EP1072948A1 - Wärmeentwickelbares Bildaufzeichnungsmaterial - Google Patents

Wärmeentwickelbares Bildaufzeichnungsmaterial Download PDF

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Publication number
EP1072948A1
EP1072948A1 EP00114958A EP00114958A EP1072948A1 EP 1072948 A1 EP1072948 A1 EP 1072948A1 EP 00114958 A EP00114958 A EP 00114958A EP 00114958 A EP00114958 A EP 00114958A EP 1072948 A1 EP1072948 A1 EP 1072948A1
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Prior art keywords
group
image recording
recording material
processed image
formula
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EP00114958A
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English (en)
French (fr)
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EP1072948B1 (de
Inventor
Katsuyuki Fuji Photo Film Co. Ltd. Watanabe
Masaru Fuji Photo Film Co. Ltd. Takasaki
Kouta Fuji Photo Film Co. Ltd. Fukui
Hisashi Fuji Photo Film Co. Ltd. Okamura
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Fujifilm Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • 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

Definitions

  • the present invention relates to a thermally processed image recording material. More particularly, the present invention relates to a thermally processed image recording material which causes almost no fog and exhibits high sensitivity as well as superior storage stability before development and superior image stability after development.
  • a large number of photosensitive materials are known which have a photosensitive layer on a support and form image by imaging exposure.
  • Examples of a system that enables environmental conservation or simplification of image formation includes a technique of forming an image by heat development.
  • the photothermographic material contains a reducible light-insensitive silver source (e.g., organic silver salt), a photocatalyst (e.g., silver halide) in a catalytically active amount, and a reducing agent for silver, which are usually dispersed in an organic binder matrix.
  • a reducible light-insensitive silver source e.g., organic silver salt
  • a photocatalyst e.g., silver halide
  • a reducing agent for silver which are usually dispersed in an organic binder matrix.
  • This photothermographic material is stable at an ambient temperature, but when the material is heated at a high temperature (e.g., 80°C or higher) after light exposure, silver is produced through an oxidation-reduction reaction between the reducible silver source (which functions as an oxidizing agent) and the reducing agent.
  • the oxidation-reduction reaction is accelerated by catalytic action of a latent image generated upon exposure.
  • the silver produced by the reaction of the reducible silver salt in the exposed region provides a black image and this presents a contrast to the non-exposure region to form an image.
  • JP-A means an "unexamined published Japanese patent application”
  • thiouracils U.S. Patent No.4,002,479
  • sulfinic acid JP-A-50-123331
  • metal salts of thiosulfonic acid U.S. Patent Nos.
  • JP-A-53-20923 and JP-A-53-19825 metal salts of thiosulfonic acid and sulfinic acid
  • JP-B-62-50810 thiosulfonic acid esters
  • polyhalogenated compounds are extremely effective components for dry silver photosensitive materials as an antifoggant and a stabilizer for storage, and such compounds have been disclosed in JP-B-54-165, EP 605981A, EP 631176A, U.S. Patent Nos. 4,546,075, 4,756,999, 4,452,885, 3,874,946, 3,955,982, JP-A-10-171063, JP-A-10-197989, JP-A-9-265150 and so forth.
  • those compounds have drawbacks, for example, insufficient anti-fog effect, insufficient storage stability of photosensitive materials before development, insufficient image stability after heat development (for example, coloration of non-image areas caused by heat or light), and decrease of sensitivity and Dmax when those compounds are added in such an amount that sufficiently suppresses the fog.
  • an object of the present invention is to solve those problems of the related art.
  • the object of the present invention is to provide a thermally processed image recording material which causes almost no fog and exhibits high sensitivity as well as superior storage stability before development and superior image stability against high temperature in the dark and against light.
  • the inventors of the present invention assiduously studied in order to achieve the aforementioned object. As a result, they found that superior thermally processed image recording materials can be provided with desired advantages by using polyhalogenated compounds of a specific structure which have a melting point within a specific range or a log P value within a specific range. Thus, the present invention has been accomplished.
  • a thermally processed image recording material which comprises, on a support, at least (a) a reducible silver salt, (b) a reducing agent, (c) a binder, and (d) at least one kind of compound having a melting point of 115°C to 180°C which is selected from the group consisting of polyhalogenated compounds represented by the following formula (1) and dimer compounds thereof: wherein Z 1 and Z 2 independently represent a halogen atom, X 1 represents a hydrogen atom or an electron withdrawing group, Y 1 represents -CO- group or -SO 2 -, Q represents an arylene group which may have one or more substituents or a divalent heterocyclic group which may have one or more substituents, L 1 represents -CONH-*, -SO 2 NH-* or -COO-* where * represents a bonding site for W, L 2 represents -O-, an alkylene group, an arylene group or a combination thereof, W
  • a thermally processed image recording material which comprises, on a support, at least (a) a reducible silver salt, (b) a reducing agent, (c) a binder, and (d) at least one kind of compound having a log P value of 3.0 to 7.0 which is selected from the group consisting of polyhalogenated compounds represented by the following formula (1) and dimer compounds thereof: wherein Z 1 and Z 2 independently represent a halogen atom, X 1 represents a hydrogen atom or an electron withdrawing group, Y 1 represents -CO- group or -SO 2 -, Q represents an arylene group which may have one or more substituents or a divalent heterocyclic group which may have one or more substituents, L 1 represents -CONH-*, -SO 2 NH-* or -COO-* where * represents a bonding site for W, L 2 represents -O-, an alkylene group, an arylene group or a combination thereof, W represents
  • Z 1 , Z 2 and X 1 represent a bromine atom
  • Y 1 represents -SO 2 -
  • Q represents an arylene group which may have one or more substituents
  • W represents a hydrogen atom or an alkyl group which may have one or more substituents
  • n is 0.
  • the thermally processed image recording material of the present invention is a photothermographic material which further comprises a photosensitive silver halide.
  • the compound represented by the formula (1) has a melting point of 115°C to 180°C and a log P value of 3.0 to 7.0.
  • the compound represented by the formula (1) has a log P value of 3.5 to 6.0.
  • the electron withdrawing group represented by X 1 in the formula (1) is cyano group, a C 2-30 alkoxycarbonyl group, a C 7-30 aryloxycarbonyl group, a C 1-30 carbamoyl group, a sulfamoyl group with may be substituted with a C 0-30 alkyl group, a C 1-30 alkylsulfonyl group, a C 6-30 arylsulfonyl group, a halogen atom or an acyl group.
  • the substituent on the arylene group represented by Q in the formula (1) is selected from a group consisting of a halogen atom such as fluorine atom, chlorine atom, bromine atom or iodine atom; an alkyl group including a cycloalkyl group, an active methine group and so forth; an aralkyl group; an alkenyl group; an alkynyl group; an aryl group; a heterocyclic group including N-substituted nitrogen-containing heterocyclic group such as morpholino group; an alkoxycarbonyl group; an aryloxycarbonyl group; a carbamoyl group; an imino group; an imino group substituted at the N atom; a thiocarbonyl group; a carbazoyl group; cyano group; a thiocarbamoyl group; an alkoxy group; an aryloxy group; a heterocyclyloxy group; an acyloxy
  • the heterocycle in the heterocyclic group represented by Q in the formula (1) is a ring of pyridine, pyrazine, pyrimidine, benzothiazole, benzimidazole, thiadiazole, quinoline, isoquinoline or triazole.
  • L 1 in the formula (1) represents -CONH-*
  • the compounds represented by the formula (1) is added to the image-forming layer or a layer adjacent thereto.
  • the compounds represented by the formula (1) is added in an amount of 1 ⁇ 10 -4 to 1 mole per mole of the light insensitive silver salt of the image-forming layer.
  • the thermally processed image recording material of the present invention comprises, on a support, an image-forming layer containing an organic silver salt as a reducible silver salt and a binder, and contains a reducing agent in a layer on the image-forming layer side.
  • the thermally processed image recording material of the present invention preferably further comprises a photosensitive silver halide, and the image-forming layer is preferably a photosensitive layer containing a photosensitive silver halide.
  • one of the characteristics of the thermally processed image recording material of the present invention is that it contains at least one kind of compound having a melting point within a specific range or a log P value within a specific value which is selected from the group consisting of polyhalogenated compounds represented by the formula (1) and dimer compounds thereof in a layer on the image-forming layer side.
  • the superior advantages of the present invention could be achieved by using the compounds of the formula (1) having a melting point of 115°C to 180°C, and it could not have been expected at all. If a compound of the formula (1) having a melting point lower than 115°C is used, sensitivity is decreased. On the other hand, if a compound of the formula (1) having a melting point higher than 180°C is used, the effects for suppressing fog and improving image storability become insufficient.
  • the melting point is preferably 120°C to 180°C.
  • the log P value is preferably 3.5 to 6.0.
  • the log P value represents a logarithm of distribution coefficient P between an aqueous phase and a non-polar liquid phase, and defined in Medicinal Chemistry, p.25 [Ishiyaku Shuppan Co., Ltd.] and so forth.
  • Log P value is generally used as an indicator of hydrophobicity in the chemical field, and larger value of log P means larger hydrophobicity.
  • the experimental procedure for the determination of log P value is described in Experimental Section of Journal of Organic Chemistry., 32, 2584-2585 (1967).
  • the log P value can conveniently determined by using MacLog P (ver 2.0.3), which is a software sold by Biobyte Co., Ltd.
  • the formula (1) which represents the structures of the polyhalogenated compounds used in the present invention, will be explained.
  • the formula (1) is shown below.
  • Z 1 and Z 2 independently represent a halogen atom.
  • the halogen atom referred to in the present specification may be any of fluorine, chlorine, bromine and iodine. It is preferred that both of Z 1 and Z 2 represent a bromine atom.
  • X 1 is a hydrogen atom or an electron withdrawing group.
  • the electron withdrawing group used herein is a substituent having a Hammett's substituent constant ⁇ p of a positive value, and specific examples thereof include cyano group, a C 2-30 alkoxycarbonyl group, a C 7-30 aryloxycarbonyl group, a C 1-30 carbamoyl group, a sulfamoyl group with may be substituted with a C 0-30 alkyl group, a C 1-30 alkylsulfonyl group, a C 6-30 arylsulfonyl group, a halogen atom, an acyl group, a heterocyclic group and so forth.
  • X 1 is preferably a halogen atom, more preferably a bromine atom.
  • Z 1 , Z 2 and X 1 represent a bromine atom.
  • Y 1 is -CO- or -SO 2 -, and it is preferably -SO 2 -.
  • Q represents an arylene group which may have one or more substituents or a divalent heterocyclic group which may have one or more substituents.
  • the arylene group represented by Q in the formula (1) is preferably a monocyclic or condensed ring arylene group having 6-30 carbon atoms, preferably a monocyclic or condensed ring arylene group having 6-20 carbon atoms. Examples thereof include, for example, phenylene, naphthylene and so forth, and it is particularly preferably a phenylene group.
  • the arylene group represented by Q may have one or more substituents. If there are two or more substituents, they may be identical or different. The substituent on the arylene group may be any group so long as it does not adversely affect photographic performance.
  • Examples thereof include, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), an alkyl group (including a cycloalkyl group, an active methine group and so forth), an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (including N-substituted nitrogen-containing heterocyclic group such as morpholino group), an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted at the N atom, a thiocarbonyl group, a carbazoyl group, cyano group, a thiocarbamoyl group, an alkoxy group, an aryloxy group, a heterocyclyloxy group, an acyloxy group, an (alkoxy or aryloxy)carbonyloxy group,
  • Particularly preferred substituents on the arylene group represented by Q in the formula (1) are an alkyl group, an alkoxy group, an aryloxy group and a halogen atom.
  • the heterocycle of the divalent heterocyclic group represented by Q may be a saturated or partially saturated or aromatic 5- to 7-membered heterocycle containing at least one of N, O and S atoms.
  • the heterocycle may consist of a single ring, or may form a condensed ring with another ring or other rings.
  • Examples of the heterocycle in the heterocyclic group represented by Q include, for example, rings of pyridine, pyrazine, pyrimidine, benzothiazole, benzimidazole, thiadiazole, quinoline, isoquinoline, triazole and so forth.
  • the heterocyclic group may have one or more substituents. If there are two or more substituents, they may be identical or different. Examples of the substituent on the heterocyclic group include, for example, those mentioned for the substituent on the arylene group represented by Q.
  • Q is preferably an arylene group, and it is particularly preferably a phenylene group.
  • L 2 represents -O-, an alkylene group (having preferably 1-30 carbon atoms, more preferably 1-20 carbon atoms, particularly preferably 1-10 carbon atoms), an arylene group (having preferably 6-30 carbon atoms, more preferably 6-20 carbon atoms, particularly preferably 6-10 carbon atoms) or a group composed of a combination of the foregoing.
  • L 2 is preferably an alkylene group, -O- or a group composed of a combination thereof.
  • n 0 or 1, preferably 0.
  • L 1 represents -CONH-*, -SO 2 NH-* or -COO-*, preferably -CONH-*, where * represents a bonding site for W.
  • W represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and these groups may have one or more substituents.
  • the alkyl group, alkenyl group and alkynyl group represented by W in the formula (1) are liner, branched or cyclic groups or groups composed of a combination thereof.
  • W is preferably an alkyl group having preferably 1-20 carbon atoms, more preferably 1-12 carbon atoms, particularly preferably 1-6 carbon atoms.
  • Examples thereof include, for example, methyl, ethyl, allyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, sec-pentyl, iso-pentyl, 3-pentyl, n-hexyl, n-octyl, n-dodecyl, cyclohexyl and so forth.
  • the alkyl group, alkenyl group and alkynyl group represented by W in the formula (1) may have a substituent, preferably a substituent having 3 or less of carbon atoms and ⁇ value (a value defined as ⁇ value in Journal of Medical Chemistry, 1973, 1207) of -0.3 or higher.
  • halogen atom e.g., fluorine atom, chlorine atom, bromine atom
  • an alkoxy group e.g., methoxy group, ethoxy group
  • a nitro group an amino group (e.g., dimethylamino group), an alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group), an acylthio group (e.g., acetyl thio group), a silyl group, an alkylthio group (e.g., methylthio group, ethylthio group), a heterocyclic group and so forth.
  • the substituent is preferably a halogen atom or an alkoxy group.
  • the aryl group represented by W in the formula (1) is a monocyclic or condensed ring aryl group having preferably 6-20 carbon atoms, more preferably 6-16 carbon atoms, particularly preferably 6-10 carbon atoms. Examples thereof include, for example, phenyl group, naphthyl group and so forth, and it is preferably a phenyl group.
  • the aryl group represented by W may have a substituent, and examples thereof include those mentioned for the substituent on the arylene group represented by Q.
  • the heterocyclic group represented by W in the formula (1) may be a saturated or partially saturated or aromatic 5- to 7-membered heterocyclic group containing at least one of N, O and S atoms.
  • the heterocyclic group may consist of a single ring, or it may form a condensed ring with another ring or other rings.
  • Examples of the heterocyclic group include, for example, pyridyl, pyrazinyl, pyrimidinyl, thiazolyl, imidazolyl, benzothiazolyl, benzimidazolyl, thiadiazolyl, quinolyl, isoquinolyl, triazolyl and so forth. These may have a substituent, and examples thereof include those mentioned for the substituent on the arylene group represented by Q.
  • W in the formula (1) is preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group.
  • a dimer compound of a compound represented by the formula (1) may also be used.
  • the dimer compound is a compound where two compounds of the formula (1) is bonded directly at their terminals of the group represented by W via a bridging group such as -O-.
  • a compound of the formula (1) (monomer compound), a dimer compound thereof or a combination thereof may be used.
