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
  • G03C1/89—Macromolecular substances therefor
  • G03C1/895—Polyalkylene oxides
• • 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
  • Y10S430/131—Anticurl layer
• • 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
  • Y10S430/156—Precursor compound
  • Y10S430/16—Blocked developers

Definitions

• Antistatic agents which have heretofore been used can display antistatic effects when applied to lightsensitive materials containing saponin and the like surface active agents of natural origin as coating aids, but most of them cannot display sufficient antistatic effects when applied to light-sensitive materials containing synthetic surface active agents. Accordingly, there has been a definite need for antistatic agents that are capable of displaying sufficient antistatic effects even when applied to light-sensitive materials containing synthetic surface active agents.
• An object of the present invention is to provide an effective means for the antistatic treatment of lightsensitive photographic materials, particularly those which are high in sensitivity.
• Another object of the invention is to provide an effective means for the antistatic treatment of lightsensitive photographic materials which is effective even when applied to photographic materials containing synthetic surface active agents such as coating aids.
• the above objects can be accomplished by incorporating an ethylene oxide addition polymer of a phenolforrnalin condensate into at least one of such outer layers of a light-sensitive photographic material such as a photographic film as the protective layer, overcoating layer, backing layer, antihalation layer and anti-curling layer, or by coating said addition polymer on the surface of at least one of said layers and the film support.
• a light-sensitive photographic material such as a photographic film as the protective layer, overcoating layer, backing layer, antihalation layer and anti-curling layer
• the present invention provides a lightsensitive silver halide photographic material having a film support and a light-sensitive silver halide emulsion layer, characterized in that an ethylene oxide addition polymer of a phenol-formalin condensate in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate, is present in or on at least one of the outer layers constituting said photographic material.
• the present invention also specifically provides a multi-layered, light-sensitive silver halide photographic material, comprising at least one of the outer layers constituting the photographic material comprising an ethylene oxide addition polymer of a phenol-formalin condensate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate.
• the ethylene oxide addition polymer of phenolformalin condensate used in the present invention is obtained by addition polymerizing ethylene oxide with a phenol-formalin condensate of the structural formula,
• R and R are individually a hydrogen or halogen atom, or a nitro, carboxyl, alklcarboxy alkoxycarbonyl, alkyl, substituted alkyl or alkoxy group, and m is an integer of l to 100.
• the ethylene oxide addition polymer of the phenolformalin condensate used in the present invention is obtained by addition polymerizing ethylene oxide with one or more of such phenol-formalin condensates as mentioned above.
• the amount of ethylene oxide to be addition-polymerized is preferably up to about 30 moles, on the average, per recurring structural unit of the phenol-formalin condensate.
• Suitable examples of ethylene oxide addition polymers of phenol-formalin condensates that can be used in the present invention are such compounds as shown below, but it is to be understood that the compounds usable in the present invention are not limited only to these.
• Compound (1-1) Polymer obtained by adding 720 moles of ethylene oxide to 4-methylphenol-formalin resin (polymerization degree 90), (an average of 8 moles of ethylene oxide per structural unit of the resin).
• Compound (1-2) Polymer obtained by adding 450 moles of ethylene oxide to Z-methylphenol-formalin resin (polymerization degree 30), (an average of 15 moles of ethylene oxide per structural unit of the resin).
• Compound (I-3) Polymer obtained by adding 500 moles of ethylene oxide to 4-nonylphenol-forrnalin resin (polymerization degree 50), (an average of 10 moles of ethylene oxide per structural unit of the resin).
• Compound (l-4) Polymer obtained by adding 150 moles of ethylene oxide to 2-octylphen0l-formalin resin (polymerization degree 10), (an average of moles of ethylene oxide per structural unit of the resin).
