EP0531014A2 - Schwarz-weiss Film für graphische Kunst empfindlich für Multiwellenlängenbereiche - Google Patents

Schwarz-weiss Film für graphische Kunst empfindlich für Multiwellenlängenbereiche Download PDF

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Publication number
EP0531014A2
EP0531014A2 EP92307545A EP92307545A EP0531014A2 EP 0531014 A2 EP0531014 A2 EP 0531014A2 EP 92307545 A EP92307545 A EP 92307545A EP 92307545 A EP92307545 A EP 92307545A EP 0531014 A2 EP0531014 A2 EP 0531014A2
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EP
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Prior art keywords
silver halide
emulsions
pat
emulsion
spectrally sensitized
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English (en)
French (fr)
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EP0531014A3 (en
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Brian C. c/o Minnesota Mining and Willett
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3M Co
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Minnesota Mining and Manufacturing Co
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infrared processes
    • 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
    • G03C1/061—Hydrazine compounds
    • 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
    • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer

Definitions

  • the present invention relates to black-and-white silver halide photographic elements, and in particular to high contrast photographic elements with emulsions containing hydrazides.
  • the elements may be used with various laser scanners in graphic arts or for imagesetter applications.
  • Hydrazines find a variety of uses in silver halide photography. They have been used in negative working surface latent image forming silver halide emulsions to increase speed and/or contrast. They have been used in direct positive internal latent image forming emulsions as nucleating agents.
  • Hydrazines may also be used for internal latent image direct positive emulsions such as those described in U.S. Pat. No. 3,227,552 and reviewed in Research Disclosure No. 235 (1983) item 23510.
  • the most efficient hydrazines employed in silver halide photographic systems employ a combination of substituents to balance activity and stability.
  • the stability of hydrazines is increased by attaching directly to one of the nitrogen atoms a tertiary carbon atom, such as the carbon atom of an aromatic ring.
  • the art has long recognized that the activity of these stabilized hydrazines can be advantageously modified by the direct attachment of an acyl group to the remaining nitrogen atom.
  • the most commonly employed hydrazines are arylhydrazides.
  • Silver halide emulsions and/or developers containing hydrazines are disclosed, for example, in U.S. Pat. Nos. 2,419,975, 2,563,785, 3,227,552, 3,386,831, 3,730,727, 4,030,925, 4,031,127, 4,080,207, 4,168,977, 4,224,401, 4,243,739, 4,245,037, 4,255,511, 4,266,013, 4,272,614, 4,276,364, 4,323,643, 4,478,928 and 4,560,638 and U.K. Patent Specifications Nos. 1560005, 1579956, 2034908A and 2066492B.
  • U.S. Pat. No. 2,419,975 discloses that high-contrast negative images are obtained by the addition of hydrazine compounds.
  • This patent describes that extremely high-contrast photographic characteristics, such as a gamma ( ⁇ ) of more than 10, can be obtained by adding a hydrazine compound to a silver chlorobromide emulsion and developing at a pH as high as 12.8.
  • the strongly alkaline developer having a pH of nearly 13 is susceptible to air oxidation and is too unstable to be stored or used for long periods.
  • U.S. Pat. No. 4,168, 977 discloses the use of a hydrazine of the formula: R1NHNHCHO in which R1 represents an aryl group, in combination with silver chlorobromide or silver chlorobromoiodide emulsions. This combination is capable of functioning at a lower pH than the hydrazines of U.S. Pat. No. 2,419,975 and a pH of 11.5 is exemplified.
  • U.S. Pat. No. 4,224,401 discloses the use of a hydrazine of the formula: R1NHNHCOR2 in which R1 an aryl group and R2 is a hydrogen atom, C1 to C3 alkyl or phenyl optionally substituted with substitutents which are preferably electron withdrawing, in combination with silver bromide or silver iodobromide emulsions.
  • R1NHNHCOR2 in which R1 an aryl group and R2 is a hydrogen atom, C1 to C3 alkyl or phenyl optionally substituted with substitutents which are preferably electron withdrawing, in combination with silver bromide or silver iodobromide emulsions.
  • This combination is also functional at a pH lower than that disclosed in U.S. Pat. No. 2,419,975 and a pH of 11.5 is exemplified when R2 is hydrogen.
