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
• • 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

Definitions

• SILVER BROMIDE EMULSION SENSITIZED WITH 1,4,TRIAZINES A number of methods have previously been described for increasing the'sensitivity of photographic silver halide emulsions. The incorporation of certain colored compounds or dyes in the emulsions increases the optical range of sensitivity, and for this reason such dyes are commonly referred to as optical or spectral sensitizing dyes. It is also well known to increase the sensitivity of photographic emulsions by addition of sulfur compounds capable of reacting with silver salts to form silver sulfide, or by addition of reducing agents (compounds of these types are also naturally present in gelatin), or with salts of gold or other noble metals, or with combinations of two or more of the'aforementioned compounds generally known as chemical sensitizers.
• 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.
• sensitivity it is intended to refer to the sensitivity of photographic emulsions through the whole spectrum.
• spectral sensitivity it is intended to refer to the sensitivity of the photographic emulsion to light ofa certain range of the spectmm.
• R represents hydrogen or an alkyl group containing up to carbon atoms preferably methyl
• R stands for (1) hydrogen, (2) a linear or branched alkyl group containing up to 12 carbon atoms, preferably up to 5 carbon atoms, which alkyl radicals may be substituted with phenyl, hydroxyl, cyano, carboxyl, esterified carboxyl or alkoxy groups, (3) aryl, especially a radical of the phenyl series which may be substituted, (4) acyl, especially acyl derived from aliphatic carboxylic acids preferably having up to 5 carbon atoms, (5) carbamoyl in which the amide group may be substituted with alkyl having preferably up to 5 carbon atoms, aralkyl such as benzyl, or aryl especially phenyl, or (6) an amino group in which the hydrogen atoms may be substituted with alkyl groups, preferably alkyl having up to 5 carbon atoms, aryl, especially phenyl, or acyl, especially those of the type mentioned above; the amino group may in addition be substitute
• nitrogen-atom of the morpholine ring is capable of forming simple salts or quaternary ammonium salts, these may, of course, also be used in the process according to the invention.
• Suitable quaternary groups are alkyl groups containing up to 12 carbon atoms, preferably up to 5 carbon atoms, which may be substituted, e.g. with phenyl groups as in benzyl or phenyl ethyl groups.
• any anions may occur in these compounds, e.g. halides, perchlorates and the like.
• the nitrogen atom of the morpholine ring cannot be quatemized if the basic properties of the nitrogen are suppressed by electro negative substituents. This occurs, e.g. when R isphenyl, carbamoyl or acyl.
• 1,4-Thiazanes substituted on the nitrogen atom are prepared from the corresponding unsubstituted thiazane which is reacted according to known processes with a suitable halogenated compound with the addition of acid binding agents.
• the other compounds given above can be obtained by reacting unsubstituted thiazane with acid chlorides or with isocyanates.
• N-Amino-1,4-thiazane can be prepared by introducing a nitroso group into thiazane followed by reduction.
• the acid salts and quaternary salts are prepared by known methods.
• 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 3 mg. to 20 g. preferably 3 mg. to 6 g. per mol of silver halide. The compounds are also effective when they are added to the developer solution in which case they are preferably used in similar quantities 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 thiomorpholine derivatives of the invention are used in silver bromide emulsions wh ich may contain a small amount of silver iodide of up to 10 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) pp. 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, styryl dyes, oxonoles and the like. Sensitizers of this type have been described in the work by F. M. Hamer (The Cyanine Dyes n R te Q g g qg 111? my ,7 W w,
• 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. phenylmercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
• the silver halide emulsion layers may contain any suitable film-forming and water-permeable 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.
• EXAMPLE 1 600 mg. of saponin as wetting agent, 200 mg. of 4-hydroxy- 6-methyl-1,3,3a,7-tetraazaindene as stabilizer and 10 ml. of a 10% aqueous solution of formaldehyde are added to a silver iodobromide gelatin emulsion which contains 60 g. of silver per liter in the form of silver halide which has a silver iodide content of 6 mols percent.
