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
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
• • 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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/30—Hardeners
• • 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

Definitions

• the present invention relates to a silver halide photographic light-sensitive material having an antistatic property.
• a light-sensitive material comprising an electrically insulated support and photographic component layers is liable to accumulate static electricity thereon due to friction caused by contact with or stripping from the same or foreign materials.
• Diagnosis or examination with an X-ray photograph is usually made by direct observation of a silver image.
• the tone of a silver image is very important. Fading or generation of a stain not only hinders smooth observation but also may lead to wrong diagnosis or evaluation. Therefore, a light-sensitive material for X-ray photography is strongly required to form a clear silver image of pure black.
• toning agents such as a mercapto compound have been employed to adjust the tone of a silver image.
• Japanese Patent O.P.I. Publication Nos. 285445/1986 and 276539/1987 disclose the use of a specific dye as a toning agent in a silver halide emulsion with a prescribed covering power. These methods are defective in sensitivity and shelf life.
• a light-sensitive material containing this dye can produce a silver image of pure black. Further, by changing the kind and amount of the dye, the tone of a silver image can be controlled arbitrarily.
• the inventor tried to provide the preceding electroconductive layer disclosed in Japanese Patent O.P.I. Publication No. 84658/1980 in the anthraquinone dye-containing light-sensitive material.
• the provision of this layer favorably affected the tone of a silver image, but was unexpectedly accompanied by generation of a large amount of static marks due to insufficient lowering in surface specific resistance.
• An object of the invention is to provide a silver halide photographic light-sensitive material imparted with an antistatic property having no adverse effects on photographic properties.
• Another object of the invention is to provide a silver halide photographic light-sensitive material having an antistatic property having no adverse effects on the abrasion (scratches) resistance of a wet light-sensitive material during rapid processing.
• Still another object of the invention is to provide a silver halide photographic light-sensitive material imparted with an antistatic property which is hardly impaired even after development.
• a further object of the invention is to provide a silver halide photographic light-sensitive material imparted with an antistatic property with an antistatic agent causing no fogging even when a light-sensitive material is subjected to rapid drying in its production or is bent in its handling.
• a still further object of the invention is to provide a silver halide photographic light-sensitive material capable of forming a silver image of pure black.
• the silver halide photographic light-sensitive material of the invention has a support and a silver halide emulsion layer, which material comprises an antistatic layer containing (1) a water-soluble electroconductive polymer, (2) hydrophobic polymer particles, and (3) a hardener, and a hydrophilic colloid layer containing a polyhydric alcohol compound.
• the hydrophilic coloidal layer containing the polyhydric alcohol compound is a silver halide emulsion layer or a layer adjacent layer to the silver halide emulsion layer, and preferably a silver halide emulsion layer.
• the hydrophobic polymer particles may contain a dye having an absorption maximum wave length between 400 and 510 nm.
• the light-sensitive silver halide photographic material may further comprises an electric conductive layer, which comprises a water-soluble electric conductive polymer, hydrophilic polymer particles and a hardener over a hydrophilic colloid layer nearest to the support.
• This layer may be provided on the silver halide emulsion layer or at the outermost.
• the layers of a light-sensitive material hardly take scratches during rapid processing and hardly peel off even in the dry state, when the antistatic layer is provided on a between a hydrophilic colloid layer nearest to a support and a layer adjacent to said layer and/or at the outermost surface.
• the water-soluble electroconductive polymer (1) is a polymer containing at least one electric conductive group selected from a sulfonic acid group, a sulfuric ester group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group, a polyethylene oxide group. Of them, a sulfonic acid group, a sulfuric ester group and a quaternary ammonium salt are preferable.
• An electroconductive group is needed to be contained in a proportion of not less than 5 wt% per molecule of the polymer.
• x, y and z each represent the molar proportion (%) of the monomeric unit of each polymer, and M represents the number average molecular weight.
• the most preferable polymer has a number average molecular weight of about 1,000 to 10,000,000.
• the electroconductive polymer is contained in the antistatic layer or the electroconductive layer preferably in an amount of 0.001 to 10 g in terms of solid component, more preferably 0.05 to 5 g, per square meter of the light-sensitive material.
• the hydrophobic polymer particles are contained in the water-soluble electroconductive polymer layer in the form of a latex which is substantially insoluble in water.
• the hydrophobic polymer can be obtained by polymerization of monomers combinedly selected arbitrarily from styrene, a styrene derivative, alkyl acrylate, alkyl methacrylate, an olefin derivative, a halogenated ethylene derivative, an acrylamide derivative, a methacrylamide derivative, a vinyl ester derivative and acrylonitrile.
• the hydrophobic polymer preferably contain a styrene derivative, alkyl acrylate and alkyl methacrylate in an amount of at least 30 mol%, more preferably not less than 50 mol%.
• a latex of the hydrophobic polymer can be obtained by subjecting monomers to emulsion polymerization or by a method in which the polymer in the solid state is dissolved in a low boiling point solvent to disperse it finely, followed by distillation off of the solvent.
• the former method is preferable since it can produce a latex consisting of smaller polymer particles of uniform size.
• An anion or nonion surfactant is preferably employed in the emulsion polymerization.
• An excessive amount of a surfactant impairs the transparency of the electroconductive layer.
• the preferable amount is not more than 10 wt% relative to the weight of the monomers.
• the average molecular weight of the hydrophobic polymer does not affect significantly the transparency of the electroconductive layer.
• a suitable number average molecular weight is not less than 3,000.
• hydrophobic polymer examples are given below:
• This polymer can be obtained readily by polymerizing monomers which are commercially available or can be prepared by known methods.
• the conductivity of the antistatic layer or the electroconductive layer as referred to herein means such a property as will make the specific resistance of the surface of the layer not more than 1010 ⁇ /cm2 (23°C, 20% RH), provided that said layer is obtained by applying the polymer alone on a polyethylene terephthalate film in an amount of not less than 2 g/m2.
• the surface of the antistatic layer is activated by a corona discharge, a glow discharge, an UV light treatment or a flame treatment.
• a corona discharge is most preferable.
• the energy intensity of a corona discharge is preferably 1 mw to 1 kw/m2 ⁇ min, more preferably 0.1 w to 1w/m2 ⁇ min.
• a coating liquid for the antistatic layer or the electroconductive layer which is obtained by mixing the water soluble electroconductive polymer, the hydrophobic polymer particles and a hardener is applied on a subbed support or a hydrophilic layer.
• a coating liquid for the antistatic layer or the electroconductive layer which is obtained by mixing the water soluble electroconductive polymer, the hydrophobic polymer particles and a hardener is applied on a subbed support or a hydrophilic layer.
