Classifications

• • 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
  • G03C5/56—Processes using photosensitive compositions covered by the groups G03C1/64 - G03C1/72 or agents therefor
• • 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
  • G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances

Definitions

• This invention relates generally to a photographic composition. More particularly, it relates to a photographic image stabilizer used for stabilizing images obtained with organic photosensitive compositions comprising N-vinyl heterocyclic and organic halogen compounds.
• Photographic images produced in an organic photosensitive coating on baryta paper are liable to color change when subjected to daylight exposure for a period of 3 to 7 days. During this period, a yellow-tobrown color change would take place in the lightstruck areas, and a further exposure to daylight would turn the whole areas to brown. Such color change is detrimental to the preservation of photographic images for an extended period of time.
• Color change may be attributable to a number of factors which include photo-oxidization of dyes p'roduced upon exposure to light, subsequent photoreaction of the unexposed areas, and a subsequent photo-reaction of unreacted substances which may be present in the dyes. Color change may also depend on the amount of organic halogen compounds present in the lightexposed areas.
• additives and stabilizers For purposes of stabilizing images, additives and stabilizers have been proposed which include peroxides (U.S. Pat. No. 3,544,320), aldehyde-NaHSO (U.S. Pat. No. 3,503,742), Na SO and NaHSO (U.S. Pat. No. 3,512,976) and various mixtures thereof (U.S. Pat. No. 3,544,322).
• peroxides U.S. Pat. No. 3,544,320
• aldehyde-NaHSO U.S. Pat. No. 3,503,742
• Na SO and NaHSO U.S. Pat. No. 3,512,976
• various mixtures thereof U.S. Pat. No. 3,544,322
• the image stabilizer comprises as its main constituent an azabicycloene compound ofa cyclic amidine expressed generally by the following formula:
• the image stabilizer according to the invention is obtained by dissolving 0.5 to 20% by weight of the azabicycloene compound into an aqueous solution of, for example, about 20% polyvinyl alcohol.
• a preferred value of the azabicycloene content in the solution is from 4 to l% by weight.
• the azabicycloene compounds employed in the practice of the present invention are l,5-diazabicyclo [5,4,0] undecane-S ene and 1,5- diazabicyclo [4,3,0] nonene-S.
• These azabicycloene compounds may be dissolved either in water, in an aqueous solution containing a water-soluble resin or a polymer dissolving organic solvent organic.
• the lightexposed film may be dipped into the solution or it may be sprayed or wiped with the solution and the solvent is then removed by drying the film in the ambient atmosphere.
• These azabicycloene compounds are strongly alkaline and therefore they serve to decompose organic halogen compounds present in the light-exposed areas as intermediates of a photo-reaction to thereby stabilize the images formed.
• the desensitizing compounds would allow the whiteness of background areas to increase, which would otherwise turn to light yellowgreen. This could result in an increase in the image contrast.
• azabicycloene compounds also have a desensitizing effect on this background areas by increasing their whiteness while penetrating deeply into the photosensitive composition with the aid of a heavy metal salt of a surface active agent which will be described hereinbelow.
• the desensitizing effect is enhanced by heating the film at a temperature of about 50C for a period of about 30 seconds.
• the aforementioned water soluble resin may be natural high polymers such as gelation and agar-agar, or polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone and polyacryl acid.
• the organic solvent may be, for example, alcohol, acetone, tetrahydrofuran, dimethylformamide, etc.
• polymers dissolved in one of the above-stated organic solvents such substances as polyacrylate, polyvinyl compounds, polycondensated compounds including polyamid derivatives may be used.
• the present invention contemplates the use of other compounds as additives to the azabicycloene compounds such as a heavy metal salt of a surface active agent such as sulfate, sulfonate, or phosphate.
• a surface active agent such as sulfate, sulfonate, or phosphate.
• the surface active agent usually a sodium salt
• the desensitizing effect can be further enhanced by the use of a heavy metal salt such as, for example, a zinc, tin or an iron salt.
