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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/32—Development processes or agents therefor
  • G03C8/36—Developers
• • 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
  • G03C1/42—Developers or their precursors
• • 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
  • G03C5/29—Development processes or agents therefor
  • G03C5/30—Developers
  • G03C5/3021—Developers with oxydisable hydroxyl or amine groups linked to an aromatic ring
• • 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
  • G03C5/29—Development processes or agents therefor
  • G03C5/315—Tanning development

Definitions

• This invention relates to silver halide developing agents and antifoggants.
• the invention is directed to bridged polyhydroxynaphthalenes and bridged dihydroxyanthracenes as silver halide developing agents in developer compositions and/or incorporated in photographic elements.
• silver halide developing agents in processing silver halide emulsions. It is also known to incorporate silver halide developing agents in photographic silver halide emulsion layers. Such emulsions are developed after light exposure, by treating them in alkaline solutions which may or may not contain a developing agent. Following development by either system, the developed silver image can be fixed, for example, by treating the developed silver halide layer in a conventional sodium thiosulfate fixing bath. The developed and fixed photographic emulsion layer can then be washed and dried.
• the difference in absorption between the gelatin relief areas and the background can be used for imbibition of dye solutions for transfer to mordanted receiving sheets.
• the relief can also be used in photomechanical processes, such as typography or gravure.
• the difference in inkwater receptivity of the gelatin relief and the hydrophobic support can be employed in lithographic printing or the relief can be transferred to other supports, such as silk screen for stencil printing and the like.
• the difference in the ink receptivity of the reacted and unreacted areas can be employed directly without washoif as in the lithographic printing process of U.S. Patent 3,146,104, issued Aug. 25, 1964, to Yackel and Abbott.
• the exposed photographic element comprising a support having at least one gelatin silver-halide emulsion layer thereon, is immersed in a developing bath containing a silver halide photographic developing agent.
• the developing bath is normally maintained as a separate processing bath and with continuous use, the bath usually becomes less efficient so that special techniques and replenishments are required to maintain optimum processing efficiency.
• the developing baths of the prior art normally contain a developing agent, a preservative, such as sodium sulfite, alkali to activate the developing agent, and can also contain other materials, such as sodium bromide as a restrainer, antifoggants, etc.
• tanning developing agents suitable for use as incorporated developers are disclosed in U.S. Patent 2,592,368. These compounds are broadly identified as dihydroxydiphenyl tanning developing agents, and are particularly useful in processes where a high degree of tanning is desired. However, in certain situations, the degree of tanning must be such as to permit ready removal of the unhardened areas such as by washing with warm water, but must be such as to permit stripping of the tanned or hardened areas from the support.
• a suitable developing agent should preferably be water soluble. Accordingly, it has been desirable to find a water soluble tanning agent which would have a satisfactory degree of tanning for certain processes such as for use in gravure printing processes and which would also have satisfactory stability when incorporated in a silver halide emulsion.
• one object of this invention is to provide novel silver halide developing agents. Another object is to provide silver halide emulsions having incorporated therein improved developing agents. A further object is to provide silver halide emulsions having incorporated therein improved tanning developing agents which are photographically compatible and which are stable to atmospheric oxygen. Another object is to provide silver halide photographic materials having an incorporated tanning developer suitable for use in a stripping product such as that used for preparing gravure printing plates. A further object is to provide a tanning developing agent which provides a degree of hardness in the tanned silver halide emulsion, which permits it to be stripped from a temporary support.
• a still further object is to provide an antifoggant for use in developing solutions and for incorporation in photographic emulsions, which has improved antifoggant properties over prior art antifoggants.
• the silver halide developing agents of the invention comprise bridged dihydro-l,4-dihydroxynaphthalenes, bridged tetrahydro-1,4-dihydroxynaphthalenes, bridged dihydro-1,Z-dihydroxynaphthalenes, bridged tetrahydro-l, Z-dihydroxynaphthalenes, bridged tetrahydro-9,10-dihydroxyanthracenes, bridged hexahydro-9,IO-dihydroxyanthracenes and bridged octahydro-9,lo-dihydroxyanthracenes within the following general formulas:
• R R and R are each hydrogen; alkyl, for example, alkyl containing 1 to about 20 carbon atoms, such as ethyl, propyl, amyl, decyl and tridecyl; aryl, for example, phenyl, tolyl, or xylyl; hydroxy; alkoxy, e.g.
• lower alkoxy such as methoxy, ethoxy or propoxy
• a sulfonic acid group halogen
• amino such as NH NHZ, or NZ in which Z is a lower alkyl group
• a thio group such as SY wherein Y represents hydrogen or an isocyclic group, for example, an aryl group such as phenyl, naphthyl, tolyl, xylyl or a heterocyclic group, for example, a tetrazolyl, a thiazolyl or a quinolinyl group; at least one of R R or R being hydroxy, R R R R R 8, R9, R10, R11, R12, R13, R14 and R15 each are hydrogen, aryl, for example, phenyl, tolyl, xylyl, and the like, or
• lower alkyl for example, methyl, ethyl, propyl, butyl or amyl
• x and y which can be either the same or different, each represents on each of the number 5 and 8 carbon atoms in Formulae I and II, and on each of the number 1, 4, 5 and 8 carbon atoms in Formulae III, IV, and V, an oxygen atom, or a methylene or ethylene group, which groups may be optionally substituted with a halogen atom, an aryl group, for example, those enumerated above, or a. lower alkyl group, for example, methyl, ethyl, propyl, butyl or amyl.