• To increase the mechanical strength of the electroconductive layer it is possible to set the cross-linking degree of these components to a certain level.
• care must be taken to the mixing ratio of the electroconductive polymer and the hydrophobic polymer particles, conditions under which the electroconductive layer is provided and dried, and the kind and amount of the hardener.
• the hardener which is employed for the electroconductive layer use can be made of conventional hardeners for gelatin.
• Aldehyde hardeners such as:
• the polyfunctional aziridine hardener is represented by the following formula: wherein R1 represents a hydrogen atom, an alkyl or aryl group having 1 to 20 carbon atoms, a hydroxy group or a halogen atom; and R2 represents a hydrogen atom, or an alkyl group having up to 10 carbon atoms.
• An ⁇ -cyanoacrylate type compound is represented by the following formula: wherein R represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms:
• R1 to R3 each represent a substituted or unsubstituted alkyl group, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group or an alkoxy group.
• triphenyl phosphine is not limitative, but the preferred examples are as follows: (5)
• the bifunctional ethylene oxide type compound is represented by the following formula: wherein L represents a substituted or unsubstituted alkylene oxide chain group.
• Bifunctional ethylene oxide type compounds are conventionally hardened by cross-linking with heating. This method is defective since reaction rate is too low and it cannot attain a sufficient cross linkage.
• these compounds are hardened by irradiating them with an electron beam or an X-ray.
• the intensities of an electron beam and an X-ray are as follows: Intensity of an electron beam: 10 ⁇ 2 - 106 KW/m2 (50 KW/m2 is especially preferred) Intensity of an X-ray: 10 ⁇ 2 - 106 KW/m2 (300 KW/m2 is especially preferred) (6)
• the examples of the N-methylol type compound are given below, though not limitative.
• the examples of the metal complex containing zinc and zirconium are given below, though not limitative.
• the preceding metal complex in an amount of 10 ⁇ 3 to 103 mol per mol electroconductive polymer.
• silane coupling agents are also usable in the invention as the hardener.
• a carboxy group-activated hardener is also usable.
• the examples include the following carboxyimido type hardeners:
• an antistatic layer is provided on a subbed polyethylene terephthalate support.
• This antistatic layer may contain an antistatic agent such as a known surfactant (e.g., surfactants described in Japanese Patent O.P.I. Publication Nos. 21922/1978, 208743/1983, 74554/1984, 80839/1985 and 94126/1985) or an inorganic compound (e.g., NaCl, LiCl, KNO3) and a metal oxide (e.g., a metal oxide described in Japanese Patent O.P.I. Publication Nos. 23848/1985, 62649/1983 and 118242/1982).
• a known surfactant e.g., surfactants described in Japanese Patent O.P.I. Publication Nos. 21922/1978, 208743/1983, 74554/1984, 80839/1985 and 94126/1985
• an inorganic compound e.g., NaCl, LiCl, KNO3
• a metal oxide e.g., a metal oxide described in Japanese Patent O.P.I
• a hydrophilic colloid layer such as a silver halide emulsion layer, an anti-halation layer, an intermediate layer and a backing layer is provided as the lst layer.
• the 1st layer is preferably a silver halide light-sensitive emulsion layer or a backing layer.
• the electroconductive layer consisting of Components (1), (2) and (3) may be provided as the 2nd layer.
• a protective layer, an intermediate layer, a silver halide emulsion layer, a filter layer, a development controlling layer, an antistatic layer or a UV absorbing layer may be provided thereon as the 3rd layer.
• the 3rd layer be a protective layer or a silver halide emulsion layer which substantially does not have light sensitivity.
• a light-sensitive material consists of the preceding three layers.
• the antistatic property of a light-sensitive material is significantly improved by the provision of the 4th layer at the outermost surface.
• the 4th layer is the electroconductive layer which consists of the preceding Components (1), (2) and (3) as the antistatic layer.
• the hydrophilic colloid layer as referred to herein means a layer being hydrophilic and containing a binder such as gelatin, which is ordinary provided in a silver halide light-sensitive material, and the examples of which include a silver halide emulsion layer, a protective layer, an intermediate layer, an anti-halation layer, a filter layer, a development controlling layer, a UV absorbing layer, a subbing layer and a backing layer.
• a binder such as gelatin
• the kind and mixing ratio of the water soluble electroconductive polymer (1) and the hydrophobic polymer particles (2), the kind and amount of the hardener which is used as a cross-linking agent, and drying conditions be optimized.
• the degree of cross-linking in the antistatic layer or the electroconductive layer provided by the hardener can be known from the degree of swelling.
• the degree of swelling is preferably 0.2 to 100%, more preferably 2 to 50%.
• the thickness of the antistatic or electroconductive layer is closely related to its electroconductivity, and the electroconductive property improves as the unit volume increases. It is therefore better to increase the film thickness, but film flexibility is degraded at the same time. Good results are obtained with a film thickness of the layer between 0.1 and 100 ⁇ , preferably between 0.1 and 10 ⁇ .
• the silver halide photographic light-sensitive emulsion of the present invention may comprise any silver halide such as silver iodobromide, silver iodochloride or silver iodochlorobromide, but silver iodobromide is preferred, since it offers high sensitivity.
• the silver halide grains present in the photographic emulsion may be completely isotropically grown grains such as cubic, octahedral or tetradecahedal grains, multiplane crystalline grains such as spherical grains, grains comprising twins involving a plane defect, their mixtures or their complexes. These silver halide grains may range from fine grains having a diameter of not more than 0.1 ⁇ m to large grains having a diameter of up to 20 ⁇ m.
• a preferred mode of embodiment of the present invention is a monodispersible emulsion wherein silver iodobromide is localized inside the grains.
• a monodispersible emulsion is defined as an emulsion comprising silver halide grains wherein at least 95% by grain number or weight of the grains fall in the range of ⁇ 40%, preferable ⁇ 30%, of the average grain size, as measured by a standard method.
• the grain size distribution of the silver halide may be monodispersible with a narrow distribution or polydispersible with a wide distribution.
• the crystalline structure of the silver halide may be such that the inside and outside silver halide compositions differ from each other.
• a preferred mode of the emulsion of the present invention is a core/shall type monodispersible emulsion having a distinct double layer structure comprising a core with a higher iodide content and a shell layer having a lower iodide content.
• the silver iodide content of the high iodide content portion of the invention is 20 to 40 mol%, preferably 20 to 30 mol%.
