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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
  • G03C5/383—Developing-fixing, i.e. mono-baths

Definitions

• Photographic compositions comprising (1) a silver halide developing agent, (2) a water-soluble silver halide solvent and (3) a weak silver halide complexing agent. ln one embodiment the above composition can be used to rapidly develop or stabilize image records in silver halide emulsions which contain addenda which lower the rate of dissolution of silver halide in a potassium thiocyanate solution.
• This invention relates to new processes for obtaining stable images in silver halide compositions.
• this invention relates to new compositions which can be used to obtain stable images in silver halide compositions.
• this invention relates to means for obtaining stable image records in direct-print emulsions.
• this invention relates to novel monobaths for stabilizing image records in photographic compositions.
• 1t is still another object of this invention to provide means for stabilizing image records in internally sensitive silver halide compositions.
• the weak silver complexing agents of this invention all have the inherent characteristic property of not being capable of reducing silver halide to metallic silver. ln one embodiment the weak silver complexing agent is additionally characterized in that it contains the ethenic group such as benzene, toluene, aniline, etc. In another embodiment the weak silver complexing agent is additionally characterized as being a halogenated hydrocarbon. The complexing agents are also substantially free of mercaptan groups (or tautomers thereof) which would provide other predominant characteristics. In still another embodiment we have found that polyhydric compounds such as lactose, maltose, glucose, and the like can be added to said stabilizing compositions to improve image discrimination when stabilizing a silver halide image record.
• the silver halide compositions which can be stabilized or developed according to this invention are those which are internally sensitive to electromagnetic radiation, i.e., light, X- rays, electrons, etc.
• Suitable silver halides include internally sensitive silver bromide, silver bromoiodide, silver chlorobromide, silver chlorobromoiodide, and the like.
• the preferred emulsions are those wherein the silver halide is predominantly silver bromide. 1n a typical embodiment preferred emulsions according to this invention have higher internal sensitivity than surface sensitivity.
• Typical suitable emulsions are disclosed in Davey et al., U.S. Pat. No. 2,592,250 issued Apr. 8, 1952; U.S. Pat. No. 3,206,316; Porter et al., U.S. Pat. No. 3,206,313, Glafkides, Photographic Chemistry, Vol. 1. pp.
• intemal image emulsions can be used in the invention, such having silver halide grains wherein a predominant amount of the sensitivity is internal to the grains.
• Such internal image emulsions are those which, when measured according to normal photographic techniques by coating a test portion of the emulsion on a transparent support, exposing to a light intensity scale having a fixed time between 1X10" and l second, bleaching 5 minutes in a 0.3 percent potassium ferricyanide solution at 65 F. in Developer B below (an internal-type developer), have a sensitivity, measured at a density of 0.1 above fog, greater than the sensitivity of an identical test portion which has been exposed in the same way and developed for 6 minutes at 68 F. in developer A below (a surface-type" developer).
• the stabilizing or developing baths of this invention provide unexpected increases in the stabilizing or development rate of silver halide compositions which contain addenda which lower the dissolution rate of silver halides in potassium thiocyanate.
• direct-print compositions containing a halogen acceptor which lowers the rate of dissolution of silver halide in potassium thiocyanate can be effectively and quickly stabilized to form permanent image records having high image discrimination.
• Typical direct-print emulsions which are preferably stabilized according to this invention contain halogen acceptors such as l-n-butyl-l,2,5-6- tetrachydro-l ,3,5-triazine-4-thiol, 2,2,4-trimethyl-6-mercapto-metadiazine, 5-methyl-2-mercapto-oxazoline, phenyl thiosemicarbazide and dithiomalonamide.
• halogen acceptors such as l-n-butyl-l,2,5-6- tetrachydro-l ,3,5-triazine-4-thiol, 2,2,4-trimethyl-6-mercapto-metadiazine, 5-methyl-2-mercapto-oxazoline, phenyl thiosemicarbazide and dithiomalonamide.
• the photographic elements processed according to the present invention can contain only latent images or they can contain visible image records, such as in the instance of a photodeveloped direct-print element.