  • U.S. Pat. No. 4,925,832 describes a novel class of hydrazines which provide high contrast and undergo a cyclization process during their photographic activity. These are a preferred class of hydrazines.
  • Argon ion lasers which emit at 488 nm
  • helium-neon lasers which emit at 633 nm
  • infrared lasers which emit between 700 and 1300 nm, and especially at about 780, 800, 810, 830, 850 and 880 nm
  • laser diodes which can be designed to emit in portions of the visible through the infrared
  • a film It is generally necessary for a film to be optimally spectrally sensitive to a narrow range of wavelengths. Unless different imaging systems emitted at similar wavelengths, a single film cannot be used for multiple systems. Each film is therefore generally optimized for a single imaging system.
  • a multiwavelength sensitive high contrast hydrazide-containing photographic silver halide element may be produced with a substrate carrying at least three different silver halide emulsion layers on the same side of the support. Each emulsion layer contains a black-and-white emulsion which is spectrally sensitized to a portion of the electromagnetic spectrum different from that to which the other emulsion layers are spectrally sensitized.
  • a contrast enhancing hydrazide compound is present in at least one of the emulsion layers. This element can be imaged at any of the wavelengths to which any of the at least three emulsion layers has been spectrally sensitized and still provide high densities, high speed and high contrast. This can be done at silver coating weights below 5.0 g/m.
  • the present invention describes a high contrast black-and-white silver halide photographic element which can be exposed by at least three different wavelengths of radiation and provide high speed imaging, high density images, and high contrast for each of the three different wavelengths.
  • a number of different types of photographic elements may be made according to the teachings of the present invention.
  • a black-and-white silver halide photographic element comprising a substrate having at least two silver halide emulsion layers thereon, the total weight of silver on said substrate being less than 5.0 g/m2, said at least two silver halide emulsions being spectrally sensitized to at least two different wavelengths of the electromagnetic spectrum which differ by at least 50 nm, and at least one of said silver halide emulsion layers containing a contrast enhancing hydrazine.
  • a black-and-white silver halide photographic element comprising a substrate having at least three silver halide emulsion layers thereon, each of said at least three silver halide emulsion layers being spectrally sensitized to different wavelengths of the electromagnetic spectrum which differ from each other by at least 50 nm, and the total weight of silver on said substrate being less than 5.0 g/m2, at least one of said silver halide emulsion layers containing a contrast enhancing hydrazide.
  • one of said different wavelengths is also desirable for one of said different wavelengths to be within the infrared region of the spectrum and the silver halide emulsion spectrally sensitized to the infrared is not the outermost silver halide emulsion layer from said support.
  • the present invention also teaches us a process for making a black-and-white silver halide photographic element comprising at least two separate black-and-white silver halide emulsions, separately spectrally sensitizing each of said silver halide emulsions to different wavelengths of the electromagnetic spectrum which differ by at least 50 nm, and coating said emulsions onto a support layer to form said element, said element additionally containing a contrast enhancing hydrazide in reactive association with said silver halide emulsion layers.
  • the process is particularly effective when said spectrally sensitized emulsions are coated onto said support as separate layers, and at least three separate emulsions are separately spectrally sensitized to at least three different wavelengths of the electromagnetic spectrum, and when said at least three separate emulsions are coated onto said support as separate layers.
  • the process is particularly desirable when one of said layers is spectrally sensitized to the infrared and that layers sensitized to the infrared is not the outermost silver halide emulsion layer from said support.
  • the sensitizing dyes used in the present invention are added to the silver halide emulsion in amounts of 5 x 10 ⁇ 7 mole to 1 x 10 ⁇ 2 mole, and most preferably in the amounts of 1 x 10 ⁇ 6 to 1 x 10 ⁇ 3 mole per mole of silver.
  • the sensitizing dyes are used to spectrally sensitize each of the different emulsions to the desired wavelengths for laser imaging.
  • Reasonable sensitizing ranges would include 400 to 550 nm, 400 to 450 nm, 470 to 500 nm (esp. 488 nm), 600 to 680 nm (esp. 633 nm and 670 nm), 700 to 1300 nm, and 750 to 900 nm, (esp. 780 nm, 800 nm, 810 nm, 830 nm, 850 nm and 880 nm).
