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
  • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

• this invention relates to photographic elements containing a ruthenium cationic complex having a predominance of ammine or amine ligands. In another aspect. this invention relates to photographic elements containing such com plexes and further containing an azaindene.
• this invention is comprised of a photographic element having coated thereon at least one layer comprising a photographic silver halide emulsion.
• a development accelerating amount of a ruthenium cationic complex having a predominance of coordination bonds formed by ligands chosen from the class consisting of ammine and amine ligands.
• the cationic ruthenium complex is present in a concentration of less than IOU mg per mole of silver.
• the present invention comprises the above described photographic element further including in or adjacent the emulsion layer at least one azaindene.
• Cadmium salts have long been employed in the pho tographic field for a variety of purposes. For example. it is stated in Glafkides. Photographic Chemistry". Volume l. I958. page l that cadmium chloride can be used to increase the contrast in the silver halide emulsion.
• US Pat. No. 3.488.709 issued Jan. 6. I970. to Sidebotham teaches that cadmium bromide stabilizes silver halide emulsions precipitated in the pres ence of rhodium salts in that it reduces the loss of con trast and speed change upon storage and also that cad mium bromide acts to increase the contrast in a synergistic manner.
• R represents a hydrogen atom. an alkali metal atom or an ammonium radical
• M represents a metal atom selected from group ⁇ III of the periodic arrangement of the elements hming an atomic weight greater than 100. i.e.. ruthenium. rhodium. palladium. osmium. iridium and platinum
• X represents a halogen atom. c.g.. a chlorine or bromine atom.
• Smith and 'I'ri ⁇ elli recognize that these compounds will fog photographic emulsions and. therefore. suggest the use of concentrations below that which produces any substantial fog. Quantities of from (1.8 to somewhat less than 39.4 mg of metal compound for each IOO grams of silver in the emulsion are suggested. It is to be noted that ammonium radicals are Lewis acids. whereas ammonia and amine compounds are Lewis bases. Further. in the above Smith and Trivelli compounds. the metal atom is coordinated in a complex having an overall negative charge.
• trivalent cationic complexes of trivalent metals such as Ru(III). Cotlll) and Cr(lll) with amine or amine li' gands to be useful addcnda for lithographic silver chloride emulsions.
• These trivalent cationic complexes when incorporated in concentrations of from 0.2 to 5.0 grams per mole of silver are disclosed to promote increased photographic speed and development acceleration in a manner similar to the cadmium salts previously employed for this purpose.
• the contrast obtained with photographic elements utilizing rutheniumtlll) complexes was noted to be too low for use in lithographic elements. This is because ruthenium(lll) complexes when employed in the concentration levels investigated produce an elevated level of emulsion fogging.
• cobalt complexes are effective only where the cobalt is in its trivalent oxidation state. It is surprising that the effectiveness of ruthenium is not de pendent on its being in its trivlcnt oxidation state. Additionally. whereas cobalttlll) and chromium(lll) com plexes are disclosed in Ser. No. 3 l 2.1 59 to be sensitiz ers and development accelerators only for silver halide emulsions in which the halide consists of at least 50 mole percent chloride. the ruthenium complexes of my present invention are effective in sensitizing and devel opmcnt of silver halide emulsions generally.
• cobaltl III cobaltl III
• chromium(lll) complexes were disclosed in my earlier filed patent application only in highcontrast lith-type silver halide emulsions.
• the ruthenium complexes as herein disclosed are useful in proper concentration ranges in improving both high and low contrast emulsions.
• the ruthenium complexes are distinctly superior to cobalttlll) and chromium(lll) complexes when em- 3 ployed in high contrast emulsions lacking alkylenc oxide development restrainers. Additionally.
• the emulsions containing the rutheniunt complexes of this invention are useful with a wider range of developers than cobalt(lll) or chromiumtllll complexes. it is. ac cordingly. apparent that the ruthenium complexes are considerably more versatile in providing sensitization and development acceleration than eobalttlll) and chromium-(ll!) complexes.