• Compound (1-5) Polymer obtained by adding 1,400 moles of ethylene oxide to 4-octadecylphenol-formalin resin (polymerization degree 70), (an average of moles of ethylene oxide per structural unit of the resin).
• Compound (1-6) Polymer obtained by adding 750 moles of ethylene oxide to 4-nonylphenol/4-methylphenol-formalin resin [polymerization degree 50 (molar ratio 30/20)], (an average of 15 moles of ethylene oxide per structural unit of the. resin).
• Compound (1-7) Polymer obtained by adding 60 moles of ethylene oxide to 4-nonylphenol/2,4-dinony1phenyl-forma1in resin [polymerization degree 3 (molar ratio 1/2)], (an average of 20 moles of ethylene oxide per structural unit of the resin).
• Compound (1-8) Polymer obtained by adding 200 moles of ethylene oxide to 2-chlorophenol-formalin resin (polymerization degree 40), (an average of 5 moles of ethylene oxide per structural unit of the resin).
• Compound (1-9) Polymer obtained by adding 900 moles of ethylene oxide to 3-nitrophenol-formalin resin (polymerization degree 60), (an average of 15 moles of ethylene oxide per structural unit of the resin).
• Compound (I-IO) Polymer obtained by adding 280 moles of ethylene oxide to 2-chloro-4-hydroxyethylphenol/4- methylcarboxyphenol-formalin resin [polymerization degree 40 (molar ratio 2/38)], (an average of 6 moles of ethylene oxide per structural unit of the resin).
• Compound (1-11) Polymer obtained by adding 1,360 moles of ethylene oxide to 4-methoxycarbonylphenol-formalin resin (polymerization degree (an average of 17 moles of ethylene oxide per structural unit of the resin).
• Compound (1-12) Polymer obtained by adding 600 moles of ethylene oxide to 4-tetradecy1pheno1-formalin resin (polymerization degree 20), (an average of 30 moles of ethylene oxide per structural unit of the resin).
• the above-mentioned compounds can be synthesized according to the processes disclosed in Kogyo Kagaku Zasshi (Journal of the Chemical Society of Japan, Industrial Chemistry Section), Vol. 66, 391 (1963), Abura Kagaku (Oil Chemistry), Vol. 12, 625 (1963) and Japanese Patent No. 279,014, but may be synthesized according to other processes.
• These compounds are viscous, pasty, waxy or semi-solid resins, in general, but are soluble in water and organic solvents such as acetone, alcohol, etc.
• the compound used in the present invention can be added to coating liquids used to form said layers, either as is or in the form of a solution in one or more of the aforesaid solvents.
• a solution of the compound in one or more of the aforesaid solvents-is spray-coated on the said surface, or the support or outer layer is dipped in said solution and then dried.
• the compound used in the present invention is an excellent antistatic agent which, even when incorporated into a coating liquid used to form an outer layer of light-sensitive material, does not degrade the coatabil: ity of said coating liquid nor deteriorate the sensitivity, gamma, fog and the like photographic properties of silver halide emulsion layers adjacent to the resulting.
• the compound used in the present invention displays its excellent antistatic effect when used in an amount of to 10 mole per m of light-sensitive photographic material.
• the amount of the compound used is not limited to said range, and the optimum amount capable of displaying a desired effect can optionally be selected.
• Light-sensitive materials to which the present invention is applicable include all light-sensitive silver halide photographic materials such as ordinary black-white photographic materials, specific black-white photographic materials, color photographic materials, lithographic films and roentogenographic materials (X-ray films).
• the compound of the present invention can be effectively applied regardless of the kinds of supports used and the kinds of additives and binders used in silver halide emulsion layers and the like layers constituting the above-mentioned light-sensitive materials.
• the supports are polyethylene terephthalate, polycarbonate, polystyrene, polyethylene, polypropylene and cellulose triacetate films
• the binders are gelatin, polyvinyl alcohol, cellulose triacetate and cellulose acetate phthalate.
• the compound according to the present invention is able to display a markedly high antistatic effect to effectively prevent the formation of static marks.
