EP0478669B1 - Dopage d'emulsions d'halogenure d'argent avec un sel de potassium de sélénocyanate afin de former des grains photoactifs améliorés - Google Patents

Dopage d'emulsions d'halogenure d'argent avec un sel de potassium de sélénocyanate afin de former des grains photoactifs améliorés Download PDF

Info

Publication number
EP0478669B1
EP0478669B1 EP90910066A EP90910066A EP0478669B1 EP 0478669 B1 EP0478669 B1 EP 0478669B1 EP 90910066 A EP90910066 A EP 90910066A EP 90910066 A EP90910066 A EP 90910066A EP 0478669 B1 EP0478669 B1 EP 0478669B1
Authority
EP
European Patent Office
Prior art keywords
silver
silver halide
precipitation
grains
halide grains
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
EP90910066A
Other languages
German (de)
English (en)
Other versions
EP0478669A1 (fr
Inventor
George Fu Liang C/O Eastman Kodak Company Wu
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.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
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
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to AT90910066T priority Critical patent/ATE95321T1/de
Publication of EP0478669A1 publication Critical patent/EP0478669A1/fr
Application granted granted Critical
Publication of EP0478669B1 publication Critical patent/EP0478669B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • G03C1/0051—Tabular grain 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/07—Substances influencing grain growth during silver salt formation
    • 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
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • 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
    • G03C2001/03511—Bromide content
    • 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
    • G03C2001/03558—Iodide content
    • 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
    • G03C2200/43—Process