• the ruthenium complexes herein disclosed also exhibit unique and surprising properties as regards the ligands associated therewith. While l have found ruthe nium complexes containing only ammine or amine ligands to be distinctly superior. l have further observed that ruthenium complexes containing one or two ruthenium coordination bonds formed by ligands other than ammine or amine ligands afford substantial sensitization and development acceleration improvement and are superior to corresponding cobalt(lll) and chromiumtlll) complexes. even when differences in effective concentrations are ignored.
• the ruthenium complexes herein employed not only act as sensitizers and development accelerators. but they also act to reduce the development time dependence of the characteristic H and D curves of the photographic elements in which they are incorporated.
• H and D characteristic curves are translated along the log F. axis as a function of development time. Shorter develop ment times show the photographic elements to be of slower speed while longer development periods show the same photographic elements to be faster. Since some variation in development times occurs as a practical matter in photographic element processing. it is desirable to manufacture photographic elements which can tolerate a substantial latitude in processing times. If a pair of identical photographic elements lacking the ruthenium complexes of this invention are processed at differing development times. they will exhibit a substantial difference in their log F.
• the cationic ruthenium complexes employed in the practice of this invention comprise a ruthenium ion surrounded by certain other molecules which are referred to as ligands.
• the ruthenium ion is a Lewis acid; the ligands are Lewis bases. Werner complexes are well known examples of these complexes.
• ruthenium can exhibit a variety of valences. Because of their availability. ru thenium complexes incorporating ruthenium(ll) and ruthenium(lll) are preferred. although the effective ness of the cationic ruthenium complexes has not been observed to depend on the oxidation state ofthe ruthenium.
• the cationic ruthenium complexes employed in the practice of this invention include a predominance of ammine or amine ligand coordination bonds.
• the amine ligands include primary. secondary and tertiary amine ligands as well as diamine ligands.
• the amine ligands are preferably aliphatic amines and are most preferably comprised of alkyl. alkylenc and alkanol aliphatic moieties. Each aliphatic moiety preferably in cludes 6 or fewer carbon atoms. Dialkanol amines have been found particularly useful in forming bidentate ligands as have alkylene diamines.
• Bidentatc ligands which form with the ruthenium atom 5 to 8 membered rings have been found to produce particularly stable complexes.
• Exemplary preferred ammine and ligandforming compounds include ammonia. ethylene diaminc. trimethylene diamine. diethanol amine. dipropanol amine. diethylene triamine. alkyltetramines.
• a minor proportion of the coordination bonds making up the cationic ruthenium complex can be provided by ligands other than ammine or amine ligands.
• a ruthenium(ll) and (Ill) complex can contain 1 or 2 monodentate ligands. such as water. halogen. thiocyanate. etc. or a single bidentate ligand.
• anions associated with the foregoing complex cations Any anion which does not exert undesirable effects upon the finished photographic element may be employed.
• anions which will be found useful may be listed chloride. bromide. sulfite. sulfate. perchlorate. nitrite. nitrate. zinc bromide. tetrafluoroborate. hexafluorophosphate. thiocyanatc. dithionatc. methyl sulfonate. tolyl sulfonate. and the like.
• the ruthenium complexes employed in the practice of this invention are incorporated within a silver halide emulsion or in a layer adjacent to a silver halide emulsion layer.
• the silver halide emulsions can comprise. for example. silver chloride. silver bromide. silver bromoiodide. silver chlorobromidc. silver chloroiodide. silver chlorobromoiodide crystals or mixtures thereof.
• the emulsions can be coarse or fine grain emulsions and can be prepared by a variety of techniques. eg. single jet emulsions such as those described in Trivelli and Smith. The llmmgruphir Journal. Vol. LXXIX. May. I939 (pages 33tl-338l. double jet emulsions.
