EP0494121A1 - Matériau photographique à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0494121A1
EP0494121A1 EP92300086A EP92300086A EP0494121A1 EP 0494121 A1 EP0494121 A1 EP 0494121A1 EP 92300086 A EP92300086 A EP 92300086A EP 92300086 A EP92300086 A EP 92300086A EP 0494121 A1 EP0494121 A1 EP 0494121A1
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EP
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Prior art keywords
group
layer
silver halide
backing
dye
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EP92300086A
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German (de)
English (en)
Inventor
Hiroyuki Konica Corporation Ushiroyama
Kazuhiko Konica Corporation Hirabayashi
Shiyouji Konica Corporation Nishio
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0494121A1 publication Critical patent/EP0494121A1/fr
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/95Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83Organic dyestuffs therefor
    • G03C1/832Methine or polymethine dyes

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material, more specifically to a silver halide photographic light-sensitive material which has improved transportability for scanners, facsimile plotters, etc.
  • scanners and facsimile plotters are used.
  • the use of these scanners and facsimile plotters can pose a problem of light-sensitive material transportation failure therein.
  • Photographic light-sensitive materials usually incorporate gelatin as a binder; they become prone to aggregate under humid conditions to cause transportation failure in scanners and facsimile plotters.
  • Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 42653/1986 describes a combined use of a polymer matting agent of over 3 ⁇ m, preferably 3.5 to 6.0 ⁇ m in average grain size and a silicone lubricant to improve the charge control property and sliding quality, but this method does not offer a sufficient improving effect on the transportability in scanners and facsimile plotters.
  • a silver halide photographic light-sensitive material comprising a support and provided thereon, a silver halide emulsion layer and at least two backing layers on the support opposite to said silver halide emulsion layer, wherein an uppermost layer of said silver halide emulsion layer or an uppermost layer of said backing layers contains a lubricant and a backing layer other than said uppermost backing layer contains a matting agent having an average particle size of more than 10 ⁇ m.
  • Typical examples of lubricants which can be used for the present invention include the silicone lubricants described in US Patent Nos. 3,042,522, 3,080,317, 4,004,927, 4,047,958 and 3,489,567, British Patent Nos. 955,061 and 1,143,118 and Japanese Patent O.P.I. Publication No. 140341/1985, the higher fatty acid, alcohol or acid amide lubricants described in US Patent Nos. 2,454,043, 2,732,305, 2,976,148 and 3,206,311 and German Patent Nos. 1,284,295 and 1,284,294, the metallic soaps described in British Patent No. 1,263,722 and US Patent No.
  • lubricants may previously be added along with the dispersing agent used upon synthesis of an organic matting agent.
  • the matting agent for the present invention is a powder of an organic or inorganic compound.
  • the organic compound includes water-dispersible vinyl polymers such as polymethyl methacrylate, and cellulose acetate propionate and starch, with preference given to spherical matting agents of water-dispersible vinyl polymers such as homopolymers of acrylates such as methyl methacrylate, glycidyl acrylate and glycidyl methacrylate, or copolymers of these acrylates or copolymers with other vinyl monomer.
  • inorganic compounds which can be preferably used include silver halide strontium barium sulfate, calcium carbonate, silicon dioxide, magnesium oxide, boron nitride, hollow silica (produced by Japan Fillite Co., Ltd.), ethylene tetrafluoride and titanium oxide.
  • the content of the matting agent is 1 mg/m2 to 1000 mg/m2, preferably 50 mg/m2 to 500 mg/m2.
  • Average grain size is greater than 10 ⁇ m, preferably not more than 30 ⁇ m. Average grain sizes exceeding 100 ⁇ m are undesirable because the matting agent becomes liable to detach from the film surface and can cause a plotter failure.
  • Grain size can be determined using an electron micrograph or Coulter counter.
  • the silver halide photographic light-sensitive material of the invention preferably has a layer containing a water-aoluble dye.
  • a water-soluble dye having an absorption maximum at a wavelength of not less than 670 nm selected from the group consisting of compounds represented by the following Formulas Ia, Ib, Ic, II, III and IV.
  • dyes I, III and IV are suitable for semiconductor laser, while the dye represented by Formula II is suitable for LED light sources.
  • R1, R2, R3, R4, R5 and R6 independently represent an alkyl group Y1 and Y2 independently represent a group of non-metal atoms necessary to form a pyrrolopyridine ring, provided that the ring of Y1 contains a group and the ring of Y2 contains a group.