• Such a monodispersible emulsion can be produced by known methods, including those described in J. Phot. Sci. 12, 242-251 (1963), Japanese Patent Publication Open to Public Inspection Nos. 36890/1973, 16364/1977, 142329/1980 and 49938/1983, British Patent No. 1,413,748, and US Patent Nos. 3,574,628 and 3,655,394.
• the monodispersible emulsion described above is preferably an emulsion prepared by growing grains by supplying silver ion and halide ion to a seed crystal as the growth nucleus.
• Methods of obtaining a core/shell emulsion are described in detail in British Patent No. 1,027,146, US Patent Nos. 3,505,068 and 4,444,877 and Japanese Patent Publication Open to Public Inspection No. 14331/1985, for instance.
• the silver halide emulsion used for the present invention may comprise tabular grains having an aspect ratio of not less than 5.
• Such tabular grains are advantageous in that they offer increase in spectral sensitization efficiency, improvement in image graininess and sharpness and other favorable aspects, and can be prepared by the methods described in British Patent No. 2,112,157 and US Patent Nos. 4,439,520, 4,433,048, 4,414,310 and 4,434,226, for instance.
• Examples of light-sensitive silver halide grains for the silver halide photographic light-sensitive material of the present invention include monodispersible light-sensitive silver halide grains having an inside silver halide content of not less than 8 mol%, preferably 8 to 40 mol%, an overall silver iodide content of not more than 3.5 mol%, preferably 0.8 to 3.0 mol%, and a silver bromide content of not less than 90%, preferably 90 to 97%.
• Examples of the light-sensitive silver halide emulsion for the silver halide photographic light-sensitive material of the present invention include light-sensitive silver halide emulsions having a silver iodide content of not more than 4.0 mol%, preferably 0.1 to 3.5 mol% and a silver bromide content of not less than 90%, preferably 90 to 99% and containing tabular grains having a grain diameter to thickness ratio between 4.0 and 30, preferably 5.0 to 20, in a ratio of not less than 50%, preferably 40 to 90%.
• the polyhydric alcohol having a molecular weight of not more than 150 used in a silver halide emulsion layer has at least two hydroxyl groups in its molecular structure and a melting point above 40°C.
• the polyhydric alcohol may be present in any layer, but it is preferable to be contained in a silver halide emulsion layer or an adjacent hydrophilic colloidal layer, more preferably to a light-sensitive silver halide emulsion layer.
• the polyhydric alcohol content is not subject to limitation, it is preferably in the range of from 0.1 to 2.0 g, more preferably 0.2 to 1.0 g, per m2 of one support face.
• the polyhydric alcohol may be dispersed directly in the hydrophilic colloid, or may be added after being dissolved in an organic solvent such as methanol or acetone.
• the polyhydric alcohol for the present invention may be such that 2 to 6 hydroxyl groups and 2 to 8 carbon atoms are present in its molecular structure and the hydroxyl groups are not conjugated via a conjugation chain, i.e., no oxidized form is present, with preference given to an alcohol compound having a total molecular weight of not more than 150, more preferably not less than 100 and not more than 150, and a melting point between 40°C and 300°C.
• the antistatic layer or an adjacent hydrophilic colloidal layer for the silver halide photographic light-sensitive material of the present invention may incorporate a plasticizer for the purpose of providing plasticity.
• plasticizer Any plasticizer can be used, as long as it exhibits plasticizing action, but it is preferable to use a polyalkylene oxide compound.
• the polyalkylene oxide compound used for the present invention means a compound having at least two and at most 500 polyalkylene oxide chains in its molecular structure. It can be synthesized by condensation of polyalkylene oxide with a compound having an active hydrogen atom such as an aliphatic alcohol, a phenol, a fatty acid, an aliphatic mercaptane or an organic amine, or condensation of a polyol such as polypropylene glycol or a polyoxytetramethylene polymer with an aliphatic mercaptane, an organic amine, ethylene oxide or propylene oxide.
• a compound having an active hydrogen atom such as an aliphatic alcohol, a phenol, a fatty acid, an aliphatic mercaptane or an organic amine
• condensation of a polyol such as polypropylene glycol or a polyoxytetramethylene polymer with an aliphatic mercaptane, an organic amine, ethylene oxide or propylene
• the polyalkylene oxide compound described above may be a block copolymer having in its molecular structure not a single polyalkylene oxide chain but two or more divided chains. In this case, it is preferable that the total degree of polymerization of the polyalkylene oxide be not less than 3 and not more than 100.
• these compounds When using these compounds for the present invention, they may be added to a liquid for preparation of layer, comprising a reaction product of (1) a water-soluble electroconductive polymer, (2) hydrophobic polymer grains and (3) a hardener, after being dissolved in a hydrophilic solvent such as methanol, ethanol or Methyl Cellosolve. They may also be added to such a layer coated adjacent to this antistatic layer, such as a gelatin layer or a silver halide emulsion layer.
• a hydrophilic solvent such as methanol, ethanol or Methyl Cellosolve.
• the amount of addition varies depending on the type of the compound, it is preferable to add the compound in a ratio of 0.01 to 0.5 g, more preferably 0.03 to 0.3g, per unit m2 as solid content.
• a metal oxide may be added to the component layers of the light-sensitive material.
• the examples of the metal oxide used in the electroconductive layer include indium oxide, tin oxide, a metal oxide doped with an antimony or phosphor atom, and a combination thereof.
• indium oxide examples include In2O and In2O3.
• In2O3 is preferable.
• tin oxide examples include stannous oxide (SnO) and stannic oxide (SnO2).
• a metal oxide doped with an antimony atom or a phosphor atom include tin oxide and indium oxide. These metal oxides can be doped with antimony or phosphor by mixing a halide, an alkoxy compound or a nitrate compound of tin or indium with a halide, an alkoxy compound or a nitrate compound of antimony or phosphor, followed by oxidation and calcination. These metal oxides can be procured readily.
• the amount of antimony or photophore is preferably 0.5 to 10 wt% relative to the weight of tin or indium.
• these inorganic compounds be added in the form of a dispersion obtained by dispersing them in a hydrophilic colloid such as gelatin or a polymeric compound such as acrylic acid or maleic acid, and in an amount of 1 to 100 wt% relative to the weight of a binder.
• a hydrophilic colloid such as gelatin or a polymeric compound such as acrylic acid or maleic acid
• the dyes used for the present invention are a combination of a dye having an absorption maximum wavelength between 400 and 510 nm, preferably between 430 and 480 nm, another dye having an absorption maximum wavelength between 520 and 560 nm, preferably between 530 and 555 nm, and still another dye having an absorption maximum wavelength between 570 and 700 nm, preferably between 580 and 650 nm.
