JPH11212230A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method for attaining the improved film quality of a developed image, as for a thermal developing diffusion transfer system image forming method. SOLUTION: As for the image forming method for forming an image on photosensitive material or on pressed image receiving material by image- exposing the thermal developing photosensitive material equipped with a photosensitive silver halide emulsion layer, thereafter, or simultaneously, overlaying the material on the processed image receiving material, thermal-developing under the coexistence of reducer and water and peeling one from the other, the peeled photosensitive material or processed image receiving material is immersed in water solution containing hardening agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an image forming method using a photothermographic material, and more particularly to an image forming method capable of forming an image having excellent film quality after processing.

[0002]

2. Description of the Related Art Photothermographic materials containing silver halide are known. For example, a photothermographic material and a process for forming an image using the photothermographic material are described in, for example,
"Basics of Photographic Engineering", Non-Silver Salt Photo Edition (Corona Corp., 1982), pp. 242-255, U.S. Pat.
626, etc.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized form of a developing agent and a coupler is disclosed in US Pat. Nos. 3,761,270 and 4,023.
1, 240 and the like. A method of forming a positive color image by a photosensitive silver dye bleaching method is described in U.S. Pat. No. 4,235,957.

Recently, a method has been proposed in which a diffusible dye is released or formed in an image form by thermal development, and the diffusible dye is transferred to a dye fixing element (processed image receiving material). In this method, both the negative dye image and the positive dye image can be obtained by changing the type of the dye-donating compound used or the type of the silver halide used. This method is described in more detail in U.S. Pat. Nos. 4,500,626, 4,483,914, 4,503,137 and 4,559,290, JP-A-58-149046, JP-A-60-133449
Nos. 59-218443 and 61-238056
, European Patent Publication No. 220746A, Published Technical Report 87-6
199, European Patent Publication 210660A2 and the like.

Further, many methods have been proposed for obtaining a positive color image by thermal development. For example,
U.S. Pat. No. 4,559,290 includes a so-called DRR.
Using a compound in the form of an oxidized compound having no color image emission ability, after oxidizing the reducing agent in accordance with the exposure amount of silver halide by thermal development, the remaining oxidized reducing agent, There has been proposed a method of releasing a diffusible dye by reducing the resulting compound. Also, European Patent Publication 2207
46A, Published Technical Report 87-6199 (Vol. 12, No. 22)
As a compound that releases a diffusible dye by the same mechanism, a compound that releases a diffusible dye by reductive cleavage of an NX bond (X represents an oxygen atom, a nitrogen atom, or a sulfur atom) is used. Developed color photosensitive materials are described.

Furthermore, Japanese Patent Application Laid-Open No. 62-129848 discloses that a black-and-white image can be formed with a transferred dye image by performing thermal development using a small amount of water. JP-A-62-283332, JP-A-63-198050, JP-A-60-194448 and the like use a heat-developable photosensitive material having a photosensitive silver halide emulsion layer and process by heat-developed silver salt diffusion transfer. A method for forming a silver image on an image receiving material is described. Further, Japanese Patent Application Laid-Open No. 8-179458,
No. 339065 discloses an image forming method in which silver remaining in a photothermographic material is used as an image in the above-mentioned heat-developable silver salt diffusion transfer method.

When an image is formed by the thermal development (silver salt or dye) diffusion transfer method as described above, both the heat-developable photosensitive material and the processed image-receiving material have opposite images having a negative-positive relationship with each other. It is formed. When an image formed on the photosensitive material side is used, the processed image receiving material can be considered as a simple processing material.

Conventionally, in a method of forming a dye image or a silver image by thermal development diffusion transfer as described above,
When moisture adheres to the surface of the material on which an image is formed after processing, when the moisture is rubbed with a finger or the like, a pinhole may be generated, and improvement has been required.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming method of a heat development diffusion transfer system in which the quality of an image formed after a development process is improved.

[0010]

Means for Solving the Problems When the water (including sweat, saliva, etc.) adheres to the surface of the material on which an image is formed after thermal development stripping, the portion is wiped off. As a result of studying the problem of the occurrence of pinholes, it was found that pinholes were generated due to peeling of the partially swollen film due to moisture. According to a further study by the present inventors, it is possible to suppress the occurrence of pinholes by immersing the material forming an image after thermal development stripping in an aqueous solution containing a hardener to reduce the amount of swelling. It was revealed.

Furthermore, the effect of the pinhole improvement is that the swelling amount of the material after immersion in water is preferably 70% or less, more preferably 60% or less, particularly preferably 50% or less with respect to the swelling amount before immersion. It became clear when it became. The term "swelling amount" as used in the present invention refers to an increase in film thickness when the photosensitive material reaches an equilibrium when immersed in a solution such as water.

According to the present invention, the above object of the present invention is achieved by the following image forming methods (1) to (5). (1) A photothermographic material having at least one photosensitive silver halide emulsion layer formed on a support is superimposed on a processed image-receiving material after or simultaneously with imagewise exposure, and a reducing agent And heat development in the presence of water, and then peeling from the processed image receiving material, in the method of forming an image on the photothermographic material, the peeled photothermographic material,
An image forming method characterized by immersing in an aqueous solution containing a hardener. (2) The amount of swelling of the photothermographic material after immersion in water is
The image forming method according to the above (1), wherein the swelling amount before immersion is 70% or less. (3) A photothermographic material having at least one photosensitive silver halide emulsion layer formed on a support is superimposed on the processed image-receiving material after or simultaneously with imagewise exposure, and a reducing agent In the method of forming an image on the processed image-receiving material by peeling from the photothermographic material after thermal development in the presence of water and water, the peeled processed image-receiving material is immersed in an aqueous solution containing a hardener. An image forming method. (4) The image forming method according to the above (3), wherein the amount of swelling of the processed image receiving material in water after immersion is 70% or less of the amount of swelling before immersion. (5) The photothermographic material contains a basic metal compound which is hardly soluble in water, and the processed image-receiving material contains a base precursor capable of chelating metal ions constituting the basic metal compound. The image forming method according to any one of the above (1) to (4). The present invention is described in detail below, and other objects, advantages and effects of the present invention will become apparent.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention comprises the steps of: developing a photothermographic material after imagewise exposure or simultaneously with imagewise exposure; When the image is formed on the photothermographic material or the processed image receiving material by peeling off the photothermographic material and the processed image receiving material, the photothermographic material or the processed image receiving material is peeled and the image is formed.
This is a method of improving the film quality of an image by immersion in an aqueous solution containing a hardener.

