US3891442A - Lithographic materials containing metal complexes - Google Patents

Lithographic materials containing metal complexes Download PDF

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US3891442A
US3891442A US398515A US39851573A US3891442A US 3891442 A US3891442 A US 3891442A US 398515 A US398515 A US 398515A US 39851573 A US39851573 A US 39851573A US 3891442 A US3891442 A US 3891442A
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silver halide
iii
layer
silver
cobalt
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US398515A
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Dorothy Johnson Beavers
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US398515A priority Critical patent/US3891442A/en
Priority to FR7341551A priority patent/FR2209126B1/fr
Priority to CA187,103A priority patent/CA994591A/en
Priority to JP48136456A priority patent/JPS5855494B2/ja
Priority to GB5614373A priority patent/GB1456543A/en
Priority to DE2360327A priority patent/DE2360327C2/de
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Publication of US3891442A publication Critical patent/US3891442A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/15—Lithographic emulsion

Definitions

  • a photographic element which comprises a support having coated thereon at least one layer comprising a photographic silver halide emulsion and in said layer or in a second layer adjacent thereto from about 0.2 to about 5.0 grams per mole of silver of at least one hexacoordinated trivalent cationic complex comprising a trivalent metal ion selected from the group consisting of cobalt (111) and chromium (111) in combination with at least one ligand selected from the group consisting of ammonia, ethylene diamine, trimethylene diamine, diethanolamine and dipropanolamine; said silver halide emulsion comprising silver halide grains in which the halide consists of at least about 50 mole percent chloride, up to about 10 mole percent iodide and
  • This invention relates to photographic materials, their preparation and use. In one aspect, this invention relates to photographic elements containing hexacoordinated trivalent cationic complexes. In another aspect, this invention relates to photographic elements containing such complexes and further containing an azaindene.
  • Cadmium salts have long been employed in the photographic field for a variety of purposes. For example, it is stated in Glafkides, Photographic Chemistry", Vol. 1, I958, page 151, that cadmium chloride can be used to increase the contrast in the silver halide emulsion.
  • US. Pat. No. 3,488,709 issued Jan. 6, 1970 to Sidebotham teaches that cadmium bromide stabilizes silver halide emulsions precipitated in the presence of rhodium salts in that it reduces the loss of contrast and speed change upon storage annd also that cadmium bromide acts to increase the contrast in a synergistic manner.
  • the present invention comprises improved photographic elements which contain a metal complex and, optionally, an azaindene in the silver halide layer or in a second layer adjacent thereto in place of a cadmium salt.
  • the present invention comprises a photographic element comprising a support having coated thereon a least one layer comprising a photographic silver halide emulsion in the said layer or in a second layer adjacent thereto from about 0.2 to about 5.0 grams per mole of silver of at least I hexacoordinated trivalent cationic complex comprising a trivalent metal ion selected from the group consisting of cobalt (III) and chromium (III) in combination with at least one ligand selected from the group consisting of ammonia, ethylene diamine, trimethylene diamine, diethanol amine and dipropanol amine; said silver halide emulsion comprising silver halide grains in which the halide consists of at least about 50 mole percent chloride, up to about 10 mole percent iodide and any remaining halide being bromide.
  • the present invention comprises above-described photographic element further comprising at least one azaindene.
  • the cationic complexes of this invention comprise an ion surrounded by certain other molecules which are referred to as ligands.