• a permanent visible substantially uniform image record having good image discrimination will be obtained regardless of whether film is entirely photodeveloped to a visible image record or contains no visible image record.
• the stabilizing or developing bath can contain a wide variety of compounds which reduce silver halide to silver.
• Typical developers include N-methyl-p-aminophenol sulfate, hydroquinone, 1-phenyl-3-pyrazolidone, l-phenyl-4methyl-4 '-hydroxymethyl-3-pyrazolidone, ascorbic acids, and the like or mixtures of the same.
• the developing agent comprises 1-phenyl-3pyrazolidone/hydro quinone I or l-phenyl-3-pyrazolidone/ascorbic acid.
• the developing compositions also can contain agents such as anhydrous sodium sulfite, stabilizing agents such as, for example, sodium or potassium carbonate amines or amino and S clathrates and other agents such as antifoggant agents commonly used in developer compositions.
• agents such as anhydrous sodium sulfite, stabilizing agents such as, for example, sodium or potassium carbonate amines or amino and S clathrates and other agents such as antifoggant agents commonly used in developer compositions.
• the stabilizers or developers of this invention contain a silver halide solvent or fixing agent such as for example, watersoluble thiocyanates. ln one embodiment the thiocyanates are used in combination with organic thioethers. Suitable organic thioethers include those which when utilized in aqueous solutions (60 C.) at 0.02 molar concentrations, are capable of dissolving more than twice the amount (by weight) of silver chloride than that which can be dissolved by water at 60 C. Typical preferred organic thioethers which can be used according to this invention contain at least one moiety wherein oxygen and sulfur are separated by an ethylene radical (e.g., -0Cl-l CH- .S).
• an ethylene radical e.g., -0Cl-l CH- .S
• the subject thioethers have one to three thioether atoms (-8- although thioether compounds having more than three thioether atoms can be used.
• Typical thioethers are disclosed in McBride, U.S. Pat. No. 3,271,157 issued Sept. 6, 1966. These organic thioethers play also the part of weak complexing agents such as defined hereinafter.
• Typical thiocyanates useful according to the invention include potassium thiacyanate, sodium thiocyanate, ammonium thiocyanate, and the like.
• the watersoluble thiocyanate is present in concentrations of about 25 grams to about 500 grams per liter and preferably from about 150 grams to about 450 grams per liter.
• Other suitable fixing agents can also be used within the scope of the invention; however, the thiocyanates are the preferred fixing agents.
• the weak silver complexing agents are all characterized by the common property of not being capable of reducing silver halide to metallic silver.
• the weak complexing agents are generally incorporated in the stabilizing or developer compositions in concentrations of about 1 gram/liter to about 150 grams/liter and preferably from about 10 grams/liter to about 100 grams/liter
• the weak silver complexing agents are those compounds which can be additionally characterized as hydrocarbons having an ethenic group halogen groups or combinations of these groups in the compound.
• the weak silver complexing agents contain at least one halogen group and more preferably at least one halogen group and at least one ethenic group.
• the weak silver complexing agents contain at least two ethenic groups and more preferably at least three ethenic groups.
• Typical compounds useful in the invention which have the above characteristic properties are acyclic ethylene compounds such as trichloroethylene and the like; cyclic ethylene compounds such as dicyclopentadiene and the like; aromatic compounds such as benzene, toluene, maminophenol, aniline, anisol, benzoic acid, benzylamine, benzylic alcohol, benzylic aldehyde, chlorobenzene,
• ethylbenzene N-methyl aniline, m-phenylene diamine, resorcinol, salicylic aldehyde, o-toluidine, primary phenylethyl alcohol, l-methyl-B-phenylpropylamine, phenylethlamine, and the like; unsaturated heterocyclic compounds such as lutidines, 2-Bphenylethyl isoquinolinium bromide and the like; halogenated compounds such as disclosed by l... J. Andrews and R. W. Keefer in J.A.C.S.
• halomethanes such as methyl iodide, diiodomethane, chloroform and the like
• dihaloethylenes such as diiodoethylenes, dichloroethylenes and the like
• halobenzenes such as chlorobenzene, diiodebenzenes and the like.
• polyhydroxy compounds can be effectively added to the above developing or stabilizing baths of this invention to increase the discrimination (Dmax-Dmin) of the image record.
• carbohydrates are employed such as lactose, maltose, levulose, glucose, mannitol, dextrose and the like.