In the method of the present invention, the photothermographic material or the processed image-receiving material from which an image has been formed by peeling is processed by immersion in an aqueous solution containing a hardener. US Pat. No. 4,678,739 is an example of a hardener which is a component of an aqueous solution in which a photothermographic material or a processed image-receiving material is immersed.
No. 41, 4,791,042, JP-A-59-1
No. 16,655, No. 62-245,261, No. 61-
18, 942 and JP-A-4-218,044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners,
Epoxy hardener, vinyl sulfone hardener (N, N '
-Ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N-methylol-based hardening agents (dimethylol urea, etc.), potassium aluminum sulfate, aluminum sulfate,
Boric acid, metaboric acid or a polymer hardener (JP-A-62
-234,157 etc.).
In the method of the present invention, the concentration of the hardener is from 0.1% by weight to
It is preferably 100% by weight, particularly preferably 1% by weight to 1% by weight.
00% by weight.

The aqueous solution to be immersed may contain, in addition to a hardener, a pH adjuster, a surfactant, an image preservability improver (an antioxidant, an ultraviolet absorber, a silver stain inhibitor, a metal complex,
Water-soluble substances such as preservatives), a slipping agent, a matting agent, and a color tone agent. pH adjusters include KOH, N
inorganic bases such as aOH, organic bases such as guanidine, sulfuric acid,
Acids such as acetic acid and phosphoric acid and salts thereof. The surfactant may be any of an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. In addition, the same compounds as those used in the light-sensitive material and the processed image-receiving material described below may be added to the aqueous solution.

One type of aqueous solution may be used, or two or more types may be used. When two or more kinds are used, they may be used in one dipping step, or the dipping step may be divided into two or more steps and used in each step. Also,
The same type of aqueous solution may be used in two or more steps. When performing two or more immersion steps, the aqueous solution used in the first immersion step may be used in the second and subsequent immersion steps.
Alternatively, the aqueous solution used in the second step may be used in the first step.

The method of immersion is not particularly limited, and the photothermographic material or the processed image-receiving material on which an image is formed may be completely immersed in an aqueous solution, or only the surface to be processed may be immersed in the aqueous solution. . Moreover, you may apply | coat to a surface with a roller etc. Further, a method of dropping an aqueous solution from a nozzle onto a surface on which an image is formed, or an aqueous solution may be sprayed like an ink jet.

After immersion in an aqueous solution and treatment, drying is preferred. As the drying step, one of the heating, dehumidifying, and blowing processes can be performed alone, or a combination of two or more processes can be performed. The liquid temperature of the aqueous solution to be immersed is preferably 20 to 60 ° C, more preferably 30 to 50 ° C.
It is.

The treatment of dipping in the aqueous solution containing the hardener of the present invention may be carried out immediately after image formation or after a sufficient time has passed. In particular, with regard to the improvement of the pinhole, which is the object of the present invention, the effect remains unchanged regardless of the time from completion of development to immersion treatment.

In the method of the present invention, the imagewise exposed photothermographic material is superimposed on the processed image receiving material after or simultaneously with the imagewise exposure. The processed image-receiving material used has a processed layer containing physical development nuclei. This processing layer preferably contains a physical development nucleus and a silver halide solvent. The physical development nucleus is for reducing a soluble silver salt diffused from the photosensitive silver halide emulsion layer of the photothermographic material to convert it into physically developed silver, which is fixed to the processing layer. Substances constituting the physical development nucleus include heavy metals such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, ruthenium, noble metals such as palladium, platinum, silver, and gold, and sulfurs thereof. Any known physical development nuclei such as colloidal particles of chalcogen compounds such as selenium and tellurium can be used.
Silver, silver sulfide, palladium sulfide and the like are preferably used as physical development nuclei. When the physically developed silver transferred to the complexing agent sheet is used as an image, palladium sulfide, silver sulfide, and the like are preferably used because Dmin is cut off and Dmax is high.

These physical development nuclei substances are prepared by reducing the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, hydroquinone, etc. to form a metal colloid dispersion, or by dissolving a soluble sulfide, selenide or It can be obtained by mixing telluride solutions to form a colloidal dispersion of water-insoluble metal sulfide, metal selenide or metal telluride. Also, these dispersions are preferably formed in a hydrophilic binder such as gelatin. Examples of a method for preparing colloidal silver particles include a method described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excess salt known in the method for preparing a silver halide emulsion may be performed. The size of these physical development nuclei is 2 to
Those having a particle size of 200 nm are preferably used. These physical development nuclei are usually added to the processing layer of the processed image-receiving material in an amount of from 0.
001 to 100 mg / m ² , preferably 0.01 to 10
mg / m ² . Physical development nuclei can be separately prepared and added to a coating solution, but in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or gold chloride and a reducing agent are reacted. May be created.

As the silver halide solvent which is a component contained in the processing layer of the processed image receiving material, a known silver halide solvent can be used. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, sulfites such as sodium sulfite and sodium hydrogen sulfite, thiocyanates such as potassium thiocyanate and ammonium thiocyanate, and 1,8 described in JP-B-47-11386. Thioether compounds such as -di-3,6-dithiaoctane, 2,2'-thiodiethanol, 6,9-dioxa-3,12-dithiatetradecane-1,14-diol; and JP-A-8-179458.
Compounds having a 5- or 6-membered imide ring such as uracil and hydantoin described in JP-A-53-144319;
The compounds of the following general formula (I) described in the above item can be used. In addition, AnalytiKemikaAkta (Analyti
Also preferred are the trimethyltriazolium thiolate and meso-ion thiolate compounds described in Ca Chemica Acta) 248, pp. 604-614 (1991). Also, JP-A-8-6909
Compounds described in No. 7 which can fix and stabilize silver halide can also be used as a silver halide solvent.

General formula (I): N (R ¹ ) (R ² ) -C (= S) -XR ^{3 In the} formula, X represents a sulfur atom or an oxygen atom. R ¹ and R
² may be the same or different and each represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic residue or an amino group. R ³ represents an aliphatic hydrocarbon group or an aryl group. R
¹ and R ² or R ² and R ³ may combine with each other to form a 5- or 6-membered heterocycle. In the present invention, the above-mentioned silver halide solvents may be used alone or in combination of two or more. Among the above compounds, compounds having a 5- or 6-membered imide ring such as sulfite, uracil and hydantoin are particularly preferred. In particular, uracil or hydantoin is preferably added as a potassium salt since the reduction in gloss during storage of the processed image receiving material can be improved.

The total silver halide solvent content in the processing layer is 0.01 to 50 mmol / m ² , preferably 0.1 to 30 mmol / m ² . More preferably,
1 to 20 mmol / m ² . In molar ratio to the coated silver amount in the photosensitive silver halide emulsion layer of the photothermographic material,
It is desirable that the ratio be 1/20 to 20 times, preferably 1/10 to 10 times, and more preferably 1/3 to 3 times. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropyl glycol, or an alkaline or acidic aqueous solution, or may be dispersed as solid fine particles and added to a coating solution. .

