US3582345A - Light developable direct print silver halide compositions containing phosphonium salts - Google Patents

Light developable direct print silver halide compositions containing phosphonium salts Download PDF

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Publication number
US3582345A
US3582345A US718340A US3582345DA US3582345A US 3582345 A US3582345 A US 3582345A US 718340 A US718340 A US 718340A US 3582345D A US3582345D A US 3582345DA US 3582345 A US3582345 A US 3582345A
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silver halide
compositions
phosphonium salts
silver
print
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US718340A
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Clarence E Mcbride
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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
    • 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
    • G03C1/49—Print-out and photodevelopable emulsions

Definitions

  • direct-print compositions comprising said phosphonium salts have improved photographic speed and improved image densities.
  • R is an alkyl group and wherein Z is an anion.
  • direct-print compositions containing from about 1 mole percent to about 2 moles per mole of silver of said phosphonium compound have improved photographic speed and increased D
  • the improved photographic properties achieved by use of said phosphonium salt and especially by use of large amounts of said phosphonium salts are quite unexpected. It is known that certain phosphonium salts act as antifoggants; but it is quite unexpected that both photographic speed and improved image density could be obtained in direct-print or print-out emulsions.
  • each R represents an alkyl group which can be the same or a different alkyl group, substituted or unsubstituted, and Z represents any anion which does not exhibit a deleterious effect in a photographic system.
  • R represents a lower alkyl group such as methyl, ethyl, propyl, or butyl and Z represents anions such as nitrate, perchlorate, halides, e.g., chloride bromide, iodide, etc.
  • the phosphonium salts can be generally employed in amounts greater than 10 mg. per mole of silver to provide improved photographic properties in silver halide systems according to this invention. Preferably concentrations of at least about 1 mole percent to about 2 moles per mole of silver are utilized in the silver halide compositions.
  • Preferred compounds falling within the above formula are tetrakis(hydroxymethyl)phosphonium salts and tetrakis(hydroxyethyl)phosphonium salts.
  • these salts are tetrakis(hydroxymethyl)phosphonium chloride (THPC manufactured by Hooker Chemical Company) and tetrakis(hydroxyethyl)phosphonium chloride.
  • THPC tetrakis(hydroxymethyl)phosphonium chloride
  • tetrakis(hydroxyethyl)phosphonium chloride tetrakis(hydroxymethyl)phosphonium chloride
  • the latter compound can be obtained by the procedure described in Messenger and Engles, Ber. 21: 326 (1888).
  • the general equation for the production is 4CH CHO+HCl+PH (CH CHOH).,P Cl
  • Suitable silver halides which can be used according to this invention include silver bromide, silver bromoiodide,
  • compositions are those wherein the halide of the silver is predominantly bromide.
  • preferred compositions are direct-print silver halide compositions having higher internal sensitivity than surface sensivitiy as described by Hunt in Photographic Science and Engineering, vol. 5, No. 2, March- April, 1961, pp. 104-108.
  • suitable compositions reference is made to Davey et al., US. Pat. 2,592,250, issued Apr. 8, 1952; US. Pat. 3,206,316; Porter et al., US. Pat. 3,206,313; Sutherens, British Pat. 1,096,- 053; Kitze, Belgium Pat.
  • the silver halide compositions are direct-print compositions which contain halogen acceptors.
  • suitable halogen acceptors are compounds which enhance the photolytic yield (as determined by radiographic analysisfor example) and/ or the photolytic density of a print-out emulsion.
  • Typical halogen acceptors useful in the present compositions include those disclosed in McBride, US. Pat. 3,287,137; McBride, US. Pat. 3,271,157; and Kitze, US. Pat. 3,241,- 971.
  • nitrogen containing halogen acceptors according to the McBride patents, above are utilized in the emulsions.
  • the halogen acceptors are of the type disclosed in Kitze, US. Pat. 3,241,971, which contain mercaptan groups and especially the heterocyclic mercaptans and thiones.
  • compositions of the invention are generally made with a slight excess of halide ion present over that necessary initially to precipitate all of the silver halide in the preparation thereof.
  • water soluble iodides are added to the composition after its precipitation but before it is coated. More generally, about .1 to 50 mole percent and preferably about 0.5 to 10 mole percent of Water-soluble iodide based on the silver halide in the composition are added to the subject emulsions.
  • Typical water-soluble iodides include the ammonium, calcium, lithium, magnesium, potassium, and sodium salts.
  • the silver halide compositions of this invention can be sensitized with various dyes. Typical dyes are disclosed in McBride, US. Pat. 3,287,136; Brooker, U.S. Pats. 1,846,301 issued Feb. 23, 1932, 1,846,302 issued Feb. 23, 1932, and 1,942,854 issued Jan. 9 .1934; White, US. Pat. 1,990,507 issued Feb. 12, 1935; Brooker and White,
  • the sensitizing amount of the spectral sensitizing dyes utilized can be widely varied.
  • concentration of the dyes will vary according to the type of composition and according to the effect desired.
  • the suitable and most economical concentration for any given composition will be apparent to those skilled in the art upon making the ordinary tests and observations customarily used in the art of emulsion making.
  • about 1 to 1000 mg. of dye per mole of silver halide in the composition are utilized.
  • about .05 to 1 mole percent of sensitizing dye based on the silver halide in the composition is a typical working range.
  • a single dye or combinations of several dyes can be used in the present compositions for spectral sensitization.
