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
• • 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
  • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives

Definitions

• This invention relates to an antistatic layer for plastic film use and, more particularly, to a silver halide photographic light-sensitive material excellent in antistatic characteristics.
• plastic films are so strong that there are many instances where many restrictions are imposed on their application.
• a polyethylene terephthalate support is generally used.
• the discharge may produce a static-mark or may make a foreign matter such as dusts adhere to the light-­sensitive material, thereby producing pin-holes or the like, so that the quality of the light-sensitive material may seriously be worsened.
• the working efficiency will seriously be lowered.
• an anti- static agent is generally used in light-­sensitive materials and, in recent years, a fluorine containing-surfactant, a cationic surfactant, an amphoteric surfactant, a surfactant or high molecular compound containing a polyethylene oxide group, or a polymer having an intramolec­ular sulfonic acid group or a phosphoric acid group is used.
• Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 49-91165/1974 and 49-121523/1974 disclose each the examples of applying an inon-type polymer having an ionic dissociation group to a polymer principal chain.
• Another object of the invention is to provide a silver halide photographic light-sensitive material excellent in antistatic property.
• a plastic film having thereon an antistatic layer comprising a water-soluble electric conductive polymer and particles of a hydrophobic polymer, and hardened with a hardening agent, wherein said haydrophobic polymer has a -SO3M group or a -OSO3M group, in which M is a hydrogen atom or a cation, and a silver halide photographic light-sensitive material using the plastic film as the support thereof.
• the water-soluble conductive polymers of the invention include, for example, a polymer having at least one conducivelytive group selected from the group consisting of a -SO3M group, a -OSO3M group in which M is a hydrogen atom or a cation, a quaternary ammonium salt group, a tertiary ammonium salt group, a carboxyl group, and a polyethylene oxide group.
• a -SO3M group, a -OSO3M group, and a quaternary ammonium salt group are preferable.
• the above-­mentioned at least one conductive group is required to be not less than 5% by weight of the polymer.
• the water-soluble conductive polymer is preferable to contain a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, or a vinylsulfone group.
• a hydroxy group an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, or a vinylsulfone group.
• Each of these groups is referably required to be not less than 5% by weight of the polymer.
• the molecular weight of each polymer is 3000 to 100000 and, preferably, 3500 to 50000.
• x, y, w represent each a mol% of a monomer component
• M represents an average molecular weight which means a number average molecular weight in this specification.
• the above-given polymers can be synthesized by poly­merizing any monomers available on the market or prepared in an ordinary method.
• the hydrophobic polymer particles which are contained in the water-soluble conductive polymer layer of the invention, are to have at least one of a -SO3M group and a -OSO3M group, in which M is a hydrogen atom of a cation, and are contained therein in the form of the so-called latexes which are substantially insoluble to water.
• Such hydrophobic polymers are preferably requied to contain at least one group selected from the group consisting of an N-methylol and its derivative group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinylsulfone group, and a blocked isocyanate group.
• hydrophobic polymers can be prepared by polymerizing the polymers selected from any combination consisting of a styrene and the derivative thereof, an alkyl acrylate, an alkyl methacrylate, an olefin derivative, a halogenoethylene derivative, an acrylamide derivative, a methacrylamide derivative, a vinyl ester derivative, and an acrylonitrile.
• hydrophobic polymers ones containing a styrene derivative an alkyl acrylate or an alkyl methacrylate in a proportion of not less than 30 mol% and, particularly, not less than 50 mol% are preferable.
• R represents an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, or a halogen atom.
• L represents a divalent group which has 1 to 6 carbon atoms and at least one group selected from the group consisting of a linking groups of , -NH-, and -O-.
• the divalent group may be an arylene group or a substituted arylene group.
• A represents an alkylene or alkenylene group heaving 1 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms.
• a, b are each an integer of 0 or 1.
• X represents -SO3M, or -OSO3M. in which M represents a cation or a hydrogen atom.
• the monomers represented by Formula I include preferably the following examples:
• the monomers having a sulfonic acid group, a sulfuric acid ester group, or the derivatives thereof in a proportion of 0.1 mol% to 20 mol% more preferably, 0.5 mol% to 10 mol%.
• hydrophobic polymers be in the latex form, one is to emulsion-polymerizing them, and another is to dissolve solid polymers in a low boiling solvent so as to be finely dispersed them in an aqueous medium and the solvent is then distilled off.
• the emulsion-polymer­ization method is preferable, because the resulting particles are small and uniform in size.
• the anionic or nonionic surfactants are preferably used, and such surfactants are used preferably in a proportion of not more than 10% by weight to the monomers used. An excessive amount of the surfactant will cause a conductive layer being clouded.