  • sensitizing dyes are usually dissolved in a suitable solvent such as methanol, ethanol, dimethyl formamide, cellusolve, acetone, water, pyridine, or a mixture thereof before adding them to the emulsion. Once added, the mixture is stirred well and the dye compounds are added, usually just prior to coating.
  • a suitable solvent such as methanol, ethanol, dimethyl formamide, cellusolve, acetone, water, pyridine, or a mixture thereof.
  • any of the various types of photographic silver halide emulsions may be used in the practice of the present invention.
  • Silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and mixtures thereof may be used for example. Any configuration of grains, cubic orthorhombic, hexagonal, epitaxial, lamellar, tabular or mixtures thereof may be used.
  • These emulsions are prepared by any of the well-known procedures, e.g., single or double jet emulsions as described by Wietz et al., U.S. Pat. No. 2,222,264, Illingsworth, U.S. Pat. No. 3,320,069, McBride, U.S. Pat. No. 3,271,157 and U.S. Pat. Nos. 4,425,425 and 4,425,426.
  • the silver halide emulsions sensitized with the dyes of this invention can be unwashed or washed to remove soluble salts.
  • the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed e.g., by the procedures described in Hewitson et al., U.S. Pat. No. 2,618,556; Yutzy et al., U.S. Pat No. 2,614,928; Yackel, U.S. Pat. No. 2,565,418; Hart et al., U.S. Pat. No. 3,241,969; and Waller et al., U.S. Pat. No. 2,489,341.
  • Photographic emulsions in accordance with this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • chemical sensitizers such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
  • Suitable chemical sensitization procedures are described in Shepard, U.S. Pat. No. 1,623,499; Waller, U.S. Pat. No. 2,399,083; McVeigh, U.S. Pat. No. 3,297,447; and Dunn, U.S. Pat. No. 3,297,446.
  • the sensitized silver halide emulsions of this invention can contain speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper, U.S. Pat. No. 2,886,437; Chechak, U.S. Pat. No. 3,046,134; Carroll et al., U.S. Pat. No. 2,944,900; and Goffe, U.S. Pat. No. 3,294,540.
  • speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper, U.S. Pat. No. 2,886,437; Chechak, U.S. Pat. No. 3,046,134; Carroll et al., U.S. Pat. No. 2,944,900; and Goffe, U.S. Pat. No. 3,294,540.
  • Silver halide emulsions of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable antifoggants and stabilizers which can be used alone or in combination, include the thiazolium salts described in Staud, U.S. Pat. No. 2,131,038 and Allen U.S. Pat. No. 2,694,716; the azaindenes described in Piper, U.S. Pat. No. 2,886,437 and Heimbach, U.S. Pat. No. 2,444,605; the mercury salts described in Allen, U.S. Pat. No. 2,728,663; the urazoles described in Anderson, U.S. Pat. No.
  • Silver halide emulsions in accordance with the invention can be dispersed in colloids that can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy compound, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides, e.g., dialdehyde starch, oxyguargum, etc.
  • various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy
  • Photographic emulsions described herein can contain various colloids alone or in combination as vehicles or binding agents.
  • Suitable hydrophilic materials include both naturally-occurring substances such as proteins, for example gelatin, gelatin derivatives (e.g., phthalated gelatin), cellulose derivatives, polysaccharides such as dextran gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds, e.g., poly(vinylpyrrolidone) acrylamide polymers or other synthetic polymeric compounds such as dispersed vinyl compounds in latex form, and particularly those which increase the dimensional stability of the photographic materials.
  • Suitable synthetic polymers include those described, for example, in U.S. Pat. Nos.
  • Emulsions in accordance with this invention can be used in photographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Pat. Nos. 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Pat. No. 3,428,451.
  • antistatic or conducting layers such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Pat. Nos. 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Pat. No. 3,428,451.
  • Photographic emulsions of the invention can be coated on a wide variety of supports.
  • Typical supports include polyester film, subbed polyester film, poly(ethyleneterephthalate) film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related 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.
  • Emulsions of the invention can contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robins, U.S. Pat. No. 2,588,765 and Duane, U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Patent 955,061.
  • plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robins, U.S. Pat. No. 2,588,765 and Duane, U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Patent 955,061.
