WO2007145094A1 - Matériau photosensible pouvant être developpé thermiquement - Google Patents

Matériau photosensible pouvant être developpé thermiquement Download PDF

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Publication number
WO2007145094A1
WO2007145094A1 PCT/JP2007/061274 JP2007061274W WO2007145094A1 WO 2007145094 A1 WO2007145094 A1 WO 2007145094A1 JP 2007061274 W JP2007061274 W JP 2007061274W WO 2007145094 A1 WO2007145094 A1 WO 2007145094A1
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Prior art keywords
group
silver
groups
photosensitive
image forming
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PCT/JP2007/061274
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English (en)
Japanese (ja)
Inventor
Hideki Komatsu
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Konica Minolta Medical & Graphic, Inc.
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Priority to JP2008521154A priority Critical patent/JPWO2007145094A1/ja
Publication of WO2007145094A1 publication Critical patent/WO2007145094A1/fr

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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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49863—Inert additives, e.g. surfactants, binders
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49809—Organic silver compounds
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49818—Silver halides
    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49827—Reducing agents
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content

Definitions

  • the present invention relates to a photothermographic material containing a non-photosensitive organic silver salt, photosensitive halogenated silver particles, a binder and a silver ion reducing agent on a support (also simply referred to as a heat-developable material or a photosensitive material). About.
  • the photothermographic material itself has been proposed for a long time (see, for example, Patent Documents 1 and 2).
  • This photothermographic material is characterized in that all the materials necessary for the reaction are contained in the film and remain in the film after processing.
  • Many studies have been conducted and reported to achieve both storability and developability.
  • there are techniques for bleaching capri nuclei generated during the storage period with polyhalogen compounds for example, see Patent Document 3
  • methods for controlling the Tg and degree of polymerization of the binder It is effective (for example, refer to Patent Documents 4 to 6).
  • each method has a sufficient level of damage to developability and meets the market demands.
  • Patent Document 1 U.S. Pat.No. 3,152,904
  • Patent Document 2 U.S. Pat.No. 3,457,075
  • Patent Document 3 Japanese Patent Laid-Open No. 07-002781
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-341483
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2002-156727
  • Patent Document 6 Japanese Patent Laid-Open No. 2004-279500 Disclosure of the invention
  • the present invention has been made in view of the above-described background circumstances, and an object thereof is to provide a photothermographic material having both storability before development and developability.
  • a photothermographic material having an image forming layer containing a non-photosensitive aliphatic carboxylic acid silver salt particle, a photosensitive silver halide particle, a silver ion reducing agent and a polymer binder on the support.
  • the binder amount of the forming layer is 25 to 35% by mass with respect to the total solid content contained in the image forming layer, and the binder contains a polymer having a polymerization degree of 1000 or more and 3000 or less.
  • An isocyanate compound is added to the image forming layer in a range of more than 0% by mass and 3.5% by mass or less with respect to the noinder amount of the image forming layer 1
  • the non-photosensitive aliphatic carboxylic acid silver salt particle force comprising a silver salt of a fatty acid having a behenic acid content of 70 to 99.99mo 1%, according to any one of 1 to 4, Photothermographic material.
  • R represents a hydrogen atom or a substituent.
  • R and R each independently represents the number of carbon atoms.
  • a and A are each independently a hydroxyl group or a reduction or deprotection
  • n and m represent an integer of 3 to 5.
  • the total silver amount of the non-photosensitive aliphatic carboxylic acid silver salt particles and the photosensitive halogenated silver halide particles is 0.8 to 1.5 gZm 2 , The thermal image light-sensitive material described.
  • a photothermographic material having both preservative preservability and developability can be provided.
  • the binder made of the polymer contained in the image forming layer according to the present invention can carry silver salt, silver halide grains, a reducing agent, and other components.
  • the binder preferably used is transparent or translucent, Generally, it is colorless and includes natural polymers, synthetic polymers and copolymers, and other media for forming a film, for example, those described in paragraph “0069” of JP-A-2001-330918.
  • particularly preferred examples include high molecular compounds having an acetal group, alkyl methacrylates, aromatic methacrylates, and styrenes.
  • polymers polymer compounds
  • a polymer compound having an acetal group is a polyvinyl compound having an acetacetal structure.
  • the power of being setanore is more preferable than S, and in the f row, polybules shown in U.S. Pat.Nos. 2,358,836, 3,003,879, 2,828,204, British Patent 771,155, etc. Acetal can be mentioned.
  • Preferred for the present invention! /! Binders are polyvinyl acetals, particularly preferably polyvinyl butyral, which is preferably used as the main binder of the photosensitive layer.
  • the main binder as used herein refers to “a state in which the polymer occupies 50% by mass or more of the total binder in the image forming layer”. Therefore, other polymers may be blended and used within the range of less than 50% by weight of the total binder!
  • the polybutacetal rosin is preferably one that has been synthesized with the power butyl aldehyde and Z or acetoaldehyde, which is synthesized by the aceter Louis reaction of polybulal alcohol and various aldehydes.
  • the specific force of the acetalized portion of the polybutacetal resin is preferably in the range of 60 to 100% with respect to the total acetalized portion, more preferably 85% or more.
  • the portion acetalized by aldehyde is 60% or more, the water that causes capri when the obtained polyvinyl acetal resin is hard to absorb moisture becomes the heat-sensitive material of the present invention. It is preferable in order to prevent it from being brought in.
  • any aldehyde that can be acetalized such as formaldehyde, acetaldehyde, butyraldehyde, propyl aldehyde, and the like may be used.
  • each butyraldehyde is used alone. It is preferable to use a combination of butyraldehyde and acetoaldehyde.
  • the photothermographic material of the present invention is characterized in that the amount of binder in the image forming layer is 25 to 35% by mass with respect to the total solid content contained in the image forming layer.
  • the total solid content contained in the image forming layer includes all binders, non-photosensitive aliphatic carboxylic acid silver salt particles, photosensitive silver halide particles, silver ion reducing agents, etc. contained in the image forming layer. Refers to the solid mass of the material.
  • the material contained in the image forming layer is not particularly limited, and the image forming layer may contain a wide variety of materials as described in the following specification. When two or more types of solder are included, the binder amount in the present invention refers to the sum of the masses of all binders. [0021] (Binder polymerization degree of image forming layer)
  • the binder contained in the image forming layer according to the photothermographic material of the invention preferably contains at least one polymer having a polymerization degree of 1000 or more and 3000 or less. Furthermore, those having a degree of polymerization in the range of 1250 to 2750 are preferred. Further, when a plurality of binders are used, it is preferable that the polymer having a polymerization degree of 1000 or more and 3000 or less is 20% by mass to 95% by mass (20 to 95% by mass) with respect to the total binder amount. Is preferably 30% by mass or more and 50% by mass or less.
  • the photothermographic material of the present invention preferably has a glass transition temperature (Tg) of 70 to 105 ° C. or higher for the noinder used for the image forming layer. Furthermore, the temperature is preferably 70 to 95 ° C.
  • Tg of the binder is a value that is a measure of the thermal phase transition temperature inside each layer. If the Tg is too low, it promotes changes in photographic performance due to diffusion of the material during storage and changes in density after heat development. Therefore, it is not preferable. On the other hand, if Tg is too high, it is impossible to optimize the fluidity of the resin at a high temperature such as the drying temperature or the heat development temperature.
  • Tg the drying speed of the coating solution solvent
  • Tg the drying speed of the coating solution solvent
  • the diffusion speed of the material necessary for image formation is decreased.
  • cellulose esters which are polymers having a higher softening temperature, especially triacetyl cellulose. Polymers such as cellulose acetate butyrate are preferred. If necessary, two or more binder resins can be used in combination.
  • binders are used in an effective range to function as a binder for fixing elements of each layer.
  • the effective range can be easily determined by one skilled in the art.
  • the photothermographic material of the present invention can link binders together by bridging.
  • An isocyanate compound can be contained as a cross-linking agent.
  • the addition amount is preferably in the range of more than 0 and not more than 3.5% by mass with respect to the noinder.
  • the isocyanate compound used in the present invention is an isocyanate having at least two isocyanate groups and an adduct thereof (specifically, an aliphatic diisocyanate, cyclic).
  • Aliphatic diisocyanates having a group benzene diisocyanates, naphthalene diisocyanates, biphenyl diisocyanates, diphenylmethane diisocyanates, triphenylmethane diisocyanates, Examples include triisocyanates, tetraisocyanates, adducts of these isocyanates, and adducts of these isocyanates with divalent or trivalent polyalcohols.
  • an isocyanate compound described on pages 10 to 12 of JP-A-5 6-5535 can be used.
  • the adduct of isocyanate and polyalcohol has particularly high ability to improve interlayer adhesion, and prevent layer peeling, image shift and bubble generation.
  • the strong isocyanate may be contained in any part of the photothermographic material.
  • the support especially when the support is paper, it can be included in the size composition
  • image forming layer photosensitive layer
  • surface protective layer intermediate layer, antihalation layer, subbing layer, etc.
  • many 3.5 mass 0/0 is preferably added in the range, than 0 for.
  • the non-photosensitive aliphatic carboxylic acid silver salt that can be used in the present invention is relatively stable to light, but is 80 ° C or higher in the presence of exposed photosensitive silver halide and a reducing agent.
  • the non-photosensitive aliphatic carboxylic acid silver salt can be any aliphatic carboxylate salt that can supply silver ion that can be reduced by a reducing agent!
  • the silver salt of an aliphatic carboxylic acid is particularly a silver salt of a long chain aliphatic carboxylic acid (having 10 to 30, preferably 15 to 28 carbon atoms). preferable.
  • the aliphatic carboxylic acid silver salt examples include silver lignocerate, silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver cabrate, silver myristate, silver palmitate, Including strong acid silver and mixtures thereof.
  • the aliphatic carboxylic acid silver salt preferably contains 70 to 99 mol% of silver behenate. Further, it is preferable to contain 80 mol% or more and less than 90 mol% of silver behenate. Further, it is preferable to use an aliphatic carboxylic acid silver salt having a silver uric acid silver content of 2 mol% or less, more preferably 1 mol% or less, and still more preferably 0.1 mol% or less.
  • the aliphatic carboxylic acid silver salt of the present invention can be used in a desired amount, but the total silver amount including halogenated silver is preferably 0.8 to 1.5 gZm 2 and more preferably 1.0 to 1. A range of 3 gZm 2 is preferred.
  • the non-photosensitive aliphatic carboxylic acid silver salt particles of the present invention preferably have a spherical equivalent diameter of 0.05 ⁇ m or more and 0.5 m or less. More preferably, it is 0.10 111 or more and 0.5 m or less.
  • the particle size distribution is preferably monodisperse.
  • the monodispersity can be expressed by the standard deviation of the average diameter, and the standard deviation of the aliphatic carboxylic acid silver salt particles of the present invention is preferably 0.3 m or less. Furthermore, it is preferably 0.2 m or less.
  • the particle size and size distribution are calculated from a laser diffraction method, a centrifugal sedimentation light transmission method, an X-ray transmission method, an electrical detection band method, a light shielding method, ultrasonic attenuation spectroscopy, and an image.
  • the particle size distribution can be determined by a generally known particle size distribution measurement method. Among these, for fine particles, a laser diffraction method or a method of calculating from an image is preferable. Further, the aliphatic carboxylic acid silver salt particles dispersed in a liquid preferred by the laser diffraction method can be carried out by a commercially available laser diffraction particle size distribution measuring apparatus.
  • the aliphatic carboxylic acid silver salt particles in the present invention may be prepared by reacting a solution containing silver ions with an aliphatic alkanoic acid alkali metal salt solution or suspension. And are preferred.
  • the solution containing silver ions is preferably an aqueous silver nitrate solution
  • the aliphatic carboxylic acid metal salt solution or suspension is preferably an aqueous solution or aqueous dispersion.
  • the addition and mixing are preferably performed at the same time.
  • the method of adding to the liquid surface of the reaction bath or the method of adding to the liquid may be used, but the method of adding and mixing in the transfer means is preferred.
  • Mixing in the transfer means means line mixing, and mixing of a solution containing silver ions with an alkali metal salt of an aliphatic carboxylic acid salt or suspension before entering a batch storing a mixture containing reactants. It is preferred to be done ⁇ . Any means such as a mechanical mixer such as a homomixer, a static mixer, or a turbulent effect may be used as the stirring means in the mixing section, but it is preferable not to use mechanical stirring.
  • the mixing in the transfer means includes a third solution such as water or a circulating solution of the mixed solution stored in the batch after mixing. Liquids or suspensions may be mixed.
  • the concentration of the aqueous silver nitrate solution is preferably 1 to 15% by mass, and the concentration of the aliphatic carboxylic acid metal salt aqueous solution or the aqueous dispersion is preferably 1 to 5% by mass. Outside the above concentration range, productivity is significantly degraded in the low concentration region, and it is difficult to adjust the particle size and size distribution within the range of the present invention in the high concentration region which is not practical.
  • the mixed molar ratio of silver nitrate to the aliphatic carboxylic acid alkali metal salt is preferably in the range of 0.9 to 1.1, the particle size and size distribution should be adjusted within the range of the present invention.
  • the yield of aliphatic carboxylic acid silver salt is reduced, and the formation of acid silver that causes capri is likely to occur.
  • the prepared aliphatic carboxylic acid silver salt is preferably washed with water and then dried from the viewpoint of storage stability. Washing with water is performed mainly to remove unreacted ions, but may be performed with an organic solvent in consideration of the subsequent drying step.
  • the washing with water is preferably performed at 50 ° C or lower. Furthermore, it is preferable to carry out at 30 ° C or less. If it is carried out at 50 ° C. or higher, it is difficult to adjust the particle size and size distribution within the scope of the present invention.
  • the drying is preferably performed at a temperature lower than the phase transition temperature of the aliphatic carboxylic acid silver salt. Furthermore, it is preferable to carry out at 50 ° C or less, and it is preferred to carry out at a low temperature as much as possible! For drying above the phase transition temperature, the particle size and size distribution are It becomes difficult to adjust to the range.
  • the preparation of the aliphatic carboxylic acid silver salt is preferably carried out in the absence of photosensitive halogenated silver particles.
  • the aliphatic carboxylic acid silver salt of the present invention can be used in a desired amount, but the total silver amount including the halogenated silver is 0.8 to 1.5 g / m 2 as the coating amount of the photothermographic material. Further preferably, it is preferably in the range of 1.0 to 1.3 g / m 2 .
  • alkali metal salts examples include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Of these, it is preferable to use one kind of alkali metal salt such as potassium hydroxide, but it is also preferable to use sodium hydroxide and potassium hydroxide in combination. As a combination ratio, it is preferable that the molar ratio of the above-mentioned hydroxide salt is in the range of 10:90 to 75:25. When used in the above range when reacted with an aliphatic carboxylic acid to form an alkali metal salt of an aliphatic carboxylic acid, the viscosity of the reaction solution can be controlled in a good state.
