US3726684A - Spectrally sensitizing quick-processing photographic material - Google Patents

Spectrally sensitizing quick-processing photographic material Download PDF

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Publication number
US3726684A
US3726684A US00206203A US3726684DA US3726684A US 3726684 A US3726684 A US 3726684A US 00206203 A US00206203 A US 00206203A US 3726684D A US3726684D A US 3726684DA US 3726684 A US3726684 A US 3726684A
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United States
Prior art keywords
quick
silver
emulsion
processing
photographic material
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Expired - Lifetime
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US00206203A
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English (en)
Inventor
O Riester
A Voigt
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/134—Brightener containing

Definitions

  • a light-sensitive photographic material comprising at least one silver halide emulsion layer, which contains developer substances and is suitable for quick-processing, can be spectrally sensitized by certain benzimidazole trimethine cyanines.
  • This invention relates to developer-containing quickprocessing photographic materials comprising at least one photosensitive silver halide emulsion layer which is spectrally sensitized by certain trimethine cyanine dyes.
  • trimethine cyanines corresponding to the general formula shown below sensitize silver halide emulsions with a very high level of intensity, retaining adequate darkroom safety, in addition to which they are compatible with other emulsion additives, especially developer substances, and finally, after quickprocessing, give completely colorless and speckle-free images. For this reason, they are eminently suitable for sensitizing quick-processing materials.
  • the invention relates to a developer-containing photosensitive photographic quick-processing material comprising at least one silver halide emulsion layer,
  • R R and R identical or diflerent radicals, including:
  • R and.R identical or different radicals, including: (1) alkyl or alkenyl with up to 4 carbon atoms, such as methyl, ethyl, isopropyl, propyl, butyl, isobutyl or allyl, optionally substituted by halogen, such as fluorine or chlorine, or by hydroxy, alkoxy, acyloxy, aryl such as phenyl, by acid radicals such as car-boxy, sulfo, sulfato, thiosulfato, phosphonic acid,
  • R -(1) alkyl or alkenyl with up to 4 carbon atoms, optionally substituted, for example by halogen such as fluorine or chlorine, hydroxy, alkoxy, acyloxy, aryl, carboxy, sulfo, sulfato or thiosulfato; (2) cycloalkyl, for example cyclohexyl; or (3) aryl, for example phenyl;
  • Z the atoms required to complete an optionally substituted saturated 5- or 6-membered heterocyclic ring; preferred heterocyclic rings are those derived from thiazoline, selenazoline, pyrroline or tetrahydorpyridine; and
  • X6 any photographically inert anion, for example halide such as bromide or iodide, perchlorate, p-toluene sulfonate, alkyl sulfate, tetrafluoroborate, thiocyanate, nitrate, sulfate, phosphate, oxalate or acetate; X6 can be omitted when one of the radicals R to R contains an acid group in anionic form, so that a betaine is present.
  • halide such as bromide or iodide, perchlorate, p-toluene sulfonate, alkyl sulfate, tetrafluoroborate, thiocyanate, nitrate, sulfate, phosphate, oxalate or acetate
  • dyes such as these are known as spectral sensitizers and are described, for example, in German patent specifications No. 700,781; 725,303; 728,043; 732,704 and 934,084. It was by no means predictable, however, that they would be compatible with developer substances in the large quantities in which these would normally be used in quick-processing materials, nor in particular was it predictable that materials containing these sensitizing dyes could be decolorized in the short processing time.
  • the sensitizing dyes can be used in any silver halide emulsions.
  • Suitable silver halides include silver chloride, silver bromide, or mixtures thereof, optionally with a small silver iodide content of up to 5 mol percent.
  • Silver chloride emulsions with a low silver bromide or silver iodide content are, however, preferred.
  • the silver halides can be dispersed in the usual hydrophilic binder compounds, for example in carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters or amides, or preferably in gelatin.
  • hydrophilic binder compounds for example in carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters or amides, or preferably in gelatin.
  • the sensitizing dyes used in accordance with the invention are preferably added to the photographic emulsion after chemical ripening and before casting.
  • the methods used for this purpose are generally known to the expert.
  • the sensitizing dyes are generally incorporated into the emulsion in solution in a water-soluble solvent, which must, of course, be compatible with the binder and should not have any adverse etfect upon the photographic properties of the emulsion.
  • Water or alcohols, such as methanol or ethanol, or mixtures thereof, are generally preferred as solvents.
  • the quantity of sensitizing dye added can be varied within wide limits, for example from 10 to 1000 mg. per mole of silver halide, preferably from 30 to 300 mg. per mole of silver halide.
  • the concentration of the dye can be adapted to suit the requirements of the type of emulsion used, and the required sensitizing effect. The most suitable concentration for any given emulsion can readily be determined by the tests conventionally employed in photographic practice.
  • the hydroxyaryl compounds known as photographic developers can be used as developers in the quickprocessing materials according to the invention.
  • the developers are preferably present in the photosensitive silver halide emulsion layer, although they can also be incorported in a layer of binder adjacent to the silver halide emulsion layer.