• Compounds of this type have been described by O. Diels and K. Alder, Bericht, 62, 2337 (1929) and by Porter et al., J. Org. Chem., 29, 588 (1964).
• R is hydrogen; aryl, such as phenyl, tolyl and xylyl; alkyl, such as those containing 1 to about 20 carbon atoms, including methyl, ethyl, propyl, butyl, t-butyl, and octyl, especially lower alkyl; hydroxy; alkoxy, especially lower alkoxy such as methoxy, ethoxy, or propoxy; sulfonic acid; halogen, especially chlorine, bromine, or iodine; amino, including NH NHZ and NZ wherein Z is lower alkyl; or thio, such as SY wherein Y is as defined above, including, for example, tetrazolyl, etc.,
• One embodiment of the invention is a photographic element comprising a support having a hydrophilic colloid layer containing a compound of the class consisting of bridged dihydro-1,4-dihydroxynaphthalenes, bridged tetrahydro-l,4-dihydroxy-naphthalenes, bridged tetrahydro-l, Z-dihydroxynaphthalenes, bridged tetrahydro-9,lO-dihydroxyanthracenes, bridged hexahydro-9,10-dihydroxyanthracenes, and bridged octahydro-9,l-dihydroxyanthra cenes.
• the hydrophilic colloid layer can be a photographic silver halide emulsion layer on a support, or it can be a layer contiguous to a silver halide emulsion layer.
• the element also can be a multilayer photographic element comprising a support having thereon at least one photographic layer sensitive to the blue region of the spectrum, at least one photographic layer sensitive to the green region of the spectrum and at least one photographic layer sensitive to the red region of the spectrum, containing in at least one layer of said element a compound of the class consisting of bridged dihydro-lA'dihydroxynaphthalenes, bridged tetrahydro-1,4-dihydroxynaphthalenes, bridged dihydro-1,2-dihydroxynaphthalenes, bridged tetrahydro-l,2-dihydroxy-naphthalenes, bridged tetrahydro-9,IO-dihydroxyanthracenes, bridged hexahydro-9,10- dihydroxyanthracenes, and bridge
• a hydrophilic colloid such as a silver chlorobromide gelatin emulsion
• a suitable support e.g., over a stripping layer on a temporary film support.
• This material can be exposed and then processed in an alkaline solution after which the emulsion is transferred to a copper cylinder for use as etching resist to obtain a gravure printing plate.
• dihydro or tetrahydro bridged 1,4-dihydroxynaphthalene developing agent such as those within the scope of structure XII, is dissolved in water and the pH of the aqueous solution raised to about 10 by the addition of alkali e.g., sodium hydroxide, after which an exposed silver halide emulsion is developed by immersing or otherwise contacting the exposed meulsion with the solution for a sufficient time to produce the desired density.
• alkali e.g., sodium hydroxide
• these developing agents can be used as mixtures and particularly as mixtures of tanning developing and non-tanning developing agents where desirable. They may also be used as mixtures with other developers known in the art and can be used in any suitable forrn for developing an exposed photographic element.
• aqueous silver halide developer solution or liquid concentrate as a component of a solid particulate developer composition suitable for dissolving in an aqueous solvent, as a viscous developer composition containing various thickening agents, as a packaged component of a kit for mixing with various photographic processing agents or as a component of a fusible solid such as a solid comprising a homogeneous mixture of an alkylene oxide polymer and a developing agent of the invention which melts above about room temperature, and the like.
• the compounds of this invention when used as antifoggants, they can be incorporated in a conventional developing solution or incorporated in the silver halide photographic emulsion. If desired, they may be used both both in the developing solution and in the emulsion and various combinations of species Within the generic class of these compounds may be used, such as mixtures or a combination of different species with respect to the incor porated antifoggant and the antifoggant in the developing solution.
• a silver halide emulsion such as a medium-grained silver bromoiodide gelation emulsion is prepared and a bridged dihydroxy compound of this invention, such as 3,6-dihydroxy benzonorbornane is added to the emulsion in an amount which may usefully be about 6.0 g./rnole of silver halide present in the photographic emulsion.
• concentrations of 1.2 to 6.0 g./mole of silver halide can be used although the amount can be varied depending upon the particular compounds, and the presence of other components including other antifoggants and developers.
• a species can be employed as an antifoggant, whereas a different species can be incorporated as a developing agent.
• the antifoggant can be in the developing solution, such as in an amount of about 100-300 mg./l. However, of course, this may be varied widely depending upon other addenda in the developing solution and in the emulsion.
• activator baths can be used with an emulsion containing an incorporated developer of the invention, such as for example, an aqueous solution of an alkaline material, such as sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, mixtures of sodium hydroxide and sodium sulfite, etc.
