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
• • 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

Definitions

• the invention relates to silver halide emulsions, the speed of which is increased by silicone containing amines. These compounds can be present either in the emulsion or in the developer bath.
• Such chemical sensitizers are believed to react with the silver halide to form, on the surface of the silver halide, minute amounts of silver sulfide or of silver or of other noble metals, and these processes are capable of increasing the sensitivity of emulsions by very large factors.
• the process of chemical sensitization reaches a definite limit beyond which further addition of sensitizer, or of further digestion with the sensitizer present, merely increases the fog of the photographic emulsion leaving the sensitivity constant or even decreasing it.
• lt is among the objects of the present invention to increase the general sensitivity or speed of silver halide emulsion layers.
• a further object is to provide photographic silver halide emulsions and emulsion layers having an increased general sensitivity without concomitant increase in fog level.
• sensitivity it is intended to refer to the sensitivity of photographic emulsions through the whole spec trum.
• spectral sensitivity it is intended to refer to the sensitivity of the photographic emulsion to light of a certain range of the spectrum.
• Suitable sensitizers include those of the following formulas:
• R R R R stand for hydrogen, alkyl containing up to 12 carbon atoms, preferably up to six carbon atoms, cycloalkyl such as cyclohexyl; R and R or R and R. may together represent the ring members necessary for completing a saturated 5-, 6- or 7-membered heterocyclic ring such as a pyrrolidine, morpholine, thiomorpholine, hexamethylene imine or hexahydropyridine ring.
• R represents alkyl containing up to six carbon atoms
• the preparation of photographic silver halide emulsions includes three separate steps:
• Emulsification and physical ripening which is also called Ostwald ripening
• the sensitizers of the present invention can be added to the emulsion before, during or after the chemical ripening or they can be added immediately prior to the casting.
• the particular quantity of the sensitizers of the invention used in a given emulsion can vary, depending upon the effects desired, silver content of the emulsion, the silver halide composition etc. Generally they are added in amounts of 5 mg. to 5 g. per liter of emulsion preferably 50 mg. to l g. of emulsion which corresponds from 16 mg. to 16 g. per mol of silver ha lide.
• the compounds are also effective when they are added to the developer solution in which case they are preferably used in quantities of between approximately 50 mg. and 2 g. per liter of the aqueous developer bath.
• the sensitizers can be dissolved in water or a solvent miscible with water or a mixture of water and water-miscible solvents, and added in this form to the emulsion.
• the solvent is not critical and should be selected so that it should have no harmful effect to the photographic properties of the silver halide emulsion.
• the optimum amount for any sensitizer of the present invention can be determined for any particular emulsion by running a series of comparison tests in which the quantity of the sensitizer is varied over a given range. Exposure of the emulsion containing the sensitizer in a manner well-known and measuring of the sensitivity in conventional apparatuses will reveal most advantageous concentrations. Such technique is well understood by those skilled in the art.
• the substances according to the invention may be used in any silver halide emulsions.
• Suitable silver halides are silver chloride, silver bromide or mixtures thereof, which may con tain a small amount of silver iodide of up to mol percent.
• the photographic emulsion in which the sensitizers according to the invention are used can be chemically sensitized by any of the known procedures. They can be sensitized, for example, with sulfur compounds as referred to, e.g. in the book The Theory of the Photographic Process by Mees (1954) pages 149-161.
• the emulsions can also be chemically sensitized with salts of noble metal such as gold, ruthenium, rhodium, palladium, iridium and platinum, used in amounts below that which produce any substantial fog.
• noble metal such as gold, ruthenium, rhodium, palladium, iridium and platinum
• Representative compounds are ammonium chloropalladate, potassium, chloroplatinate, potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and the like.
• the emulsions can be sensitized with reducing agents, stannous salts or polyamines and the like.
• the emulsions can also be optically sensitized with cyanine, merocyanine or rhodacyanine dyes.
• the emulsions may also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styry] dyes, oxonoles and the like. Sensitizers of this type have been described in the work by F. M. Hamer (The Cyanine Dyes and Related Compounds" (1964)).
