US3745015A - Spectral sensitization of photodevelopable silver halide emulsions - Google Patents

Spectral sensitization of photodevelopable silver halide emulsions Download PDF

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Publication number
US3745015A
US3745015A US00160883A US3745015DA US3745015A US 3745015 A US3745015 A US 3745015A US 00160883 A US00160883 A US 00160883A US 3745015D A US3745015D A US 3745015DA US 3745015 A US3745015 A US 3745015A
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United States
Prior art keywords
emulsion
silver halide
photodevelopable
image
group
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Expired - Lifetime
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US00160883A
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English (en)
Inventor
Pee P Van
H Depoorter
T Ghys
J Berendsen
W Vanassche
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C1/06—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >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
    • G03C1/49—Print-out and photodevelopable emulsions

Definitions

  • a photodevelopable direct-print radiation sensitive silver halide emulsion which comprises an iodine compound, a cadmium compound and an imidacarbocyanine spectrall sensitizing dye in which at least one of the benzorings carries one or more substituents characterized by a Hammet constant 0-,, of at least 0.25, nitro being excluded.
  • the present invention relates to the spectral sensitization of photographic elements having a photodevelopable radiation-sensitive silver halide emulsion layer.
  • Photodevelopable silver halide elements possess desirable properties for high speed recording, such as high speed oscillographic recording, of events which occur in rapid sequence.
  • Photodevelopable silver halide materials for direct recording are radiation-sensitive materials in which a visible image can be obtained after an exposure to a high-intensity source of radiation has been initially utilized to form a latent image, by an additional exposure to a radiation of lower intensity such as dilfuse daylight or artificial light.
  • the secondary exposure, also called latensification is an overall exposure including exposing the areas in which the initial latent image was formed as well as the surrounding background to an additional amount of radiation.
  • Photodevelopable silver halide emulsions can be orthochromatically and panchromatically sensitized for instance in view of their use with high pressure mercury vapour lamps and tungsten lamps.
  • the spectrally sensitizing dyes used are generally not or incompletely bleached during photodevelopment so that the background areas of the image records are coloured and thus the minimum density is increased which results in less image discrimination
  • the sensitizing effect of most of the common spectral sensitizing dyes, when used in photodevelopable silver halide emulsions is reduced in that they are de sorbed from the silver halide grains by the halogen acceptor used.
  • a silver iodide sol and/or a compound that releases iodide ions in aqueous medium such as inorganic and organic iodides, organic compounds with labile iodine atom and onium chloroiodates examples of which can be found among others in United Kingdom patent specification 1,160,956 are added.
  • a silver iodide sol and/or a compound that releases iodide ions in aqueous medium such as inorganic and organic iodides, organic compounds with labile iodine atom and onium chloroiodates examples of which can be found among others in United Kingdom patent specification 1,160,956 are added.
  • the amount of iodine compound added to the emulsion may vary within wide limits. In general an amount from 0.01 g. to 20 g., preferably from 0.1 g. to 5 g. per mole of silver halide is applied.
  • the spectrally sensitized photodevelopable silver halide emulsions of the invention also comprise a cadmium compound.
  • These compounds are preferably inorganic watersoluble cadmium salts such as cadmium nitrate, cadmium iodide, cadmium chloride and especially cadmium bromide, but also include organo-cadrnium compounds and cadmium complexes.
  • the cadmium compounds suppress the sensitivity of the emulsion in the unexposed areas and thus reduce the background density on latensification. They are added to the emulsions after precipitation of the silver halide and prior to coating. They may be used in amounts varying between very wide limits usually from 1 to 20 g. and preferably from 5 to 15 g. of cadmium compound per mole of silver halide.
  • irnidacrbocyanines for use according to the present invention are those corresponding to the formula:
