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
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
• • 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
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

• Photographic elements having a radiation-sensitive, colloid-silver halide emulsion layer and a contiguous light insensitive stratum containing a thiazolidine compound, preferably L-thiazolidine-4-carboxylic acid.
• This invention relates to photography and to photographic elements with improved ratios of speed (or light sensitivity) to fog.
• the photographic element of this invention comprises a support, a light-sensitive layer comprising silver halide in a hydrophilic colloid binder, and in operative association therewith, a light-insensitive layer containing a thiazolidine compound of the formula Where the Rs (which may be the same or different) are H, alkyl of 1-4 carbons, e.g., CH C H C H C H or aryl, e.g., phenyl.
• the particularly preferred thiazolidine compound is L- thizaolidine 4 carboxylic acid which will subsequently be referred to as TCA.
• a thiazolidine compound of Formula I is incorporated in the antiabrasion layer of any conventional photographic element.
• the compound may be present in another light-insensitive layer adjacent to the silver halide layer, e.g., in the substratum layer, filter layer, nonhalation layer or separator layer, but as stated above preferably is in an antiabrasion layer contiguous with a silver halide layer.
• the silver halide emulsion may be of any of the usual types (black and white or color) such as those employed for medical or industrial X-ray, cine, graphic arts or portrait use.
• the silver halide crystal may also be any one of the usually types such as silver chloride, silver bromide, silver bromochloride or silver iodobromide. Particularly useful results have been obtained with high speed medical X- ray films containing silver iodobromide crystals.
• Gelatin is the preferred binder for the silver halide crystals but it may be partially or completely replaced with other natural or synthetic binders as known in the art.
• binders used to improve covering power e.g., dextran, dextrin, polyvinyl pyrrolidone, etc. as well as latices of polymers such as polyethylacrylate which are useful in improving dimensional stability are advantageously included in many types of silver halide emulsions employed according to this invention.
• the range of concentration of the thiazolidine compound of Formula I depends somewhat on the emulsion, a higher concentration being desirable as the silver halide molar surface area increases (i.e., as the emulsion sensitivity decreases).
• the concentration is best expressed in terms of the quantity of compound contained in an area of the light-insensitive layer adjacent to an area of the lightsensitive layer containing one mole of silver halide.
• a useful range of concentration of the thiazolidine compound is from 0.0005 to 0.5 millimole per mole of silver halide with a preferred range being from 0.001 to 0.1 millimole.
• Concentrations are expressed in terms of the amount of the thiazolidine compound present in an area of the light-insensitive layer corresponding to the area of the silver halide emulsion layer containing one mole of silver halide.
• the light-insensitive layer containing the thiazolidine compound which is normally the antiabrasion layer, conveniently has gelatin as the binder.
• gelatin could be replaced, totally or in part, with other hydrophilic colloid binders, as stated above.
• a typical antiabrasion layer is coated from an aqueous solution of gelatin containing the thiazolidine compound, coating aids and gelatin hardeners such as aldehydes, e.g., formaldehyde and glutaraldehyde, glyoxal, mucochloric acid, and chrome alum. From economic considerations, the coating is applied as a very thin layer, e.g., about 10 mg./dm. of gelatin. Since the thiazolidine compound apparently should migrate into the silver halide layer to be effective, a thicker light-insensitive layer would require a higher concentration of the thiazolidine compound for a given concentration to reach the silver halide layer.
• the support for the photographic element preferably is a polyethylene terephthalate film base as described in Alles et al. U.S.P. 2,627,088, Feb. 3, 1953 but other coated and uncoated supports including those listed in Cohen et al. U.S.P. 3,252,801, May 24, 1966 can be used.
• Any of the usual emulsion adjuvants may be present in the silver halide layer, e.g., emulsion sensitizers, sensitizing dyes, coating aids, etc.
• Example I A high-speed gelatino-silver iodobromide emulsion containing 1.2 mole percent silver iodide and 98.8 mole percent silver bromide was made in the usual manner and then coagulated and washed as taught in Moede, U.S.