• the emulsion was divided into three equal samples and the following substances were added per liter of emulsion to the individual samples:
• Sample A Comparison sample without additive
• Sample B 300 mg. of compound 1
• Sample C 600 mg. of compound II]
• the casting solutions are applied onto a support of cellulose triacetate, exposed in a sensitometer customarily employed in the art behind a grey step wedge and developed for 10 minutes in a developer of the following composition:
• An increase by 3 represents a sensitivity gain of one shutter stop or double sensitivity.
• EXAMPLE 2 A silver iodobromide gelatin emulsion containing 4.5 5 mol percent silver iodide which has been ripened to optimum sensitivity with gold and sulfur compounds in known manner is sensitized by the addition of 45 mg. of the following sensitizing dye per kg. of emulsion:
• ingredients are added per kg. of emulsion: g. of 1-(3'-sulfo-4'-phenoxy)-phenyl-3-heptadecyl-pyrazolone as magenta coupler; 250 mg. of 1,3,3a,7- tetraaza-4-hydroxy-6-methyl indene as stabilizer; ml. of a 5% aqueous solution of saponin as wetting agent; 2.5 ml.
• the emulsion was divided into 7 equal samples and the following substances were added per kg. of emulsion to the individual samples:
• Sample A Comparison sample without additive
• Sample B 1.0 g. of compound I
• Sample C 3.0 g. of compound I-II
• Sample D 1.0 g. of compound XII
• Sample E 1.0 g. of compound IV
• Sample F 0.3 g. of compound XI
• Sample G 1.0 g. of compound XIV
• the samples are applied onto a support of cellulose acetate and dried. They are then exposed behind a step wedge and processed in the usual manner. Processing is carried out as follows:
• the color developer has the following composition:
• the color density of the magenta layers was determined with a Macbeth Quanta Log, Model TD- 102 densitometer, a green color filter being interposed in the path of the beam of measuring light.
• An increase by 3 here also represents double sensitivity or a sensitivity increase of one shutter stop.
• EXAMPLE 3 The thiomorpholine compounds of the invention are also effective when applied in color developers, as illustrated by the following Example. Each of the following substances is added to a color developer in an amount of l g. per liter:
• Sample A Comparison sample without additive
• Sample B compound I
• Sample C compound 11
• Sample D compound XV (0.5 g. per liter).
• the color developer has the following composition: Diethyl-p-pheny1enediamine sulfate 2.75 g., hydroxylamine sulfate 1.2 g., sodium sulfite anhydrous 2.0 g., sodium hexametaphosphate 2.0 g., potassium carbonate anhydrous 75.0 g., potassium bromide 2.0 g., make up to 1 liter with water.
• a conventional commercial color photographic multilayer material having on a support'a red-sensitive silver bromide emulsion layer with a cyan coupler, a green-sensitive emulsion layer with a magenta coupler and a blue-sensitive emulsion layer containing a yellow coupler, is exposed behind a step wedge and processed in the usual manner.
• the color densities of the individual layers of the multilayer material are measured with a Macbeth Quanta Log, Model TD 102" densitometer, the appropriate color filter" being interposed in each case into the path of the beam.
• An increase by 3 again denotes a sensitivity increase of one shutter stop or double the sensitivity.
• R stands for hydrogen or alkyl containing up to 5 carbon atoms
• R represents (1) hydrogen, (2) a linear or branched alkyl group containing up to 12 carbon atoms, (3) a radical of the phenyl series, (4) an aliphatic carboxylic acyl group having up to five carbon atoms, (5) a carbamoyl group, or (6) an amino group. 7.
• the emulsion of claim 6 containing additionally up to 10 mol percent of silver iodide based on the silver bromide.
• R represents alkyl, substituted with phenyl, hydroxyl, cyano, carboxyl or alkoxy.

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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)

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Cited By (5)

Citations (6)

• 1968
  • 1968-05-06 DE DE19681772375 patent/DE1772375A1/de active Pending
• 1969
  • 1969-04-22 US US818381A patent/US3617280A/en not_active Expired - Lifetime
  • 1969-04-24 CH CH623569A patent/CH526794A/de not_active IP Right Cessation
  • 1969-04-30 GB GB21930/69A patent/GB1256393A/en not_active Expired
  • 1969-05-06 FR FR6914464A patent/FR2007937A1/fr not_active Withdrawn
  • 1969-05-06 BE BE732547D patent/BE732547A/xx unknown

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