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
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings

Definitions

• This invention relates to light-sensitive silver halide photographic materials characterized in that the constitutive elements of light-sensitive silver halide photographic materials are incorporated with acylhydrazinium salts represented by the general formula shown later.
• a principal object of the present invention is to provide light-sensitive silver halide photographic materials less in drawbacks due to electrostatic charge.
• Another object is to provide light-sensitive black and white photographic materials improved in tone of developed silver image, and light-sensitive color photographic materials excellent in image resolution and graininess.
• said drawbacks are brought about in such production stages as coating of emulsions, and cutting and packaging of lightsensitive materials; at the time of withdrawing sheet films from boxes; at the time of taking photographs, particularly filming; and at the time of handling prior to development. Further, such electrostatic drawbacks are sometimes observed also in the case where light-sensitive materials are peeled, in addition to the above-mentioned case where they undergo abrasion.
• light-sensitive materials are wound up, in general, and, in the case of unwinding said materials in succession in order to, transfer them to the subsequent step or in the case of unrolling rolled printing papers in succession in order to subject them to printing, static charge is generated by peeling between the surface and the reverse side of the lightsensitive material at the moment when it is peeled from the rolled portiton.
• release static charge is generated between the metal surface and the surface of the light-sensitive material, at the time when it is peeled, to bring about such a phenomenon that'the superposition of the printing paper cannot be effected immediately.
• antistatic agents are required to be such that they should not give any detrimental effect to the photographic characteristics of light-sensitive materials, such as the sensitivity, gradation, fog and stability thereof. It is therefore extremely difiicult to find excellent antistatic agents applicable to light-sensitive silver halide photographic materials.
• the present inventors made various studies on excellent antistatic agents having no detrimental effect on lightsensitive silver halide photographic materials. As the result, the inventors have found that compounds represented by the general formula wherein R R and R are individually a lower alkyl group, an aralkyl group, or a group derived therefrom; R is a hydrogen atom or an alkyl group; and X is an anion residue, are excellent antistatic agents.
• the above-mentioned compounds are incorporated into at least one layer of the constitutive elements of light-sensitive silver halide photographic materials, such as silver halide emulsion layer, sublayer, inter layer, filter layer, antihalation layer, protective layer and backing layer, it is possible to obtain light-sensitive silver halide photograhic materials markedly less in electrostatic drawbacks. Further, the incorporation of said compounds not only gives no detrimental effect to the efficiencies of light-sensitive photographic materials, such as sensitivity, gradation, fog and the like, but also has such favorable effects as to inhibit the fog and to increase the stability thereof.
• the above-mentioned compounds When applied to light-sensitive black and white photographic materials, the above-mentioned compounds give such advantages as to bring the color tones of developed silver images to bluish black, in addition to the prevention of electrostatic drawbacks. Further, when applied to incorporated type of color photographic emulsions, the compounds improve the dispersibility of color formers to make it possible to obtain lightsensitive color-photographic materials excellent in image resolution and graininess.
• acylhydrazinium salts having the aforesaid general formula include those shown in the table below.
• qinpblihds areto begqq d bu may. e. sq mm' ued. as f.-0 .1-mg.- 1 g.; per sgpare meterof the light-sensitive applicable to .the static charge prevention of films, molded articles. and fibers of. cellulose esters, polyesters, polystyrenes, polycarbonates, polyethylenes, polypropylenes and the like synthetic resins.
• EXAMPLE 1 An aqueous solution containing 1% (CH NNHCOC H Br (exemplified as III) was sprayed onto the surface of a high speed X-ray film, in the amount of 10 mg. per square meter of the film, and the sprayedfilm was then dried to prepare a sample. Further, the same X-ray film as above was immersed for 1 minute in the above-mentioned solution and was then dried to prepare another sample. n the other hand, two control samples were prepared in the same manner as above, except that the treatments were effected by use of pure water containing no said acylhydrazinium compound. After allowing these 4 samples to stand for 24 hours at 25 C.
• CH NNHCOC H Br (exemplified as III)
• the samples were rubbed on the surfaces with nylon and polyester cloths and were then subjected, without exposure to light, to development according to an ordinary procedure using a developer for X-ray film.
• the generation of considerable marked static marks was observed, whereas on the films treated with the solution of acylhydrazinium compound, no generation of static marks was observed.
• these 4 kinds of films were subjected to sensitometry according to the procedures regulated in I IS, whereby not only no influence was observed in sensitivity, gradation and fog of the light-sensitive silver halide photographic materials of the present invention but also the color tones of developed silver images changed to bluish black to obtain favorable results. Further, the films were individually stored in a thermostat at 55 C. for 3 days or at 50 C. and 80% RH for 3 days, and were then developed. In this case also, the lightsensitive silver halide photographic materials of the present invention gave favorable results.
• EXAMPLE 2 CH3 CHs N NHCOC HnB F2 (exemplified as X) was prepared to a 2% aqueous solution. To a 3% aqueous gelatine solution employed for a protective layer, the above-mentioned solution was added in an amount of cc. per liter of said gelatine solution. The mixed solution was further incorporated with 2 cc. of a 5% saponin solution as a coating aid. The thus prepared solution was applied as a protective layer onto a high speed X-ray film and was then dried. The resulting light-sensitive material was subjected to entirely the same tests as in Example 1, together with a light-sensitive material having a protective layer which had not been incorporated with the above-mentioned compound, whereby the same results as in Example 1 were obtained. 1
• EXAMPLE 3 (CHa)2 NGBNHCOCMHMCKMG (exemplified as x1 was prepared to a 3% methanol solution. To a greensensitive high speed color photographic silver iodobromide emulsion, the above-mentioned solution was added in an amount of 30 cc. per liter of said emulsion. This emulsion was then incorporated with a solution prepared by dissolving in a l N-caustic soda solution, g. of 1-(4- carboxyphenyl) 3 (4-palmitoylaminobenzoylamino)- 5-pyrazolone (magenta color former), and the pH of the emulsion was adjusted to 6.8 by means of citric acid.
• the thus prepared emulsion was applied onto a cellulose triacetate base and was then dried.
• the resulting film was subjected to entirely the same tests as in Example 1, together with a sample film to which no acylhydrazinium compound had been added.
• the processing was carried out according to such ordinary procedures that the films were developed by use of a color developer containing diethyl-p-phenylenediamine and were then subjected to water-washing, bleaching, water-washing, fixing, water-washing and drying.
• the results of incubation test of the films were as set forth in the table below, and it was observed that the light-sensitive material of the present invention had been somewhat improved in stability.
• the resulting light-sensitive material was subjected to entirely the same tests as in Example 1 to recognize that the light-sensitive silver salide photographic material of the present invention had been inhibited from the generation of static marks and no detrimental influence had been given to the sensitivity, gradation, fog and stability of the photographic emulsion.
• a light-sensitive silver halide photographic material characterized by containing in the constitutive elements of the light-sensitive silver halide photographic material, an acylhydrazinium salt represented by the general formula wherein R R and R are individually a lower alkyl group, an aralkyl group or a group derived therefrom; R is a hydrogen atom or an alkyl group; and X is an anion residue.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (5)

Citations (3)

• 1968
  • 1968-07-03 US US742144A patent/US3549369A/en not_active Expired - Lifetime
  • 1968-07-06 DE DE19681772809 patent/DE1772809A1/de active Pending
  • 1968-07-08 GB GB1227374D patent/GB1227374A/en not_active Expired

Patent Citations (3)

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