Definitions

  • This invention relates to radiation sensitive material. It particularly relates to radiation sensitive silver halide grains and their preparation.
  • silver halide emulsions can be chemically sensitized by adding sensitizers of certain material such as sulfur or gold after formation of silver halide grains.
  • Photographic products may be chemically sensitized with chemical sensitizers such as with reducing agents such as sulfur, selenium, tellurium, gold, platinum, or palladium compounds.
  • chemical sensitizers such as with reducing agents such as sulfur, selenium, tellurium, gold, platinum, or palladium compounds.
  • tabular silver halide grains such as disclosed in the above patents of Kofron et al and Solberg et al patents have been successful in producing grains that have superior speed-granularity relationship. Nevertheless it is desired that films of even higher performance be formed that can be enlarged to even greater extent without excessive granularity.
  • An object of the invention is to produce films having improved speed-granularity relationship.
  • Another object of the invention is to provide a process resulting in improved silver halide grains.
  • the silver halide grains are preferably formed by an accelerated flow technique.
  • the double jet precipitation technique is preferably used for the invention.
  • a method of forming silver halide grains comprising forming a precipitation dispersion for silver halide grains, precipitating silver halide grains by introducing silver and halide salts into the precipitation dispersion until 65 to 90 percent of the silver salt that will form the silver mass to be precipitated has been added to said precipitation dispersion, then adding to said precipitation dispersion potassium selenocyanate salt dopant in an amount between 1.4 X 10 ⁇ 6 and 7 X 10 ⁇ 5 mole per mole of silver, based on the total mass of silver to be precipitated, continuing precipitation until all the silver mass has been added and said silver halide grains reach a desired size, and ending the precipitation process, with the further proviso that said silver halide grains comprise between 1 and 12 mole percent of silver iodide and between 88 and 99 mole percent silver bromide, and said silver halide grains at the completion of precipitation have an aspect ratio of at least 8 to 1.
  • Grains formed by this process will have their outer third comprising selenium with the silver halide.
  • the invention provides several advantages over prior practices.
  • the emulsions of the invention provide better raw stock keeping, and improved speed/fog ratio.
  • speed/fog ratio it is meant that a higher speed film is possible at the same amount of fog or less fog is possible at the same speed.
  • the invention process is more efficient in that doping of the emulsions during precipitation produces a better speed/fog ratio than attempting to achieve the same effect by sensitization processes. This is because with doping it is easier to control fog and rate of sensitization.
  • the formation of the silver halide emulsions of the invention may be carried out by processes such as generally disclosed in U.S. 4,439,520-Kofron et al referred to above and hereby incorporated by reference.
  • improved silver halide emulsions may be formed by doping silver halide grain with a selenocyanate salt in an amount of between 0.2 and 1.0 mg per mole of silver during the later stage of precipitation.
  • a silver halide grain is formed by emulsion precipitation process, sensitized, and coated into a multilayer color film to result in a film that has surprisingly improved raw stock keeping properties, improved speed/fog ratio and more reliable reproducibility than when the speed/fog ratio is attempted to be improved only by sensitization.
  • a dispersing medium is initially contained in the reaction vessel.
  • the dispersing medium is comprised of an aqueous peptizer suspension.
  • Peptizer concentrations of from 0.2 to 10 percent by weight, based on the total weight of emulsion components in the reaction vessel, can be employed. It is common practice to maintain the concentration of the peptizer in the reaction vessel in the range of below 6 percent, based on the total weight, prior to and during silver halide formation and to adjust the emulsion vehicle concentration upwardly for optimum coating characteristics by subsequent supplemental vehicle additions.
  • the emulsion as initially formed will contain from 5 to 50 grams of peptizer per mole of silver halide, preferably 10 to 40 grams of peptizer per mole of silver halide. Additional vehicle can be added later to bring the concentration up to as high as 1000 grams per mole of silver halide. Preferably the concentration of vehicle in the finished emulsion is above 50 grams per mole of silver halide. When coated and dried in forming a photographic element the vehicle preferably forms 30 to 70 percent by weight of the emulsion layer.
  • Vehicles for the emulsions of the invention can be selected from those conventionally employed in photographic silver halide emulsions.
  • Preferred peptizers are hydrophilic colloids, that can be used alone or in combination with hydrophobic materials.
  • Useful hydrophilic materials include both naturally occurring substances, such as proteins, protein derivatives, cellulose derivatives, such as cellulose esters, gelatin, such as alkali treated gelatin or acid treated gelatin, gelatin derivatives, such as acetylated gelatin and phthalated gelatin, polysaccharides, such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, agar-agar, arrowroot and albumin and other vehicles and binders known in the photographic art. Gelatin is highly preferred.
