US3241970A - Preparation of photographic emulsions - Google Patents

Preparation of photographic emulsions Download PDF

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Publication number
US3241970A
US3241970A US143290A US14329061A US3241970A US 3241970 A US3241970 A US 3241970A US 143290 A US143290 A US 143290A US 14329061 A US14329061 A US 14329061A US 3241970 A US3241970 A US 3241970A
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US
United States
Prior art keywords
complex
silver
solution
preparation
solvent
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
Application number
US143290A
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English (en)
Inventor
Stanley P Popeck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GAF Chemicals Corp
Original Assignee
General Aniline and Film Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE623226D priority Critical patent/BE623226A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US143290A priority patent/US3241970A/en
Priority to GB35482/62A priority patent/GB1023578A/en
Priority to DEG36086A priority patent/DE1171736B/de
Application granted granted Critical
Publication of US3241970A publication Critical patent/US3241970A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C2200/00—Details
    • G03C2200/06—Additive

Definitions

  • This invention relates to a novel process for the preparation of silver halide photographic emulsions. More particularly, this invention relates to a novel process for the preparation of silver bromide, silver iodide and mixed silver bromide-silver iodide photographic emulsions.
  • the instant invention is based on the discovery that silver bromide, silver iodide, or mixtures of the two, complex with the aforesaid solvent in the presence of excess bromide ions.
  • the complex is soluble in the solvent up to 20% by weight.
  • the solution of this complex is colorless and is not sensitive to light. It should become immediately obvious that such a complex is particularly adapted to the photographic emulsion art when the silver halide or halides can be made to precipitate out of the complex onto a suitable carrier so that they will become light sensitive again.
  • the complex is conveniently prepared simply by adding silver bromide, silver iodide or mixtures of the two to the normally liquid nitrogen containing solvent in the presence of excess bromide ions and stirring.
  • Suitable solvents for my purpose are dimethyl forrnamide, pyrrolidone, pyriconvenient source of bromide ions is hydrobromic acid so that this acid is preferred as a bromide source.
  • the photographic emulsions can be prepared simply by adding the silver halide complex to a suitable carrier contained in a material which acts both as a solvent for the carrier and as a precipitate for the complex.
  • suitable carrier contained in a material which acts both as a solvent for the carrier and as a precipitate for the complex.
  • the solvent-precipitants which can be employed include water, the lower molecular weight aliphatic alcohols, i.e. methanol, propanol, iso propanol, butanol, amyl alcohol and other organic solvents which are miscible with the normally liquid nitrogen containing complexing agent.
  • the preferred solvents are water and aliphatic alcohols of from 1-5 carbon atoms, with water being particularly preferred.
  • the complex can be added to the solvent-precipitant which contains dissolved in place of the carrier an anionic, cationic, nonionic or amphoteric dispersing agent such as sodium lauryl sulfate, iso-octyl phenoxy polyoxyethylene ethanol, sodium N-methyl N-oleoyl taurate, sodium N-lauroyl sarcosinate.
  • an anionic, cationic, nonionic or amphoteric dispersing agent such as sodium lauryl sulfate, iso-octyl phenoxy polyoxyethylene ethanol, sodium N-methyl N-oleoyl taurate, sodium N-lauroyl sarcosinate.
  • My invention offers the special advantage that all operations up to the re-precipitation can be carried out in full light, only the subsequent steps requiring the use of a dark room.
  • a mixture of 450 cubic centimeters of water and 3.5 grams of gelatin was placed in a constant temperature bath at 70 C. and stirred. To this was added the complex and the entire mixture was stirred for three minutes. The mixture was ripened for ten minutes, precipitated and washed. After several washings the silver halide crys tals were redispersed at 40 C. by the addition of 48 grams of gelatin dissolved in 475 cubic centimeters of water. The resulting emulsion was after-ripened and coated on a suitable film base.
