US3600177A - Liquid amides as silver halide developer solvents - Google Patents

Liquid amides as silver halide developer solvents Download PDF

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US3600177A
US3600177A US669863A US3600177DA US3600177A US 3600177 A US3600177 A US 3600177A US 669863 A US669863 A US 669863A US 3600177D A US3600177D A US 3600177DA US 3600177 A US3600177 A US 3600177A
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silver halide
emulsion
silver
solvent
photographic
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Thomas I Abbott
Robert N Woodward
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • 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
    • Y10S430/141—Direct positive material

Definitions

  • n is l or 2; R represents an alkyl group of at least four carbon atoms when n is 1; R represents an aryl group when n is 2; and R and R may be hydrogen, lower alkyl of from 1 to 4 carbon atoms, or may represent an aryl group or may be joined to form a heterocyclic nucleus, are used for incorporating developers in photographic emulsions either alone or in conjunction with high boiling oil solvents.
  • This invention relates to photographic emulsions and elements.
  • this invention relates to 3 emulsions containing liquid amides as solvents for incorporated silver halide developing agents.
  • developing agents in silver halide emulsions.
  • Water insoluble developing agents can be incorporated in certain oil solvents such as, for instance, tricresyl phosphate, dibutyl phosphate, etc. It appears that the solvent is in liquid particles in the dried emulsion. However, a large excess of the oil solvent is necessary to keep the development agent in a specific layer until released by an alkaline activator.
  • oil solvents such as, for instance, tricresyl phosphate, dibutyl phosphate, etc. It appears that the solvent is in liquid particles in the dried emulsion. However, a large excess of the oil solvent is necessary to keep the development agent in a specific layer until released by an alkaline activator.
  • the use of the dispersed developing agents results in photographic elements exhibiting very low photographic speed. This is particularly evident in the use of direct positive elements.
  • the support contains a gelatin layer having therein an incorporated developing agent over which is coated a light sensitive silver emulsion followed by a top layer of a fogged emulsion.
  • the developing agent develops the light sensitive emulsion in the exposed areas while the developing agent in the unexposed areas migrates to the top fogged emulsion while development takes place to obtain a direct positive image.
  • One object of this invention is to provide substituted amides which can be used as liquid solvents for silver halide developing agents dispersed in silver halide emulsions. Another object is to provide a photographic element 0 having at least one incorporated developing agent in the silver halide emulsion. A further object is to provide lithographic printing plates having thereon direct positive silver halide emulsions containing incorporated developing agents. A further object is to provide a lithographic element having better lithographic differential, better physical properties, better emulsion stability and higher photographic speed. A still further object is to provide a method of making silver halide emulsions having therein an incorporated developing agent. Additional objects will be evi- 0 dent from the following disclosure.
  • R represents an alkyl group of at least 4, and generally about 4 to 20 carbon atoms, such as, for example, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, tridecyl, lauryl, palmityl, stearyl, eicosyl; wherein each of R and R are hydrogen, lower alkyl from 1 to 4 carbon atoms, or represent an aryl group or are joined to form a heterocyclic nucleus.
  • R is aryl, such as, for example, phenyl or naphthyl which can contain substituents such as halogen, lower alkyl, amide, lower alkoxy, hydroxy and the like.
  • the amount of amide solvent to developer is advantageously within range of about 1:1 to about 1:15 by weight, preferably 1:4 to 1:7. If used in conjunction with an oil solvent such as liquid inert esters, it may be mixed in any proportion. However, a particularly advantageous solvent mixture comprises at least 25% by weight of the developer solvent of our invention.
  • the oil solvents for developers substantially water insoluble, low molecular weight, organic oils having boiling points above about C.
  • One embodiment of our invention relates to a lithographic printing plate comprising a direct positive emulsion having therein a liquid amide such as, for example, diethyllauramide in which is dispersed a silver halide developing agent such as, for example, 4-phenyl catechol.
  • a liquid amide such as, for example, diethyllauramide in which is dispersed a silver halide developing agent such as, for example, 4-phenyl catechol.
  • This plate is exposed, processed in an alkaline activator solution and printed on a lithographic printing press giving a positive lithographic print.
  • the emulsion as described above also contains an oil solvent such as, for example, tricresyl phosphate.
  • an oil solvent such as, for example, tricresyl phosphate.
