converted-halide photographic emulsions and elements having composite silver halide crystals |
US4435501A (en) | 1981-11-12 | 1984-03-06 | Eastman Kodak Company | Controlled site epitaxial sensitization |
US4463087A (en) * | 1982-12-20 | 1984-07-31 | Eastman Kodak Company | Controlled site epitaxial sensitization of limited iodide silver halide emulsions |
US4643966A (en) * | 1985-09-03 | 1987-02-17 | Eastman Kodak Company | Emulsions and photographic elements containing ruffled silver halide grains |
EP0215612A2 (fr) | 1985-09-03 | 1987-03-25 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Emulsions photographiques à l'halogénure d'argent avec des grains à faces |
EP0793139A1 (fr) * | 1996-02-21 | 1997-09-03 | Imation Corp. | Matériaux photographiques avec ton de l'image amélioré |
US5851751A (en) * | 1996-02-21 | 1998-12-22 | Imation Corp. | Photographic materials with improved image tone |
Also Published As
Publication number | Publication date |
---|---|
FR2151106A1 (fr) | 1973-04-13 |
GB1377407A (en) | 1974-12-18 |
DE2144127C3 (de) | 1983-12-15 |
BE787868A (fr) | 1973-02-23 |
DE2144127A1 (de) | 1973-03-08 |
FR2151106B3 (fr) | 1975-10-03 |
DE2144127B2 (de) | 1979-10-31 |
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