  • the photographic emulsion as described herein can contain surfactants such as saponin, anionic compounds such as the alkylarylsulfonates described in Baldsiefen, U.S. Pat. No. 2,600,831, fluorinated surfactants, and amphoteric compounds such as those described in Ben-Ezra, U.S. Pat. No. 3,133,816.
  • surfactants such as saponin
  • anionic compounds such as the alkylarylsulfonates described in Baldsiefen, U.S. Pat. No. 2,600,831, fluorinated surfactants
  • amphoteric compounds such as those described in Ben-Ezra, U.S. Pat. No. 3,133,816.
  • Photographic elements containing emulsion layers sensitized as described herein can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. No. 2,992,101 and Lynn, U.S. Pat. No. 2,701,245.
  • matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. No. 2,992,101 and Lynn, U.S. Pat. No. 2,701,245.
  • Spectrally sensitized emulsions of the invention can be utilized in photographic elements which contain brightening agents including stilbene, triazine, oxazole and coumarin brightening agents.
  • Brightening agents including stilbene, triazine, oxazole and coumarin brightening agents.
  • Water soluble brightening agents can be used such as those described in Albers et al., German Patent 972,067 and McFall et al., U.S. Pat. No. 2,933,390 or dispersions of brighteners can be used such as those described in Jansen, German Patent 1,150,274 and Oetiker et al., U.S. Pat. No. 3,406,070.
  • Photographic elements containing emulsion layers sensitized according to the present invention can be used in photographic elements which contain light absorbing materials and filter dyes such as those described in Sawdy, U.S. Pat. No. 3,253,921; Gaspar, U.S. Pat. No. 2,274,782; Carroll et al., U.S. Pat. No. 2,527,583 and Van Campen, U.S. Pat. No. 2,956,879.
  • the dyes can be mordanted, for example, as described in Milton and Jones, U.S. Pat. No. 3,282,699.
  • Contrast enhancing additives such as rhodium, iridium, ruthenium and combinations thereof are also useful in addition to the hydrazides.
  • Photographic emulsions of this invention 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, U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Pat. No. 2,761,791 and Wynn, British Patent 837,095.
  • photographic addenda such as coating aids, antistatic agents, acutance dyes, antihalation dyes and layers, antifoggants, latent image stabilizers, antikinking agents, and the like may also be present.
  • HIRF high intensity reciprocity failure
  • stabilisers for this purpose are chloropalladites and chloroplatinates (U.S. Pat. No. 2,566,263), iridium and/or rhodium salts (U.S. Pat. Nos. 2,566,263; 3,901,713), cyanorhodates (Beck et al., J. Signaletzorulsmaterialen, 1976, 4, 131), ruthenium and cyanoiridates.
  • C infrared sensitive dye
  • C infrared sensitive dye
  • the separately finalled emulsions were then either mixed together just prior to coating or better yet coated as separate layers at the same time with a topcoat and in-line mixed hardener (triazine).
  • a topcoat and in-line mixed hardener triazine
  • an emulsion was attempted to be sensitized to all three wavelength regions at once by adding all three dyes to the one emulsion in various orders of addition.
  • All film samples were exposed on a laser sensitometer which can selectively expose with either an Argon ion, He-Ne or IR laser through a 0 - 3.0 density continuous tone wedge with a midrange exposure level of 5, 2 or 20 erg/cm sq at the film plane, respectively.
  • all samples were processed through Excelerate chemistry at 97°F and 35 seconds processing time in a RA-66 processor. These materials were coated on the opposite side of 4 mil (0.1mm) PET coated with an IR AH (Infrared Anti-halo layer) and hardened with triazine hardener.
  • IR AH Infrared Anti-halo layer
  • the IR dye is not adsorbed strongly enough to prevent it being displaced by the other dyes upon mixing all three emulsions together, even just prior to coating. This desorption may also be due to the difference in quantities of dye necessary for optimum sensitizing between the AR and HN dyes, which are added at roughly 10 times greater levels, and the IR dye.
  • a hydrazine compound (hydrazide) has to be present during development of the exposed element.
  • the hydrazine compound (hydrazide) can be incorporated in the photographic element or in the developing solution or both in the developing solution and in the photographic element. It is preferred to be in at least the element itself.
  • Hydrazine and any water soluble hydrazine derivatives are effective in increasing contrast when incorporated in the developing solution in combination with the diarylmethanol compound incorporated in the photographic element.