• Suitable ba'ths can comprise, for example, an aqueous solution containing about 1 percent sodium hydroxide and percent sodium sulfite.
• a bath of the latter type is quite suitable for developing an exposed emulsion layer in about 30 seconds when the activator bath is at about 68 F. Modifications can easily be made in the activator baths Without departing from the spirit and scope of the invention.
• an aqueous solution comprising about 4 percent sodium carbonate and 5 percent sodium sulfite produces development in about 30 seconds at about 68 F.
• Another aqueous activator solution comprising 2 percent sodium hydroxide and 5 percent sodium sulfite produces useful photographic images in a few seconds when heated at 130 F.
• Particularly useful activator solutions have a pH of at least 8.5.
• the activator solutions may be applied to an exposed photographic element in any number of known ways, such as, by dipping, spraying, or other suitable surface applications. If desired, a thickener can be added to the activator solution to increase the viscosity of the composition and make it more adaptable for continuous processing. Viscous compositions can then be removed by squeegeeing or water spraying.
• the concentration of the developing agents used in our invention will vary depending upon the particular chemical compound involved and the location of the compound Within the puhotographic element. That is, if the developing agent of the invention is incorporated within the silver halide emulsion undergoing development, it may be desirable to use a somewhat different concentration than would be used if the developer were incorporated in a layer contiguous to the photographic silver halide emulsion.
• the useful concentration of developer .for incorporation in the emulsion is from about 0.01 to about 4.0 moles/mole of silver halide. A particularly useful range is from 0.1 to 2.0 moles/mole of silver halide, with especially useful results being obtained within the range of about 0.4 to 1.0 mole/mole of silver halide. For incorporation in a layer contiguous to the silver halide emulsion layer, somewhat larger concentrations of developer can be tolerated without adverse effects.
• Photographic silver halide emulsions useful in our invention comprise any silver halide emulsions ordinarily employed as developing out emulsions, such as silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, silver bromide and silver bromoiodide developing-out emulsions.
• Any of the conventionally employed water-permeable hydrophilic colloids can be employed in the silver halide emulsions, or in a layer contiguous thereto.
• Typical water-permeable hydrophilic colloids include gelatin, albumin, polyvinyl alcohol, agar agar, sodium alginate, hydrolyzed cellulose esters, hydrophilic polyvinyl copolymers, etc.
• the silver halide emulsions of our invention may be chemically sensitized with compounds of the sulfur group, e.g. sulfur sensitizers, selenium sensitizers, tellurium sensitizers, noble metal salts, such as gold or reduction sensitizers with reducing agents or combinations of such sensitizers.
• sulfur sensitizers e.g. sulfur sensitizers, selenium sensitizers, tellurium sensitizers, noble metal salts, such as gold or reduction sensitizers with reducing agents or combinations of such sensitizers.
• the silver halide emulsions of this invention may contain spectral sensitizers, such as the cyanines, merocyanines, styryls, hemicyanines, speedincreasing compounds such as polyalkylene glycols, onium salts and thioethers, stabilizers such as azaindenes, cadmium and other divalent salts, mercury compounds, azoles and mercaptans, coating aids, such as non-ionic, anionic and amphoteric surface active agents, etc.
• spectral sensitizers such as the cyanines, merocyanines, styryls, hemicyanines, speedincreasing compounds such as polyalkylene glycols, onium salts and thioethers, stabilizers such as azaindenes, cadmium and other divalent salts, mercury compounds, azoles and mercaptans, coating aids, such as non-ionic, anionic and amphoteric
• the addenda which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other non-optically sensitized emulsions, they may also be used in orthochromatic, panchromatic, infrared sensitive emulsions, and lith type emulsions which usually are developed to high contrast in developing solutions having a low concentration of sulfite ions. They may be added to the emulsion before or after any sensitizing dyes which are used.
• the agents described herein can be used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other colorgenerating materials, emulsions of the mixed-packet type, such as described in Godowsky, U.S. Patent 2,698,794, issued Jan. 9, 1955; or emulsions of the mixed-grain type, such as described in Carroll and Hanson, U.S. Patent 2,592,243.
• auxiliary developing agents include polyhydroxybenzene developing agents, such as hydroquinone, t-butylhydroquinone, chlorohydroquinone, pyrocatechol and the like, p-aminophenols, such as 2,4-diaminophenols, and 3- pyrazolidone compounds containing an alkyl, e.g. methyl or ethyl, or aryl substituent, e.g. phenyl, p-tolyl, etc.
• polyhydroxybenzene developing agents such as hydroquinone, t-butylhydroquinone, chlorohydroquinone, pyrocatechol and the like
• p-aminophenols such as 2,4-diaminophenols
• pyrazolidone developing agents can contain an acyl or acyloxy substituent which can be hydrolyzed from the 3-pyrazolidone compound by treatment with the above activator solutions to produce the desired auxiliary developing compound.