  • R1, R2, R3, R4, R5, R6, Y1 and Y2 in Formula Ia, R1, R2, R3, R4, R5, R6, Y1 and Y2 in Formula Ib and R1, R2, R3, R4, R5, R6, Y1 and Y2 in Formula Ic independently represent a group which allows the dye molecule to have at least two acid residues or a group which allows the dye molecule to have at least two substituents having one or more -CH2CH2OR groups, wherein R represents a hydrogen atom or an alkyl group.
  • L represents a methine group
  • X ⁇ represents an anion
  • m represents an integer of 4 or 5
  • n represents an integer of 1 or 2.
  • Q represents an aliphatic group or aromatic group
  • R represents a hydrogen atom, aliphatic group or aromatic group
  • M represents a cation
  • L represents a methine group
  • n is 0, 1 or 2
  • p is 1 or 2.
  • R1, R2, R3, R4, R5, R6, Z1 and Z2 independently represent a group which allows the dye molecule to have at least four acid residues.
  • L represents a substituted or unsubstituted methine group;
  • X ⁇ represents an anion;
  • n is 1 or 2.
  • n is 1.
  • V1 and V2 independently represent a sulfo group or carboxyl group; n represents 1, 2, 3 or 4; m represents 1, 2 or 3; n and m do not represent 1 at the same time.
  • R1, R2, R3, R4, R5 and R6 independently represent an alkyl group
  • Y1 and Y2 independently represent a group of non-metal atoms necessary to form a pyrrolopyridine ring
  • the ring of Y1 contains a group
  • the ring of Y2 contains a group.
  • R1, R2, R3, R4, R5, R6, Y1 and Y2 in Formula Ia, R1, R2, R3, R4, R5, R6, Y1 and Y2 in Formula Ib and R1, R2, R3, R4, R5, R6, Y1 and Y2 in Formula Ic independently represent a group which allows the dye molecule to have at least two acid groups or a group which allows the dye molecule to have at least two substituents having one or more -CH2CH2OR groups, wherein R represents a hydrogen atom or alkyl group.
  • L represents a methine group
  • X ⁇ represents an anion
  • m represents an integer of 4 or 5
  • n represents an integer of 1 or 2.
  • Examples of acid groups for Formulas Ia, Ib and Ic include a sulfonic acid group, a carboxylic acid group and a phosphonic acid group, which acid groups include salts thereof.
  • Examples of such salts include salts of alkali metals such as sodium and potassium, ammonium salts and organic ammonium salts such as triethylamine and pyridine.
  • the alkyl groups represented by R1, R2, R3, R4, R5 and R6 preferably represent a lower alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, i-propyl, butyl and other groups, and may have a substituent other than the acid substituent or -CH2CH2OR group described above.
  • the alkyl group represented by R is preferably a lower alkyl group having 4 or less carbon atoms.
  • Examples of the substituent containing a -CH2CH2OR group include the hydroxyethyl group, hydroxyethoxyethyl group, methoxyethoxyethyl group, hydroxyethylcarbamoylmethyl group, hydroxyethoxyethylcarbamoylmethyl group, N,N-dihydroxyethylcarbamoylmethyl group, hydroxyethylsulfamoylethyl group and methoxyethoxyethoxycarbonylmethyl group.
  • substituents which may be possessed by Y1 and Y2 include the sulfo group (including its salt), carboxyl group (including its salt), hydroxy group, cyano group and halogen atoms such as atoms of fluorine, chlorine and bromine.
  • the methine group represented by L may also have a substituent.
  • substituents include substituted or unsubstituted lower alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, 3-hydroxypropyl, 2-sulfoethyl and other groups, halogen atoms such as atoms of fluorine, chlorine and bromine, aryl groups such as phenyl group, alkoxy groups such as methoxy and ethoxy groups.
  • the substituents for the methine group may bind to form a 6-membered ring containing three methine groups, such as 4,4-dimethylcyclohexene ring.
  • the anion represented by X ⁇ is not subject to limitation. Examples thereof include halogen ions, p-toluenesulfonic acid ions and ethyl sulfate ions.
  • the dye of the present invention can be synthesized in accordance with the Journal of the Chemical Society, 189 (1933), US Patent No. 2,895,955 and Japanese Patent O. P. I. Publication No. 123454/1987.
  • the parent nucleus for the dye of the present invention is exemplified by the following compounds
  • Compound A can be synthesized by the method described in the Journal of the Chemical Society, 3202 (1959) and British Patent No. 870,753.