  • Preferred hydrazine derivatives to be used in the developing solution of this invention include compounds of formula (I): wherein R5 is an organic radical and R6, R7, and R8 each are hydrogen or an organic radical.
  • Organic radicals represented by R5, R6, R7, and R8 include hydrocarbon groups, such as an alkyl group, an aryl group, an arylalkyl group and an alicyclic group and such groups can be substituted with substituents such as alkoxy groups, carboxy groups, sulfonamido groups and halogen atoms.
  • hydrazine derivatives which can be incorporated in the developing solutions, are hydrazides (including aryl hydrazides and formyl hydrazides), acyl hydrazines, semicarbazides, carbohydrazides and aminobiuret compounds.
  • the hydrazine compound is incorporated in the photographic element, for example, in a silver halide emulsion layer or in a hydrophilic colloidal layer, preferably a hydrophilic colloidal layer adjacent to the emulsion layer in which the effects of the hydrazine compound are desired. It can, of course, be present in the photographic element distributed between the emulsion and the hydrophilic colloidal layers, such as a subbing layer, interlayers and protective layers.
  • Hydrazine compounds suitable to be incorporated into the photographic element according to the present invention are disclosed in G. B. Patent Specification 598,108 and in U.S. Patent Specification 2,419,974; they include the water soluble alkyl, aryl and heterocyclic hydrazine compounds, as well as the hydrazide, semicarbazide and aminobiuret compounds.
  • Particularly preferred hydrazine compound for use according to this invention incorporated in the photographic element, are the formylhydrazine compounds corresponding to the formula (II): wherein R4 represents a substituted or unsubstituted aromatic group.
  • aromatic groups represented by R4 include a phenyl group and a naphthyl group.
  • Such aromatic groups may be substituted with one or more substituents which are not electron attracting, such as straight or branched-chain alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-hexyl, tert-octyl, n-decyl, n-dodecyl, etc.), arylalkyl groups (e.g., methoxy, ethoxy, 2-methyl-propyloxy, etc.), amino groups which are mono- or disubstituted with alkyl groups, acylaminoaliphatic groups (e.g., acetylamino, benzoylamino, etc.), etc., as disclosed in U.S.
  • substituents which are not electron attracting such as straight or branched-chain alkyl groups (e.g., methyl, ethyl,
  • Patent 4,168,977 and a CA Patent 1,146,001 Such aromatic groups may also be substituted with a ureido group of formula (III):
  • R9 and R10 each represents hydrogen, a aliphatic group (such as a straight or branched-chain alkyl groups, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group and an alkynyl group), an aromatic group (such as a phenyl group and a naphthyl group) or a heterocyclic group;
  • R11 represents hydrogen or an aliphatic group (such as those listed above) as described in U.S. Patent 4,323,643.
  • hydrazine compounds for use according to this invention, incorporated in the photographic element are those represented by the formula (IV): wherein R12 represents the same aromatic group of the formula above and R13 represents an alkyl group have 1 to 3 carbon atoms, which may be a straight or branch-chain alkyl (e.g., methyl, ethyl, n-propyl and isopropyl) or a phenyl group.
  • the phenyl group may be substituted with one or more substituents which preferably are electron attracting groups, such as halogen atoms (chlorine, bromine, etc.), a cyano group, a trifluoromethyl group, a carboxy group or a sulfo group, etc.
  • substituents such as halogen atoms (chlorine, bromine, etc.), a cyano group, a trifluoromethyl group, a carboxy group or a sulfo group, etc.
  • hydrazine compounds for use according to this invention incorporated in the photographic element, are those corresponding to the formula (V): wherein R14 represents hydrogen, an aliphatic group which may be substituted; Y represents a divalent linking group; m represents 0 or 1; X represents a divalent aromatic groups (such as for example a phenylene group, a naphthylene group and the analogous substituted groups thereof); R15 represents a hydrogen atom, an aliphatic groups which may be substituted and Z represents a non metallic atom group necessary to form a 5- or a 6-membered heterocyclic ring.
  • R14 represents hydrogen, an aliphatic group which may be substituted
  • Y represents a divalent linking group
  • m represents 0 or 1
  • X represents a divalent aromatic groups (such as for example a phenylene group, a naphthylene group and the analogous substituted groups thereof)
  • R15 represents a hydrogen atom, an aliphatic groups which may be
  • R11 is as defined previously above
  • M is NH2 or OH
  • a compound of the above formula in which M is OH, p is zero and t is zero is known; the remaining compounds are novel and form a further aspect of this invention.