  • the silver halide emulsions are preferably washed to remove soluble salts. Any of the processes and compositions known in the photographic art for this purpose are useful for washing the silver halide emulsions of the invention.
  • the soluble salts can be removed by decantation, filtration, and/or chill setting and leaching, coagulation washing, by centrifugation, and by other methods and means known in the photographic art.
  • the photographic silver halide can be chemically sensitized by procedures and with compounds known in the photographic art.
  • the silver halide can be chemically sensitized with active gelatin, or with sulfur, selenium, tellurium, gold, platinum, indium, palladium, osmium, rhodium, rhenium, or phosphorous sensitizers or combinations of these sensitizers, such as at pAg levels within the range of 5 to 10 and at pH levels within the range of 5 to 8 at temperatures within the range of 30 to 80°C.
  • the silver halide can be chemically sensitized in the presence of antifogants, also known as chemical finish modifiers, such as compounds known to suppress fog and increase speed during chemical sensitization, such a azaindenes, azapyridazines, azapyrimidines, benzothiazolium salts, and sensitizers having one or more heterocyclic nuclei.
  • antifogants also known as chemical finish modifiers, such as compounds known to suppress fog and increase speed during chemical sensitization, such a azaindenes, azapyridazines, azapyrimidines, benzothiazolium salts, and sensitizers having one or more heterocyclic nuclei.
  • antifogants also known as chemical finish modifiers, such as compounds known to suppress fog and increase speed during chemical sensitization, such a azaindenes, azapyridazines, azapyrimidines, benzothiazolium salts, and sensitizers having one or more
  • the photographic silver halide emulsion can be spectrally sensitized by, for example, dyes of a variety of classes, including the polymethine dye class, including cyanines, merocyanines, complex cyanines and merocyanines, oxonols, hemioxonols, styryls, merostyryls and streptocyanines. Combinations of spectral sensitizers are also useful.
  • the photographic silver halide elements can be either single color (monochrome), or multicolor elements.
  • a cyan dye-forming coupler is typically associated with a red-sensitive emulsion
  • a magenta dye-forming coupler is typically associated with a green-sensitive emulsion
  • a yellow dye-forming coupler is associated with a blue-sensitive emulsion.
  • Multicolor elements typically contain dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers. The layers of the element and the image-forming units can be arranged in various orders as known in the photographic art. Color photographic reversal materials are preferred for use of the emulsions of this invention.
  • the photographic element can contain added layers, such as filter layers, interlayers, overcoat layers, subbing layers and other layers known in the art.
  • any coupler or combination of couplers known in the photographic art can be used with the silver halide emulsions as described.
  • Examples of useful couplers are described in, for example, Research Disclosure Section VII, paragraphs D,E,F and G and in U.S. Patent 4,433,048 and the publications cited therein.
  • the couplers can be incorporated as described in Research Disclosure Section VII and the publications cited therein.
  • the photographic emulsions and elements can contain addenda known to be useful in the photographic art.
  • the photographic emulsions and elements can contain brighteners (Research Disclosure Section V), antifoggants and stabilizers (Research Disclosure Section VI), antistain agents and image dye stabilizers (Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (Research Disclosure Section VIII), hardeners (Research Disclosure Section XI), plasticizers and lubricants (Research Disclosure Section XII), antistatic agents (Research Disclosure Section XIII), matting agents (Research Disclosure Section XVI) and development modifiers (Research Disclosure Section XXI).
  • the photographic elements can be coated on a variety of supports, such as film and paper base, as described in Research Disclosure Section XVII and the references described therein.
  • the photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible image using processes and compositions known in the art, such as described in Research Disclosure Section XIX and U.S. Patent 4,433,048 and the references described therein.
  • Processing of a color photographic element as described to form a visible dye image includes the step of contacting the element with a color photographic silver halide developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with at least one coupler to yield a dye.
  • Preferred color developing agents are p-phenylenediamines.
  • 4-amino-3-methyl-N,N-diethylaniline hydrochloride 4-amino-3-methyl-N-ethyl-N- ⁇ -(methanesulfonamido)-ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate, 4-amino-3- ⁇ -(methanesulfonamido)ethyl-N,N-diethyl-aniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid.
  • this processing step leads to a negative image.
  • this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniform fogging of the element to render unexposed silver halide developable.
  • the silver halide emulsions of this invention are preferably employed in photographic elements designed to be processed to form a color negative image.