• Silver halide emulsions can form latent images predominantly on the surface olthc silver halide grains. or predominantly on the interior of the silver halide grains. such as those described in Davey et al. US. Pat. No. 2.592.250 issued May 8. 1952; Porter et al. US. Pat.
• the ruthenium complexes employed in the practice of this invention will produce sensitization and development acceleration when incorporated in a photographic element in one or more silver halide emulsion layers or in a layer immediately adjacent thereto in a concentration of as much as 5.0 grams per mole ofsilver. as indicated in my abovenoted earlier filed patent application. However. since fogging increases dramatically at higher concentration levels. concentrations of the ruthenium complexes below 1.0 gram per mole silver are presently contemplated.
• the ruthenium complexes remain highly effective as sensitizers and development accelerators in concentration ranges of from 100 to 0.1 mg of ruthenium complex per mole of silver while their emulsion fogging characteristic is dramatically reduced. Accordingly. at concentrations below 100 mg per mole of silver. the ruthenium complexes can be employed in silver halide emulsions generally. including particularly those requiring high contrast. For most applications. I prefer to incorporate from 50 to 0.5 milligrams ruthenium complex per mole of silver. Generally. concentrations offrom about to l milligram per mole silver have been observed to be optimum concentration ranges in photographic ele ments.
• the photographic silver halide emulsions employed in the practice of this invention are lithographic silver halide emulsions in which the halide generally comprises at least about 50 mole percent chloride. up to about 10 mole percent iodide and any remaining halide being bromide.
• these emulsions are referred to herein as lithographic silver halide emulsions.
• These high contrast emulsions preferably contain at least 60 mole percent chloride. less than 40 mole percent bromide and less than 5 mole percent iodide.
• the silver halides employed in the practice of this invention can be precipitated in the presence of a rhodium salt.
• a rhodium salt as disclosed in Sidebotham LES. Pat. No. 3.488.709. cited above and British Pat. No. 775.197.
• Typical useful rhodium salts are. for example. rhodium chloride. rhodium trichloridc. rhodium ammonium chloride. etc.
• the rhodium salts can be employed in any concentration which is effective for the intended purpose. Especially good results are obtained when the concentration is from about 0.01 to about 0.35 milligram per mole of silver halide.
• the photographic elements of this invention further comprise at least one azaindene. locted either in the photogrphic silver halide emulsion layer or in a layer immediately adjacent thereto.
• the azaindcne can be incorporated for the purpose of re ducing fog formation within the photographic element attributable to the presence of the cationic ruthenium complex.
• the azaindene also has a sensitizing effect.
• the azaindene will generally be present in a concentration of from about 0.2 to about 5.0 grants per mole of silver. preferably from about 0.3 to about 3.0 grams per mole of silver and. most preferably. from about 0.5 to about 1.0 gram per mole of silver.
• 4-hydroxy-6-alkyll.3.3u.7-tetrazaindenes such as. 4-hydroxy-6-mcthyll.3.3u,7-tctrazaindene. 5-carboxy4-hydroxyl .3.3u.7- tetrazaindcne. (i-methyl-l.3.3u.7'tetrazindene-4-thiol. 5.7-dimethyl-4.6-dioxo-4.5.6.7 tetrahydro l .2.3.5.7- pentazaindene.
• 6-phenyl-l .3 .3a.7-tetrazaindcne-4- thiol 5-broino-4hydroxy-o-methyl-l.3.3u.7 tetrazaindene-4-thiol. 2.6-dimethyll .3.3u.7- tetrazaindene-4-thiol. 6-methyl-2-methylthio-1.3.3u.7- tctrazaindene-4-thiol. 5-ethyl-6-methyl-l .3.3a.7- tetrazaindene-4-thiol. 5-isobutyl-6-methyl- 1 .3.3u.7- tetrazaindenc-4 thiol. S-phenyll .2.3a.