  • the emulsion containing the aliphatic carboxylic acid silver salt grains according to the present invention is a mixture of free aliphatic carboxylic acid and aliphatic carboxylic acid silver salt that forms a silver salt, but the former ratio is the latter. Is low from the viewpoint of image storage stability and the like. That is, the emulsion according to the present invention preferably contains an aliphatic carboxylic acid in an amount of 3 to 1 Omol% with respect to the aliphatic carboxylic acid silver salt grains. The content is particularly preferably 4 to 8 mol%.
  • the aliphatic carboxylic acid silver salt and the free aliphatic carboxylic acid amount and the respective ratios or The ratio of free fatty acids to total aliphatic carboxylic acids will be calculated.
  • the shape of the aliphatic carboxylic acid silver salt that can be used in the present invention is not particularly limited and may be any shape such as a needle shape, a rod shape, a flat plate shape, and a flake shape.
  • flake-shaped aliphatic carboxylic acid silver salts and short needle-shaped or rectangular parallelepiped-shaped carboxylic acid silver salts having a major axis / minor axis length ratio of 5 or less are preferably used.
  • the flaky aliphatic carboxylic acid silver salt is defined as follows. Observe the aliphatic carboxylic acid silver salt with an electron microscope, approximate the shape of the aliphatic carboxylic acid silver salt particle to a rectangular parallelepiped, and define the sides of the rectangular parallelepiped as a, b, c (c is b ) When calculating with the shorter numbers a and b, calculate X as follows.
  • X is obtained from about 200 particles, and when the average value X (average) is obtained, particles satisfying the relationship of x (average) ⁇ 1.5 are defined as flakes. Preferably 30 ⁇ x (average) ⁇ 1.5, more preferably 20 ⁇ x (average) ⁇ 2.0. Incidentally, an acicular shape is l ⁇ x (average) less than 1.5.
  • a can be regarded as the thickness of a tabular particle having a main plane with b and c as sides.
  • the average of a is 0.01 ⁇ m or more, 0.23 ⁇ 111 or more, more preferably 0.1 m or more and 0.20 m or less.
  • the average of cZb is preferably 1 or more and 6 or less, more preferably 1.05 or more and 4 or less, further preferably 1.1 or more and 3 or less, and particularly preferably 1.1 or more and 2 or less.
  • the aliphatic carboxylic acid silver salt according to the present invention may be a crystal particle having a core Z shell structure as disclosed in European Patent 1168069A1 and Japanese Patent Application Laid-Open No. 2002-23303.
  • the core Z shell structure all or part of either the core part or the shell part is made of an organic silver salt other than silver aliphatic carboxylate, for example, an organic compound such as phthalic acid or benzimidazole.
  • Silver salt may be used as a constituent of the crystal grains.
  • the tabular aliphatic carboxylic acid silver salt particles may be preliminarily dispersed together with a binder, a surfactant or the like, if necessary, and then dispersed and pulverized with a media disperser or a high-pressure homogenizer.
  • a general stirrer such as an anchor type or a propeller type, a high-speed rotating centrifugal radiation type stirrer (dissolver), or a high-speed rotating shear type stirrer (homomixer) can be used.
  • a rolling mill such as a ball mill, a planetary ball mill, and a vibration ball mill
  • a bead mill that is a medium agitation mill, an attritor, and other basket mills
  • high-pressure homogenizers can be used, such as a type that collides with walls, plugs, etc., a type that divides the liquid into multiple parts that collide with each other at high speed, and a type that passes a thin orifice.
  • Ceramics used for the ceramic beads used when dispersing the media include yttrium-stabilized zircoure and zircoua reinforced alumina (these are because of the low generation of impurities due to friction with the beads and the disperser during dispersion).
  • a ceramic containing zircoure is hereinafter preferably abbreviated as zircoyu).
  • the apparatus used for dispersing the tabular aliphatic carboxylic acid silver salt particles according to the present invention for example, zirconium, alumina, nitriding Ceramics such as silicon and boron nitride or diamond Among them, it is preferable to use zircoyu.
  • zirconium, alumina, nitriding Ceramics such as silicon and boron nitride or diamond Among them, it is preferable to use zircoyu.
  • a binder concentration of 0.1 to 10% of the weight of the aliphatic carboxylic acid silver. It is preferable that the liquid temperature does not exceed 45 ° C throughout the dispersion.
  • the number of operations is preferably 2 times or more.
  • the peripheral speed is preferably 6 to 13 mZ seconds.
  • the non-photosensitive aliphatic carboxylic acid silver salt particles are formed in the presence of a compound that functions as a crystal growth inhibitor or a dispersant.
  • the compound that functions as a crystal growth inhibitor or dispersant is preferably an organic compound having a hydroxyl group or a carboxyl group.
  • the compound functioning as a dispersant and not a crystal growth inhibitor for aliphatic silver carboxylate particles coexists with the compound in the production process of aliphatic silver carboxylate particles.
  • a compound having a function and an effect of monodispersing with a smaller particle size than that produced under the conditions is described.
  • Specific examples include monohydric alcohols having 10 or less carbon atoms, preferably secondary alcohols, tertiary alcohols, glycols such as ethylene glycol and propylene glycol, polyethers such as polyethylene glycol, and glycerin.
  • the preferred amount of added calories is 10 to 200% by mass with respect to the silver aliphatic carboxylate.
  • branched fat containing isomers such as isoheptanoic acid, isodecanoic acid, isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachidic acid, isobehenic acid, isohexaconic acid, etc.
  • Group carboxylic acids are also preferred.
  • preferred side chains include an alkyl group or a alkenyl group having 4 or less carbon atoms.
  • aliphatic unsaturated carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, moloctic acid, eicosenoic acid, arachidonic acid, eicosapentaenoic acid, enolekaic acid, docosapentaenoic acid-docosahexaenoic acid, and ceracolonic acid
  • acids include acids.
  • a preferable addition amount is 0.5 to: LOmol% of silver aliphatic carbonate.
  • Glycosides such as dalcoside, galactoside, fructoside, trehalose, sucrose, etc.
  • Trehalose-type disaccharides polysaccharides such as glycogen, dextrin, dextran, alginic acid, cellosolves such as methyl ceguchi sorb, ethyl ceguchi sorb, water-soluble organic solvents such as sorbitan, sorbit, ethyl acetate, methyl acetate, dimethylformamide, polyvinyl alcohol
  • water-soluble polymers such as polyacrylic acid, acrylic acid copolymer, maleic acid copolymer, carboxymethylenosenorose, hydroxypropenoresenorerose, hydroxypropinoremethenoresenorelose, polybylpyrrolidone, and gelatin.
  • a preferable addition amount is 0.1 to 20% by mass with respect to the silver aliphatic carboxylate.
  • Alcohols having 10 or less carbon atoms preferably secondary alcohols such as isopropyl alcohol, and tertiary alcohols such as t-butyl alcohol increase the solubility of the aliphatic carboxylic acid alkali metal salt in the particle production process. By reducing the viscosity, the dispersion is monodispersed and has a small particle size by increasing the stirring efficiency.
  • Branched aliphatic carboxylic acids and aliphatic unsaturated carboxylic acids have higher steric hindrance than the straight chain aliphatic carboxylic acid silver, which is the main component, when the aliphatic carboxylic acid silver is crystallized, and the disorder of the crystal lattice is larger. As a result, large crystals are not formed, resulting in a small particle size.
  • the compound represented by the general formula (1) it is preferable to use the compound represented by the general formula (1) alone or in combination with another reducing agent having a different chemical structure as a silver ion reducing agent.
  • the reducing agent used here is preferably a bisphenol type reducing agent.
  • Examples of reducing agents that can be used in combination with the compound represented by the general formula (1) include paragraph numbers “0043” to “0045” of JP-A-11-65021, page 7 line 34 to page 18 of European Patent Publication (EP0803764A1).
  • the compound represented by the general formula (1) is preferably contained in an image forming layer containing an organic acid silver salt, but may be contained in an adjacent non-image forming layer!
  • R represents a hydrogen atom or a substituent.
  • R represents a hydrogen atom or a substituent.
  • a hydrogen atom, an alkyl group, a cycloalkyl group, or a alkenyl group is preferable, and a hydrogen atom or an alkyl group is more preferable.
  • These substituents may further have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkyl group, an alkyl group, an aryl group, and a heterocyclic group.
  • R2 and R3 each represent a branched alkyl group having 3 to 8 carbon atoms.
  • branched alkyl groups include t-butyl, t-amyl, i-propyl, i-butyl, i-propyl, 1,1-dimethylbutyl, 1-methylcyclopentyl, 1-methylcyclobutyl, Examples include 1-methylcyclopropyl group, 1methylbutyl group, 1,3 dimethylbutyl group, 1-methylpropyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, and the like.
  • a t-butyl group, a 1,1-dimethylbutyl group or a tamyl group is preferable, and a tamyl group is more preferable.
  • These branched alkyl groups may further have a substituent, and examples of the substituent include a hydroxyl group, a cyano group, a mercapto group, a halogen atom, an amino group, an imide group, a silyl group, and a hydrazino group.
  • a and A are each a hydroxyl group or deprotected to form a hydroxyl group.
  • Examples of the group that can be deprotected to form a hydroxyl group include groups that can be deprotected by the action of acid and Z or heat to form a hydroxyl group.
  • ether groups (methoxy, t-butoxy, aryloxy, benzyl Oxy, triphenyl methoxy, trimethylsilyloxy, etc.), hemiacetal group (tetrahydroloxy, etc.), ester group (acetyloxy, benzoyloxy, p-trobenzoyloxy, formyloxy, trifluoroacetyloxy, bivaluloyloxy, etc.), carbonate Groups (such as ethoxycarbonyloxy, phenoxycarbonyloxy, t-butyloxycarboxyloxy, etc.), sulfonate groups (such as p-toluenesulfo-loxy, benzensulfo-loxy, etc.), strong rubamoyloxy groups (such as phenylcarbamoyloxy) Thiocarboxoxy group (benzylthiocarboxoxy etc.), nitrate ester group, sulphateate group (2,4
  • the melting point is preferably 80 to 250 ° C and the thermal decomposition temperature is preferably 200 ° C or higher.
  • Thermal development in which a reducing agent remains in the photosensitive material after development processing
  • the reducing agent with higher crystallinity suppresses material diffusion during storage, so the concentration of the capri portion due to the reduction reaction during image storage Since the fluctuation is small, the crystallinity of the reducing agent is high, which is better.
  • the reducing agent may be contained in the coating solution by any method such as a solution form, an emulsified dispersion form, or a solid fine particle dispersion form, and may be contained in the photothermographic material.
  • 3,801,321 such as 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4benzenesulfonamidophenol, 4-benzensulfonamidonaphthol, etc.
  • Such sulfonamide phenols or sulfonamide naphthols can also be used as a silver ion reducing agent.
  • the amount of reducing agent used varies depending on the type of aliphatic carboxylic acid silver salt, reducing agent, and other additives. L0 mol, preferably 0.1 to 3 mol is suitable.
  • a reducing agent is added to and mixed with a photosensitive emulsion solution composed of light-sensitive silver halide and aliphatic carboxylic acid silver salt grains and a solvent immediately before coating. Small and preferred.
  • Photosensitive silver halide also referred to as “halogen-silver” is intrinsically light-absorbing as a characteristic of halogen-silver crystals, or artificially physicochemically radiates visible to infrared light. When absorbing light in any region within the light wavelength range from the ultraviolet light region to the infrared light region, it can absorb, and there is a physical / physical change in the silver halide crystal and in the Z or crystal surface. It refers to halogen-molybdenum crystal grains that have been processed and produced as possible.
  • the halogenated silver of the present invention can be prepared as a halogenated silver grain emulsion (also called a halogenated silver emulsion) using a known method. That is, any of acid method, neutral method, ammonia method, etc. can be used. As a method of reacting a soluble silver salt and a soluble halogen salt, any one of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like can be used. Of these methods, the so-called controlled double jet method is preferred, in which halogen silver halide grains are prepared while controlling the formation conditions.
  • a silver halide silver seed grain is divided into two stages: grain nucleation and grain growth, and these can be performed continuously at once. Nuclei (seed grain) formation and grain growth are also possible. Alternatively, the method may be performed separately.
  • the controlled double jet method which controls the particle formation conditions such as pAg and pH, is preferable because the particle shape and size can be controlled. For example, when performing a method in which nucleation and grain growth are performed separately, first, a silver salt Aqueous solution and halide solution are uniformly and rapidly mixed in gelatin solution, and after nucleation (nucleation process), particles are grown while supplying silver salt solution and halide solution under controlled pAg, pH, etc.
  • Halogenated silver particles are prepared by a grain growth process. After the formation of grains, the desired salt halide emulsion can be obtained by removing unnecessary salts, etc. by a known desalting method such as noodle method, fluorination method, ultrafiltration method, electrodialysis method, etc. Obtainable.
  • the particle size distribution of the halogen silver halide grains according to the present invention is preferably monodisperse.
  • the monodispersion here means that the coefficient of variation of the particle diameter obtained by the following formula is 30% or less. Preferably it is 20% or less, More preferably, it is 15% or less.
  • silver halide grains examples include cubes, octahedrons, tetrahedral grains, tabular grains, spherical grains, rod-shaped grains, and potato grains. Among these, cubic, octahedral grains, etc. A tetradecahedral, tabular halogen silver halide grain is preferred.
  • the average aspect ratio is preferably 1.5 to 100, more preferably 2 to 50. These are described in U.S. Pat. Nos. 5,264,337, 5,314,798, and 5,320,958 to easily obtain the desired tabular grains. Can do. Further, grains having rounded corners of silver halide grains can be preferably used.
  • the crystal habit of the outer surface of the silver halide grain is selected according to the adsorption reaction of the sensitizing dye on the surface of the halogenated silver grain.
  • a sensitizing dye having a property it is preferable to use silver halide grains having a relatively high ratio of crystal habits adapted to the selectivity.
  • the ratio of the [100] face is high on the outer surface of the silver halide grain. It is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more.
  • the ratio of the Miller index [100] plane is based on the adsorption dependency of the [111] plane and the [100] plane in the adsorption of the sensitizing dye. T. Tani, J. ImagingSci., 29, 165 (1985).
  • the silver halide grains used in the present invention are preferably prepared using a low molecular weight gelatin having an average molecular weight of 50,000 or less at the time of forming the grains, but particularly used at the time of nucleation of the silver halide silver grains. Is preferred.
  • the low molecular weight gelatin preferably has an average molecular weight of 50,000 or less, more preferably 2,000 to 40,000, and particularly preferably 5,000 to 25,000.
  • the average molecular weight of gelatin can be measured by gel filtration chromatography.
  • Low molecular weight gelatin can be hydrolyzed by adding gelatin-degrading enzyme to a commonly used gelatin aqueous solution with an average molecular weight of about 100,000, heating by adding acid or alkali, and heating at atmospheric pressure or under pressure.
  • the concentration of the dispersion medium at the time of nucleation of the silver halide grains is preferably 5% by mass or less, more preferably 0.05 to 3.0% by mass.
  • the halogen silver halide grains used in the present invention preferably use a compound represented by the following general formula at the time of grain formation.
  • ⁇ represents a hydrogen atom, SO M, or CO—B—COOM
  • M represents a hydrogen atom
  • m and n each represents 0 to 50, and p represents 1 to 100.