• Typical auxiliary developing agents include, for example, 1-phenyl-3-pyrazolidone, 1-p-tolyl-3- pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, l-acetamidophenyl 3 pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone (Enol ester), Z-(pyridinium acetyl)-1-phenyl-3- pyrazolidone chloride, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, l-phenyl-Z-benzoyl-3-pyrazolidone, 1-phenyl-2-lauroy1-3-pyrazolidone, 1- phenyl-2-chloroacety
• auxiliary developing agents can be varied and, of course, no auxiliary developing agent need be employed unless so desired.
• Useful concentrations of auxiliary developing agents vary from about 0.01 mole to 2.0 moles per mole of developing agent. Depending upon the particular auxiliary developing agent employed, larger or smaller quantities can be used.
• the developers of the invention can be used in colloid transfer processes and elements such as that set out in U.S. Patent 2,596,752, issued May 13, 1952.
• the developing agents of this invention can be used in emulsions intended for use in diffusion transfer processes which utilize the undeveloped silver halide in the nonimage areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer.
• diffusion transfer processes which utilize the undeveloped silver halide in the nonimage areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer.
• Such processes are described in Rott U.S. Patent 2,352,014, issued June 20, 1944, and Land U.S. Patents 2,584,029, issued I an. 29, 1952; 2,698,236, issued Dec. 28, 1954, and 2,543,181, issued Feb. 27, 1951; and Yackel et al. U.S. Patent 3,020,155, issued Feb. 6, 1962.
• the developing agents of the invention can, for instance, be employed in photographic dye developer image transfer systems, such as described in U.S. Patents 3,253,915Weyerts et al., issued May 31, 1966; U.S. Patent 2,559,643-Land, issued July 10, 1951; and U.S. Patent 2,698,798-Land, issued Jan. 4, 1955.
• a dye diffusion transfer takes place.
• Compounds which contain in the same molecule, both the chromoporic system of a dye and a photographic silver developing moiety have been described as useful compounds in photographic elements for preparing color images by diffusion transfer processes. Such compounds are commonly called dye developers.
• Photographic elements containing such dye developers generally comprise a plurality of photosensitive silver halide emulsions wherein each of the emulsions is selectively sensitized to a different region of the spectrum.
• a dye developer is typically positioned contiguous to the silver halide in each of such emulsions.
• Such a photographic element can according to the invention contain a developer within the scope of the above structures in one of the layers of the element, such as in a gelatin overcoat layer.
• the photographic element after exposure can he processed with an alkaline composition with the latent image being developed in the image areas With the dye developers, this development immobilizing the dye developers in such image areas.
• the dye developers in the unexposed image areas diffuse to the surface imagewise and are transferred to a reception layer or receiving sheet to form a positive multicolor image.
• such dye diffusion transfer systems can be used to prepare single color transfer prints.
• the developers within the scope of the invention can typically be employed as auxiliary developers in dye developer image transfer elements and processes.
• Bridged 5,8 dihydro 1,2 dihydroxynaphthalenes or bridged 5,6,7,8 tetrahydro 1,2 dihydroxynaphthalenes, such as 5,8-methano-5,6,7,8-tetrahydro-1,2-dihydroxynaphthalene, within the scope of the above structures are suitable according to the invention as tanning developers.
• These compounds can 'be used as so-called external tanning developers, such as in aqueous developer solutions in which an exposed photographic emulsion is immersed until the desired density is achieved. They can also be used as so-called incorporated tanning developers, such as in colloid transfer processes and systems.
• tanning developers are especially suitable in coatings of the type described in U.S. Patent 2,596,756.
• a coating of the type described in U.S. Patent 2,596,756 containing 5,8-methano-5,6,7,8-tetrahydro-1,2- dihydroxynaphthalene when activated with an alkali metal carbonate and urea solution and brought into contact with a receiving sheet according to U.S. Patent 2,596,756, produces a good colloid transfer.
• Example 1 A product is prepared having the following layers:
• Stripping layer comprising gelatin and cellulose nitrate.
• This coating strips easily, the Dmax is high, and has good development uniformity (no mottle).
• Example 2 Example 1 is repeated except hydroquinone is used as a tanning developing agent in place of 3,6-dihydroxybenzonorbornane. When exposed and processed as in Example 1, this coating does not strip easily, and the Dmax is too low. This coating has poor development uniformity (high mottle).
• Example 3 Example 1 is repeated except that 4-phenyl catechol is used as the tanning developing agent in place of 3,6-dihydroxybenzonorbornane.
• this coating does not tan at low density levels and therefore gives poor dot quality.
• This coating also has poor development uniformity (high mottle).
• Example 4 Example 1 is repeated except that chlorohydroquinone is used as the tanning developing agent in place of 3,6-dihydroxybenzonorbornane. When exposposed and processed as in Example 1, this coating does not strip easily and the Dmax is too low. This coating also has poor development uniformity (high mottle).
• Example 5 A fine grain unhardened chlorobromide emulsion is hand coated on a cellulose acetate film support at a coverage of mg. silver per square foot.
• the tanning developer to be tested is incoporated in the emulsion at a coverage of 0.13 mole per mole of Ag.
