US3817756A - Manufacture of photographic silver halide materials - Google Patents

Manufacture of photographic silver halide materials Download PDF

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Publication number
US3817756A
US3817756A US00251650A US25165072A US3817756A US 3817756 A US3817756 A US 3817756A US 00251650 A US00251650 A US 00251650A US 25165072 A US25165072 A US 25165072A US 3817756 A US3817756 A US 3817756A
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silver
grains
silver halide
chloride
photographic
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US00251650A
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English (en)
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F Claes
M Libeer
W Vanassche
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • 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

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  • FIG. 3 MANUFACTURE OF PHOTOGRAPHIC SILVER HALIDE MATERIALS Filed May 9, 1972 I 4 Sheets-Sheet z FIG-4 FIG. 3
  • the present invention relates to a photographic silver halide material, its manufacture and use.
  • photosensitive recording materials which contain, dispersed in a binder, silver chloride grains and/or silver chlorobromide grains that preferably contain at most 90 mole percent of bromide, which grains have (110) crystal planes.
  • said crystals illustrate in subsequent order the different crystal lattice structures characteristic for cubic, rhombododecahedral and octahedral silver chloride crystals.
  • the cubes representing the silver ions are marked with a plus sign and the cubes representing the chloride ions are marked with a minus sign.
  • Details about silver halide crystals having a cubic or octahedron habit are given by G. F. Dufiin, in Photographic Emulsion Chemistry-The Focal Press, London 1966), pp. 66-74.
  • Silver chloride and silver chlorobromide crystals suited for the purpose of the invention and in which (110) planes can be recognized are prepared by carrying out the silver halide crystal lattice formation (nucleation) or crystal growth under special conditions as described herein.
  • the formation by precipitation and/or the grain growth of silver chloride crystals and/or silver chlorobromide crystals containing at most 90 mole percent of bromide is carried out in aqueous medium in the presence of a protective hydrophilic colloid and a substance or substances that when incorporated in an aqueous solution containing a dye partly in its aggregated and partly in monomeric (i.e. non-aggregated) form enhance(s) the intensity of the absorption band characteristic of the monomers of the dye.
  • a wide variety of said substances having this property of enhancing the intensity of the monomer absorption band is at ones disposal, and although not all the substances that give a positive result in the test as described hereinafter will be active in the formation of silver chloride or silver chlorobromide crystals with (110) planes, the great majority (more than 80%) will do so.
  • the substance to be tested is dissolved in water in a preferred amount of 1 gram per litre and added to an equal volume of an aqueous solution of methylene blue.
  • the methylene blue is dissolved preferably in an amount of 20 mg. per litre.
  • the absorption spectrum of the obtained mixture is compared with that of a same aqueous solution of methylene blue, to which an equal volume of pure water was added.
  • the greater part of substances that enhance the monomer absorption band (the absorption band of the nonaggregated molecules) of the methylene blue is suited for use as substance controlling crystal habit and promoting the formation of silver chloride or silver chlorobromide containing crystal planes.
  • the preparation of a silver halide emulsion comprises a number of stages, which are as follows:
  • the substances controlling the crystal habit and used according to the present invention will be applied in stage 1 and/or 2, not excluding, however, the embodiment in which one type of silver halide is converted in another type of silver halide e.g. by replacing other, e.g.
  • the first stage which is also called emulsification or precipitation is achieved by mixing a solution containing a water-soluble chloride optionally combined with a limited amount of water-soluble bromide, with a solution of water-soluble silver salt in the presence of a protective colloid e.g. gelatin and said substance controlling the crystal habit.
  • a protective colloid e.g. gelatin and said substance controlling the crystal habit.
  • the chloride and bromide may be that of an alkaline metal such as sodium or potassium, or alternatively ammonium chloride or bromide.
  • the quantities of halide and silver ions need not be equivalent.
  • aqueous silver salt solution e.g. silver nitrate solution
  • a stirred solution containing the halide in the present invention a dissolved chloride optionally combined with a certain amount of bromide, a protective colloid e.g. gelatin, and other ingredients one of which is the substance controlling the crystal habit.
  • a solution of a water-soluble silver salt and a solution of the halide, equivalent to that of the silver salt e.g. silver nitrate are added simultaneously by two separate jets to -a stirred solution of a protective colloid e.g. gelatin and optionally also a chloride.
  • a protective colloid e.g. gelatin and optionally also a chloride.
  • a further quantity of protective colloid is incorporated optionally into the halide solution and sometimes in the solution containing silver ions.
  • the substance controlling the crystal habit is used preferably in the medium containing the protective colloid.
  • said substance need not be present from the very beginning of the precipitation and the crystals may have reached a certain size and habit already before the habit control and (110) plane formation is started.
  • the growth of the silver halide grains formed by precipitation to the appropriate size normally proceeds by thermal treatment. This is called physical ripening to distinguish it from the chemical ripening. In the physical ripening an amount of crystals grows at the expense of other crystals. This process is continued until the crystals have attained the desired grain size and grain size distribution.
  • the physical ripening of a silver halide emulsion containing silver chloride grains or silver chlorobromide grains with at most mole percent of bromide is carried out in the presence of said substance controlling the crystal habit.
  • the crystal growth will only occur in the presence of suitable silver halide solvents, usual representatives of which are disclosed by G. F. Duflin in the already mentioned book on pp. 59-60.
  • the substance controlling the crystal habit of use according to the present invention controls the sequence of arrangement of the silver and chloride ions or mixture of chloride and bromide ions in the lattice pattern in such a way that places characterized by step-faces are formed as illustrated in FIG. 3.
  • the amount of substance controlling the crystal habit is preferably in the range of about 10 to about 50 millimole per mole of silver chloride to be formed.
  • the substance controlling the crystal habit may be removed from the emulsion by washing after the desired crystal habit has been obtained.
  • the substance controlling the crystal habit does not need but may be present in the emulsion as finally coated.