  • Compound B can be synthesized by the method described in the Journal of the Chemical Society, 584 (1961).
  • Compound C can be synthesized by the method described in British Patent No. 841,588.
  • N-alkyl-N-pyridylhydrazine in accordance with the method described in the Journal of the Chemical Society, 3202 (1959) and the Journal of the Chemical Society, 584 (1961) and cyclize it via hydrazone and treat with acid as necessary to yield a 1-alkyl-substituted 3H-pyrrolopyridine derivative, and use it as a starting material.
  • the dye is dissolved in an appropriate solvent such as water, methanol, ethanol or another alcohol, methyl cellosolve or a mixture thereof and added to a hydrophilic colloid layer coating solution for the present invention.
  • the dye of the present invention can be used in combination of two or more kinds.
  • At least one of the compounds represented by Formulas Ia, Ib and Ic is contained in the light-sensitive material to be treated, and may be used in any combination, for example, a combination of two or more kinds of the same compound or a combination of compounds represented by different formulas.
  • the amount of the compound represented by Formulas Ia, Ib and Ic varies depending on the purpose of its use, it is preferably 10 ⁇ 3g/m2 to 1.0 g/m2, more preferably 10 ⁇ 2g/m2 to 0.5 g/m2.
  • Q represents an aliphatic group or aromatic group
  • R represents a hydrogen atom, aliphatic group or aromatic group
  • M represents a cation
  • L represents a methine group
  • n is 0.1 or 2
  • p is 1 or 2.
  • the aliphatic group represented by Q is exemplified by alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group and n-butyl group.
  • the aromatic group is exemplified by aryl groups such as phenyl group and naphthyl group. These aliphatic groups and aromatic groups may contain an additional substituent other than the sulfo group, such as an atom of a halogen (e.g., fluorine, chlorine), alkyl group (e.g., methyl group, ethyl group), hydroxy group or alkoxy group (e.g., methoxy group).
  • a halogen e.g., fluorine, chlorine
  • alkyl group e.g., methyl group, ethyl group
  • hydroxy group e.g., methoxy group
  • Examples of the aliphatic group represented by R include alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group and propyl group.
  • Examples of the aromatic group include aryl groups such as phenyl group and naphthyl group.
  • aliphatic groups and aromatic groups may contain an additional substituent such as an atom of a halogen (e.g., fluorine, chlorine, bromine), alkyl group (e.g., methyl group, ethyl group), aryl group (e.g., phenyl group), carboxyl group, sulfo group, hydroxyl group, alkoxy group (e.g., methoxy group), aryloxy group (e.g., phenoxy group).
  • a halogen e.g., fluorine, chlorine, bromine
  • alkyl group e.g., methyl group, ethyl group
  • aryl group e.g., phenyl group
  • carboxyl group e.g., sulfo group
  • alkoxy group e.g., methoxy group
  • aryloxy group e.g., phenoxy group
  • the cation represented by M is exemplified by cations of hydrogen atom, alkali metals such as sodium and potassium, alkaline earth metals such as calcium, ammonia and organic bases such as triethylamine, pyridine, piperidine and morpholine.
  • the methine group represented by L may be substituted by an alkyl group, aryl group or halogen atom.
  • alkyl group include methyl group and ethyl group.
  • aryl group include phenyl group.
  • halogen atom include chlorine atom and bromine atom.
  • Typical examples of the oxonol dye represented by Formula II are given below, but the oxonol dye relating to the present invention is not limited by these examples.
  • the dye represented by Formula II may be used as an anti-irradiation dye in a silver halide photographic light-sensitive emulsion or as a filter dye or anti-halation dye in a non-light-sensitive hydrophilic colloid layer. Two or more kinds of the dye may be used in combination, and the dye may be used in combination with another dye.
  • the dye for the present invention can easily be added to a silver halide photographic light-sensitive emulsion or another hydrophilic colloid layer by an ordinary method.
  • an aqueous solution of the dye or an organic or inorganic alkali salt thereof is added to the coating solution, and the coating solution is coated to yield a silver halide photographic light-sensitive material containing the dye.
  • the content of the dye represented by Formula II varies depending on the purpose of use, the coating solution is coated so that its amount will be 1.0 to 1000 mg per m2 of light-sensitive material.
  • a sulfonic acid group means a sulfo group or its salt
  • a carboxylic acid group means a carboxyl group or its salt
  • salts examples include salts of alkali metals such as sodium and potassium, ammonium salts and organic ammonium salts such as triethylamine, tributylamine and pyridine.