  • the polyethylene oxide compound represented by the above general formula is a process for producing a gelatin aqueous solution in the production of a normal silver halide photographic light-sensitive material, a water-soluble halide and a water-soluble compound in the gelatin solution. It has been used preferably as an antifoaming agent for significant foaming when the emulsion raw materials are stirred or moved, such as the step of adding a functional silver salt and the step of coating an emulsion on a support. A technique used as a foaming agent is described in, for example, JP-A-44 9497.
  • the polyethylene oxide compound also functions as an antifoaming agent during nucleation.
  • the compound represented by the above general formula is preferably used in an amount of 1% by mass or less based on silver, more preferably 0.01 to 0.1% by mass.
  • the polyethylene oxide compound is preferably added in advance to the dispersion medium before nucleation as long as it exists at the time of nucleation, but it may be added during nucleation.
  • the silver salt aqueous solution to be used may be added to the ride aqueous solution. Preferably, it is used by adding 0.01 to 2.0% by mass to the aqueous solution of Rhino, Ride or both.
  • the compound is preferably present for a time of at least 50% of the nucleation step, more preferably 70% or more.
  • the polyethylene oxide compound may be added as a powder, or may be added in a solvent such as methanol.
  • the temperature at the time of nucleation is usually 5 to 60 ° C, preferably 15 to 50 ° C. Even if the temperature is constant, the temperature rise pattern (the temperature at the start of nucleation is Even when the temperature is increased gradually during nucleation at 25 ° C and the temperature at the end of nucleation is 40 ° C) or vice versa, it is preferable to control within the above temperature range. .
  • the concentration of the silver salt aqueous solution and halide aqueous solution used for nucleation is preferably 3.5 mol ZL or less, and more preferably 0.01 to 2.5 mol ZL.
  • the pH at the time of nucleation is usually a force that can be set in the range of 1.7 to 10.
  • the pH on the alkali side broadens the particle size distribution of the nuclei to be formed, and is preferably pH 2 to 6.
  • pBr at the time of nucleation is usually 0.05 to 3.0, preferably 1.0 to 2.5, more preferably 1.5 to 2.0.
  • the average grain size of the silver halide grains is usually 10 to 50 nm, preferably 10 to 40 nm, and more preferably 10 to 35 nm. If the average grain size of the silver halide grains is smaller than lOnm, the image density will decrease, or the light-irradiated image will be stored (the image obtained by thermal development will be used for diagnosis in a bright room, or stored in a bright room) The storage stability) may deteriorate. If it exceeds 50 nm, the image density may be lowered.
  • the average particle size referred to here means that the halogen-silver particles contained in the halogen-silver particle emulsion are cubic or octahedral so-called normal crystals. Say the length of the ridge.
  • the silver halide grains are tabular grains, it means the diameter when converted into a circular image having the same area as the projected area of the main surface.
  • the diameter when considering a sphere equivalent to the volume of the halogenated silver particle is calculated as the particle size. Measurement is performed using an electron micrograph, The average particle size was determined by averaging the measured values of the particle size of 300 particles.
  • the gradation of image density can be adjusted by using silver halide grains having an average particle diameter of 55 to 100 nm and halogenated silver grains having an average particle diameter of 10 to 50 nm in combination.
  • the image density can be improved, and the decrease in image density over time can be improved (smaller).
  • the ratio (mass ratio) of the silver halide grains having an average particle diameter of 10 to 50 nm and the silver halide grains having an average particle diameter of 55 to 100 nm is preferably 95: 5 to 50:50, more preferably 90: 10-60: 40.
  • the two types of silver halide emulsions may be mixed and contained in the photosensitive layer.
  • the photosensitive layer is composed of two or more layers for gradation adjustment and the like, and each layer contains the silver halide emulsions having the two average grain sizes separately. .
  • silver halide grains containing silver iodide can be preferably used.
  • the silver iodide content is preferably 5 to: LOO mol%. More preferably 40 to: LOO mol 0/0, more preferably 70: A LOO mol 0/0, preferably especially 90: a LOO mol%. If the silver iodide content is in this range, the intra-grain halogen composition distribution may be uniform, may be changed stepwise, or may be changed continuously. Further, halogen silver halide grains having a core Z shell structure having a high silver iodide content in the interior and Z or on the surface can also be preferably used. The preferred structure is a double to five-fold structure, more preferably a two to four-fold core Z seal particle.
  • a method for introducing silver iodide into silver halide grains a method of adding an aqueous alkali iodide solution during grain formation, fine grain silver iodide, fine grain silver iodobromide, fine grain silver iodochloride, fine grain iodine, A method of adding at least one fine particle among silver chlorobromide and a method using an iodide ion releasing agent described in JP-A-5-323487 and JP-A-6-11780 are preferred.
  • the silver halide grains according to the present invention preferably exhibit direct transition absorption derived from a silver iodide crystal structure at a wavelength of 350 to 440 nm. Whether these silver halides have light absorption of direct transition can be easily distinguished by the fact that exciton absorption due to direct transition is observed in the vicinity of 400 to 430 nm. [0101] (Heat conversion internal latent image type silver halide grains)
  • the photosensitive silver halide silver particle according to the present invention is a heat conversion internal latent image type (internal latent image type after heat development) halogen silver halide particle disclosed in JP-A-2003-270755 and JP-A-2005-106927, that is,
  • the silver halide grains are preferably silver halide grains whose surface sensitivity is lowered by conversion from the surface latent image type to the internal latent image type by heat development.
  • a latent image that can function as a catalyst for a development reaction (reduction reaction of silver ions by a silver ion reducing agent) is formed on the surface of the halogen silver halide grains, and after the thermal development process has elapsed.
  • a larger number of latent images are formed in the interior of the silver halide grains than the surface of the silver halide grains. It is preferable in terms of storage stability.
  • the heat-converted internal latent image type silver halide grains are 0.00 per mol of an aliphatic carboxylic acid silver salt that can function as a silver ion source. It is preferably used in the range of 1 to 0.7 mol, preferably 0.03 to 0.5 mol.
  • the aggregation of silver halide grains is prevented, the silver halide grains are dispersed relatively uniformly, and finally the developed silver is dispersed. It is preferable that the desired shape can be controlled.
  • the hydrophilic groups such as amino and carboxyl groups of gelatin are chemically modified according to the conditions of use, etc., to improve the properties of gelatin. Those modified are preferred.
  • the hydrophobization modification of the amino group in the gelatin molecule includes forces such as phenylcarbamoylation, phthalation, hatching, acetylation, benzoylation, ditrophylation, etc. is not.
  • the substitution rate is preferably 95% or more, more preferably 99% or more.
  • methyl esterification or amidation which may be combined with a hydrophobic modification of a carboxyl group, may be mentioned, but it is not particularly limited thereto.
  • the substitution rate of the carboxyl group is preferably 50 to 90%, more preferably 70 to 90%.
  • the hydrophobic group in the above-mentioned hydrophobization modification refers to a group whose hydrophobicity is increased by substituting the amino group and / or carboxyl group of gelatin.
  • the halogen silver halide emulsion is prepared by using a polymer that dissolves in both water and an organic solvent as described below, instead of gelatin or in combination with gelatin.
  • the silver halide silver halide emulsion is uniformly dispersed in an organic solvent system.
  • organic solvent include alcohol-based, ester-based, and ketone-based compounds.
  • ketone organic solvents such as methanol, acetone, methyl ethyl ketone, and jetyl ketone are preferable.
  • the polymer that is soluble in both water and the organic solvent may be any of natural polymers, synthetic polymers, and copolymers.
  • synthetic polymers for example, gelatins, rubbers and the like modified so as to belong to the category of the present invention can be used.
  • polymers belonging to the following classifications can be used by introducing functional groups suitable for the purpose of preventing aggregation and uniform dispersion.
  • polystyrene-butadiene copolymers examples include polybulu alcohols, hydroxyethyl celluloses, cellulose acetates, cellulose acetate butyrates, polybutylpyrrolidones, casein, starch, polyacrylic acid and acrylic esters, polymethyl Methacrylic acid and methacrylic acid esters, polyvinyl chlorides, polymethacrylic acids, styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, polybulucetals ( Polybulformal and Polybutyral), polyesters, polyurethanes, phenoxy resins, polysalts and vinylidenes, polyepoxides, polycarbonates, polyvinyl acetates, polyolefins, cellulose esters, polyamides And the like.
  • these polymers may be copolymers, but particularly preferred are polymers obtained by
  • the polymer may be a polymer that dissolves in both water and an organic solvent in the same state, but may be dissolved in water or an organic solvent by pH control or temperature control, or may be insoluble. included.
  • a polymer having an acidic group such as a carboxyl group becomes hydrophilic in a dissociated state depending on the type, but becomes lipophilic when it is lowered to a non-dissociated state and can be made soluble in a solvent.
  • polymers having amino groups become lipophilic when the pH is raised, and become ionic and water-soluble when the pH is lowered.
  • the cloud point phenomenon is well known for non-active agents.
  • the polymer that dissolves in both the water and the organic solvent may be adjusted by dissolving the pH and the like as described above, or may be unadjusted, but at least 1% by mass or more (25 ° C with respect to water).
  • C) and an organic solvent having a solubility of 5% by mass or more (25 ° C.) in methyl ethyl ketone is preferred.
  • so-called block polymers, graft polymers, comb polymers, and the like are more suitable as polymers that are soluble in both water and organic solvents used in the present invention.
  • Comb polymers are particularly preferred.
  • the isoelectric point of the polymer is preferably pH 6 or less.
  • an ethylenically unsaturated monomer containing a polyoxyalkylene group such as ethylene oxide or propylene oxide.
  • a polyoxyalkylene group-containing ethylenically unsaturated monomer those having a polyoxyalkylene group represented by the following general formula are particularly preferable.
  • E represents an ethylene group
  • P represents a propylene group
  • T represents a butylene group
  • R represents a substituent.
  • the butylene group include tetramethylene and i-butylene groups.
  • k represents an integer of 1 to 300
  • m represents an integer of 0 to 60
  • ⁇ Preferably, ⁇ MA ki ma 1 ⁇ 200, mi ma 0 ⁇ 30, ⁇ ma 0 ⁇ 20.
  • k + m + n ⁇ 2 is preferable in order to be a comb polymer.
  • the polyoxyalkylene group-containing ethylenically unsaturated monomer may be used alone or in combination of two or more.
  • the substituent represented by R represents an alkyl group, an aryl group, a heterocyclic group, and the like, and examples of the alkyl group include methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl and the like.
  • alkyl group examples include methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl and the like.
  • aryl groups include phenyl and naphthyl groups
  • heterocyclic groups include enyl and pyridyl groups.
  • These groups further include halogen atoms, alkoxy groups (methoxy, ethoxy, butoxy, etc.), alkylthio groups (methylthio, butylthio, etc.), acyl groups (acetyl, benzoyl, etc.), alkanamide groups (acetoamide, propionamide, etc.) ), An arylamide group (such as benzoylamide) or the like. Further, these substituent groups may be further substituted by these groups.
  • the polyoxyalkylene group represented by the general formula can be introduced into the polymer by using an ethylenically unsaturated monomer having the polyoxyalkylene group.
  • the ethylenically unsaturated monomer having these groups include polyoxyalkylene acrylate (and meta acrylate), which are commercially available hydroxypoly (oxyalkylene) materials such as trade name " Pull mouth-g '[Pluronic (Asahi Denki Kogyo Co., Ltd.)], Ade force polyether (Asahi Denka Kogyo Co., Ltd.), Carbowax [Carbowax (Glico-Products Co., Ltd.)], Triton [Roriton And PE G (Daiichi Kogyo Seiyaku Co., Ltd.) and the like can be produced by reacting them with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride by a known method.
  • acrylic acid meth
  • commercially available monomers include, as a hydroxyl group-terminated polyalkylene glycol mono (meth) ate acrylate manufactured by NOF Corporation, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer AE-90.
  • Blemmer AE 200, Blemmer AE 400, Blemmer PP—1000, Blemmer PP—500, Blemmer PP—800, Blemmer AP—150, Blemmer AP—400, Blemmer AP—550, Blemmer AP—800, Blemmer 50PEP— 300, Blemmer 70PEP-350B, Blemmer AEP series, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-80, Blemmer AET series, Blemmer 30PPT-800, Blemmer 50 ⁇ -800, Blemmer 70 ⁇ -800, Blemmer APT series , Blemmer 10PPB-500B, Blemmer 10APB-500B and the like.
  • LIGHT ESTER MC LIGHT ESTER 130MA, LIGHT ESTER 041MA, LIGHT ATALYLATE BO-A, LIGHT ATTALRATE EC— A, light attalate MTG A, Light Atari les over preparative 130A, light Atari rate dpm A, Light Atari rate P- 200A, light Atari rate NP- 4EA, Light Atari rate NP- 8EA and the like.
  • a graft polymer using a so-called macromer can also be used.
  • the useful molecular weight is in the range of 10,000 to 100,000, the preferred range is 10,000 to 50,000, and the particularly preferred range is in the range of 10,000 to 20,000. If the molecular weight is less than 10,000, the effect cannot be exerted, and if it exceeds 100,000, the polymerizability with the copolymerization monomer forming the main chain deteriorates. Specifically, Toagosei Co., Ltd. AA-6, AS-6S, AN-6S, etc. can be used.
  • polyoxyalkylene group-containing ethylenically unsaturated monomer may be used alone or in combination of two or more.
  • Other monomers specifically reacted with the above monomers include (meth) acrylic acid esters, (meth) acrylamides, aryl esters, aryloxyethanols, buresters, bur esters. , Dialkyl itaconate, mono (or di) alkyl esters of fumaric acid, etc., crotonic acid, itaconic acid, (meth) acrylonitrile, maleylnitrile, styrene, etc. [0119] Specific examples include the following compounds.
  • Acrylic acid esters methyl acrylate, ethyl acrylate, propyl acrylate, chloro ethino rare acrylate, 2-hydroxy ethino rare acrylate, trimethylol propane mono acrylate, benzyl acrylate, methoxy benzyl Atalylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.
  • methacrylic acid esters methyl methacrylate, ethyl methacrylate, propyl methacrylate, chlorethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate Trimethylolpropane monometatalylate, benzenoremetatalylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, acrylamides: acrylamide, N-alkyl Acrylamide (Alkyl group
  • alkyloxyacrylamide, methoxymethylacrylamide, butoxymethylacrylamide, etc. methacrylamides: methacrylamide, N-alkylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide, N2-acetamidoethyl N-acetyl Merylamide, methoxymethyl methacrylamide, butoxymethyl methacrylamide, etc.
  • allylic compounds allylic esters (alaryl acetate, allylic acid proallyl, allylic caprylate, allylic laurate, allylic palmitate, allylic stearate, benzoic acid) Acid aryl, acetoacetyl acetate, lactyl lactate, etc.), aryloxetano mononole, etc., butyl ethers: alkyl butyl ether (hexyl vinyl ether, octino levinino leetenore, decino levinino) Leetenore, ethinorehexinorevininoreethenore, methoxetinorevininoreetenore, ethoxyethinorevininoatenore, chronoretinolinobine ether, 1 methyl 2, 2-dimethylpropyl vinyl ether, 2 ethino lebutinore vininore Tenole, hydroxyeth
  • Dialkyl esters or monoalkyl esters of fumaric acid dibutyl fumarate, etc., crotonic acid, itaconic acid, acrylonitrile, metatalonitrile, maleylnitrile, styrene, etc.