  • the compounds of the formula (1) can be synthesized by usual organic synthesis reactions known to those skilled in the art. For example, they can be synthesized by the method described below.
  • melting points or log P values of P-1 to P-25 and P'-1 to P'-26 as specific examples of the compound used in the present invention will be shown below.
  • the compounds that can be used in the present invention are not limited to these compounds.
  • the melting points were measured by using Model 530 produced by BUCHI, and the Log P values were calculated by the software MacLogP (ver 2.0.3) sold by Biobyte Co., Ltd.
  • the compounds represented by the formula (1) may be used for the thermally processed image recording material of the present invention by dissolving said compounds in water or a suitable organic solvent, for example, alcohols such as methanol, ethanol, propanol and fluorinated alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dimethylformamide, dimethyl sulfoxide, methyl cellosolve and so forth. If the compounds have an acidic group bonded thereto, they may be neutralized with equivalent alkali and added as salts.
  • a suitable organic solvent for example, alcohols such as methanol, ethanol, propanol and fluorinated alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, dimethylformamide, dimethyl sulfoxide, methyl cellosolve and so forth.
  • the compounds of the formula (1) may also be used in the thermally processed image recording material as an emulsified dispersion mechanically prepared according to an already well known emulsification dispersion method by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, ethyl acetate or cyclohexanone as an auxiliary solvent for dissolution.
  • the compounds may be used after dispersion of a powder thereof in water by using a ball mill, a colloid mill, a sand grinder mil, MANTON GAULIN, a microfluidizer, or by means of ultrasonic wave according to a known method for solid dispersion.
  • the compounds represented by the formula (1) may be added to any layers on a support provided on the image-forming layer side, i.e., the image-forming layer and/or the other layers provided on the same side.
  • the compounds may preferably be added to the image-forming layer or a layer adjacent thereto. Two or more kinds of the compounds represented by the formula (1) may be used in combination.
  • the addition amount of the compounds represented by the formula (1) may be 1 ⁇ 10 -4 to 1 mole, preferably 1 ⁇ 10 -3 to 0.8 mole, more preferably 5 ⁇ 10 -3 to 0.5 mole, per mole of the light insensitive silver salt of the image-forming layer.
  • the thermally processed image recording material of the present invention comprises an organic silver salt as a reducible silver salt.
  • An organic silver salt that can be used in the present invention is a silver salt relatively stable against light, but forms a silver image when it is heated at 80°C or higher in the presence of an exposed photocatalyst (e.g., a latent image of photosensitive silver halide) and a reducing agent.
  • the organic silver salt may be any organic substance containing a source capable of reducing the silver ion.
  • Such light insensitive organic silver salts are disclosed in JP-A-10-62899, paragraphs 0048 to 0049 and EP 0803763A1, page 18, line 24 to page 19, line 37.
  • x The values of x are obtained for about 200 grains seen in the field, and an average of them (x (average)) is obtained.
  • Samples that satisfy the requirement of x (average) ⁇ 1.5 are defined to be scaly.
  • Scaly grains preferably satisfy 30 ⁇ x (average) ⁇ 1.5, more preferably 20 ⁇ (average) ⁇ 2.0.
  • acicular (needle-like) grains falls satisfy 1 ⁇ x (average) ⁇ 1.5.
  • a corresponds to the thickness of tabular grains of which main planes are defined by the sides of b and c.
  • the average of a is preferably from 0.01 ⁇ m to 0.23 ⁇ m, more preferably from 0.1 ⁇ m to 0.20 ⁇ m.
  • the average of c/b is preferably from 1 to 6, more preferably from 1.05 to 4, even more preferably from 1.1 to 3, particularly preferably from 1.1 to 2.
  • the grain size distribution of the organic silver salt is preferably monodispersed.
  • the term "monodispersed" as used herein means that the percentage of the value obtained by dividing the standard deviation of the length of the short axis or long axis by the length of the short axis or long axis, respectively, is preferably 100% or less, more preferably 80% or less, further preferably 50% or less.
  • the shape of the organic silver salt can be determined from a transmission electron microscope image of organic silver salt dispersion. Another method for determining the monodispesibility is a method involving obtaining the standard deviation of a volume weight average diameter of the organic silver salt.
  • the percentage (coefficient of variation) of the value obtained by dividing the standard deviation by the volume weight average diameter is preferably 100% or less, more preferably 80% or less, further preferably 50% or less.
  • the grain size (volume weight average diameter) can be determined by irradiating organic silver salt dispersed in a solution with a laser ray and determining an autocorrelation function of the fluctuation of the scattered light on the basis of the change in time.
  • the organic acid silver salt used for the present invention is prepared by allowing a solution or suspension of alkali metal salt (e.g., Na salt, K salt, Li salt) of the above-described organic acid to react with silver nitrate.
  • alkali metal salt e.g., Na salt, K salt, Li salt
  • the organic acid alkali metal salt can be obtained by treating the organic acid with an alkali.
  • the preparation of the organic acid silver salt may be performed batchwise or continuously in any appropriate reaction vessel. Stirring in the reaction vessel may be effected by any stirring method according to the required properties of the grains.
  • the organic acid silver salt is preferably prepared by a method of gradually or rapidly adding an aqueous silver nitrate solution to a reaction vessel containing an organic acid alkali metal solution or suspension, a method of gradually or rapidly adding a previously prepared organic acid alkali metal salt solution or suspension to a reaction vessel containing an aqueous silver nitrate solution, or a method of previously preparing an aqueous silver nitrate solution and an organic acid alkali metal salt solution or suspension and simultaneously adding those solutions to a reaction vessel.
  • the aqueous silver nitrate solution and the organic acid alkali metal salt solution or suspension may have any concentration so as to control the grain size of the organic acid silver salt to be prepared and may be added at any addition rate.
  • the aqueous silver nitrate solution and the organic acid alkali metal salt solution or suspension each may be added by a method of adding the solution or suspension at a constant rate or a method of adding the solution or suspension while increasing or decreasing the addition rate with any time function.
  • the solution may also be added to the liquid surface or in the liquid of the reaction solution.
  • aqueous silver nitrate solution and an organic acid alkali metal salt solution or suspension are previously prepared and then simultaneously added to a reaction vessel, either of the aqueous silver nitrate solution and the organic acid alkali metal salt solution or suspension may be added in advance, but the aqueous silver nitrate solution is preferably added in advance by a precedence degree of from 0 to 50 volume %, more preferably from 0 to 25 volume %, of the entire addition amount. Furthermore, a method of adding the solution while controlling the pH or silver potential of the reaction solution during the reaction described in JP-A-9-127643 may be preferably used.
  • the pH of the aqueous silver nitrate solution and the organic acid alkali metal salt solution or suspension added may be adjusted according to the required properties of the grains.
  • any acid or alkali may be added.
  • the temperature in the reaction vessel may be suitably selected.
  • the temperature of the aqueous silver nitrate solution and the organic acid alkali metal salt solution or suspension added may also be suitably controlled.
  • the solution is preferably heated and maintained at a temperature of 50°C or higher.
  • the organic acid silver salt for use in the present invention is preferably prepared in the presence of a tertiary alcohol.
  • the tertiary alcohol preferably has a total carbon number of 15 or less, more preferably 10 or less. Examples of preferred tertiary alcohols include tert-butanol.
  • the tertiary alcohol may be added in any timing during the preparation of the organic acid silver salt.
  • the tertiary alcohol is preferably added at the time of preparation of the organic acid alkali metal salt to dissolve the organic alkali metal salt.
  • the tertiary alcohol may be added in any amount of from 0.01 to 10 in terms of the weight ratio to H 2 O used as a solvent for the preparation of the organic acid silver salt, and preferably added in an amount of from 0.03 to 1 in terms of the weight ratio to H 2 O.
  • the scaly organic silver salt for use in the present invention is prepared by reacting an aqueous solution of a water-soluble silver salt with an aqueous solution of an alkali metal salt of an organic acid in a aqueous tertiary alcohol solution in a reaction vessel (the method includes a step of adding the aqueous tertiary alcohol solution containing an alkali metal salt of an organic acid into a liquid already existing in a reaction vessel), wherein the temperature difference between the liquid already existing in the reaction vessel and the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid to be added thereto falls between 20°C and 85°C.
  • the liquid existing in the reaction vessel in advance is preferably an aqueous solution of a water-soluble silver salt put into the reaction vessel in advance.
  • the liquid existing in the reaction vessel is water or a mixed solvent of water and a tertiary alcohol, as will be mentioned hereinafter.
  • the reaction vessel may contain water or a mixed solvent of water and a tertiary alcohol.
  • the crystal shape of the organic silver salt to be formed can favorably controlled.
  • the water-soluble silver salt is preferably silver nitrate.
  • the concentration of the water-soluble silver salt in the aqueous solution is preferably 0.03 mole/liter to 6.5 moles/liter, more preferably 0.1 mole/liter to 5 moles/liter.
  • the pH of the aqueous solution is preferably 2 to 6, more preferably 3.5 to 6.
  • the aqueous solution of a water-soluble silver salt may contain a tertiary alcohol having from 4 to 6 carbon atoms.
  • the amount of the tertiary alcohol, if any, in the aqueous solution is 70% by volume or less, preferably 50% by volume or less, based on the total volume of the aqueous solution.
  • the temperature of the aqueous solution is preferably 0°C to 50°C, more preferably 5°C to 30°C.
  • the temperature of the solutions is most preferably 5°C to 15°C.
  • the alkali metal of the alkali metal salt of an organic acid include Na and K.
  • the alkali metal salt of an organic acid may be prepared by adding NaOH or KOH to an organic acid. In this step, it is desirable that the amount of the alkali to be added to an organic acid is not larger than the equivalent amount of the organic acid so that unreacted organic acid can remain in the reaction mixture. In this case, the amount of the remaining unreacted organic acid may be 3 mole % to 50 mole %, preferably 3 mole % to 30 mole %, per mole of the total organic acid. After the alkali is added in an amount larger than the intended amount, additional acid such as nitric acid or sulfuric acid may be added to neutralize the excess alkali to perform the preparation.
  • additional acid such as nitric acid or sulfuric acid may be added to neutralize the excess alkali to perform the preparation.
  • the pH of the reaction system may be controlled.
  • any acid or alkali may be used.
  • the aqueous solution of a water-soluble silver salt, the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid, or even the liquid existing in the reaction vessel in advance (solvent etc.) may be optionally added with compounds of the formula (1) described in JP-A-62-65035, water-soluble group-containing N-heterocyclic compounds such as those described in JP-A-62-150240, inorganic peroxides such as those described in JP-A-50-101019, sulfur compounds such as those described in JP-A-51-78319, disulfide compounds such as those described in JP-A-57-643, hydrogen peroxide and so forth.
  • the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid is preferably in a mixed solvent of water and a tertiary alcohol having 4 to 6 carbon atoms for ensuring uniformity of the solution.
  • Alcohols in which the number of carbon atoms exceeds the defined range are not preferred as their miscibility with water becomes poor.
  • tertiary alcohol having 4 to 6 carbon atoms most preferred is tert-butanol as its miscibility with water is the highest of all.
  • Alcohols other than such tertiary alcohols are also unfavorable as mentioned above since they have a reducing property and adversely affect the process of forming the intended organic silver salts.
  • the amount of the tertiary alcohol that may be used in the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid may be 3% by volume to 70% by volume, preferably 5% by volume to 50 % by volume, relative to the volume of water in the aqueous solution.
  • the concentration of the alkali metal salts of an organic acid in the aqueous tertiary alcohol solution of the alkali metal salts of an organic acid may be 7% by weight to 50% by weight, preferably 7% by weight to 45% by weight, more preferably 10% by weight to 40% by weight.
  • the temperature of the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid to be added into a reaction vessel is preferably 50°C to 90°C, more preferably 60°C to 85°C, most preferably 65°C to 85°C, in order that the alkali metal salt of an organic acid in the solution should be kept at a temperature sufficient for preventing the salt from being crystallized or solidified.
  • the temperature of the aqueous solution should be controlled to be a temperature falling within the defined range all the time.
  • the organic silver salt preferably used for the present invention may be prepared according to i) a method comprising first putting the total amount of an aqueous solution of a water-soluble silver salt into a reaction vessel, followed by adding thereto an aqueous tertiary alcohol solution of an alkali metal salt of an organic acid as a single portion (single addition method), or ii) a method comprising simultaneously putting both an aqueous solution of a water-soluble silver salt and an aqueous tertiary alcohol solution of an alkali metal salt of an organic acid into a reaction vessel at least any time (simultaneous addition method).
  • the latter simultaneous addition method is preferred, since the mean grain size of the organic silver salt produced can be well controlled to narrow the grain size distribution thereof by the latter method.
  • this method it is desirable that at least 30% by volume, more preferably from 50 to 75% by volume, of the total amount of the two is simultaneously put into the reaction vessel. In a case where any one of the two is put into the reaction vessel in advance, it is desirable that the solution of a water-soluble silver salt is put into the vessel.
  • the temperature of the liquid previously existing in the reaction vessel is preferably 5°C to 75°C, more preferably 5°C to 60°C, most preferably 10°C to 50°C.
  • the reaction temperature is preferably controlled to be a constant temperature falling within the defined range. As the case may be, however, the reaction temperature may be controlled in some temperature profiles varying within the defined range.
  • the temperature difference between the liquid existing in the reaction vessel and the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid to be added is preferably 20°C to 85°C, more preferably 30°C to 80°C. In this case, it is desirable that the temperature of the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid should be higher than that of the liquid already existing in the reaction vessel.
  • the rate at which the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid having a higher temperature is rapidly cooled by the reaction vessel and precipitated to give fine crystals, and the rate at which the deposited alkali metal salt is reacted with the water-soluble silver salt to give an organic silver salt are both favorably controlled, and therefore the crystal shape, crystal size and crystal size distribution of the organic silver salt can be favorably controlled.
  • the properties of the thermally processed material in particular, as a photothermographic image recording material, can also be improved.
  • the reaction vessel may contain a solvent in advance, and water is preferably used as the solvent which is contained in advance.
  • a mixed solvent of water and a tertiary alcohol may also be preferably used.
  • the aqueous tertiary alcohol solution of an alkali metal salt of an organic acid, the aqueous solution of a water-soluble silver salt, or the reaction mixture may optionally be added with a dispersing aid that is soluble in aqueous media.
  • the dispersing aid may be any one capable of dispersing the organic silver salt formed. Specific examples thereof include those mentioned below as the dispersing aid for organic silver salts.
  • the salts formed are preferably desalted and dehydrated.
  • the methods for desalting and dehydrating the salts are not particularly limited, and well known conventional method may be used.
  • preferably used are known filtration methods including centrifugation filtration, suction filtration, ultrafiltration, flocculation by the coagulation method followed by washing with water and so forth.
  • supernatant removal by centrifugal precipitation is also preferably used.
  • the desalting and dehydration may be effected once or may be repeated. Addition and removal of water may be effected continuously or separately.
  • the desalting and the dehydration is preferably effected to such a degree that the finally removed water should have a conductivity of 300 ⁇ S/cm or less, more preferably 100 ⁇ S/cm or less, most preferably 60 ⁇ S/cm or less.
  • the conductivity there is no particular lower limit, it may generally be 5 ⁇ S/cm or so.
  • the organic silver salt formed is preferably further processed in a process comprising dispersing it in water, forming a high-pressure and high-speed flow of the resulting aqueous dispersion, and re-dispersing the salt by lowering the pressure to form a fine aqueous dispersion of the salt.
  • the dispersion medium preferably consists of water alone, but may contain an organic solvent so long as it is in an amount of 20% by weight or less of the dispersion medium.