  • Silver halide emulsions which are used in the practice of our invention include the conventional silver halide emulsions such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
  • the ink receptive areas of the printing plates on a background of hydrophilic material are obtained by alkaline activation of a silver salt, preferably silver halide, developing agent in the presence of a gelatin, silver salt emulsion layer.
  • a silver salt preferably silver halide
  • developing agent in the presence of a gelatin, silver salt emulsion layer.
  • the result is to form a silver image and oxidized developing agent in the region of development.
  • the element can then be inked in the developed areas with greasy printing ink and a posi tive print made therefrom in a lithographic press.
  • the gelatin in the emulsion layer can undergo additional hardening at the same time as development.
  • the developing agents employed in the practice of this invention include any developing agents which are capable of oxidation in the presence of the hardened gelatin present in the photographic emulsion layer to produce an image receptive to greasy printing ink, i.e. upon development, they render the gelatin in the developed areas oleophilic.
  • the polyhydroxy benzene developing agents substituted with halogen, monocyclic aryl groups of the benzene series and alkyl groups of at least 2 and preferably from 2 to 6 carbon atoms have this property.
  • the 1,2- dihydroxy benzene developing agents substituted by halogen, monocyclic aryl of the benzene series and alkyl groups of at least 2 carbon atoms and preferably 2 to 6 carbon atoms are particularly useful in the process.
  • Developing agents possessing the necessary properties thus include certain polyhydroxy benzene developing agents such as pyrogallol and substituted polyhydroxy benzene developing agents, particularly dihydroxy benzenes substituted with, for example, halogen, alkyl groups of at least 2 and preferably from 2 to 6 carbon atoms and a monocyclic aryl group of the benzene series, e.g.
  • esters are intended to be included in the specification and claims where reference is made to polyhydroxy benzene developing agents.
  • an auxiliary developing agent such as monomethyl-p-aminophenol or a 3-pyrazolidone which latter developing agents by themselves do not yield oleophilic images in the processes described, but which do appear to act synergistically with the polyhydroxy benzenes to yield oleophilic images.
  • the developing agents are generally employed in the photographic elements at coverages of about 5 to about 200, preferably about to about 50 mg./ft. of support and are incorporated in a layer which is no farther from the support than the photographic emulsion layer, i.e. they are incorporated into the photographic emulsion layer or a layer between the emulsion layer and the support, e.g. an adjacent or contiguous layer.
  • the photographic emulsion layer may advantageously be a gelatin layer having a hardness depending upon the purpose for which the emulsion is intended. For instance, if the emulsion is to be used in a colloid transfer system such as that described in U.S. Pat. 2,596,756, issued May 13, 1952 to Yutzy et al., the emulsion is substantially unhardened. However, if the intended emulsion is to be used for preparing a printing plate of the type disclosed in U.S. Pat. 3,146,104, the emulsion layer should be substantially hardened in order to prevent the process plate from adhering to printing blankets, papers, etc.
  • the emulsion should 4 be as hard as a gelatin layer containing at least about 2 grams and preferably about 2 to 15 grams of dry formaldehyde per pound of gelatin, i.e. it should have a melting point in water greater than 150 F. and preferably greater than 200 F.
  • colloids can be used either with gelatin or substituted for gelatin as vehicles or binding agents in the photographic emulsion layers employed in the practice of this invention.
  • gelatin or gelatin derivatives which are primarily gelatin, are used for at least a part, for example, at least 10%, by weight, of the binder in the photographic element.
  • Other binding agents which can be used with the gelatin or colloidal material such as colloidal albumin, cellulose derivatives, synthetic resins, such as polyvinyl compounds, acrylamide polymers, or the like.
  • gelatin can be the sole binding agent, it is often advantageous to employ combinations of binding agents, particularly mixtures of gelatin with aqueous dispersions of polymerized ethylenically unsaturated compounds.
  • the binding agent is generally coated at a coverage in the range of about 50 to 2000, advantageously about mg. to about 1000 mg. per square foot of support.
  • Direct positive emulsions which may be used include 1) solarizing silver halide emulsions and (2) internal latent image silver halide emulsions forming the latent image mostly inside the silver halide grains.
  • the solarizing direct positive silver halide emulsions are silver halide emulsions which have been effectively fogged either chemically or by radiation, to a point which corresponds approximately to the maximum density of the reversal curve as shown by Mees, The Theory of the Photographic Process, published by Macmillan Co., New York, N.Y., 1942, pages 261-297.