• the essential ingredients of the stabilizing or developing composition according to this invention namely the developers, the weak silver complexing agents and the silver halide solvent can be prepackaged in a kit in diluted, concentrated, or powder form and can be either mixed together or packaged individually for use in making the permanizing composition of this invention. Either one or all of the essential ingredients can also be coated in a separate layer on the photographic element which can subsequently be activated by an aqueous solution.
• the respective compositions are generally prepackaged individually and can be readily added to water to form a bath. Therefore, it is understood that kits prepared for making stabilizing or developing compositions comprising the essential ingredients of this invention are contemplated to be within the scope of this invention.
• the stabilizing or developing baths of this invention are particularly useful to stabilize the image record in silver halide compositions containing addenda which lower the rate of dissolution of silver halides in potassium thiocyanate.
• addenda which lower the rate of dissolution of silver halides in potassium thiocyanate.
• Solution I Potassium Thincyanate Water (sufficient quantity to obtain Solution 11 150 g. 15 ml.
• the six samples are exposed through a 0.30 neutral density step tablet for l under a lighting of approximately l000 1x, they are then photodeveloped for minutes under a lighting of 540 lx, and finally, a first series of samples is treated in a control stabilizing developer such as developer F:
• Celon E tetrasodium salt of tetracetic ethylenediamine acid
• Anhydrous sodium sulfite 40 40 Methylaminoethanol -S0, S0,) 70 g. l-phenyl-4-metjyl-4-hydroxymethyl-3- pyrazolidone 22 g.
• Ascorbic acid [2 gr Potassium thiocyanate I50 g.
• the second series of samples is treated separately in a treatment monobath according to the invention (developer G) with the formula:
• Example 3 shows that the association of an emulsion addenda, such as a halogen acceptor, and a weak complexing silver agent useful according to the invention makes it possible to inhibit the development of a surface image in a surface developer.
• an emulsion addenda such as a halogen acceptor
• a photographic product comprising a silver bromide photographic emulsion layer applied on a paper support, it is then exposed through a 0.15 neutral density step tablet for a microsecond by means ofa flash bulb placed at 1 meter from the original (lighting of approximately 1 lumen per second).
• the photographic product exposed in this manner contains an internal image.
• the photographic product is divided into five samples TABLE IV AD L54 Dmin Dmax
• Example 4 This example shows that the association of certain addenda and a weak complexing silver agent useful according to the invention make it possible to develop an internal image in a solvent developer, without development of a surface image.
• a photographic paper such as that of example 3, is divided into five samples which are exposed as in example 4 and which are treated, respectively, in one of the developers mentioned in the following table V.
• These developers are prepared from developer l which develops at the same time both the internal and surface images; the other developers used for treating the various samples being derived from developer 1 to which the compounds mentioned in the following table V have been added.
• N-methylaniline is replaced with other weak silver complexing agents, useful according to the invention and previously mentioned, a good inhibition of the surface image is noticed, while the internal image is well developed.
• Direct-print emulsions which have been exposed and photodeveloped generally comprise two distinct images: an image essentially internal which displays the exposed part, i.e., image of interest, since it represents the sought information (it is also often called trace) and a background image due to the photodevelopment of the previously unexposed crystals.
• the present invention makes it possible to inhibit the development of the background image.
• Stabilizing developers according to the invention are used which develop the internal image without developing the background image.
• the use of this stabilizing developer also makes it possible to reduce treatment time necessary to stabilize aphotographic element.
• Example 5 four samples which are treated for 1 minute respectively with one of the following treatment baths (developers J, C, D. E). Exposed but not photodeveloped samples are also treated with these developers.
• Developer J has the following composition:
