US3628956A - Process for preparing direct positive images by photosolubilization - Google Patents

Process for preparing direct positive images by photosolubilization Download PDF

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Publication number
US3628956A
US3628956A US771347A US3628956DA US3628956A US 3628956 A US3628956 A US 3628956A US 771347 A US771347 A US 771347A US 3628956D A US3628956D A US 3628956DA US 3628956 A US3628956 A US 3628956A
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Prior art keywords
silver halide
silver
organic compound
process according
percent
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Expired - Lifetime
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US771347A
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English (en)
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Eugene Frederick Haugh
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/492Photosoluble emulsions

Definitions

  • Goodrow Attorney-Lynn Barratt Morris ABSTRACT Process for forming a positive silver halide image by treating an imagewise-expo'sed, light-sensitive silver halide layer with a photosolubilizing compound, e.g., Z-mercapto-4-phenylthiazole, and then removing the exposed silver halide with a silver halide solvent.
  • a photosolubilizing compound e.g., Z-mercapto-4-phenylthiazole
  • the invention concerns a process for forming a positive silver halide image by treating an imagewise exposed light-sensitive silver halide layer with a photosolubilizing compound and then removing the exposed silver halide by dissolution development (i.e., treating with a silver halide solvent solution).
  • the invention is an improvement over the prior art in the sense that it enables one to obtain a positive image by reduction dissolution techniques in normal silver halide layers.
  • an auxiliary organic compound devoid of ionizsble iodine or oxidizing groups which are active at the working pH, which further reduces the rate of dissolution of unexposed silver halide in a silver halide solvent, thereby effecting the solubilization of the silver halide in the more exposed areas at a rate substantially greater than in the less exposed areas until a positive image comprised of silver halide is produced.
  • the silver halide solvent is an aqueous solution of an alkali metal thiosulfate, e.g., sodium or potassium thiosulfate.
  • an alkali metal thiosulfate e.g., sodium or potassium thiosulfate.
  • Suitable auxiliary compounds or D maintaining agents that can be used in accordance with the present invention include those defined and classified in aforesaid U.S. Pat. Nos. 3,493,373, 3,495,982 and 3,495,983.
  • a colloid-silver halide photographic emulsion layer coated on a suitable support, is exposed imagewise to actinic radiation.
  • the exposed element is then treated with a solution containing an organic compound as described above, e.g., 2-mercapto-4-phenylthiazole, the silver salt of which is of lower solubility in water than silver chloride, so as to reduce the rate of dissolution of unexposed silver halide solvent, e.g., a solution of sodium thiosulfate.
  • a positive modified silver halide image is formed in the silver halide emulsion layer.
  • the modified silver halide image may be intensified in various ways, as described in U.S. Pat. No. 3,155,507.
  • the most useful means of intensification involves reducing the white to yellow silver halide image to a black, metallic silver image, preferably using a photographic silver halide developing agent.
  • the silver halide image may be fogged prior to reduction by flashing to actinic radiation.
  • Other methods of intensifying the silver halide image e.g., by toning, color developing, etc., are disclosed in U.S. Pat. No. 3,155,507.
  • step (b) in treating the exposed photographic element are mercaptans
  • various other organic compounds may be used such as those disclosed in the above U.S. patents and applications for the manufacture of photosoluble elements.
  • the organic compounds disclosed in U.S. Pat. No. 3,155,519 are especially useful, e.g., 2-mercapto-4-phenylthiazole (MPT).
  • the silver halide solvent solution used in step (c) is an aqueous solution comprising two or three essential compounds: a silver halide solvent and a reducing agent, and, if desired, a D, maintaining agent.
  • Thesilver halide solvent may be any soluble thiosulfate, e.g., ammonium or alkali metal thiosulfate, but sodium thiosulfate is the preferred solvent.
  • Suitable reducing agents and their useful concentrations are those disclosed in assignee's copending application, U.S. Ser. No. 684,924, filed Nov. 22, 1967.
  • Reducing agents of the class recognized as conventional photographic developing agents for silver halide emulsions are preferred although other reducing agents are useful, including preferably N-methyl-p-aminophenol, 1- phenyl-4-methyl-3-pyrazolidone and l-phenyl-3- pyrazolidone.
  • Particularly useful D, maintaining compounds are o-phenylphenol, 2-butoxyethanol, and 1-(1- naphthyl )-2 -thiourea.
  • the silver halide layers or elements used in accordance with this invention may be silver chloride, silver bromide, silver chlorobromide, etc., and may contain gelatin or other macromolecular organic water-permeable colloid binding "was: rnm
  • the elements may be modified by variations in the silver halide, the binder (if present), and the adjuvants generally employed in silver halide systems, the supports, and in the relative concentrations of the various components in the layers.