• the gelatin has a coverage of 236 g. of gelatin/ mole Ag.
• samples are activated 30 seconds in a 5 percent solution of sodium carbonate and then sprayed for 30 seconds with 110 F. water. The unexposed areas are washed away in the 110 F.
• Example 6 A photographic element as described in Example 1 is prepared except that the tanning developer is omitted from the silver halide emulsion. Instead, the tanning developer, 3,6-dihydroxybenzonorbornane, is incorporated in the developing solution in the amount of g. per liter. The remaining steps in the processing cycle are used as in Example 1. It is found that a similar satisfactory coating is obtained which strips easily at a high Dmax and good development uniformity.
• Example 7 To 13.0 ml. of a silver chlorobromide emulsion is added 2.0 ml. of 10 percent saponin, g. of 10 percent gelatin, 213 mg. of 2-methyl-5,8-methano-5,S-dihydro-1,4-dihydroxynaphthalene dissolved in methanol, 1.2 ml. of sodium bisulfite solution (1 mg./ml. distilled water), and distilled water to 50 ml. (5.5 kg./mole Ag, 236 g. gelatin/mole Ag). The emulsion is coated on cellulose acetate film support at a coverage of about 190 mg. Ag/ft.
• Example 8 To 26 g. of 10 percent gelatin is added 2 ml. of 10 percent saponin, 4 ml. of sodium bisulfite solution (mg./ml.), and 680 mg. of 2-methyl-5,8-methano-5,8-dihydro-1,4- dihydroxynaphthalene dissolved in methanol, 0.8 ml. of 10 percent formaldehyde and distilled Water to 50 ml. The mixture is coated on cellulose acetate film support at a coverage of 500 mg. gelatin/ft), and dried. Over this coating is coated the emulsion containing the compound as described in Example 7 except that it also contains hardener.
• dihydro-1,4-dihydroxynaphthalene and 5,8-methano-5,8- dihydro-I,4-dihydroxynaphthalene are coated at equimolar levels in an identical manner and provide satisfactory results.
• Example 9 To 13 ml. of a silver chlorobromide emulsion are added 2.0 ml. of 10 percent saponin, 15 g. of 10 percent gelatin, 230 mg. of Z-methyl-S,8-ethano-5,8-dihydro-1,4- dihydroxynaphthalene dissolved in 18.5 ml. methanol containing 0.25 ml. dimethylacetamide, and 1.2 ml. of sodium bisulfite solution (1 mg./ml. distilled water) (5.5 kg./mole Ag, 236 g. gelatin/mole Ag). The emulsion is coated on a cellulose acetate support at a coverage of about 190 mg.
• Example 10 A sample of 270 mg. of l,4,5,8-tetrahydro-1,4; 5,8- dimethanoanthracene-9,10-diol is coated, exposed and processed in the same manner as Example 9. All of the emulsion is removed from the coating by the spray of water at 110 F. indicating no tanning by oxidized developer.
• Example 11 A mixture of 1.63 g. of 2-phenyl-5,8-mehano-5,8-dihydro-1,4-dihydroxynaphthalene and 30 ml. water is ball milled for 18 hours. From the 23.6 g. of foamy mixture recovered, 6.5 g. of clear water i decanted leaving 17.1 g. of mixture representing 1.2 g. of the compound. A 4.1 g. sample (286 mg. of compound) of the mixture is added to a mixture of 13 ml. of a chlorobromide emulsion, 2 ml. of 10 percent saponin, 15 g. of 10 percent gelatin and 1.2 ml. of sodium bisulfite solution (1 mg./ml.
• Example 12 A sample of 200 mg. of 5,8-methano-5,6,7,8-tetrahydro- 1,4-dihydroxynaphthalene is coated, exposed and processed in the same manner as Example 9. The emulsion is removed only in the non-exposed and very weakly exposed region of the coating by the stream of 110 F. water indicating good tanning in the more heavily exposed regions.
• Example 13 A mixture of 1.24 g. of 5,8-ethano-5,6,7,8-tetrahydro- 1,4-dihydroxynaphthalene and 30 ml. of water is ball milled for 18 hours from which 24.1 g. of a foamy mixture is recovered, representing 955 mg. of compound.
• a 5.5 g. sample of the mixture (218 mg. of compound) is coated in the same manner as Example 11 and exposed and processed in the same manner as Example 9. The emulsion i removed only in the non-exposed and the very weakly exposed regions of the coating by the stream of 110 F. water indicating good tanning in the more heavily exposed regions.
• Examples 9, 10 and 11 show non-tanning development occurring with 2-substituted bridged 1,4-dihydroxynaphthalenes and an anthracene-1,10-diol derivative While Examples 12 and 13 show tanning development with derivatives lacking such Z-substitution.
• Example 14 A gelatin undercoat containing developing agent is prepared by mixing 26 g. of 10 percent gelatin, 2 ml. of 10 percent saponin, 735 mg. of Z-methyl-5,8-ethano-5,8-dihydro-1,4-dihydroxynaphthalene dissolved in 17 ml. methanol and 0.25 ml. dimethylacetamide, 4 ml. of sodium bisulfite solution (1 mg./ml. distilled water), and 0.8 ml. of 10 percent formaldehyde. The mixture is coated on cellulose acetate support at a coverage of 500 mg. gelatin/ft. and dried. Over this undercoat is coated the emulsion prepared like Example 9 except for having in addition 0.6 ml.