  • amphiphilic polymer for preparing halogenated silver used in the present invention.
  • the present invention is not limited to these.
  • an azo polymer polymerization initiator an azo polymer polymerization initiator or an organic peroxide can be used.
  • the azo polymer polymerization initiator ABN-R (2, 2'-azobisisobuty-tolyl), ABN-V (2, 2'-azobis (2,4-dimethylvaleronitrile) manufactured by Nippon Hydrazine Kogyo Co., Ltd. )), ABN- ⁇ (2, 2 '-azobis (2-methyl petit-tolyl))).
  • Organic Peroxides include benzoyl peroxide, dimethyl ethyl ketone peroxide, lauryl peroxide, Pertetra A, Perhexa HC, Perhexa TMH, Parhexa C, and Monohex, manufactured by NOF Corporation.
  • Examples of the polymerization inhibitor include hydroquinone and ⁇ -methoxyphenol, which are quinone-based inhibitors. Seiko Chemical's phenothiazine, methoquinone, non-flex arno, ⁇ (methylhydroquinone), TBH (t-butylhydroquinone), PBQ (p-benzoquinone), tolquinone, TBQ (t-butyl-p-benzoquinone), 2,5-diphenyl p-benzoquinone Etc.
  • the isoelectric point of the polymer is preferably pH 6 or less. If a polymer with a high isoelectric point is used, as will be described later, when desalting of silver halide silver particles by the coagulation precipitation method, decomposition of the silver halide grains is promoted, and photographic performance is adversely affected. It is. In addition, when dispersing the silver or silver oxide fine particles in the solvent, it is necessary to disperse unless the pH is raised.
  • the isoelectric point of the polymer is measured by, for example, isoelectric focusing or measuring the pH after passing a 1% aqueous solution through a mixed bed column of cation and cation exchange resin.
  • Various acidic groups can be introduced to lower the isoelectric point of the polymer.
  • examples include a carboxyl group and a sulfo group.
  • a polymer containing methyl methacrylate or the like can be obtained by partially hydrolyzing.
  • carboxyl group styrene sulfo
  • 2-acrylamide-2-methylpropanesulfonic acid it can also be introduced after polymer preparation by various sulfuric acid methods.
  • carboxylic acid is particularly preferable because the property can be changed to water-soluble by neutralization or semi-neutralization in which the solubility in a solvent is relatively high in an unneutralized state.
  • Neutralization can be carried out with sodium or potassium salts, and organic salts such as ammonia, monoethanolamine, diethanolamine, triethanolamine and the like may be used. Imidazoles, triazoles and amidoamines can be used.
  • Polymerization is preferably carried out in the presence of a solvent from the viewpoint of workability that can be carried out in the presence or absence of a solvent.
  • a solvent from the viewpoint of workability that can be carried out in the presence or absence of a solvent.
  • Preferred solvents include alcohols such as ethanol, i-propyl alcohol, butanol, i-butanol, and t-butanol, ketones such as acetone, methyl ethyl ketone, methyl-i-butyl ketone, and methyl amyl ketone, and acetic acid.
  • Esters such as methyl, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-oxypropion Acid butyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropionate
  • Monocarboxylic acid esters such as butyl onate, polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, ethers such as methyl solvosolve, cellosolve, butylcerosolve, butyl carbitol, ethylcetosolve sorb acetate, propylene Propylene glycols such as lenglycol, propylene glycolenomonomethylenole ether, propylene glycolenomonoethylenoate acetate, propylene glycolenomonoethylenoate acetate, propylene glycol monobutyl ether acetate, and esters thereof, 1, 1, 1 Halogen solvents such as trichloroethane and chloroform, ethers such as tetrahydrfuran and dioxane, aromatics such as benzene, toluene and xylene, and perfluoro Tan, fluorine I
  • a dropping polymerization method in which a monomer and an initiator are added dropwise to a reaction vessel is also effective for obtaining a polymer having a uniform composition.
  • Column filtration, re- Unreacted monomer can be removed by removal by precipitation purification, solvent extraction or the like.
  • low-boiling unreacted monomers can be removed by stripping.
  • the photosensitive silver halide grains can be chemically sensitized.
  • a compound that releases chalcogens such as sulfur, selenium, and tellurium
  • a noble metal compound that releases noble metal ions such as gold ions.
  • a chemical sensitization center (chemical sensitization nucleus) capable of capturing electrons or holes generated by photoexcitation of photosensitive silver halide grains or spectral sensitizing dyes on the grains. it can.
  • it is preferably chemically sensitized by an organic sensitizer containing a chalcogen atom.
  • the organic sensitizer containing a chalcogen atom is preferably a compound having a group capable of adsorbing to halogenated silver and an unstable chalcogen atom site.
  • These organic sensitizers are disclosed in JP-A-60-150046, JP-A-4-109240, JP-A-11-218874, JP-A-11-218875, JP-A-11-218876, JP-A-11-194447, etc.
  • Organic sensitizers having various structures can be used, and among them, at least one compound having a structure in which a chalcogen atom is bonded to a carbon atom or a phosphorus atom by a double bond It is preferable.
  • a thiourea derivative having a heterocyclic group and a triphenylphosphine sulfide derivative are preferred.
  • techniques according to various chemical sensitization techniques conventionally used in the production of silver halide light-sensitive materials for conventional wet processing can be used (TH James edition “The Theory of”). the Photograph ic Process "4th edition, Macmillan Publishing Co., Ltd. 1977, edited by the Japan Society of Photography,” Basics of Photographic Engineering (Silver Salt Photography), Corona, 1979).
  • chemical sensitization can be performed by a conventional method.
  • the amount of chalcogen compound used as an organic sensitizer varies depending on the chalcogen compound used, silver halide grains, the reaction environment during chemical sensitization, etc. 10- 8 ⁇ : L0- 2 more preferably moles preferably fixture 10- 7 ⁇ : L0- 3 molar is used.
  • the optical sensitization using these organic sensitizers is preferably performed in the presence of a heteroatom-containing compound having adsorptivity to the spectral sensitizing dye or the halogen silver halide particles.
  • a heteroatom-containing compound having adsorptivity to the spectral sensitizing dye or the halogen silver halide particles By performing chemical sensitization in the presence of a compound having adsorptivity to the silver halide silver particles, dispersion of the chemically sensitized central core can be prevented, and high sensitivity and low capri can be achieved.
  • Spectral sensitizing dyes will be described later, but nitrogen-containing heterocyclic compounds described in JP-A No. 3-24537 are preferred as heteroatom-containing compounds having adsorptivity to halogenated silver. As an example.
  • examples of the heterocyclic ring include pyrazole, pyrimidine, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,2,3-thiadiazole, 1, 2, 4-thiadiazole, 1, 2, 5-thiadiazole, 1, 2, 3, 4-tetrazole, pyridazine, 1, 2, 3-thiadiazine ring, these ring forces ⁇ 3 bonded
  • examples of the ring include triazolotriazole, diazaindene, triazaindene, and pentazaindene rings.
  • a heterocyclic ring condensed with a monocyclic heterocyclic ring and an aromatic ring for example, phthalazine, benzimidazole, indazole, benzthiazole ring and the like can also be applied.
  • azaindene ring is preferable, and an azaindene compound having a hydroxyl group as a substituent, for example, hydroxytriazaindene, tetrahydroxyazaindene, hydroxypentazaindene compound and the like are more preferable.
  • U an azaindene compound having a hydroxyl group as a substituent, for example, hydroxytriazaindene, tetrahydroxyazaindene, hydroxypentazaindene compound and the like are more preferable.
  • the heterocyclic ring may have a substituent other than a hydroxyl group.
  • substituents include an alkyl group, a substituted alkyl group, an alkylthio group, an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group, an arylamino group, a carboxyl group, an alkoxy group, a carbonyl group, a halogen atom, and a cyano group. And so on.
  • the amount of the heterocyclic compound added depends on the size, composition, and other conditions of the halogenated silver particles.
  • the amount of force approximate to Wataru connection vary over a wide range depending on the matter or the like is in the range of 1 0 one 6 -1 mole per Harogeni ⁇ 1 mol, preferably 10 4 to 1 0 - is 1 mols .
  • the photosensitive silver halide can be subjected to noble metal sensitization by using a compound that releases noble metal ions such as gold ions.
  • a compound that releases noble metal ions such as gold ions.
  • chloroaurate and organic gold compounds can be used as gold sensitizers.
  • the gold sensitization technique disclosed in JP-A-11-194447 is a reference.
  • reduction sensitization methods and the like can also be used.
  • a shell-like compound for reduction sensitization ascorbic acid, diacid thiourea, stannous chloride, A hydrazine derivative, a borane compound, a silane compound, a polyamine compound, or the like can be used.
  • reduction sensitization can be performed by ripening the emulsion while maintaining the pH at 7 or more or pAg at 8.3 or less.
  • the silver halide grains subjected to chemical sensitization were formed in the presence of an aliphatic carboxylic acid silver salt, but the aliphatic carboxylic acid silver salt was not present. It may be formed under conditions, or a mixture of both.
  • the chemical sensitization effect substantially disappears after the thermal development process.
  • the effect of chemical sensitization substantially disappears when the sensitivity of the imaging material obtained by the chemical sensitization technique is chemically sensitized after the thermal development process! / Sensitive, say that the sensitivity decreases to 1.1 times or less.
  • an oxidant that can destroy the chemical sensitization center (chemical sensitization nucleus) by an acid-oxidation reaction at the time of heat development for example, release of the above-mentioned halogen radicals.
  • the content of the oxidant is preferably adjusted in consideration of the oxidizing power of the oxidant, the decrease in the chemical sensitization effect, and the like.
  • the photosensitive silver halide is preferably subjected to spectral sensitization by adsorbing a spectral sensitizing dye.
  • a spectral sensitizing dye cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemiyanine dyes, oxonol dyes, hemioxonol dyes, and the like can be used.
  • JP-A-63-159841, 60-140335, 63-231437, 63-259 651, 63-304242, 63-15245, U.S. Patents 4, 639, 414, 4, 7 40, 455, 4, 741, 966, 4, 751, 175, Sensitizing dyes described in US Pat. No. 4,835,096 can be used.
  • Useful sensitizing dyes used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) 17643IV—A (December 23, 1978), RD18431X (August 1978 4 page 37) ) Is described in the literature described or cited.
  • RD Research Disclosure
  • the power of using sensitizing dyes with spectral sensitivity suitable for the spectral characteristics of various laser imagers and scanner light sources is preferred.
  • the compounds described in JP-A Nos. 934078, 954409, and 980679 are preferably used.
  • Useful cyanine dyes are cyanine dyes having basic nuclei such as thiazoline nucleus, oxazoline nucleus, pyrroline nucleus, pyridine nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus and imidazole nucleus.
  • basic nuclei such as thiazoline nucleus, oxazoline nucleus, pyrroline nucleus, pyridine nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus and imidazole nucleus.
  • preferred merocyanine dyes are preferably thiohydantoin, rhodanine, oxazolidinedione, thiazolinedione, barbituric acid, thiazolinone, malono-tolyl and pyrazo. Includes acidic nuclei such as Ron nuclei.
  • a sensitizing dye having spectral sensitivity particularly in the infrared can also be used.
  • infrared spectral sensitizing dyes examples include infrared spectral sensitizing dyes disclosed in US Pat. Nos. 4,536,473, 4,515,888, and 4,959,294. It is
  • the sensitizing dye represented by the following general formula (SD1) and the following general formula (SD2) as described in JP-A-2004-309758 It is preferable that at least one sensitizing dye is selected and contained.
  • L to L each represent a methine group.
  • R 1 and R 2 each represent an aliphatic group.
  • R 4 each represents a lower alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group.
  • W, W, W, and W are each a hydrogen atom, a substituent, or
  • nl and n2 each represents 0, 1 or 2; However, nl and n2 are not 0 at the same time.
  • the above infrared sensitizing dyes are, for example, the authors of F'Nom's: The Chemistry of Heterociciic and ompounds, ⁇ 3 ⁇ 418 ⁇ , The Cyanme Dyes and Related and o mpounds (A. Weissberger ed. Interscience Company dried (J, New York, 1964) [It can be easily synthesized by this method.
  • These infrared sensitizing dyes may be added at any time after the preparation of halogen silver, for example, added to a solvent or dispersed in the form of fine particles in a so-called solid dispersion state. It can be added to a light-sensitive emulsion containing grains or halogenated silver grains Z aliphatic carboxylic acid silver salt grains. Similarly to the compound containing a helium atom having an adsorptivity to the above-described halogen silver particles, it is added to the halogen silver particles prior to chemical sensitization and adsorbed. Then, chemical sensitization can be performed, which can prevent dispersion of the chemical sensitization central core and achieve high sensitivity and low capri.
  • the above-mentioned spectral sensitizing dye may be used alone, but as described above, it is preferable to use a combination of plural kinds of spectral sensitizing dyes. This combination is often used for the purpose of supersensitization and enlargement or adjustment of the photosensitive wavelength region.
  • a substance that does not absorb and exhibits a supersensitizing effect may be included in the emulsion, so that the silver halide grains may be supersensitized!
  • M is a hydrogen atom or an alkali metal atom
  • Ar is an aromatic ring or condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium, or tellurium atoms.
  • the heteroaromatic ring is preferably benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, triazine. , Pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline, or quinazoline. However, other heteroaromatic rings are also included.
  • Mercapto derivative compounds that substantially produce the above mercapto compounds when contained in a dispersion of an aliphatic carboxylic acid silver salt or a silver halide grain emulsion are also included.
  • preferred examples include mercapto derivative compounds represented by the following.
  • Ar has the same meaning as in the case of the mercaptoic compound represented above.
  • the above heteroaromatic ring includes, for example, a halogen atom (chlorine, bromine, iodine), a hydroxyl group, Amino group, carboxyl group, alkyl group (having 1 or more carbon atoms, preferably having 1 to 4 carbon atoms) and alkoxy group (1 or more carbon atoms, preferably 1 to 4 carbon atoms) It may have a substituent selected from the group consisting of those having atoms.
  • a halogen atom chlorine, bromine, iodine
  • a hydroxyl group Amino group
  • carboxyl group alkyl group (having 1 or more carbon atoms, preferably having 1 to 4 carbon atoms)
  • alkoxy group (1 or more carbon atoms, preferably 1 to 4 carbon atoms
  • a macrocyclic compound having a heteroatom disclosed in JP-A-2001-330918 can also be used as the supersensitizer.
  • the supersensitizer is preferably used in a photosensitive layer containing an aliphatic carboxylic acid silver salt and a silver halide silver particle in an amount of 0.001 to 1.0 mol per mol of silver. Particularly preferred is 0.01 to 0.5 mole per silver mole.