  • L represents a substituted or unsubstituted methine group
  • X ⁇ represents an anion.
  • the anion represented by X ⁇ is exemplified by ions of halogens such as chlorine and bromine, p-toluenesulfonic acid ions and ethyl sulfate ions.
  • n 1 or 2; when the dye forms an intramolecular salt, n is 1.
  • the alkyl groups represented by R1, R2, R3, R4, R5 and R6 preferably represent a lower alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group and n-pentyl group, and may have a substituent such as a sulfonic acid group, carboxylic acid group or hydroxyl group.
  • R1 and R4 independently represent a lower alkyl group having 1 to 5 carbon atoms and a sulfonic acid group, such as 2-sulfoethyl group, 3-sulfopropyl group or 4-sulfobutyl group.
  • Examples of the substituent for the benzo-condensed ring or naphtho-condensed ring formed by the group of non-metal atoms represented by Z1 or Z2 include sulfonic acid group, carboxylic acid group, hydroxyl group, atoms of halogens such as fluorine, chlorine and bromine, cyano group, substituted amino groups such as dimethylamino group, diethylamino group, ethyl-4-sulfobutyl group and di(3-sulfopropyl)amino group, and substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms bound to the ring directly or via a divalent bonding group, such as methyl group, ethyl group, propyl group and butyl group.
  • Examples of preferable substituents include sulfonic acid group, carboxylic acid group and hydroxyl group.
  • preferable divalent bonding groups include -O-, -NHCO-, NHSO2-, -NHCOO-, -NHCONH-, -COO-, -CO- and -SO2-.
  • Examples of preferably substituents for the methine group represented by L include substituted or unsubstituted lower alkyl groups having 1 to 5 carbon atoms, such as methyl group, ethyl group, 3-hydroxypropyl group, benzyl group and 2-sulfoethyl group, atoms of halogens such as fluorine, chlorine and bromine, substituted or unsubstituted aryl groups such as phenyl group and 4-chlorophenyl group, and lower alkoxy groups such as methoxy group and ethoxy group.
  • substituted or unsubstituted lower alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, 3-hydroxypropyl group, benzyl group and 2-sulfoethyl group, atoms of halogens such as fluorine, chlorine and bromine, substituted or unsubstituted aryl groups such as phenyl group and 4-chlorophenyl group
  • the substituents for the methine group represented by L may bind to form a 6-membered ring containing three methine groups, such as 4,4-dimethylcyclohexene ring.
  • the dye represented by Formula III has an absorption maximum in the wavelength range of from 730 to 850 nm, and can be synthesized in accordance with the Journal of the Chemical Society, 189 (1933) and Synthesis Examples for US Patent No. 2,895,955.
  • the dye can be used in solution in an appropriate solvent such as water, methanol, ethanol or another alcohol, methyl cellosolve or a mixture thereof in a hydrophilic colloid layer coating solution for forming the desired colored layer of light-sensitive material.
  • an appropriate solvent such as water, methanol, ethanol or another alcohol, methyl cellosolve or a mixture thereof in a hydrophilic colloid layer coating solution for forming the desired colored layer of light-sensitive material.
  • the dye of the present invention can be used in combination of two or more kinds.
  • the content of the dye represented by Formula III varies depending on the purpose of its use, it is preferably 10 ⁇ 3g/m2 to 0.5 g/m2, more preferably 10 ⁇ 2g/m2 to 0.2 g/m2.
  • V1 and V2 independently represent a sulfo group or carboxyl group; n represents 1, 2, 3 or 4; m represents 1, 2 or 3; n and m do not represent 1 at the same time.
  • These dyes may be used in combination of two or more kinds.
  • the content of the dye represented by Formula IV varies depending on the purpose of its use, it is preferably 10 ⁇ 2g/m2 to 2.0 g/m2, more preferably 5 x 10 ⁇ 2g/m2 to 1.0 g/m2.
  • the dye of the present invention is preferably contained to a loewer layer of the backing layers.
  • the silver halide photographic light-sensitive material of the invention may comprise an electroconductive layer containing an electroconductive metal oxide or organic electroconductive polymer coated on at least one side of the support.
  • the metal oxide in the electroconductive layer for the present invention may be indium oxide, tin oxide or a metal oxide doped with an antimony atom or phosphorus atom, or a combination thereof.