• Example 15 A gelatin undercoat containing developing agent is prepared and coated exactly like that of Example 14 except for using 865 mg. of 1,4,5,8-tetrahydro-1,4,5,8-dimethanoanthracene-9,10-diol as the developer. On this is coated the emulsion prepared like Example 10 except for having in addition 0.6 ml. of 10 percent formaldehyde. Two strips of the coating are exposed and processed exactly like those of Example 14.
• Example 16 A gelatin undercoat containing developing agent is prepared and coated exactly like that of Example 14 except that 12.9 g. of the ball milled mixture of Example 11, representing 910 mg. of 2-phenyl-5,8methano-5,8-dihydro-l,4-dihydronaphthalene is used as the developer and the undercoat mixture is taken to a total of 49' g. with Water. On top of this is coated the emulsion mixture prepared like Example 11 except for having in addition 0.6 ml. 10 percent formaldehyde. Two strips of the coating are exposed and processed exactly like those of Example 14.
• Example 17 A gelatin undercoat containing developing agent is prepared and coated exactly like that of Example 14 except that 640 mg. of 5,8-methano-5,6,7,8-tetrahydro-1,4-dihydroxynaphthalene is used as the developer. On this is coated an emulsion mixture prepared exactly like that of Example 12 except that 125 mg. of the compound is used and 0.6 ml. of 10 percent formaldehyde is added. Two strips of the coating are exposed and processed exactly like those of Example 14.
• Example 18 A gelatin undercoat containing developing agent is prepared and coated exactly like that of Example 14 except that 17.4 g. of the ball milled mixture of Example 13, representing 690 mg. of 5,8-methano-5,6,7,8-tetrahydro- 1,4-dihydroxynaphthalene is used as the developer and the 0 undercoat mixture is taken to a total of 49 g. with water. On top of this is coated the emulsion mixture prepared like Example 13 except for having in addition 0.6 ml. of
• Example 20 For activator development tests a gelatin undercoat of the developer is coated on cellulose acetate film support at a coverage of 500 mg. gelatin/ft. and dried. On top of this, an emulsion layer containing the developer is coated at a coverage of about mg. Ag 1 ft.
• the undercoat mixture is prepared by adding about 17 ml. of the developer solution to a mixture of 26 g. of 10 percent gelatin, 2 ml. of 1 0 percent saponin and 4 ml. of sodium bisulfite solution (1 mg./ml.) and then adding 0.8 ml. of 10 percent formaldehyde.
• the emulsion mixture is prepared by adding 18.5 milliliters of the developer solution to a mixture of 13 ml.
• the emulsion coat containing the developer is prepared as described above (except that the formaldehyde solution is omitted) and coated directly on cellulose acetate film support. Two strips of each coating are exposed, processed for 30 seconds in 5 percent aqueous sodium carbonate solution (68 F.), and immersed in stop bath. One strip is fixed in Kodak F-S fixing bath, washed and dried for evaluation of development. The other strip is subjected for 30 seconds to a spray of water at 110 F. All of the emulsions are removed from the coatings of compounds of Examples 3 and 7 but only emulsion in the unexposed areas is removed from coatings of compounds of Examples 1, 2, 5 and 6. The compound of Example 4 is not tested.
• ACTIVATOR A 1 liter working solution 45% potassium hydroxide solution ml 150 Sodium bisulfite grams 40 Potassium bromide do 2 Sequestering agent do 1 Water to make 1 liter.
• Example 21 When used as antifoggants, the following compounds are added to a medium-grained silver bromoiodide gelatin emulsion:
• the efficiency of the various antifoggants is determined by incubation of the emulsion after coating for one week at a temperature of 120 F. and at a relative humidity of 50 percent.
• the eificiency is determined by measuring speed, gamma, and fog of the incubated samples contalning an antifoggant and comparing these measurements with those of the same emulsion before incubation. Also, similar measurements are made on the same emulsion containing no antifoggant, before and after incubation.
• the exposures are made to an intensity scale test object on an Eastman Type 1b sensitometer and developed for 5 minutes at 68 F. in a developer of the following composition:
• the tested samples are subsequently fixed, washed, and dried in the conventional manner as shown in the following results:
• sitive silver bromoiodide 219 mg. of 86. 0
• a second photographic product, B is prepared the same as A with the exception that 8 milligrams per square foot of a developing agent, 4-methylphenyl hydroquinone is added to layer 9.
• a third photographic product, C is prepared the same as A with the exception that an amount, equimolar to that of the developing agent employed in B, of 2-phenyl-5,8- methano-5,-8-dihydro-1,4-dihydroxynaphthalene, is added to layer 9.
• Each of the photographic products, A, B and C, are exposed in the same way imagewise to light. Each is thereafter identically processed by applying an alkaline activator solution to the emulsion surface and superimposing identical receiver sheets thereover.