  • the resulting emulsion was of excellent quality, was low in fog and was comparable in speed to normal positive type film.
  • EXAMPLE II Ammonia type emulsion A mixture of 83.0 grams of silver bromide and 1.6 grams of silver iodide was added to 120 cubic centimeters of dimethyl formamide and stirred for one minute. 80 cubic centimeters of a 48% solution of hydrobromic acid was then added with stirring. 300 cubic centimeters of dimethyl formamide was then added in two portions of cubic centimeters each, stirring for a few minutes after the first addition and until dissolved after the second. The resulting complex was then added to a solution maintained at 56 C. of 6.5 grams of gelatin, 260.0 cubic centimeters of water and 70.0 cubic centimeters of a 28% solution of ammonium hydroxide. After stirring for nineteen minutes and digesting for ten minutes, the emulsion was precipitated and washed several times with cold water.
  • dimethyl formamide in the examples may be replaced by any other of the enumerated complexing agents, e.g. pyrrolidone, pyridine, butylamine, N-dimethylaniline, dibutylamine, etc.
  • complexing agents e.g. pyrrolidone, pyridine, butylamine, N-dimethylaniline, dibutylamine, etc.
  • My invention can also be carried out by dissolving a colloidal carrier material such as gelatin in the solution containing the silver halide complex and adding this solution to the precipitating medium.
  • a colloidal carrier material such as gelatin
  • the solution of the complex may be sprayed into a chamber containing steam.
  • the steam can be brought into the chamber flowing in the form of a counter current to the direction of travel of the silver complex spray.
  • a process for the preparation of photographic emulsions which comprises adding a silver halide selected from the group consisting of silver bromide, silver iodide and mixtures of the two to a normally liquid organic nitrogen containing solvent in the presence of excess bromide ions so as to form a complex soluble in said solvent, and then adding the resulting solution of said complex to a solution of carrier, the solvents used in the preparation of the carrier solution being miscible with the said nitrogen containing solvent and capable of breaking the complex, thereby forming a dispersion of silver halide in the solution of the carrier.
  • the normally liquid nitrogen containing solvent is selected from the class consisting of dimethyl formamide, pyridine, pyrrolidone, N-dimethylaniline, butylamine and dibutyla- 4 mine.
  • a process for the preparation of photographic emulsions which comprises adding mixtures of silver bromide and silver iodide to dimethyl formamide and hydrobromic acid to form a complex soluble in dimethyl formamide and then adding the resulting solution of said complex in dimethyl formamide to an aqueous solution of gelatin.
  • a process for the preparation of photographic emulsions which comprises adding a silver halide selected from the group consisting of silver bromide, silver iodide, mixtures of the two and silver bromoiodide to a normally liquid organic nitrogen containing solvent in the presence of excess bromide ions so as to form a complex soluble in said solvent, and then adding the resulting solution of said complex in said solvent to a solution of surfactant in a solvent miscible with said nitrogen containing solvent, thereby re-forming the silver halide, and admixing to the dispersion thus obtained a colloidal carrier material so as to form a light sensitive silver halide emulsion.
  • a process which comprises adding a silver halide selected from the group consisting of silver bromide, silver iodide and mixtures of the two to dimethyl formamide in the presence of excess bromide ions so as to form a complex soluble in dimethyl formamide.
  • a process which comprises adding a mixture of silver bromide and silver iodide to dimethyl formamide in the presence of hydrobromic acid to form a complex soluble in dimethyl formamide.
  • a process which comprises mixing together silver bromide, dimethyl formamide and hydrobromic acid so as to form a complex soluble in dimethyl formamide.
  • a process which comprises mixing together silver iodide, dimethyl formamide and hydrobromic acid so as to form a complex soluble in dimethyl formamide.