  • spectral sensitization is performed by adsorbing a spectral sensitizing dye to the surface of photosensitive halogen silver halide grains, and the spectral sensitization effect is substantially reduced after the thermal development process. It is preferable to disappear.
  • the spectral sensitization effect substantially disappears when the sensitivity of the imaging material obtained with a sensitizing dye, supersensitizer, etc. is spectrally sensitized after the thermal development, 1. It means to decrease to less than 1 times.
  • a spectral sensitizing dye that is easily detached from the halogenated silver particles by heat is used during thermal development, or Z and the spectral sensitizing dye are acidified. It is necessary to contain an appropriate amount of an oxidizing agent that can be destroyed by the reaction, such as the halogen radical-releasing compound, in the emulsion layer or Z and the non-photosensitive layer of the imaging material.
  • the content of the oxidizing agent is preferably adjusted in consideration of the oxidizing power of the oxidizing agent, the reduction range of the spectral sensitization effect, and the like.
  • the cool image tone means a pure black tone or a bluish black tone of a black image.
  • a warm image tone is said to be a dark black tone with a black image, but in order to allow a more precise quantitative discussion, the International Lighting Commission (CIE) ), Based on the recommended expression.
  • CIE International Lighting Commission
  • the hue of the photothermographic material of the present invention after development is in the range of hue angle hab of 180 degrees, hab, 270 degrees, and more preferably 200. It was found to be hab 270 degrees, most preferably 220 hab 260 degrees. This is disclosed in Japanese Patent Laid-Open No. 2002-6463.
  • u, V * or a *, b * in the CIE 1976 (L * u * v *) color space or (LW) color space near an optical density of 1.0 is a specific numerical value. It is known that a diagnostic image with a favorable visual color tone can be obtained by adjustment, and is described in, for example, Japanese Patent Application Laid-Open No. 2000-29164.
  • the horizontal axis is u * or a * in the CIE 1976 (L uV *) color space or (L * aV) color space.
  • the linear regression line is set to a specific range. By adjusting to, it was found that it has a diagnostic ability equal to or better than that of conventional wet silver salt light-sensitive materials. The preferred range of conditions is described below.
  • the present invention it is directly and indirectly involved in the development reaction process of a reducing agent (developer), silver halide grains, aliphatic carboxylic acid silver and the following toning agent.
  • a reducing agent developer
  • silver halide grains e.g., silver halide grains
  • aliphatic carboxylic acid silver e.g., silver halide grains
  • aliphatic carboxylic acid silver e.g., silver halide grains, aliphatic carboxylic acid silver and the following toning agent.
  • the developed silver shape can be optimized to obtain a preferable color tone. For example, if the developed silver shape is dendritic, it becomes a bluish direction, and if it is a filament shape, it becomes a yellowish direction. That is, the adjustment is made in consideration of the tendency of the developed silver shape.
  • phthalazinone or phthalazine, phthalic acids, and phthalic anhydrides are generally used as toning agents.
  • suitable toning agents are disclosed in RD17029, US Pat. Nos. 4,123,282, 3,994,732, 3,846,136, 4,021,249 and the like.
  • the color tone is adjusted using couplers disclosed in JP-A-11 288057, European Patent 1,134,611A2, etc., and leuco dyes described in detail below. It can also be adjusted. In particular, it is preferable to use a coupler or a leuco dye for fine adjustment of the color tone.
  • the photothermographic material can also be adjusted in color tone using a leuco dye as described above.
  • the leuco dye is preferably heated at a temperature of about 80 to 200 ° C. for about 0.5 to 30 seconds.
  • any leuco dye that forms a pigment by being oxidized by an oxidized form of the above reducing agent or the like which is any colorless or slightly colored compound that is oxidized to a colored form, can be used.
  • Compounds that are pH sensitive and can be oxidized to a colored state are useful.
  • Representative leuco dyes suitable for use in the present invention are not particularly limited.
  • biphenol leuco dyes phenol leuco dyes, indoor-phosphorus leuco dyes, acrylic vinyl leuco dyes, phenoxazine leuco dyes, Nojiazine leuco dye and phenothiazine leuco dye.
  • leuco dyes of various colors singly or in combination of a plurality of types.
  • the use of a highly active reducing agent changes the color tone (especially yellowishness) depending on the amount and ratio of use, or the use of fine-grain silver halide makes the concentration particularly 2.
  • a leuco dye that develops yellow and cyan in combination and adjust the amount of use.
  • the color density is preferably adjusted appropriately in relation to the color tone of the developed silver itself.
  • the color is adjusted so as to have a reflection optical density of 0.01 to 0.05 or a transmission optical density of 0.005 to 0.50, and the color tone is adjusted so that an image in the color tone range is preferable. It is preferable. It is preferable that the sum of the maximum densities at the maximum absorption wavelength of the dye image formed by the leuco dye is 0.01 to 0.50, more preferably 0.02 to 0.30, and particularly preferably 0. It is preferable to develop the color so as to have 03 to 0.10.
  • the photothermographic material can also be adjusted in color tone using a leuco dye as described above.
  • a color image forming agent that increases the absorbance at 360 to 450 nm when oxidized is preferably used as the yellow color-forming leuco dye.
  • These color image forming agents are particularly preferably color image forming agents represented by the following general formula (YA). [0182] [Chemical Formula 17] General formula (YA>
  • R represents a substituted or unsubstituted alkyl group, and R represents a hydrogen atom, substituted or unsubstituted.
  • R 1 and R 2 representing substituted alkyl or acylamino groups are 2-hydroxyphenyl groups.
  • R represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • R 1 represents a substituent that can be substituted on the benzene ring.
  • R represents a substituted or unsubstituted alkyl group, and R represents a substituent other than a hydrogen atom.
  • R represents an alkyl group.
  • the alkyl group is an alkyl group having 1 to 30 carbon atoms.
  • methyl, ethyl, butyl, octyl, i-propyl, t-butynole, t-octyl, t-pentyl, sec-butyl, cyclohexenole, 1-methyl-cyclohexyl and the like are sterically larger than i-propyl.
  • tertiary alkyl groups such as t-butyl, t-octyl, and t-pentyl.
  • substituent that R 1 may have include a halogen atom, an aryl group,
  • Examples thereof include an alkoxy group, an amino group, an acyl group, an acylamino group, an alkylthio group, an arylothio group, a sulfonamide group, an acyloxy group, an oxycarbonyl group, a strong rubamoyl group, a sulfamoyl group, a sulfonyl group, and a phosphoryl group.
  • R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an acyl amino group.
  • the kill group is preferably an alkyl group having 1 to 30 carbon atoms
  • the acylamino group is preferably an acyl group having 1 to 30 carbon atoms.
  • the explanation of the alkyl group is the same as R. Asyl
  • the amino group may be unsubstituted or substituted, and specific examples include an acetylylamino group, an alkoxyacetylylamino group, an aryloxycetylamino group, and the like.
  • R 12 or a hydrogen atom or an unsubstituted alkyl group having 1 to 24 carbon atoms.
  • R and R are 2-hydroxyphenol
  • R represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • alkyl group a substituted or unsubstituted alkyl group.
  • alkyl group having 1 to 30 carbon atoms is the same as that for R.
  • R is preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 24 carbon atoms.
  • R and R examples include methyl, i-propyl, t-butyl and the like.
  • R and R is water
  • R represents a substitutable group on the benzene ring, for example, the substitution in the general formula (RD1)
  • R is preferably a substituted or unsubstituted carbon.
  • alkyl groups are a C1-C30 alkyl group and a C2-C30 oxycarbonyl group, and a C1-C24 alkyl group is more preferable.
  • substituent of the alkyl group include aryl, amino, alkoxy, oxycarbol, acylamino, acyloxy, imide, ureido, aryl, amino, oxycarbonyl and alkoxy. The group is more preferred. These alkyl group substituents may be further substituted with these substituents.
  • Z is —S— or — C (R) (R
  • R 21 21 ′ each represents a hydrogen atom or a substituent.
  • R 1 and R ′ include R 1 in the general formula (RDl).
  • 21 21 ′ is preferably a hydrogen atom or an alkyl group.
  • R 1, R 2, R 'and R' each represent a substituent.
  • the substituent is represented by the general formula (RDl)
  • R 1, R 2, R 'and R' are preferably an alkyl group, a alkenyl group or an alkyl group.
  • 22 23 22 23 ′ is more preferably a tertiary alkyl group such as t-butyl, t-pentyl, t-octyl, 1-methyl-cyclohexyl and the like.
  • R 1 and R 'each represents a hydrogen atom or a substituent, and examples of the substituent include those represented by the general formula (R
  • Examples thereof include the same groups as the substituents exemplified in the description of R 4 in D1).
  • Examples of the compounds represented by the general formulas (YA) and (YB) include compounds II 1 to -40 described in paragraphs "0032" to “0038” of JP-A-2002-169249, Mention may be made of the compounds ITS-1 to ITS-12 described in paragraph "0026" of European Patent 1,211,093.
  • the addition amount of the compound of general formula (YA) (including the compound of hindered dorfolhi compound and the compound of general formula (YB)) is usually 0.0001 to 0.01 mol per mol of silver, preferably Is from 0.0005 to 0.01 mol, more preferably ⁇ 0.001 to 0.008 mol.
  • the molar ratio of the addition ratio of the yellow color-forming leuco dye to the total of the reducing agents is preferably 0.001 to 0.2. More preferred.
  • the photothermographic material of the present invention can also be adjusted in color tone using a cyan color-forming leuco dye in addition to the yellow color-forming leuco dye.
  • the cyan chromophoric leuco dye is preferably any colorless or slightly colored compound that oxidizes into a colored form when heated at a temperature of about 80-200 ° C for about 0.5-30 seconds. Any leuco dye that forms a pigment by oxidation with an oxidant of a reducing agent can be used. Compounds that are pH sensitive and can be oxidized to a colored state are useful.
  • a color image forming agent that increases the absorbance at 600 to 700 nm when oxidized is preferably used as the cyan color-forming leuco dye.
  • these compounds for example, Japanese Patent Application Laid-Open No. 59-206831 (particularly compounds having ⁇ max in the range of 600 to 700 nm), Compounds of general formulas (I) to (IV) of JP-A-5-204087 (specifically, compounds of (1) to (18) described in paragraphs “0032” to “0037”) and JP-A-11-231460 And compounds of the general formulas 4 to 7 (specifically, compounds No. 1 to No. 79 described in the paragraph “0105”)
  • the cyan color-forming leuco dye preferably used in the present invention is a compound represented by the following general formula (CLA) or general formula (CLB-I).
  • CLA general formula
  • CLB-I general formula
  • the color image forming agent represented by the general formula (CLB-I) is particularly preferable in that it can adjust the color tone even when added in a small amount due to its high coloring efficiency and is excellent in image storage stability.
  • R 1 and R 2 are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkyl,
  • Kenyl group, alkoxy group, NHCOR group (R is an alkyl group, aryl group, heterocyclic group
  • R 1 and R 2 are connected to each other to form an aliphatic hydrocarbon ring or aromatic carbon
  • A is a group that forms a hydrogen ring or a heterocyclic ring.
  • A is — NHCO group, —CONH group or
  • R is a substituted or unsubstituted alkyl group, aryl group or
  • -A R may be a hydrogen atom.
  • the —A R moiety represents a hydrogen atom
  • A represents one NHCO group, CONH group or one NHCONH group, and R
  • 3 33 represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group.
  • W is a hydrogen atom or —CONHR group, —COOR group or —COOR group (R is substituted or
  • 35 35 represents an unsubstituted alkyl group, aryl group or heterocyclic group.
  • Halogen atom substituted or unsubstituted alkyl group, alkenyl group, alkoxy group, force Rubamoyl group or -tolyl group is represented.
  • R is CONHR, —COR or CO
  • OR group (R represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group.)
  • X represents a substituted or unsubstituted aryl group or heterocyclic group.
  • examples of the halogen atom represented by R 1 and R 2 include fluorine atom
  • the alkyl group includes alkyl groups having up to 20 carbon atoms (methyl group, ethyl, butyl, dodecyl, etc.), and the alkyl group includes carbon atoms. Up to 20 alkenyl groups (bule, allyl, butyl, hexyl, hexagenole, etheninore 2 propenole, 3 butenore, 1-methylolene 3 propenyl, 3 pentale, 1-methyl-3 butyr, etc.) Examples of the alkoxy group include alkoxy groups having up to 20 carbon atoms (methoxy, ethoxy, etc.).
  • the alkyl group represented by R in the NHC OR group is an alkyl group having up to 20 carbon atoms.
  • aryl groups include phenyl and naphthyl.
  • Groups having 6 to 20 carbon atoms such as ruthenium, and examples of the heterocyclic group include chenyl, furyl, imidazolyl, pyrazolyl, pyrrolyl and the like.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, such as phenol.
  • heterocyclic groups include, for example, chael, furyl, imidazolyl, pyrazolyl, pyrrolyl and the like.
  • the alkyl group is preferably an alkyl group having up to 20 carbon atoms, and examples thereof include methyl, ethyl, butyl, dodecyl and the like, and the aryl group preferably has from 6 to 20 carbon atoms.
  • Examples of the aryl group include phenyl and naphthyl, and examples of the heterocyclic group include chenyl, furyl, imidazolyl, pyrazolyl and pyrrolyl.
  • halogen atom represented by R examples include fluorine, chlorine, bromine, iodine and the like.
  • alkyl group examples include chain or cyclic alkyl groups such as methyl, butyl, dodecyl, cyclohexyl and the like
  • alkenyl group examples include alkenyl groups having up to 20 carbon atoms (bulu, allyl, butyr, Hexane, Hexagel, Etul 2 Lopeninole, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl-3-butenyl, etc.)
  • alkoxy groups examples include methoxy, butoxy, tetradecyloxy, Examples thereof include jetyl carbamoyl, phenol carbamoyl and the like.
  • a nitrile group is also preferred. Among these, a hydrogen atom and an alkyl group are more preferable.
  • R 1 and R 2 may be linked to each other to form a ring structure.
  • the above groups are further single
  • Typical substituents include halogen atoms (fluorine, chlorine, bromine, etc.), alkyl groups (methyl, ethyl, propyl, butyl, dodecyl, etc.), hydroxyl groups, cyano groups, nitro groups, alkoxy groups (methoxy, ethoxy).
  • alkylsulfonamide groups (methylsulfonamide, octylsulfonamide, etc.), arylsulfonamides (phenylsulfonamide, naphthylsulfonamide groups, etc.), alkylsulfamoyl groups (ptylsulfamoyl etc.), arylsulfa Moyl (phenylsulfamoyl, etc.), alkyloxycarbonyl group (methoxymethoxy, etc.), aryloxycarboro group (phenoloxycarbol, etc.), aminosulfonamide group, acylamino group, carbon Vamoyl, sulfol, sulfiel, sulfoxy, sulfo, Ruoki sheet group, alkoxy group, alkyl carboxymethyl - group, Arirukarubo - group, Aminokarubo - group, and the like.
  • R or R is preferably a phenol group, more preferably a halogen atom or cyan.
  • a full group having a plurality of groups as substituents having a plurality of groups as substituents.