• the silver halide emulsions of this invention can con vcniently be ortho-sensitixed or pairsensiti/ed with spectral sensitizing dyes. Sensitizing dyes useful in sensitiling these silver halide emulsions are described. for
• the silver halide emulsion can contain any of the hydrophilic water-permeable binding materials known in the art to be suitable for this purpose. Suitable materials include gelatin. colloidal albumin. polyvinyl compounds. cellulose derivatives. acrylamide polymers. etc. Mixtures of these binding agents can also be used.
• the binding agents for the emulsion layer of the photographic element can also contain dispersed polymer ized vinyl compounds. Typical synthetic polymers in elude those described in Nottorf U.S. Pat. No. 3.142.568 issued July 28. 1964; White U.S. Pat. No. 3.193.386 issued July 6. 1965; Houck et a1. U.S. Pat. No. 3.062.674 issued Nov. 6. 1962; Houck et a1.
• the vinyl polymers are generally em' ployed in concentrations in the range of about to about 80 percent. most often concentrations at least 50 percent. by weight. based on the weight of the binding agent.
• Silver halide emulsions wherein the binding agent contains dispersed polymerized vinyl compound provide particularly good results in eliminating drag streaks and dot distortions in lithographic materials.
• the silver halide emulsions can be sensitized using any of the well known techniques in emulsion making. for example. by digesting with naturally active gelatin or various sulfur. selenium. tellurium compounds and- /or gold compounds.
• the emulsions can be sensitized with salts of noble metals ofGroup Vlll ofthe Periodic Table which have an atomic weight greater than 100.
• the emulsions can also contain addenda which increase speed and/or contrast such as quaternary ammonium salts. thioether sensitizers or combinations thereof.
• Spectral sensitizers which can be used include the cyanines. mero cyanines. complex (trior tetranuclearl cyanines. holopolar cyanines. styryls. hemicyanines (e.g.. enamine cyanines). oxonols and hemioxonols.
• the silver halide emulsion can contain development modifiers that function as restrainers in silver halide emulsions requiring high contrast. such as lithographic silver halide emulsions. It is preferred to employ alkylcne oxides in the emulsion for this purpose.
• Typical useful alkylene oxides include polyethylene glycol. polyethylene glycol oleyl ether. polyethylene glycol eetyl ether. polyethylene oxide derivatives. block copolymers. such as those comprising blocks of polyoxypropylene. polyoxyethylene and the like. water-soluble organosilicone polyalkylenoxide polymers and the like.
• the alkylene oxide polymer can be used in any concentration effective for the intended purpose.
• the alkylene oxide polymer When the alkylene oxide polymer is present in the photographic element. good results are obtained when the concentration is less than about 2 grams per mole of silver in the silver halide emulsion.
• a preferred concentration range for the polymer in this embodiment is from about 10 to about 800 mg per mole of silver in the silver halide emulsion.
• cobalt( 111) or chromium(lll) cationic complexes can additionally be incorporated into the emulsion to supplement the action ofthe cationic ruthenium complex in sensitizing or accelerating development.
• cobaltl Ill and chromium(lll) cationic complexes are fully described in my previously filed patent application. noted above.
• the cobalt( Ill 1 and chromium( lll) complexes are octahedral complexes formed by the metal atom acting as a Lewis acid with other associated molecules or ligands acting as Lewis bases. These complexes have coordination numbers of 6.
• the cohalttlll) and chromium(lll) cationic complexes useful in the practice of this invention in combination with cationic ruthenium complexes are formed entirely of ammine or amine ligands. which can be identical to those previously described as useful in the ruthenium complexes.
• the cobalt( 11]) and chromium(lll) cationic complexes are useful in concentration ranges of from 0.2 to 5.0 grams per mole of silver.
• cobalt(lll) and chromium(lll) complexes can be located directly within an emulsion layer or layers or in one or more layers immediately adjacent thereto. similarly as the ruthenium complexes.