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)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US143290A 1961-10-06 1961-10-06 Preparation of photographic emulsions Expired - Lifetime US3241970A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE623226D BE623226A (de) 1961-10-06
US143290A US3241970A (en) 1961-10-06 1961-10-06 Preparation of photographic emulsions
GB35482/62A GB1023578A (en) 1961-10-06 1962-09-18 Improvements in or relating to the preparation of photographic emulsions and complexes therefor
DEG36086A DE1171736B (de) 1961-10-06 1962-10-05 Verfahren zur Herstellung photographischer Emulsionen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US143290A US3241970A (en) 1961-10-06 1961-10-06 Preparation of photographic emulsions

Publications (1)

Publication Number Publication Date
US3241970A true US3241970A (en) 1966-03-22

Family

ID=22503421

Family Applications (1)

Application Number Title Priority Date Filing Date
US143290A Expired - Lifetime US3241970A (en) 1961-10-06 1961-10-06 Preparation of photographic emulsions

Country Status (4)

Country Link
US (1) US3241970A (de)
BE (1) BE623226A (de)
DE (1) DE1171736B (de)
GB (1) GB1023578A (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907573A (en) * 1970-08-21 1975-09-23 Minnesota Mining & Mfg Silver halide photographic emulsions with improved physical characteristics
US3941600A (en) * 1973-07-27 1976-03-02 Polaroid Corporation Method of forming a photographic emulsion layer
US4076539A (en) * 1973-07-23 1978-02-28 Fuji Photo Film Co., Ltd. Process for preparing silver halide dispersions
US4370412A (en) * 1978-09-14 1983-01-25 Eastman Kodak Company Aqueous hydrophilic colloid coating composition containing a combination of anionic surfactants
EP0881533A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamine-Silberchlorid-Komplexverbindung und deren Verwendung als einzige Quelle für die Keimbildung von Silberchloridkristallen
EP0881531A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberchlorjodid-Komplexverbindung und deren Verwendung als einzige Quelle für die Einbringung von Jodid in Silberchloridkristalle
EP0881532A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberbromojodid-Komplexverbindung und deren Verwendung als einzige Quelle für die Einbringung von Jodid in Silberbromidkristalle
EP0881530A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Emulsion von hohem Chloridgehalt hergestellt mittels Dimethylamine-Silberchlorojodid-Komplexverbindungen und Antischleiermittel
EP0881534A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberbromid-Komplexverbindung und deren Verwendung als einzige Quelle für die Keimbildung von Silberbromidkristallen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB471366A (de) *
US2875052A (en) * 1949-08-06 1959-02-24 Weyde Edith Photographic material for the direct production of positive photographic images
US3031304A (en) * 1958-08-20 1962-04-24 Albert J Oliver Fine grain nuclear emulsion

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE151752C (de) *

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB471366A (de) *
US2875052A (en) * 1949-08-06 1959-02-24 Weyde Edith Photographic material for the direct production of positive photographic images
US3031304A (en) * 1958-08-20 1962-04-24 Albert J Oliver Fine grain nuclear emulsion

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907573A (en) * 1970-08-21 1975-09-23 Minnesota Mining & Mfg Silver halide photographic emulsions with improved physical characteristics
US4076539A (en) * 1973-07-23 1978-02-28 Fuji Photo Film Co., Ltd. Process for preparing silver halide dispersions
US3941600A (en) * 1973-07-27 1976-03-02 Polaroid Corporation Method of forming a photographic emulsion layer
US4370412A (en) * 1978-09-14 1983-01-25 Eastman Kodak Company Aqueous hydrophilic colloid coating composition containing a combination of anionic surfactants
EP0881533A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamine-Silberchlorid-Komplexverbindung und deren Verwendung als einzige Quelle für die Keimbildung von Silberchloridkristallen
EP0881531A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberchlorjodid-Komplexverbindung und deren Verwendung als einzige Quelle für die Einbringung von Jodid in Silberchloridkristalle
EP0881532A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberbromojodid-Komplexverbindung und deren Verwendung als einzige Quelle für die Einbringung von Jodid in Silberbromidkristalle
EP0881530A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Emulsion von hohem Chloridgehalt hergestellt mittels Dimethylamine-Silberchlorojodid-Komplexverbindungen und Antischleiermittel
EP0881534A1 (de) * 1997-05-30 1998-12-02 Eastman Kodak Company Herstellung einer Dimethylamin-Silberbromid-Komplexverbindung und deren Verwendung als einzige Quelle für die Keimbildung von Silberbromidkristallen

Also Published As

Publication number Publication date
GB1023578A (en) 1966-03-23
DE1171736B (de) 1964-06-04
BE623226A (de)

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