• Example 1 A high sensitivity silver iodobromide gelatin emulsion containing 15 mole percent of silver iodide was subjected to gold sensitization at the time of second ripening. After completion of the second ripening, the emulsion was incorporated with normal amounts of stabilizer, sensitizer, film-hardener and the like additives, and with l g. per liter of the emulsion of the exemplified compound (II-5) as a coating aid. The thus treated emulsion was coated on a polyethylene terephthalate support and then dried to form a silver iodobromide gelatin emulsion layer on the support. The lightsensitive film thus obtained wascut into several specimens.
• an aqueous gelatin solution containing a hardener was charged with l g. per liter of the solution of the exemplified compound (II-3) as a coating aid, and then the resulting protective layer-forming solution was equally divided into two solutions.
• One of these two solutions was incorporated with 4 g. per liter of the solution of the exemplified compound (1-3) as an antistatic agent, and the other solution was left untreated.
• Each of the two solutions was coated on one of the aforesaid specimens and then dried.
• the surface resistivity of each sample film was measured by the use of two electrodes of 10 cm. in length which had been arranged at a distance of 1 cm.
• the surface resistivity at 20C. and 50 percent RH of the film having the protective layer incorporated with no antistatic agent was 6 X 10 (2,
• Example 2 A high sensitivity silver iodobromide-gelatin emulsion containing 2.0 mole percent of silver iodide was subjected to gold sensitization at the time of second ripening. After completion of the second ripening, the emulsion was subjected to spectral sensitization, and then had incorporated therein normal amounts of stabilizer, hardener and coating aid saponin. The thustreated emulsion was coated on a polyester (polyethylene terephthalate) support and then dried to prepare a light-sensitive film which was cut into several pieces.
• a polyester polyethylene terephthalate
• an aqueous gelatin solution containing a hardener was prepared and was equally divided into two solutions.
• 0.5 g/l of saponin was incorporated therein.
• 0.5 g/l of the exemplified compound (11-14) was added to the other one as coating aid.
• Each one of the resulting solutions, which were now useful as a protective layer-forming solution, were equally divided into three portions. The first one was used as a blank.
• Other two were further included, 3 g/l of the exemplified compound (1-6) and 3 g/l of benzyl dimethyl tetradecyl ammonium chloride (control compound A), respectively, as antistatic agent.
• each of these solutions totalling six in number was coated on each of the cut pieces of the aforesaid light-sensitive film and then dried to form a protective layer thereon.
• the exemplified compound (I-6) displayed excellent antistatic effect even when used in combination with any of the natural surface active agents (saponin) and the synthetic surface active agents [exemplified compound (11-14)] used as coating aids, whereas the control compound A, which is a conventional antistatic agent, displayed antistatic effect when used in combination with the natural surface active agent (saponin) but showed no antistatic effect when used in combination with the synthetic antistatic agent [exemplified compound (11-14)].
• Example 3 A silver iodobromide color photographic emulsion containing 4 mole percent of silver iodide was subjected to gold sensitization at the time of second ripening. After completion of the second ripening, normal amounts of stabilizer, hardener, saponin as a coating aid, etc., and l-hydroxy-2-N-[6(2,4-di-tertamylphenoxy)butyl]-naphthamide as a cyan coupler, which had been dissolved at an elevated temperature in a mixed solvent comprising di-N-butyl phthalate and ethyl acetate and dispersed in a gelatin solution by use of sodium alkylbenzenesulfonate, were incorporated into the emulsion. The thus-treated emulsion was coated on a cellulose triacetate support and then dried to obtain a light-sensitive film which was then cut into several pieces.
• Sample films pieces all having a protective layer prepared in the above manner were moistened at 20 percent RH for 24 hours at 25C., rubbed with a poly vinyl chloride rod, and then subjected to ordinary color development treatment to observe the state of formation of static marks.
• the film having a protective layer with no antistatic agent therein and the film having the protective layer with the control compound A incorporated therein formed extremely large numbers of static marks, whereas the film having a protective layer in which the exemplified compound (1-1) had been incorporated as antistatic agent formed no static marks.
• Example 4 A 10 percent aqueous solution of the exemplified compound (1-9) was spray-coated on one side of a cellulose triacetate support and then dried. Subsequently, the same silver iodobromide emulsion as in Example 1 was coated on the other side of the support and then dried.