  • the method for finely dispersing the organic silver salt for example, it can be mechanically dispersed in the presence of a dispersing aid by a known dispersing apparatus (e.g., a high-speed mixer, a homogenizer, a high-speed impact mill, a Banbary mixer, a homomixer, a kneader, a ball mill, a vibrating ball mill, a planetary ball mill, an attriter, a sand mill, a bead mill, a colloid mill, a jet mill, a roller mill, a trone mill or a high-speed stone mill).
  • a known dispersing apparatus e.g., a high-speed mixer, a homogenizer, a high-speed impact mill, a Banbary mixer, a homomixer, a kneader, a ball mill, a vibrating ball mill, a planetary ball mill, an attriter, a sand mill, a bead mill
  • the organic silver salt is dispersed substantially in the absence of a photosensitive silver salt, since the photosensitive silver salt will increase fog and markedly lower sensitivity, if it is present during the dispersion.
  • the amount of the photosensitive silver salt that may be in the aqueous dispersion of the organic silver salt should be 0.1 mole % or less per mole of the organic silver salt, and the photosensitive silver salt is not added intentionally.
  • a dispersion method comprising the steps of converting an aqueous dispersion that contains an organic silver salt and an aqueous solution of dispersant into a high-speed flow, and then releasing the pressure, is preferred.
  • the re-dispersion method used in the present invention comprises steps of supplying a water dispersion containing at least an organic silver salt into a pipeline under a positive pressure by means of a high-pressure pump or the like, passing the dispersion through a narrow slit provided inside the pipeline, and then subjecting the dispersion to rapid pressure reduction to perform fine dispersion.
  • the high-pressure homogenizer it is generally considered that fine and uniform dispersion can be achieved therein by enhancing (a) "shear force" to be generated at the passage of a dispersoid through a narrow slit (75 ⁇ m to 350 ⁇ m or so) under high pressure at high speed and (b) "cavitation force" to be generated by the pressure releasing, but without changing the preceding impact force resulting from the liquid-liquid collision or the liquid-wall collision in the high-pressure narrow space.
  • a dispersion apparatus of this type is a Golline homogenizer.
  • a liquid to be dispersed introduced under high pressure is converted into a high-speed flow when it is passed through a narrow gap formed on the wall of a cylindrical surface. Then, the flow collides against a surrounding wall with its own force, and is emulsified and dispersed by the impact force.
  • a Y-type chamber of Microfluidizer for example, there can be mentioned a Y-type chamber of Microfluidizer, a spherical chamber utilizing a spherical check valve such as that described in JP-A-8-103642 mentioned below and so forth.
  • a Z-type chamber of Microfluidizer for the liquid-wall collision, there can be mentioned a Z-type chamber of Microfluidizer and so forth.
  • the pressure is generally 100 to 600 kg/cm 2 , and the flow rate is generally a few meters/sec to 30 meters/sec.
  • some apparatuses are designed wherein the high flow rate area is so modified as to have a serrated configuration, thereby increasing the frequency of collision.
  • Typical examples of such devices are Golline homogenizer, Microfluidizer from Microfluidex International Corporation, Microfluidizer from Mizuho Kogyo Co., Ltd., Nanomizer from Tokushu Kika Kogyo Co., Ltd and so forth.
  • Other examples of such apparatuses are described in JP-A-8-238848, JP-A-8-103642 and U.S. Patent No. 4,533,254.
  • dispersion having a desired grain size may be obtained by controlling the flow rate, the difference in the pressure before and after at the pressure releasing and the frequency of the processing.
  • the flow rate is preferably from 200 to 600 m/sec and the difference in the pressure at the pressure releasing is preferably from 900 to 3,000 kg/cm 2 , and more preferably, the flow rate is from 300 to 600 m/sec, and the difference in the pressure at the pressure releasing is from 1,500 to 3,000 kg/cm 2 .
  • the frequency of the dispersion processing may be appropriately chosen as required, and is usually from 1 to 10 times. From a viewpoint of productivity, the frequency is approximately from 1 to 3 times.
  • the water dispersion under a high pressure is preferably not warmed at a high temperature from viewpoints of dispersibility and photographic performance. At a high temperature above 90°C, a grain size may readily become large and fog may be increased. Accordingly, the water dispersion is preferably kept at a temperature of from 5°C to 90°C, more preferably from 5°C to 80°C, particularly preferably from 5°C to 65°C, by using a cooling apparatus in a step before the conversion into a high-pressure and high-speed flow, or a step after the pressure release, or both of the steps. It is particularly effective to provide the cooling step at the time of dispersion under a high pressure of from 1,500 to 3,000 kg/cm 2 .
  • the cooling apparatus may be appropriately selected from a double pipe or triple pipe with a static mixer, a multi-tubular exchanger, a coiled heat exchanger and so forth depending on an amount of heat exchange to be reqired.
  • the size, wall thickness or material of a pipe may be appropriately selected to increase heat exchange efficiency depending on an applied pressure.
  • a refrigerant used in the cooling apparatus may be a well water at 20°C or a chilled water at from 5 to 10°C cooled by a refrigerator, and if desired, a refrigerant such as ethylene glycol/water at -30°C may also be used.
  • the organic silver salt is dispersed into solid fine grains preferably in the presence of a dispersing aid.
  • the dispersing aid can be selected from, for example, synthetic anion polymers such as polyacrylic acid, acrylic acid copolymer, maleic acid copolymer, maleic acid monoester copolymer and acryloylmethylpropanesulfonic acid copolymer, semisynthetic anionic polymers such as carboxymethyl starch and carboxymethyl cellulose, anionic polymers such as alginic acid and pectic acid, anionic surfactants described in JP-A-52-92716, International Patent Publication WO88/04794 and so forth, the compounds described in JP-A-9-179243, known anionic, nonionic or cationic surface active agents, known polymers such as polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, hydroxypropyl cellulose and hydroxypropylmethyl cellulose, and naturally-occurring polymer compounds such as gelatin.
  • the dispersing aid is generally mixed with the organic silver salt in a form of powder or wet cake before the dispersing process, and fed as slurry into a dispersing apparatus.
  • the dispersing aid may also be mixed with the organic silver salt beforehand, and then the mixture may be subjected to a treatment such as by heating or with a solvent to form an organic silver salt powder or wet cake.
  • the pH may be controlled with a suitable pH modifier before, during or after the dispersing operation.
  • the organic silver salt can be made into microparticles by roughly dispersing the salt in a solvent through pH control, and then changing the pH in the presence of a dispersing aid.
  • an organic solvent may be used as a solvent for the rough dispersion, and such organic solvent can be removed after the formation of grains.
  • the dispersion prepared can be stored with stirring to prevent precipitation of the grains during storage, or stored in a highly viscous state formed by means of a hydrophilic colloids (e.g., a jelly state formed with gelatin). Furthermore, the dispersion may contain a preservative in order to prevent proliferation of microorganisms during storage.
  • a hydrophilic colloids e.g., a jelly state formed with gelatin.
  • the organic silver salt prepared by a method for preparing organic silver salts is preferably dispersed in an aqueous solvent, and then mixed with an aqueous solution of a photosensitive silver salt to provide a coating solution for photosensitive image-forming media.
  • the stock solution is preferably roughly dispersed (preparatory dispersion).
  • the rough dispersion may be performed using a known dispersion means (for example, a high-speed mixer, a homogenizer, a high-speed impact mill, a Banbary mixer, a homomixer, a kneader, a ball mill, a vibrating ball mill, a planetary ball mill, an attriter, a sand mill, a bead mill, a colloid mill, a jet mill, a roller mill, a trone mill or a high-speed stone mill).
  • a known dispersion means for example, a high-speed mixer, a homogenizer, a high-speed impact mill, a Banbary mixer, a homomixer, a kneader, a ball mill, a vibrating ball mill, a planetary ball mill, an attriter, a sand mill, a bead mill, a colloid mill, a jet
  • the stock solution may be roughly dispersed in a solvent by controlling pH and thereafter formed into fine grains in the presence of a dispersion aid by changing pH.
  • the solvent used for the rough dispersion may be an organic solvent. The organic solvent is usually removed after the completion of fine grain formation.
  • the dispersion thus obtained is then mixed with an aqueous photosensitive silver salt solution to produce a coating solution for photosensitive image-forming media.
  • the coating solution enables the manufacture of a thermally processed image recording material exhibiting low haze and low fog, and having high sensitivity.
  • a photosensitive silver salt coexists at the time of dispersing process under a high-pressure by conversion into a high-speed flow, fog may increase and sensitivity may often highly decrease.
  • an organic solvent is used as a dispersion medium instead of water, haze and fog may increase and sensitivity may be likely to decrease.
  • sensitivity may be likely to decreased.
  • the above-described water dispersion obtained using conversion into high-speed flow under a high-pressure is substantially free of a photosensitive silver salt.
  • the content thereof is 0.1 mole % or less based on the light insensitive organic silver salt, and the photosensitive silver salt is not added intentionally.
  • the grain size (volume weight average diameter) in the solid fine grain dispersion of organic silver salt can be determined by, for example, irradiating the solid fine grain dispersion dispersed in a solution with a laser ray and determining an autocorrelation function of the fluctuation of the scattered light on the basis of the change in time (volume weight average diameter).
  • the solid fine grain dispersion preferably has an average grain size of 0.05 to 10.0 ⁇ m, more preferably from 0.1 to 5.0 ⁇ m, further preferably from 0.1 to 2.0 ⁇ m.
  • the organic silver salt solid fine grain dispersion preferably used in the present invention comprises at least an organic silver salt and water.
  • the ratio of the organic silver salt to water is not particularly limited.
  • the organic silver salt preferably accounts for from 5 to 50 weight %, more preferably from 10 to 30 weight % of the entire dispersion.
  • a dispersing aid is preferably used as described above but it is preferably used in a minimum amount within the range suitable for attaining a minimum grain size, specifically, in an amount of from 1 to 30 weight %, more preferably from 3 to 15 weight %, based on the organic silver salt.
  • a photothermographic material may be produced by mixing an organic silver salt aqueous dispersion and a photosensitive silver salt aqueous dispersion.
  • the mixing ratio of the organic silver salt and the photosensitive silver salt may be selected according to the purpose.
  • the ratio of the photosensitive silver salt to the organic silver salt is preferably from 1 to 30 mole %, more preferably from 3 to 20 mole %, still more preferably from 5 to 15 mole %.
  • two or more organic silver salt aqueous dispersions are preferably mixed with two or more photosensitive silver salt aqueous dispersions, so that the photographic properties can be controlled.
  • the organic silver salt may be used in any desired amount in the present invention. However, it is preferably used in an amount of from 0.1 to 5 g/m 2 , more preferably from 1 to 3 g/m 2 , in terms of silver.
  • the thermally processed image recording material of the invention contains a reducing agent for the organic silver salt.
  • the reducing agent for the organic silver salt may be any substance capable of reducing silver ions into silver, but is preferably an organic substance. Some examples of the reducing agent are described in JP-A-11-65021, paragraphs 0043 to 0045 and EP 0803764A1, from page 7, line 34 to page 18, line 12.
  • Especially preferred for use in the present invention are bisphenol-type reducing agents (e.g., 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane ).
  • the amount of the reducing agent is preferably from 0.01 to 5.0 g/m 2 , more preferably from 0.1 to 3.0 g/m 2 .
  • the amount of the reducing agent is preferably 5 to 50 mole %, more preferably 10 to 40 mole %, per mole of silver in the image-forming layer.
  • the reducing agent is preferably contained in the image
  • the reducing agent used in the invention is preferably added in the form of a dispersion of solid microparticles.
  • the microparticle dispersion of the reducing agent may be prepared in any known means for preparing fine particles (e.g., ball mill, vibration ball mill, sand mill, colloid mill, jet mill, roller mill etc.).
  • a dispersing aid may be used in preparing the solid microparticle dispersion.
  • the thermally processed image recording material of the present invention is preferably a photothermographic material which further contains a photosensitive silver halide.
  • the photosensitive silver halide that can be used for the present invention is not particularly limited as for the halogen composition, and silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide may be used.
  • the halide composition may have a uniform distribution in the grains, or the compositions may change stepwise or continuously in the grains.
  • Silver halide grains having a core/shell structure may be preferably used. Core/shell grains having preferably a double to quintuple structure, more preferably a double to quadruple structure may be used.
  • a technique for localizing silver bromide on the surface of silver chloride or silver chlorobromide grains may also be preferably used.
  • photosensitive silver halide For the preparation of the photosensitive silver halide, methods well known in the art, e.g., the methods described in Research Disclosure, No. 17029 (June, 1978) and U.S. Patent No. 3,700,458, can be used. More specifically, applicable methods for the present invention include a method comprising the step of preparing photosensitive silver halide grains by adding a silver-supplying compound and a halogen-supplying compound to a solution of gelatin or another polymer and then mixing the prepared grains with an organic silver salt.
  • the grain size of the photosensitive silver halide As for a grain size of the photosensitive silver halide, smaller grains are desirable to prevent cloudiness of the photosensitive material after image formation.
  • the grain size may preferably be not greater than 0.20 ⁇ m, preferably from 0.01 to 0.15 ⁇ m, more preferably from 0.02 to 0.12 ⁇ m.
  • the term "grain size” used herein means a diameter of a sphere having the same volume as the grain where the silver halide grains are regular crystals in cubic or octahedral form and where the silver halide grains are irregular crystals such as spherical or rod-like grains. Where silver halide grains are tabular grains, the term means the diameter of a circle having the same area as a projected area of the main surface of the tabular grain.
  • Examples of the form of silver halide grains include a cubic form, octahedral form, tabular form, spherical form, rod-like form and potato-like form. In particular, cubic grains are preferred for the present invention. Silver halide grains having round corners are also preferably used in the present invention.
  • Surface index (Miller index) of outer surfaces of the photosensitive silver halide grains is not particularly limited. However, it is desirable that [100] face be present in a high proportion that can achieve high spectral sensitizing efficiency when a spectral sensitizing dye adsorbed thereto. The proportion of [100] face may be preferably not lower than 50%, more preferably at least 65%, still more preferably at least 80%. The proportion of Miller index [100] face can be determined using the method described in T. Tani, J. Imaging Sci., 29, 165 (1985), where the difference in adsorption of a sensitizing dye to [111] face and [100] face is utilized.
  • the photosensitive silver halide grain used in the present invention contains a metal or metal complex of Group VIII to Group X in the periodic table of elements (including Group I to Group XVIII).
  • the metal or the center metal of the metal complex of Group VIII to X of the periodic table is preferably rhodium, rhenium, ruthenium, osmium or iridium.
  • the metal complex may be used alone, or two or more complexes of the same or different metals may also be used in combination.
  • the metal complex content is preferably from 1 ⁇ 10 -9 to 1 ⁇ 10 -3 mole per mole of silver. Such metal complexes are described in JP-A-11-65021, paragraphs 0018 to 0024.
  • an iridium compound is preferably contained in the silver halide grains.
  • the iridium compound include hexachloroiridium, hexammineiridium, trioxalatoiridium, hexacyanoiridium and pentachloronitrosyliridium.
  • the iridium compound is used after dissolving it in water or an appropriate solvent, and a method commonly used for stabilizing the iridium compound solution, more specifically, a method comprising adding an aqueous solution of hydrogen halogenide (e.g., hydrochloric acid, bromic acid, fluoric acid) or halogenated alkali (e.g., KCl, NaCl, KBr, NaBr) may be used.
  • hydrogen halogenide e.g., hydrochloric acid, bromic acid, fluoric acid
  • halogenated alkali e.g., KCl, NaCl, KBr, NaBr
  • separate silver halide grains previously doped with iridium may be added and dissolved at the time of preparation of silver halide.