• the absorption maximum wavelength of a dye of the present invention is obtained while the dye is present in the light-sensitive material.
• dyes having a given absorption maximum wavelength are selected out of the group comprising anthraquinone dyes, azo dyes, azomethine dyes, indoaniline dyes, oxonol dyes, carbocyanine dyes, styryl dyes, triphenylmethane dyes, pyrazolidone dyes, pyrazoloazoleazomethine dyes and other dyes. It is preferable to select fast dyes not subject to discoloration, leakage or tone change due to development, fixation or washing, or fading due to light exposure. Particularly, in the case of a film for X-ray radiography, it is desirable to use highly light-fast dyes, since the film is sometimes exposed to high luminance viewer for a long time.
• appropriate dyes are selected out of the group comprising anthraquinone dyes, azo dyes, azomethine dyes and indoaniline dyes.
• hydrophobic dyes having an absorption maximum wavelength of 400 to 700 nm used for the present invention are described below.
• the yellow dye having an absorption maximum wavelength of 400 to 510 nm used for the present invention is a compound represented by the following formula [C-I], [C-II] or [C-III].
• R1 represents an alkyl group or an aryl group
• R2 and R3 independently represent an alkyl group
• R4 represents an alkyl group or an alkoxy group
• R5 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group or a sulfonamido group.
• R1 and R2 whether identical or not, independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a subsituted amino group, a carbamoyl group, a sulfamoyl group, a nitro group or an alkoxycarbonyl group.
• R3 and R4 whether identical or not, independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, an acyl group or a sulfonyl group, and R3 and R4 may bind to each other to form a 5- or 6-membered ring.
• X and Y independently represent an electron-attracting group, whether identical or not.
• Q1 and Q2 independently represent a group necessary for the formation of a heterocyclic ring; L represents a methine group.
• the heterocyclic ring formed by the group of nonmetallic atoms represented by Q1 and Q2 be a 5- or 6-membered ring, whether a single ring or condensed ring.
• heterocyclic rings include a 5-pyrazolone ring, barbituric acid, isooxazolone, thiobarbituric acid, rhodanine, imidazopyridine, pyrazolopyrimidine and pyrrolidone.
• the magenta dye having an absorption maximum wavelength of 520 to 560 nm used for the present invention is a compound represented by the following formula [A-I], [A-II] or [A-III].
• R1 and R2 whether identical or not, independently represent a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted heterocyclic group
• R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group
• R4 and R5 whether identical or not, independently represent a substituted or unsubstituted alkyl group, and R4 and R5 may bind to each other to form a ring.
• Z represents -NHCO-, -NH-, -NHCONH-, -COO-, -O- or -CONH-.
• n represents 0 or 1.
• the alkyl group represented by R1 or R2 is a linear or branched alkyl group having a carbon number of 1 to 20, which may have a substituent such as a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, an acylamino group, a carbamoyl group, a sulfamoyl group or a cyano group.
• a substituent such as a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, an acylamino group, a carbamoyl group, a sulfamoyl group or a cyano group.
• the aryl group represented by R1 or R2 may have 1 or more substituents (e.g., an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfonamido group, an arylsulfonamido group, a sulfamoyl group, an alkylsulfamoyl group, a cyano group and a nitro group).
• substituents e.g., an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group
• the heterocyclic group represented by R1 or R2 may have a substituent listed above for the aryl group.
• the group for R1 is preferably a phenyl group wherein at least one ortho position is substituted by an alkyl group, a halogen atom, an alkoxy group or the like.
• the alkyl group represented by R3 has the same definition as the alkyl group represented by R1 or R2 having a carbon number of 1 to 20 described above.
• the alkyl group represented by R4 or R5 is preferably an alkyl group having a carbon number of 1 to 6 (e.g., a methyl group, an ethyl group, an n-butyl group, an isopropyl group, an n-hexyl group) or a substituted alkyl group having a total carbon number of 2 to 10 carbon atoms (examples of the substituent include a hydroxyl group, a sulfonamido group, a sulfamoyl group, an alkoxy group, a halogen atom, an acylamino group, a carbamoyl group, an ester group and a cyano group).
• Examples of the ring formed by R4 and R5 in cooperation include a piperidine ring, a pyrrolidine ring and a morpholine ring.
• Q1 and Q2 independently represent a group necessary for the formation of a heterocyclic ring; L represents a methine group.
• the heterocyclic ring represented by Q1 and Q2 has the same definition as of formula [C-III] above.
• R1 and R2 independently represent an alkyl group which may have a substituent
• R3 represents a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group.
• R4 represents an alkyl group which may have a substituent or an aryl group;
• X represents a hydrogen atom, a halogen atom, a cyano group, a nitro group or SO2R5;
• R5 represents an alkyl group.
• Examples of the cyan dye having an absorption maximum wavelength between 570 and 700 nm used for the present invention include compounds represented by the following formulas [I] through [V].
• Q1 and Q2 independently represent a group necessary for the formation of a carbon ring or a heterocyclic ring; L represents a methine group. n represents the integer 1 or 2.
• the heterocyclic ring represented by Q1 and Q2 has the same definition as of formula [C-III] above.
• R1, R2, R3 and R4 independently represent a hydrogen atom, an alkyl group, an aryl group, or the like;
• R5, R6 and R7 independently represent an alkyl group, an alkoxy group, an amino group, a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom or another group;
• R5, R6 and R7 may have a number of substituents.
• X ⁇ represents an acid anion;
• P represents the integer 1 or 2.
• R1 represents a hydrogen atom, a sulfo group, a carboxyl group, a carbamoyl group, a carboxylate group, an amino group or an acyl group
• R2 and R3 independently represent a substituent such as a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a halogen atom
• R2 and R3 may bind to each other to form a ring.
• R4 represents a substituent such as an alkyl group, an alkoxy group, an amino group, a sulfo group, a carboxyl group or a halogen atom, which may have a number of substituents.
• R5 and R6 independently represent an alkyl group or an aryl group.
• Q1 represents a group necessary for the formation of a heterocyclic ring
• L represents a methine group.
• R1, R2 and R3 independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
• X ⁇ represents an anion;
• m represents 0 or 1.
• the heterocyclic ring represented by Q1 is preferably a 5- or 6-membered ring, such as an indole ring.
• Q1 and Q2 independently represent a group necessary for the formation of a carbon ring or a heterocyclic ring;
• L represents a methine group.
• R4 and R5 independently represent an alkyl group which may have a substituent;
• X ⁇ represents an anion;
• m represents 1 or 2.