• the receiver sheets are composed of a white pigmented cellulose acetate support having a dye developer receiving layer containing a mixture of gelatin at a coverage of 300 mg. per square foot and 1-phenyl-S-mercaptotetrazole at a coverage of 15 milligrams per square foot.
• the receiver sheets and the products A, B and C are permitted to remain in contact for one minute at 21 C. and then stripped apart.
• the alkaline activator solution which is applied has the following composition:
• Patent 2,698,798, Land produces unexpected lower minimum density, and increased relative speed in the green and blue sensitive layers.
• Example 23 A multilayer color photographic element is prepared by coating the following layers on a cellulose acetate support employing the color formers and silver halide emulsions set out in US. Patent 3,046,129:
• the element is exposed imagewise and processed to a color negative by (a) immersing the element for several seconds in a bath having the following composition:
• Example 24 The procedure set out in Example 23 is repeated with the exception that 79.2 mg./ft. of 5,8-methano-5,8-dihydro-1,4-dihydroxynaphthalene are incorporated in layer 1, 92.3 mg./ft. of this compound are incorporated in layer 4 and 140.2 mg./ft. of this compound are incorporated in layer 7.
• a single red-sensitive layer of silver bromoiodide emulsion is prepared and coated on a cellulose acetate support as set out in US. Patent 3,046,129. 104 mg./ft. of 5,8- methano 5,6,7,8 tetrahydro 1,4,7,9 tetrahydroxynaphthalene, also known as exo-anti-1,2,3,4-tetrahydro- 19 1,4-methanonaphthalene-2,5,8,9-tetrol and represented by the formula on l noon 45% KOH ml 150 NaHS g KBr g 2 Distilled water to 1 liter.
• Example 26 The procedure set out in Example 25 is repeated with the exception that 94 mg./ft. of 2-methyl-5,8-methano- 5,8-dihydro-l,4-dihydroxybenzene is incorporated in the red-sensitive silver bromoiodide emulsion before coating on the support. Upon processing as in Example 25, a developed image is produced.
• Example 27 The procedure set out in Example 25 is repeated with the exception that 88 mg./ft. of 5,8-methano-5,6,7,8- tetrahydro-l,4-dihydroxynaphthalene is incorporated in the red-sensitive silver bromoiodide emulsion before coating on the support. Upon processing, as in Example 25 a developed image is produced.
• Bridged 5,6,7,8-tetrahydro-1,2 dihydroxynaphthalenes can be prepared b the following steps respectively, which refer to the preparation of 4-phenyl-5,8-methano 5,6,7,8- tetrahydro-l,Z-dihydroxynaphthalene, but are not limited thereto:
• This o-quinone aduct can also be prepared by oxidation with potassium ferricyanide buffered with sodium acetate in an aqueous acetone system.
• Example 28 This example employs 4-methyl-5,8-methano-5,6,7,8- tetrahydro-1,2-dihydroxynaphthalene as an incorporated developer in a silver halide emulsion and in an overcoat over the emulsion.
• a gelatin layer containing 4-methyl-5,8-methano-5,6,7, S-tetrahydro-1,2-dihydroxynaphthalene is coated as a cellulose acetate support at the rate of 0.7 millimoles of developer per square foot and 500 milligrams of gelatin per square foot.
• a fine grain silver bromoiodide photographic emulsion is coated over this layer at the rate of 190 mg. Ag/ftF, 415 mg. of gelatin/ft. and 0.224 millimoles of 4-methyl-5,S-methano-S,6,7,8-tetrahydro-l,2- dihydroxynaphthalene.
• the ratio of the bridged 1,2-dihydroxynaphthalene compound to silver is 0.53 mole of developer per mole of silver.
• Strips of the resulting photographic element are exposed imagewise and processed for 5 seconds at 21 C. in an activator solution having the following composition:
• the strips are then immersed in an acetic acid stop bath for a few seconds, fixed and washed with water.
• Example 29 This example employs 5,S-methano-5,6,7,8-tetrahydro- 1,2-dihydroxynaphthalene in an aqueous alkaline developer solution for developing a latent image in a silver halide photographic emulsion.
• An aqueous developer solution containing 0.4% by weight of 5,8-methano-5,6,7,S-tetrahydro-1,2-dihydroxynaphthalene and 4% by weight sodium carbonate is prepared by admixing the sodium carbonate and bridged-1,2- dihydroxynaphthalene into the appropriate amount of water.
• the amounts used may be varied widely depending upon the emulsion used, whether the emulsion contains 21 a developing agent, the result desired, the other components in the developing solution such as one or more other developers in admixture, etc.
• the supports which may be used for the silver halide emulsions referred to herein include those customarily used, such as paper, glass, metal, wood, cloth, polymeric materials such as polyolefins, polyesters, cellulose esters, polyamides, polystyrene, polycarbonates, etc.
• a particularly useful support is paper coated with a polyolefin such as polyethylene.
