US3672901A - Process of precipitating silver halide in the presence of a colloid and a water-soluble iron salt - Google Patents

Process of precipitating silver halide in the presence of a colloid and a water-soluble iron salt Download PDF

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Publication number
US3672901A
US3672901A US37618A US3672901DA US3672901A US 3672901 A US3672901 A US 3672901A US 37618 A US37618 A US 37618A US 3672901D A US3672901D A US 3672901DA US 3672901 A US3672901 A US 3672901A
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United States
Prior art keywords
solution
ferric
silver halide
photographic
silver
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Expired - Lifetime
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US37618A
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English (en)
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Kinji Ohkubo
Junpei Noguchi
Kunioki Ohmura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances

Definitions

  • a process for producing a silver halide photographic emulsion including a step of precipitating a silver halide in a colloidal solution by reaction between a halide and a silver salt, characterized in that said precipitation is done in the presence of a water-soluble iron compound in an amount of to 10- mol per mol of the silver salt contained in said solution.
  • This invention relates to a process for production of a photosensitive photographic emulsion for use in a silver halide photographic material, and more particularly, to a process for production of a silver halide photographic emulsion for use in a photographic material which forms a high contrast image.
  • incorporation of a polyalkylene oxide and a colloid of a noble metal possibly in conjunction with a colloid of a metal sulfide (silver sulfide, zinc sulfide) in a gelatin binder of the silver halide photographic emulsion, will produce the desired photographic materials.
  • a noble metal silver, gold, platinum, palladium
  • a colloid of a metal sulfide silver sulfide, zinc sulfide
  • the rhodium salts exhibit remarkable eifects on silver chloride, but have the defect of causing a marked desensitization.
  • the iridium salts only show a marked effect in obtaining high contrast images with flash exposure in a photographic emulsion prepared by precipitating a silver halide at a pH of less than 6.5.
  • the cobalt-cyano complex salts are effec tive on silver chloride, but are toxic and require careful handling.
  • An object of the present invention is to provide a process for producing a silver halide photographic emulsion of high contrast easily and economically.
  • This process includes a step of precipitating a silver halide in a colloidal solution, such as a gelatin solution, by reaction of a halide with a silver salt. This precipitation is done in the presence of a water-soluble iron compound in an amount of 10* to 10- mols per mol of the silver salt contained in said solution.
  • the critical featture of the present invention resides in the proportion of the water-solution iron compound to be added to the reaction system. It has unexpectedly been found that the presence of a very small amount of the water-soluble iron compound in the reaction system leads to the preparation of a photographic emulsion capable of forming a high contrast photographic image without a marked reduction in sensitivity.
  • the iron compounds used in the invention are watersoluble divalent or trivalent iron salts or complex salts.
  • hexacyanoferrates (II), hexaeyanoferrates (III), and ferric thiocyanate exhibit especially marked effects.
  • the iron compound described above is added during the formation of silver halide particles to a gelatin solu tion, a halide solution, or a silver salt solution. It is also possible to add a separately prepared solution of the iron compound to a suspension of a silver halide during the formation of silver halide particles to a gelatin soluprocedures may be employed conjointly. In any of the procedures, it is desirable that an amount of the iron compound to be added is 10* to 10- mol per mol of silver present in the silver salt solution. Amounts of the iron compound below 10 mol scarcely show a high contrast image producing effect, while amounts above 10- mol cause a marked reduction in the photographic sensitivity of the resulting silver halide photographic material.
  • the silver halide may be silver chloride, silver chlorobromide, silver bromide, silver iodobromide, or silver chloroiodobromide.
  • the use of the iron compound in accordance with the invention is effective for a photographic emulsion prepared by any of the ammonia, neutral or acidic methods to produce a high contrast image.
  • the conventionally known high contrast image producing agents such as rhodium or iridium salts, may be added together with the iron compound to obtain an additive high contrast image forming effect.
  • various metal salts such as nickel salts, copper salts, zinc salts, cadmium salts, mercury salts, lead salts and thallium salts can also be used to improve the sensitivity or gradation of the photographic emulsion.
  • a silver halide suspension obtained in accordance with the process of the invention by forming silver halide particles in the presence of an iron compound can be chemically ripened with a usual method. Specifically, the suspension is directly sent to the next chemical ripening step or it is redissolved after setting, shredding, and rinsing with water. In another method, it is coagulated and precipitated with gelatin and then re-dispersed in a solution of gelatin. In the chemical ripening procedure, a suitable noble metal salt, sulfur sensitizer, reduction sensitizer, etc., are added, and the resulting mixture is heated to raise the sensitivity.
  • noble metal salts gold salts, palladium salts, iridium salts, platinum salts, etc.
  • suitable additives such as 3 color sensitizers, anti-foggants, wetting agents, or gelatin hardening agents are added, and the finished emulsion is coated on a support and dried.