Further, a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone described in JP-A-8-179458 as a constituent component is contained in the processing layer of the processed image-receiving material, whereby the silver image in the photothermographic material can be obtained. It is possible to increase the concentration.

In the method of the present invention, it is preferable to use a base or a base precursor to promote image formation, but it is preferable to include them in the processing layer of the processed image receiving material from the viewpoint of storage stability. In the case where a base is generated by the reaction of two or more substances, only one of them is contained in the constituent layer of the processed image-receiving material, and the other is contained in any of the layers constituting the photothermographic material. include. As the base and the base precursor, known compounds used in the development processing of the photothermographic material can be used.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement. Specific examples thereof are described in US Pat. No. 4,514,493.
No. 4,657,848 and No. 5 (19)
(Aztec Co., Ltd., March 22, 1991), pp. 55-86 and the like. Also, EP 210,660, US 4,740,4
No. 45, a combination of a basic metal compound which is hardly soluble in water and a compound having a chelating ability to a metal ion constituting the basic metal compound (referred to as a complex-forming compound) is used as a base precursor. When used, basic metal compounds that are hardly soluble in water can be used in photothermographic materials.
The complex forming compound is preferably added to the processed layer of the processed image receiving material.

The amount of base or base precursor used is
It is 0.1 to 20 g / m ² , preferably 1 to 10 g / m ² .

In the present invention, it is preferable that after applying dampening water to the photothermographic material, the photothermographic material is heated and developed by being superposed on a processed image receiving material provided with a processing layer. In particular, it is effective when a combination of the above-mentioned basic metal compound and a complex-forming compound which is hardly soluble in water is used as the base precursor.

As the binder for the treatment layer, a hydrophilic binder is preferably used. Examples thereof include those described in the aforementioned Research Disclosure and pages (71) to (75) of JP-A-64-13546. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also,
U.S. Pat. No. 4,960,681, JP-A-62-24
No. 5,260, etc., the superabsorbent polymer,
A homopolymer of a vinyl monomer having COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers with each other or with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical (Sumikagel L-5H manufactured by Co., Ltd.) is also used. These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable.

The gelatin may be selected from lime-treated gelatin, acid-treated gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes.
It is also preferable to use them in combination. The amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g.
It is appropriate to: Further, it is useful to provide a protective layer on the processing layer of the processed image receiving material.

The photothermographic material used in the method of the present invention has a support and at least one photosensitive silver halide emulsion layer formed on the support.

The support for the photothermographic material and the processed image-receiving material is not particularly limited as long as it can withstand the processing temperature. In general, papers and synthetic polymers (films) described in pages 223 to 240 of Coronation Co., Ltd. (1979), "Basics of photographic engineering-silver halide photography-" edited by The Photographic Society of Japan. And photographic supports.
Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride,
Films made of polystyrene, polypropylene, polyimide, celluloses (for example, triacetylcellulose), or films containing pigments such as titanium oxide in these films, and synthetic paper made of polypropylene or the like, polyethylene, etc. Mixed paper made from synthetic resin pulp and natural pulp, Yankee paper, baryta paper,
Coated paper (especially cast-coated paper) or the like is used. Further, a film obtained by depositing aluminum on a synthetic polymer film is also preferably used. A support mainly composed of a styrene polymer having a syndiotactic structure can also be preferably used. Further, a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or other antistatic agent, etc. are applied to the surface of the support opposite to the photosensitive element and the processing element. You may. When using an aluminum vapor-deposited film, it is preferable to add a boron compound to the lowermost layer of the light-sensitive material and the processed image-receiving material. Preferred boron compounds include borate esters.

In particular, as a support for a photosensitive material, JP-A-6-41281, JP-A-6-43581, and JP-A-6-514 can be used.
Nos. 26, 6-51437, 6-51442, 6-82961, 6-82961, 6-123
937, 6-82959, 6-67346,
6-266050, 6-202277, 6-
Nos. 175282, 6-118561, 7-219
No. 129, 7-219144, and the hardly curled supports described in JP-A-7-219144 can be preferably used.
Also, JP-A-4-124645 and JP-A-5-40321.
It is preferable to record photographic information and the like using a support having a magnetic layer described in JP-A-6-35092 and JP-A-6-317875.

The photosensitive silver halide emulsion layer formed on the support of the photothermographic material may be composed of one layer or two or more layers. A photothermographic material having this photosensitive silver halide emulsion layer is disclosed in JP-A-8-220.
No. 686, a black-and-white silver image is formed, a color image is formed by coupling as described in the prior art, and an image is formed by releasing a diffusible dye in the form of an image. And the like.

The silver halide which is a component of the photosensitive silver halide emulsion may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. In particular, when a black-and-white silver image is formed, the silver halide in the photosensitive silver halide emulsion preferably has a silver chloride content of 80 mol% or more.

The silver halide emulsion may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or a light fogging agent. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and is disclosed in JP-A-1-167743.
No. 4,223,463, a method of mixing monodispersed emulsions and adjusting the gradation is preferably used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
One having regular crystals such as a tetradecahedron, one having an irregular crystal system such as a sphere and a high aspect ratio plate, one having a crystal defect such as a twin plane, or a composite system thereof Any other may be used.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,
029 (1978), No. 17, 643 (1978)
No. 18,716 (197)
Nov. 1997), p. 648, ibid. No. 307, 105 (19
Nov. 1989) pp. 863-865, JP-A-62-25
No. 3,159, No. 64-13,546, JP-A No. 2-2
Nos. 36,546 and 3-110,555, and Grafkid, "Physics and Chemistry of Photography", published by Paul Monte (P.Gl.
afkides, Chemieet Phisique Photographique, Paul M
ontel, 1967), Duffin's "Photographic Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emuls)
ion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (V.
L. Zelikman et al., Making and Coating Photographic
Any of silver halide emulsions prepared by the method described in Emalusion, Focal Press 1964) can be used.

In the process of preparing a photosensitive silver halide emulsion, it is preferable to carry out so-called desalting for removing excess salts. As a means for this, a Nudel water washing method in which gelatin is gelatinized may be used, and inorganic salts composed of polyvalent anions (for example, sodium sulfate), an anionic surfactant, and an anionic polymer (for example, polystyrene sulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly contained in the particles, or may be localized inside or on the surface of the particles. Specifically, Japanese Patent Application Laid-Open Nos. 2-236542 and 1-116, 6
Emulsions described in JP-A Nos. 37 and 5-181246 are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion, rhodan salts, ammonia, 4-substituted thiourea compounds and JP-B-47-11,386 are used as silver halide solvents.
Organic thioether derivatives described in
No. 4,319, for example, can be used.