• the additive to the azabicycloene compounds may preferably be heavy metal laurylsulfate, oleylsulfate, stearylsulfate, laurylsulfonate, dibutylnaphtalenesulfonate, dodecylbenzenesulfonate, oleyletherphosphate and laurylphosphate. More preferably, the additive may be Zn-dibutyl-naphthalenesulfonate or stannous sulfonate. These additives are used in a concentration of about 0.5 to 20 weight percent in the solvent.
• pyrrolidone is reacted with acrylonitrile by heating in the presence of potassium hydroxide and hydroquinone.
• the product is acidified with hydrochloric acid and then concentrated under a reduced pressure to give I-( 2-cyanoethyl )-pyrrolidone.
• the thus obtained nitrile is dissolved in a mixture of methanol and ammonia and subjected to catalytic reduction by the use of a Ni-Al catalyst, followed by filtration, vacuum concentration and vacuum distillation.
• the distilled product which is l-( 3-aminopropyl)-pyrrolidone, is then dissolved in xylol and admixed with p-toluenesulfonic acid, followed by reflux for a dehydration reaction.
• the final reaction product is subjected to filtration and vacuum distillation.
• All the above sulfates, sulfonates and phosphates are well known and are commercially available surface active agents as their respective sodium salts.
• the heavy metal salts for the stabilizer of the invention are known and can be easily obtained by usual replacement reactions of such sodium salts with, e.g., chlorides of the preferred heavy metals, which reactions require no detailed description for one skilled in general chemistry.
• a sheet of baryta paper was coated with the thus obtained composition.
• the photosensitive film thus formed on the baryta paper had a wet thickness of microns.
• the coated sheet After the coated sheet had been dried, it was subjected to an imagewise exposure by a 250 watt xenon lamp from a distance of about I meter for 1 second through a suitable image pattern placed in an intermediate position between the lamp and the film.
• a second exposure was made by subjecting the film to light of wavelengths above 5300 A from a 100 watt tungsten lamp through an optical filter for a period of 5 seconds.
• a negative image was produced in the film when it was left under the influence of ambient light radiation.
• a stabilizer was prepared by mixing the following constituents and the image produced on the baryta paper was coated with the mixture:
• the stabilizer coated film was heated to, and kept at 50C for 30 seconds: For purposes of comparison, a separate negative image without the stabilizer coating was also produced in the same manner as described above and exposed to the radiation of a 40 watt fluorescent light from a distance of 30cm. The light-exposed areas started to change their color to yellow in 3 days and turned totally brown within one week. In contrast, the stabilizer-coated image did not appreciably change in color even after a one-week exposure to the same fluorescent radiation.
• a sheet of baryta paper was coated with the thus obtained composition.
• the photosensitive film was subjected to light exposures as described in Example I to develop a negative image.
• a stabilizer was prepared by mixing the following constituents and the image produced on the baryta paper was coated with the mixture:
• Example 1 A similar desensitizing effect was observed as in Example 1 when the film was subjected to a one-week exposure to the 40 watt fluorescent light.
• n and n are each an integer ranging from 2 to 6; and drying the wet image and background areas at a temperature ranging from room temperature to 50C.
• said aqueous solution further contains up to 50% by weight of a water-soluble resin selected from the group consisting of gelatin, agar-agar, polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone and polyacryl acid.
• a water-soluble resin selected from the group consisting of gelatin, agar-agar, polyvinyl alcohol, polyethylene glycol, polyacrylamide, polyvinylpyrrolidone and polyacryl acid.
• said aqueous solution further contains 0.5 to by weight of a heavy metal salt of a surface active agent selected from the group consisting of a sulfate, sulfonate and phosphate, said heavy metal being selected from the group consisting of zinc, tin and iron.
• azabicycloene compound is selected from the group consisting of l,5-diazabicyclo( 4,3,0)nonene-5 and 1,5-

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (1)

• 1972
  • 1972-05-31 JP JP47054670A patent/JPS5218021B2/ja not_active Expired
• 1973
  • 1973-05-29 US US364315A patent/US3881929A/en not_active Expired - Lifetime

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