  • Photographic materials prepared in the absence of an iron compound under the above conditions have a lesser contrast than those materials prepared under these conditions in the presence of '11011. I
  • a photographic material may also be prepared by adding a developing agent to a gelatin-silver halide photographic emulsion prepared in accordance with the process of the present invention, or by disposing a layer containing a developing agent adjacent to the emulsion layer.
  • Such photographic material is exposed, and developed by contact with an alkaline solution (to be referred to as activator treatment).
  • activator treatment an alkaline solution
  • the presence of an iron compound in the preparation of the photographic material enhances contrast in the photographic material.
  • the process of the present invention exhibits an adwantage that photographic materials of high contrast can be manufactured readily and at low cost.
  • Citric acid 1.3 g.
  • Solution (1) was stirred in the dark, and solution (2) was added thereto.
  • Solution (3) was further added over a period of 3 minutes.
  • the resulting mixed solution was left to stand for minutes, and then solution (4) was added.
  • the resulting mixed solution was stirred, and ripened for 90 minutes at 60 C.
  • 24 cc. of a 10 wt. percent aqueous solution of formaldehyde was added to the solution to form a coating solution.
  • the coating solution was applied to barvta paper to produce a photographic paper.
  • the amount of the silver halide present in the resulting emulsion layer was 1.8 g./m. calculated as silver.
  • a photographic paper was prepared in the same manner as described above except that solution (2) was not added. This was a comparative specimen, whereas the photographic paper obtained above was a specimen that comes within the scope of the invention.
  • the photographic emulsion prepared by the process of the invention is excellent in that it improves the gradation of the developed image.
  • EXAMPLE 2 A photographic emulsion was prepared in the same manner as set forth in Example 1 except that 3 cc. of a 0.01 wt. percent aqueous solution of potassium hexacyanoferrate (H) was used in place of the potassium hexacyanoferrate (III) as solution (2). A photographic paper was prepared using the resulting emulsion. The photographic characteristics of this specimen were measured in the same way as in Example 1, and the gamma value of the developed image was found to be 2.21. Comparison of this specimen with the comparative specimen shown in Example 1 indicates that the emulsion prepared in accordance with the invention is excellent in photographic properties.
  • Citric acid 1.3 g.
  • EXAMPLE 4 A photographic paper was prepared in the same manner as set forth in Example 3 except that 4 cc. of a 0.01 wt. percent aqueous solution of potassium hexacyanofer-rate (II) was used instead of the potassium hexacyanoferrate (III) as solution (2).
  • the photographic paper was treated in the same way as in Example 3 to form a photographic image.
  • the developed image had a gamma value of 1.67.
  • LEXAM PLE 5 A photographic paper was prepared in the same way as set forth in Example 3 except that 4 cc. of a 0.01 wt.
  • Potassium bromide 33.6 g.
  • Sodium chloride 16.8 g.
  • Distilled water (maintained at 48 C.): 350 cc.
  • the emulsion was left to stand for 60 minutes, followed by addition of 24 cc. of a wt. percent aqueous solution of formaldehyde to form a coating solution.
  • the coating solution was applied to baryta paper.
  • the amount of the silver halide present in the formed emulsion layer was 2.0 g./m. calculated as silver.
  • a comparative specimen was prepared in the same manner as described above except that solution (2) was not added.
  • EXAMPLE 7 Two photographic emulsions (specimen of the invention and comparative specimen) were prepared in the same manner as set forth in Example 6, Hydrochloric acid was added to each of the emulsions to adjust its pH to 4.0. 30 grams of hydroquinone was added per kilogram of the emulsion, and 24 cc. of a 10 wt. percent aqueous solution of formaldehyde was added to baryta paper.
  • the present invention exhibits excellent effects in any specific embodi- 6 ments and is very useful in improving the quality of photographic images.
  • a process for producing a silver halide photographic emulsion consisting essentially of precipitating silver halide particles in a colloidal solution by reacting a silver salt and a halide in the presence of, during said precipitation step, from 10"" to 10- mole, per mole of the silver salt, of a water-soluble iron compound.
  • colloidal solution is produced by mixing separate solutions of said halide, said silver salt and a colloidal material.
  • said water-soluble iron compound is a divalent or trivalent iron salt or a complex salt of an iron.
  • said water-soluble iron compound is a hexacyanoferrate (II), a hexacyanoferrate (III) or a ferric thiocyanate.
  • said water-soluble iron compound is a hexacyanoferrate (II), a hexacyanoferrate (III) or ferric thiocyanate.
  • said water-soluble iron compound is selected from the group consisting of ferrous arsenate, ferrous bromide, ferrous carbonate, ferrous chloride, ferrous citrate, ferrous fluoride, ferrous formate, ferrous gluconate, ferrous hydroxide, ferrous iodide, ferrous lactate, ferrous oxalate, ferrous phosphate, ferrous succinate, ferrous sulfate, ferrous thiocyanate, ferrous nitrate, ammonium ferrous sulfate, potassium hexacyanoferrate (II), potassium pentacyanoamine-ferrate (II), basic ferric acetate, ferric albuminate, ammonium ferric acetate, ferric bromide, ferric chloride, ferric chromate, ferric citrate, ferric fluoride, ferric formate, ferric glycero-phosphate, ferric hydroxide, acidic ferric phosphate, ferric nitrate, ferric
  • a process for producing a silver halide photographic emulsion consisting of precipitating silver halide particles in a gelatin solution by reacting a silver salt and a halide in the presence of, during said precipitation step, from 10- to 10 mole, per mole of the silver salt, of a water-soluble iron compound.
  • said water-soluble iron compound is a hexacyanoferrate (II), a hexacyano ferrate (III) or ferric thiocyanate.