  • Known indium oxide compounds are primary indium oxide (In2O) and secondary indium oxide (In2O3), with preference given to secondary indium oxide for the present invention.
  • Known tin oxide compounds are stannous oxide (SnO) and stannic oxide (SnO2), with preference given to stannic oxide for the present invention.
  • metal oxides doped with antimony atom or phosphorus atom include tin oxide and indium oxide.
  • a halide, alkoxy derivative or nitrate of tin or indium is mixed with a halide, alkoxy derivative or nitrate of antimony or phosphorus, followed by oxidative burning.
  • the ratio of antimony or phosphorus doped is 0.5 to 10% by weight of tin or indium. It is preferable to add these inorganic compounds in dispersion in a hydrophilic colloid such as gelatin or in dispersion in a polymer compound such as acrylic acid or maleic acid.
  • the ratio per binder is preferably 1 to 100% by weight.
  • the organic electroconductive polymer in the electroconductive layer for the present invention is a compound having a molecular weight of 1000 to 1000000, more preferably 1000 to 500000 wherein a sulfonic acid group or its base is bound to an aromatic ring or heterocyclic group directly or via a divalent bonding group.
  • the polymer can easily be synthesized by polymerizing a monomer which is commercially available or can be obtained by a conventional method.
  • electroconductivity means that the surface resistivity with an amount of single coating of over 2 g/m2 on the polyethylene terephthalate film is not less than 1010 ⁇ /cm (23°C, 20% RH).
  • the organic electroconductive polymer used in the backing layer for the present invention can be selected out of the examples given above of the organic electroconductive polymer contained in the electroconductive layer.
  • the electroconductive layer for the present invention is preferably activated on its surface by corona discharge, glow discharge, ultraviolet irradiation, flaming or other treatment.
  • the particularly preferable activating treatment is corona discharge, preferably at 1 mW to 1 kW/(m2 ⁇ min).
  • Energy intensity is preferably in the range of from 0.1 W to 1 W/(m2 ⁇ min).
  • the electroconductive layer for the present invention is preferably provided with an adhesive layer of gelatin or gelatin derivative thereon.
  • an adhesive layer may be layered simultaneously with coating the electroconductive layer or may be coated after drying.
  • the adhesive layer is preferably subjected to heat treatment at 70 to 200°C.
  • Various hardeners can be used in the adhesive layer; from the viewpoint of crosslinking in the lower electroconductive layer and crosslinking in the upper backing layer, any hardener can be selected from the groups comprising acrylamide, aldehyde, aziridine, peptide, epoxy and vinyl sulfone hardeners.
  • the film thickness of an electroconductive layer is closely related to its electroconductivity. Since the electroconductivity improves with the increase in unit volume, it is better to thicken the film; however, it is preferable to set the film thickness in the range of from 0.1 to 100 ⁇ , more preferably 0.1 to 10 ⁇ for good results because film flexibility lowers when the film is too thick.
  • the electroconductive polymer is exemplified by the following compounds:
  • the polymer which serves best for the present invention generally has an average molecular weight of about 1000 to 1000000 as stated above.
  • the electroconductive polymer content in the electroconductive layer of the silver halide photographic light-sensitive material of the present invention is preferably 0.001 to 10 g, more preferably 0.05 to 5 g per unit m2 as solid content.
  • the amount of its addition is preferably 0.01 to 10 g as solid content.
  • the silver halide emulsion for the light-sensitive material of the present invention may be obtained by any of the acid method, the neutral method and the ammoniacal method, with its grain size preferably ranging from 0.2 ⁇ m to 0.5 ⁇ m.
  • the silver halide grains used in the emulsion of the present invention are prepared by adding a water-soluble rhodium salt and an water-soluble iridium salt to incorporate them therein and/or thereon.
  • the amount of addition is preferably 10 ⁇ 6 to 10 ⁇ 9 mol per mol of silver halide.
  • the silver halide grains may have a uniform silver halide composition distribution therein or be core/shell grains with different silver halide compositions between the core and surface layers, and may be grains wherein latent images are formed mainly on the surface, or grains wherein latent images are formed mainly inside the grains.
  • the shape of the silver halide grains for the present invention may be any one.
  • a preferred shape is a cube having ⁇ 100 ⁇ planes to form the crystal surface. It is also possible to use octahedral, tetradecahedral, dodecahedral or other forms of grains prepared by the methods described in US Patent Nos. 4,183,756 and 4,225,666, Japanese Patent O.P.I. Publication No. 26589/1980, Japanese Patent Examined Publication No. 42737/1980 and the Journal of Photographic Science, 21 , 39 (1973). Grains having twin crystal planes may also be used.