  • the alkyl group having 36 to 37 37 37 is preferably an alkyl group having up to 20 carbon atoms, and examples thereof include methyl, ethyl, butyl, dodecyl and the like.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms. Examples thereof include phenol, naphthyl and the like, and examples of the heterocyclic group include chenyl, furyl, imidazolyl, pyrazolyl, pyrrolyl and the like.
  • Examples of the substituent that the group represented by R can have include R 1 to R 5 in the general formula (CLA).
  • the aryl group represented by X has 6 to 20 carbon atoms such as phenol and naphthyl.
  • heterocyclic groups include, for example, chenyl, furyl, imidazolyl, and pyridine. Examples include lazolyl and pyrrolyl. As a substituent that the group represented by X can have
  • These groups may include photographically useful groups.
  • CLA cyan color-forming leuco dye
  • the compound represented by the general formula (CLB-I) is preferably a compound represented by the following general formula (CLB-II) or (CLB-III), and most preferably a compound represented by (CLB-III). Masle.
  • R 1, R 2, R 3 and R 4 are each a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group
  • R is a hydrogen atom, aliphatic group, aromatic group, acyl group, alkoxycarbon
  • R 1, R 2, R 3 and R 4 include an alkyl group, an alkyl group,
  • hydrocarbon groups such as a nyl group and an alkynyl group. These hydrocarbon groups preferably have 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms.
  • alkyl group having 1 to 25 carbon atoms include methyl, ethyl, propyl, i-propyl, t-butyl, pentyl, hexyl, cyclohexyl, etc.
  • examples of the cycloalkyl group include cyclohexyl, cyclopentyl group, etc.
  • aromatic group represented by R 1, R 2, R 3 and R 4 include an aryl group (phenol).
  • heterocyclic groups pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazyl, pyrimidinyl, pyridazyl, selenazolyl, sriphoral, piperidinyl, pyrazolyl, tetrazolyl, etc.).
  • alkoxy group examples include methoxy, ethoxy, i-propoxy group, t-butoxy group.
  • Specific examples of the isotropic aryloxy group include phenoxy and naphthyloxy isosyl.
  • acyl amino group acetylamino-containing benzoylamino and the like, and specific examples of the sulfonamide group include methanesulfonamide, butanesulfonamide, octanesulfonamide, Benzenesulfonamide, etc.
  • the halogen atom is chlorine, bromine or iodine.
  • R 1 and R 2 are preferably aliphatic groups, alkoxy groups, aryloxy groups, and more preferably.
  • an alkyl group or an alkoxy group more preferably a secondary or tertiary alkyl group or an alkoxy group.
  • R 1 and R 2 are preferably a hydrogen atom, an aliphatic group, more preferably a hydrogen atom.
  • Examples of the aliphatic group, aromatic group, alkoxy group, and aryloxy group represented by R include
  • acyl group represented by R include acetyl, propionyl, butanol, and
  • alkoxycarbonyl group represented by R include a methoxycarbonyl group
  • Examples thereof include a toxicarbol group and a t-butoxycarbonyl group.
  • arylcarbonyl group represented by R include phenoxycarboro.
  • Examples of the powerful rubamoyl group include amino carbonate, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, phenylaminocarbonyl, and the like. , 2-pyridylamino force, and the like.
  • Examples of the sulfamoyl group include methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl.
  • Examples of the sulfol group include methylsulfonyl, butylsulfol, and octylsulfo- And the like.
  • R is preferably a hydrogen atom, an alkyl group, or an acyl group, more preferably a hydrogen atom or carbon.
  • substitutable group on the benzene ring represented by X and X include 1 carbon atom. ⁇ 25 alkyl groups (methyl, ethyl, propyl, isopropyl, t-butyl, pentyl, hexylcyclohexyl, etc.), cycloalkyl groups (cyclohexyl, cyclopentyl, etc.), alkenyl groups (bulu, allyl, butenyl, hexyl) Kiseru, Hexager, Etul
  • alkyl groups such as etul, propargyl
  • glycidyl groups such as etul, propargyl
  • glycidyl groups such as etul, propargyl
  • metatalylate groups such as etul, propargyl
  • Aryl groups such as phenol and naphthyl
  • heterocyclic groups such as pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrajur, pyrimidinyl, pyridazyl, selenazolyl, sriphoral, piperidyl, pyrazolyl, tetrazolyl Etc.
  • halogen atoms chlorine, bromine, iodine, fluorine, etc.
  • alkoxy groups methoxy, ethoxy, propyloxy, pentyloxy, cyclopentyloxy, hexyloxy, cycl
  • Borol pentylaminocarbol, cyclohexylaminocarbole, phenylaminocarbole, 2-pyridylaminocarbol, etc.), amide group (acetamido, propionamido, butanamido, hexaneamido, benzamido) ), Sulfo group (methylsulfol, ethinolesnorehoninore, butinolesnorehoninore, cyclohexenoresnorehoninore, pheninolesnorehoninole, 2-pyridylsulfol, etc.), sulfone Amide group (methylsulfonamide, octylsulfonamide, phenylsulfonamide, naphthylsulfonamide, etc.), amino group (amiethyl ester) Dimethylamino-containing butylamino, cyclopenty
  • X and X are preferably an alkoxy group, an aryloxy group, a strong rubamoyl group, an amide
  • R 1, R 2 and R 3 have the same meanings as R 1, R 2 and R in the above general formula (CLB—I), respectively.
  • 41 42 43 41 42 43 X and X are each an aliphatic group, aromatic group, amino group, alkoxy group or arylo group.
  • silyl group examples include an aliphatic group, an aromatic group represented by X and X in the general formula (CLB—I),
  • 43 is preferably an alkoxy group, an aryloxy group or an amino group, more preferably
  • R 1, R 2, R 3 and R 4 each represent a hydrogen atom or an alkyl group.
  • R 1, R 2, R and R are preferably an alkyl group having 1 to 10 carbon atoms, more preferably
  • the compounds represented by the general formulas (CLB-I) to (CLB-III) can be easily synthesized by a conventionally known method such as the method described in JP-B-7-45477.
  • the power of the present invention is not limited to these examples showing specific examples of leuco dyes represented by the general formulas (CLB-I) to (CLB-III).
  • the amount of the cyan chromophoric leuco dye added is usually from 0.0001 to 0.05 mole per mole of silver, preferably 0.005 to 0.02 monolayer, more preferably 0.00. 001 ⁇ 0.01 Mono.
  • the ratio of the added amount of cyan chromogenic leuco dye to the total of the reducing agents is 0.001 to 0.2 force girls, and 0.005 to 0.1 force girls.
  • the photothermographic material of the present invention has a maximum absorption of a dye image formed with a cyan leuco dye. It is preferable to set the sum of the maximum densities at the collection wavelength to be 0.01-0.50, more preferably 0.02-0.30, particularly preferably 0.03-0.10. Rikishi.
  • a subtle color tone can be adjusted by using a magenta chromogenic leuco dye or a yellow chromogenic leuco dye in combination with the cyan chromogenic leuco dye.
  • the yellow color-forming leuco dye and the cyan color-forming leuco dye represented by the general formulas (YA) and (YB) may be added by a reducing agent addition method represented by the general formula (1). It can be added by the same method, and it can be added to the coating solution by any method such as solution form, emulsified dispersion form, solid fine particle dispersion form, etc.
  • the reducing agent of the general formula (1), the yellow coloring leuco dye and the cyan coloring leuco dye of the general formula (YA), (YB) are contained in a photosensitive layer containing an aliphatic carboxylic acid silver salt. Although it is preferable that one is contained in the photosensitive layer and the other may be contained in the non-photosensitive layer adjacent to the photosensitive layer, or both may be contained in the non-photosensitive layer. If the photosensitive layer is composed of a plurality of layers, each layer may be contained in a separate layer.
  • the photosensitive layer or the non-photosensitive layer according to the present invention may contain a silver saving agent.
  • a silver saving agent refers to a compound that can reduce the amount of silver necessary to obtain a certain silver image density.
  • the covering power of developed silver means the optical density per unit amount of silver.
  • This silver saving agent can be present in the photosensitive layer, the non-photosensitive layer, or any of them.
  • Preferred examples of the silver saving agent include hydrazine derivative compounds, vinyl compounds, phenol derivatives, naphthol derivatives, quaternary onium compounds, and silane compounds. Specific examples include silver saving agents disclosed in paragraphs “0195” to “0235” of JP-A-2003-270755.
  • silver saving agent As the silver saving agent according to the present invention, particularly preferred silver saving agents are compounds represented by the following general formulas (SE1) and (SE2). [0259] General formula (SE1)
  • Q is an aromatic group bonded to NHNH Q at the carbon atom site, or a heterocycle
  • Q represents a strong rubamoyl group, an acyl group, an alkoxy carbo group, an aryl group.
  • a bonyl group, a sulfonyl group, or a sulfamoyl group is represented.
  • R represents an alkyl group, an acyl group, an acylamine group, a sulfonamide group, an alkoxy group, a carbonyl group, or a group of rubamoyl groups.
  • R 12 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylothio group, an acyloxy group, or a carbonate group.
  • R 13 and R 14 each represent a group that can be substituted on the benzene ring.
  • R 13 and R 14 may be linked to each other to form a condensed ring.
  • the condensed ring when R 13 and R "are connected to each other to form a condensed ring, the condensed ring is particularly preferably a naphthalene ring.
  • the general formula (SE2) is a naphthol-based compound.
  • R 11 is preferably a strong rubamoyl group, particularly preferably a benzoyl group
  • R 12 is particularly preferably an alkoxy group, preferably an alkoxy group or an aryloxy group. Better!/,.
  • the photothermographic material of the present invention preferably contains a thermal solvent.
  • the thermal solvent is defined as a material capable of lowering the heat development temperature by 1 ° C. or more compared to a heat-developable photosensitive material containing no heat solvent. More preferred are materials that can lower the heat development temperature by 2 ° C or more, and particularly preferred are materials that can lower the temperature by 3 ° C or more.
  • a photothermographic material A containing a thermal solvent is different from a photothermographic material A containing a thermal solvent.
  • the photothermographic material containing B is a photothermographic material
  • the photothermographic material is exposed to the photothermographic material B and processed at a heat developing temperature of 120 ° C and a heat developing time of 20 seconds.
  • a heat solvent is used when the heat development temperature for A with the same exposure and heat development time is 119 ° C or less.
  • the thermal solvent has a polar group as a substituent and is preferably represented by the general formula (TS), but is not limited thereto.
  • Y represents an alkyl group, an alkyl group, an alkyl group, an aryl group or a heterocyclic group.
  • Z is a hydroxyl group, carboxy group, amino group, amide group, sulfonamide group, phosphoric acid amide group, cyano group, imide, ureido, sulfoxide, sulfone, phosphine, phosphinoxide or nitrogen-containing heterocyclic group.
  • n represents an integer of 1 to 3, which is 1 when Z is a monovalent group, and is the same as the valence of Z when Z is a divalent or higher group. When n is 2 or more, multiple Ys may be the same or different.
  • Y may further have a substituent, and may have a group represented by Z as a substituent. Y will be described in more detail.
  • Y is a linear, branched or cyclic alkyl group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 25 carbon atoms such as methyl, ethyl, n -Propyl, iso-propyl, sec-butyl, t-butyl, t-octyl, n-amyl, t-amyl, n-dodecyl, n-tridecyl, octadecyl, icosyl, docosyl, cyclopentyl, cyclohexyl, etc.
  • An alkenyl group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 25 carbon atoms such as vinyl, aryl, 2-butyl, and 3-pentale).
  • Aryl groups preferably having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 25 carbon atoms such as phenol, p-methylphenol, and naphthyl).
  • Heterocyclic group Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms such as pyridyl, virazil, imidazolyl and pyrrolidyl).
  • substituents may be further substituted with other substituents. These substituents may be bonded to each other to form a ring.
  • substituent which Y may further have a substituent include the substituent described in "0015" of JP-A-2004-21068.
  • the reason why development activity is achieved by using a hot solvent is that the hot solvent melts near the development temperature, so that it is compatible with the substances involved in the development, and the temperature is lower than when no thermal solvent is added. This is thought to be possible in order to make the reaction possible.
  • Thermal development is a reduction reaction involving a highly polar carboxylic acid or silver ion transporter, so it has a polar group! / Is preferred to form ⁇ .
  • the thermal solvent preferably used in the present invention has a melting point of 50 ° C or higher and 200 ° C or lower, more preferably 60 ° C or higher and 150 ° C or lower.
  • a thermal solvent having a melting point of 100 ° C. or higher and 150 ° C. or lower is preferable.
  • thermal solvent examples include compounds described in "0017” of JP-A-2004-21068, compounds described in "0027” of US Published Patent No. US2002Z0025498, MF-1 to MF-3 MF6, MF-7, MF-9 to MF-12, MF-15 to MF-22.
  • thermo solvent in the present invention is 0. 01 ⁇ 5.
  • Og / m 2 is preferred instrument than good Mashiku be the 0.1 05-2 at. 5g / m 2, more preferably Is between 0.1 and 1.5 g / m 2 .
  • the thermal solvent is preferably contained in the photosensitive layer.
  • the said thermal solvent may be used independently, you may use it in combination of 2 or more type.
  • the thermal solvent may be contained in the coating solution by any method such as a solution form, an emulsion dispersion form, or a solid fine particle dispersion form, and may be contained in the photosensitive material.
  • an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or jetyl phthalate, or a co-solvent such as ethyl acetate or cyclohexanone is used. And a method of mechanically preparing an emulsified dispersion.
  • a powder of a hot solvent is dispersed in an appropriate solvent such as water by a ball mill, a colloid mill, a vibrating ball mill, a sand mill, a jet mill, a roller mill or ultrasonic waves, and solid dispersion is performed.
  • an appropriate solvent such as water by a ball mill, a colloid mill, a vibrating ball mill, a sand mill, a jet mill, a roller mill or ultrasonic waves, and solid dispersion is performed.
  • protection Colloids for example, polyvinyl alcohol
  • surfactants for example, surfactants such as sodium triisopropylnaphthalene sulfonate (a mixture of three isopropyl groups having different substitution positions)
  • surfactants for example, surfactants such as sodium triisopropylnaphthalene sulfonate (a mixture of three isopropyl groups having different substitution positions
  • beads such as zirconium are usually used as a dispersion medium, and Zr and the like eluted from these beads may be mixed in the dispersion. Although it depends on the dispersion conditions, it is usually in the range of lppm to 1000ppm. If the Zr content in the photosensitive material (photothermographic material) is 0.5 mg or less per lg of silver, there is no practical problem.
  • the aqueous dispersion preferably contains a preservative (eg, benzoisothiazolinone sodium salt).
  • an anti-capri agent for preventing the occurrence of force preserving during storage before heat development, and an image stabilization for preventing image deterioration after heat development. It is preferable to contain an agent.
  • an anti-capri and image stabilizer that can be used in the present invention will be described.
  • reducing agents having protons such as bisphenols and sulfonamidophenols are mainly used as reducing agents, these hydrogens are stabilized and the reducing agents are deactivated.
