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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
• • 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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
  • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
• • 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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
  • G03C1/20—Methine and polymethine dyes with an odd number of CH groups with more than three CH groups
• • 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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/26—Polymethine chain forming part of a heterocyclic ring
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03564—Mixed grains or mixture of emulsions
• • 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03594—Size of the grains
• • 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
  • G03C2200/00—Details
  • G03C2200/39—Laser exposure
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes

Definitions

• the present invention relates to a silver halide photographic light-sensitive material for laser-beam-scanning use, whose aptitude for the medical diagnosis is improved by reducing the surface gloss of its processed image.
• a film for laser printer which is spectrally sensitized to the spectral wavelength range from red to near infrared, corresponding to the laser light emission wavelength range.
• attempts have been made to make its silver halide grains much finer or to improve it for silver-saving.
• inorganic materials such as silica and polymer beads are used in order to restrain the surface gloss of a light-sensitive material, but there is a problem that the use of such materials degrades the transparency of the light-sensitive material after being processed, so that some measures otherwise have been called for.
• a silver halide photographic light-sensitive material for laser-beam-scanning use being a single-sided light-sensitive material comprising a support having on one side thereof a silver halide emulsion layer having a silver coated weight of not more than 3.5g/m2, in which the silver halide emulsion layer comprises chemically unripened silver halide grains having an average grain diameter of 0.8 to 2.0 ⁇ m and chemically ripened silver halide grains having an average grain diameter of 0.1 to 0.6 ⁇ m in a ratio by weight of 30:70 to 5:95, and which comprises at least one polymer matting agent on the emulsion side thereof.
• the chemically unripened silver halide grains of the invention implies silver halide grains that have been subjected to physical ripening treatment alone for grain formation; i.e., generally, second ripening (chemical ripening)-omitted silver halide grains after removing the excessive salt therefrom.
• the silver halide grains comprise chemically unripened grains having an average grain diameter of preferably 0.8 to 2.0 ⁇ m, more preferably 0.9 to 1.2 ⁇ m, and chemically ripened grains having an average grain diameter of preferably 0.1 to 0.6 ⁇ m, more preferably 0.15 to 0.40 ⁇ m, in a proportion by weight of preferably 30:70 to 5:95 and more preferably 20:80 to 5:95.
• the light-sensitive material of the invention is a single-sided light-sensitive material with a light-sensitive silver halide emulsion coated on one side alone of its support, and the whole silver coated weight of the light-sensitive material is preferably not more than 3.5g/m2, more preferably 2.0 to 3.3g/m2.
• the single-sided light-sensitive material contains a polymer matting agent on the emulsion layer side of its support.
• the polymer matting agent herein is one not specially limited but an organic matting agent such as polyacrylate, polymethyl methacrylate, cellulose acetate-propionate and polystyrene.
• the polymer matting agent is preferably contained in an amount of 10 to 100mg/m2 on the emulsion side of the silver halide photographic light-sensitive material of the invention.
• the matting agent may be contained in any one of the emulsion layer, non-emulsion hydrophilic layer, protective layer and the like on the emulsion side of the light-sensitive material, but is most preferably contained in the protective layer located on the emulsion layer.
• the matting agent of the invention may be used in combination with an inorganic matting agent such as silica, i.e., silicon dioxide, a noninventive matting agent.
• an inorganic matting agent such as silica, i.e., silicon dioxide, a noninventive matting agent.
• the silver halide photographic light-sensitive material for laser-beam-scanning use of the invention is spectrally sensitized to the wavelength region of 600nm and upwards corresponding to the laser light emission wavelength region.
• the spectral sensitization of the light-sensitive material may be carried out according to any one of those known methods therefor, more preferably by using those spectrally sensitizing dyes represented by the Formulas 1, 2 and 3 described in JP Application No. 84132/1992, applied for by the same applicant as that of the present invention.
• Z1 and Z2 each represent a group of non-metallic atoms necessary to form an azole ring which may have a substituent; R1 and R2 each represent an alkyl group or a substituted alkyl group; X ⁇ is a counter ion; and n is an integer of 1 or 2, provided it is 1 when an intramolecular salt is formed.