• the heterocyclic ring represented by Q1 and Q2 is preferably a 5- or 6-membered ring, such as an indole ring.
• dyes preferred for the present invention include cyan dyes of the oxonol, anthraquinone, azo and other types.
• the dye In the case of an oxonole type dye, it is preferable that the dye have a 5-pyrazolone nucleus. It is preferable to use a cyan dye having an electron-donating or weakly electron-attractive substituent at the 3-position in its 5-pyrazolone nucleus.
• the hydrophobic dye with a ballast group along with a hydrophobic polymer used for the present invention, is dispersed as follows:
• the dye and the hydrophobic polymer are mixed in the presence of an auxiliary solvent in which both are soluble.
• the resulting mixture is dispersed incontinuously in the zol of an aqueous colloidal binder to form a finely granular dispersion like gelatin.
• the resulting mixture is then desirably kept standing cool, shredded and washed with water (preferably distilled water) and dried. All portion of the solvent used is removed in this process.
• the hydrophobic colloid containing a substantially uniform dispersion of fine grains of the dye-hydrophobic polymer mixture is thoroughly mixed with an aqueous polymer of the invention and a hardener of the present invention and used to prepare an electroconductive layer.
• the fine grains of the dye-hydrophobic polymer mixture are normally smaller than 3 microns. It is desirable that the grains have a size of not more than 1 micron on average.
• any conventional auxiliary solvent can be used to dissolve the dye and the hydrophobic polymer.
• auxiliary solvents include alcohols, ketones, esters and halogenated hydrocarbons, specifically ethyl acetate, chloroform, benzyl alcohol, methyl acetate, propyl acetate, butyl acetate, isobutyl ketone, isopropyl acetate, ethyl propionate and secondary butyl alcohol.
• a dye content for the present invention is selected so that the tone at the unexposed portion after development becomes neutral black.
• Optimum amount of dye addition depends on support concentration, dye extinction coefficient, dye absorption maximum wavelength and developed silver tone. This applies to the content ratios of the dye having an absorption maximum wavelength between 400 and 520 nm, the dye having an absorption maximum wavelength between 520 and 560 nm, and the dye having an absorption maximum wavelength between 570 and 700 nm. It is preferable to add each dye in a ratio of 1 x 10 ⁇ 7 to 1 x 10 ⁇ 4 mol/m2, more preferably 2 x 10 ⁇ 7 to 2 x 10 ⁇ 5 mol/m2, and ideally 5 x 10 ⁇ 7 to 1.5 x 10 ⁇ 5 mol/m2.
• Appropriate supports include plastic films, which may be coated with a subbing layer or subjected to corona discharge, ultraviolet irradiation or other treatment for the purpose of obtaining better coating layer adhesion.
• a subbing layer or subjected to corona discharge, ultraviolet irradiation or other treatment for the purpose of obtaining better coating layer adhesion.
• One or both of the support faces thus treated may be coated with an emulsion of the present invention.
• a fluorescent intensifying screen mainly comprising a phosphor which generates near ultraviolet light or visible light upon exposure to transmitting radiation is used. It is desirable that exposure be carried out by keeping this fluorescent intensifying screen in close contact with both faces of the light-sensitive material formed with an emulsion of the present invention on both faces.
• transmitting radiation means a high energy electromagnetic wave, i.e., X-ray or gamma ray.
• the fluorescent intensifying screen includes an intensifying screen containing calcium tungstate as the main fluorescent component and a fluorescent intensifying screen containing a terbium-activated rare earth compound as the main component.
• Silver iodobromide grains containing 30 mol% of silver iodide were grown at pH 9.3 and pAg 7.5 on monodispersed silver iodobromide seed grains having an average grain size of 0.2 ⁇ m and a silver iodide content of 2.0 mol%, and then molar equivalents of potassium bromide and silver nitrate were added thereto at pH 7.8 and pAg 8.9 so as to prepare monodispersed emulsions having an average silver iodide content of 2.3 mols and three different average grain sizes of 1.25 ⁇ m (A), 0.98 ⁇ m (B), and 0.60 ⁇ m (C) were prepared.
• the emulsions were desalinated by a conventional flocculation method; that is, a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added for flocculation while keeping the temperature at 40°C. After decantation, demineralized water of 40°C or below was added and the aqueous solution of magnesium sulfate was added again for reflocculation followed by decantation.
• a conventional flocculation method that is, a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added for flocculation while keeping the temperature at 40°C.
• demineralized water of 40°C or below was added and the aqueous solution of magnesium sulfate was added again for reflocculation followed by decantation.
• each of the desalinated grains (A), (B) and (C) were added 1.9 X 10 ⁇ 3 mol/mol AgX of ammonium thiocyanate, proper amounts of chloroauric acid and hypo, and the following spectral sensitizing dyes A and B in a total amount of 800 mg/mol AgX at an A-to-B weight ration of 200:1 to perform chemical ripening.
• 200 mg/mol AgX of potassium iodide was added, then each emulsion was stabilized with the addition of 3 X 10 ⁇ 2 mol of 4-hydroxy-6-methyl-1,3,3a,7-­tetrazaindene.
• the three types of emulsion grains were mixed at a ratio of (A)25%, (B)40% and (C)35%, and additions of the following additives and lime-treated gelatin were followed to prepare the coating emulsion (1).
• grains (B), (C) and (D) were treated in the same manner and mixed at a ratio of (B)15%, (C)45% and (D)40% to prepare the coating emulsion (2).
• the spectral sensitizing dyes used in the coating emulsions are as follows:
• the additives used in each of the coating emulsions are as follows. Amounts of addition are per mol of silver halide.
• a component solution containing a water-soluble electroconductive polymer (a), hydrophobic polymer particles (b) and a hardener (c) in a weight ratio of 5.5:3.6:0.9 was coated thereon to a dry film thickness of 0.7 ⁇ m at a speed of 45 m/min with a roll fit coating pan and an air knife. Then, the film was dried for 2 minutes at 90°C and heat-treated for 90 seconds at 140°C.
• the samples have a 4-layered configuration with the 1st layer nearest to the support.
• the electroconductive layers used in this example were as follows:
• the hardeners used in the antistatic layer of this example are as follows:
• the antistatic properties of the samples were evaluated by preparing the preserved samples (1) and (2) and measuring the surface specific resistances of such preserved samples. The measurement was carried out for 1 minute on a sample placed between a pair of brazen electrodes (interval: 0.14 cm, length: 10 cm) with a resistance meter model TR 8651 made by Takeda Riken Kogyo. Before measurement, each sample was conditioned for 3 hours at 23°C and 20% RH.