• a photographic silver halide element comprising a support having a layer containing a compound of the class consisting of bridged dihydro-1,4-dihydroxynaphthalenes, bridged tetrahydro-1,4-dihydroxynaphthalenes, bridged dihydro-1,Z-dihydroxynaphthalenes, bridged tetrahydro-1,Z-dihydroxynaphthalenes, bridged tetrahydro- 9,IO-dihydroxyanthracenes, bridged heXahydro-9,10-dihydroxyanthracenes, and bridged octahydro-'9,l0-dihydroxyanthracenes.
• a photographic element as in claim 1 comprising a support having a photographic silver halide emulsion layer containing an antifoggant concentration of a compound of the class consisting of bridged dihydro-l,4-dihydroxynaphthalenes, bridged tetrahydro 1,4 dihydroxynaphthalenes, bridged dihydro-l,2-dihydroxynaphthalenes, bridged tetrahydro-1,2-dihydroxynaphthalenes, bridged tetrahydro-9,IO-dihydroxyanthracenes, bridged hexahydro- 9,lO-dihydroxyanthracenes, and bridged octahydro-9,10- dihydroxyanthracenes.
• a compound of the class consisting of bridged dihydro-l,4-dihydroxynaphthalenes, bridged tetrahydro 1,4 dihydroxynaphthalenes, bridged dihydro-l,2-dihydroxynaphthalenes,
• said colloid layer contains at least one of (a) 5,8-methano or 5,8-ethano-5, 8-dihydro-1,4-dihydroxynaphthalene;
• said colloid layer contains at least one of 1,4,*5,8-tetrahydro- 1,4; 5,8-dimethano or 1,4; 5,8-diethanoanthracene-9,10- diol,
• a photographic element as in claim 1 containing at least one layer containing a color coupler compound.
• a photographic element as in claim 1 comprising a support having thereon at least one photographic layer sensitive to the blue region of the spectrum, at least one photographic layer sensitive to the green region of the spectrum and at least one photographic layer sensitive to the blue region of the spectrum, containing in at least one layer of said element a compound of the class consisting of bridged dihydro-l,4-dihydroxynaphthalenes, bridged tetrahydro-1,4-dihydroxynaphthalenes, bridged dihydro- 1,Z-dihydroxynaphthalenes, bridged tetrahydro-1,2-dihydroxynaphthalenes, bridged tetrahydro 9,10 dihydroxyanthracenes, bridged hexahydro-9,IO-dihydroxyanthracenes, and bridged octahydro-9,IO-dihydroxyanthracenes.
• a photographic silver halide developer composition comprising an alkaline development activator, a compound of the class consisting of bridged dihydro-1,4-dihydroxynaphthalenes, bridged tetrahydro 1,4 dihydroxynaphthalenes, bridged dihydro-l,Z-dihydroxynaphthalenes, bridged tetrahydro-l,Z-dihydroxynaphthalenes, bridged tetrahydro-9,IO-dihydroxyanthracenes, bridged octahydro- 9,10-hydroxyanthracenes, bridged heXahydro-9,l0-dihydroxyanthracenes and an auxiilary silver halide developing agent.
• a composition as in claim 14 comprising an aqueous alkaline silver halide developer solution.
• a composition as in claim 14 comprising a solid silver halide developer composition.
• composition as in claim 14 wherein said compound is 5,8-methano or 5,8-ethano-5,8-dihydro-1,2 or 1,4-dihydroxynaphthalene.
• composition as in claim 14 wherein said compound is 5,8-methano or 5,8-ethano-5,6,7,8-tetrahydro- 1,2- or 1,4-dihydroxynaphthalene.
• composition as in claim 14 wherein said compound is 2-l0wer alkyl or 2-phenyl, 5,8-meth'ano or 5,8- ethano-5,8-dihydro-1,4-dihydroxynaphthalene. thalene.
• composition as in claim 14 wherein said compound is 1,4,5,8-tetrahydro-1,4; 5,8-dimethanoanthracene- 9,10-dio1.
• a process for developing a latent image in an exposed photographic silver halide emulsion comprising contacting said emulsion with an aqueous alkaline solution containing a compound of the class consisting of bridged dihydro-1,4-dihydroxynaphthalenes, bridged tetrahydro-1,4-dihydroxynaphthalenes, bridged dihydro-1,2- dihydroxynaphthalenes, bridged tetrahydro-l,Z-dihydroxynaphthalenes, bridged tetrahydro-9,10 dihydroxyanthracenes, bridged hexahydro-9,IO-dihydroxyanthracenes, and bridged octahydro-9,10-dihydroxyanthracenes.
• a compound of the class consisting of bridged dihydro-1,4-dihydroxynaphthalenes, bridged tetrahydro-1,4-dihydroxynaphthalenes, bridged dihydro-1,2- dihydroxy

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• 1967
  • 1967-07-13 US US653031A patent/US3459549A/en not_active Expired - Lifetime
• 1968
  • 1968-06-28 FR FR1570337D patent/FR1570337A/fr not_active Expired
  • 1968-07-01 BE BE717467D patent/BE717467A/xx unknown
  • 1968-07-02 GB GB31519/68A patent/GB1203845A/en not_active Expired

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