• Z3 and Z5 each represent a group of non-metallic atoms necessary to form a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring or a naphthoxazole ring which each may have a substituent;
• Z4 represents a 5- or 6-member carbocyclic ring which may have a substituent;
• R3 and R4 each represent an alkyl group or a substituted alkyl group;
• X ⁇ is a counter ion; and n is an integer of 1 or 2, provided it is 1 when an intramolecular salt is formed.
• R5 and R6 each represent an alkyl group or a substituted alkyl group
• R7 is a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group
• Y is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group or a halogen atom
• Z6 is a 5- or 6-member nitrogen-containing heterocyclic group
• X ⁇ is a counter ion
• m, n and p each are an integer of 1 or 2.
• the silver halide photographic light-sensitive material of the invention may have an antistatic layer comprising (1) the water-soluble conductive polymer, (2) the hydrophobic polymer and (3) the reaction product of the hardening agent that are all described in JP O.P.I. No.80744/1992, applied for by the applicant of the present invention.
• the above antistatic agent is coated either directly on or indirectly through a subbing layer on the support. For details reference can be made to JP O.P.I. No. 80744/1992.
• the silver halide composition of the silver halide emulsion to be subjected to the chemical ripening of the invention may be any of, e.g., silver bromide, silver iodobromide and silver chloroiodobromide.
• the most preferred silver halide composition is a silver iodobromide emulsion containing not more than 30mol% silver iodide.
• the silver halide grain as long as it is of the composition specified in the invention, may be of any crystal form such as octahedral or tetradecahedral single crystal, or multi-twin crystal grain having various forms.
• the emulsion used in the silver halide photographic light-sensitive material of the invention may be prepared according to known, appropriate methods; for example, the method described in 'Emulsion Preparation and Types' in p.22-23 of Research Disclosure RD No. 17643 (Dec. 1978) or the method described in p.648 of RD No. 18716 (Nov. 1979).
• the emulsion for the silver halide photographic light-sensitive material of the invention may also be prepared according to the method described in, e.g., T. H. James, 'The Theory of the Photographic Process,' 4th ed., Macmillan (1977) p.38-104; G. F. Duffin, 'Photographic Emulsion Chemistry,' Focal Press (1966); P. Glafkides, 'Chimie et Physique Photographique' Paul Montel (1967); or V. L. Zelikman et al, 'Making and Coating Photographic Emulsion,' Focal Press (1964).
• the emulsion may be prepared under various conditions comprising in appropriate combination the use of specific solutions differing according to the acidic, ammoniacal or neutral method; mixing conditions differing according to the reverse precipitation process, double-jet process, controlled double-jet process, etc.; and grains growing conditions differing according to the conversion process or core/shell process.
• the silver halide grains have an average grain diameter of 0.1 to 0.6 ⁇ m, and may be of either a monodisperse emulsion having a narrow grain diameter distribution or a polydisperse emulsion having a broad grain diameter distribution.
• the monodisperse emulsion herein implies a silver halide emulsion whose grain diameters' variation coefficient defined in JP O.P.I. No. 162244/1985 is not more than 0.20.
• the monodisperse emulsion includes a silver halide emulsion comprising silver halide grains having an average grain diameter of not smaller than 0.1 ⁇ m, at least 95% by weight of which are grains whose diameters are within the range of its average grain diameter ⁇ 40%, and a silver halide emulsion comprising silver halide grains having an average grain diameter of 0.25 ⁇ m to 2 ⁇ m, at least 95% by weight of or at least 95% by number of which are silver halide grains whose diameters are within the range of its average grain diameter ⁇ 20%.
• the emulsion for the silver halide photographic light-sensitive material of the invention there may be used an emulsion prepared by a method for obtaining the above-mentioned monodisperse emulion, in which, e.g., seed crystals are used as growing nuclei, to which are supplied silver and halide ions to thereby grow silver halide grains.