  • Conventional silver halide developing solutions can be used to develop a direct positive image in the solarizing emulsions.
  • the internal latent image direct positive silver halide emulsions used in the invention are those well known in the art which upon exposure form the latent image mostly inside the silver halide grains, the direct positive properties of the emulsions being attributable to the crystalline structure of the silver halide grains. That is, a number of authorities in the field of photography have shown that there are imperfections or flaws, in the crystal structure (on the surface or internally) of silver halide which is used in photography, at which flaws the latent image forms by trapping photoelectrons to give development centers. Development, therefore, commences at the sites of these flaws. Journal of Photographic Science. Photographic Sensitivity, text of a lecture given on July 1, 1957 by J. W. Mitchell; vol. 6, No. 3 (1958).
  • photographic reversal emulsions may be used including those containing grains comprising a central core of a water insoluble silver salt containing centers which promote the deposition of photolytic silver and an outer shell or covering for such core of a fogged or spontaneously developable water insoluble silver salt.
  • the fogged shell of such grains is developed to silver without exposure. Emulsions of this type are described in Berriman US. Pat. 3,367,778, issued Feb. 6, 1968.
  • the core forming emulsion is first chemically or physically treated by methods previously described in the prior art to produce centers which promote the deposition of photolytic silver, i.e., latent image nucleating centers.
  • centers can be obtained by various techniques as described by Antoine Hautot and Henri Saubenier in Science et Industries Photographiques, vol. XXVIII, January 1957, pages 57-65, are particularly useful.
  • Such chemical sensitization includes three major classes, namely, gold or noble metal sensitization, sulfur sensitization, such as labile sulfur compound and reduction sensitization, i.e. treatment of the silver halide with a strong reducing agent which introduces small specks of metallic silver into the silver salt crystal or grain.
  • the core forming emulsions can be chemically sensitized by any method suitable for this purpose.
  • the core forming emulsions can be digested with naturally active gelatin or sulfur compounds can be added to those described in Shepard US. Pat. 1,574,944, issued Mar. 2, 1926, Shepard et al. US. Pat. 1,623,499, issued Apr. 5, 1927 and Shepard et al. US. Pat. 2,410,689, issued Nov. 5, 1946.
  • the core forming emulsions can also be chemically sensitized with gold salts as described in Waller et al. US. Pat. 2,399,083, issued Apr. 23, 1946 and Damschroder et al. US. Pat. 2,642,361, issued June 16, 1953.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, aurictrichloride and 2-aurosulfobenzothiazole methylchloride.
  • the core forming emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U.S. Pat. 2,487,850, issued Nov. 15, 1949), polyamines such as diethylenetriamine (Lowe and Jones US. Pat. 2,618,598, issued Aug. 15, 1950), polyamines such as spermine (Lowe and Allen US. Pat. 2,521,925, issued Sept. 12, 1950) or bis-(beta-aminoethyl)sulfide and its water soluble salts (Lowe and Jones US. Pat. 2,521,926, issued Sept. 12, 1950).
  • reducing agents such as stannous salts (Carroll U.S. Pat. 2,487,850, issued Nov. 15, 1949), polyamines such as diethylenetriamine (Lowe and Jones US. Pat. 2,618,598, issued Aug. 15, 1950), polyamines such as spermine (Lowe and Allen US. Pat. 2,521,925, issued Sept. 12, 1950) or bis-(be
  • the shell of the grains comprising the emulsions used in practicing this invention is prepared by precipitating over the core grains a light sensitive water insoluble silver salt that can be fogged and which fog is removable by bleaching.
  • the shell is of sufficient thickness to prevent access of the developer used in processing the emulsions of the invention to the core.
  • the silver salt shell is surface fogged to make it developable to metallic silver with conventional surface image developing compositions.
  • the silver salt of the shell is sufiiciently fogged to produce a density of at least about 0.5 when developed for 6 minutes at 68 F. in Developer A below when the emulsion is coated at a silver coverage of 100 mg. per square foot.
  • Such fogging can be effected by chemically sensitizing to fog with the sensitizing agents described for chemically sensitizing the core forming emulsion, high intensity light and like fogging means well known to those skilled in the art.