Other conditions are described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte, Inc. (P. Glaf)
kides, Chemie et Phisique Photographique, Paul Mon
tel., 1697), "Photographic Emulsion Chemistry" by Duffin, Focal Press (GFDuffin, Photographic Emulsion Che)
mistry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (VLZelikm)
an et al., Makingand Coating Photographic Emulsio
n, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-142329).
No. 5-158,124, U.S. Pat. No. 3,650,575). Further, the stirring method of the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is 2.2-7.0, more preferably 2.5-6.0.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, chalcogen sensitization methods such as sulfur sensitization method, selenium sensitization method, tellurium sensitization method, etc., which are well-known in emulsions for conventional light-sensitive materials, gold, platinum, A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, JP-A-3-110,555,
No. 5-241264, etc.). Further, these chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, the fogging inhibitor described below can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-40,464
The method described in No. 46 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 1.
0.5, more preferably 6.8 to 9.0.

In the present invention, the coating amount of the photosensitive silver halide emulsion layer formed on the support is from 1 mg to silver equivalent.
It is in the range of 10 g / m ² .

Further, in a photothermographic material mainly used for forming a color image, particularly for photographing, in order to give the photosensitive silver halide green sensitivity, red sensitivity and infrared sensitivity, The photosensitive silver halide emulsion is subjected to spectral sensitization with a methine dye or the like. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region.

Dyes used for spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, US Patent No. 4,617,257
No., JP-A-59-180,550 and 64-13,5
No. 46, JP-A-5-45,828 and JP-A-5-45,83
Sensitizing dyes described in No. 4 and the like. These sensitizing dyes may be used alone, or a combination thereof may be used.A combination of sensitizing dyes is often used particularly for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. Can be

Further, together with the sensitizing dye, a dye having no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (hereinafter, referred to as a compound).
(E.g., "supersensitizer") may be contained in the emulsion (for example, U.S. Pat. No. 3,615,641;
3,145, etc.).

These sensitizing dyes and supersensitizers may be added to the emulsion at or before or after chemical ripening, and may be added to US Pat. Nos. 4,183,756 and 4,225.
According to No. 666, it may be before or after nucleation of silver halide grains. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The addition amount is generally about 1 × 10 ^-8 to 1 × 10 ^-2 mol per mol of silver halide.

The additives used in such a process and the known photographic additives that can be used in the present invention include the above-mentioned RDN.
o. 17, 643, No. 18, 716 and No. 30
7, 105, and the corresponding portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer ~ page 649, right column 4. Brightener 24, page 648, right column, page 868 5. Fogging prevention 24 ~ 25, page 649, right column, 868 ~ 870 page Agents, stabilizers 6. Light absorbers, 25 ~ Page 26 Page 649 Right column Page 873 Filters-Page 650 Left column Dye, UV absorber 7. Dye image Page 25 650 Page Left column 872 Stabilizer 8. Hardening agent Page 26 651 Left column 874-875 9 Binder page 26 page 651 left column 873-874 10. Plasticizer, page 27 650 page right column 876 lubricant 11. Coating aid, page 26-27 page 650 right column 875-876 surfactant 12. Static 27 pages 650 right column 876-877 Inhibitor 13. Matting agent 878-879

In the present invention, the photosensitive silver halide emulsion layer can contain an organic metal salt as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in U.S. Pat. No. 4,500,626, columns 52-53. The acetylenes described in U.S. Pat. No. 4,775,613 are also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is a photosensitive silver halide 1
0.01 to 10 mol, preferably 0.01 to 10 mol
１1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 0.05 to 10 g in terms of silver.
/ M ² , preferably 0.1 to 4 g / m ² .

The kind and amount of the binder as a component contained in the photosensitive silver halide emulsion layer are the same as those of the above-mentioned processed image receiving material.

When a color image is obtained by coupling in the method of the present invention, a coupler is contained in the photosensitive silver halide emulsion layer of the photothermographic material.

The coupler usable in the present invention may be a 4-equivalent coupler or a 2-equivalent coupler. Further, the diffusion-resistant group may form a polymer chain. Specific examples of couplers
THJames "The Theory of the Photographic Proces
s "4th edition pp. 291-334, and 354-361,
58-123533, 58-149046, 5
No. 8-149047, No. 59-111148, No. 59
-124399, 59-174835, 59-
No. 231539, No. 59-231540, No. 60-2
No. 950, No. 60-2951, No. 60-14242
Nos. 60-23474, 60-66249, 8-110608, 8-146552, and 8-1
No. 46578 and the like.

It is preferable to use the following couplers. Yellow coupler: Formulas (I) and (I) described in EP502,424A
A coupler represented by I); a formula described in EP513,496A
Couplers represented by (1) and (2);
No. 48, a coupler represented by the general formula (I) of claim 1; a coupler represented by the general formula D described in column 1, line 45 or line 55 of US Pat. No. 5,066,576;
No. 4,425, couplers of the general formula D described in paragraph 0008; EP 498,38 A1 on page 40 of claim 1; EP 447,969 A1 on page 4 of the formula (Y), US Pat. No. 4,476,219. And magenta couplers represented by formulas (I) to (IV) described in lines 7 to 36 of column 7 of JP-A-3-39737 and JP-A-6-39.
-43611, JP-A-5-204106, 4-3
No. 626. Cyan coupler: JP-A-4-204843, JP-A-4
Couplers described in JP-A-43345 Polymer couplers: Couplers described in JP-A-2-44345.

Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,570, and DE.
Those described in 3,234,533 are preferred.

The silver halide emulsion layer may contain the following functional coupler. Couplers for correcting unnecessary absorption of color-forming dyes include yellow colored cyan couplers described in EP 456,257A1, EP 456,257A
Yellow colored magenta coupler according to 1, US 4,83
Magenta colored cyan couplers described in 3,069, US4,
Colorless masking couplers represented by the formula (2) described in No. 837,136 and the formula (A) in claim 1 of WO92 / 11575 (especially the exemplified compounds on pages 36 to 45).

Examples of compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds represented by formulas (I) to (IV) described on page 11 of EP378,236A1, compounds represented by formula (I) described on page 7 of EP436,938A2, JP-A-5-307248, 1345
Compound represented by formula (1) described in No. 23, EP440,19
Release of compounds represented by formulas (I), (II) and (III) described on pages 5 and 6 of 5A2, compound-ligand represented by formula (I) described in claim 1 of JP-A-6-59411. Compound,
A compound represented by LIG-X according to claim 1 of US Pat. No. 4,555,478.