• the surface resistivity at 20C. and 20 percent RH of the film which had been subjected to the abovementioned treatment was 3.5 X 10 0, whereas that of the film which had not been subjected to the abovementioned treatment was 8 X 10 0.
• Example 2 Further, the same static mark test as in Example 1 was effected. As a result, the untreated film showed large numbers of static marks, whereas the treated film showed no static marks.
• Example 5 An aqueous gelatin solution containing Malachite Green as an antihalation dye and saponin was incorposolution was coated on the aforesaid emulsion layer rated with the compound Further, the same static mark test as in Example 1 was effected. As a result, the film having the backing and protective layers without the exemplified compound (l-lO) incorporated therein as antistatic agent showed large numbers of static marks, whereas the film having the backing andprotective layers with $513 compound incorporated therein showed no static marks.
• l-lO exemplified compound
• the light-sensitive photographic materials of the present invention can not only be effectively prevented from generating static electricity during the production thereof but also can be successfully prevented, even at low humidity, from generating frictional electricity at the time when the photographic materials are packed in cameras or casettes, and the said antistatic effects are not reduced or diminished with time. Further, the photographic materials according to the present invention can be developed, after exposure, without any accumulation of static electricity due to friction with rollers and the like equipment of the developing machine, and the developed photographic materials are not statically charged and hence can be prevented from adhesion of dust and the like.
• the antistatic agents used in the present invention display excellent antistatic effects even with lightsensitive materials containing synthetic surface active agents as coating aids, and can successfully prevent the formation of static marks which take place after development of light-sensitive photographic materials that have been statically charged.
• a light-sensitive silver halide photographic material comprising a film support and a light-sensitive silver halide emulsion layer on one side of the film support, an ethylene oxide addition polymer of a phenylformalin condensate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate, said addition polymer being present in an outer layer on the other side of the film support or in an outer layer on the lightsensitive layer, or in the light-sensitive layer at least at the outer surfacethereof.
• R and R individually are hydrogen, halogen, a nitro group, a carboxy group, an alkylcarboxy group, an alkoxy carbonyl group, an alkyl group, an alkoxy group or an alkyl group substituted by hydroxy, iodine, or chlorine, and m is an integer of l to 100.
• a multi-layered, light-sensitive photographic material comprising a film support, a light-sensitive silver halide emulsion layer on said support, and an outer layer on said film support or on said emulsion layer, an ethylene oxide addition polymer of a phenol-formalin condensate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate, said addition polymer being present in or on said outer layer.
• a photographic material comprising a film support, a light-sensitive silver halide emulsion layer on said film support, said photographic material having opposite surfaces, and an antistatic material disposed on one of said surfaces or in the substance of the photographic material at said surface, said antistatic material ethylene oxide is not more than 30 moles per structural being an ethylene oxide addition polymer of a phenolunit of the phenol-formalin condensate. formalin condensate, in which the molar proportion of

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Laminated Bodies (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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Cited By (11)

Citations (3)

• 1971
  • 1971-07-15 JP JP46052095A patent/JPS519610B1/ja active Pending
• 1972
  • 1972-07-12 CA CA146,989A patent/CA973750A/en not_active Expired
  • 1972-07-13 US US00271535A patent/US3850641A/en not_active Expired - Lifetime
  • 1972-07-13 DE DE2234471A patent/DE2234471A1/de not_active Withdrawn
  • 1972-07-14 GB GB3319672A patent/GB1371874A/en not_active Expired
  • 1972-07-17 BR BR4729/72A patent/BR7204729D0/pt unknown

Patent Citations (3)

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