  • Merocyanine spectral sensitizing dyes are preferably utilized in the compositions of the invention as any stain imparted to compositions containing such dyes is substantially bleached or made colorless during photodevelopment. Also, merocyanine dyes tend to be less easily displaced or desorbed from the silver halide crystals of the compositions of the invention than cyanine dyes by many halogen acceptors that are utilized in light-developable, direct-print silver halide emulsions.
  • colloids can be used as vehicles or binding agents in preparing the silver halide compositions of this invention.
  • Satisfactory colloids which can be used for this purpose include any of the hydrophilic colloids generally employed in the photographic field, including, for example, gelatin, colloidal albumin, polysaccharides, celdescribed in Heiland, U.S. Pat. 2,580,427, issued Ian. 1, 1952, high intensity visible light, x-radiation and the like, to form a latent image in the composition of the photographic element, and thereafter the resulting latent image is photodeveloped by overall exposure of the emulsion to a radiation source of lower intensity than the original exposure, such as to a conventional fluorescent light, light from incandescent lamps commonly used for general illumination, or even ordinary daylight.
  • a radiation source of lower intensity than the original exposure such as to a conventional fluorescent light, light from incandescent lamps commonly used for general illumination, or even ordinary daylight.
  • the latent image formed in the composition in the first instance is not visible and does not become visible until photodevelopment.
  • Heat is desirably utilized during the photodevelopment step.
  • the subject compositions are heated to a temperature of about 90 C. to 200 C. for about 1 to 30 seconds and photodeveloped after the initial high intensity exposure.
  • EXAMPLE 1 A silver bromochloride (95 mole percent bromide, 5 mole percent chloride) emulsion is prepared according to Example 8 of McBride U.S. Pat. 3,271,157 issued Sept. 6, 1966 except that 1,8-dihydroxy-3,6-dithiooctane was used as the thioether. After preparation of the emulsion mole percent of tetrakis (hydroxymethyl)phosphonium chloride per mole of silver is added to a portion of the emulsion and it is then coated on a paper support and dried. Another portion is coated as a control.
  • the samples are exposed in a Honeywell Visicorder oscillograph with a galvanometer reading of 120 cycles per second and at a paper transport speed of inches per second.
  • Portions of the samples are photodeveloped (for the time specified in the following table) to 60 foot-candles of fluorescent light. Another portion of each respective sample is exposed imagewise, as above, and then held in contact with a heated surface at 100 C. and simultaneously photodeveloped for a few seconds to a 1000 footlulose derivatives, synthetic resins such as polyvinyl comcandle fluorescent light source.
  • the vehicle or binding agent can also contain hydrophobic colloids such as dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials.
  • hydrophobic colloids such as dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials.
  • Suitable compounds of this type include water-insoluble polymers of alkyl acrylates or methacrylates, acrylic acid, sulfoalkyl acrylates, or metharcylates, and the like.
  • compositions of the invention can be coated on a wide variety of supports in accordance with usual practice.
  • Typical supports for photographic elements of the invention include glass, metal, paper, polyolefin-coated paper, cellulose nitrate film, cellulose acetate film, polystyrene film, polyester films such as polyethylene terephthalate film, heat resistant polymeric films such as high temperature polyester, polyimide, polycarbonate films, and the like.
  • the photographic element is initially exposed to a relatively short duration and high intensity source of electromagnetic radiation (e.g., at least about .1 foot-candle second at an intensity of more than about 100 footcandles) such as a high intensity light source rich in blue and ultraviolet light such as are used in oscillographs
  • a relatively short duration and high intensity source of electromagnetic radiation e.g., at least about .1 foot-candle second at an intensity of more than about 100 footcandles
  • a high intensity light source rich in blue and ultraviolet light such as are used in oscillographs
  • EXAMPLE 2 An emulsion is prepared according to Example 1 and then divided into portions. Samples were treated respectively with 1.0 mole percent, 10 mole percent, 20 mole percent, 40 mole percent and mole percent of tetrakis (hydroxymethyl)phosphonium chloride per mole of silver. A control sample was prepared which did not contain any of said phosphonium salt.
  • Example 1 The respective samples are exposed and developed as described in Example 1. In each instance the samples containing said phosphonium salts exhibited significantly increase Dmax and substantially improved speed when compared with the control sample.
  • a light developable direct-print silver halide emulsion comprising at least 10 mg. per mole of silver of a phosphonium salt of the formula:
  • a light developable direct-print silver halide emulsion according to claim 2 comprising silver halide grains having a predominant amount of sensitivity internal to said grains.
  • a photgraphic element comprising the emulsion of claim 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US718340A 1968-04-03 1968-04-03 Light developable direct print silver halide compositions containing phosphonium salts Expired - Lifetime US3582345A (en)

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US71834068A 1968-04-03 1968-04-03

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US3582345A true US3582345A (en) 1971-06-01

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US (1) US3582345A (enrdf_load_stackoverflow)
BE (1) BE730954A (enrdf_load_stackoverflow)
FR (1) FR2005479A1 (enrdf_load_stackoverflow)
GB (1) GB1257822A (enrdf_load_stackoverflow)

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GB1257822A (enrdf_load_stackoverflow) 1971-12-22
FR2005479A1 (enrdf_load_stackoverflow) 1969-12-12
BE730954A (enrdf_load_stackoverflow) 1969-09-15

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