• the silver halide composition of the chemically unripened silver halide emulsion of the invention may be anyone of silver bromide, silver iodobromide, silver chloroiodobromide, and the like, and is preferably a silver iodobromide emulsion containing not more than 30 mol% silver iodide.
• the chemically unripened silver halide grains have an average grain diameter of 0.8 ⁇ m to 2.0 ⁇ m and may be of either a monodisperse emulsion having a narrow grain diameter distribution or a polydisperse emulsion having a broad grain diameter distribution.
• the silver halide grain may be of any crystal form such as an octahedral or tetradecahedral single crystal, or multi-twin crystal having various forms.
• the chemically unripened silver halide grain can be prepared in similar manner to the foregoing chemically ripened silver halide grain of the invention.
• the emulsion comprising the above chemically ripened silver halide and chemically unripened silver halide grains of the invention may be of a two-phase crystal grain structure with difference in the silver halide composition between the inside and the outside thereof.
• the most preferred embodiment of the emulsion is one comprising silver halide grains each having a substantially two-distinct-phase structure (core/shell-type structure) composed of a high-iodide core phase and a low-iodide shell phase.
• the high-iodide core phase is a silver iodide-rich phase having a silver iodide content of preferably 20 to 40 mol%, more preferably 20 to 30 mol%.
• the silver halide composition other than the silver iodide in the core phase may be any of silver bromide and silver chlorobromide, but is preferably silver chlorobromide having a high silver bromide content.
• the outermost shell phase is silver halide containing preferably not more than 5 mol% and more preferably not more than 2 mol% silver iodide.
• the silver halide other than the silver iodide in the outermost phase may be any of silver chloride, silver bromide and silver chlorobromide, but is preferably a silver halide having a high silver bromide content.
• the above core/shell-type emulsion may be prepared according to any of known methods therefor; for the preparation of it reference can be made to the methods described in J. Phot. Sci., 24-198 (1976); U.S. Patent Nos. 2,592,250, 3,505,068, 4,210,450 and 4,444,877; and JP O.P.I. No. 143331/1985.
• Removal of the soluble salts from the emulsion may be carried out by noodle washing method or flocculation sedimentation method.
• Preferred washing methods include a method which uses the aromatic hydrocarbon aldehyde resins containing a sulfo group described in JP E.P. No. 16086/1960 and a desalting method which uses the exemplified compounds G-3, G-8, etc., as high-molecular flocculants described in JP O.P.I. No. 158644/1988.
• the emulsion for the silver halide photographic light-sensitive material of the invention may have various photographic additives added thereto in the process before or after the physical ripening or chemical ripening treatment thereof.
• a plastic film is suitable as the support, whose surface may be provided with a subbing layer or subjected to corona discharge treatment or UV irradiation treatment for the purpose of improving its adhesion property to a layer coated thereon.
• the silver halide photographic light-sensitive material of the invention may have on the support thereof hydrophilic colloid layers comprising silver halide emulsion layers, protective layer, intermediate layers, filter layers, UV absorbing layer, antistatic layer, antihalation layer and backing layer.
• gelatin and various synthetic high-molecular compounds may be used as the binder or protective colloid thereof.
• the above gelatin includes lime-treated gelatin, acid-treated gelatin and gelatin derivatives.
• the synthetic high-molecular materials other than gelatin include cellulose derivatives such as hydroxyethyl cellulose, and homo- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl-pyrrolidone, polyacrylic acid, polyacrylamide, and the like.
• the light-sensitive material of the invention may be photographically processed by using those processing solutions as described in the foregoing RD-17643, XX-XXI, p.29-30; or RD-308119, XX-XXI, p.1011-1012.
• the above processing used may be either a black-and-white processing to form a silver image or a color photographic processing to form a dye image.
• the processing is made normally at a temperature of from 18°C to 50°C.
• the developing agent used in the black-and-white processing includes dihydrobenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, aminophenols such as N-methyl-p-aminophenol and the like. These may be used alone or in combination.
• known additives such as preservative, alkali agent, pH buffer, antifoggant, hardener, development accelerator, surfactant, defoaming agent, toning agent, water softener, dissolution assistant, viscosity-providing agent, and the like.