  • each of Z; and Z the same or different stands for the atoms necessary to complete a fused-on benzene nucleus or substituted benzene nucleus, at least one of Z and Z representing the atoms necessary to complete a fused-on benzene nucleus carrying one or more substituents characterized by a Hammet constant a, of at least 0.25, nitro being excluded, for example a cyano group, an alkoxy carbonyl group such as ethoxycarbonyl, a fiuorosulphonyl group, an alkylsulphonyl such as methylsulphonyl or a substituted alkylsulphonyl group such as alkylsulphonyl wherein the alkyl group is substituted by one or more fluorine and/or chlorine atoms, an alkylsulphinyl group or substituted alkylsulphinyl group such as alkylsulphinyl wherein the alkyl group is substituted by one or more fluor
  • each of R R R and R the same or diiferent stands for a substituent of the type contained 111 cyanine dyes on the cyanine nitrogen atom, for example an aliphatic group including a saturated aliphatic group, an unsaturated aliphatic group and a cycloaliphatic group such as alkyl, aralkyl, allyl and cycloalkyl or an aromatic group, which groups may carry substituents; more particularly an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl, a substituted alkyl group such as fi-hydroxyethyl, B-acetoxyethyl, carboxymethyl, carboxyethyl, sulphoethyl, sulphopropyl, sulphobutyl, sulphatopropyl, sulphatobutyl, phosphonoethyl, phosphonopropyl phosphonobuty
  • B represents hydrogen, alkyl, substituted alkyl, amino, substituted amino e.g. acylamino, diethylamino with the proviso however that B each of R and R stands for hydrogen or R together with R and/or R together with R represent the atoms of the type described in French patent specification 1,337,260 necessary to form a fused-on ring such as z z 2)3-,
  • X- stands for an anion of the type contained in cyanine dye salts such as halide, perchlorate, methyl sulphate, benzene sulphonate, p-toluene sulphonate, etc. but does not exist when one of R -R itself contains an anionic group in which case the dye is a betaine dye salt.
  • imidacarbocyanines suitable for use in accordance with the present invention are does not represent hydrogen when V stands for carlisted in the following table.
  • the methine dye salts for spectrally sensitizing photodevelopable silver halide emulsions in accordance with the present invention may be used in amounts varying between very wide limits. Generally they are used in amounts comprised between 1 mg. and 1000 mg. preferably between 50 mg. and 500 mg. per mole of silver halide.
  • the methods of incorporating the dyes in the emusion are simple and well known to those skilled in the art of emulsion making. They are generally added to the emulsion in the form of a solution in a suitable solvent e.g. an alcohol such as methanol or a mixture of alcohol and water.
  • a suitable solvent e.g. an alcohol such as methanol or a mixture of alcohol and water.
  • the solvent must of course be compatible with the emulsion and substantially free from any deleterious effect on the photodevelopable material.
  • the sensitizing dyes of use according to the present invention can be incorporated in the emulsion at any stage of emulsion preparation and should be uniformly distributed throughout the emulsion. They are preferably incorporated just before coating of the emulsion on a support.
  • the silver halides used in the preparation of the photodevelopable radiation-sensitive silver halide emulsions of the present invention include silver bromide, silver bromoiodide, silver chlorobromide and silver chlorobromoiodide emulsions.
  • Silver chlorobromide and silver bromide emulsions which may comprise minor amounts of silver iodide, preferably not more than 5 mole percent relative to the total amount of silver halide, are favoured.
  • the photodevelopable radiation-sensitive emulsions form latent images predominantly inside the silver halide grains.
  • a silver halide emulsion that mainly or entirely forms an internal latent image and only to a little extent an external latent image is an emulsion in which only a few or no exposed grains at all are developable into silver by a developing solution that cannot act as a developer for a latent image inside the grains i.e. a so-called surface developer, such as:
  • G p-Hydroxyphenyl glycine 10 Sodium carbonate (cryst.) 100 Water to 1000 ccs.
  • a developing solution that acts as a developer for latent image inside the grains i.e. a so-called internal developer such as the following solution:
  • a silver halide emulsion that mainly forms internal latent image and little external latent image there is more particularly meant a silver halide emulsion, a test layer of which upon exposure to a light intensity scale for a fixed time between ,5 and 1 sec. and development for 3 min. at 20 C. in the above internal developer, exhibits a maximum density at least 5 times the maximum density obtained when an identical test layer of the said silver halide emulsion is equally exposed and then developed for 4 min. at 20 C. in the above surface developer.