  • a compound capable of preventing and preventing the reaction of reducing silver ions is contained.
  • a compound capable of acid bleaching tanned metallic silver (silver cluster) is contained.
  • compounds having these functions for example, biimidazolyl compounds, ododonium compounds and halogen atoms described in paragraphs “0096” to “0128” of JP-A-2003-270755 are released as active species. List possible compounds.
  • Preferable specific examples include sulfone and Z or j8-halosulfone, and various capri prevention and image stabilizers such as vinyl type inhibitors having an electron withdrawing group described in JP-A-2005-107496.
  • the reducing agent used in the present invention has an aromatic hydroxyl group (-OH), particularly in the case of bisphenols, it has a group capable of forming a hydrogen bond with these groups. It is preferable to use a non-reducing compound in combination.
  • particularly preferred hydrogen bonding compounds in the present invention include, for example, paragraphs “0061” to “0” of JP-A-2002-90937.
  • the amount of these compounds added is preferably within a range in which the increase in printout silver due to the formation of halogenated silver due to the reaction of halogen released from the compound with silver ions does not become a problem.
  • Specific examples of compounds that generate these active halogen atoms include compounds (III-1) to (III) described in paragraphs “0086” to “0087” of JP-A-2002-169249 in addition to the above-mentioned patents.
  • Examples of the capri inhibitor preferably used in the present invention include compound examples a to j described in paragraph "0012" of JP-A-8-314059, and paragraph "0028" of JP-A-7-209797.
  • compounds of vinyl sulfones and Z or ⁇ -halosulfones compounds described in paragraph “0013” of JP-A-6-208192, VS—1 to VS-7, compound HS—1 to HS-5, sulfo-benzotriazole Compound KS-1 to KS-8 as described in JP-A-2000-330235,
  • the photothermographic material may contain various compounds conventionally known as anti-capriformants, but has the same reaction activity as the above compounds. Even if it is a compound which can produce
  • antifoggants include compounds disclosed in US Pat. No. 5,028,523 and European Patents 600,587, 605,981, and 631,176.
  • a fluorine-based surfactant represented by the following general formula (SF) is used in order to improve film transportability and environmental suitability (accumulation in a living body) in a laser imager (heat development processing apparatus). Is preferably used.
  • Rf represents a substituent containing a fluorine atom
  • Lf represents a divalent linking group having no fluorine atom
  • Yf represents a (pi + ql) -valent linking group having no fluorine atom
  • Af represents a cation group or a salt thereof
  • nl and ml each represents an integer of 0 or 1
  • pi represents an integer of 1 to 3
  • ql represents an integer of 1 to 3.
  • ql is 1, nl and ml are not 0 at the same time.
  • examples of the substituent containing a fluorine atom represented by Rf include a fluorinated alkyl group having 1 to 25 carbon atoms (trifluoromethyl, trifluoroethyl, perfluoroethyl, fluorobutinole, perfluorooctinole. Perfluorododecinole and perfluorooctadecyl) or a fluorinated group (perfluoroprobe, perfluorobutur, perfluoronone and perfluorododecyl, etc.).
  • Rf preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • Rf is 2-12 fluorine atoms
  • the number of fluorine atoms is 3-12.
  • Divalent linking groups having no fluorine atom represented by Lf include, for example, alkylene groups (methylene, ethylene, butylene, etc.), alkyleneoxy groups (methyleneoxy, ethyleneoxy, butyleneoxy, etc.), oxyalkylenes, etc. Group (oxymethylene, oxyethylene, oxybutylene, etc.), oxyalkyleneoxy group (oxymethyleneoxy, oxyethyleneoxy, oxyethyleneoxyethyleneoxy, etc.), phenylene group, oxyphenylene group , A phenyl group, an oxyphenyl group, or a group obtained by combining these groups.
  • Af represents the power of a cation group or a salt thereof, for example, a carboxyl group or a salt thereof (a sodium salt, a potassium salt and a lithium salt), a sulfo group or a salt thereof (a sodium salt, a potassium salt and a lithium salt), sulfuric acid And a non-festel group or a salt thereof (sodium salt, potassium salt and lithium salt), a phosphoric acid group or a salt thereof such as thorium salt and potassium salt thereof, and the like.
  • Examples of the (pi + ql) -valent linking group having no fluorine atom represented by Y include, for example, a trivalent or tetravalent linking group having no fluorine atom and a nitrogen or carbon atom as the center.
  • a group of atoms. nl represents an integer of 0 or 1, and is preferably 1.
  • the fluorine-based surfactant represented by the general formula (SF) is an alkyl compound having 1 to 25 carbon atoms into which a fluorine atom is introduced (trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorooctyl and perfluorooctyl).
  • the compound obtained by addition reaction or condensation reaction with 3 to 4 aromatic compounds or hetero compounds (partially Rf-modified alkanol compounds) is further added to, for example, sulfate ester compounds. It can be obtained by introducing a cation group (Af) by means such as ⁇ .
  • Examples of the tri- to hexavalent alkanol compound include glycerin, pentaerythritol, 2-methyl-2-hydroxymethyl 1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentene, 1, 2, 6-hexanetriol, 1, 1, 1-tris (hydroxymethyl) propane, 2,2-bis (butanol) -3, aliphatic triol, tetramethylolmethane, D-sorbitol, xylitol, D-man -Tall and so on.
  • aromatic compounds and hetero compounds having 3 to 4 sil groups include 1,3 5-trihydroxybenzene (fluorodalcine) and 2 4 6-trihydroxypyridine.
  • the fluorine-based surfactant represented by the general formula (SF) can be added according to a known addition method. That is, it can be dissolved in an alcohol such as methanol or ethanol, a ketone such as methyl ethyl ketone or acetone, or a polar solvent such as dimethylsulfoxide or dimethylformamide.
  • fine particles of 1 m or less can be added by dispersing in water or an organic solvent by sand mill dispersion, jet mill dispersion, ultrasonic dispersion or homogenizer dispersion. Regarding the fine particle dispersion technique, many techniques have been disclosed.
  • the fluorine-based surfactant represented by the general formula (SF) is preferably added to the outermost protective layer.
  • the addition amount of the fluorine-based surfactant represented by the general formula (SF) is lm 2 per 1 X 10- 8 ⁇ 1 X 1 0 1 mole preferably tool 1 X 10- 5 1 X 10- mol are particularly preferred. If the range is less than the former range, the charging characteristics may not be obtained. If the range exceeds the former range, humidity dependence is high, and the storage stability under high humidity may deteriorate.
  • the photothermographic material is used in the manufacturing process such as coating, drying, processing, etc., when the photosensitive material is scraped, turned over, brought into contact with various devices during transportation, or between the photosensitive surface and the backing surface.
  • the contact between photosensitive materials is often undesirably affected.
  • the surface of the photosensitive material may be scratched or slipped, or the photosensitive material may be transported in a developing device or the like.
  • the photothermographic material in order to prevent scratches on the surface and deterioration in transportability, any one of the constituent layers of the material, particularly on the support. It is preferable that the outermost layer contains a lubricant, a matting agent or the like to adjust the surface physical properties of the photosensitive material.
  • the outermost layer on the support contains organic solid lubricant particles having an average diameter of l30 / zm, and these organic solid lubricant particles are dispersed by a polymer dispersant. This is what it is.
  • the melting point of the lubricant particles is preferably higher than the heat development processing temperature, preferably 80 ° C or higher, more preferably 110 ° C or higher.
  • organic solid lubricant particles used in the present invention compounds that lower the surface energy are preferred.
  • polyethylene, polypropylene, polytetrafluoroethylene, and copolymers thereof are pulverized. Examples thereof include formed particles.
  • organic solid lubricant particles having polyethylene and polypropylene power include polytetrafluoroethylene, polypropylene / polyethylene copolymer, polyethylene (low density), polyethylene (high density), and polypropylene.
  • the organic solid lubricant particles are preferably a compound represented by the following general formula (SC1) or general formula (SC2).
  • each R R represents a C 6 60 substituted or unsubstituted alkyl group
  • X and X each contain a nitrogen atom
  • L is a substituted or unsubstituted p2 + q2 valent alkyl group, alkyl-
  • R group aralkyl group or aryl group.
  • M represents a Z-valent metal ion.
  • the total number of carbon atoms is not particularly limited, but generally 20 or more is preferable, and 30 or more is more preferable. Definition of R and R
  • Examples of the substituent that the alkyl group, alkenyl group, aralkyl group or aryl group in SCI SC2 may have include a halogen atom, a hydroxyl group, a cyan group, an alkoxy group, an aryloxy group, an alkylthio group, Aryloyl group, alkoxycarbol group, aryloxycarbol group, amino group, acylamino group, sulfo-lumino group, ureido group, force rubermoyl group, sulfamoyl group, isacyl group, sulfol group, sulfiel group, aryl group And an alkyl group.
  • These groups may further have a substituent, and preferred substituents include a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an alkoxycarbo group, an acylamine group, a sulfo-amino group, an acyl group, and the like. And an alkyl group.
  • a halogen atom a fluorine atom and a chlorine atom are preferable.
  • the alkyl component in the alkoxy group, the alkylthio group, and the alkoxycarbonyl group is the same as the alkyl group of R 1 described later.
  • the amino group of the acylamino group and sulfo-lumino group is the same as the alkyl group of R 1 described later.
  • the group may be an N-substituted amino group, and the substituent is preferably an alkyl group.
  • the groups bonded to the acyl group, the carbo group of the acyl group, and the sulfo group of the sulfoamino group are an alkyl group and an aryl group, and the above alkyl groups are preferable.
  • R 1 and R 2 have 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 10 carbon atoms.
  • alkyl groups alkenyl groups, aralkyl groups, or aralkyl groups
  • these alkyl groups, alkenyl groups, and aralkyl groups may be linear, branched, or containing a cyclic structure. A mixture of these may be used.
  • RSCl SC2 includes octyl, t-octyl, dodecyl, tetradecyl, hexadecyl, 2-hexyldecyl, octadecyl, C H (n is 20 to 60), eicosyl, docosal, melicyl.
  • Divalent linking groups X and X containing a nitrogen atom are preferably CON (R) —, —N (R
  • R to R are each a hydrogen atom or a substitution
  • L represents a substituted or unsubstituted p + q-valent alkyl group, alkenyl group, aralkyl group,
  • carbon number of these hydrocarbon groups is not specifically limited, Preferably it is 1-60, More preferably, it is 1-40, More preferably, it is 10-40.
  • p2 + q2 valent hydrocarbon in p2 + q2 valent hydrocarbon group means that p2 + q2 hydrogen atoms in the hydrocarbon are removed and p 2 X — groups and q2 X groups are bonded Indicates to do.
  • p2 and q2 are integers from 0 to 6
  • the compound represented by the general formula (SC1) may be a synthetic product or a natural product. Even if it is a natural product or a synthetic product, synthetic compounds made from higher fatty acids and alcohols of natural products, including those with different carbon numbers, straight-chain and branched compounds, and the ability to form a mixture of these compounds It's okay to use a mixture! / ⁇ . From the viewpoint of the quality stability of the composition, a synthetic product is preferred.
  • the organic solid lubricant is preferably used in a state of being dispersed in advance in the coating solution.
  • organic solid lubricants are slippery on the surface, so the affinity of water and organic solvents is often not sufficiently high. Aggregation or sedimentation may occur. Aggregation or sedimentation in the coating solution is undesirable because it causes coating failure when processed into a film.
  • Methods for improving the stability of the dispersion include a method of modifying the surface and using an electrostatic effect, and a method of using the effect of steric hindrance using a surface adsorbing layer by a polymer dispersant.
  • the former is a general dispersion stabilization method.
  • the use of the photothermographic material is likely to affect the other performance of the surface modifier itself, and it is effective for both aqueous and non-aqueous methods. The latter method, which is easy to express, is preferred.
  • a binder used in the photosensitive material can be used. Specifically, polybutyl butyral, polyvinyl acetal, poly vinyleno cornole, senorelose acetate butyrate, senorelose acetate propionate and the like can be used.
  • the amount of the polymer dispersant is preferably used in the range of 1 to 200% by mass with respect to the organic solid lubricant particles to be dispersed.
  • the dispersion method is not particularly limited, but a resolver set, an ultrasonic method, a pressure method, or the like can be used, and it is preferable to perform the dispersion treatment with a dispersion device with a cooling device so as not to generate heat.
  • the average particle size of the organic solid lubricant particles refers to the average particle size after dispersion by the following method.
  • a dispersion liquid containing lubricant particles is diluted, dropped onto a grid with a strong support film, and dried, and then a transmission electron microscope (manufactured by Nippon Denshi Co., Ltd.) is used. : 2000FX type, etc.), directly after taking a photo at 5000x magnification, the scanner captures the negative as a digital image, and using an appropriate image processing software, each particle size (equivalent circle diameter) is 300 The average particle size can be obtained from the arithmetic average measured as described above.
  • At least one layer on the support contains the compound represented by the general formula (SC), and a nonionic fluorine-containing surfactant and an anionic fluorine-containing interface.
  • U which preferably contains an activator.
  • the nonionic fluorine-containing surfactant that can be used is not particularly limited, but a compound represented by the following formula (AIF) is preferred.
  • AO represents a divalent group having at least one alkyleneoxy group
  • n3 represents an integer of 1 to 30
  • the fluorine-containing aliphatic group represented by Rf and Rf includes linear, branched and cyclic groups, or
  • fluorine-containing aliphatic groups include fluoroalkyl groups having 1 to 20 carbon atoms (—C F, 1 C F, etc.), sulfofluoroalkyl groups (C F SO—, C F SO—, etc.), C
  • R is a hydrogen atom, alkyl group having 1 to 20 carbon atoms,
  • Coxyl group, alkyl carboxyl group or aryl group, and R each have 1 to 20 carbon atoms.
  • AO is a group having an alkyleneoxy group such as ethyleneoxy, propyleneoxy, i-propyleneoxy and the like, and may have a substituent such as an amino group at the terminal.
  • n is preferably an integer of 5 to 15.
  • nonionic fluorine-containing surfactants represented by the general formula (AIF) are CF (CH CH O) CF, CF (CH CH O) CF, CF CH CH (OH) CH (CH CH O) CH CH (OH) CH CF, CF (CH CH O) CF, CF (CH C
  • the present invention is not limited to these.
  • ionic fluorine-containing surfactant FA
  • specific compounds are shown below, but the present invention is not limited thereto.
  • S0 3 Na is 4th or 5th or a mixture of them
  • the amount of each fluorine-containing surfactant used is generally from 0.01 to lm 2 of photosensitive material: Lg is preferred, and 10 to 500 mg is preferred! / ⁇ . More preferably, it is 50 to 300 mg.
  • fluorine-containing surfactants include ionic fluorine-based surfactants described in JP-A-60-244945, JP-A-63-306437, and JP-A-1-24245; Fluorosurfactants used in combination with cation cation as described in 197, 068, 5-204115, etc. can be used.
  • a filter layer is formed on the same side as or opposite to the photosensitive layer in order to control the amount of light transmitted through the photosensitive layer or the wavelength distribution. It is preferable to contain a dye or a pigment. As the dye used, known compounds that absorb light in various wavelength regions can be used depending on the color sensitivity of the photosensitive material.