• the emulsions can be stabilized with any of the known stabilizers, e.g. homopolar or salt-type compounds of mercury with aromatic or heterocyclic compounds (for example mercaptotriazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds.
• suitable stabilizers include azaindenes, especially tetraor pentaazaindenes, in particular those which are substituted with hydroxyl or amino groups. Such compounds have been described in the article by Birr, Z. Wiss. Phot. 47, 2-58 (-1952).
• Other suitable stabilizers include heterocyclic mercapto compounds, e.g.
• the silver halide emulsion layers may contain any suitable film-forming and waterpermeable colloid as binding agent, such as gelatin but the gelatin can be replaced partially with products like alginic acid and derivatives thereof such as salts, preferably with alkali metals, esters with lower aliphatic alcohols or amides.
• the gelatin can also be partially replaced with polyvinyl alcohol, polyvinyl pyrrolidone, starch, carboxymethyl cellulose and the like.
• the emulsions may be hardened in the usual manner, for example, with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
• formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
• the compounds according to the invention are effective for both black-white emulsions and for color photographic emulsions which contain color couplers.
• saponin as wetting agent 200 mg. of 4-hydroxy-6-methyl-l,3,3a,7-tetraazaindene as stabilizer and 10 ml. of a 10 percent aqueous solution of formaldehyde as hardener.
• the emulsion is divided into 3 parts and the following compounds are added per liter of emulsion:
• Sample A Comparison sample without additive
• Sample B 0.1 g. of substance IV
• Sample C 0.3 g. ofsubstance IV.
• EXAMPLE 2 A silver iodo-bromochloride gelatin emulsion containing 60 g. of silver nitrate per kg. in the form ofsilver halide which contains as in example 1 4-hydroxy-6-methyl-l ,3,3a,7- tetraazaindene as stabilizer, saponin as wetting agent and formalin as hardener, is divided into 8 equal parts. Subsequent treatment and the development are carried out as given in example l,
• Sample A Comparison sample without additive
• Sample B 100 mg. ofsubstance 1V
• Sample C 3.0 g. of compound 1
• Sample D 3.0 g. of compound 11
• Sample E 300 mg. ofcompound 111.
• An increase by 3 denotes double sensitivity or a sensitivity increase of one shutter stop.
• a mixed emulsion which is composed of percent of a silver iodobromide and percent of silver iodo-bromochloride gelatin emulsion and which has been chemically ripened to optimum sensitivity in known manner using gold and sulfur compounds.
• Sample A Comparison sample without additive
• Sample B 1.0 g. of Substance I
• Sample C 3.0 g. of Substance II
• Sample D 3.0 g. of Substance III.
• the color developer bath has the following composition:
• Dicthyl-p-phenylenediaminc sulfate 2.75 g. hydroxylaminc sulfate L20 g. sodium sulfite anhydrous 2.00 g. sodium hexametaphosphate 2.00 g. potassium carbonate anhydrous 75.00 g. potassium bromide 2.00 g.
• An increase by 3 denotes double sensitivity or a sensitivity increase of one shutter stop.
• An increase by 3.0 denotes double sensitivity or a sensitivity increase of one shutter stop.
• R R R R represent hydrogen or alkyl having up to 12 carbon atoms; or R and R or R and R, together may represent the ring membersnecessary for completing a pyrrolidine, morpholine, thiomorpholine, hexamethylene, imine or hexahydropyridine;
• R stands for alkyl having up to six carbon atoms; in amounts ranging from 5 mg. to 5 g. per liter of emulsion or 50 mg. to 2 g. per liter of the developer bath.
• a light-sensitive photographic material having at least one supported silver halide emulsion layer containing a tetraalkyl-bis-aminomethyl disiloxane of the following formula:
• R,, R R R represent hydrogen or alkyl having up to 12 carbon atoms; or R and R or R and R together may represent the ring members necessary for completing a pyrrolidine, morpholine, thiomorpholine, hexamethylene, imine or hexahydropyridine;
• R stands for alkyl having up to six carbon atoms, in an amount ranging from 5 mg. to 5 g. per liter of emulsion.

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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)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

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• 1968
  • 1968-04-27 DE DE19681772315 patent/DE1772315A1/de active Pending
• 1969
  • 1969-04-09 CA CA048174A patent/CA917986A/en not_active Expired
  • 1969-04-09 US US815280A patent/US3615526A/en not_active Expired - Lifetime
  • 1969-04-10 CH CH548169A patent/CH530654A/de not_active IP Right Cessation
  • 1969-04-24 GB GB1257983D patent/GB1257983A/en not_active Expired
  • 1969-04-24 BE BE731987D patent/BE731987A/xx unknown
  • 1969-04-25 FR FR6913315A patent/FR2007133A1/fr not_active Withdrawn

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