• the silver halide emulsions of this invention can also contain conventional addenda such as gelatin plasticizers. coating aids. antifoggants and hardeners as described in Product Licensing Index. Vol. 92. December. 1971. publication 9232. pages 107-110.
• the photographic emulsions above described can be coated 9 onto a photographic support to form one or more silver halide emulsion layers.
• One or more nonimaging layers can also be coated onto the support along with the silver halide emulsion layer or layers.
• the nonimaging layers can take the form of subbing layers. interlayers and/or overlayers of conventional character.
• the nonimaging layer be comprised of a hydrophilic. waterpermeablc binding material similar to those described in connection with the silver halide emulsions.
• the layers coated onto the photographic supports can be coated by various coating procedures including dip coating. air knife coating. curtain coating. or extrusion coating using hoppers of the type described in Beguin US. Pat. No. 2.681.294 issued June 15. 1954. If desired. two or more layers can be coated simulta neously by the procedures described in Russell U.S. Pat. No. 2.761.791 issued Sept. 4. 1956; Huges U.S. Pat. No. 3.508.947 issued Apr. 28. 1970; Wynn British Pat. No. 837.095 published June 9. 1960'. and Herzhof et :11. British Pat. No. 1.208.809 published Oct. 14. 1970. Also. silver halide layers can be coated by vacuum evaporation as described in British Pat. No. 968.453 published Sept. 2. 1964. and LuValle et al. U.S. pat. No. 3.219.451 issued Nov. 23. 1965.
• the photographic layers including silver halide emulsion layers and other layers of the photographic element. can be coated on a wide variety of supports.
• Typical supports include cellulose nitrate film. cellulose acetate film. polytvinyl acetal) film. polystyrene film. poly(ethylene terephthalate) film. polycarbonate film and related films or resinous materials. as well as glass. paper. metal and the like.
• a flexible support is employed. especially a paper support. which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer. particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms. such as polyethylene. polypropylene. ethylenebutene copolymers and the like.
• the ruthenium complexes. azaindenes and other addenda employed in the practice ofthis invention can be incorporated into the compositions forming the layer prior to coating or can be incorporated in a suitable solvent and added to the photographic element after coating. In most instances. water is the preferred solvent.
• the addenda can be added using various procedures. including those described in Collins el al. U.S. Pat. No. 2.912.343 issued Nov. 10. 1959; McCrossen et al. U.S. Pat. No. 3.342.605 issued Sept. 19. 1967; Audran U.S. Pat. No. 2.996.287 issued Aug. 15. 1961. and Johnson et al. U.S. Pat. No. 3.425.835 issued Feb. 4. 1969.
• the silver halide photographic elements ofthis invention can be used for making lithographic printing plates such as by the colloid transfer of undeveloped and unhardened areas of an exposed and developed emulsion to a suitable support as described in Clark et al US. Pat. No. 2.763.553 issued Sept. 18. 1956; to provide a relief immage as described in Woodward U.S. Pat. No. 3.402.045 issued Sept. 17. 1968. or Spencer U.S. Pat. No. 3.053.658 issued Sept. ll. 1962; to prepare a relief printing plate as described in Baxter et al. US Pat. No. 3.271.150 iss'ued Sept. 6. 1966'. to prepare a silver salt diffusion transfer plate as described in Hcpher et al. British Pat.
• the photographic elements are intended to produce high contrast images upon exposure. that they be developed in developers containing one or more amines and/or amine derivatives.
• a particularly desirable developer composition is described in Masseth U.S. Pat. No. 3.573.914 which comprises a developing agent. a carbonyl bisulfite-amine condensation product. and at least about 0.075 mole of free amine per liter of developer composition.
• the developing agents which can be employed in these developer compositions can be any of those suitable for the intended purpose.