  • the aforementioned developers are frequently mixed with other developer substances, for example with N-methylaminophenol or phenidone(1-phenyl- 19 3-pyrazolidone) or alkyl-substituted derivatives thereof, with which they are known to produce a synergistic etfect.
  • aldehyde/bisulfite or ketone/bisulfite addition compounds such as formaldehyde bisulfite or cyclohexanone bisulfite can also be added to the emulsion.
  • the emulsion can also be chemically sensitized, for example by the addition of sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea and sodium thiosulfate.
  • sulfur-containing compounds for example allyl isothiocyanate, allyl thiourea and sodium thiosulfate.
  • suitable chemical sensitizers include reducing agents, for example the tin compounds described in Belgian patent specifications No. 493,464 and 568,687, also polyamines such as diethylene triamine, or aminomethane sulfinic acid derivatives, for example in accordance with Belgian patent spectification No. 547,323.
  • Noble metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium, are also suitable chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky in Z. Wiss. Phot. 46, 65-72 (1951).
  • the emulsions can also be chemically sensitized with polyalkylene oxide derivatives, for example with polyethylene oxide having a molecular weight of from 1000 to 20,000, and with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have molecular weights of at least 700, preferably of more than 1000.
  • these sensitisers can, of course, be used in combination with one another, as described in Belgian patent specification No. 537,278, and in British patent specification No. 727,982.
  • Quaternary ammonium salts can also be added to the emulsions as development accelerators.
  • the emulsions can contain the conventional stabilisers, for example homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • the conventional stabilisers for example homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • Suitable stabilizers include azaindenes, preferably tetraor penta-azaindenes, especially those of the kind substituted by hydroxy or amino groups. Compounds of the kind are described in the article by Birr in Z. Wiss. Phot. 47, 2-58 (1952).
  • Other suitable stabilizers include inter alia heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quanternary benzthiazole derivatives and benztriazole.
  • Heterocyclic mercapto compounds containing acid groups, of the kind described in German Auslegeschrift No. 1,151,731 are particularly suitable stabilizers. Compounds such as these can be used with particular advantage because they additionally are able to increase the spectral sensitivity provided by the dyestutfs used according to the invention to higher intensity.
  • the emulsions can be hardened in the usual way, for example with chromium salts or with organic hardening agents such as formaldehyde, glutaraldehyde, mucobromic acid or N,N', "-tris-acryloylhexahydro 1,3,5 triazine divinyl sulphone. In some instances, it is even possible to use several hardening agents in combination with one another.
  • the emulsions of the quick-processing materials according to the invention can also contain further additives, for example pla-sticisers, wetting agents such as saponin, nonionic alkyl ethylene oxide compounds or fiuoroalkyl sulphonic acids, or white toners, for example salts of bis- (triazinylamino)-stilbene sulfonic acids, and gelatin substitutes such as polyvinyl alcohol, styrene/maleic acid polymers, polyvinyl pyrrolidone and polyacrylamides.
  • pla-sticisers wetting agents such as saponin, nonionic alkyl ethylene oxide compounds or fiuoroalkyl sulphonic acids, or white toners, for example salts of bis- (triazinylamino)-stilbene sulfonic acids, and gelatin substitutes such as polyvinyl alcohol, styrene/maleic acid polymers, polyvinyl pyrrolidone and polyacrylamides
  • Exposure in a spectral apparatus gives an excellent sensitization curve in the blue-green region of the spectrum with a maximum at approximately 505 nm.
  • EXAMPLE 2 14 mg. of dyestuff No. 3 dissolved in 28 ml. of methanol are added to 1 kg. of a silver bromide emulsion containing 0.18 mole of silver of which 1.2 mol percent is in the form of silver iodide. Thereafter 2 ml. of a 5% solution of N-phenyl N benzotriazolyl-(5)-urea in dimethyl formamide, 15 ml. of 10% aqueous saponin solution, 2 ml. of 30% aqueous Formalin solution, 20 g. of hydroquinone and 20 ml. of a 43% aqueous solution of formaldehyde sodium bisulfite, are added.
  • the silver coating, protective layer, processing and quality are all as in Example 2.
  • Example 4 In the presence of the additives described in Example 4 (40 ml. of a 43% aqueous solution of formaldehyde bisulfite, 17.5 g. of hydroquinone and 20 ml. of a 10% aqueous saponin solution), 20 mg. of dyestuff No. 14 per kg. of the emulsion mentioned in Example I produce a spectral sensitization in the blue-green with a sensitization maximum at around 507 nm. The overall sensitivity obtained amounts to 22 stages After storage for 2 days under tropical conditions at 40 C./82% relative humidity, it falls to 13 stages, accompanied by serious fogging.
  • a developer-containing photosensitive photographic quick-processing material which comprises at least one silver halide emulsion layer and a sensitising dyestufl of the formula:
  • R and R identical or different radicals, including alkyl, alkenyl, cycloalkyl or aryl; or one of the radicals R and R can be attached to the a-carbon atom of the trimethine chain or to the carbon atom in the 4- or 7-position of the benzimidazole group to form an additional 5- or 6-membered ring;
  • X an anion, which can be omitted when one of the radicals R to R contains an acid group in anionic form, so that a betaine is present.
  • a photographic quick-processing material as claimed in claim 1 which contains hydroquinone as the developer.
  • a photographic quick-processing material as claimed in claim 1 which in addition contains a heterocyclic mercapto compound with an acid group as stabiliser.
  • a photographic quick-processing material as claimed in claim 1 which contains a white toner.