• the surface specific resistances were also measured on a portion of the preserved samples (1) which were developed with an automatic developer model SRX-501 made by Konica Corp. in the following processing solutions at a developing temperature of 35°C, a fixing temperature of 32°C, a washing water flow rate of 3l/min, and a drying temperature of 45°C.
• a sample humidified at 23°C, 48% RH for 4 hours was scratched with a 0.3-mm radius sapphire needle at a speed of 1 cm/min while continuously changing the load, then the sample was developed in the same manner as mentioned above.
• a load at which blacking begins is shown in Table 1.
• a larger value means a higher abrasion resistance.
• any sample of the invention was excellent in abrasion resistance and had a low surface specific resistance even after the forced deterioration, exhibiting a satisfactory antistatic property. Particularly, surface specific resistance was low in a processed sample.
• An emulsion consisting of tabular silver iodobromide grains having an average grain diameter of 1.10 ⁇ m and an aspect ratio of 8:1 was prepared by the method described with respect to Emulsion 3 (example) of Japanese Patent O.P.I. Publication No. 113927/1983.
• silver iodobromide grains account for more than 80% of the total projection area.
• the preceding spectral sensitizing dyes A and B were added to these grains at an A-to-B weight ratio of 200:1 and in a total amount of 1,000 mg/mol AgX.
• Example 2 To the resultant emulsion, the same additives as in Example 1 were added to prepare the coating emulsion 3. As the protective layer, the same layer as in Example 1 was used.
• Coating solution for the lower backing layer Materials used per liter of the coating solution Lime-treated gelatin 70 g Acid-treated gelatin 5 g Trimethylol propane 1.5 g Backing dye A (described below) 1.0 g Backing dye B (described below) 1.0 g
• An emulsion containing tabular silver iodobromide grains having an average grain diameter of 0.7 ⁇ m and an aspect ratio of 6:1 was prepared in the same manner as in Example 2.
• the resultant emulsion was chemically ripened by adding 2.0 X 10 ⁇ 3 mol/mol AgX of ammonium thiocyanate and proper amounts of chloroauric acid and hypo.
• the coating emulsion 4 was prepared.
• Composition of the protective was the same as that of Example 1.
• a backing layer there was prepared a backing layer solution consisting of 400 g of gelatin, 2 g of polymethylmethacrylate, 6 g of sodium dodecylbenzene sulfonate, 20 g of the following antihalation dye, and glyoxal.
• a solution of the following composition was prepared.
• the above backing layers ware simultaneously formed by a multi-layer coating method on a film base provided with an antistatic layer like Example 2. Then, an emulsion layer, a protective layer and electroconductive layers were coated thereon and dried in the same manner as in Example 1 to give the layer configuration shown by Table 3. Samples 57 through 70 were thus obtained.
• silver iodobromide containing 30 mol% of silver iodide was grown at pH 9.8 and pAg 7.8.
• a mixed solution containing 0.55 mol of potassium iodide and 2.0 mols of potassium bromide was added to the emulsion together with the silver nitrate solution over a period of 13.3 minutes, while maintaining pBr at 1.7 and accelerating the addition speed so as to finish the addition at a speed of 1.5 times as large as that at the start (35.9% of the total added amount of silver nitrate was consumed).
• 1.5 g/mol Ag of sodium thiocyanate was added, then the emulsion was allowed to stand for 25 minutes.
• the emulsion was subjected to desalination in the same manner as in the foregoing monodispersed emulsion, followed by addition of gelatin.
• 14.5 kg of an emulsion having a pH of 5.90 and a pAg of 8.71 was obtained.
• the average grain size ( r ) was 0.51 ⁇ m
• the dispersed of grain size (S/ r ) was 0.24
• the emulsion so prepared was referred to as multi-dispersed grains (3).
• ammonium thiocyanate was added in amounts of 4 X 10-3 mol/mol AgX to (1)-1, 2 X 10 ⁇ 3 mol/mol AgX to (1)-2, 1 X 10 ⁇ 3 mol/mol AgX to (1)-3, 2 X 10 ⁇ 3 mol/mol AgX to (2), and 3 X 10 ⁇ 3 mol/mol AgX to (3), further, proper amounts of chloroauric acid and hypo were added to each of the above to start chemical ripening, while keeping the pH at 6.15 and the silver potential at 50 mv.
• the resultant grains (1)-1, (1)-2 and (1)-3 were mixed at a ratio of 15%: 50%: 35%, and the following additives were added thereto to obtain a monodispersed emulsion preparation (Emulsion 1). Likewise, these additives were respectively added to the tabular grains (2) and the multi-dispersed grains (3) to obtain a tabular emulsion preparation (Emulsion 2) and a multi-dispersed emulsion preparation (Emulsion 3).
• dispersion (a) consisting of 0.12 ⁇ m diameter oily droplets containing the following compounds (1), (2) and (3) and dispersion (b) consisting of 0.09 ⁇ m diameter oily droplets containing the compounds (2), (3) and (4) in the following amounts per mol of silver halide.
• Dispersion (a) was prepared by the method described in item (3) of Example 1 in Japanese Patent O.P.I. Publication No. 285445/1986, and Dispersion (b) by the method described on page 35 from the 15 line downward of Japanese Patent O.P.I. Publication No. 243654/1985.
• the additives used in the coating emulsions were as follows. Amounts of addition are per mol of silver halide.
• Polyhydric alcohol of the invention an amount shown in Table 2-2 1-Ephenyl-5-mercaptotetrazole 50 mg
• the additives used in the coating solution for protective layer were as follows. Amounts of addition are per liter of the solution.
• Coating was performed so as to provide an emulsion layer having an coating weight of 1.48 g/m2 in terms of silver and that of 1.98 g/m2 in terms of hydrophilic colloid and a protective layer having a gelatin coating weight of 0.99 g/m2, at a speed of 60 m/min with two slide hopper type coaters, on one side of a 175 ⁇ m thick polyethylene terephthalate film base subbed with a 10% aqueous dispersion of a copolymer made from 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate and 40 wt% of butyl methacrylate.
• a film base coated with the electroconductive layer of the invention was prepared in the following manner.
• a resultant sample was sandwiched between fluorescent intensifying screens (KO-250, sold by Konica Corp.) and subjected to X-ray irradiation for 0.05 second at a lamp voltage of 90 KVP, 20mA. Then, a sensitometry characteristic curve was made by the distance method. Development was performed in a developer XD-90 for 90 seconds with an automatic developer model KK-500 made by Konica Corp. The fogging value and sensitivity were evaluated on each sample.