• Suitable silver halide developing agents for example. include the dihydroxy benzenes. such as hydroquinone. chlorohydroquinone. bromohydroquinone. isopropylhydroquinone. toluhydroquinone. methylhydroquinone. 2.3- dichlorohydroquinone. 2.5-dimethylhydroquinone. 2.3-dibromohydroquinone. 1.4-dihydroxy-2- acetophenone-Z.5-dimethylhydroquinone. 2.5- diethylhydroquinone.
• the carbonyl bisulfiteamine condensation products which can be used in this developer composition are preferably formaldehyde bisulfitc-amine condensation products.
• formaldehyde bisulfitc-amine condensation products such as sodium-2- hydroxyethylaminomethane sulfonate. odium-2 hydroxypropylaminomethane sulfonate. sodium'Lldimethyl-Z-hydroxylaminomcthanc sulfonate. sodium- 1 .1-bis(hydroxymethyl)ethylaminomethane sulfonate. sodium-tristhydroxymethyl)methylaminomethane sulfonate. sodium-3-hydr0xypropylaminomethane su1fonate.
• sodium-bist2-hydroxyethyl)aminomethane sulfonate sodium-N.N-bis(2 H lhydroxylpropyllaminomethane sulfonate.
• sodium-N methylN-(2 hydroxycthyl)aminomethane sulfonate sodium-bist2-hydroxyethyl)aminomethane sulfonate.
• sodium-N.N-bis(2 H lhydroxylpropyllaminomethane sulfonate sodium-N- isopropyl-N-( 2 hydroxyethyl )aminomethane sulfonate.
• the carbonyl bisulfite-amine condensation products can be used alone or in any combinations and can be employed in any concentration which is effective to provide a low l 1 level of sullite ion for the developer composition.
• a suitable concentration for the carbonyl bisultitc-amine condensation product is from about to about 1.0 mole per liter ol liquid developer composition and is preferably from about 0.25 to about 0.50 mole per liter of liquid developer composition.
• the carbonyl bisulfite-amine condensation product can be added to the developer composition as a sepa rate compound or formed in situ. Methods for preparing these compounds are disclosed, for example. in U.S. Pat. No. 2.388.816 of Bean issued Nov. 13. 1945.
• the free or uncombined amine compounds which can be employed in these developer compositions include primary and secondary amines such as 2- aminocthanol. l-amino-Z-propanol. 2amino-2-methyll-propanol. 2-amino-2-methyl-l.3propanediol. 2- amino-2( hydroxymethyl )-l ,3-propanediol. 3aminol propanol. 2-2'-iminodietbanol. di-iso-propanolamine. Lisopropylaminoethanol. 2-ethylaminoethanol. methylaminoethanol, etc.
• amines can be used alone or in any combination and should be employed in a concentration of at least about 0.075 mole per liter of developer composition.
• a suitable range of concentra tions for the amine compound is from about 0.075 to about 3.0 moles per liter of developer composition and is preferably from about 0.20 to about 0.90 mole per liter of developer composition.
• the free amine present in the developer composition can be the same amine used to prepare the carbonyl bisulfite-amine condensation product or it can be a different amine.
• the photographic elements of this invention can be developed with conventional photographic developers exhibiting a pH in the range of from about 9 to l3.
• These developers are typically rendered basic by inorganic solutes. such as alkali metal hydroxides, carbonates. phosphates. silicates. etc.
• the developer also preferably contains at least a 0.001 molar concentration of a stabilizer. such as an alkali metal or amine bisulfitc.
• the developing agent can take the form of ascorbic acid or a polyhydroxybenzene. such as pyrogallol or any of the hydroquinoncs noted above in the Masscth developers.
• Developing agent concentrations of from 0.0] to 0.5 mole ofdeveloping agent per liter of developer are typically preferred.
• Other conventional developer addenda can. of course. also be incorporated. if desired.
• the chromium(lll) complex similarly processed exhibited a curve compression of L36 log F. as compared to a curve compression of 1.26 log E for the control photographic element processed along with it.