  • the addition amount of the iridium compound is preferably 1 ⁇ 10 -8 to 1 ⁇ 10 -3 mole, more preferably 1 ⁇ 10 -7 to 5 ⁇ 10 -4 mole, per
  • metal complexes that can be contained in the silver halide grains used for the present invention (e.g., [Fe(CN) 6 ] 4- ), desalting methods and chemical sensitization method are described in JP-A-11-84574, paragraphs 0046 to 0050 and JP-A-11-65021, paragraphs 0025 to 0031.
  • one kind of photosensitive silver halide emulsion may be used or two or more kinds of photosensitive silver halide emulsions (for example, those different in the average grain size, different in the halogen composition, different in the crystal habit or different in the chemical sensitization conditions) may be used in combination.
  • photosensitive silver halide emulsions for example, those different in the average grain size, different in the halogen composition, different in the crystal habit or different in the chemical sensitization conditions
  • Sensitivity difference among the emulsions is preferably 0.2 log E or more.
  • the addition amount of the photosensitive silver halide is preferably 0.03 to 0.6 g/m 2 , more preferably 0.05 to 0.4 g/m 2 , most preferably 0.1 to 0.4 g/m 2 , in terms of the coated silver amount per 1 m 2 of the photosensitive material.
  • the addition amount of the photosensitive silver halide is preferably from 0.01 to 0.5 mole, more preferably from 0.02 to 0.3 mole, still more preferably from 0.03 to 0.25 mole, per mole of the organic silver salt.
  • the method and conditions for mixing photosensitive silver halide and organic silver salt, which are prepared separately, are not particularly limited so long as the effect of the present invention can be attained satisfactorily.
  • a method of mixing the silver halide grains and the organic silver salt after completion of respective preparations in a high-speed stirring machine, a ball mill, a sand mill, a colloid mill, a vibrating mill or a homogenizer or the like, or a method involving preparing organic silver salt while mixing therewith light-sensitive silver halide after completion of the preparation in any timing during preparation of the organic silver salt, or the like may be used.
  • Preferred addition time point for the silver halide into the coating solution for image-forming layer resides in a period of from 180 minutes before the coating to immediately before the coating, preferably 60 minutes to 10 seconds before the coating.
  • the method and conditions for mixing are not particularly limited so long as the effect of the present invention can be attained satisfactorily.
  • Specific examples of the mixing method include a method in which the mixing is performed in a tank designed so that a desired average residence time therein can be obtained, which residence time is calculated from addition flow rate and feeding amount to a coater, a method utilizing a static mixer described in N. Harnby, M.F. Edwards, A.W. Nienow, "Ekitai Kongo Gijutsu (Techniques for Mixing Liquids)", translated by Koji Takahashi, Chapter 8, Nikkan Kogyo Shinbunsha, 1989 and so forth.
  • the thermally processed image recording material of the present invention contains a binder.
  • the binder used for the present invention will be explained below.
  • the performance of the thermally processed image recording material of the present invention is improved if the layer containing an organic silver salt is formed by applying a coating solution comprising 30% by weight or more of water as to the total solvent and drying it, and if the binder of the layer containing an organic silver salt comprises a polymer latex soluble or dispersible in an aqueous solvent (water solvent) and showing an equilibrated moisture content of 2 weight % or less at 25°C and relative humidity of 60%.
  • the polymer latex is prepared to have an ion conductivity of 2.5 mS/cm or less.
  • a method for preparing such polymer latex there can be mentioned a method comprising synthesizing a polymer and purifying it by using a functional membrane for separation.
  • the aqueous solvent in which the polymer binder is soluble or dispersible is water or a mixed solvent of water and 70% by weight or less of a water-miscible organic solvent.
  • a water-miscible organic solvent include, for example, alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; ethyl acetate, dimethylformamide and so forth.
  • aqueous solvent referred to herein is also used for systems in which the polymer is not thermodynamically dissolved but is present in a so-called dispersed state.
  • the "equilibrated moisture content at 25°C and relative humidity of 60%" referred to herein for polymer latex is represented by the following equation, in which W1 indicates the weight of a polymer in humidity-conditioned equilibrium at 25°C and relative humidity of 60%, and W0 indicates the absolute dry weight of the polymer at 25°C.
  • Equilibrated moisture content at 25°C and relative humidity of 60% [(W1 - W0)/W0] ⁇ 100 (weight %)
  • the equilibrated moisture content at 25°C and relative humidity of 60% of the binder polymer used for the present invention is preferably 2% by weight or less, more preferably from 0.01 to 1.5% by weight, even more preferably from 0.02 to 1% by weight.
  • polymers dispersible in aqueous solvents are particularly preferred.
  • dispersed state examples include, for example, that of a polymer latex in which fine solid particles of polymer are dispersed, that in which a polymer is dispersed in a molecular state or as micelles and so forth. All of them are preferred.
  • hydrophobic polymers such as acrylic resins, polyester resins, rubber resins (e.g., SBR resins), polyurethane resins, polyvinyl chloride resins, polyvinyl acetate resins, polyvinylidene chloride resins and polyolefin resins can preferably be used.
  • the polymers may be linear, branched or crosslinked. They may be so-called homopolymers in which a single kind of monomer is polymerized, or copolymers in which two or more different kinds of monomers are polymerized.
  • the copolymers may be random copolymers or block copolymers.
  • the polymers may have a number average molecular weight of 5000 to 1000000, preferably from 10000 to 200000. Polymers having a too small molecular weight suffer from insufficient mechanical strength of the emulsion layer, and those having a too large molecular weight suffer from bad film forming property. Therefore, the both are not preferred.
  • aqueous solvent refers to a dispersion medium of which composition comprises at least 30% by weight of water.
  • the dispersion condition those in any condition may be used, including, for example, emulsion dispersion, micellar dispersion, molecular dispersion of a polymer having a hydrophilic moiety in the molecule and so forth.
  • polymer latex is particularly preferred.
  • polymer latex Preferred examples of the polymer latex are mentioned below. They are expressed with the constituent monomers.
  • the numerals parenthesized indicate the contents in terms of % by weight.
  • the molecular weights are number average molecular weights.
  • polymer latexes mentioned above are also commercially available, and those mentioned below can be used, for example.
  • acrylic resins are CEBIAN A-4635, 46583, 4601 (all from Daicel Chemical Industries), Nipol Lx811, 814, 821, 820, 857 (all from Nippon Zeon) etc.
  • polyester resins are FINETEX ES650, 611, 675, 850 (all from Dai-Nippon Ink & Chemicals), WD-size, WMS (both from Eastman Chemical) etc.
  • examples of polyurethane resins are HYDRAN AP10, 20, 30, 40 (all from Dai-Nippon Ink & Chemicals) etc.
  • examples of rubber resins are LACSTAR 7310K, 3307B, 4700H, 7132C (all from Dai-Nippon Ink & Chemicals), Nipol Lx416, 410, 438C, 2507 (all from Nippon Zeon) etc.
  • polyvinyl chloride resins are
  • polymer latexes may be used each alone, or two or more kinds of them may be blended as required.
  • styrene/butadiene copolymer latex is particularly preferred.
  • the weight ratio of styrene monomer units to butadiene monomer units is preferably 40/60 to 95/5.
  • the ratio of the styrene monomer units and the butadiene monomer units preferably account for from 60 to 99% by weight of the copolymer.
  • the preferred range of the molecular weight of the copolymer is similar to that mentioned above.
  • styrene/butadiene copolymer latexes preferably used for the present invention include the aforementioned P-3 to P-8, commercially available products, LACSTAR-3307B, 7132C, Nipol Lx416 and so forth.
  • the layer containing organic silver salt of the thermally processed image recording material of the invention may optionally contain a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose and hydroxypropyl cellulose.
  • a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose and hydroxypropyl cellulose.
  • the addition amount of the hydrophilic polymer is preferably 30% by weight or less, more preferably 20% by weight or less, of the total binder in the layer containing organic silver salt.
  • the layer containing organic silver salt (that is, the image-forming layer) of the thermally processed image recording material of the invention is preferably formed by using polymer latex.
  • the amount of the binder in the layer containing organic silver salt is such an amount that the weight ratio of total binder/organic silver salt should be 1/10 to 10/1, more preferably 1/5 to 4/1.
  • the layer containing organic silver salt usually also serves as a photosensitive layer (emulsion layer) containing a photosensitive silver salt, that is, a photosensitive silver halide.
  • a photosensitive layer emulsion layer
  • the weight ratio of total binder/silver halide is preferably 5 to 400, more preferably 10 to 200.
  • the total amount of the binder in the image-forming layer is preferably 0.2 to 30 g/m 2 , more preferably 1 to 15 g/m 2 .
  • the image-forming layer may optionally contain a crosslinking agent, a surfactant for improving coating property of the coating solution and so forth.
  • the solvent for the coating solution for the layer containing organic silver salt of the thermally processed image recording material of the invention is an aqueous solvent containing at least 30% by weight of water.
  • any water-miscible organic solvents including, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate and so forth may be used.
  • the water content of the solvent for the coating solution is preferably at least 50% by weight, more preferably at least 70% by weight.
  • sensitizing dye As a sensitizing dye that can be used for the present invention, there can be advantageously selected those sensitizing dyes which can spectrally sensitize silver halide grains within a desired wavelength range after they are adsorbed by the silver halide grains and have spectral sensitivity suitable for spectral characteristics of the light source to be used for exposure.
  • sensitizing dyes and addition methods therefor are described in JP-A-11-65021, paragraphs 0103 to 0109 and EP 0803764A1, page 19, line 38 to page 20, line 35, and there can be mentioned the compounds of formula (II) described in JP-A-10-186572.
  • the sensitizing dye is added to the silver halide emulsion preferably during the period after the desalting step and before the coating step, more preferably during the period after the desalting step and before the start of the chemical ripening.
  • antifoggants stabilizers and stabilizer precursors that can be used for the present invention, there can be mentioned, for example, those mentioned in JP-A-10-62899, paragraph 0070 and EP 0803764A1, from page 20, line 57 to page 21, line 7.
  • Antifoggants preferably used for the present invention are organic halides. Examples thereof include, for example, those disclosed in JP-A-11-65021, paragraphs 0111 to 0112.
  • the antifoggant is preferably added in the form of a solid microparticle dispersion.
  • the solid microparticle dispersion is performed by using a known pulverizing means (e.g., a ball mill, a vibration ball mill, a sand mill, a colloid mill, a jet mill, a roller mill).
  • a dispersing aid such as anionic surfactant (e.g., sodium triisopropylnaphthalenesulfonate (mixture of those having three isopropyl groups on different positions)) may be used.
  • antifoggant examples include the mercury(II) salts described in JP-A-11-65021, paragraph 0113 and the benzoic acids described in the same, paragraph 0114.
  • the thermally processed image recording material of the invention may contain an azolium salt as the antifoggant.
  • the azolium salt include, for example, the compounds of the formula (XI) described in JP-A-59-193447, the compounds described in JP-B-55-12581 and the compounds of the formula (II) described in JP-A-60-153039.
  • the azolium salt may be present in any site of the thermally processed image recording material, but is preferably in a layer on the photosensitive layer side, more preferably in the layer containing organic silver salt.
  • the azolium salt may be added at any time during the preparation of the coating solution.
  • the azolium salt When the azolium salt is added to the layer containing organic silver salt, it may be added at any time during the period of from the preparation of the organic silver salt to the preparation of the coating solution.
  • the azolium salt is preferably added during the period after the preparation of the organic silver salt and immediately before the coating.
  • the azolium salt may be added in any form such as powder, solution and microparticle dispersion. It may also be added as a solution that also contains other additives such as sensitizing dye, reducing agent and color tone adjuster.
  • the amount of the azolium salt to be added is not particularly limited, but it is preferably 1 ⁇ 10 -6 mole to 2 moles, more preferably 1 ⁇ 10 -3 mole to 0.5 mole, per mole of silver.
  • the thermally processed image recording material of the invention may optionally contain any of mercapto compounds, disulfide compounds and thione compounds in order to control development by retarding or accelerating it, or enhance spectral sensitivity, or improve storage stability before and after development.
  • mercapto compounds include, for example, those described in JP-A-10-62899, paragraphs 0067 to 0069, those of the formula (I) mentioned in JP-A-10-186572 and those mentioned in the paragraphs 0033 to 0052 of the same as specific examples, and those described in EP 0803764A1, page 20, lines 36 to 56.
  • preferred are mercapto-substituted heteroaromatic compounds.
  • a color tone adjuster it is preferable to add a color tone adjuster.
  • the color tone adjuster are mentioned in JP-A-10-62899, paragraphs 0054 to 0055 and EP 0803764A1, page 21, lines 23 to 48.
  • Preferred are phthalazinone, phthalazinone derivatives (e.g., 4-(1-naphthyl)phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone, 2,3-dihydro-1,4-phthalazinone and other derivatives) and metal salts thereof; combinations of phthalazinones and phthalic acid or derivatives thereof (e.g., phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, tetrachlorophthalic anhydride etc.); phthalazines including phthalazine and phthalazine derivatives (e.g., 4-(1-naphthyl)phthalazine, 6-isopropylphthal
  • Plasticizers and lubricants that can be used in the present invention for the photosensitive layer are described in JP-A-11-65021, paragraph 0117; ultrahigh contrast agents for forming ultrahigh contrast images are described in the same but in paragraph 0118; and hardness enhancement promoters are described in the same but in paragraph 0102.
  • the thermally processed image recording material of the present invention may preferably contain, as an ultrahigh contrast agent, one or more substituted alkene derivatives, substituted isooxazole derivatives, and specific acetal compounds represented by the following formulas (2) to (4), respectively.
  • R 1 , R 2 and R 3 each independently represents a hydrogen atom or a substituent, and Z represents an electron withdrawing group or a silyl group.
  • R 1 together with Z, R 2 together with R 3 , R 1 together with R 2 , or R 3 together with Z may be combined with each other to form a ring structure.
  • R 4 represents a substituent
  • X and Y independently represent a hydrogen atom or a substituent
  • a and B independently represent an alkoxyl group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclyloxy group, a heterocyclylthio group or a heterocyclylamino group
  • X together with Y, or A together with B may be combined with each other to form a ring structure.
  • R 1 , R 2 and R 3 independently represent a hydrogen atom or a substituent, and Z represents an electron withdrawing group or a silyl group.
  • R 1 together with Z, R 2 together with R 3 , R 1 together with R 2 , or R 3 together with Z may be combined with each other to form a ring structure.
  • R 1 , R 2 or R 3 represents a substituent
  • substituents include a halogen atom (e.g., fluorine, chlorine, bromide, iodine), an alkyl group (including a cycloalkyl group and active methine group), an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (including N-substituted nitrogen-containing heterocyclic group), a quaternized nitrogen-containing heterocyclic group (e.g., pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, carboxyl group or a salt thereof, an imino group, an imino group substituted at N atom, a thiocarbonyl group, a sulfonylcarbamoyl group, an acylcarbamoyl group, a
  • the electron withdrawing group represented by Z in the formula (2) is a substituent that gives a positive value of the Hammett's substituent constant ⁇ p, and specific examples include cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted at N atom, a thiocarbonyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, nitro group, a halogen atom, a perfluoroalkyl group, a perfluoroalkanamido group, a sulfonamido group, an acyl group, a formyl group, a phosphoryl group, carboxyl group (or a salt thereof), sulfo group (or a salt thereof), a heterocyclic group, an alkenyl group, an alkynyl group, an
  • the heterocyclic group mentioned above is a saturated or unsaturated heterocyclic group, and examples include a pyridyl group, a quinolyl group, a quinoxalinyl group, a pyrazinyl group, a benzotriazolyl group, an imidazolyl group, a benzimidazolyl group, a hydantoin-1-yl group, a succinimido group and a phthalimido group.