  • Silver halide emulsions that meet the above requirement are generally not or only slightly chemically ripened silver halide emulsions, since the extent of the surface latent image-forming capability increases with the degree of chemical ripening. After precipitation of the silver halide grains the emulsion may or may not be, but preferably is washed.
  • the emulsions may be prepared according to all known and conventional techniques of emulsion preparation.
  • a method according to which emulsions are prepared and which has proven to be particularly suitable for the purpose of the invention is the so-called conversion method according to which an emulsion of a silver salt that has a higher degree of water solubility than silver bromide is converted into a silver chlorobromide or silver bromide emulsion that occasionally contains small amounts of silver iodide. This conversion is carried out preferably very slowly for instance by several consecutive steps.
  • Gelatin is preferably used as the hydrophilic colloid binder but other colloidal materials such as colloidal albumin, cellulose derivatives and synthetic resins e.g. polyvinyl compounds or mixtures thereof with gelatin can also be used.
  • the light-sensitive silver halide emulsion may contain all kinds of ingredients which are generally known in the art of photodevelopable emulsion preparation.
  • the emulsion may contain in addition to the specific ingredients as set forth above hardening agents e.g. formaldehyde, coating aids e.g. saponine, plasticizers e.g. glycerol, develop ment accelerators, compounds that render the material resistant to wrinkling and less brittle, compounds that stabilize the photodeveloped image e.g. thiocyanate such as potassium thiocyanate, etc.
  • halogen acceptors such as N-containing halogen acceptors of the thiourea type, of the hydrazine type, thiouracil, urazole and thiourazole halogen acceptors, mercapto-triazoles, mercaptoimidazoles, imidazolidinethiones, mercaptotriazines, hydrazo thiocarbonamide, thiosemicarbazide; further aromatic mercaptans such as thiosalicylic acid, phenylenediamines, aminophenols, hydroquinones, 3-pyrazolidones, nitriles, phenols, and the like hologen acceptors well known to those skilled in the art including stannous salts such as stannous chloride.
  • the photodevelopable radiation-sensitive silver halide elements according to the invention may comprise any of the wide variety of supports in accordance with usual practice.
  • suitable supports are paper, polyethylenecoated paper, polyproplyene-coated paper, cellulose acetate film, polyvinyl acetal film, polyestyrene film, polyethylene terephthalate film, films of other resinous ma.- terials, glass and metal supports.
  • the radiation-sensitive silver halide element is first image-Wise exposed to radiation in the spectrum range in which the silver halide is sensitive to such an extent that a latent image is formed in the silver halide material but taking care that the silver halide is not caused to print-out.
  • such an exposure can be effected with high as well as with low intensity radiation.
  • the imagewise exposure mostly occurs with high-intensity actinic radiation, e.g. from Xenon tubes, U.V.-la-mps or high pressure mercury vapour lamps.
  • the image-wise exposure may occur by means of light-spots or spots of another actinic radiation (trace beam; oscilloscope traces).
  • the high-intensity radiation source used for the initial ex- 7 posure may be an actinic light or other electromagnetic radiation of either visible or invisible wavelength, X-rays, gamma rays or an electron beam.
  • the sharpness of the recorded trace or image may be further increased by a short preliminary and overall exposure of the photodevelopable radiation-sensitive material according to the invention to ordinary light, e.g. daylight, prior to exposing the material image-wise to the high-intensity radiation. Indeed, by this short prelimary exposure the gradation in the toe of the characteristic curve and the contrast or net density of the recorded trace of image are increased.
  • ordinary light e.g. daylight
  • oscillographs operate according to this principle: after the latent-image exposure the material is passed over a heated plate while being overall exposed so that a visible image is produced almost immediately. By applying heat in this way when high writing speeds and thus high paper transport speeds are used it is not necessary to expose considerable lengths of material to ambient light at the same time, which would lead to a handling problem.
  • the material may be chemically developed and fixed during or after the photodevelopment by means of the common developing and fixing solutions.
  • the image-wise exposed photographic element according to the present invention may, of course, also be developed and then fixed without a photodevelopment being carried out.