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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)
  • Plural Heterocyclic Compounds (AREA)
US00206203A 1970-12-11 1971-12-08 Spectrally sensitizing quick-processing photographic material Expired - Lifetime US3726684A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702060939 DE2060939A1 (de) 1970-12-11 1970-12-11 Spektral sensibilisiertes photographisches Schnellverarbeitungsmaterial

Publications (1)

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US3726684A true US3726684A (en) 1973-04-10

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US (1) US3726684A (enrdf_load_stackoverflow)
BE (1) BE776273A (enrdf_load_stackoverflow)
CA (1) CA968212A (enrdf_load_stackoverflow)
CH (1) CH568584A5 (enrdf_load_stackoverflow)
DE (1) DE2060939A1 (enrdf_load_stackoverflow)
FR (1) FR2117675A5 (enrdf_load_stackoverflow)
GB (1) GB1348818A (enrdf_load_stackoverflow)
IT (1) IT945351B (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841878A (en) * 1971-09-17 1974-10-15 Agfa Gevaert Nv High temperature processing of photographic silver halide elements
US3932186A (en) * 1974-01-02 1976-01-13 Polaroid Corporation Spectrally sensitized photographic silver halide emulsion
US4138551A (en) * 1975-03-18 1979-02-06 Ciba-Geigy Ag Spectral sensitization of photographic material and new spectral sensitizers
US4592991A (en) * 1983-12-22 1986-06-03 Fuji Photo Film Co., Ltd. Silver halide photographic printing paper
US4769384A (en) * 1985-07-03 1988-09-06 Nippon Shinyaku Co. Ltd. Benzimidazole derivatives

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841878A (en) * 1971-09-17 1974-10-15 Agfa Gevaert Nv High temperature processing of photographic silver halide elements
US3932186A (en) * 1974-01-02 1976-01-13 Polaroid Corporation Spectrally sensitized photographic silver halide emulsion
US4138551A (en) * 1975-03-18 1979-02-06 Ciba-Geigy Ag Spectral sensitization of photographic material and new spectral sensitizers
US4592991A (en) * 1983-12-22 1986-06-03 Fuji Photo Film Co., Ltd. Silver halide photographic printing paper
US4769384A (en) * 1985-07-03 1988-09-06 Nippon Shinyaku Co. Ltd. Benzimidazole derivatives

Also Published As

Publication number Publication date
FR2117675A5 (enrdf_load_stackoverflow) 1972-07-21
CA968212A (en) 1975-05-27
DE2060939A1 (de) 1972-06-15
GB1348818A (en) 1974-03-27
BE776273A (fr) 1972-06-06
CH568584A5 (enrdf_load_stackoverflow) 1975-10-31
IT945351B (it) 1973-05-10

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