  • the electron withdrawing group represented by Z in the formula (2) may further have one or more substituents, and examples of such substituents include those described as the substituent on the groups represented by R 1 , R 2 or R 3 in the formula (2).
  • R 1 together with Z, R 2 together with R 3 , R 1 together with R 2 , or R 3 together with Z may be combined with each other to form a ring structure.
  • the ring structure formed is a non-aromatic carbocyclic ring or a non-aromatic heterocyclic ring.
  • the silyl group represented by Z in the formula (2) may preferably be trimethylsilyl group, t-butyldimethylsilyl group, phenyldimethylsilyl group, triethylsilyl group, triisopropylsilyl group or trimethylsilyldimethylsilyl group.
  • the electron withdrawing group represented by Z in the formula (2) may preferably be a group having a total carbon atom number of 0 to 30 such as cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a thiocarbonyl group, an imino group, an imino group substituted at N atom, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, nitro group, a perfluoroalkyl group, an acyl group, a formyl group, a phosphoryl group, an acyloxy group, an acylthio group or a phenyl group substituted with one or more electron withdrawing groups, more preferably cyano group, an alkoxycarbonyl group, a carbamoyl group, an imino group, a sulfamoyl group, an alkylsulfonyl group
  • the group represented by Z in the formula (2) is preferably an electron withdrawing group.
  • the substituent represented by R 1 , R 2 or R 3 in the formula (2) may preferably be a group having a total carbon atom number of 0 to 30, and specific examples of the group include a the same groups as those explained as the electron withdrawing group represented by Z in the formula (2), as well as an alkyl group, hydroxyl group (or a salt thereof), mercapto group (or a salt thereof), an alkoxyl group, an aryloxy group, a heterocyclyloxy group, an alkylthio group, an arylthio group, a heterocyclylthio group, an amino group, an alkylamino group, an arylamino group, a heterocyclylamino group, a ureido group, an acylamino group, a sulfonamido group and a substituted or unsubstituted aryl group and the like.
  • R 1 is preferably an electron withdrawing group, an aryl group, an alkylthio group, an alkoxyl group, an acylamino group, hydrogen atom, or a silyl group.
  • the electron withdrawing group may preferably be a group having a total carbon atom number of 0 to 30 such as cyano group, nitro group, an acyl group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a thiocarbonyl group, an imino group, an imino group substituted at N atom, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, carboxyl group (or a salt thereof), a saturated or unsaturated heterocyclic group, more preferably cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted at N atom, a sulfamo
  • R 1 represents an aryl group
  • the aryl group is preferably a substituted or unsubstituted phenyl group having a total carbon atom number of from 6 to 30.
  • the substituent may be any substituent, and an electron withdrawing substituent is preferred.
  • R 1 is more preferably an electron withdrawing group or an aryl group.
  • the substituent represented by R 2 or R 3 in the formula (2) may preferably be the same group as those explained as the electron withdrawing group represented by Z in the formula (2), as well as an alkyl group, hydroxyl group (or a salt thereof), mercapto group (or a salt thereof), an alkoxyl group, an aryloxy group, a heterocyclyloxy group, an alkylthio group, an arylthio group, a heterocyclylthio group, an amino group, an alkylamino group, an anilino group, a heterocyclylamino group, an acylamino group or a substituted or unsubstituted phenyl group.
  • R 2 and R 3 is hydrogen atom and the other is a substituent.
  • the substituent may preferably be an alkyl group, hydroxyl group (or a salt thereof), mercapto group (or a salt thereof), an alkoxyl group, an aryloxy group, a heterocyclyloxy group, an alkylthio group, an arylthio group, a heterocyclylthio group, an amino group, an alkylamino group, an anilino group, a heterocyclylamino group, an acylamino group (particularly, a perfluoroalkanamido group), a sulfonamido group, a substituted or unsubstituted phenyl group or a heterocyclic group, more preferably hydroxyl group (or a salt thereof), mercapto group (or a salt thereof), an alkoxyl group, an aryloxy group, a heterocyclyloxy group, an alkylthio group, an aryl
  • Z together with R 1 or R 2 together with R 3 form a ring structure.
  • the ring structure formed is a non-aromatic carbocyclic ring or a non-aromatic heterocyclic ring, preferably a 5-, 6- or 7-membered ring structure having a total carbon atom number, including those of substituents thereon, of 1 to 40, more preferably 3 to 30.
  • the compound represented by the formula (2) is more preferably a compound wherein Z represents cyano group, a formyl group, an acyl group, an alkoxycarbonyl group, an imino group or a carbamoyl group; R 1 represents an electron withdrawing group or an aryl group, and one of R 2 and R 3 represents hydrogen atom and the other represents hydroxyl group (or a salt thereof), mercapto group (or a salt thereof), an alkoxyl group, an aryloxy group, a heterocyclyloxy group, an alkylthio group, an arylthio group, a heterocyclylthio group or a heterocyclic group.
  • a class of most preferable compounds represented by the formula (2) are constituted by those wherein Z and R 1 form a non-aromatic 5-, 6- or 7-membered ring structure, and one of R 2 and R 3 represents hydrogen atom and the other represents hydroxyl group (or a salt thereof), mercapto group (or a salt thereof), an alkoxyl group, an aryloxy group, a heterocyclyloxy group, an alkylthio group, an arylthio group, a heterocyclylthio group or a heterocyclic group.
  • Z which forms a non-aromatic ring structure together with R 1 is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group or a sulfonyl group, and R 1 is preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted at N atom, an acylamino group or a carbonylthio group.
  • examples of the substituent represented by R 4 include those explained as the substituent represented by R 1 , R 2 or R 3 in the formula (2).
  • the substituent represented by R 4 in the formula (3) may preferably be an electron withdrawing group or an aryl group.
  • the electron withdrawing group may preferably be a group having a total carbon atom number of 0 to 30, such as cyano group, nitro group, an acyl group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, an imino group or a saturated or unsaturated heterocyclic group, more preferably cyano group, an acyl group, a formyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfon
  • R 4 represents an aryl group
  • the aryl group may preferably be a substituted or unsubstituted phenyl group having a total carbon atom number of 0 to 30.
  • substituents include those described as the substituent represented by R 1 , R 2 or R 3 in the formula (2).
  • R 4 in the formula (3) is most preferably cyano group, an alkoxycarbonyl group, a carbamoyl group, a heterocyclic group or a substituted or unsubstituted phenyl group, and most preferably cyano group, a heterocyclic group or an alkoxycarbonyl group.
  • X and Y independently represent hydrogen atom or a substituent
  • a and B independently represent an alkoxyl group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclylthio group, a heterocyclyloxy group or a heterocyclylamino group
  • X together with Y or A together with B may be combined with each other to form a ring structure.
  • Examples of the substituent represented by X or Y in the formula (4) include those described as the substituent represented by R 1 , R 2 or R 3 in the formula (2).
  • Specific examples include an alkyl group (including a perfluoroalkyl group and a trichloromethyl group), an aryl group, a heterocyclic group, a halogen atom, cyano group, nitro group, an alkenyl group, an alkynyl group, an acyl group, a formyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an imino group, an imino group substituted at the nitrogen atom, a carbamoyl group, a thiocarbonyl group, an acyloxy group, an acylthio group, an acylamino group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a phosphoryl group,
  • X together with Y may be combined with each other to form a ring structure, and the ring structure formed may be either a non-aromatic carbocyclic ring or a non-aromatic heterocyclic ring.
  • the substituent represented by X or Y may preferably be a substituent having a total carbon number of from 1 to 40, more preferably from 1 to 30, such as cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imino group, an imino group substituted at the nitrogen atom, a thiocarbonyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, nitro group, a perfluoroalkyl group, an acyl group, a formyl group, a phosphoryl group, an acylamino group, an acyloxy group, an acylthio group, a heterocyclic group, an alkylthio group, an alkoxyl group or an aryl group.
  • cyano group an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoy
  • X and Y are more preferably cyano group, nitro group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a formyl group, an acylthio group, an acylamino group, a thiocarbonyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an imino group, an imino group substituted at the nitrogen atom, a phosphoryl group, a trifluoromethyl group, a heterocyclic group , a substituted phenyl group or the like, most preferably cyano group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylthio group, an acylamino group, a thiocarbonyl group,
  • X and Y may also be preferably combined with each other to form a non-aromatic carbocyclic ring or a non-aromatic heterocyclic ring.
  • the ring structure formed is preferably a 5-, 6- or 7-membered ring having a total carbon atom number of 1 to 40, more preferably 3 to 30.
  • X and Y for forming a ring structure are preferably an acyl group, a carbamoyl group, an oxycarbonyl group, a thiocarbonyl group, a sulfonyl group, an imino group, an imino group substituted at the nitrogen atom, an acylamino group, a carbonylthio group or the like.
  • a and B independently represent an alkoxyl group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an anilino group, a heterocyclylthio group, a heterocyclyloxy group or a heterocyclylamino group, which may be combined with each other to form a ring structure.
  • the substituents represented by A and B in the formula (4) are preferably a group having a total carbon atom number of 1 to 40, more preferably 1 to 30, and the group may further have one or more substituents.
  • a and B are more preferably combined with each other to form a ring structure.
  • the ring structure formed is preferably a 5-, 6- or 7-membered non-aromatic heterocyclic ring having a total carbon atom number of 1 to 40, more preferably 3 to 30.
  • Examples of a structure (-A-B-) formed by the linking of A and B include -O-(CH 2 ) 2 -O-, -O-(CH 2 ) 3 -O-, -S-(CH 2 ) 2 -S-, -S-(CH 2 ) 3 -S-, -S-ph-S-, -N(CH 3 )-(CH 2 ) 2 -O-, -N(CH 3 )-(CH 2 ) 2 -S-, -O-(CH 2 ) 2 -S-, -O-(CH 2 ) 3 -S-, -N(CH 3 )-ph-O-, -N(CH 3 )-ph-S-, -N(ph)-(CH 2 ) 2 -S- and the like.
  • the compound represented by the formula (2), (3) or (4) for use in the present invention may be introduced with an adsorbing group capable of adsorbing to silver halide.
  • an adsorbing group capable of adsorbing to silver halide. Examples of the adsorbing group include the groups described in U.S. Patent Nos.
  • the adsorbing group to silver halide may be formed as a precursor.
  • Examples of the precursor include the groups described in JP-A-2-285344.
  • the compound represented by the formula (2), (3) or (4) for use in the present invention may be introduced with a ballast group or a polymer commonly used in the field of immobile photographic additives such as a coupler.
  • the compounds incorporated with the ballast group may be preferred for the present invention.
  • the ballast group is a group having 8 or more carbon atoms and being relatively inactive in the photographic performance. Examples of the ballast group include an alkyl group, an aralkyl group, an alkoxyl group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like.
  • Examples of the polymer include those described in JP-A-1-100530 and the like.
  • the compound represented by the formula (2), (3) or (4) for use in the present invention may contain a cationic group (specifically, a group containing a quaternary ammonio group or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom), a group containing an ethyleneoxy group or a propyleneoxy group as a repeating unit, an (alkyl, aryl or heterocyclic)thio group, or a dissociative group capable of dissociation by a base (e.g., carboxyl group, sulfo group, an acylsulfamoyl group, a carbamoylsulfamoyl group), preferably a group containing an ethyleneoxy group or a propyleneoxy group as a repeating unit, or an (alkyl, aryl or heterocyclic)thio group.
  • a cationic group specifically, a group containing a quaternary ammonio group or a nitrogen-containing heterocyclic group
  • the compounds represented by the formulas (2) to (4) for use in the present invention may be used after being dissolved in water or an appropriate organic solvent such as an alcohol (e.g., methanol, ethanol, propanol, fluorinated alcohol), a ketone (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide or methyl cellosolve.
  • an alcohol e.g., methanol, ethanol, propanol, fluorinated alcohol
  • a ketone e.g., acetone, methyl ethyl ketone
  • dimethylformamide dimethyl sulfoxide or methyl cellosolve.
  • the compounds may also be used as an emulsified dispersion mechanically prepared according to an already well known emulsification dispersion method by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, ethyl acetate or cyclohexanone as an auxiliary solvent for dissolution.
  • an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, ethyl acetate or cyclohexanone
  • the compounds may be used after dispersion of a powder in a suitable solvent such as water by using a ball mill, a colloid mill or the like, or by means of ultrasonic wave according to a known method for solid dispersion.
  • the compounds represented by the formulas (2) to (4) for use in the present invention may be added to any layers on a support provided at the side of the image-forming layer, i.e., the image-forming layer and/or the other layers provided on the same side.
  • the compounds may preferably be added to the image-forming layer and a layer adjacent thereto.
  • the amount of the compounds represented by the formulas (2) to (4) for use in the present invention is preferably from 1 ⁇ 10 -6 to 1 mole, more preferably from 1 ⁇ 10 -5 to 5 ⁇ 10 -1 mole, most preferably from 2 ⁇ 10 -5 to 2 ⁇ 10 -1 mole per mole of silver.
  • the compounds represented by formulas (2) to (4) can be easily synthesized according to known methods.
  • the compounds may be synthesized by referring to the methods described in U.S. Patent Nos. 5,545,515, 5,635,339 and 5,654,130, International Patent Publication WO97/34196 or Japanese Patent Application Nos. 9-354107, JP-A-11-133546, JP-A-11-95365.
  • the compounds represented by the formulas (2) to (4) may be used alone or in combination of two or more compounds.
  • any of the compounds described in U.S. Patent Nos. 5,545,515, 5,635,339 and 5,654,130, International Patent Publication WO97/34196, U.S. Patent No. 5,686,228 or Japanese Patent Application Nos. 9-228881, JP-A-11-119372, Japanese Patent Application Nos. 9-354107, JP-A-11-133546, JP-A-11-119373, JP-A-11-109546, JP-A-11-95365, JP-A-11-95366, JP-A-11-149136 may also be used in combination.
  • hydrazine derivatives described in JP-A-10-339932 and JP-A-10-161270 may be used in combination.
  • the following hydrazine derivatives may also be used in combination: the compounds represented by (Chem.
  • JP-B-6-77138 specifically, compounds described at pages 3 and 4 of the publication
  • the compounds represented by the formula (I) of JP-B-6-93082 specifically, Compounds 1 to 38 described at pages 8 to 18 of the publication
  • the compounds represented by the formulas (4), (5) and (6) of JP-A-6-230497 specifically, Compounds 4-1 to 4-10 described at pages 25 and 26, Compounds 5-1 to 5-42 described at pages 28 to 36 and Compounds 6-1 to 6-7 described at pages 39 and 40 of the publication
  • JP-A-6-313936 specifically, compounds described at pages 6 to 19 of the publication; the compound represented by (Chem. 1) of JP-A-6-313951, specifically, the compounds described at pages 3 to 5 of the publication; the compound represented by the formula (I) of JP-A-7-5610, specifically, Compounds I-1 to I-38 described at pages 5 to 10 of the publication; the compounds represented by the formula (II) of JP-A-7-77783, specifically, Compounds II-1 to II-102 described at pages 10 to 27 of the publication; the compounds represented by the formulas (H) and (Ha) of JP-A-7-104426, specifically, Compounds H-1 to H-44 described at pages 8 to 15 of the publication; the compounds characterized by having in the vicinity of the hydrazine group an anionic group or a nonionic group capable of forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine, described in EP713131A, particularly, the compounds represented
  • hydrazine derivatives for use in the present invention may be used after being dissolved in water or an appropriate organic solvent such as an alcohol (e.g., methanol, ethanol, propanol, fluorinated alcohol), a ketone (e.g., acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide or methyl cellosolve.