  • hydrophilic colloids known in the art such as gelatin are used as binder for the silver halide grains.
  • Preferred photographic materials according to the present invention contain at least one silver halide emulsion layer comprising as the sole photosensitive silver halide silver chloride grains containing (110) crystal planes, wherein said grains are dispersed in a hydrophilic colloid binder.
  • the present invention includes, however, also such photographic materials in which these grains are present together with silver halide grains of another crystal habit or halide type or of which the crystal grains only partially contain (110) planes, e.g. they contain mixtures of 110) with (100) and of (110) with (111) planes.
  • the invention includes any method of forming a photographic image or record, which comprises informationwise or record-wise exposing to visible light or to other active radiation a material, which is sensitive to such radiation and which comprises silver chloride or silver ch1orobromide grains having (110) crystal planes, such grains being dispersed in a binder, the said material preferably comprising a radiation-sensitive layer composed of microcrystals of silver chloride and/or silver chloro-bromide grains having such planes and dispersed in a protective colloid binder.
  • Photographic silver halide emulsion materials containing silver chloride and/or silver chlorobromide crystals characterized by (110) crystal planes possess a lower tendency to fog than silver chloride emulsions containing the already known silver chloride crystals containing (100) crystal planes.
  • This property makes it possible to chemically sensitize the (110) type silver halide to a higher extent than the (100) type silver chloride crystals without surpassing an acceptable fog level.
  • a practical test proving this advantage is given in the Examples 2 and 3, the test results of which are illustrated in FIG. 5.
  • photographic silver halide emulsion materials containing the (110) type crystals lies in the possibility to obtain therewith by means of a spectral sensitizing agent an increased spectral absorption in the shorter wavelengths and a decreasedabsorption in the higher wavelengths as compared with photographic materials containing (100) type silver chloride crystals.
  • This different spectral sensitizability is probably due to another aggregation pattern of the sensitizing dye molecules on the (110) planes.
  • a practical test proving this property is given in Example 4 and the results are shown in FIG. 6.
  • the photographic emulsions containing (110) type silver chloride and/or silver bromochloride crystals can be used for all photographic purposes known from silver halide photography, in other words, there is no photographic silver halide material, in which they cannot be used. So, they can be used, e.g., in black-and-white materials as well as in color materials, in negative materials as well as in reversal or direct positive materials e.g. of the composite (core-shell) grain type.
  • EXAMPLE 1 A 3 molar aqueous solution of silver nitrate and a 3 molar aqueous solution of sodium chloride were added at 60 C. to a stirred solution of 36 g. of gelatin dissolved in 500 ml. of distilled water. The rate of addition of said solutions was such that the pAg expressed in m-illivolts remained constantly at +300 mv. and the pH was kept at 5.8.
  • the precipitation was continued until a crystal grain size of about 0.4 micron was reached.
  • T0600 g. of the thus obtained silver chloride dispersion having a silver chloride content equivalent with g. of silver nitrate were added 1.5 g. of the substance No. 2 controlling the crystal habit, which substance had been dissolved in 250 ml. of water.
  • the silver chloride precipitation was continued at a pAg expressed in millivolt of +70 mv. and a pH of 5.8.
  • the finally obtained silver chloride dispersion contained silver chloride grains having a practically pure rhombododecahedral shape.
  • the dispersion was freed from its water-soluble byproducts by noodling and washing, and after remelting emulsion portions thereof were treated as described in the Examples 2, 3, and 4.
  • EXAMPLE 2 A gelatin silver chloride emulsion (emulsion B) prepared as described in Example 1 and a gelatin silver chloride emulsion (emulsion A) prepared as described in Example 1 but in the absence of the substance controlling the crystal habit, so that the silver chloride grains characterized by planes, were sulphur-sensitized by adding thereto pro rata of 60 g. of silver chloride 1 mg. and 1.5 mg. of bis-(dimethylthiocarbamoyl)sulphide respectively.
  • the sulphur sensitization was carried out for both emulsions at the same temperature (46 C.), the same pH (6.00) and the same pAg (7.5).
  • the speed and fog results versus time expressed in hours (h.) can be learned from curves 1 of FIG. 5.
  • Example 2 was repeated with the difference, however, that the chemical sensitization was a sulphurand gold sensitization that was carried out with respect to the emulsion A with 1 mg. of bis-(dimethylthio carbamoyl)sulphide and 3 ml. of a 0.06% by weight solution of gold(I) thiocyanate.
  • the chemical sensitization of emulsion B was carried out with 1.5 mg. of bis-(dimethylthiocarbamoyl)sulphide and ml. of a 0.06% by weight solution of gold(I) thiocyanate in water.
  • test strips was the same as in Example 2.
  • EXAMPLE 5 A gelatin silver chloride emulsion was prepared as described in Example 1 but in the absence of the substance controlling the crystal habit.
  • the silver chloride grains obtained had a mean grain size of 0.4 micron.
  • the thus obtained silver chlorobromide grains have a regular rhombododecahedral shape.
  • Example 5 The procedure of Example 5 was repeated with the difference, however, that in the second precipitation stage a 3 molar aqueous solution of a mixture of sodium chloride and potassium bromide (50:50 mole percent) was used.
  • the obtained silver halide grains also had a regular rhombododecahedral shape.
  • Example 7 The procedure of Example 5 was repeated with the difference, however, that in the second precipitation stagea 3 molar aqueous solution of sodium chloride and potassium bromide (25:75 mole percent) was used.
  • the silver halide grains obtained contained planes as well as (111) planes.
  • a photographic material containing silver chloride and/ or silver chlorobromide grains that have (110) 'crystal planes and that are dispersed in a binder.
  • a method of preparing a photographic silver halide emulsion containing silver chloride and/or silver chlorobromide grains wherein the formation by precipitation of said grains and/ or the growth of said grains is carried out in an aqueous medium in the presence of a. protective hydrophilic colloid and at least one substance that when incorporated in an aqueous solution containing methylene blue dye partly in its aggregated and partly in its monomeric (non-aggregated) form enhances the intensity of the absorption band characteristic for the non-aggregated dye and acts to control the crystal habit and promote the ⁇ 110 ⁇ crystal habit of silver chloride or sflver chlorobromide grams.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (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)
US00251650A 1971-05-11 1972-05-09 Manufacture of photographic silver halide materials Expired - Lifetime US3817756A (en)