• the sensitivity was defined by a reciprocal of an exposure necessary for increasing a black density by 1.0 and shown by a value relative to the sensitivity of Sample 1 in Table 2-2 which was set at 100.
• the other one of the two sheets was exposed through an optical wedge 3 minutes later the bending and developed. Black densities of respective wedges were measured on this sample, and the difference in density between a desensitized portion caused by the bending on the portion of density 1.0 ⁇ 0.1 and a portion where no bending was performed was defined as ⁇ D2. Then, ⁇ D2 was divided by each density D2, and a mean value of ⁇ D2/D2 was used as the criterion for judging pressure desensitization. A smaller value means a better resistance to pressure desensitization.
• a sample was conditioned at 23°C and 20% RH for 2 hours in a dark room, and then rubbed with a neoprene roller. After developing the sample with the automatic developing machine in the foregoing manner, generation of static marks was visually observed.
• a developed sample was placed between a pair of brazen electrodes (electrode interval: 0.14 cm, length: 10 cm), and subjected to measurement for 1 minute with a resistance meter model TR-8651 made by Takeda Riken Kogyo. Prior to measurement, the sample was conditioned at 23°C and 20% RH for 3 hours.
• Table 2-2 Sample No. No. of emulsion used No. of base used Polyhydric alcohol Photographic properties Presure resistance Antistatic property Remarks Exemplified No. (g/mol AgX) Fogging Sensitivity ⁇ D1 ⁇ D1/D2 Static marks Surface specific resistance after processing ( ⁇ ) 1 3 0 - 0 0.10 100 0.21 0.13 Observed 8x1012 Comparison 2 1 0 - 0 0.07 124 0.12 0.18 Observed 8x1012 Comparison 3 2 0 - 0 0.08 120 0.38 0.06 Observed 8x1012 Comparison 4 3 1 - 0 0.15 100 0.27 0.17 Not observed 7x1011 Comparison 5 1 1 - 0 0.14 124 0.15 0.22 Not observed 7x1011 Comparison 6 2 1 - 0 0.15 120 0.44 0.08 Not observed 7x1011 Comparison 7 3 0 1-1 14 0.07 98 0.17 0.11 Observed 1.8x1012 Comparison 8 1 0 1 1
• the samples of the invention were less liable to cause sensitivity deterioration and fog, in addition to excellent pressure resistance.
• Such effects of the present invention are much more heightened when a monodispersed emulsion (1) having an internal high iodine portion or a tabular grain emulsion (2) is used rather the use of a multi-dispersed emulsion (3).
• Sample 32 which was prepared in the same manner as in Sample 11 except that the following VS-1 was used as a hardener in the protective layer, had good photographic properties, pressure resistance and antistatic property.
• a silver iodobromide layer having an iodine-to-bromine molar ratio of 4:6 was grown to a grain size of 0.45 ⁇ m outside of a monodispersed silver chloroiodide inner nucleus having an average grain size of 0.18 ⁇ m and an iodine-to-bromine molar ratio of 10:1. Then, a silver iodobromide layer having an iodine-to-bromine molar ratio of 1:99 to 0.69 ⁇ m.
• the resultant silver halide grains were slightly rounded tetradecahedrons.
• the dispersed was s/ r ⁇ 0.16, showing a good monodispersed.
• the resultant silver halide grains had an average diameter of 1.27 ⁇ m and an average diameter/thickness ratio of 5.1.
• a multi-dispersed emulsion for comparison was prepared by the normal mixing method.
• Solution A nitric acid 100 g aqueous ammonia (28%) 78 ml water to make 240 ml
• Solution B ossein gelatin 8 g potassium bromide 80 g potassium iodide 2.2 g water to make 550 ml
• Solution C aqueous ammonia 6 ml glacial acetic acid 10 ml water to make 34 ml
• Solution D glacial acetic acid 226 ml water to make 400 ml
• Solutions B and C were poured into a reaction vessel for emulsion preparation and stirred at 300 rpm with a propeller stirrer at 45°C. Then, 100 ml of Solution A was added thereto over a period of 2 minutes. After stirring for 8 minutes, the remaining 200 ml of Solution A was added in 2 minutes and stirring was continued for 15 minutes. Then, Solution D was poured into the mixture of Solutions A, B and C, and the pH was adjusted to 6 to terminate the reaction. Thus, a multi-dispersed emulsion for comparison having an average grain size of 0.71 ⁇ m was prepared.
• ammonium thiocyanate was added in amounts of 1.8 X 10 ⁇ 3 mol/mol Ag to (4), 1.8 X 10 ⁇ 3 mol/mol Ag to (5) and 2.5 X 10 ⁇ 3 mol/mol Ag to (4); further, proper amounts of chloroauric acid and hypo were added to each of them to initiate chemical ripening.
• the pH and silver potential during the ripening were 5.95 and 60 mv, respectively.
• the same additives as in Example 4 were added to them to obtain coating emulsions.
• a coating solution for the protective layer was also the same as that in Example 4.
• Coating was carried out so as to provide an emulsion layer having an coating weight of 1.51 g/m2 as converted amount into silver and that of 2.02 g/m2 in terms of hydrophilic colloid and a protective layer having a gelatin coating weight of 1.02 g/m2, at a speed of 60 m/min with two slide hopper type coaters, on one side of a 175 ⁇ m thick polyethylene terephthalate film base subbed with a 10% aqueous dispersion of a copolymer made from 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate and 40 wt% of butyl methacrylate.
• an aqueous solution containing 8.33 g of silver nitrate was added over a period of 7.5 minutes so as to double the flow rate from start to finish. Then, an aqueous solution of silver nitrate and that of potassium bromide were added by the controlled double-jet method while maintaining the potential at pAg 8.1. In the course of the addition, the flow rate was accelerated so as to be 8 times that of the start at the end of addition. After the addition, 15 ml of 2N potassium thiocyanate solution was added, and then 50 ml of 1% potassium iodide aqueous solution was added in 30 seconds.
• the temperature was lowered to 35°C, and soluble salts were removed by the flocculation method.
• 68 g of gelatin and 2 g of phenol were added; then, the pH and pAg were adjusted to 6.40 and 8.45 respectively with the addition of sodium hydroxide and potassium bromide.
• the emulsion so prepared consisted of grains having an average projection area diameter of 0.43 ⁇ m, average thickness of 0.096 ⁇ m and aspect ratio of 4.48.
• a tabular grain emulsion B was prepared.
• the emulsion consisted of grains having an average projection area diameter of 0.83 ⁇ m, average thickness of 0.161 ⁇ m and aspect ratio of 5.16.