  • an alcohol e.g., methanol, ethanol, propanol, fluorinated alcohol
  • a ketone e.g., acetone, methyl ethyl ketone
  • dimethylformamide dimethyl sulfoxide or methyl cellosolve.
  • the compounds may also be used as an emulsified dispersion mechanically prepared according to an already well known emulsification dispersion method by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, ethyl acetate or cyclohexanone as an auxiliary solvent for dissolution.
  • an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, ethyl acetate or cyclohexanone
  • the compounds may be used after dispersion of a powder in water by using a ball mill, a colloid mill or the like, or by means of ultrasonic wave according to a known method for solid dispersion.
  • the hydrazine derivatives may be added to any layers on a support provided at the side of the image-forming layer, i.e., the image-forming layer and/or the other layers provided on the same side.
  • the compounds may preferably be added to the image-forming layer and a layer adjacent thereto.
  • the amount of the hydrazine derivatives is preferably from 1 ⁇ 10 -6 to 1 mole, more preferably from 1 ⁇ 10 -5 to 5 ⁇ 10 -1 mole, most preferably from 2 ⁇ 10 -5 to 2 ⁇ 10 -1 mole per mole of silver.
  • the acrylonitrile compounds disclosed in U.S. Patent No. 5,545,515, more specifically the compounds CN-1 to CN-13 disclosed therein and the like may also be used as the ultrahigh contrast agent.
  • a contrast accelerator may be used in combination with the above-described ultrahigh contrast agent for the formation of an ultrahigh contrast image.
  • the thermally processed image recording material of the present invention may have a surface protective layer, for example, to prevent adhesion of the image-forming layer.
  • a surface protective layer for example, to prevent adhesion of the image-forming layer.
  • the details of the surface protective layer are described in, for example, JP-A-11-65021, paragraphs 0119 to 0120.
  • PVA polyvinyl alcohol
  • Gelatin is preferred for the binder in the surface protective layer of the thermally processed image recording material of the present invention, but polyvinyl alcohol (PVA) is also preferably used.
  • PVA includes, for example, completely saponified PVA-105 [having a polyvinyl alcohol (PVA) content of at least 94.0% by weight, a degree of saponification of 98.5 ⁇ 0.5 mole %, a sodium acetate content of 1.5% by weight or less, a volatile content of 5.0% by weight or less, a viscosity (4% by weight at 20°C) of 5.6 ⁇ 0.4 mPa ⁇ s]; partially saponified PVA-205 [having a PVA content of 94.0% by weight, a degree of saponification of 88.0 ⁇ 1.5 mole %, a sodium acetate content of 1.0% by weight, a volatile content of 5.0% by weight, a viscosity (4% by weight at 20°C) of 5.0 ⁇
  • the temperature at which the coating solution for the image-forming layer is prepared is preferably 30°C to 65°C, more preferably 35°C to 60°C but lower than 60°C, even more preferably 35°C to 55°C.
  • the temperature of the coating solution is preferably kept at 30°C to 65°C immediately after the addition of polymer latex.
  • a reducing agent and an organic silver salt are mixed preferably before the addition of polymer latex.
  • the organic silver salt-containing liquid or the coating solution for the thermographic image-forming layer is a preferably so-called thixotropic flow.
  • Thixotropy indicates a property of a fluid that viscosity of the fluid lowers with the increase of shear rate. While any apparatus may be used for measuring the viscosity of fluids, RFS Fluid Spectrometer from Rheometrics Far East Co., Ltd. is preferably used and the measurement is performed at 25°C.
  • the organic silver salt-containing liquid or the coating solution for the photothermographic image-forming layer preferably has a viscosity of 400 mPa ⁇ s to 100,000 mPa ⁇ s, more preferably 500 mPa ⁇ s to 20,000 mPa ⁇ s, at a shear rate of 0.1 sec -1 .
  • the viscosity is preferably 1 mPa ⁇ s to 200 mPa ⁇ s, more preferably 5 mPa ⁇ s to 80 mPa ⁇ s, at a shear rate of 1000 sec -1 .
  • thixotropic fluids indispensably contain a large amount of fine solid microparticles.
  • the fluids shall contain a viscosity-increasing linear polymer, or the contained fine solid microparticles shall have anisotropic shapes and have an increased aspect ratio.
  • Use of an alkaline viscosity-increasing agent or a surfactant is also effective for that purpose.
  • the photothermographic emulsion layer used in the present invention is formed as one or more layers on the support.
  • the layer When it consists of one layer, the layer must contain an organic silver salt, a silver halide, a developing agent and a binder, as well as optional additional materials such as color tone adjuster, coating aid and other auxiliary agents.
  • the first emulsion layer In general, this is directly adjacent to the support
  • the second emulsion layer or the two layers must contain the other ingredients.
  • Another type of two-layer structure in which one layer is a single emulsion layer containing all the necessary ingredients and the other layer is a protective top coat layer.
  • Multicolor photothermographic image recording material may contain these two layers for each color, or may contain all the necessary ingredients in a single layer as described in U.S. Patent No. 4,708,928.
  • the individual emulsion layers are contained in the material in such a state that they are partitioned each other by using a functional or non-functional barrier layer between the adjacent photosensitive layers as described in U.S. Patent No. 4,460,681.
  • the photosensitive layer of the thermally processed image recording material of the present invention may contain various types of dyes and pigments for improving the color tone, for preventing interference fringes generated during laser exposure, and for preventing irradiation.
  • dyes and pigments are described in International Patent Publication WO98/36322.
  • Preferred dyes and pigments for the photosensitive layer are anthraquinone dyes, azomethine dyes, indoaniline dyes, azo dyes, indanthrone pigments of anthraquinone type (e.g., C.I. Pigment Blue 60 etc.), phthalocyanine pigments (e.g., copper phthalocyanines such as C.I.
  • Pigment Blue 15 metal-free phthalocyanines such as C.I. Pigment Blue 16
  • triarylcarbonyl pigments of printing lake pigment type indigo
  • inorganic pigments e.g., ultramarine, cobalt blue etc.
  • These dyes and pigments may be added to the layer in any desired manner. For example, they may be added as solutions, emulsions or dispersions of fine solid microparticles, or they may be added in such a state that they are mordanted on a polymer mordant.
  • the amount of these compounds to be used may vary depending on the intended absorbance, but they are preferably used in an amount of 1 ⁇ g to 1 g per m 2 of the thermally processed image recording material, in general.
  • an antihalation layer may be provided at a position opposite to the light source with respect to the photosensitive layer.
  • the details of the antihalation layer are described in JP-A-11-65021, paragraphs 0123 to 0124.
  • a decoloring dye and a base precursor are preferably added to a light insensitive layer of the thermally processed image recording material so that the light insensitive layer should function as a filter layer or an antihalation layer.
  • Thermally processed image recording materials generally have light insensitive layers in addition to photosensitive layers. Depending on their positions, the light insensitive layers are classified into (1) a protective layer to be disposed on a photosensitive layer (remoter from the support than the photosensitive layer); (2) an intermediate layer to be disposed between photosensitive layers or between a photosensitive layer and a protective layer; (3) an undercoat layer to be disposed between a photosensitive layer and a support; (4) a backing layer to be disposed on a side opposite to that on which a photosensitive layer is disposed.
  • the filter layer is provided in the photosensitive material as the layer (1) or (2).
  • the antihalation layer is provided in the photosensitive material as the layer (3) or (4).
  • the decoloring dye and the base precursor are preferably added to the same light insensitive layer. However, they may be added separately to adjacent two light insensitive layers. If desired, a barrier layer may be disposed between the two light insensitive layers.
  • a solution, emulsion or solid microparticles dispersion of the dye can be added to a coating solution for the light insensitive layer.
  • the dye may also be added to the light insensitive layer by using a polymer mordant.
  • polymer mordant are the same as those generally employed for adding dyes to ordinary thermally processed image recording materials.
  • Polymer latex used for impregnated polymers are described in U.S. Patent No. 4,199,363, German Patent Laid-Open Nos. 25,141,274, 2,541,230, EP-A-029104, and JP-B-53-41091.
  • a method for emulsification by adding a dye to a polymer solution is described in International Patent Publication WO88/00723.
  • the amount of the decoloring dye to be added is determined depending on the use of the dye.
  • the dye is used in such an amount that the dye added can ensure an optical density (absorbance), measured at an intended wavelength, of larger than 1.0.
  • the optical density is preferably 0.2 to 2.
  • the amount of the dye capable of ensuring the optical density within the range may be generally from 0.001 to 1 g/m 2 or so, preferably from 0.005 to 0.8 g/m 2 or so, particularly preferably from 0.01 to 0.2 g/m 2 or so.
  • Decoloring the dyes in that manner can lower the optical density of the material to 0.1 or less.
  • Two or more different types of decoloring dyes may be used in the thermodecoloring type recording materials or thermally processed image recording materials.
  • two or more different types of base precursors may be used in combination.
  • the thermally processed image recording material of the present invention is preferably a so-called single-sided photosensitive material comprising at least one photosensitive layer containing a silver halide emulsion on one side of support, and a backing layer on the other side.
  • the thermally processed image recording material of the present invention preferably contains a matting agent for improving the transferability of the material. Matting agents are described in JP-A-11-65021, paragraphs 0126 to 0127.
  • the matting agent is added in an amount of preferably 1 to 400 mg/m 2 , more preferably 5 to 300 mg/m 2 , in terms of the amount per 1 m 2 of the image recording material.
  • the matting degree of the surface of the emulsion layer is not particularly limited so long as the matted emulsion layer surface is free from stardust defects.
  • Beck's smoothness of the matted surface is preferably 50 seconds to 10000 seconds, more preferably 80 seconds to 10000 seconds.
  • the matting degree of the backing layer in the present invention is preferably falls 10 seconds to 1200 seconds, more preferably 30 seconds to 700 seconds, even more preferably 50 seconds to 500 seconds, in terms of the Beck's smoothness.
  • the matting agent is preferably contained in the outermost surface layer, or in a layer functioning as an outermost surface layer, or in a layer near to the outer surface of the image recording material. It is also preferably contained in a layer functioning as a protective layer.
  • a hardening agent may be added to the photosensitive layer, the protective layer, the backing layer and other layers in the thermally processed image recording material of the present invention.
  • the details of the hardening agent are described in T.H. James, "THE THEORY OF THE PHOTOGRAPHIC PROCESS, FOURTH EDITION", Macmillan Publishing Co., Inc., 1977, pp. 77-87.
  • preferably used are polyvalent metal ions described on page 78 of the reference; polyisocyanates described in U.S. Patent No. 4,281,060 and JP-A-6-208193; epoxy compounds described in U.S. Patent No. 4,791,042; vinylsulfone compounds described in JP-A-62-89048 and so forth.
  • the hardening agent is added to coating solutions as a solution.
  • Preferred addition time point for the solution into the coating solution for protective layer resides in a period of from 180 minutes before the coating to immediately before the coating, preferably 60 minutes to 10 seconds before the coating.
  • the method and conditions for mixing are not particularly limited as far as the effect of the present invention can be attained satisfactorily.
  • Specific examples of the mixing method include a method in which the mixing is performed in a tank designed so that a desired average residence time therein can be obtained, which residence time is calculated from addition flow rate and feeding amount to a coater, a method utilizing a static mixer described in N. Harnby, M.F. Edwards, A.W. Nienow, "Ekitai Kongo Gijutsu (Techniques for Mixing Liquids)", translated by Koji Takahashi, Chapter 8, Nikkan Kogyo Shinbunsha, 1989 and so forth.
  • Transparent supports for the thermally processed image recording material of the present invention may be colored with blue dyes (e.g., with Dye-1 described in Examples of JP-A-8-240877), or may be colorless. Techniques for undercoating the supports are described in JP-A-11-84574, JP-A-10-186565 and so forth.
  • the thermally processed image recording material of the invention is preferably of a monosheet type.
  • the monosheet type does not use any additional sheets such as image receiving materials, but can form images directly on the material itself.
  • the thermally processed image recording material of the present invention may further contain an antioxidant, a stabilizer, a plasticizer, a UV absorber or a coating aid.
  • an antioxidant e.g., a sulfur dioxide, a carbonate, a carbonate, a carbonate, a carbonate, a carbonate, a carbonate, a carbonate, a carbonate, a carbonate, a carbonate, a carbonate, a carbonate, carbonate, carbonate, ethylene glycol dimethacrylate, poly(ethylene glycol) terpolymer, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polymethyl methacrylate, polysulfate, polyurethane, polyurethane, polyurethane, polyurethane, ethylene glycol dimethoxysulfate, ethylene glycol dimethoxysulfate, ethylene glycol dimethacrylate,
  • the thermally processed image recording material of the present invention can be produced by using any coating method.
  • coating methods include various types of coating techniques, for example, extrusion coating, slide coating, curtain coating, dip coating, knife coating, flow coating, extrusion coating utilizing a hopper of the type described in U.S. Patent No. 2,681,294 and so forth.
  • Preferably used are extrusion coating and slide coating described in Stephen F. Kistler, Petert M. Schweizer, "LIQUID FILM COATING", published by CHAPMAN & HALL Co., Ltd., 1997, pp.399-536, and particularly preferably used is the slide coating.
  • An example of the shape of a slide coater used for the slide coating is shown in Figure 11b, 1, on page 427 of the aforementioned reference.
  • two or more layers may be formed at the same time, for example, according to the methods described from page 399 to page 536 of the aforementioned reference, or the methods described in U.S. Patent No. 2,761,791 and British Patent No. 837,095.
  • a method for preventing uneven processing caused by dimensional change of the thermally processed image recording material of the present invention during the aforementioned heat development effectively used is a method comprising heating the material for 5 seconds or more at a temperature of from 80°C to a temperature lower than 115°C (preferably 113°C or lower) so as not to produce images and then performing heat development at a temperature of 110°C or higher (preferably 130°C or higher) to form images (so-called multi-step heating method).
  • FIG. 1 depicts a side view of a heat-developing apparatus.
  • the apparatus shown in Fig. 1 comprises carrying-in roller pairs 11 (lower rollers are heating rollers), which carry a thermally processed image recording material 10 into the heating section while making the material in a flat shape and preheating it, and carrying-out roller pairs 12, which carry out the thermally processed image recording material 10 after heat development from the heating section while maintaining the material to be in a flat shape.
  • the thermally processed image recording material 10 is heat-developed while it is conveyed by the carrying-in roller pairs 11 and then by the carrying-out roller pairs 12.
  • a conveying means for carrying the thermally processed image recording material 10 under the heat development is provided with multiple rollers 13 so that they should be contacted with the side of the image-forming layer, and a flat surface 14 consisting of non-woven fabric (composed of aromatic polyamide, Teflon etc.) or the like is provided on the opposite side so that it should be contacted with the back surface.
  • the thermally processed image recording material 10 is conveyed by driving of the multiple rollers 13 contacted with the image-forming layer side, while the back surface slides on the flat surface 14.
  • heaters 15 are provided over the rollers 13 and under the flat surface 14 so that the thermally processed image recording material 10 should be heated from the both sides. Examples of the heating means include panel heaters and so forth. While clearance between the rollers 13 and the flat surface 14 may vary depending on the member of the flat surface, it is suitably adjusted to a clearance that allows the conveyance of the thermally processed image recording material 10. The clearance is preferably 0-1 mm.
  • the material of the surface of the rollers 13 and the member of the flat surface 14 may be composed of any materials so long as they have heat resistance and they should not cause any troubles in the conveyance of the thermally processed image recording material 10.
  • the material of the roller surface is preferably composed of silicone rubber
  • the member of the flat surface is preferably composed of non-woven fabric made of aromatic polyamide or Teflon (polytetrafluoroethylene).