• hydrophobic polymers have a molecular weight of not less than 3000. There is almost no difference in transparency of the conductive layer, even if the molecular weight is varied.
• a conductive layer is coated over a transparent support.
• the supports applicable thereto include any kinds of supports for photographic use. Among them, the preferable ones are those made of polyethylene terephthalate or cellulose triacetate, which are so prepared as to transmit not less than 90% of visible rays of light.
• tranparent supports are prepared in the methods having been well-known in the art. If occasion requires, the supports are allowed to be bluish by adding a small amount of dyes so as not to substantially inhibit light from trans­mitting through the supports.
• the support After the support is subject to a corona-discharge treatment, it is allowed to coat thereon a subbing layer containing a latex polymer.
• a corona-discharge treatment When treating the corona-­discharge, it is more preferable to apply an energy value of 1 mW to 1 KW/m2 ⁇ min.
• the agents for hardening the conductive layers of the invention include, preferably, a multifunctional aziridine compound and, more preferably, a bifunctional or trifunctional one having a molecular weight of not more than 600.
• the conductive layers of the invention may be arranged either to the support side closer than a light-sensitive layers or to the opposite side of the support, that is, the back side thereof, with respect to the light-sensitive layers.
• This invention can be applied to any light-sensitive material formed on a support, including, for example, a silver halide color light-sensitive material, a radiographic material, and a graphic arts light-sensitive material.
• any silver halides applicable to ordinary silver halide emulsions may be used, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide.
• Any silver halide grains may be used in the invention, provided, they are prepared in an acidic method, a neutral method, or an ammoniacal method.
• Such silver halide grains may be either those having a uniform silver halide composition distribution therein or core/shell type grains having the different silver halide composition between the inside of the grains and the furface layer thereof. They are further allowed to be either those capable of forming a latent image mainly on the surface thereof or those capable of forming a latent image mainly inside thereof.
• the silver halide emulsions applicable to the invention can be stabilized with the use of such a compound as described in, for example, U.S. Patent Nos. 2,444,607, 2,716,062, and 3,512,982, West German DAS Patent Nos. 1,189,380, 2,058,626, and 2,118,411, Japanese Patent Examined Publication No. 43-­4133/1968, U.S. Patent No. 3,342,596, Japanese Patent Examined Publication No. 47-4417/1972, West German DAS Patent No. 2,149,789, and Japanese Patent Examined Publication Nos. 39-­2825/1964 and 49-13566/1974.
• These compounds for stabilization preferably include, for example, 5,6-­trimethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5,6-­tetramethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-­methyl-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-7-­hydroxy-S-triazolo(1,5-a)pyrimidine, 7-hydroxy-S-triazolo-­(1,5-a)pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-triazolo-­(1,5-a)pyrimidine, gallates such as isoamyl gallate, dodecyl gallate, propyl gallate, and sodium gallate, mercaptans such as 1-phenyl-5-mercaptotetrazole, and 2- mercaptobenzthiazole, benzotriazoles such as 5-bromobenz- triazole, and 5-­methylbenztriazole
• the silver halide photographic light-sensitive materials and/or the developers, each relating to the invention, may contain an amino compound.
• a developing agent such as phenidone and hydroquinone, and an inhibitor such as benztriazole may be contained in the emulsion side.
• a developing agent or inhibitor may be contained in a backing layer.
• hydrophilic colloids particularly advantageous to light-sensitive materials of the invention include, for example, gelatin.
• Either alkali-processed and acid-processed gelatins may be applicable.
• ossein gelatin it is preferable to remove calcium or iron contents.
• the calcium contents are preferably 1 to 999 ppm and, more preferably, 1 to 500 ppm.
• the iron contents are preferably 0.01 to 50 ppm and, more preferably, 0.1 to 10 ppm.
• Such calcium and iron contents may be adjusted by passing an aqueous gelatin solution through an ion-exchanging apparatus.
• the developing agents applicable thereto include, for example, catechol, pyrogallol and the derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone, methylehydroquinone, 2,3-dibromohydroquinone, 2,5-diethylhydroquinone, 4-chloro­catechol, 4-phenylcatechol, 3-methoxycatechol, 4-acetyl­pyrogallol, and sodium ascorbate.
• the heterocyclic type developing agents include, for example, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-­phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl- 4-­hydroxymethyl-3-pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, and 5-aminouracil.
• 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-­phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl- 4-­hydroxymethyl-3-pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, and 5-aminouracil.
• the developing agents effectively applicable to the invention include those described in, for example, T.H. James, 'The Theory of Photographic Process', 4th Ed., pp. 291-334, and 'Journal of the American Chemical Society', Vol. 73, p. 3,100, 1951. These developing agents may be used independently or in combination. It is, however, preferable to use them in combination.