  • a squarylium dye having a thiopyrylium nucleus as disclosed in JP-A-2001-83655 (this specification)
  • a thiopyrylium squarium dye a squarylium dye having a pyrylium nucleus
  • Support materials used for photothermographic materials include various polymer materials, glass, wool cloth, cotton cloth, paper, metal (aluminum, etc.), etc. What can be processed into a certain sheet or roll is suitable. Accordingly, the support in the photothermographic material of the present invention includes cellulose acetate film, polyester film, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polyamide film, polyimide film, cellulose triacetate film (TAC). ) Or a plastic film such as a polycarbonate (PC) film is preferred, and a biaxially stretched PET film is particularly preferred.
  • the thickness of the support is about 50 to 300 ⁇ m, preferably 70 to 180 ⁇ m.
  • a metal oxide and a conductive compound such as z or a conductive polymer can be included in the constituent layers. These may be contained in any layer, but are preferably contained in the backing layer or the surface protective layer on the photosensitive layer side, the undercoat layer, and the like.
  • the conductive compounds described in columns 14 to 20 of US Pat. No. 5,244,773 are preferably used.
  • the surface protective layer on the backing layer side contains a conductive metal oxide.
  • the conductive metal oxide is a crystalline metal oxide particle that contains oxygen defects and a small amount of foreign atoms that form donors with respect to the metal oxide used.
  • metal oxides include ZnO, TiO, SnO, AlO, InO, SiO, MgO, BaO, MoO, VO, etc.
  • ZnO, TiO and SnO are preferred.
  • heteroatoms include heteroatoms
  • the metal oxide fine particles used in the present invention have electrical conductivity, and the volume resistivity thereof is 10 7 ⁇ 'cm or less, particularly 10 5 ⁇ 'cm or less. These acid compounds are described in JP-A Nos. 56-143431, 56-120519, 58-62647 and the like. Furthermore, using a conductive material in which the above metal oxide is attached to other crystalline metal oxide particles or fibrous materials (such as titanium oxide) as described in JP-B-59-6235. Also good.
  • the particle size that can be used is preferably 1 ⁇ m or less, but if it is 0.5 m or less, the stability after dispersion is good and it is easy to use. In order to make the light scattering property as small as possible, it is very preferable to use conductive particles of less than 0. This makes it possible to form a transparent photosensitive material.
  • the conductive metal oxide is needle-like or fibrous
  • the length is preferably 30 / zm or less and the diameter is preferably 1 ⁇ m or less, and particularly preferably the length is 10 ⁇ m or less and the diameter is 0 ⁇ m. It is 3 ⁇ m or less, and the length Z diameter ratio is 3 or more.
  • SnO is commercially available from Ishihara Sangyo Co., Ltd.
  • the photothermographic material of the present invention has a photosensitive layer which is at least one image forming layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-image forming layer on the photosensitive layer. For example, it is preferable that a protective layer is provided on the photosensitive layer for the purpose of protecting the photosensitive layer. On the opposite side of the support, a “clump” is formed between the photosensitive materials or in the photosensitive material roll. In order to prevent “sticking”, a knock coat layer is provided.
  • two or more photosensitive layers may be provided on one side of the support or one or more layers on both sides of the support for gradation adjustment and the like.
  • the photothermographic material is preferably formed by preparing a coating solution in which the above-described constituent materials are dissolved or dispersed in a solvent, applying a plurality of coating solutions simultaneously, and then performing a heat treatment.
  • “multiple simultaneous multi-layer coating” means that the coating solution for each component layer (photosensitive layer, protective layer, etc.) is prepared, and when this is applied to the support, the coating and drying are repeated for each layer individually. This means that the constituent layers are formed in such a state that the multilayer coating is simultaneously performed and the drying process can be performed simultaneously. That is, the upper layer is provided before the remaining amount of all the solvents in the lower layer reaches 70% by mass or less (more preferably 90% by mass or less).
  • the silver coating amount is preferably selected in accordance with the purpose of the light-sensitive material, but is preferably 0.8 to 1.5 g / m 2 for the purpose of medical images. G 1.0 to 1.3 g / m 2 is more preferred.
  • the coated silver amounts those derived from halogenated silver preferably occupy 2-18% of the total silver amount, and more preferably 5-15%.
  • the coating density of halogen silver particles of 0.01 m or more (equivalent particle diameter equivalent to a sphere) is preferably 1 ⁇ 10 14 to 1 ⁇ 10 18 particles / m 2 . Furthermore, 1 ⁇ 10 15 to 1 ⁇ 10 17 / m 2 is preferable.
  • the photothermographic material of the present invention contains a solvent in the range of 5 to 1, OOOmgZm 2 during development! /, I prefer to be. It is more preferable to be adjusted so that 10 ⁇ 150mg / m 2! /. As a result, the photothermographic material has high sensitivity, low capri and high maximum density.
  • the solvent include those described in JP-A-2001-264930, paragraph “0030”, but are not limited thereto. These solvents can be used alone or in combination of several kinds.
  • the content of the solvent in the photosensitive material can be adjusted by changing conditions such as temperature conditions in the drying process after the coating process. The content of the solvent can be measured by gas chromatography under conditions suitable for detecting the contained solvent.
  • the heating means may be any means such as contact heating with a heating drum or a heating plate, non-contact heating such as radiation, but contact heating with a heating plate is preferred.
  • the contact heating surface may be either the image forming layer (photosensitive layer) side or the non-image forming layer (non-photosensitive layer) side.
  • the non-image forming layer (photosensitive layer) side is the contact heating surface for stability to the processing environment. I prefer to be there.
  • the developing unit is configured by combining a plurality of zones and a plurality of means that are independently temperature controlled, and further includes at least one heat retention zone that maintains a specific developing temperature. Preferably it is.
  • the heat development process can employ a separate structure for the temperature raising portion and the heat retaining portion, and in the temperature raising portion, heating means such as a heating member can be used.
  • heating means such as a heating member
  • the heat retaining part uses an optimum heating method that is different between the temperature rising part and the heat retaining part, which does not require such close contact, It is possible to achieve a configuration that allows rapid processing of the thermal development process, downsizing of the apparatus, and cost reduction while maintaining high image quality without density unevenness.
  • the temperature raising unit heats the sheet film while pressing the sheet film against a plate heater by a counter roller, and the heat retaining unit is interposed between guides having at least one heater.
  • the sheet film can be heated in the formed slit.
  • the sheet heater is pressed against the plate heater by the opposing roller and brought into contact with the plate heater, so that the plate heater and the sheet film can be brought into close contact with each other. Therefore, it is only necessary to transport while keeping the temperature between the slits (heat insulation), so there is no need for drive parts for the transport system, and the size of the device can be reduced and the cost can be reduced without requiring much accuracy of the slit dimensions.
  • a coating solution for the undercoat layer on the image forming surface side having the following composition is applied so as to have a dry film thickness of 0.25 m, and then the undercoat layer on the image forming surface side having the following composition.
  • the coating solution was applied to a dry film thickness of 0.06 / zm and then dried at 140 ° C. These were heat-treated at 140 ° C. for 2 minutes to obtain an undercoated support.
  • Tin oxide sol solid content 10%, synthesized by the method described in JP-A-10-059720
  • Surfactant SA-1 for subbing layer 0.5g
  • Distilled water was added to make 1,000 ml to make the coating solution.
  • True spherical silica matting agent (Seahoster KE-P50: manufactured by Nippon Shokubai Co., Ltd.) Distilled water was added to 0.3 g or more to make 1,000 ml to obtain a coating solution.
  • 0.022 part of manganese acetate tetrahydrate was added and transesterification was carried out while distilling methanol at 170-220 ° C under a nitrogen stream.
  • 0.04 part of trimethyl phosphate, 0.04 part of antimony trioxide as a polycondensation catalyst and 6.8 parts of 1,4-cyclohexanedicarboxylic acid were added, and the reaction temperature of 220-235 ° C was almost theoretical.
  • Distilled water was added to make 1,000 ml to make the coating solution.
  • Modified water-based polyester for image forming surface * (Solid content 18%) 80.
  • Og Surfactant for subbing layer 0.4 g
  • True spherical silica matting agent (Seahoster KE-P50: mentioned above) Distilled water was added to 0.3 g or more to make 1,000 ml, and a coating solution having a solid content concentration of 0.5% was obtained.
  • Phthalated gelatin phthalated modification rate 98% 66. 2g
  • Surfactant AO-1 (10% methanol aqueous solution) 10ml Potassium bromide 32g
  • This emulsion was monodisperse cubic silver iodobromide grains having an average grain size of 0.043 ⁇ m and a (100) plane ratio of 92%.
  • MEK methyl ethyl ketone
  • a solution obtained by dissolving 40 g of N-iso-propylacrylamide in 43 g of MEK was dropped into a separable flask over 2 hours. Thereafter, the temperature was raised over 1 hour, and when it was refluxed, 0.17 g of lauryl peroxide was dissolved in 33 g of MEK. The liquid was dropped into the flask over 2 hours and reacted at the same temperature for another 3 hours. Thereafter, a solution obtained by dissolving 0.33 g of methylhydroquinone in 107 g of MEK was added, and after cooling, a 30% polymer solution for amphiphilic dispersion was obtained.
  • 1,850 g and 90% of pure water adjusted to 5% concentration are stirred at 85 ° C.
  • 1036 ml of 5 molZL potassium hydroxide aqueous solution was added over 5 minutes and then reacted for 60 minutes to obtain an aliphatic potassium carboxylate aqueous solution.
  • additional pure was added so that the concentration of the aqueous potassium aliphatic carboxylate solution was 5%.
  • 38 and 300 g of a 5% silver nitrate aqueous solution were prepared and kept at 10 ° C.
  • Aliphatic potassium carboxylate aqueous solution and silver nitrate power A pump capable of feeding at a constant flow rate was prepared, and a reaction device was prepared so that both solutions could react in a Y-shaped mixing device.
  • the stock tank was kept at 35 ° C. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water at 25 ° C. until the conductivity of the permeated water reached S / cm.
  • An aliphatic carboxylic acid silver salt dispersion emulsion was prepared by supplying to DISPERMAT SL-C125 EX type (VMA-GETZMANN) and dispersing at a mill peripheral speed of 9 mZs.
  • the solid content concentration of the obtained aliphatic carboxylate silver salt dispersion emulsion was about 27%.
  • An image forming layer and a slip layer are placed on the undercoat of the undercoated support on the image forming layer side so that the silver amount is 1.26 g / 0.06 gZm 2 , and the wet weight is 23 gZm 2 .
  • a surface protective layer was applied in multiple layers.
  • the back layer was applied on the opposite side of the image forming layer side undercoat so that the wet weight was 25 gZm 2 .
  • Each drying was performed at 60 ° C for 2 minutes.
  • a photothermographic material was obtained by carrying out heat treatment at 79 ° C for 10 minutes while conveying the sample coated on both sides.
  • DesmodurN3300 (Movey Corp .: polyfunctional aliphatic isocyanate)
  • Reducing agent 1-1 160 g and dye- A: 500 mg was dissolved in MEK and finished to 800 g to obtain a developer solution.
  • Fluorine-based acrylic copolymer (Daikin Kogyo Co., Ltd .: Optoflon FM450) 1.6 g Amorphous saturated copolyester (Toyobo Co., Ltd .: Byron 240P) 12 g True spherical cross-linking matting agent (Sekisui Chemical Co., Ltd .: MBX-8) 4. Og surfactant CF O (CHCHO) CF 7. lg
  • the photothermographic material sample prepared as described above was processed into half-cut size (34.5 cm x 43. Ocm), and then two samples of samples wrapped in the following packaging material in a 25 ° C 50% environment were prepared. . After storing at room temperature for 2 weeks, one bag was stored at 23 ° C ZlO days, and the other bag was stored at 55 ° CZlO days, and then the following evaluation was performed.
  • a laser imager equipped with a 786nm semiconductor laser with a maximum output of 50mW was exposed to heat and developed at 129 ° C for 8 seconds.
  • the resulting image was evaluated with a densitometer.
  • heat development at the same time as exposure means a sheet of photosensitive material made of photothermographic material that is partially exposed and developed on a part of the sheet that has already been exposed. But Means to be started.
  • the distance between the exposed area and the developed area was 12 cm, and the linear velocity at this time was 30 mmZ seconds.
  • the transport speed from the photosensitive material supply unit to the image exposure unit, the transport rate at the image exposure unit, and the transport rate at the thermal development unit were each 30 mmZ seconds.
  • the exposure was performed in a stepped manner while reducing the exposure energy amount by logEO.05 for each step from the maximum output.
  • a characteristic curve consisting of light intensity and vertical axis density was created.
  • the sensitivity is defined as the reciprocal of the exposure that gives a density 1.0 higher than the unexposed area, and the minimum density capri density (minimum density) and the maximum density were measured.
  • Sensitivity was expressed as a relative value with the value of Sample 1 stored at 23 ° C for 10 days as 100.

Abstract

La présente invention concerne un matériau photosensible pouvant être développé thermiquement qui excelle simultanément en termes de capacité de stockage avant traitement et de développement. Elle concerne un matériau photosensible pouvant être développé thermiquement comportant un support et, superposée sur celui-ci, une couche de formation d'image contenant des grains de sel d'argent d'acide carboxylique aliphatique non photosensible, des grains d'halogénure d'argent photosensible, un agent de réduction d'ions d'argent et un liant, caractérisé par le fait que la quantité de liant comme constituant de la couche de formation d'image est de l'ordre de 25 à 35 % en masse sur la base du contenu solide total constituant la couche de formation d'image, et qu'au moins un type de liant a un degré de polymérisation de 1000 à 3000.
PCT/JP2007/061274 2006-06-16 2007-06-04 Matériau photosensible pouvant être developpé thermiquement WO2007145094A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
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JP2006-167191 2006-06-16

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003075953A (ja) * 2001-08-31 2003-03-12 Konica Corp 銀塩光熱写真ドライイメージング材料、その画像記録方法及び画像形成方法
JP2003295381A (ja) * 2002-03-29 2003-10-15 Fuji Photo Film Co Ltd 熱現像感光材料
JP2004004650A (ja) * 2002-04-23 2004-01-08 Konica Minolta Holdings Inc 熱現像感光材料及びその画像記録方法
JP2005024744A (ja) * 2003-06-30 2005-01-27 Sekisui Chem Co Ltd 熱現像感光材料用バインダー及び熱現像感光材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003075953A (ja) * 2001-08-31 2003-03-12 Konica Corp 銀塩光熱写真ドライイメージング材料、その画像記録方法及び画像形成方法
JP2003295381A (ja) * 2002-03-29 2003-10-15 Fuji Photo Film Co Ltd 熱現像感光材料
JP2004004650A (ja) * 2002-04-23 2004-01-08 Konica Minolta Holdings Inc 熱現像感光材料及びその画像記録方法
JP2005024744A (ja) * 2003-06-30 2005-01-27 Sekisui Chem Co Ltd 熱現像感光材料用バインダー及び熱現像感光材料

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