The light-sensitive silver halide emulsion layer of the photothermographic material used in the present invention has a reduced development time, improved sensitivity,
For the purpose of improving the image density or the like, it is preferable that the oxidized product formed by silver development incorporates a color developing agent capable of forming a dye by coupling with the coupler described above.

In this case, US Pat. No. 3,531,256
Phenol or active methylene coupler as a p-phenylenediamine developing agent, 3,761,270
No., combinations of p-aminophenol-based developing agents and active methylene couplers can be used. U.S. Pat. No. 4,021,240, JP-A-60-128438 and the like.
The combination of equivalent couplers is excellent in raw preservation when incorporated in the photosensitive silver halide emulsion layer of the photothermographic material,
This is a preferred combination.

When the photosensitive silver halide emulsion layer contains a color developing agent, a precursor of the color developing agent may be used. For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat.
And Schiff base compounds described in Research Disclosure Nos. 14,850 and 15,159.
Aldol compounds described in 3,924, US Pat. No. 3,719,4
No. 92 metal salt complexes and urethane compounds described in JP-A-53-135628.

Further, sulfonamide phenol-based active compounds described in JP-A-9-15806, JP-A-8-28634
Nos. 0 and 8-234388 are also preferable.

When a diffusion-resistant developing agent is used,
If necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination to promote electron transfer between the diffusion-resistant developing agent and the developable silver halide. Particularly preferably, said US Patent No. 5,139,
No. 919 and European Patent Publication No. 418,743 are used. JP-A-2-230143, JP-A-2-230143;
A method of stably introducing the compound into the layer as described in JP-A-235,044 is preferably used.

The electron transfer agent or its precursor can be selected from the above-mentioned developing agents or its precursors. It is desirable that the electron transfer agent or the precursor thereof has mobility higher than that of the diffusion-resistant developing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3-
Pyrazolidones or aminophenols. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used.

Further, the intermediate layer and the protective layer constituting the light-sensitive silver halide emulsion layer can contain various reducing agents for various purposes such as prevention of color mixing and improvement of color reproduction. Specifically, European Patent Publication Nos. 524,649 and 357,
040, JP-A-4-249,245, JP-A-2-46,
No. 450 and JP-A-63-186,240 are preferably used. In addition, Japanese Patent Publication 3-63,733
No., JP-A-1-150,135, JP-A-2-46,450
Nos. 2,64,634, 3-43,735 and EP-A-451,833 are also used.

In addition, the photosensitive silver halide emulsion layer
A reducing agent as described below may be contained. Examples of the reducing agent used in the present invention include U.S. Pat.
No. 626, columns 49-50, 4,839,272,
JP-A-4,330,617, JP-A-4,590,152, JP-A-5,017,454, JP-A-5,139,919 and JP-A-60-140,335, Nos. (17) to (18). Page, 57-
Nos. 40, 245, 56-138, 736, 59-
178,458, 59-53,831, 59-
182,449, 59-182,450, 60
-119,555, 60-128,436, 6
Nos. 0-128,439, 60-198,540, 60-181,742, 61-259,253,
Nos. 62-244,044, 62-131,253
Nos. 62-131 and 256 and 64-13 and 546
And reducing agent precursors described in JP-A-1-120,553, EP-A-220,746A2, pages 78-96, and the like. Also,
Various combinations of reducing agents, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

The above-mentioned developing agent or reducing agent may be contained in the processed image-receiving material, but is preferably contained in the photosensitive silver halide emulsion layer.

In the present invention, the total amount of the developing agent and the reducing agent is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

In the present invention, when a diffusible dye is released in the form of an image, a non-diffusible colorant which emits a diffusible dye corresponding to silver development or reversely is used. The compound used as the non-diffusible colorant is represented by the following general formula [L1]. ((Dye) m-Y) n-Z [L1] In the above formula, Dye represents a diffusible dye group, Y represents a simple linking group, and Z represents a photosensitive silver salt having an image-like latent image. L1 itself represents a group having the property of releasing non-diffusible (Dye) m-Y correspondingly or inversely, m represents an integer of 1 to 5, and n represents 1 Or 2 and when m and n are not 1, both Dyes may be the same or different.

Specific examples of the coloring material represented by the general formula [L1] include the following compounds 1 to 4.
Incidentally, the following 1 to 3 release the diffusible dye in correspondence with the silver halide development, and 4 release the diffusible dye in response to the silver halide development. 1． U.S. Pat. Nos. 3,134,764 and 3,362
Nos. 819, 3,597,200, 3,544,5
No. 45, No. 3, 482, 972, Tokuhei 3-6838
No. 7, etc., a dye developing agent in which a hydroquinone developing agent and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide. 2. As described in U.S. Pat. No. 4,503,137, non-diffusible compounds which release a diffusible dye in an alkaline environment but lose their ability when reacted with silver halide can also be used. Examples include U.S. Pat.
Compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 354 or the like.

3. U.S. Pat. No. 4,559,290; EP 220,746 A2; U.S. Pat.
No. 3,396, Published Technical Report 87-6,199, JP-A-64
As described in JP-A-13546, a non-diffusible compound which reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. Examples thereof include U.S. Pat. Nos. 4,139,389 and 4,139,379.
And JP-A-59-185333 and 57-84453.
No. 4,232,107, compounds disclosed in JP-A-59-101649, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction.
No. 61-88257, RD24,025 (1984)
Compounds which release a diffusible dye by an electron transfer reaction in the molecule after reduction, described in West German Patent No. 3,008,588A, JP-A-56-142530.
Nos. 4,343,893 and 4,619,
No. 4,884 and the like, compounds which release a diffusible dye by cleavage of a single bond after reduction, US Pat.
Nitro compounds which release a diffusible dye after electron acceptance as described in U.S. Pat. No. 4,609,223;
No. 610 and the like, which release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220,746A2, published technical report 87-6,199,
U.S. Pat. No. 4,783,396, JP-A-63-201
No. 653, No. 63-201654, No. 64-1354
No. 6, etc., a compound having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, a compound described in JP-A-1-26842 A compound having an SO ₂ -X (X is as defined above) and an electron-withdrawing group, and a PO-X bond (X is as defined above) and an electron withdrawing in one molecule described in JP-A-63-271344. compounds having sex group, described in JP-a-63-271341, C-X 'bond (X' in one molecule X as defined or or -SO ₂ - represents a) and having an electron-withdrawing group Compounds. Also, JP-A-1-161237,
No. 16,1342, a compound capable of releasing a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used. Among these, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include compounds (1) to (3), (7) to (10), (12), and (1) described in European Patent No. 220,746A2 or U.S. Patent No. 4,783,396.
3), (15), (23) to (26), (31), (3)
2), (35), (36), (40), (41), (4)
4), (53) to (59), (64), (70), and compounds (11) to (11) described in Published Technical Report 87-6,199.
(23) and compounds (1) to (84) described in JP-A-64-13546.