  • the ion in the center of these complexes is a Lewis acid; the ligands are Lewis bases.
  • Werner complexes are well known examples of such complexes.
  • the metal complexes of this invention have coordination numbers of 6 and are known as octahedral complexes.
  • the metal ions which can be employed to prepare the complexes of this invention are cobalt (III) or chromium (III). Complexes based upon cobalt (III) are preferred.
  • the ligands employed in the practice of this invention comprise ammonia, ethylene diamine, trimethylene diamine, diethanol amine and dipropanol amine. Accordingly, as exemplary of those hexacoordinated trivalent cationic complexes which can be employed in the practice of this invention can be listed hexammine cobalt (III), tris(ethylenediamine) cobalt (Ill), bis(diethanol amine)cobalt (III), bis(dipropanol) amine cobalt (III), hexammine chromium ([II), tris(ethylenediamine) chromium (III), bis(diethanolamine) chromium (III), bis(dipropanolamine) chromium (III), tris(trimethylenediamine) cobalt (III), tris(trimethylenediamine) chromium (III), ethylenediaminebis(trimethylenediamine) cobalt (III), ethylenediaminebis(- trimethylened
  • metal complexes are located in the photographic elements of this invention either in the layer comprising the photographic silver halide emulsion or in a layer immediately adjacent thereto. They are present in a concentration of from about 0.2 to about 5.0 grams per mole of silver. A preferred range is from about 0.3 to about 3.0 grams of metal complex per mole of silver and the most preferred range is from about 0.5 to about 1.0 gram of metal complex per mole of silver.
  • the complexes employed in the practice of this invention have a reduction potential (E,) in the range of from about 0.2 to about 0.8 volt when measured in a carbonate buffer solution at pH 10.
  • 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 mole percent iodide and any remaining halide being bromide. 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.
  • Suitable silver halides include, for example, silver chloride, silver chlorobromide, silver chlorobromoiodide and the like.
  • the photographic elements of this invention further comprise at least one azaindene, located either in the photographic silver halide emulsion layer or in a layer immediately adjacent thereto.
  • the azaindene will generally be present in a concentration of from about 0.2 to about 5.0 grams 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, Among those azaindenes which may be employed in the practice of this invention can be listed, for example, 4-hydroxy-6-alkyl- 1,3,3a, 7-tetrazaindenes, such as, 4hydroxy-6-methyl- 1,3,3a, 7-tetrazaindene, 5-carboxy-4-hydroxy-1,3,3a, 7-tetrazaindene, 6-methyl-1,3,3a, 7-tetrazaindene-4- thiol, 5,7-dimethyl-4,6-dioxo-4,5,6,7t
  • the element is processed in one continuous motion by transporting it into and out of at least one processing solution in the manner shown, for example, by U.S. Pat. Nos. 3,025,779 of Russell and Kunz issued Mar. 20, 1962; 3,078,024 of Sardeson issued Feb. 19, 1963; 3,122,086 of Fitch issued Feb. 25, 1964; 3,149,551 of Cramer issued Feb. 22, 1964; 3,156,173 of Meyer issued Nov. 10, 1964; and 3,224,356 of Fleisher and Hixon issued Feb. 21, 1965.
  • 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 include the dihydroxybenzenes such as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3- dichlorohydroquinone, 2,5-dimethylhydroquinone,
  • a suitable concentration for the developing agent is from about 0.05 to about 0.50 mole per liter of developer composition and is preferably from about 0.10 to about 0.03 mole per liter of developer composition.
  • the carbonyl bisulfite-amine condensation products which can be used in this developer composition are r ferably formaldehyde bisulfite-amine condensation products such as sodium-Z-hydroxyethylaminomethane sulfonate, sodium-2-hydroxy-propylaminomethane sulfonate, sodium-l l -dimethyl-2-hydroxylaminomethane sulfonate, sodium-l.l bis(hydroxymethyl )ethylaminomethane sulfonate, sodiumtris( hyd roxymethyl )methylaminomethane sulfonate, sodium-3-hydroxypropylaminomethane sulfonate,