  • the silver halide grains for the present invention may be of a single shape or a mixture of various shapes.
  • Emulsions with wide grain size distribution may be used, and emulsions with narrow grain size distribution (referred to as monodispersed emulsion) may be used singly or in combination of two or more kinds. Furthermore, a polydispersed emulsion and a monodispersed emulsion may be used in combination.
  • the silver halide emulsion may be used in combination of two or more separately formed silver halide emulsions.
  • the silver halide emulsion for the present invention is preferably a monodispersed silver halide emulsion.
  • the weight of silver halide grains which fall in the grain size range of ⁇ 20% of the average grain size r preferably accounts for not less than 60% of the total weight of silver halide grains, more preferably not less than 70%, and still more preferably not less than 80%.
  • the average grain size r is defined as the grain diameter ri which gives a maximum value for ni x ri3, wherein ri denotes the grain diameter and ni denotes the number of grains having a diameter of ri (significant up to three digits, rounded off at the last digit).
  • the grain diameter stated here is the diameter of the silver halide grain when the grain is spherical or the diameter of a circle converted from a grain projection image with the same area when the grain is not spherical.
  • Grain size can be obtained by measuring the diameter of the grain or the area of projected circle on an electron micrograph taken at x 10000 to 50000 (the number of subject grains should be not less than 1000 randomly).
  • a highly monodispersed emulsion preferred for the present invention has a degree of monodispersion of not more than 20, more preferably not more than 15 as calculated using the following equation 1.
  • Grain size standard deviation average grain size x 100 degree of monodispersion
  • a monodispersed emulsion can be prepared in accordance with Japanese Patent O.P.I. Publication Nos. 48521/1979, 49938/1983 and 122935/1985.
  • the light-sensitive silver halide emulsion may be used as a primitive emulsion without chemical sensitization, but it is the common practice to subject it to chemical sensitization.
  • Chemical sensitization can be achieved by the methods described in publications by Glafkides or Zelikman et al., or Die Grundlagen der Photographischen mit Silberhalogeniden, Akademische Verlagsgesellschaft, 1968, edited by H. Frieser.
  • sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, the reduction sensitization method using a reducing agent, and other methods using gold or another noble metal compound singly or in combination.
  • sulfur sensitizers which can be used include thiosulfates, thioureas, thiazoles, rhodanines and other compounds, exemplified in US Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668 and 3,656,955.
  • reduction sensitizers which can be used include stannous salts, amines, hydrazine derivatives, formamidosulfininc acid and silane compounds, exemplified by US Patent Nos. 2,487,850, 2,419,974, 2,518,698, 2,983,609, 2,983,610 and 2,694,637.
  • complex salts of metals in Group VII in the periodic table of elements such as platinum, iridium and palladium can be used in addition to complex salt of gold, exemplified in US Patent Nos. 2,399,083 and 2,448,060 and British Patent No. 618,061.
  • pH is preferably 4 to 9, more preferably 5 to 8; pAg is preferably 5 to 11, more preferably 7 to 9.
  • Temperature is preferably 40 to 90°C, more preferably 45 to 75°C.
  • the photographic emulsion for the present invention may be subjected to the reduction sensitization method using a reducing agent, the noble metal sensitization method using a noble metal compound and other methods in combination with the sulfur sensitization method and gold-sulfur sensitization method described above.
  • the light-sensitive emulsion may be used singly or in combination of two or more kinds.
  • various stabilizers can be used, such as 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 5-mercapto-1-phenyltetrazole and 2-mercaptobenzothiazole.
  • a silver halide solvent such as thioether or a crystal habit control agent such as a mercapto-containing compound or sensitizing dye may be used as necessary.
  • the emulsion for the present invention allows the unnecessary soluble salts to be removed or remain contained after completion of growing silver halide grains.
  • the salts can be removed in accordance with the method described in Research Disclosure No. 17643.
  • the photographic emulsion may contain various compounds for preventing sensitivity reduction and fogging during preparation, storage or processing of the silver halide photographic light-sensitive material.
  • the silver halide photographic light-sensitive material of the present invention may contain in its photographic structural layer an alkyl acrylate latex as described in US Patent Nos. 3,411,911 and 3,411,912 and Japanese Patent Examined Publication No. 5331/1970.