  • Various auxiliary layers such as abrasion overcoatings, subbing layers, and antihalation undercoats or backing layers may be present in the photographic elements used in accordance with this invention.
  • the elements may include multilayer as well as monolayer structures.
  • the various layers, including the support may include inert ingredients, e.g., pigments, organic polymer latices, and matting agents.
  • EXAMPLE i A film strip of a gelatino-silver bromochloride emulsion (30% AgBr, 70% AgCl) on a polyethylene terephthalate support was exposed through a photographic 5 step wedge to a high-intensity, tungsten filament, incandescent lamp (General Electric Reflector Photoflood Lamp No. PHIRFLZ) at a distance of 2 feet for 5 minutes.
  • MPT 2-mercapto-4- phenylthiazole
  • a direct positive silver halide image resulted which was intensified by developing for 1 minute in the following photographic developer solution to yield an image having as maximum density (D,,,,,,) of 3.2 and a minimum density (D,,,,,.,) of 1.0:
  • EXAMPLE lll A strip of the exposed film described in example I (except that exposure was for 20 minutes) was soaked in hot water (about i130 F.) for 3 minutes, soaked in a 0.] percent by wt. aqueous solution of l-naphthyHZ-thiourea for l minute, washed for 2 minutes, treated for 1 minute in the dissolution developer of example I and intensified as in example I.
  • EXAMPLEV A pure silver chloride emulsion having an average grain diameter of about 0.5 micron was chemically sensitized with gold and sulfur sensitizers, and spectrally sensitized with a merocyanine dye.
  • a film strip of this emulsion coated on a polyethylene terephthalate support was exposed through a photographic 2 wedge for 1 sec. at a distance of 76 cm. to a SOD-watt tungsten filament incandescent lamp operated at a color temperature of 2,890 K., and fitted with a Wratten No. 79 filter.
  • the exposed strip was soaked for 15 sec. in a solution prepared by dissolving 0.l6l g. of Z-rnercaptoquinoline in 50 ml.
  • EXAMPLE VI A sample of the emulsion of example V was coated, exposed and processed as in example V, except that the strip was soaked in the Z-mercaptoquinoline solution for 30 sec. and had a D of3.70 and a D,,,,,, of 0.4l.
  • EXAMPLE Vll A strip of the coated emulsion of example V was exposed as in example V, except that the exposure was for 2 sec. The exposed strip was soaked for l minute in a solution made by dissolving 0.l93 g. of 2-mercapto-4-phenylthiazole in 50 ml. of ethanol, adding 350 ml. of distilled water and adjusting the pH to 9. This solution was kept at ll5 F. The soaked strip was then treated as in example V, except that the treatment with the reducing dissolution developer was for 6 minutes. The strip had a D of 2.99 and a D of 0.25.
  • EXAMPLE Vlll A sample of the coated emulsion of example V was exposed as in example Vll. The exposed sample was processed as in example Vll, except that the dissolution developer contained no o-phenylphenol. After intensification as in example l, D was 3.36 and D,,,,,, 0.80.
  • EXAMPLE 1X A strip of the coated emulsion of example V was exposed as in example V. The exposed strip was soaked in a solution containing 0.34 g. of l,2-naphthatriazole per I00 ml. of distilled water with pH adjusted to 9, for l minute at F. The treated strip was then developed for l minute at 70 F. in the reducing dissolution developer of example i, washed for 30 sec, and intensified in the photographic developer of example I for 1 minute at 70 F. A direct positive image was obtained having a D of0.89 and a D of0.20.
  • the present invention has the advantages of the basic process of photosolubilization of Blake U.S. Pat. No. 3 ,l 55 ,507 and embodies simple processing to obtain a positive image.
  • Conventional emulsions may be used by this process to yield the same results as obtained with specially prepared photosoluble emulsion layers described in said patent.
  • said silver halide solvent of step (c) also contains a D maintaining amount of an auxiliary organic compound devoid of ionizable iodine or oxidizing groups which are active at the working pH, which further reduces the rate of dissolution of unexposed silver halide in a silver halide solvent, thereby effecting the solubilization of the silver halide in the more exposed areas at a rate substantially greater than in the less exposed areas until a positive image comprised of silver halide is produced.
  • R is a hydrocarbon nucleus of 4-l 2 carbon atoms.

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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)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US771347A 1967-12-08 1968-10-28 Process for preparing direct positive images by photosolubilization Expired - Lifetime US3628956A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68899667A 1967-12-08 1967-12-08
US77134768A 1968-10-28 1968-10-28

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US3628956A true US3628956A (en) 1971-12-21

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BE (1) BE725071A (esLanguage)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3155507A (en) * 1961-12-08 1964-11-03 Du Pont Photographic processes
US3495982A (en) * 1967-06-23 1970-02-17 Du Pont Process for dissolution development using thiourea compounds as dmax maintainers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3155507A (en) * 1961-12-08 1964-11-03 Du Pont Photographic processes
US3155519A (en) * 1961-12-08 1964-11-03 Du Pont Photographic compositions, layers and elements
US3495982A (en) * 1967-06-23 1970-02-17 Du Pont Process for dissolution development using thiourea compounds as dmax maintainers

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