  • the doping of the invention will take place during the growth stage of the silver halide grains.
  • the silver halide grain size is increased by a double jet accelerated flow procedure with silver nitrate and potassium bromide and iodide.
  • Dopant is added after 65 to 90% of the silver halide mass has been precipitated. After a desired size grain has been reached the grain growth is stopped by washing to remove the soluble salts, particularly nitrate and bromide.
  • the present invention provides color films utilizing the the grains which have better raw stock keeping and low fog.
  • This addition of potassium selenocyanate at the latter stages of precipitation produces a grain that has dispersed in the outer third of its surface the doping material.
  • the core remains the silver halide, preferably silver bromide and silver iodide, without the doping compound that is present in about the outer third of the grain.
  • the high aspect ratio tabular grain silver halide emulsions that have been doped with the Group VIB metallic salt, preferably potassium selenocyanate are then preferably chemically sensitized in conventional manner such as discussed in the above-referenced Kofron et al patent.
  • a preferred sensitizing dye for use with the Group VI metal doped silver halide emulsions of the invention are anhydro- 5-chloro-9-ethyl-5'-phenyl-3'-(3-sulfobutyl)-3-(sulfo-propyl)oxa-carbocyanine hydroxide, sodium salt, and anhydro-11-ethyl-1,1'-bis(3-sulfopropyl)naphth[1,2-d]-oxazolocarbocyanine hydroxide, sodium salt.
  • the emulsion is washed after precipitation is complete to a desired size grain. Washing by coagulation wash to remove the excess bromide ions to stop grain growth at the desired size is preferred. Further the emulsion is redispersed and chilled to 4.5°C to solidify. The emulsion may be remelted and liquefied prior to sensitization with conventional materials such as gold and sulfur.
  • the addition of the inorganic selenium salt is preferably carried out between 65 and 90% of desired grain growth. If the selenium salt is added after 90% of grain growth is done it is at least partially removed during the washing operation and the grain will not have the desired properties.
  • the optimum time of addition is after 67 percent of the total silver halide mass to be precipitated has been added to the precipitation for best raw stock keeping and speed/fog ratio increase.
  • the grains of the invention are preferably formed with a silver halide comprising silver bromide and iodide. Generally the grains have an amount between 1 and 44 mole percent silver iodide with the remainder 56-99 mole percent silver bromide. A preferred amount has been found to be between 1 and 12 mole percent silver iodide with between 99 and 88 percent silver bromide.
  • the grains suitably have a high aspect ratio of at least 8 to 1. The aspect ratio is preferred to be at least 20 to 1 for best performance as more surface area is present.
  • the following examples demonstrate the formation process of the silver halide grains of the invention. Further the examples demonstrate the superior performance in regard to raw stock keeping and speed/fog ratio of the emulsions of the invention as compared with other emulsions produced by the Kofron et al process referenced above.
  • a 2.4 ⁇ m diameter and 0.12 ⁇ m thick silver bromoiodide (overall average iodide 3.0 mole percent) tabular grain emulsion prepared by a double-jet precipitation technique using accelerated flow as follows:
  • aqueous gelatin solution (solution A, 0.087 molar sodium bromide, 0.6 percent by weight bone gelatin) at 35°C and pBr 1.18 are added with stirring over a minute and a half period (consuming 0.18 percent of the total silver) an aqueous silver nitrate solution (solution C-3, 0.376 molar).
  • solution C-3 aqueous silver nitrate solution
  • Twenty liters of aqueous phthalated gelatin solution (solution D, 4% by weight) are added to the reaction vessel. The temperature is then raised to 65°C. The pBr of the contents of the reaction vessel is 1.46 at 65°C.
  • a control emulsion is precipitated in the same manner as above, except the dopant potassium selenocyanate (solution H) is omitted.
  • Both of these emulsions are sensitized with 150 mg/Ag mole sodium thiocyanate, 4.5 mg/Ag mole sodium thiosulfate, 1.5 mg/Ag mole potassium tetrachloroaurate and 17 mg/Ag mole 3-methylbenzothiazolium iodide, and spectrally sensitized with 228 mg/Ag mole of dye E and 386 mg/Ag mole of dye F.
  • the sensitized emulsion is combined with a cyan coupler 2-naphthalenecarboxamide, N-[4-[2,4-6(1,1-dimethylpropyl) phenoxy]butyl]-1 hydroxy in an amount of 55 mg/silver mole, then coated onto a polyester film, exposed for 1/100 second at 5500K, and processed in C-41 developer for two minutes and fifteen seconds.
  • the photographic test results show that the selenium doped emulsion is 0.14 log E faster than the control emulsion without the dopant.
  • the invention has been described with preferred tabular silver halide emulsions. However the invention also would find advantages in doping of other types of silver halide grains for improved speed/fog and raw stock keeping. Further the invention also would find utilization in the formation of black and white films where improved speed/fog grain ratio is desirable as well as improved raw stock keeping. The invention is only intended to be limited by the scope of the claims attached hereto.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