• the fixing solution contains a fixing agent such as a thiosulfate or a thiocyanate, and may further contain a hardener, e.g., a water-soluble aluminum salt such as aluminum sulfate or potassium alum. In addition, it may also contain a preservative, pH adjusting agent, water softener, and the like.
• a fixing agent such as a thiosulfate or a thiocyanate
• a hardener e.g., a water-soluble aluminum salt such as aluminum sulfate or potassium alum.
• it may also contain a preservative, pH adjusting agent, water softener, and the like.
• a silver iodobromide emulsion (silver iodide content: 2 mol%) having an average grain diameter of 0.3 ⁇ m was used as a seed emulsion, which was grown to prepare by an ammoniaca process a silver iodobromide monodisperse emulsion (silver iodide content: 3 mol%) having an average grain diameter of 0.7 to 2.2 ⁇ m, whose variation coefficient ( ⁇ /r) was within the range of from 0.15 to 0.20.
• a silver iodobromide seed emulsion (silver iodide content: 2 mol%) having an average grain diameter of 0.1 ⁇ m was used to be grown by adding according to a double-jet process thereto an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution to thereby prepare a silver iodobromide cubic grains monodisperse emulsion (average silver iodide content: 0.4 mol%) having an average grain diameter of 0.25 ⁇ m, whose variation coefficient ( ⁇ /r) was 0.17.
• This emulsion was divided into two parts; one was dissolved immediately before its chemical ripening, and to it, when its temperature became constant, were added the following dye (1) to prepare Emulsion (A), while to the other was added the following dye (2) to prepare Emulsion (B).
• the used amount of each dye was 90 mg per mol of silver halide.
• each emulsion was subjected to chemical sensitization treatment by adding ammonium thiocyanate, chloroauric acid and hypo thereto, and then further added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
• Emulsions A and B and the chemically unripened emulsion were mixed in the ratios by weight shown in Table 1, and then the following materials were added in the following described amounts per mol of silver halide, whereby red-sensitive silver halide emulsion coating liquids were prepared.
• Emulsion-side protective layer coating liquid Emulsion-side protective layer coating liquid
• a polyethylene terephthalate support of 180 ⁇ m in thickness was subjected to biaxial stretching/thermal setting treatment, and then both sides of it were subjected to corona discharge treatment. After that, on the support was formed a subbing layer by coating a latex (compound of synthesis example 1) that is described in the Example 1 of JP O.P.I. No. 18945/1984.
• an antistatic layer comprising the following compound that is described in JP O.P.I. No. 80744/1992, filed for by the same applicant as for the present invention.
• Water-soluble conductive polymer (Exemplified compound P4)
• 0.6g/m2 Hydrophobic polymer (Exemplified compound HP1)
• 0.5g/m2 Hardening agent (Exemplified compound AH5) 2x10 ⁇ 3mol/dm2
• the above materials were coated at a rate of 30 meters per minute by a roll-fit-coating pan/air knife coating process, and then was again activated by corona discharge in like manner, whereby an objective support was obtained.
• the foregoing backing lower and upper layers were coated on the antistatic layer-coated side of the support.
• the obtained samples were evaluated as follows.
• Samples were prepared in the same manner as in Exemple 1 except that the grain diameter of the chemically ripened silver halide grains was changed to 0.3 ⁇ m, and the spectral sensitizing dye was replaced by Dye (2).
• Example 2 Also the sample preparation and evaluation were carried out in the same manner as in Example 1 except that the writing of SMPT pattern for the character legibility evaluation was made by a laser imager with use of 820nm semiconductor laser, and the results are shown in Table 2.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1992
  • 1992-10-15 JP JP27736992A patent/JP3146387B2/ja not_active Expired - Fee Related
• 1993
  • 1993-09-30 EP EP93115811A patent/EP0592882A1/de not_active Withdrawn
• 1995
  • 1995-01-26 US US08/378,934 patent/USH1547H/en not_active Abandoned

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