4. A compound (DRR compound) that is reducible to silver halide or an organic silver salt and releases a diffusible dye when the partner is reduced. Since this compound does not require the use of another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,928,312 and 4,053,312.
Nos. 4,055,428 and 4,336,322
And JP-A-59-65839 and JP-A-59-69839.
No. 53-3819, No. 51-104343, R
D17,465, U.S. Pat. No. 3,725,062,
JP-A-3,728,113, JP-A-3,443,939, JP-A-58-11637, JP-A-57-179840,
This is described in U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compound (1) described in the above-mentioned U.S. Pat. )-(3), (10)-
(13), (16) to (19), (28) to (30),
(33)-(35), (38)-(40), (42)-
(64) is preferred. No. 4,639,40
The compounds described in No. 8, columns 37 to 39 are also useful.

When the diffusible dye is released in the form of an image and is diffused and transferred to a processed image receiving material, it is preferable to include a mordant in the processed layer of the processed image receiving material. As the mordant, those known in the field of photography can be used. Specific examples thereof include mordants described in US Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256, pages 32 to 41. JP-A Nos. 62-244043 and 62-24403
No. 6 and the like. Also US
A dye-receptive polymer compound as described in 4,463,079 may be used.

The above-mentioned hydrophobic additives such as coloring materials, couplers, color developing agents, and diffusion-resistant reducing agents can be thermally developed by a known method such as the method described in US Pat. No. 2,322,027. It can be introduced into any layer of the light-sensitive material. In this case, US Pat.
Nos. 70, 4,536,466 and 4,536,46
No. 7, 4,587,206, 4,555,476
No. 4,599,296, JP-B-3-62256, etc., using a high-boiling organic solvent in combination with a low-boiling organic solvent having a boiling point of 50 ° C. to 160 ° C. as necessary. Can be. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-donating compound used. Also, binder 1
1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for g. In addition, Japanese Patent Publication No. 51-39
No. 853, JP-A-51-59943, and the like, and a method of adding a fine particle dispersion described in JP-A-62-30242, etc., can also be adopted.

Further, in the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, Japanese Patent Application Laid-Open No.
The surfactants described in Research Disclosure, pages 7 to 38, mentioned above, can be used. Also, JP-A-7-56267 and JP-A-7-22858
No. 9, West German Published Patent No. 1,932,299A can also be used.

In the present invention, the layer of the photothermographic material may contain a compound for activating the development and stabilizing the image at the same time. Specific compounds preferably used are described in US Pat. No. 4,500,626, No. 5,
Those described in columns 1 to 52 can be mentioned.

The photothermographic material for photographing includes at least three types of photosensitive layers having different spectral sensitivities and different hues of color materials. Each photosensitive layer may have a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The three types of photosensitive layers are preferably layers sensitive to any of blue light, green light, and red light. This arrangement order is generally the order of a red photosensitive layer, a green photosensitive layer, and a blue photosensitive layer in order from the support side. However, other arrangements may be adopted depending on the purpose. For example, an arrangement as described in column 162 of JP-A-7-152129 may be used. In the present invention, the silver halide and the colorant may be contained in the same layer, but they may be added separately in separate layers as long as they can react. For example, it is effective to dispose a layer containing a coloring material which is originally colored below a layer containing silver halide, since a decrease in sensitivity can be prevented. The relationship between the spectral sensitivity of each layer and the hue of the colorant is arbitrary, but if a cyan colorant is used for the red photosensitive layer, a magenta colorant is used for the green photosensitive layer, and a yellow colorant is used for the blue photosensitive layer, the conventional color Projection exposure can be performed directly on paper or the like.

In the photothermographic material, various non-photosensitive materials such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer may be used between the silver halide emulsion layers and as the uppermost layer and the lowermost layer. A layer may be provided, and various auxiliary layers such as a back layer may be provided on the side opposite to the support.
Specifically, the layer structure described in the above patent, the undercoat layer described in US Pat. No. 5,051,335,
An intermediate layer having a solid pigment as described in JP-A-167838 and JP-A-61-20943;
Nos. 3,017,454, 5,139,919, and intermediate layers having a reducing agent and a DIR compound as described in JP-A Nos.
An intermediate layer having an electron transfer agent as described in JP-A-2-235444, a protective layer having a reducing agent as described in JP-A-4-249245, or a layer obtained by combining them can be provided. When the support is polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer has an antistatic function and a surface resistivity of 10%.
It is preferable to design so as to be ¹² Ω · cm or less.

In the present invention, a heat solvent may be added to the photosensitive silver halide emulsion layer and the other layers of the photothermographic material for the purpose of accelerating the thermal development. Examples of the thermal solvent include U.S. Pat. Nos. 3,347,675 and 3,347,675.
Organic compounds having polarity as described in US Pat. Specifically, amide derivatives (benzamide etc.), urea derivatives (methyl urea, ethylene urea etc.), sulfonamide derivatives (Japanese Patent Publication No. 1-409)
No. 74 and Japanese Patent Publication No. 4-13701), polyol compounds (such as sorbitol), and polyethylene glycols. When the thermal solvent is insoluble in water, it is preferably used as a solid dispersion. The layer to be added may be either a light-sensitive silver halide emulsion layer or a non-light-sensitive layer depending on the purpose. The amount of hot solvent added is
10% to 500% by weight of the binder of the layer to be added,
Preferably it is 20 to 300% by weight.

The photothermographic material and the processed image-receiving material used in the method of the present invention are preferably hardened with the aforementioned hardener. The hardener used is in a ratio of 0.001 to 1 g, preferably 0.1 to 1 g per 1 g of the hydrophilic binder contained in the photosensitive silver halide emulsion layer, the processing layer or other layers.
It is used at a ratio of 005 to 0.5 g.

The photosensitive silver halide emulsion layer or other layers of the photothermographic material can contain various antifoggants or photographic stabilizers and precursors thereof. Specific examples thereof include the aforementioned Research Disclosure, US Pat. Nos. 5,089,378 and 4,50.
Nos. 0,627 and 4,614,702,
No. 13564, pages (7) to (9), (57) to (71) and (81) to (97), U.S. Pat.
No. 10, 4,626,500, 4,983,49
4, JP-A-62-174747 and JP-A-62-2391.
No. 48, JP-A-1-150135 and JP-A-2-11055
7, RD 2-178650, RD 17,643 (19
78) (pages 24 to 25). These antifoggants, photographic stabilizers and precursors thereof are preferably used in an amount of 5 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver in the photosensitive silver halide emulsion layer, and more preferably ¹ to 10 mol. An amount corresponding to a ratio of × 10 ^-5 to 1 × 10 ^-2 mol is preferably used.