• EXAMPLE l4 Table V lixamplc (ompound Fresh Results No (mg/mole) Speed Fog Control none 44 NR EXAMPLES 19 AND 20
• a silver chlorobromoiodide (:9:1 mole ratio) emulsion is prepared using the double jet technique.
• potassium bromide and potassium iodide solution contained 0.15 milligram of rhodium ammonium chloride per mole of silver halide.
• the emulsion was sulfur and gold sensitized and heat finished to optimum sensitivity.
• the emulsion was then divided into equal portions and Ru(NH Cl was added to the photographic element in various concentration levels. herein expressed in milligrams of ruthenium complex per mole of silver.
• a photographic element comprising a support having coated thereon at least one layer comprising a photographic silver halide emulsion and in said layer or in a second layer coated adjacent thereto a ruthenium cationic complex including at least four ligands chosen from the class consisting of ammine and amine ligans. said ruthenium cationic complex being present in a concentration of at least 0.1 mg. but less than l gram per mole of silver.
• a photographic element according to claim 1 in which said element contains from 100 to 0.1 mg of said ruthenium complex per mole of silver.
• a photographic element according to claim 2 in which said element contains from 50 to 0.5 mg of said ruthenium complex per mole of silver.
• a photographic element according to claim 3 in which said element contains from 20 to I mg of said ru' thenium complex per mole of silver.
• a photographic element according to claim 1 in which said silver halide emulsion layer or said second adjacent layer contains an azaindenc antifoggant.
• ammine and amine ligands are chosen from the class consisting of ammine ligands and aliphatic amine ligands containing six or fewer carbon atoms.
• a photographic element according to claim 10in which said amine ligands are chosen from the class consisting ofethylenc diamine. trimethylane diaminc. diethanol amine and dipropanol amine ligands.
• a photographic element comprising a support having coated thereon a high contrast lithographic silver halide emulsion containing at least 50 mole percent silver chloride and in said emulsion layer or in a layer coated adjacent thereto from 100 to 0.1 mg per mole of silver of a hexacoordinated ruthenium cationic com plex inlcuding at least four ligands chosen from the class consisting of ammine ligands and aliphatic amine ligands containing six or fewer carbon atoms. and an azaindene antifoggant.
• a photographic element comprising a support having coated thereon a high contrast lithographic sil ver halide emulsion containing at least 50 mole percent silver chloride and in said emulsion or in a layer coated adjacent thereto 100 to 0.1 mg per mole of silver of a hexacoordinated ruthenium cationic complex including at least four ligands chosen from the class consisting of ammine ligands and aliphatic amine ligands containing six or fewer carbon atoms; and
• any remaining silver halide being a silver bromide and in said emulsion or in a layer adjacent thereto 20 to l mg per mole of silver of a hexammine ruthe nium cationic complex: ()3 to 3.0 grams per mole ol silver of a hexammine cohaltUIl) cationic complex; and 0.3 to 3.0 grams per mole of silver of 5-hromo 4- hydroxy-fimethyl l 3.3a, 7-tetrazindenev 25.

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• 1974
  • 1974-03-11 US US450263A patent/US3901712A/en not_active Expired - Lifetime
• 1975
  • 1975-02-11 CA CA219,813A patent/CA1043615A/en not_active Expired
  • 1975-03-07 FR FR7507136A patent/FR2264304B1/fr not_active Expired
  • 1975-03-07 DE DE2510073A patent/DE2510073C3/de not_active Expired
  • 1975-03-07 JP JP50027952A patent/JPS5822733B2/ja not_active Expired
  • 1975-03-11 IT IT21145/75A patent/IT1034182B/it active
  • 1975-03-11 BE BE154235A patent/BE826557A/xx not_active IP Right Cessation
  • 1975-03-11 GB GB10108/75A patent/GB1491082A/en not_active Expired

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