• Example II A very high-speed ge'latino-silver iodobromide emulsion with 1.8 mole percent silver iodide and 98.2 mole percent silver bromide was precipated, ripened, washed according to US. 2,772,165, redispersed, digested, and coated in a conventional manner. The resulting film was overcoated with antiabrasion layers, exposed, and processed as in Example I to give the following results:
• Example II Next the emulsion was coated on film base as described in Example I and overcoated with antiabrasion layers containing the below-indicated amounts of TCA. Samples of the films were given an industrial X-ray lead through screen exposure at 200 kvp. and 4 milliamps for 1 minute through a [2 aluminum step wedge. The films were developed for 5 minutes at 68 F. in the developer solution of Example I.
• Example IV A gelatino-silver bromochloride lithographic type emulsion containing 30 mole percent silver bromide and 70 mole percent silver chloride was made in the usual manner and digested with gold and sulfur to increase its sensitivity. After post-sensitization additions, including the addition of a polyethyl acrylate latex to improve dimensional stability, the emulsion was coated on the film support of Example I and dried. A portion of the coated emulsion was overcoated with an antiabrasion layer as described in Example I and two portions were overcoated with similar antiabrasion coatings containing the indicated amount of TCA. Samples of the films were given a V1010) sec. exposure with a xenon flash through a /2 step wedge at a distance of 6% inches. The exposed samples were developed for 4 minutes at 74 in the developer of Example I.
• Example V Example I was essentially repeated except that the antiabrasion layers contained various thiazolidine compounds in the concentrations indicated in the table below:
• An aqueous 3% by weight solution of gelatin was divided into two portions. To one there was added an aqueous solution of 2,2,5,5-tetramethyl-L-thiazolidinc-4- carboxylic acid while to the other portion, serving as a control, there was added an equal quantity of distilled water.
• the solutions were coated as sub-stratum layers on film base as in Example I to coating weights of about 10 mg./dm. of gelatin. Both films were then overcoated with the silver halide emulsion layer and then further overcoated with the control antiabrasion layer of Example I.
• an experimental coating with a sub-stratum layer containing a thiazolidine compound in a concentration of 1.86 mg. per area of adjacent silver halide emulsion layer containing one mole of silver halide.
• Example VII A fine grain, medium-speed, gelatino-silver halide emulsion having a silver halide composition of 96.8 mole percent silver bromide and 3.2 mole percent silver iodide was made by precipitation in the usual manner. The precipitated emulsion was coagulated and washed as described in Example I. The sensitivity of the emulsion was increased by addition of a gold salt and a sulfur sensitizer and by digestion of the modified emulsion. Following digestion, post-sensitization additives and stabilizers, e.g., KBr, antifoggants, etc., were added along with polymers as described in Cohen et al. U.S.P.
• Example II 3,252,801 to improve covering power and dimensional stability.
• the emulsion was divided into four equal portions and TCA was added to three of the portions.
• the emulsions were coated on the photographic film base of Example I.
• a standard gelatin antiabrasion layer was applied to all samples which, after drying, were given a 20-second exposure to a white light from a tungsten filament lamp through an intensity scale sensitometric step wedge. The exposure in each successive step increased by a factor of the 4throot-of-Z.
• the exposed samples were developed for 3 minutes in a continuous tone developer containing the developing agents set forth in Example I and the results are shown in the following table:
• a photographic element comprising (1) a support (2) a radiation-sensitive, colloid-silver halide emulsion layer, and in operative association therewith (3) a light-insensitive contiguous, hydrophilic colloid layer containing a thiazolidine compound of the formula:
• R R R and R is H, alkyl of 14 carbons or aryl in an amount of 0.0005 to 0.5 millimole per mole of silver halide.
• layer (3) is an outer anti-abrasion layer contiguous with layer (2).
• layers (2) and (3) contain gelatin as a binding agent.

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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)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Applications Claiming Priority (1)

Publications (1)

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Cited By (7)

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• 1967
  • 1967-05-17 US US639065A patent/US3565625A/en not_active Expired - Lifetime
• 1968
  • 1968-05-10 GB GB22434/68A patent/GB1190678A/en not_active Expired
  • 1968-05-14 DE DE1772424A patent/DE1772424C3/de not_active Expired
  • 1968-05-15 JP JP43032288A patent/JPS4946259B1/ja active Pending
  • 1968-05-16 BE BE715225D patent/BE715225A/xx not_active IP Right Cessation

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