The light-sensitive silver halide emulsion layer of the photothermographic material and the processing layer or other layers of the processed image-receiving material may have coating aids, improved releasability, improved slipperiness, antistatic properties,
Various surfactants can be contained for the purpose of accelerating development and the like. Specific examples of the surfactant to be used include the above-mentioned known art No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, and
173463, 62-183457 and the like.

Further, the photosensitive silver halide emulsion layer of the photothermographic material and the processing layer or other layers of the processed image-receiving material contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. You may not. Representative examples of the organic fluoro compound used include Japanese Patent Publication No. 57-9053.
Nos. 8-17, JP-A-61-20944, 62-62
And a fluorine-containing surfactant described in JP-B-135826, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin.

The photosensitive silver halide emulsion layer and the other layers of the photothermographic material can contain a matting agent. The same matting agent as that used for the processed image receiving material is used.

The heat-developable photosensitive material used in the present invention can be subjected to the same processing as an ordinary color negative as a photosensitive material for photographing, loaded into a camera, and directly subjected to photographing.
In addition, Japanese Patent Publication No. 2-3615, Japanese Utility Model Publication No. 3-39784
It can also be preferably used for the film unit with a lens described in the above item.

In the present invention, the photothermographic material and / or the processed image-receiving material may have a form having a conductive heating element layer as a heating means for heat development. In this case, the heat generating element described in JP-A-61-145544 can be used.

The heating temperature in the heat development step is about 50 ° C. to 2 ° C.
It is 50 ° C, but especially about 60 ° C to 180 ° C is useful. In a system using the release of a diffusible dye, the dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred at a temperature in the range of from the temperature in the heat development step to room temperature, but is particularly preferably at least 50 ° C. and up to about 10 ° C. lower than the temperature in the heat development step. . In a system utilizing the release of a diffusible dye, the transfer of the dye is caused only by heat, but the above-mentioned thermal solvent or another solvent may be used to promote the transfer of the dye.

In the method of the present invention, upon development,
It is useful to carry out development by heating in the presence of a small amount of fountain solution. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of water or lower.

Examples of the dampening solution used for accelerating the development and / or diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases are used for image formation). The one described in the section of the accelerator is used), a low-boiling solvent or a mixed solution of a low-boiling solvent and water or the basic aqueous solution. Also surfactants,
An antifoggant, a complex-forming compound with a poorly soluble metal salt, a fungicide and a bactericide may be contained in the solvent. As the water component of the dampening solution used in the steps of these thermal development and / or diffusion transfer, any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the photothermographic device used for thermally developing the photothermographic material and the processed image receiving element of the present invention, water may be used up and used.
It may be circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144354 and JP-A-63-144355,
The apparatus and water described in JP-A-62-38460 and JP-A-3-210555 may be used.

In the present invention, the amount of fountain solution applied to the photothermographic material may be not more than the weight of water corresponding to the maximum swelling volume of the entire coating film of the photothermographic material and the processed image-receiving material.

As a method of applying the dampening solution, for example, JP-A-62-253159, p.
The method described in -85544 or the like is preferably used.
Further, it is also possible to use a fountain solution by enclosing the dampening solution in microcapsules, or preliminarily containing the hydrates in the photothermographic material or the processed image-receiving material (dye-fixing element) or both. The temperature of the dampening water to be applied is determined by the method described in JP-A-63-85.
The temperature may be 30 ° C to 60 ° C as described in JP-A-544.

As a heating method in the development and / or transfer step, a heating block, a plate, a hot plate, a hot presser, a hot roller, a hot drum,
There are methods such as contacting with a halogen lamp heater, infrared and far-infrared lamp heaters, and passing through a high-temperature atmosphere.

A method of superposing a photothermographic material and a processed image receiving material is described in, for example, JP-A-62-25315.
No. 9, JP-A-61-147244 (page 27) can be applied.

In the method of the present invention, any of various heat developing apparatuses can be used for the heat development processing. For example, JP-A-59-75,247, JP-A-59-177,547,
59-181, 353, 60-18, 951,
Japanese Utility Model Application Laid-Open No. 62-25,944, Japanese Patent Application No. 4-277,51.
No. 7, 4-243, 072, 4-244, 693
Nos. 6,164,421 and 6,164,422 are preferably used. Examples of commercially available devices include Pictrostat 100, Pictrostat 200, Pictrostat 300, 330, and Pictrostat 5 manufactured by Fuji Photo Film Co., Ltd.
0, the same Pictography 4000, the same Pictography 3000, the same Pictography 2000, etc. can be used.

In the method of the present invention, no additional development stop processing is required after the development processing. However, a development stopping agent may be included in the processed image receiving material, and the development stopping agent may act simultaneously with the development. In the present invention, the development terminator is a compound that stops neutralization or reacts with a base to reduce the base concentration in the film and stop development immediately after appropriate development, or interacts with silver and a silver salt. It is a compound that suppresses development. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62
-253, 159 (31) to (32). Further, the combination described in JP-A-8-54705 or the like in which a zinc salt of mercaptocarboxylic acid is contained in a photosensitive element and the complex forming compound is contained in a processed image-receiving material is advantageous.

Similarly, a printout inhibitor of silver halide may be included in the processing sheet so that its function is developed simultaneously with the development. Specific examples of the printout inhibitor include monohalogen compounds described in JP-B-54-164, trihalogen compounds described in JP-A-53-46020, and halogens described in JP-A-48-45228. Compound bound to group III carbon atom, Tokiko 57
And polyhalogen compounds represented by tetrabromoxylene described in JP-A-8454. Further, a development inhibitor such as 1-phenyl-5-mercaptotetrazole described in British Patent No. 1,005,144 is also effective. Further, a viologen compound described in JP-A-8-184936 is also effective. The amount of the printout inhibitor is preferably 1 × 10 ^-4 to 1
Mol / Ag1 mol, particularly preferably 1 × 10 ⁻³ to 1 × 1
0 ^-1 mol / Ag1 mol.

[0098]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 (Preparation of black-and-white light-sensitive material) First, a method for preparing a light-sensitive silver halide emulsion (1) will be described. No. 1 with good stirring
Solution (I) and solution (II) having the composition shown in Table 2 were simultaneously added to the aqueous gelatin solution having the composition shown in Table 4.4 at pH 4.4 over 9 minutes. After 3 minutes, (II) having the composition shown in Table 2
Solution I) and solution (IV) were added simultaneously over 10 minutes.