  • Particularly preferred compounds of the invention are the formula (VII): in which: R11 is as defined above.
  • Such hydrazine compounds can be incorporated in the photographic element using various methods well-known in the photographic art, the most common being the method of dissolving the hydrazine derivatives in a high boiling crystalloidal solvent and dispersing the mixture in the emulsion, as described for example in U.S. Patent 2,322,027.
  • Hydrazine compounds incorporated in the developing solution in the practice of this invention are effective at low concentrations.
  • hydrazine compounds give useful results in the developing solution in a quantity of about 0.001 moles per liter to about 0.1 moles per liter, more preferably in a quantity from about 0.002 to about 0.01 moles per liter.
  • Hydrazine compounds incorporated in the photographic element are typically employed in a concentration ranging from about 5 x 10 ⁇ 4 to about 5 x 10 ⁇ 2 moles per mole of silver and preferable in a quantity from about 8 x 10 ⁇ 4 to about 8 x 10 ⁇ 3 moles per mole of silver.
  • Contrast promoting agents such as alkanolamines and diarylcarbinol compounds, preferably the diarylcarbinols such as diarylmethanol compounds described herein, are incorporated into the developer bath or preferably the photographic element prior to contact with the whole developer solution and preferably prior to the exposure of the photographic element itself, such as for example, when the diarylcarbinol compound is introduced into the element prior to or contemporaneously with the coating of the emulsion layer.
  • they can be incorporated in the silver halide emulsion layer of the element or in a hydrophilic colloidal layer of the element, particularly a hydrophilic colloidal layer adjacent to the emulsion layer in which the effects of the diarylcarbinol compounds are desired.
  • They can, for instance, be present in the photographic element distributed between the emulsion and they hydrophilic colloidal layers, such as for instance a subbing layer, interlayers and protective layers.
  • Parameters to take into proper account are solubility and boiling points of the diarylcarbionol compounds of the present invention.
  • Said compounds are to be substantially soluble in water or soluble in water miscible solvents (by "substantially soluble” in water is meant that they are to be soluble in water in a quantity of at least 1% by weight and by "soluble" in water-miscible solvents it is meant that they are to be soluble in water miscible solvents in a quantity of at least 5% by weight) in order to introduce them into the aqueous coating compositions used to form the layers of the photographic elements according to the present invention.
  • Said diarylcarbinol compounds are required to have a sufficiently high boiling point not to evaporate during drying of the layer forming coating composition.
  • Said boiling points are preferably higher than 150°C, more preferably higher than 200°C.
  • diarylcarbinol compounds include the following:
  • the image-wise exposed silver halide photographic element can be processed with a stable aqueous alkaline developing solution to produce a high contrast negative image.
  • This contrast is the slope for the straight line portion of the characteristic sensitometric curve (referred to as "average contrast") and is measured between two points located at densities of 0.10 and 2.50 above fog.
  • Averages contrast higher than 10 can be obtained according to this invention by developing an image-wise exposed element in the presence of a hydrazine compound.
  • the dihydroxybenzene developing agents employed in the aqueous alkaline developing solution for use in the practice of this invention are well-known and widely used in photographic processings.
  • the preferred developing agent of this class is hydroquinone.
  • Other useful dihydroxybenzene developing agents include chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, tolylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 1,4-dihydroxy-2-acetophenone-2,5-dimethylhydroquinone,2,5-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5-dibenzoylhydroquinone, 2,5-diacetaminohydroquinone and the like.
  • 3-pyrazolidone developing agents employed (and which may or may not be present in the aqueous alkaline developing solution or the emulsion) in the practice of this invention are also well known and widely used in photographic processings.
  • the most commonly used developing agents of this class are 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.
  • 3-pyrazolidone developing agents include: 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4-methyl-4-propyl-3-pyrazolidone, 1-p-chlorophenyl-4-methyl-4-ethyl-3-pyrazolidone, 1-p-acet-amidophenyl-4,4-diethyl-3-pyrazolidone, 1-p-Beta-hydroxy-ethylphenyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxy-phenyl-4,4-dimethyl-3-pyrazoidone, 1-p-methoxyphenyl-4,4-diethyl-3-pyrazoidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, and the like.