  • the heating means preferably comprises multiple heaters so that temperature of each heater can be adjusted freely.
  • the heating section is constituted by a preheating section A comprising the carrying-in roller pairs 11 and a heat development section B comprising the heaters 15.
  • the temperature of the preheating section A located upstream from the heat development section B is preferably selected to be lower than the heat development temperature (for example, by about 10-30°C), and the temperature and heat development time are preferably adjusted so that they are sufficient for evaporating moisture contained in the thermally processed image recording material 10.
  • the temperature of the heat development section B is also preferably selected to be higher than the glass transition temperature (Tg) of the support of the thermally processed image recording material 10 so that uneven development should be prevented.
  • guide panels 16 are provided downstream from the heat development section B, and they constitute a gradual cooling section C together with the carrying-out roller pairs 12.
  • the guide panels 16 are preferably composed of a material of low heat conductivity, and it is preferred that the cooling is performed gradually.
  • the heat-development apparatus is explained with reference to an example shown in the drawing.
  • the apparatus is not limited to the example.
  • the heat-development apparatus used for the present invention may have a variety of structures such as disclosed in JP-A-7-13294.
  • the thermally processed image recording material may be successively heated at different temperatures in such an apparatus as mentioned above, which is provided with two or more heat sources at different temperatures.
  • the thermally processed image recording material of the invention may be developed in any manner. Usually, an imagewise exposed thermally processed image recording material is developed by heating.
  • the temperature for the development is preferably 80°C to 250°C, more preferably 100°C to 140°C.
  • the development time is preferably 1 to 180 seconds, more preferably 10 to 90 seconds, even more preferably 10 to 40 seconds.
  • a plate heater system For thermal development for the material, preferred is a plate heater system.
  • the methods described in Japanese Patent Application Nos. 9-229684 and JP-A-11-133572 are preferred.
  • the plate heater system described in these references is a heat development apparatus wherein a thermally processed image recording material on which a latent image is formed is brought into contact with a heating means in a heat development section to obtain a visible image.
  • the heating means comprises a plate heater, and a plurality of presser rollers are disposed facing to one surface of the plate heater. Heat development of the thermally processed image recording material is attained by passing the material between the presser rollers and the plate heater.
  • the plate heater is preferably sectioned into 2 to 6 stages, and the temperature of the top stage is preferably kept lower by 1 to 10°C or so than that of the others. Such a method is also described in JP-A-54-30032. Such a plate heater system can remove moisture and organic solvent contained in the thermally processed image recording material out of the material, and prevent deformation of the support of the thermally processed image recording material by rapidly heating the material.
  • the thermally processed image recording material of the present invention can be exposed in any manner.
  • laser rays are preferred.
  • gas lasers Ar + , He-Ne
  • YAG lasers YAG lasers
  • dye lasers semiconductor lasers and so forth are preferred.
  • a combination of semiconductor laser and second harmonic generating device may also be used. Preferred are gas or semiconductor lasers for red to infrared emission.
  • Single mode lasers can be used for the laser rays, and the technique disclosed in JP-A-11-65021, paragraph 0140 can be used.
  • the laser output is preferably at least 1 mW, more preferably at least 10 mW. Even more preferred is high output of at least 40 mW. If desired, a plurality of lasers may be combined.
  • the diameter of one laser ray may be on the level of 1/e 2 spot size of a Gaussian beam, falling between 30 and 200 ⁇ m or so.
  • the thermally processed image recording material of the invention forms a monochromatic image based on silver image, and is preferably used as photothermographic photosensitive materials for use in medical diagnosis, industrial photography, printing and COM.
  • the monochromatic images formed can be duplicated on duplicating films, MI-Dup, from Fuji Photo Film for medical diagnosis; and for printing, the images can be used as the mask for forming reverse images on printing films such as DO-175 and PDO-100 from Fuji Photo Film, or on offset printing plates.
  • Exemplary Compound (P-1) was obtained as white crystals (yield: 81%) in the same manner as that of Synthesis Example 1 except that the octylamine was replaced with an equimolar amount of n-butylamine.
  • Exemplary Compound (P'-12) was obtained as white crystals in the same manner as that of Synthesis Example 1 except that the octylamine was replaced with an equimolar amount of 2,2,2-trifluoroethylamine.
  • Comparative Compounds 1-4 shown below correspond to Comparative Compounds 1-4 mentioned in Tables 1 and 3 mentioned later in the present specification
  • Comparative Compounds (1)-(5) shown below correspond to Comparative Compounds (1)-(5) mentioned in Tables 2 and 4 mentioned later in the present specification.
  • the PET was pelletized, and the pellets were dried at 130°C for 4 hours, melted at 300°C, extruded from a T-die, and quenched to prepare an unstretched film having such a thickness that the film thickness after thermal fixation should become 175 ⁇ m.
  • the film was stretched along the longitudinal direction by 3.3 times using rollers having different peripheral speeds and then stretched along the transverse direction by 4.5 times using a tenter.
  • the temperatures were 110°C and 130°C, respectively.
  • the film was subjected to thermal fixation at 240°C for 20 seconds and relaxed by 4% along the transverse direction at the same temperature.
  • the both edges of the film were knurled, and the film was rolled up at 4 kg/cm 2 to provide a roll of the film having a thickness of 175 ⁇ m.
  • both surfaces of the support were treated at room temperature at 20 m/minute.
  • the treated frequency in this case was 9.6 kHz and the gap clearance between the electrode and the dielectric roll was 1.6 mm.
  • 158 g 2,4-Dichloro-6-hydroxy-S-triazine sodium salt 8 % by weight aqueous solution
  • one surface (photosensitive layer coating surface side) thereof was coated with the undercoating solution of Formulation (1) by a wire bar in a wet coating amount of 6.6 ml/m 2 (per one surface) and dried at 180°C for 5 minutes.
  • the back surface thereof was coated with the undercoating solution of Formulation (2) by a wire bar in a wet coating amount of 5.7 ml/m 2 and dried at 180°C for 5 minutes.
  • the back surface thus coated was coated with the undercoating solution of Formulation (3) by a wire bar in a wet coating amount of 7.7 ml/m 2 and dried at 180°C for 6 minutes to prepare an undercoated support.
  • Solution A was prepared by adding distilled water to 37.04 g of silver nitrate to dilute it to 159 ml
  • Solution B was prepared by diluting 32.6 g of potassium bromide with distilled water to a volume of 200 ml.
  • the whole volume of Solution A was added by the control double jet method over 1 minute at a constant flow rate while pAg was maintained at 8.1.
  • Solution B was also added by the control double jet method. Then, the mixture was added with 30 ml of 3.5 % by weight aqueous hydrogen peroxide solution, and further added with 36 ml of a 3 % by weight aqueous solution of benzimidazole.
  • Solution A2 was prepared by diluting Solution A with distilled water to a volume of 317.5 ml
  • Solution B2 was prepared by dissolving tripotassium hexachloroiridate in Solution B in such an amount that its final concentration should become 1 ⁇ 10 -4 mole per mole of silver, and diluting the obtained solution with distilled water to a volume twice as much as the volume of Solution B, 400 ml.
  • Solution A2 The whole volume of Solution A2 was added to the mixture again by the control double jet method over 10 minutes at a constant flow rate while pAg was maintained at 8.1.
  • Solution B2 was also added by the control double jet method. Then, the mixture was added with 50 ml of a 0.5 % by weight solution of 2-mercapto-5-methylbenzimidazole in methanol. After pAg was raised to 7.5 with silver nitrate, the mixture was adjusted to pH 3.8 using 0.5mol/L sulfuric acid, and the stirring was stopped.
  • the mixture was subjected to precipitation, desalting and washing with water, added with 3.5 g of deionized gelatin and 1 mol/L sodium hydroxide to be adjusted to pH 6.0 and pAg of 8.2 to form a silver halide dispersion.
  • the grains in the completed silver halide emulsion were pure silver bromide grains having a mean spherical diameter of 0.053 ⁇ m and a variation coefficient of 18% in terms of spherical diameter.
  • the grain size and others were obtained from averages for 1000 grains by using an electron microscope.
  • the [100] face ratio of these grains were determined to be 85% by the Kubelka-Munk method.
  • the aforementioned dispersion was added with 0.035 g of benzoisothiazolinone (added as a 3.5 % by weight methanol solution of the compound) with stirring at 38°C, after 40 minutes since then, added with the solid dispersion (an aqueous gelatin solution) of Spectral sensitizing dye A described above in an amount of 5 ⁇ 10 -3 mole per mole of silver. After 1 minutes, the mixture was warmed to 47°C, and after 20 minutes, added with 3 ⁇ 10 -5 mole of sodium benzenethiosulfonate per mole of silver.
  • the mixture was added with Tellurium sensitizer B in an amount of 5 ⁇ 10 -5 mole per mole of silver followed by ripening for 90 minutes.
  • the mixture was added with 5 ml of a 3.5 % by weight methanol solution of N,N'-dihydroxy-N''-diethylmelamine, and after lowering the temperature to 31°C, added with 5 ml of a 3.5 % by weight methanol solution of phenoxyethanol, 7 ⁇ 10 -3 mole of 5-methyl-2-mercaptobenzimidazole per mole of silver, and 6.4 ⁇ 10 -3 mole of 1-phenyl-2-heptyl-5-mercapto-1,3,4-triazole per mole of silver to prepare Silver halide emulsion 1.
  • Silver halide emulsion 2 Furthermore, in the same manner as in the case of Silver halide emulsion 1 except that the addition amount of Spectral sensitizing dye A was changed to 4.5 ⁇ 10 -3 mole per mole of silver, the spectral sensitizer, the chemical sensitizer, 5-methyl-2-mercaptobenzimidazole and 1-phenyl-2-heptyl-5-mercapto-1,3,4-traizole were added to the dispersion to obtain Silver halide emulsion 2.
  • Silver halide emulsion 2 Furthermore, in the same manner as in the case of Silver halide emulsion 1 except that the addition amount of Spectral sensitizing dye A was changed to 6 ⁇ 10 -3 mole per mole of silver, the spectral sensitizer, the chemical sensitizer, 5-methyl-2-mercaptobenzimidazole and 1-phenyl-2-heptyl-5-mercapto-1,3,4-traizole were added to the dispersion to obtain Silver halide emulsion 2.
  • a mixture of 635 L of distilled water and 30 L of tert-butanol contained in a reaction vessel kept at 30°C was added with the whole amount of the aforementioned sodium behenate solution and the whole amount of the aqueous silver nitrate solution at constant flow rates over the periods of 62 minutes and 10 seconds, and 60 minutes, respectively.
  • the outside temperature was controlled so that the temperature in the reaction vessel should be 30°C and the liquid temperature should be constant.
  • the piping of the addition system for the sodium behenate solution was warmed by steam trace and the steam opening was controlled such that the liquid temperature at the outlet orifice of the addition nozzle should be 75°C.
  • the piping of the addition system for the aqueous silver nitrate solution was maintained by circulating cold water outside a double pipe.
  • the addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis as the center, and the positions are controlled at heights for not contacting with the reaction mixture.
  • the mixture was left with stirring for 20 minutes at the same temperature and then the temperature was decreased to 25°C. Thereafter, the solid content was recovered by a suction filtration and the solid content was washed with water until electric conductivity of the filtrate became 30 ⁇ S/cm. Thus, a fatty acid silver salt was obtained.
  • the solid content was stored as a wet cake without being dried.
  • the pre-dispersed stock dispersion was treated three times by using a dispersing machine (Microfluidizer-M-110S-EH; trade name, manufactured by Microfluidex International Corporation, using G10Z interaction chamber) with a pressure controlled to be 1750 kg/cm 2 to obtain a silver behenate dispersion.
  • a dispersion temperature of 18°C was achieved by providing coiled heat exchangers fixed before and after the interaction chamber and controlling the temperature of the refrigerant.
  • the slurry was added with 0.2 g of benzothiazolinone sodium salt and water so that the concentration of the reducing agent should become 25 % by weight to obtain a reducing agent dispersion.
  • the reducing agent particles contained in the reducing agent dispersion obtained as described above had a median diameter of 0.42 ⁇ m and the maximum particle size of 2.0 ⁇ m or shorter.
  • the reducing agent dispersion was filtered through a polypropylene filter having a pore size of 10.0 ⁇ m to remove dusts and so forth, and stored.
  • the slurry was added with water so that the concentration of the mercapto compound should become 10 % by weight to obtain a mercapto compound dispersion.
  • the mercapto compound particles contained in the mercapto compound dispersion obtained as described above had a median diameter of 0.40 ⁇ m and the maximum particle size of 2.0 ⁇ m or shorter.
  • the mercapto compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 ⁇ m to remove dusts and so forth, and stored.
  • the dispersion was filtered through a polypropylene filter having a pore size of 10 ⁇ m immediately before use.
  • the SBR latex mentioned below diluted by 10 times with distilled water was diluted and purified by using an UF-purification module FS03-FC-FUYO3A1 (manufactured by Daisen Membrane System K.K.) until the ion conductivity became 1.5 mS/cm, and added with Sandet-BL (manufactured by SANYO CHEMICAL INDUSTRIES, LTD.) to a concentration of 0.22 % by weight. Further, the latex was added with NaOH and NH 4 OH so that the ratio Na + ion:NH 4 + ion should become 1:2.3 (molar ratio) to adjust pH to 8.4. At this point, the concentration of the latex was 40 % by weight.
  • the latex had the following characteristics: mean particle size of 0.1 ⁇ m, concentration of 45%, equilibrated moisture content at 25°C, relative humidity 60% of 0.6 % by weight, ion conductivity of 4.2 mS/cm (measured for the latex stock solution (40%) by using a conductometer, CM-30S, manufactured by Toa Electronics, Ltd., at 25°C), and pH of 8.2.
  • the viscosity of the coating solution for emulsion layer described above was measured by a B-type viscometer manufactured by Tokyo Keiki K.K. and found to be 85 [mPa ⁇ s] at 40°C (Rotor No. 1, 60 rpm).
  • the viscosity of the coating solution was measured at 25°C by an RFS fluid spectrometer produced by Rheometric Far East Co., Ltd., and found to be 1500, 220, 70, 40 and 20 [mPa ⁇ s] at shear rates of 0.1, 1, 10, 100 and 1000 [1/second], respectively.
  • the viscosity of the coating solution measured by a B-type viscometer at 40°C was 21 [mPa ⁇ s].
  • 64 g of inert gelatin was dissolved in water, added with 80 g of a 27.5 % by weight latex solution of methyl methacrylate/styrene/butyl acrylate/hydroxyethyl methacrylate/acrylic acid copolymer (copolymerization ratio (by weight): 64/9/20/5/2), 64 ml of a 10 % by weight methanol solution of phthalic acid, 74 ml of a 10 % by weight aqueous solution of 4-methylphthalic acid, 28 ml of 0.5 mol/L sulfuric acid, 5 ml of a 5 % by weight aqueous solution of Aerosol OT (manufactured by American Cyanamid Company), 0.5 g of phenoxyethanol, 0.1 g of benzoisothiazolinone, and water in such an amount that gave a total amount of 750 g to form a coating solution.
  • the coating solution was mixed with 26 ml of 4 % by weight
  • the viscosity of the coating solution measured by a B-type viscometer (Rotor No. 1, 60 rpm) at 40°C was 17 [mPa ⁇ s].
  • the coating solution was mixed with 445 ml of a solution containing 4 % by weight chromium alum and 0.67 % by weight of phthalic acid by a static mixer immediately before coating to form a coating solution for surface protective layer, which was fed to a coating die in such an amount that gave a coating amount of 8.3 ml/m 2 .