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  • 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)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Colloid Chemistry (AREA)
US37618A 1969-05-17 1970-05-15 Process of precipitating silver halide in the presence of a colloid and a water-soluble iron salt Expired - Lifetime US3672901A (en)

Applications Claiming Priority (1)

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JP44038249A JPS4835373B1 (ja) 1969-05-17 1969-05-17

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US (1) US3672901A (ja)
JP (1) JPS4835373B1 (ja)
BE (1) BE750430A (ja)
CA (1) CA965635A (ja)
CH (1) CH538133A (ja)
DE (1) DE2024003C3 (ja)
FR (1) FR2049106B1 (ja)
GB (1) GB1244818A (ja)
NL (1) NL7007088A (ja)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890154A (en) * 1969-12-24 1975-06-17 Fuji Photo Film Co Ltd Light-sensitive silver halide photographic materials
US3901713A (en) * 1971-06-02 1975-08-26 Fuji Photo Film Co Ltd Process for the manufacture of silver halide photographic emulsion containing iridium and rhodium
US3957490A (en) * 1973-04-26 1976-05-18 Agfa-Gevaert N.V. Method of preparing photographic silver halide emulsions
US4332887A (en) * 1980-10-06 1982-06-01 Polaroid Corporation Method for preparing photosensitive silver halide emulsions
US5057402A (en) * 1988-01-18 1991-10-15 Fuji Photo Film Co., Ltd. Silver halide photographic materials
US5112732A (en) * 1989-03-31 1992-05-12 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic materials
US5252451A (en) * 1993-01-12 1993-10-12 Eastman Kodak Company Photographic emulsions containing internally and externally modified silver halide grains
US5256530A (en) * 1993-01-12 1993-10-26 Eastman Kodak Company Photographic silver halide emulsion containing contrast improving grain surface modifiers
US5360712A (en) * 1993-07-13 1994-11-01 Eastman Kodak Company Internally doped silver halide emulsions and processes for their preparation
US5372926A (en) * 1991-03-22 1994-12-13 Eastman Kodak Company Transition metal complex with nitrosyl ligand dopant and iridium dopant combinations in silver halide
US5385817A (en) * 1993-01-12 1995-01-31 Eastman Kodak Company Photographic emulsions containing internally and externally modified silver halide grains
US5457021A (en) * 1994-05-16 1995-10-10 Eastman Kodak Company Internally doped high chloride {100} tabular grain emulsions
US5462849A (en) * 1994-10-27 1995-10-31 Eastman Kodak Company Silver halide emulsions with doped epitaxy
US5474888A (en) * 1994-10-31 1995-12-12 Eastman Kodak Company Photographic emulsion containing transition metal complexes
US5480771A (en) * 1994-09-30 1996-01-02 Eastman Kodak Company Photographic emulsion containing transition metal complexes
US5500335A (en) * 1994-10-31 1996-03-19 Eastman Kodak Company Photographic emulsion containing transition metal complexes
US5532119A (en) * 1993-03-25 1996-07-02 Eastman Kodak Company High-speed direct-positive photographic elements utilizing core-shell emulsions
US5597686A (en) * 1993-01-12 1997-01-28 Eastman Kodak Company Photographic silver halide emulsion containing contrast improving dopants
US5916487A (en) * 1996-07-03 1999-06-29 Saint Gobain Vitrage Process for obtaining a photochromic compound and products obtained
US20030186179A1 (en) * 2002-02-14 2003-10-02 Fuji Photo Film Co., Ltd. Light-sensitive silver halide grain