  • the shell is fogged, for example, reduction fogged with a reducing agent such as stannous chloride. Fogging by means of a reduction sensitizer, a noble metal salt such as gold salt plus a reduction sensitizer, high pH and low pAg silver halide precipitating conditions, and the like can be suitably utilized.
  • the shell portion of the subject grains can also be coated prior to fogging.
  • Another direct positive silver halide emulsion which can be used is a fogged direct positive silver halide emulsion comprising silver halide grains which have a uniform diameter frequency distribution, i.e. silver halide grains which have substantially uniform diameter.
  • the direct positive photographic emulsion comprises fogged silver halide grains, at least by weight of said grains having a diameter which is within about 40% of the mean grain diameter.
  • photographic emulsions of this type comprise reduction and gold fogged silver halide grains and a compound which accepts electrons.
  • the use of low concentrations of reduction and gold fogging agents, in preparing such emulsions gives unique fogged silver halide grains which are characterized by a very high photographic speed in conventional photographic processing solutions.
  • Typical flexible supports include those generally employed in printing plates, as exemplified by metals such as aluminum, paper, cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethyene terephthalate and related films or resinous materials and other related materials.
  • Supports include paper which may be partially acetylated or coated with an alpha-olefin polymer, par ticularly a polymer of an alpha-olefin containing 2-10 carbon atoms, as exemplified by polyethylene, polypropylene, ethylenebutene copolymers and the like give good results.
  • the photographic elements or printing plates of this invention can include antihalation layers which are generally coated between the photographic emulsion layer and the support.
  • Suitable layers of this type include gelatin layers containing organic and inorganic dyes or pigments such as Naphthol Red dye, pigments such as colloidal carbon or silver, zinc oxide, titanium dioxide, iron oxide and the like which can be dyed, if desired, with such dyes as the merocyanines and the like, or paper coated with an alpha-olefin polymer employed as the support.
  • organic and inorganic dyes or pigments such as Naphthol Red dye, pigments such as colloidal carbon or silver, zinc oxide, titanium dioxide, iron oxide and the like which can be dyed, if desired, with such dyes as the merocyanines and the like, or paper coated with an alpha-olefin polymer employed as the support.
  • a dye and/or a pigment into the resin coating on the photographic emulsion side surface of the support which serves as an antihalation layer.
  • FIG. 1 a negative-positive process is illustrated and in FIG. 2 is shown a positivepositive process contemplated "by our invention.
  • layer 10 of the element of stage one represents a support such as paper, film base, etc.
  • Layer 11 is a hydrophilic organic colloid layer such as gelatin containing the developing agent and silver halide.
  • FIG. 2 is shown a positive-positive system in stage one of which the element included a support 20 such as a paper or film support, layer 23 comprising a fogged silver halide emulsion layer containing a developing agent.
  • the element Upon image exposure in region 24, followed by alkaline activation and inking, the element appears substantially as shown in stage two, the silver halide developing agent of layer 23 having developed a positive silver halide image to silver in areas 25 of layer 23.
  • the ink images 26 are accepted in areas 25 which are composed of silver and the reaction product of the organic hydrophilic colloid present in the silver halide emulsion layer and the oxidized developing agent.
  • the remaining areas 27 are hydrophilic and repel printing ink when the plate is moistened in the lithographic printing press.
  • Positive working lithographic plates can be made using conventional negative speed photographic silver halide emulsions containing an oxidizing developer solvent dispersion of this invention by the use of a processing cycle comprising the following steps:
  • Negative development in a developer such as Kodak D-72 Developer, containing at least grams of sodium sulfite per liter followed by a rinse. These developed areas are hydrophilic. The oxidizing development agents are quite insoluble in the pH range and, consequently, are not washed out during this negative development.
  • control element (Sample A) is made up as follows:
  • the wetting agent is added to the carbon black and stirred until a smooth slurry is formed.
  • the 4-phenylcatechol is added to the solvent and heated at 220 F. until dissolved.
  • the gelatin is dissolved and melted at 140 F. Solutions (1) and (3) are blended and stirred for 5 minutes. Solution (2) is added and stirred for 5 minutes. The mixture is colloid milled three times.
  • MELT PREPARATION 7.6 kgs. of dry photographic gelatin is dissolved in 56.5 kgs. of distilled water and melted at 150 F. This is cooled to 107 F. and 75.72 kgs. of the above dispersion is added; also 2000 ml. of 5% of the above wetting agent is added and the combination is coated on polyethylene coated paper base. The coating is applied at 7.16 ml. per square foot giving 31.5 mg. of 4-phenyl-catechol per square foot.