  • a light-sensitive photographic silver bromide emulsion of the light-developable type i.e. that mainly forms an internal latent image and only to a little extent an external latent image was prepared by conversion of a silver chloride emulsion into a silver bromide emulsion.
  • Said silver bromide emulsion was prepared so that an amount of silver bromide equivalent to 130 g. of silver nitrate was present per kg. of emulsion.
  • the emulsion obtained was divided into three aliquot portions. To two of these portions the additives listed in the table below were added.
  • the three emulsion samples were coated on conventional photographic paper supports such that an amount of silver halide equivalent to 4 g. of silver nitrate was present per sq. m. of light-sensitive material.
  • the three light-sensitive materials obtained were subjected to the following identical successive treatments.
  • EXAMPLE 2 To an emulsion as described in Example 1 the usual emulsion ingredients and coating aids were added and in addition thereto per kg.:8 g. of cadmium bromide for reducing the background density and 10 ml. of a 5% by weight aqueous solution of potassium iodide; no halogen acceptor was added to the emulsion.
  • the emulsion was divided into several aliquot portions. To these portions were added the spectrally sensitizing dyes listed in the table below in an amount of mg. per kg. emulsion.
  • Example 1 the emulsions were coated. on a paper support whereupon the materials formed were exposed and photodeveloped in the same way as in Example 1. The results obtained after photodevelopment for 15 min. are listed in the table below.
  • Example 1 the emulsion portions were coated on a paper support whereupon the materials formed were exposed and photodeveloped in the same way as in Example l.
  • the results obtained after photodevelopment for 15 min., 2 days, and 8 days respectively are listed in the table below.
  • each of Z and 2 stands for the atoms necessary to complete a fused-on benzene nucleus at least one of Z and Z representing the atoms necessary to complete a fused-on benzene nucleus carrying one or more substituents characterized by a Hammet constant a, of at least 0.25 and selected from the group consisting of cyano, an alkoxycarbonyl group, fiuorosulphonyl, an alkylsulphonyl group, an alkylsulphinyl group, trifiuort methyl, trifiuoromethoxy, trifiuoromethylthio, difluoromethylthio, and a sulphamoyl group,
  • each of R R R and R the same or difierent, stands for an aliphatic group or an aromatic group,
  • each of R and R stands for hydrogen or R together with R and/or R together with R represent the atoms necessary to complete a fused-on ring
  • X- stands for an anion but does not exist when 12;
  • R R or R comprises an anionic group.
  • Z represents the atoms S OZN wherein each of R and R the same or difierent, stands for hydrogen or a saturated or unsaturated aliphatic group or R together with R represent the atoms necessary to complete a heterocycle.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00160883A 1970-08-19 1971-07-08 Spectral sensitization of photodevelopable silver halide emulsions Expired - Lifetime US3745015A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856532A (en) * 1972-04-26 1974-12-24 Ilford Ltd Photographic silver halide emulsion containing a supersensitising combination
US3864134A (en) * 1971-10-28 1975-02-04 Fuji Photo Film Co Ltd Silver bromoiodide photographic emulsion with improved green sensitivity
US4375508A (en) * 1981-10-15 1983-03-01 Eastman Kodak Company Photographic compositions and elements spectrally sensitized with new methine dyes
US4520098A (en) * 1984-05-31 1985-05-28 Eastman Kodak Company Photographic element exhibiting reduced sensitizing dye stain
US20100041901A1 (en) * 2008-08-14 2010-02-18 Nicholas Cairns Sulfonyl Cyanine Dyes and Derivatives

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864134A (en) * 1971-10-28 1975-02-04 Fuji Photo Film Co Ltd Silver bromoiodide photographic emulsion with improved green sensitivity
US3856532A (en) * 1972-04-26 1974-12-24 Ilford Ltd Photographic silver halide emulsion containing a supersensitising combination
US4375508A (en) * 1981-10-15 1983-03-01 Eastman Kodak Company Photographic compositions and elements spectrally sensitized with new methine dyes
US4520098A (en) * 1984-05-31 1985-05-28 Eastman Kodak Company Photographic element exhibiting reduced sensitizing dye stain
US20100041901A1 (en) * 2008-08-14 2010-02-18 Nicholas Cairns Sulfonyl Cyanine Dyes and Derivatives
US8476462B2 (en) * 2008-08-14 2013-07-02 Combinix, Inc. Sulfonyl cyanine dyes and derivatives

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DE2140736A1 (de) 1972-02-24
GB1337277A (en) 1973-11-14

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