Un dopant est incorporé à des grains d'halogénure d'argent pendant leur précipitation. Ces grains d'halogénures d'argent sont produits par une technique à double jet d'émission à courant accéléré. Lorsque 65 % à 90 % environ de la masse d'halogénure d'argent à précipiter ont été ajoutés à la dispersion de précipitation, on y ajoute une quantité d'une solution dopante d'un sel du groupe VIB comprise entre 0,2 et 1,0 mg de sel par mole d'argent. On permet ensuite à la formation de la dispersion de s'achever en continuant à appliquer la technique de précipitation à double jet d'émulsion jusqu'à obtenir les grains de la grandeur voulue. Les grains ainsi obtenus ont leur tiers extérieur composé du sel métallique du groupe VI mélangé avec l'halogénure d'argent. Dans le mode préférentiel de réalisation du procédé, le sel métallique du groupe VIB est un sel de sélénium contenant du sélénocyanate de potassium.

Claims (5)

  1. Procédé de préparation de grains d'halogénure d'argent consistant à
       former une dispersion par précipitation des grains d'halogénure d'argent,
       précipiter des grains d'halogénure d'argent en introduisant des sels d'argent et d'halogénure dans la dispersion de précipitation jusqu'à ce que 65 à 90 % du sel qui formera la masse d'argent à précipiter ait été ajouté à la dispersion de précipitation, puis
       ajouter dans la dispersion de précipitation un dopant sel de sélénocyanate de potassium en quantité comprise entre 1,4 x 10⁻⁶ et 7 x 10⁻⁵ mole par mole d'argent, par rapport à la masse totale d'argent à précipiter,
       continuer à précipiter jusqu'à ce que toute la masse d'argent ait été ajoutée et les grains d'halogénure d'argent atteignent la taille désirée, et
       terminer la précipitation avec la condition supplémentaire que les grains d'halogénure d'argent comprennent entre 1 et 12 % en mole d'iodure d'argent et entre 88 et 99% en mole de bromure d'argent, et que les grains d'halogénure d'argent à la fin de la précipitation aient un indice de forme d'au moins 8 à 1.
  2. Procédé selon la revendication 1 dans lequel les grains d'halogénure d'argent sont précipités en utilisant une technique de double jet accéléré.
  3. Procédé selon la revendication 1 dans lequel à la fin de la précipitation on effectue un lavage par coagulation pour éliminer l'ion bromure.
  4. Procédé selon la revendication 1 dans lequel la quantité de sel est de 1,4.10⁻⁶ mole par mole d'argent par rapport à la masse d'argent précipité dans la formation des grains.
  5. Procédé selon la revendication 4 dans lequel 67% du sel d'argent a été ajouté au moment de l'addition du sel de sélénocyanate de potassium à la dispersion de précipitation.
EP90910066A 1989-06-19 1990-06-15 Dopage d'emulsions d'halogenure d'argent avec un sel de potassium de sélénocyanate afin de former des grains photoactifs améliorés Expired - Lifetime EP0478669B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90910066T ATE95321T1 (de) 1989-06-19 1990-06-15 Dotierung von silberhalogenidemulsionen mit einem kaliumselencyanat-salz zur bildung verbesserter fotoaktiver koerner.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US367904 1982-04-13
US36790489A 1989-06-19 1989-06-19

Publications (2)

Publication Number Publication Date
EP0478669A1 EP0478669A1 (fr) 1992-04-08
EP0478669B1 true EP0478669B1 (fr) 1993-09-29

Family

ID=23449094

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90910066A Expired - Lifetime EP0478669B1 (fr) 1989-06-19 1990-06-15 Dopage d'emulsions d'halogenure d'argent avec un sel de potassium de sélénocyanate afin de former des grains photoactifs améliorés

Country Status (4)