  • the coating is applied at 40 on Layer I at 15.0 cc./ sq. ft.
  • the coating is applied at 40 C. on Layer II at 45 mg. of Ag/ sq. ft.
  • Sample B utilized 1260
  • Sample C utilized 3150
  • Sample -D utilized 4400
  • Sample E utilized 6300
  • Each of samples B, C, D and E is compared to sample A which requires 17 seconds exposure in a press camera to give an acceptable print. Processing and printing are in a conventional manner used in the art.
  • Sample E-the 1:10 developer to diethyllauramide solvent coating requires 12 seconds
  • Sample Dthe 1:7 developer to diethyllauramide solvent coating requires 12 seconds
  • Sample C-the 1:5 developer to diethyllauramide solvent coating requires 13 seconds
  • Sample Bthe 1:2 developer to diethyllauramide solvent coating requires 15 seconds
  • a material made with a tricresyl phosphate dispersion to a 1:2 developer to solvent ratio will not give an acceptable print with any exposure. Better lithographic latitude as well as increased speed shown above, is observed in coatings utilizing diethyllauramide.
  • Undercoats are prepared by coating dispersions contalning the following, on a polyethylene coated paper support:
  • Sample Athe 1:10 weight ratio tricresyl phosphate material requires 100 seconds exposure to produce an acceptable print
  • Sample B-the 1:10 weight ratio developer to solvent material requires 60 seconds
  • Sample Cthe 1:5 weight ratio developer to solvent material requires 60 seconds
  • Sample D--the 1:2 weight ratio developer to solvent material requires 100 seconds
  • a material made with tricresyl phosphate at 1:2 ratio will not produce any result.
  • EXAMPLE 3 An element utilizing an autopositive emulsion is prepared incorporating a developer dispersion made from a ratio of 4-phenyl catechol to solvent as follows:
  • Sample A One part by weight developer to 7 parts diethyllauramide.
  • the developer is employed at a level of 35 g./mole of Ag.
  • Sample B The 4-phenylcatechol is employed at a level of 21.4 grams per mole of silver in a weight ratio of 1 part to 7 parts diethyllauramide.
  • Sample C The developer dispersion contains 1 part by weight of 4-phenylcatechol to 15 parts of tricresyl phosphate.
  • the developer is employed at a level of 35 g./ mole of Ag.
  • Sample D The 4-phenylcatechol is employed at a level of 21.4 grams per mole of silver in a weight ratio of 1 part developer to 15 parts tricresyl phosphate.
  • EXAMPLE 4 A positive working presensitizied lithographic printing plate is prepared using a reversal emulsion of the type described in Berriman U.S. Pat. No. 3,367,778, issued Feb. 6, 1968 in combination with polyhydroxybenzene developing agents located in an adjacent layer beneath the photographic emulsion layer. To the emulsion are added the various oil solvent dispersions of 4-phenylcatech01 as described below. The emulsion containing the incorporated developer agent dispersions is then coated, at 440 ft. per silver mole, over a paper support which contains a sublayer of Ti pigmented polyethylene and a backing layer of clear polyethylene.
  • Sample A The emulsion contains a dispersion of 60 grams of 4-phenylcatechol in 300 grams tricresyl phosphate solvent.
  • Sample B-The emulsion contains a dispersion of 60 grams of 4-phenylcatechol in 300 grams dibutyl phthalate solvent.
  • Sample C The emulsion contains a dispersion of 60 grams of 4-phenylcatechol in 300 grams diethyllauramide solvent.
  • Sample D The emulsion contains a dispersion of 60 grams of 4-phenylcatechol in a combination of 240 grams of tricresyl phosphate solvent and 60 grams of diethyllauramide solvent.
  • Sample E--The emulsion contains a dispersion of 60 grams of 4-phenylcatechol in 180 grams of tricresyl phosphate solvent and 120 grams of diethyllauramide solvent.
  • Sample F The emulsion contains a dispersion of 60 grams of 4-phenylcatechol in 120 grams of tricresyl phosphate solvent and 180 grams of diethyllauramide solvent.