  • sodium-bis(2 hydroxyethyl)aminomethane sulfonate sodium-N,N-bis( 2-[ l-hydroxy1propyl)aminomethane sulfonate, sodium-N-isopropyl-N-(Z-hydroxyethyl )aminomethane sulfonate, sodium-N-ethyl-N-( 2- hydroxyethyl)aminomethane sulfonate, and sodium-N- methyl-N-(Z-hydroxyethyl)aminomethane sulfonate.
  • the carbonyl bisulfiteamine condensation products can be used alone or in any combination and can be employed in any concentration which is effective to provide a low level of sulfite ion for the developer composition.
  • a suitable concentration for the carbonyl bisulfiteamine condensation product is from about 0.1 to about l.0 mole per liter of 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 separate 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, I945.
  • the free or uncombined amine compounds which can be employed in these developer compositions include primary and secondary amines such as 2- aminoethanol, I-amino-2-propanol, 2-amino-2-methyll-propanol, 2-amino-2-methyl-l,3-propanediol, 2- amino-2(hydroxymethyl)-1,3-propanediol, 3-aminolpropanol, 2-2'-imin0diethanol, di-iso-propanolamine, 2-isopropylamino-ethanol, 2-ethylaminoethanol, 2- methylaminoethanol, etc.
  • primary and secondary amines such as 2- aminoethanol, I-amino-2-propanol, 2-amino-2-methyll-propanol, 2-amino-2-methyl-l,3-propanediol, 2- amino-2(hydroxymethyl)-1,3-propanediol, 3-aminolpropanol, 2-2'-imin
  • 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 concentrations from 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 silver halide emulsion layer of the high contrast photographic elements of this invention can contain any of the hydrophilic water-permeable binding materials 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 high contrast photographic element can also contain dispersed polymerized vinyl compounds. Typical synthetic polymers include those described in Nottorf U.S. Pat. Nos. 3,142,568 issued July 28, I964; White 3,193,386 issued July 6, 1965; Houck et al. 3,062,674 issued Nov. 6, 1962; Houck et al. 3,220,844 issued Nov.
  • vehicle materials include those water insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, those which have crosslinking sites which facilitate hardening or curing as described in Smith U.S. Pat. No. 3,488,708 issued Jan. 6, I970 and those having recurring sulfobetaine units as described in Dykstra, Canadian Pat. No. 774,054. These compounds can also be incorporated into a separate layer of the photographic element.
  • the vinyl polymers are generally employed in concentrations in the range of about 20 to about 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.
  • the silver halide emulsion of the high contrast photographic elements of this invention can be coated on a wide variety of supports. Hydrophilic colloid layers can be coated on one or both sides of the support if desired.
  • Typical supports are cellulose nitrate film, cellulose ester film, polyvinylacetal 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 alphaolefin containing 2 to ID carbon atoms such as polyethylene, polypropylene, ethylene butene copolymers and the like.
  • the silver halide emulsions of the high contrast photographic elements of this invention 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 of Group VIII of the Periodic Table which have ann atomic weight greater than I00.
  • the emulsions can also contain addenda which increase speed and/or contrast such as quaternary ammonium salts, thioether sensitizers or combinations thereof.
  • the silver halide emulsions of the high contrast photographic elements of this invention can conveniently be ortho-sensitized or pan-sensitized with spectral sensitizing dyes.
  • Sensitizing dyes useful in sensitizing these silver halide emulsions are described, for example, in Brooker et al. U.S. Pat. Nos. 2,526,632 issued Oct. 24, 1950; Sprague 2,503,776 issued Apr. I l, 1950; Brooker et al. 2,493,748 issued Jan. I0, 1950; and Taber et al. 3,384,486 issued May 21, I968.