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8707841D0 (en) * 1987-04-02 1987-05-07 Minnesota Mining & Mfg Photographic materials
JPH07111554B2 (ja) * 1988-11-04 1995-11-29 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JP2847455B2 (ja) * 1992-07-24 1999-01-20 富士写真フイルム株式会社 ハロゲン化銀写真材料

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890154A (en) * 1969-12-24 1975-06-17 Fuji Photo Film Co Ltd Light-sensitive silver halide photographic materials
US3901713A (en) * 1971-06-02 1975-08-26 Fuji Photo Film Co Ltd Process for the manufacture of silver halide photographic emulsion containing iridium and rhodium
US3957490A (en) * 1973-04-26 1976-05-18 Agfa-Gevaert N.V. Method of preparing photographic silver halide emulsions
US4332887A (en) * 1980-10-06 1982-06-01 Polaroid Corporation Method for preparing photosensitive silver halide emulsions
US5057402A (en) * 1988-01-18 1991-10-15 Fuji Photo Film Co., Ltd. Silver halide photographic materials
US5112732A (en) * 1989-03-31 1992-05-12 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic materials
US5372926A (en) * 1991-03-22 1994-12-13 Eastman Kodak Company Transition metal complex with nitrosyl ligand dopant and iridium dopant combinations in silver halide
US5385817A (en) * 1993-01-12 1995-01-31 Eastman Kodak Company Photographic emulsions containing internally and externally modified silver halide grains
US5256530A (en) * 1993-01-12 1993-10-26 Eastman Kodak Company Photographic silver halide emulsion containing contrast improving grain surface modifiers
US5252451A (en) * 1993-01-12 1993-10-12 Eastman Kodak Company Photographic emulsions containing internally and externally modified silver halide grains
US5597686A (en) * 1993-01-12 1997-01-28 Eastman Kodak Company Photographic silver halide emulsion containing contrast improving dopants
US5532119A (en) * 1993-03-25 1996-07-02 Eastman Kodak Company High-speed direct-positive photographic elements utilizing core-shell emulsions
US5360712A (en) * 1993-07-13 1994-11-01 Eastman Kodak Company Internally doped silver halide emulsions and processes for their preparation
US5457021A (en) * 1994-05-16 1995-10-10 Eastman Kodak Company Internally doped high chloride {100} tabular grain emulsions
US5480771A (en) * 1994-09-30 1996-01-02 Eastman Kodak Company Photographic emulsion containing transition metal complexes
US5462849A (en) * 1994-10-27 1995-10-31 Eastman Kodak Company Silver halide emulsions with doped epitaxy
US5500335A (en) * 1994-10-31 1996-03-19 Eastman Kodak Company Photographic emulsion containing transition metal complexes
US5474888A (en) * 1994-10-31 1995-12-12 Eastman Kodak Company Photographic emulsion containing transition metal complexes
US5916487A (en) * 1996-07-03 1999-06-29 Saint Gobain Vitrage Process for obtaining a photochromic compound and products obtained
US20030186179A1 (en) * 2002-02-14 2003-10-02 Fuji Photo Film Co., Ltd. Light-sensitive silver halide grain
US6911303B2 (en) 2002-02-14 2005-06-28 Fuji Photo Film, Co., Ltd. Light-sensitive silver halide grain

Also Published As

Publication number Publication date
GB1244818A (en) 1971-09-02
JPS4835373B1 (ja) 1973-10-27
DE2024003B2 (de) 1978-11-23
FR2049106A1 (ja) 1971-03-26
CH538133A (de) 1973-06-15
FR2049106B1 (ja) 1973-02-02
BE750430A (fr) 1970-10-16
DE2024003A1 (ja) 1970-12-03
NL7007088A (ja) 1970-11-19
CA965635A (en) 1975-04-08
DE2024003C3 (de) 1979-07-26

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