  • the preferred aqueous alkaline photographic developing composition for use in the practice of this invention contains a sulfite preservative at a level sufficient to protect the developing agents against aerial oxidation and thereby assure good stability characteristics.
  • Useful sulfite preservatives include sulfites, bisulfites, metabisulfites and carbonyl bisulfite adducts.
  • Typical examples of sulfite preservatives include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde bisulfite salt and the like.
  • ascorbic acid is a known preservative agent against aerial oxidation of the developer for use in the bath according to this invention.
  • the aqueous alkaline developing solutions for use in the practice of this invention can vary widely with respect to the concentration of the various ingredients included therein.
  • the dihydroxybenzene developing agent is used in an amount of from 0.040 to about 0.70 moles per liter, more preferably in an amount of from 0.08 to about 0.40 moles per liter;
  • the 3-pyrazolidone developing agent is used in an amount of from about 0.001 to about 0.05 moles per liter, more preferably in an amount of from about 0.005 to about 0.01 moles per liter;
  • the sulfite preservative is used in an amount from about 0.03 to about 1.0 moles per liter, more preferably in an amount from about 0.10 to about 0.70 moles per liter.
  • the developing solutions of this invention can utilize higher levels of sulfite ions, and thereby achieve the advantages of increased stability, since a higher level of sulfite ions provides increased protection against aerial oxidation.
  • an organic antifogging agent to minimize fog formation in the processed element.
  • the organic antifogging agent can be incorporated in the photographic element or can be added to the developing solution or can be both incorporated in the photographic element and added to the developing solution.
  • more preferred organic antifogging agents for specific use in the developing solutions are benzotriazole and/or a benzimidazole antifogging agent, which proved to have beneficial effects on increasing contrast.
  • Useful compounds are both substituted and unsubstituted benzotriazole and benzimidazole compounds, with the provision that electron withdrawing substituents at least as strong as nitro groups are excluded.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19920307545 1991-09-03 1992-08-18 Multi-wavelength sensitive black-and-white graphic arts film Withdrawn EP0531014A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US75391191A 1991-09-03 1991-09-03
US753911 1991-09-03

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EP0531014A2 true EP0531014A2 (de) 1993-03-10
EP0531014A3 EP0531014A3 (en) 1993-03-24

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5589318A (en) * 1994-04-16 1996-12-31 Eastman Kodak Company High contrast photographic silver halide material
US6383711B1 (en) 1998-12-19 2002-05-07 Eastman Kodak Company High contrast photographic silver halide material
US6416924B1 (en) * 1999-11-16 2002-07-09 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2134546A (en) * 1936-07-14 1938-10-25 Agfa Ansco Corp High speed infrared film
US3227552A (en) * 1960-05-13 1966-01-04 Eastman Kodak Co Preparation of photographic direct positive color images
US4920034A (en) * 1985-10-17 1990-04-24 Fuji Photo Film Co., Ltd. Silver halide photographic material and image forming method using the same
US4950578A (en) * 1988-07-19 1990-08-21 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0480264A1 (de) * 1990-09-28 1992-04-15 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und dieses Material verwendendes Bilderzeugungsverfahren

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2134546A (en) * 1936-07-14 1938-10-25 Agfa Ansco Corp High speed infrared film
US3227552A (en) * 1960-05-13 1966-01-04 Eastman Kodak Co Preparation of photographic direct positive color images
US4920034A (en) * 1985-10-17 1990-04-24 Fuji Photo Film Co., Ltd. Silver halide photographic material and image forming method using the same
US4950578A (en) * 1988-07-19 1990-08-21 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0480264A1 (de) * 1990-09-28 1992-04-15 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und dieses Material verwendendes Bilderzeugungsverfahren

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5589318A (en) * 1994-04-16 1996-12-31 Eastman Kodak Company High contrast photographic silver halide material
US6383711B1 (en) 1998-12-19 2002-05-07 Eastman Kodak Company High contrast photographic silver halide material
US6416924B1 (en) * 1999-11-16 2002-07-09 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same

Also Published As

Publication number Publication date
EP0531014A3 (en) 1993-03-24
JPH05197058A (ja) 1993-08-06

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