  • the viscosity of the coating solution measured by a B-type viscometer (Rotor No. 1, 60 rpm) at 40°C was 9 [mPa ⁇ s].
  • the coating solution for antihalation layer and the coating solution for back surface protective layer were simultaneously applied as stacked layers so that the applied solid content amount of the solid microparticle dye in the antihalation layer should be 0.04 g/m 2 , and the applied amount of gelatin in the protective layer should be 1.7 g/m 2 , and dried to form an antihalation back layer.
  • an emulsion layer (coated silver amount of the silver halide was 0.14 g/m 2 ), intermediate layer, first protective layer, and second protective layer were simultaneously applied in this order from the undercoat layer by the slide bead application method as stacked layers to form a sample of thermally processed image recording material.
  • the coating was performed at a speed of 160 m/min.
  • the gap between the tip of coating die and the support was set to be 0.14 to 0.28 mm, and the coated width was controlled so that it spread by each 0.5 mm at both sides compared with the projecting slit width of the coating solution.
  • the pressure in the reduced pressure chamber was adjusted to be lower than the atmospheric pressure by 392 Pa. In this case, handling, temperature and humidity were controlled so that the support should not be electrostatically charged and further electrostatic charge was eliminated by ionized wind immediately before the coating.
  • the material was blown with air showing a dry-bulb temperature of 18°C and a wet-bulb temperature of 12°C for 30 seconds to cool the coating solutions.
  • the material was blown with drying air showing a dry-bulb temperature of 30°C and a wet-bulb temperature of 18°C for 200 seconds. Subsequently, the material was passed through a drying zone of 70°C for 20 seconds, and then another drying zone of 90°C for 10 seconds, and cooled to 25°C to evaporate the solvent in the coating solution.
  • the average wind velocities of the wind applied to the coated layer surface in the chilling zone and the drying zones were 7 m/sec.
  • thermally processed image recording material After each thermally processed image recording material was light-exposed by a laser sensitometer (details are given below), the thermally processed image recording material was treated at 118°C for 5 seconds and then treated at 122°C for 16 seconds (heat development).
  • the light source was proceeded along the sub-scanning direction at a pitch of 25 ⁇ m and each pixel was written 4 times.
  • the evaluation of the image obtained was performed by using a Macbeth TD904 densitometer (visible density).
  • the measurement results were evaluated as Dmin, sensitivity (evaluated by a relative value of a reciprocal of a ratio of exposure amounts giving a density higher than Dmin by 1.0, and the sensitivity of the thermally processed image recording material of Experiment No. 1 shown in Table 1 below was defined as 100), Dmax, and gradation (contrast) (fresh photographic properties).
  • the contrast was expressed by a gradient of a straight line connecting the points at the densities from which the value for Dmin was subtracted, 0.5 and 1.5, with the abscissa being a logarithm of the exposure amount.
  • Image storage stability 1 shows the change of the photographic properties after storing the thermally processed image recording materials after heat development in the dark for 24 hours at a temperature of 60°C and relative humidity of 50%
  • Image storage stability 2 shows the change of the photographic properties after storing them for 24 hours under the light irradiation of 10,000 luces at a temperature of 40°C and relative humidity of 50%.
  • the solution was added with 476 ml of an aqueous solution containing 55.5 g of silver nitrate and an aqueous halide salt solution containing 1 mole/liter of potassium bromide and 2 ⁇ 10 -5 mole/liter of K 3 IrCl 6 by the control double jet method over a period of 28 minutes and 30 seconds, while the pAg was kept at 7.7. Thereafter, by lowering the pH to cause aggregation and precipitation to attain a desalting treatment.
  • the mixture was added with 0.17 g of Compound A and 51.1 g of low molecular weight gelatin having an average molecular weight of 15,000 (calcium content: 20 ppm or less), and the pH and pAg of the mixture were adjusted to 5.9 and 8.0, respectively.
  • the obtained grains were cubic grains having a mean grain size of 0.08 ⁇ m, a variation coefficient of 9% for projected area and a [100] face ratio of 90%.
  • the silver halide grains obtained as described above were warmed to a temperature of 60°C, added with 76 ⁇ moles of sodium benzenesulfonate per mole of silver, and after 3 minutes, added with 71 ⁇ moles of triethylthiourea. Then, the mixture was ripened for 100 minutes, and added with 5 ⁇ 10 -4 mole of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and the temperature of the mixture was lowered to 40°C.
  • a mixture of 635 L of distilled water and 30 L of tert-butanol contained in a reaction vessel kept at 30°C was added with the whole amount of the aforementioned sodium behenate solution and the whole amount of the aqueous silver nitrate solution at constant flow rates over the periods of 62 minutes and 10 seconds, and 60 minutes, respectively.
  • the outside temperature was controlled so that the temperature in the reaction vessel should become 30°C and the liquid temperature should not be raised.
  • the piping of the addition system for the sodium behenate solution was maintained by steam trace and the steam amount was controlled such that the liquid temperature at the outlet orifice of the addition nozzle should be 75°C.
  • the piping of the addition system for the aqueous silver nitrate solution was maintained by circulating cold water outside a double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically with respect to the stirring axis as the center, and the positions are controlled at heights for not contacting with the reaction liquid.
  • the mixture was left with stirring for 20 minutes at the same temperature and then the temperature was decreased to 25°C. Thereafter, the solid content was recovered by a suction filtration and the solid content was washed with water until electric conductivity of the filtrate became 30 ⁇ S/cm.
  • the solid content obtained as described above was stored as a wet cake without being dried.
  • the grains were scaly crystals having a mean diameter of projected area of 0.52 ⁇ m, a mean grain thickness of 0.14 ⁇ m, and a variation coefficient of 15% for mean diameter as spheres.
  • a dispersion of silver behenate was prepared as follows. To the wet cake corresponding to 100 g of the dry solid content was added with 7.4 g of polyvinyl alcohol (PVA-217, trade name, average polymerization degree: about 1700) and water to make the total amount 385 g, and the mixture was pre-dispersed by a homomixer. Then, the pre-dispersed stock dispersion was treated three times by using a dispersing machine (Microfluidizer-M-110S-EH; trade name, manufactured by Microfluidex International Corporation, using G10Z interaction chamber) with a pressure controlled to be 1750 kg/cm 2 to obtain a silver behenate dispersion. During the cooling operation, a desired dispersion temperature was achieved by providing coiled heat exchangers fixed before and after the interaction chamber and controlling the temperature of the refrigerant.
  • PVA-217 polyvinyl alcohol
  • water water
  • the pre-dispersed stock dispersion was treated three times by using
  • the silver behenate grains contained in the silver behenate dispersion obtained as described above were grains having a volume weight mean diameter of 0.52 ⁇ m and a coefficient of variation of 15%.
  • the measurement of the grain size was carried out by using Master Sizer X manufactured by Malvern Instruments Ltd. When the grains were evaluated by an electron microscopic photography, the ratio of the long side to the short side was 1.5, the grain thickness was 0.14 ⁇ m and a mean aspect ratio (ratio of circular diameter of projected area of grain and grain thickness) was 5.1.
  • Ultrahigh contrast agent B 10 g was added with 2.5 g of polyvinyl alcohol (PVA-217, manufactured by KURARAY CO., LTD.) and 87.5 g of water and the mixture was stirred sufficiently to form a slurry, which was left for 3 hour as slurry. Thereafter, 240 g of zirconia beads having a diameter of 0.5 mm were placed in a vessel together with the slurry and the slurry was dispersed by a dispersing machine (1/4 G Sand Grinder Mill; manufactured by Imex Co.) for 10 hours to prepare a solid microparticle dispersion. In the particles, 80 % by weight of the particles had a size of 0.1 ⁇ m to 1.0 ⁇ m, and the mean particle size was 0.5 ⁇ m.
  • Binder Laxster 3307B (made by DAINIPPON INK AND CHEMICALS, INC.; SBR latex, glass transition temperature: 17°C) 500 g as solid content 1,1-Bis(2-hydroxy-3,5-dimethylphenyl-3,5,6-trimethylhexane 149 g as solid content Compound of the formula (1) Type and amount (mole) shown in Table 2
  • Ultrahigh contrast agent B 15 g as solid content Sodium ethylthiosulfonate 0.15 g 4-Methylbenzotriazole 1.04 g
  • Polyvinyl alcohol PVA-235, made by KURARAY CO.
  • the PET was pelletized, and the pellets were dried at 130°C for 4 hours, melted at 300°C, extruded from a T-die, and quenched to prepare an unstretched film having such a thickness that the film thickness after thermal fixation should become 120 ⁇ m.
  • the film was stretched along the longitudinal direction by 3.3 times using rollers having different peripheral speeds and then stretched along the transverse direction by 4.5 times using a tenter.
  • the temperatures were 110°C and 130°C, respectively.
  • the film was subjected to thermal fixation at 240°C for 20 seconds and relaxed by 4% along the transverse direction at the same temperature.
  • the both edges of the film were knurled, and the film was rolled up at 4.8 kg/cm 2 to provide a roll of the film having a width of 2.4 m, length of 3500 m and thickness of 120 ⁇ m.
  • Polystyrenesulfonate (molecular weight: 1000-5000) 2.6 mg/m 2
  • Cellosol 524 (Chukyo Yushi Co., Ltd.) 25 mg/m 2
  • Sumitex Resin M-3 water-soluble melamine compound, Sumitomo Chemical Co., Ltd.) 218 mg/m 2
  • Undercoat layer (a) and Undercoat layer (b) were applied successively on both sides of the support (base), and each dried at 180°C for 4 minutes. Then, an electroconductive layer and a protective layer are successively applied to one side provided with Undercoat layer (a) and Undercoat layer (b), and each dried at 180°C for 4 minutes to prepare a PET support having backing layers and undercoat layers.
  • the dry thickness of Undercoat layer (a) was 2.0 ⁇ m.
  • the PET support with backing layers and undercoat layers prepared as described above was introduced into a heat treatment zone having a total length of 200 m set at 160°C, and transported at a tension of 3 kg/cm 2 and a transportation speed of 20 m/minute.
  • the support was passed through a zone at 40°C for 15 seconds for post-heat treatment, and rolled up.
  • the rolling up tension for this operation was 10 kg/cm 2 .
  • the coating solution for emulsion layer was coated so that the coated silver amount should become 1.6 g/m 2 . Further, the coating solution for lower protective layer for emulsion surface was coated on the emulsion layer simultaneously with the coating solution for emulsion layer as laminated layers, so that the coated solid content of the polymer latex should be 1.31 g/m 2 . Then, the coating solution for upper protective layer for emulsion surface was coated on the coated layer, so that the coated solid content of the polymer latex should be 3.02 g/m 2 to obtain a thermally processed image recording material.
  • the film surface pH of the obtained thermally processed image recording material on the image-forming layer side was 4.9, and the Beck's smoothness was 660 seconds. As for the opposite surface, the film surface pH was 5.9 and the Beck's smoothness was 560 seconds.
  • the obtained thermally processed image recording material was light exposed for 2 ⁇ 10 -8 seconds by using a laser light-exposure apparatus of single channel cylindrical inner surface type provided with a semiconductor laser with a beam diameter (1/2 of FWHM of beam intensity) of 12.56 ⁇ m, laser output of 50 mW and output wavelength of 783 nm.
  • the exposure time was adjusted by controlling the mirror revolution number, and exposure was adjusted by changing output.
  • the overlap coefficient of the light exposure was 0.449.
  • Each light-exposed thermally processed image recording material was heat-developed by using a heat-developing apparatus as shown in Fig.1.
  • the roller surface material of the heat development section was composed of silicone rubber, and the flat surface consisted of Teflon non-woven fabric.
  • the heat development was performed at a transportation linear speed of 20 mm/second and a temperature of 90-110°C in the preheating section for 15 seconds (driving units of the preheating section and the heat development section were independent from each other, and speed difference as to the heat development section was adjusted to -0.5% to -1%), and 120°C for 20 seconds in the heat development section, and for 15 seconds in the gradual cooling section.
  • the temperature precision as for the transverse direction was ⁇ 1°C.
  • the evaluation of the image obtained was performed by using a Macbeth TD904 densitometer (visible density).
  • the measurement results were evaluated as Dmin, sensitivity (evaluated by a relative value of a reciprocal of a ratio of exposure amounts giving a density higher than Dmin by 1.0, and the sensitivity of the thermally processed image recording material of Experiment No. 1 shown in Table 1 below was defined as 100), Dmax, and gradation (contrast) (fresh photographic properties).
  • the contrast was expressed by a gradient of a straight line connecting the points at the densities from which the value for Dmin was subtracted, 0.3 and 1.5, with the abscissa being a logarithm of the exposure amount.
  • Image storage stability 1 shows the change of the photographic properties after storing the thermally processed image recording materials after heat development in the dark for 24 hours at a temperature of 60°C and relative humidity of 50%
  • Image storage stability 2 shows the change of the photographic properties after storing them for 24 hours under the light irradiation of 10,000 luces at a temperature of 40°C and relative humidity of 50%.

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  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP00114958.2A 1999-07-19 2000-07-19 Wärmeentwickelbares Bildaufzeichnungsmaterial Expired - Lifetime EP1072948B1 (de)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1199596A2 (de) * 2000-10-20 2002-04-24 Konica Corporation Photothermographisches Material enthaltend ein Silbersalz
EP1308776A2 (de) * 2001-11-05 2003-05-07 Fuji Photo Film Co., Ltd. Photothermographisches Material und Verfahren zur thermischen Entwicklung von diesem
US7135276B2 (en) 2003-10-09 2006-11-14 Fuji Photo Film Co., Ltd. Photothermographic material and method for preparing photosensitive silver halide emulsion

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4369876B2 (ja) 2004-03-23 2009-11-25 富士フイルム株式会社 ハロゲン化銀感光材料および熱現像感光材料
US20060057512A1 (en) 2004-09-14 2006-03-16 Fuji Photo Film Co., Ltd. Photothermographic material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09265150A (ja) * 1996-03-28 1997-10-07 Fuji Photo Film Co Ltd 熱現像感光材料
EP1041435A1 (de) * 1999-03-30 2000-10-04 Fuji Photo Film Co., Ltd. Wärmeentwickelbares photographisches Material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09265150A (ja) * 1996-03-28 1997-10-07 Fuji Photo Film Co Ltd 熱現像感光材料
EP1041435A1 (de) * 1999-03-30 2000-10-04 Fuji Photo Film Co., Ltd. Wärmeentwickelbares photographisches Material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF MEDICAL CHEMISTRY, 1973, pages 1207

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1199596A2 (de) * 2000-10-20 2002-04-24 Konica Corporation Photothermographisches Material enthaltend ein Silbersalz
EP1199596A3 (de) * 2000-10-20 2003-05-21 Konica Corporation Photothermographisches Material enthaltend ein Silbersalz
EP1308776A2 (de) * 2001-11-05 2003-05-07 Fuji Photo Film Co., Ltd. Photothermographisches Material und Verfahren zur thermischen Entwicklung von diesem
EP1308776A3 (de) * 2001-11-05 2003-10-22 Fuji Photo Film Co., Ltd. Photothermographisches Material und Verfahren zur thermischen Entwicklung von diesem
EP1818718A2 (de) * 2001-11-05 2007-08-15 Fuji Photo Film Co., Ltd. Photothermographisches Material und Verfahren zu dessen thermischer Entwicklung
EP1818718A3 (de) * 2001-11-05 2009-03-04 Fuji Photo Film Co., Ltd. Photothermographisches Material und Verfahren zu dessen thermischer Entwicklung
US7135276B2 (en) 2003-10-09 2006-11-14 Fuji Photo Film Co., Ltd. Photothermographic material and method for preparing photosensitive silver halide emulsion

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