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JP (1) JPS5542737B1 (enExample)
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DE (1) DE2222297C2 (enExample)
FR (1) FR2137880B1 (enExample)
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3885970A (en) * 1973-05-11 1975-05-27 Fuji Photo Film Co Ltd Photographic silver halide emulsion with silver halide grains having one twinning plane
US4067739A (en) * 1974-08-07 1978-01-10 Ciba-Geigy Ag Method of preparing a monosize silver halide emulsion involving Ostwald ripening followed by a crystal growth stage
US4193804A (en) * 1977-07-26 1980-03-18 Fuji Photo Film Co., Ltd. Process for preparing a composition for a thermally developable light-sensitive material
US4221863A (en) * 1978-03-31 1980-09-09 E. I. Du Pont De Nemours And Company Formation of silver halide grains in the presence of thioureas
US4284717A (en) * 1978-12-07 1981-08-18 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0070181A1 (en) * 1981-07-10 1983-01-19 Konica Corporation Silver halide light-sensitive color photographic material
US4469784A (en) * 1981-09-28 1984-09-04 Fuji Photo Film Co., Ltd. Silver halide emulsions
US4643966A (en) * 1985-09-03 1987-02-17 Eastman Kodak Company Emulsions and photographic elements containing ruffled silver halide grains
EP0215612A2 (en) 1985-09-03 1987-03-25 EASTMAN KODAK COMPANY (a New Jersey corporation) Silver halide photographic emulsions with novel grain faces (5)
US4683192A (en) * 1984-04-19 1987-07-28 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions and process for producing them
US4769315A (en) * 1986-02-03 1988-09-06 Konishiroku Photo Industry Co., Ltd. Silver halide grain and light-sensitive photographic material containing said silver halide grain
US4830955A (en) * 1986-04-24 1989-05-16 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material and method of processing thereof utilizing hydroxy azaindene compounds
US4917996A (en) * 1984-07-28 1990-04-17 Konishiroku Photo Industry Co., Ltd. Silver halide grains, preparation thereof and light-sensitive photographic material containing said grains
US5002865A (en) * 1985-04-24 1991-03-26 Konica Corporation Silver halide photographic material