• Developer .l is a usual developer for the internal image. if an exposed but not photodeveloped sample of the previously mentioned photographic product is developed chemically by such a developer, a copy is obtained with low Dmin and relatively high Dmax.
• the Dmin increases due to the development of the surface image formed during the photodevelopment.
• the stabilizing developers C, D, E according to the invention when used on a photodeveloped sample, provide an image record identical to that obtained with a nonphotodeveloped sample (low Dmin and relatively high Dmax). The development of the surface image is apparently suppressed by the stabilizing developers.
• Photodeveloped samples can be stabilized in developer .I when benzylamine is added to obtain permanent images having density levels similar to those obtained with nonphotodeveloped samples treated by developer .l above (usual internal developer).
• the second'sample is then treated for 1 minute in a stabilizing developer according to the invention similar to developer G of example 2 in which the benzylamine has been replaced with benzene at the point of saturation.
• EXAMPLE 7 This example illustrates the use of a halogenated compound as a weak complexing silver agent for preparing a monobath according to the invention.
• a sample according to example 6 is treated with the developer ofe'xample 6 wherein the benzene in the stabilizing developer has been replaced with methyliodide at the point of saturation.
• Photographic elements are prepared with emulsions made according to French Pat. l,450,983 which contains 3.7Xl0 mole per mole of silver of l-n-butyl-l ,2,5,6-tetrahydro-l ,3,5 -triazinethiol.
• Samples of the photographic elements are made by exposure for one one-thousandthof a second behind a 0.30 neutral density step wedge and then photodeveloped for 5 minutes at '54'0lumens.
• Carbohydrates can be used in combination with the ak silver complexingagents in the stabilizing or developing baths of this invention to provide synergistic improvements in the photographic properties of the image record.
• Photographic elements are prepared according to example l, exposed for one one-thousandth of a second behind'a 0.30 neutral density step wedge and then photodeveloped for 5 minutes at 540 lux.
• One of the photographic elements is treated for 1 minute in monobath B having the following composition:
• a second photographic element, prepared and exposed as above, is treated for 1 minute in a monobath according to monobath B with the addition of 100 grams of saccharose per liter.
• a third photographic element, prepared and exposed as above, is treated for 1 minute in a monobath according to monobath B with the addition of 15 ml. of benzylamine per liter.
• a fourth photographic element, prepared and exposed as above, is treated for 1 minute in a monobath according to monobath B with the addition of 100 grams of saccharose and 15 ml. of benzylamine per liter.
• EXAMPLE 1 A photographic element, prepared and exposed as in example 9,is treated for 1 minute in a monobath according to monobath B, additionally containing ml. of benzylamine and 100 grams of lactose per liter. The following results are obtained:
• a photographic monobath composition for developing direct-print photographic compositions comprising (1) a silver halide developing agent, (2) a water soluble thiocyanate silver halide solvent and (3) a weak silver halide complexing agent which is not capable of reducing silver halide to metallic silver.
• a photographic bath according to claim 1 wherein said weak silver halide complexing agent comprises at least one group or halogen group.
• a photographic bath according to claim 1 wherein said weak silver halide complexing agent is an aromatic compound.
• a photographic bath according to claim 1 wherein said weak silver halide complexing agent is a halogenated organic compound.
• a photographic bath according to claim I wherein said weak silver halide complexing agent is an organic thioether.
• organic thioether comprises at least one moiety of the formula OCI-l -CH -S-).
• said developing agent comprises l-phenyl-3- pyrazolidone/hydroquinone.
• a photographic bath according to claim 1 further comprising a carbohydrate.
• a photographic bath according to claim 1 wherein said weak silver complexing agent is benzylamine.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=26181987

Family Applications (1)

Country Status (5)

Cited By (3)

• 1968
  • 1968-05-07 FR FR150764A patent/FR1578037A/fr not_active Expired
  • 1968-10-16 US US768155A patent/US3615512A/en not_active Expired - Lifetime
• 1969
  • 1969-05-01 GB GB1265061D patent/GB1265061A/en not_active Expired
  • 1969-05-05 BE BE732533D patent/BE732533A/xx unknown
  • 1969-05-06 DE DE19691923112 patent/DE1923112A1/de active Pending

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