  • the silver halide photographic light-sensitive material of the present invention may contain various additives. Specifically, there can be used the thickening agents or plasticizers described in US Patent Nos. 2,960,404 and 3,767,410, Japanese Patent Examined Publication No. 4939/1968, West German Patent Publication No. 1,904,604, Japanese Patent O.P.I. Publication No. 63715/1973 and Belgian Patent Nos.
  • styrene-sodium maleate copolymer and dextran sulfate such as styrene-sodium maleate copolymer and dextran sulfate, hardeners such as those based on aldehyde, epoxy, ethylene imine, active halogen, vinyl sulfone, isocyanate, sulfonate, carbodiimide, mucochloric acid and acyloyl, the ultraviolet absorbents described in US Patent No. 3,253,921 and British Patent No.
  • 1,309,349 specifically 2-(2′-hydroxy-5-t-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3′-t-butyl-5′-butylphenyl)-5-chlorobenzotriazole and 2-(2′-hydroxy-3′,5′-di-t-butylphenyl)-5-chlorobenzotriazole.
  • additives for improving the permeability against coating aids, emulsifiers, processing solutions and others, defoaming agents, surfactants for controlling various physical properties of light-sensitive material include the anionic, cationic, nonionic or amphoteric compounds described in British Patent Nos. 548,532 and 1,216,389, US Patent Nos. 2,026,202 and 3,514,293, Japanese Patent Examined Publication Nos. 26580/1969, 17922/1968, 17926/1968, 3166/1968 and 20785/1973, French Patent No. 202,588, Belgian Patent No. 773,459 and Japanese Patent O.P.I. Publication No.
  • antistatic agents include the compounds described in Japanese Patent Examined Publication Nos. 24159/1971, 39312/1971 and 43809/1973, Japanese Patent O.P.I. Publication Nos. 89979/1973, 20785/1973, 43130/1973, 90391/1973 and 33627/1972 and US Patent Nos. 2,882,157 and 2,972,535.
  • the pH of the photographic emulsion coating solution preferably ranges from 5.3 to 7.5.
  • the coating solution mixture of the coating solutions for the layers in the ratio of the amount of coating preferably has a pH in the above-mentioned range of from 5.3 to 7.5. pH values out of this range are undesirable because hardening is retarded if the pH is lower than 5.3 and because the photographic performance is adversely affected if the pH exceeds 7.5.
  • the light-sensitive material of the present invention may contain various other additives as desired. More specifically, these additives are described in Research Disclosure (RD), Vol. 176, Item 17643 (December 1978) and Vol. 187, Item 18716 (November 1979).
  • Processing temperature is selected from the range from 18 to 50°C, but may be lower than 18°C or higher than 50°C.
  • the developing agent for the black-and-white developer for the present invention may contain singly or in combination dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, aminophenols such as N-methyl-p-aminophenol for facilitating the obtainment of better performance.
  • dihydroxybenzenes such as hydroquinone
  • 3-pyrazolidones such as 1-phenyl-3-pyrazolidone
  • aminophenols such as N-methyl-p-aminophenol for facilitating the obtainment of better performance.
  • the silver halide photographic light-sensitive material of the present invention can be processed with a developer containing an imidazole as a silver halide solvent.
  • the developer may contain various additives such as preservatives, alkalis, pH buffers and antifogging agent, and as necessary dissolution aids, tone adjusters, development accelerators, surfactants, defoaming agents, water softening agents, hardeners and tackifiers.
  • the silver halide photographic light-sensitive material of the present invention may also be developed by so-called the lith type process.
  • the light-sensitive material may contain the developing agent in its emulsion, for instance, and may be developed with an aqueous solution of alkali. If the developing agent is hydrophobic, it may be contained in an emulsin layer by the method described in Research Disclosure No. 169 and other publications. This method of development may be used in combination with a silver salt stabilizing process using thiocyanate.
  • the fixer used has a commonly used composition and may contain a water-soluble aluminum salt as a hardener.
  • various light sources can be used as appropriate, such as tungsten lamps, fluorescent lamps, arc lamps, mercury lamps, xenon sun light lamps, xenon flash lamps, cathode ray tube flying spots, laser beams, electron beams, X-ray and fluorescent screens for radiography, selected according to chemical sensitization conditions, purpose of use and other factors.
  • Exposure time is normally 1/1000 to 100 seconds, but short exposure time of 10 ⁇ 4 to 10 ⁇ 9 second is possible when using a xenon flash lamp, cathode ray tube or laser beam.