Country Link
EP (1) EP0478669B1 (fr)
JP (1) JP2921979B2 (fr)
DE (1) DE69003680T2 (fr)
WO (1) WO1990016014A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5536632A (en) * 1995-05-15 1996-07-16 Eastman Kodak Company Ultrathin tabular grain emulsions with dopants at selected locations
EP0699949B1 (fr) * 1994-08-26 2000-06-07 Eastman Kodak Company Emulsions aux grains tabulaires ultraminces avec des dopants sur des places sélectionnées

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1600736A (en) * 1924-06-06 1926-09-21 Eastman Kodak Co Art of light-sensitive photographic materials
BE437840A (fr) * 1939-02-02
US3442653A (en) * 1964-02-10 1969-05-06 Eastman Kodak Co Sensitized silver halide systems with activated nonlabile selenium compounds

Also Published As

Publication number Publication date
EP0478669A1 (fr) 1992-04-08
DE69003680T2 (de) 1994-05-05
DE69003680D1 (de) 1993-11-04
WO1990016014A1 (fr) 1990-12-27
JP2921979B2 (ja) 1999-07-19
JPH04506267A (ja) 1992-10-29

Similar Documents

Publication Publication Date Title
US5219720A (en) Silver halide grains having small twin-plane separations
US4997751A (en) Silver halide emulsions having improved low intensity reciprocity characteristics and processes of preparing them
US5166045A (en) Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains
EP0486629B1 (fr) Pellicules photographiques contenant des granules d'halogenure d'argent ayant de petites separations de plans doubles
US5334495A (en) Silver halide grains having small twin-plane separations
EP0478669B1 (fr) Dopage d'emulsions d'halogenure d'argent avec un sel de potassium de sélénocyanate afin de former des grains photoactifs améliorés
JPH01131554A (ja) ネガ型ハロゲン化銀カラー写真感光材料
US5726006A (en) Tabular grain silver halide emulsions, a method for their preparation and photographic products
EP0478710B1 (fr) Grains d'halogenure d'argent creux et leur procede de preparation
EP0432834B1 (fr) Emulsions, éléments et procédés photographiques au bromo-iodure d'argent
JP2719540B2 (ja) 高感度ハロゲン化銀写真感光材料
US5541053A (en) Process for the preparation of silver halide photographic emulsions containing grains having (100) faces with cavities and photographic emulsions so prepared
US4973548A (en) Photographic silver bromoiodide emulsions, elements and processes
US6242171B1 (en) Tabular grain silver halide emulsion and method of preparation
EP0618485B1 (fr) Produit photographique comprenant un mélange d'émulsions de sensibilités differents
USH1594H (en) Silver halide color photographic light-sensitive material
US5491056A (en) Process of forming a photographic emulsion
JPH07113738B2 (ja) 経時カブリ等の少ない改良されたハロゲン化銀写真感光材料
EP0650084B1 (fr) Emulsion d'halogénure d'argent photographique comprenant des grains à faces (100) avec des cavités
JP2683625B2 (ja) ハロゲン化銀写真感光材料
EP0466919B1 (fr) Materiau photographique en halogenure d'argent et procede de formation d'images inversibles
JP2852470B2 (ja) 還元増感されたハロゲン化銀写真乳剤、及び該乳剤を用いたハロゲン化銀カラー写真感光材料
JPH086195A (ja) ヒドロキノン誘導体の存在下に増感したハロゲン化銀写真乳剤及びその製造方法
JPH026941A (ja) ハロゲン化銀写真乳剤の製造方法
JPH03188439A (ja) 耐圧性能等が向上したハロゲン化銀写真感光材料

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19911218

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19920601

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930929

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19930929

Ref country code: DK

Effective date: 19930929

REF Corresponds to:

Ref document number: 95321

Country of ref document: AT

Date of ref document: 19931015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69003680

Country of ref document: DE

Date of ref document: 19931104

ITF It: translation for a ep patent filed
ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19940615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19940630

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960328

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960703

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970630

BERE Be: lapsed

Owner name: EASTMAN KODAK CY

Effective date: 19970630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19980101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19980101

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980625

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19980709

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000503

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050506

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050602

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060615

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060615

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060630