  • Spectral sensitizers which can be used include the cyanines, merocyanines, complex (trior tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (e.g., enamine cyanines), oxonols and hemioxonols.
  • the silver halide emulsions of the high contrast photographic elements of this invention can also contain conventional addenda such as gelation plasticizers, coating aids, antifoggants and hardeners as described in Product Licensing Index, V0. 92, December, I971, publication 9232, pages 107-l l0.
  • the silver halide photographic elements of this invention are 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. U.S. Pat. No. 2,763,553 issued Sept. 18, 1956; to provide a relief image as described in Woodward 3,402,045 issued Sept. l7, I968 or Spencer 3,053,658 issued Sept. 1 l, 1962; to prepare a relief printing plate as described in Baxter et al. U.S. Pat. No. 3,271,150 issued Sept. 6, 1966; to prepare a silver salt diffusion transfer plate as 8 is then processed in a Kodalith Roller Transport Film Processor of the type shown in U.S. Pat. No. 3,025,779 to Russell and Kunz at 2.3 feet per minute.
  • the processor contains the following developer composition:
  • Typical useful compounds include poly- P ethylene glycol, polyethylene glycol oleyl ether, polyethylene glycol cetyl ether, polyethylene oxide deriva-
  • the results are Show" Table tives, block copolymers such as those comprising EXAMPLE 2 blocks of polyoxypropylene, polyoxyethylene and the like, water-soluble organosilicone polyalkylenoxide E p e I IS repeated except that 1.0 gram of hexpolymers and the like.
  • the alkylene oxide polymer can ammine cobalt (III) chloride per mole of silver is added be used in any concentration effective for the intended to the emulsion prior to coating. The results are shown purpose.
  • Curve compression measures the photographic speed differences at a density of 1.0 when processing the element in the Roller Transport Processor at speeds of 2.3 feet per minute and 4.l feet per minute.
  • EXAMPLE I CONTROL A fine grain silver chlorobromoiodide gelatin emulsion containing 90 mole percent chloride, 9 mole percent bromide and 1 mole percent iodide is chemically sensitized with sulfur and gold sensitizers. To the emulsion is added 200 mg. of oleic ether of polyethyleneglycol (m.w. l540)/silver mole. Sixty-nine grams per mole of silver of a synthetic polymer vehicle is also added to the emulsion.
  • the vehicle added is 32/3/65 (mole percentages) methyl acrylate/3- acryloyloxypropane-l-sulfonic acid, sodium salt/2- acetoacetoxyethyl methacrylate.
  • the emulsion is then coated on a polyethylene terephthalate support at a coverage of 50.5 mg. of silver per square decimeter and 50.5 mg. of gelatin per square decimeter.
  • a normal gelatin overcoat of 9.2 of gelatin per square decimeter is coated over the emulsion layer.
  • the coated element is then exposed, using tungsten illumination, to a step wedge through a neutral halftone screen.
  • the element Dot quality if a measure of the quality of the reproduction of a halftone image.
  • the dot qualtiy used herein is a measure of the areas referred to as 50 percent dots (i.e., one-half clear and one-half developed density) and is expressed in a progressive scale where 9 is excellent and l is extremely poor. A 50 percent dot quality below 6 is generally not acceptable.
  • EXAMPLE 5 This example illustrates that all cobalt compounds do not impart desirable photographic properties. Elements are prepared and processed in a manner similar to that of Example 1 except that the following compounds are added:
  • Example 9 is repeated except that tris(ethylenedia- D 78 low .04 5 mine) cobalt (lll) chloride is substituted on an equal D .25 74 11.75 .04 6 weight basis for the hexammine cobalt (lll) chloride D 63 6 lo therein.
  • Table [I] The results are shown in Table [I].
  • Example 1 is repeated except 1.0 gram per mole of silver of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 0.5 gram per mole of silver of hexammine cobalt (lll) chloride are added to the emulsion prior to coating. The results are shown in Table III.