  • the present invention makes it possible to provide a silver halide photographic light-sensitive material having improved transportability in scanners and facsimile plotters.
  • an aqueous solution of silver nitrate and a mixed aqueous solution containing potassium bromide and sodium chloride prepared by adding potassium hexachloroiridate at 6 x 10 ⁇ 7 mol per mol of silver halide and hexabromorhodium salt at 4 x 10 ⁇ 8 mol per mol of silver halide were added by the double jet method to yield silver chlorobromide grains containing 35% silver bromide (distribution width 9%, cube, grain size 0.25 ⁇ m) while maintaining a pH of 3.0 and a pAg of 7.7. After returning the pH to 5.9, the mixture was desalted by a conventional method, and a mixture represented by the following formula 6 was added at 5 mg per mol of silver halide.
  • the resulting emulsion was sensitized with sulfur, and the sensitizing dye represented by the following formula 7 was added at 60 mg per mol of silver halide. To this mixture were added 70 mg of 1-phenyl-5-mercaptotetrazole and 1.2 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mol of silver halide.
  • a backing layer and a backing protective layer were simultaneously coated on one face of a subbed polyethylene terephthalate base of 100 ⁇ m in thickness to be a gelatin amount of 2 g/m2 and 1 g/m2, respectively.
  • the other face was coated with an emulsion layer and an emulsion protective layer at the same time so that the amount of silver coated on the emulsion layer became 3.8 g/m2, the amount of gelatin coated on the emulsion layer became 1.5 g/m2 and the amount of gelatin coated on the emulsion protective layer became 1.0 g/m2.
  • a polyethyleneterephthalate base was subjected to corona discharge treatment and coated with a coating solution containing a compound shown in Table 2 and hexamethyleneaziridine, and then the base was subjected to hot drying at 50°C for 60 minutes.
  • the emulsion protective layer contained formaldehyde added at 8 mg per gram of the gelatin on the emulsion layer side.
  • a hardener listed in Table 4 was added to the backing protective layer.
  • the samples thus obtained were prepared as sheet products and automatically transported in an atmosphere of 23°C and 80% RH using the facsimile plotter PT-503 (produced by Matsushita Graphic Communications Systems, Inc.) to evaluate their transportability.
  • the degree of hardening is expressed in the degree of swelling as calculated using the following equation 2.
  • Degree of swelling (amount of water absordes per m2) (amount of gelatin per m2) (value obtained after water immersion at 23°C for 10 seconds)
  • degree of swelling is preferably not less than 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP92300086A 1991-01-04 1992-01-06 Matériau photographique à l'halogénure d'argent sensible à la lumière Withdrawn EP0494121A1 (fr)

Applications Claiming Priority (2)

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JP9988/91 1991-01-04
JP3009988A JP2927370B2 (ja) 1991-01-04 1991-01-04 ハロゲン化銀写真感光材料

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0585672A2 (fr) * 1992-08-24 1994-03-09 Agfa-Gevaert AG Matériau d'enregistrement photographique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2039072A (en) * 1978-12-13 1980-07-30 Fuji Photo Film Co Ltd Photographic photosensitive materials
EP0303176A2 (fr) * 1987-08-11 1989-02-15 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
US4857443A (en) * 1987-05-06 1989-08-15 Fuji Photo Film Co., Ltd. Photographic element with benzoguanamine-formaldehyde polymer particles
EP0341958A2 (fr) * 1988-05-07 1989-11-15 Konica Corporation Matériau photographique à halogénure d'argent
EP0388908A1 (fr) * 1989-03-24 1990-09-26 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2039072A (en) * 1978-12-13 1980-07-30 Fuji Photo Film Co Ltd Photographic photosensitive materials
US4857443A (en) * 1987-05-06 1989-08-15 Fuji Photo Film Co., Ltd. Photographic element with benzoguanamine-formaldehyde polymer particles
EP0303176A2 (fr) * 1987-08-11 1989-02-15 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
EP0341958A2 (fr) * 1988-05-07 1989-11-15 Konica Corporation Matériau photographique à halogénure d'argent
EP0388908A1 (fr) * 1989-03-24 1990-09-26 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0585672A2 (fr) * 1992-08-24 1994-03-09 Agfa-Gevaert AG Matériau d'enregistrement photographique
EP0585672A3 (en) * 1992-08-24 1994-07-13 Agfa Gevaert Ag Photographic recording material

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JP2927370B2 (ja) 1999-07-28
JPH04234753A (ja) 1992-08-24

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