  • the direct positive photosensitive elements obtained are exposed by projection to a line original in a conventional process camera. Afiter 20 seconds activation at 75 F. in an 8% potassium phosphate solution, the plates are stopped in a phosphoric acid bath. The plates are then printed on a lithographic press giving a positive lithographic print.
  • EXAMPLE 5 A dispersion containing 4-phenylcatechol dissolved in tricresyl phosphate is added to a fogged direct positive gelation silver chloride emulsion which is coated on a polyethylene paper support at 72 mg. of silver, 215 mg. of gelatin, 45 mg. of 4-phenylcatechol and 340 mg. of tricresyl phosphate/ft? (11). A similar coating Without the dispersion is prepared as the control.
  • Solvent B is N,N,N',Ntetraethyl phthalamide.
  • Dispersions containing 4-phenylcatechol, Solvent B and gelatin are coated on polyethylene coated paper support at the following coverages:
  • Solvent B is N,N,N',N'-tetraethyl phthalamide.
  • EXAMPLE 7 Positive working lithographic plates are made using conventional negative speed photographic silver halide emul- 11 sions containing the oxidizing developer solvent dispersions of this invention by the use of a processing cycle comprising the following steps:
  • Negative development in a developer such as Kodak D-72 Developer, containing at least 10 grams of sodium sulfite per liter followed by a rinse. These developed areas are hydrophilic. The oxidizing development agents are quite insoluble in the pH range and, consequently, are not washed out during this negative development.
  • water insoluble developing agent is intended those which have a solubility of less than 5 gm. in one liter of water at 20 C. and preferably less than 1 gm. in one liter of water at 20 C.
  • R represents an alkyl group of at least four carbon atoms and when n is 2, R is a divalent aryl group; wherein each R and R is hydrogen or lower alkyl from 14 carbon atoms.
  • a photographic element comprising a support having thereon said silver halide emulsion of claim 1.
  • a photographic element comprising a support having thereon a silver halide photographic emulsion and intermediate to said emulsion a layer containing a polyhydroxybenzene or substituted polyhydroxybenzene incorporated silver halide developing agent dissolved in a liquid solvent comprising a normally liquid substituted amide of the general formula:
  • n is an integer of 1 or 2, when n is 1, R represents an alkyl group of at least four carbon atoms and when n is 2, R is a divalent aryl group; wherein each R and R is hydrogen or lower alkyl from 1-4 carbon atoms.
  • a photographic element of claim 10 in which the said solvent contains 0-75 by weight of a substantially water insoluble, low molecular weight liquid ester having a boiling point above about C. and having a high solvent action for the silver halide developing agent.
  • a photographic element of claim 10 in which the said layer is contiguous to a gelatin silver halide emulsion and contains a sufiicient amount of a polyhydroxy benzene silver halide developing agent to develop the exposed silver halide in the said emulsion, said agent selected from the class consisting of halogen substituted, phenyl substituted and 26 carbon atoms containing alkyl substituted polyhydroxybenzene developing agents, the oxidation product of which renders gelatin oleophilic, said silver halide emulsion layer uniformly hardened with a hardener such that the emulsion has a hardness equivalent to that of a gelatin layer hardened with about 2 grams to about 15 grams of dry formaldehyde per pound of gelatin.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5039928A (xx) * 1973-08-15 1975-04-12
JPS5329718A (en) * 1976-08-31 1978-03-20 Chugai Shashin Yakuhin Lith photographic original developer
US4365072A (en) * 1981-10-22 1982-12-21 Polaroid Corporation Biphenyl aldehydes
US4417064A (en) * 1981-01-05 1983-11-22 Polaroid Corporation Biphenyl compounds and method of preparing same
US20100001164A1 (en) * 2008-07-02 2010-01-07 Popco, Inc. Poster clasp

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5039928A (xx) * 1973-08-15 1975-04-12
JPS5329718A (en) * 1976-08-31 1978-03-20 Chugai Shashin Yakuhin Lith photographic original developer
JPS5442766B2 (xx) * 1976-08-31 1979-12-15
US4417064A (en) * 1981-01-05 1983-11-22 Polaroid Corporation Biphenyl compounds and method of preparing same
US4365072A (en) * 1981-10-22 1982-12-21 Polaroid Corporation Biphenyl aldehydes
US20100001164A1 (en) * 2008-07-02 2010-01-07 Popco, Inc. Poster clasp

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