  • Example 7 Example 6 is repeated except that the concentration of hexammine cobalt (lll) chloride is increased to l gram per mole of silver. The results are shown in Table Ill.
  • EXAMPLE 8 Example 7 is repeated except that tris(ethylenediamine) cobalt (lll) chloride is substituted on an equal weight basis for the hexammine cobalt (lll) chloride employed therein. The results are shown in Table III.
  • Example 2 is repeated except that bis(diethanolamine) cobalt (lll) chloride is substituted on an equal weight basis for the hexammine cobalt (lll) chloride employed therein.
  • the results are somewhat poorer than those obtained in Example 2. but better than the results obtained in Example 1.
  • Example 14 is repeated except that bis(dipropanolamine) cobalt (lll) chloride is substituted on an equal weight basis for the bis(diethanolamine) cobalt (lll) chloride employed therein. Results equivalent to those of Example l3 are obtained.
  • Example 16 Example 2 is repeated except that ethylenediaminebis (trimethylenediamine) cobalt (III) chloride is substituted on an equal weight basis for the hexammine cobalt (III) chloride employed therein. The results are shown in Table IV.
  • 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 adjacent thereto from about 0.2 to about 5.0 grams per mole of silver of each of (a) at least one azaindene and (b) at least one hexacoordinated trivalent cationic complex comprising a trivalent metal ion selected from the group consisting of cobalt (III) and chromium (III) in combination with at least one ligand selected from the group consisting of ammonia, ethylenediamine, trimethylenediamine, diethanolamine and dipropanolamine; said silver halide emulsion comprising silver halide grains in which the halide consists of at least about 50 mole percent chloride, up to about 10 mole percent iodide and any remaining halide being bromide.
  • the element of claim 1 comprising at least one layer containing an alkylcne oxide polymer.
  • the element of claim 1 further comprising at least one synthetic polymer vehicle.
  • 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 adjacent thereto from about 0.2 to about 5.0 grams per mole of silver of each of (a) at least one azaindene and (b) at least one hexacoordinated trivalent cationic complex selected from the group consist' ing of hexammine cobalt (Ill) and tris (ethylenediamine) cobalt (III); said silver halide emulsion comprising silver halide grains in which the halide consists of at least about 50 mole percent chloride, up to about l0 mole percent iodide and any remaining halide being bromide.
  • the element of claim 8 comprising at least one layer containing an alkylene oxide polymer.
  • the element of claim 8 further comprising at least one synthetic polymer vehicle.
  • a high contrast photographic element comprising a poly(ethylene terephthalate) film support having coated thereon at least one layer comprising a photographic silver halide emulsion, from about 0.3 to about 3.0 grams per mole of silver of at least one hexacoordinated trivalent cationic complex selected from the group consisting of hexammine cobalt (III) and tris (ethylenedimaine) cobalt (Ill), and from about 0.2 to about 5.0 grams per mole of silver of at least one azaindene; said silver halide emulsion comprising silver halide grains in which the halide consists of at least about 50 mole percent chloride, up to about 10 mole percent iodide and any remaining halide being bromide.
  • azaindene is selected from the group consisting of 4-hydroxy-6- methyl-1,3,3a, 7-tetrazaindene and 5-bromo-5- hydroxy-6-methyl-l ,3,3a, 7-tetrazaindene.
  • the element of claim 12 comprising at least one layer containing an alkylene oxide polymer.
  • the element of claim 12 further comprising at least one synthetic polymer vehicle.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
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US398515A 1972-12-04 1973-09-18 Lithographic materials containing metal complexes Expired - Lifetime US3891442A (en)