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69328884T2 (de) 1992-03-19 2000-12-07 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung einer photographischen Silberhalogenidemulsion
US5418124A (en) 1992-03-19 1995-05-23 Fuji Photo Film Co. Ltd. Silver halide photographic emulsion and a photographic light-sensitive material
JPH09152696A (ja) 1995-11-30 1997-06-10 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US10818358B2 (en) 2017-09-22 2020-10-27 Toshiba Memory Corporation Memory system including a semiconductor memory having a memory cell and a write circuit configured to write data to the memory cell

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE555210A (enExample) * 1956-02-23

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3885970A (en) * 1973-05-11 1975-05-27 Fuji Photo Film Co Ltd Photographic silver halide emulsion with silver halide grains having one twinning plane
US4067739A (en) * 1974-08-07 1978-01-10 Ciba-Geigy Ag Method of preparing a monosize silver halide emulsion involving Ostwald ripening followed by a crystal growth stage
US4193804A (en) * 1977-07-26 1980-03-18 Fuji Photo Film Co., Ltd. Process for preparing a composition for a thermally developable light-sensitive material
US4221863A (en) * 1978-03-31 1980-09-09 E. I. Du Pont De Nemours And Company Formation of silver halide grains in the presence of thioureas
US4284717A (en) * 1978-12-07 1981-08-18 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0070181A1 (en) * 1981-07-10 1983-01-19 Konica Corporation Silver halide light-sensitive color photographic material
US4469784A (en) * 1981-09-28 1984-09-04 Fuji Photo Film Co., Ltd. Silver halide emulsions
US4683192A (en) * 1984-04-19 1987-07-28 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions and process for producing them
US4917996A (en) * 1984-07-28 1990-04-17 Konishiroku Photo Industry Co., Ltd. Silver halide grains, preparation thereof and light-sensitive photographic material containing said grains
US5002865A (en) * 1985-04-24 1991-03-26 Konica Corporation Silver halide photographic material
US4643966A (en) * 1985-09-03 1987-02-17 Eastman Kodak Company Emulsions and photographic elements containing ruffled silver halide grains
EP0215612A2 (en) 1985-09-03 1987-03-25 EASTMAN KODAK COMPANY (a New Jersey corporation) Silver halide photographic emulsions with novel grain faces (5)
US4769315A (en) * 1986-02-03 1988-09-06 Konishiroku Photo Industry Co., Ltd. Silver halide grain and light-sensitive photographic material containing said silver halide grain
US4830955A (en) * 1986-04-24 1989-05-16 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material and method of processing thereof utilizing hydroxy azaindene compounds

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Publication number Publication date
GB1376443A (en) 1974-12-04
FR2137880B1 (enExample) 1977-08-26
FR2137880A1 (enExample) 1972-12-29
JPS5542737B1 (enExample) 1980-11-01
DE2222297C2 (de) 1985-10-10
DE2222297A1 (de) 1972-11-23
BE782893A (fr) 1972-11-03

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