• each of the emulsions A and B were subjected to chemical sensitization, or gold-sulfur sensitization by adding 1.8 X 10 ⁇ 3 mol/mol AgX of ammonium thiocyanate and proper amounts of chloroauric acid and hypo.
• 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added thereto, and then spectral sensitization was performed by added 8 X 10 ⁇ 4 mol/mol AgX of potassium iodide and the following spectral sensitizing dyes (1) and (2) in amounts of 300 mg/mol AgX and 5 mg/mol AgX respectively.
• the two emulsions A and B were mixed at a ratio of 30% : 70%; then, the following additives and lime-treated gelatin were added thereto to obtain a coating emulsion.
• the additives used in the coating emulsion are as follows. Amounts are per mol of silver halide. t-butyl catechol 400 mg Polyvinylpyrrolidone (molecular weight: 10,000) 1.0 g Trimethylol propane 10 g Diethylene glycol 5 g Nitrophenyl-triphenyl phophonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4 mg Sodium 2-mercaptobenzimidazole-5-sulfonate 15 mg
• an electroconductive layer consisting of a dye-polymer dispersion of the invention was coated on the support at a speed of 30 m/min so as to give a coating weight shown in Table 3-1 with a roll fit coating pan and an air knife; then, the film was subjected to corona treatment again.
• the dispersion of dye and hydrophobic polymer used in this example was prepared in the following manner.
• One part of a dye and 2 parts of a hydrophobic polymer were added under stirring to 8.1 parts of ethyl acetate which was maintained at 60°C.
• This dispersion was added under stirring to a mixed solution of 12.6 parts of 10% gelatin solution and 0.3 part of 10% triisopropylnaphthalene sulfonate solution, which was kept at 55°C.
• the resultant dispersion was passed through a colloid mill five times, so that dye-polymer mixed particles having an average particle size below 5 ⁇ m were obtained. After cooling the dispersion, it was divided into small portions and dried.
• a dye-polymer dispersion with an area mean particle size ranging from 0.08 ⁇ m to 0.10 ⁇ m was obtained. At the use, the dispersion was dipped in water and mechanically stirred for reproduction.
• the comparative samples shown in Table 3-1 were prepared by the following procedure.
• the dye emulsion was prepared in the following manner.
• the light-sensitive samples so prepared were evaluated for surface specific resistance and tone of images.
• a chest phantom was photographed on a sample using a fluorescent intensifying screen KO-250 made by Konica Corp. at a lamp voltage of 90 KVp. After photographing, the sample was processed in a developer XD-SR made by Konica Corp. for 90 seconds with an automatic developing machine model SPX-501 made by the same company.
• the photograph sample was subjected to standing at 50°C, 80% RH for 7 days; then, the tone of image silver under transmitted light was visually observed on a viewer.
• the evaluation criterion was as follows:
• Table 3-1 Sample No. Water-soluble electroconductive polymer (1) Dye-polymer dispersion Hardener (3) Dye dispersion (for comparison) Surface specific resistance ( ⁇ ) Tone rank Remarks Hydrophobic polymer (2) Magenta dye Cyan dye Exemplified No. (g/m2) Exemplified No. (g/m2) Exemplified No. (mg/mol AgX) Exemplified No. (mg/mol AgX) Exemplified No. (mol/dm2) Exemplified No.
• Silver iodobromide containing 30 mol% of silver iodide was grown at pH 9.3 and pAg 7.5 on silver iodobromide monodispersed seed grains having an average grain size of 0.2 ⁇ m and a silver iodide content of 2.0 mol%. Then, molar equivalents of potassium bromide and silver nitrate were added thereto at pH 7.8 and pAg 8.9 so as to prepare silver iodobromide grains having an average silver iodide content of 2.3 mol% and three different average grain sizes of 1.15 ⁇ m (C), 0.63 ⁇ m (D) and 0.38 ⁇ m (E).
• the emulsions were subjected to desalination of a normal flocculation method. That is, a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added at 40°C for flocculation. After decantation, demineralized water below 40°C was added thereto, and the aqueous solution of magnesium sulfate was added again for reflocculation, and decantation followed.
• the resultant grains (D), (E) were chemically sensitized in the same manner as in Example 6. After that, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added, and then these grains were subjected to spectral sensitization by the addition of potassium iodide and the spectral sensitizing dyes (1) and (2) as in Example 6.
• the grains (C) were subjected to chemical sensitization in a different way; that is, after adding the spectral sensitizing dyes (1) and (2) in amounts of 350 mg/mol AgX and 10 mg/mol AgX respectively, gold-sulfur sensitization was performed by the addition of ammonium thiocyanate, chloroauric acid and hypo. Then, the grains were stabilized by adding 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
• the samples were divided into three groups: the 1st group included fresh samples for immediate evaluation, the samples of the 2nd group were conditioned at 23°C and 55% RH for 3 days (preservation I). The samples of the 3rd group were conditioned at 23°C and 55% RH for 3 hours and then subjected to forced deterioration at 55°C for 3 days while being piled up in a moisture proof bag (preservation II).
• Table 3-2 Sample No. Water-soluble electroconductive polymer (1) Dye-polymer dispersion Hardener (3) Dye dispersion (for comparison) Surface specific resistance ( ⁇ ) Tone rank Remarks Hydrophobic polymer (2) Cyan dye Exemplified No. (g/m2) Exemplified No. (g/m2) Examplified No. (mg/mol AgX) Exemplified No. (mg/mol AgX) Exemplified No.
• the samples of the invention exhibited a stable surface specific resistance even after preservation under severe conditions and were capable of providing pure black image tone suited to the X-ray photographic diagnosis.
• a support provided with the electroconductive layer like Example 6 was prepared.
• Corona discharge, coating of a latex layer, coating of an electroconductive layer of the invention, and re-corona discharge were performed on both sides of a 180 ⁇ m thick polyethylene terephthalate support in the same manner as in Example 6, except that the following dispersion was used in the electroconductive layer.
• Table 3-3 Sample No. Water-soluble electroconductive polymer (1) Dye-polymer dispersion Hardener (3) Dye dispersion (for comparison) Surface specific resistance ( ⁇ ) Tone rank Remarks Hydrophobic polymer (2) Yellow dye Exemplified No. (g/m2) Exemplified No. (g/m2) Exemplified No. (mg/mol AgX) Exemplified No. (mol/dm2) Exemplified No.

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• 1990
  • 1990-10-09 EP EP19900311067 patent/EP0424010A2/fr not_active Withdrawn

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