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Application Number Priority Date Filing Date Title
US398515A US3891442A (en) 1972-12-04 1973-09-18 Lithographic materials containing metal complexes
FR7341551A FR2209126B1 (enrdf_load_stackoverflow) 1972-12-04 1973-11-22
CA187,103A CA994591A (en) 1972-12-04 1973-11-30 Lithographic materials containing metal complexes
JP48136456A JPS5855494B2 (ja) 1972-12-04 1973-12-04 シヤシンヨウソ
GB5614373A GB1456543A (en) 1972-12-04 1973-12-04 Photographic silver halide materials
DE2360327A DE2360327C2 (de) 1972-12-04 1973-12-04 Photographisches Aufzeichnungsmaterial vom Lith-Typ

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US31215972A 1972-12-04 1972-12-04
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DE (1) DE2360327C2 (enrdf_load_stackoverflow)
FR (1) FR2209126B1 (enrdf_load_stackoverflow)
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Cited By (6)

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US4108662A (en) * 1976-01-28 1978-08-22 Fuji Photo Film Co., Ltd. Process for developing photographic light-sensitive materials for the graphic arts
US4126472A (en) * 1974-02-24 1978-11-21 Fuji Photo Film Co., Ltd. Process of making a lithographic photosensitive silver halide emulsion having reduced susceptibility to pressure containing an iridium compound, a hydroxytetrazaindene and a polyoxyethylene
US4175966A (en) * 1975-08-02 1979-11-27 Konishiroku Photo Industry Co., Ltd. Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof
US4318979A (en) * 1978-09-07 1982-03-09 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
US4329417A (en) * 1979-06-22 1982-05-11 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material and method of forming high contrast silver images
US4416980A (en) * 1977-01-28 1983-11-22 Konishiroku Photo Industry Co., Ltd. High-contrast light-sensitive silver halide photographic material

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Publication number Priority date Publication date Assignee Title
JPS5917825B2 (ja) * 1975-08-02 1984-04-24 コニカ株式会社 高コントラスト銀画像の形成方法
JPS5917820B2 (ja) * 1977-01-26 1984-04-24 コニカ株式会社 高コントラスト銀画像の形成方法
CA1120765A (en) * 1979-04-05 1982-03-30 Eastman Kodak Company High chloride silver halide emulsion internally doped with cadmium, lead, copper, zinc or mixtures thereof
JPS5834443A (ja) * 1981-08-26 1983-02-28 Fuji Photo Film Co Ltd 製版用ハロゲン化銀写真感光材料及びその減力処理方法
JPS6277595U (enrdf_load_stackoverflow) * 1985-10-31 1987-05-18
JPS63158195U (enrdf_load_stackoverflow) * 1987-04-01 1988-10-17
JP2649858B2 (ja) * 1990-05-22 1997-09-03 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

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US3748138A (en) * 1971-10-14 1973-07-24 Eastman Kodak Co Metal complex in silver halide development

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BE484866A (enrdf_load_stackoverflow) * 1947-09-27
DE1030179B (de) * 1956-09-06 1958-05-14 Perutz Photowerke G M B H Verfahren zur Stabilisierung photographischer Emulsionen
US3333959A (en) * 1963-05-21 1967-08-01 Fuji Photo Film Co Ltd High edge-gradient photosensitive materials
US3488709A (en) * 1966-12-02 1970-01-06 Eastman Kodak Co Stabilizing silver halide emulsions with cadmium bromide
DE1956692A1 (de) * 1969-11-11 1971-05-19 Schlumberger Overseas Verstaerkerstufenschaltung fuer einen logarithmischen Verstaerker

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US3671258A (en) * 1971-01-11 1972-06-20 Eastman Kodak Co Speed increasing combination of stabilizers for radiographic elements
US3748138A (en) * 1971-10-14 1973-07-24 Eastman Kodak Co Metal complex in silver halide development

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4126472A (en) * 1974-02-24 1978-11-21 Fuji Photo Film Co., Ltd. Process of making a lithographic photosensitive silver halide emulsion having reduced susceptibility to pressure containing an iridium compound, a hydroxytetrazaindene and a polyoxyethylene
US4175966A (en) * 1975-08-02 1979-11-27 Konishiroku Photo Industry Co., Ltd. Light-sensitive black-white silver halide photographic material for forming a high-contrast silver image and method of treating thereof
US4108662A (en) * 1976-01-28 1978-08-22 Fuji Photo Film Co., Ltd. Process for developing photographic light-sensitive materials for the graphic arts
US4416980A (en) * 1977-01-28 1983-11-22 Konishiroku Photo Industry Co., Ltd. High-contrast light-sensitive silver halide photographic material
US4318979A (en) * 1978-09-07 1982-03-09 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
US4329417A (en) * 1979-06-22 1982-05-11 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material and method of forming high contrast silver images

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GB1456543A (en) 1976-11-24
FR2209126B1 (enrdf_load_stackoverflow) 1977-03-18
JPS5855494B2 (ja) 1983-12-09
DE2360327C2 (de) 1985-01-17
DE2360327A1 (de) 1974-06-20
JPS4990120A (enrdf_load_stackoverflow) 1974-08-28
CA994591A (en) 1976-08-10
FR2209126A1 (enrdf_load_stackoverflow) 1974-06-28

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