• the effects of the invention are not damaged even when using preservatives including, for example, sulfites such as sodium sulfite and potassium sulfite are used in the developers applicable to develop the light-­sensitive materials relating to the invention.
• Such applicable preservatives include, for example, hydroxylamine and hydrazide compounds. In this case, such a preservative is used in an amount of, preferably, 5 to 500 g and, more preferably, 20 to 200 g per liter of the developer used.
• a glycol may be contained to serve as an organic solvent.
• the glycols preferably applicable thereto include, for example, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, and 1,5-pentanediol. Among these glycols, diethylene glycol is preferable.
• Such a glycols may be used in an amount of, preferably, 5 to 500 g and, more preferably, 20 to 200 g per liter of the developer used.
• the organic solvents may be used independently or in combination.
• the silver halide photographic light-sensitive materials relating to the invention are able to display a remarkably excellent preservation stability, when they are processed with a developer as mentioned above.
• the pH values of the developers having the above-­mentioned compositions are, preferably, 9 to 13 and, more preferably, within the range of 10 to 12 from the viewpoints of the preservability and photographic characteristics of the developers.
• a potassium ion content is more than a sodium ion content, because the developer activity may be enhanced.
• the silver halide photographic light-sensitive materials relating to the invention can be processed in various condi­tions.
• the developing temperature for example, is preferably not higher than 50°C and more preferably about 25°C to 40°C.
• About the developing time it is general to complete a development within two minutes and more preferably within the range of 10 to 50 seconds to often expect a good result.
• It is discretionary to adopt other processing steps than the developing step such as a washing, stopping, stabilizing, fixing and, if required, a prehardening, and neutralizing steps. These discretionary processing steps may be appropriately omitted. Further, these processing steps may be carried out in the so-­called manual processing such as a tray or frame processing and the so-called mechanical processing such as a roller or hanger processing, either.
• a subbed polyethylene terephthalate film was subjected to a corona-discharge treatment and was then coated thereon with an antistatic solution having the following composition in an amount of 10 ml/dm2, at a coating speed of 33m/min. by means of a roll-fit-coating pan and an air-knife.
• the resulting antistatic layer-coated film support was dried at 90°C for 2 minutes and was then heat-treated at 140°C for 90 seconds. Over the antistatic layer, gelatin was coated in an amount of 2.0 g/m2, and an transmittance tests was tried.
• As the hardener for hardening gelatin formalin and sodium 2,4-dichloro-6- hydroxy-S-triazine were used. Thus obtained samples were subjected to the following transmitance test. The results thereof are shown in Table-1.
• the transmittance of the sample film support was measured by a turbidimeter Model T-2600DA manufactured by Tokyo Denshoku Company. The transmittance thereof is shown interms of percentage.
• a corona-discharge having a power of 30 W/m2 was applied to a 100 ⁇ m thick polyethylene terephthalate support.
• the support was coated on a side with a subbing solution containing a latex of butyl acrylate- styrene-t-butyl acrylate-hydroxyethyl methacrylate polymer and hexamethylene aziridine hardener, and the antistatic layer of the invention was further coated thereon in the same manner as in Example-1.
• a backing layer containing the backing dye having the following composition was coated onto the lantistatic layer.
• the gelatin layer was hardened with glyoxal and sodium 1-oxy-3,5-dichloro-S-triazine salt.
• a silver chloride emulsion containing rhodium of 10 ⁇ 5 mols per mol of silver was prepared in a controlled double-jet method under an acidic atmosphere of pH 3.0.
• Silver chloride grains of the emulsion were grown in the system containing benzyladenine in an amount of 30 mg per liter of an aqueous 1% gelatin solution.
• 6-­methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added in an amount of 600 mg per mol of the silver halide used, and then washed and desalted.
• the additives were added into each resulting emulsion so as to adjust the contents of the additives to be in the quantities given below.
• the emulsion was coated on each of the above mentioned supports.
• the emulsion was coated on the side of the support opposite to the side on which the backing layer was provided.
• a protective layer for emulsion layer was coated so as to adjust the content to be in the quantity given below.
• compositions A and B were dissolved in order into 500 ml of water to make one liter, and then the fixer was used.
• the pH of the fixer was about 5.6.
• Processing conditions Processing temperature Processing time Developing 40°C 8 seconds Fixing 35°C 8 seconds Washing Ordinary temp. 10 seconds

Landscapes

• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Laminated Bodies (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=13967009

Family Applications (1)

Country Status (2)

Cited By (2)

Citations (6)

• 1989
  • 1989-04-07 JP JP8930789A patent/JPH02266934A/ja active Pending
• 1990
  • 1990-04-05 EP EP90106498A patent/EP0391402A1/de not_active Withdrawn

Patent Citations (6)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events