[0100]

[Table 1]

[0101]

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[0102]

[Table 2]

After washing with water and desalting (adjusted to pH 3.1 with sulfuric acid using a sedimentation agent (2)) in a conventional manner, 25 g of lime-processed gelatin was added, pH 6.1, pA
After adjusting to g 7.6, preservative (1) was added, and the mixture was chemically sensitized at 60 ° C. The compounds used for chemical sensitization were sequentially added as shown in Table 3 to obtain Emulsion (1). The formed emulsion had an average side length of 0.19 μm and a standard deviation of 0.019 μm.
And a silver chloride cubic emulsion having a silver bromide content of 2.2 mol%. The yield of this emulsion was 704 g.

[0104]

[Table 3]

[0105]

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[0106]

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The silver bromide emulsion (2) shown in Table 3 used for the chemical sensitization was prepared as follows. A gelatin solution having the composition shown in Table 4 which was well stirred was added to 3
The temperature was lowered to 0 ° C., and solutions (I) and (II) having the compositions shown in Table 5 were added simultaneously over 3 minutes and 40 seconds. After 5 minutes, Solution (III) and Solution (IV) having the compositions shown in Table 5 were simultaneously added over 2 minutes while controlling the flow rate of Solution (IV) so that the silver potential became 50 mV.

[0108]

[Table 4]

[0109]

[Table 5]

After washing with water and desalting (adjusted to pH 4.1 with phosphoric acid using the above-mentioned precipitant (1)) according to a conventional method, 22 g of lime-processed gelatin was added and the pH was adjusted.
6.1, pAg 7.8 adjusted (by KBr). Further, a preservative (2) was used as a preservative. The resulting emulsion was a silver bromide cubic emulsion having an emulsion grain size of 0.05 μm. The yield was 630 g.

Next, 4.5 cc of a methanol solution containing 9 mg of the sensitizing dye (3) shown above was added to 100 g of the emulsion (1), and 4,4'-bis [4,6-di ( Naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate disodium salt
1.2 cc of a% methanol solution was added. Further, after adding 0.65 cc of a 2% aqueous solution of the mercapto compound (1) shown above, 0.06 g of the water-soluble polymer (1) was added, and 1.7 g of a polymer latex was added. Next, 1.9 g of the following compound (1) as a dispersion was further added,
A coating solution for the emulsion layer was prepared.

[0112]

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(Preparation of dispersion of reducing agent: 1,5-diphenyl-3-pyrazolizone) To 10 g of 1,5-diphenyl-3-pyrazolidone and 0.2 g of Demol made by Kao, 5.7 was added.
% Lime-processed gelatin (90 cc) was added thereto, and the mixture was further dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a gelatin dispersion of a reducing agent.

(Preparation of Zinc Hydroxide Dispersion) 12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethylcellulose and 0.1 g of sodium polyacrylate as dispersants were added to 100 cc of a 4% aqueous gelatin solution. In addition, the mixture was further dispersed in a mill using glass beads having an average particle size of 0.75 mm for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

(Preparation of Dispersion of Leuco Dye and Developing Agent) The oil phase component having the composition shown in Table 6 heated and dissolved at about 60 ° C. was heated to 60 ° C. and water having the composition shown in Table 6 was obtained. In addition to the phase components, the mixture was stirred and mixed. Next, for 10 minutes with a homogenizer,
After dispersing at 10,000 rpm, water was added to obtain a uniform dispersion of leuco dye and developer.

[0116]

[Table 6]

Note: As the surfactant (4), leuco dye and developer, those represented by the following formulas were used.

[0118]

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The thus prepared material was applied to a support in accordance with the composition and addition amount shown in Table 7 to prepare a photosensitive material K101.

[0120]

[Table 7]

Note: The hardeners (1) and (2) and the surfactants (2), (3) and (5) used were those represented by the following formulas.

[0122]

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(Preparation of Processed Image-Receiving Material) Next, preparation of a processed image-receiving material used for forming an image on a photosensitive material by processing in combination with a photosensitive material will be described.

(Preparation of emulsified dispersion of high-boiling organic solvent (A)) An emulsified dispersion of high-boiling organic solvent (A) represented by the following formula was prepared according to the following method.

[0125]

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(Preparation of Solution 1) Gelatin powder 1000 g
Was added to 6465 ml of ion-exchanged water and 12.5 ml of a 7% aqueous solution of the preservative (A), and dissolved by heating at 65 to 70 ° C. to prepare a solution A.

(Preparation of Solution 2) High boiling organic solvent (A) 20
00 g, high boiling organic solvent (B) 200 g, and surfactant
(B) 25 g were mixed and heated and stirred at 65 to 70 ° C. to make uniform.

(Preparation of Solution 3) Surfactant (C) 53 g
Was added to 40 ml of MEK and dissolved by heating at 65 to 70 ° C.

(Emulsification) Solution 2 and solution 3 were added to solution 1 and emulsified by stirring with a mixer. Thereafter, the pressure emulsification treatment is performed twice. After emulsification, 300 ml of ion-exchanged water
Was added and stirred. Next, the mixture was filtered and stored in a nylon mesh 100. Thereby, the average particle size is 0.2 to 0.3.
An emulsified dispersion of the high-boiling organic solvent (A) having a size of μm was obtained.

The above-mentioned emulsified dispersion of the high-boiling organic solvent (A) and the raw materials shown in Table 8 were used and applied to a support in accordance with the constitution and the amount of addition shown in Table 8.
Processing material R101 was produced.

[0131]

[Table 8]

Note: Preservative (A), high boiling organic solvent (B), surfactants (A), (B) and (C), silica matting agent (A), water-soluble polymer (A), (B ) And (C), hardener (A), and acetylene compound (A)
The following were used.

[0133]

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[0134]

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[0135]

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[0136]

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Next, FIG. 1 shows an immersion treatment apparatus used in this embodiment. In the apparatus shown in FIG. 1, the immersion section 200 is provided with an immersion tank 202 as a receiving tray for storing an aqueous solution. The immersion tank 202 has a rectangular outer shape, and its longitudinal direction is arranged along the width direction of the film F, and its inner cross section is recessed into a substantially U-shaped groove to serve as a storage section for the aqueous solution. A heater unit 204 for heating the immersion tank 202 is provided on the lower surface of the immersion tank 202, and the aqueous solution stored in the immersion tank 202 is kept warm and maintained at an appropriate temperature. A substantially U-shaped groove 214 having an open upper end is formed on both side surfaces in the longitudinal direction of the immersion tank 202, and the rotating shaft 218 of the immersion roller 216 is wound around the groove 214. For this reason, about ３ below the immersion roller 216 is immersed in the aqueous solution. A guide plate 224 is provided between the transport roller 222 and the immersion section 200, so that the film F is transported to the uppermost position of the immersion roller 216 without fail. The immersion roller 216 takes out the aqueous solution by its own high-speed rotation with respect to the transported film F,
A vortex is generated just before (upstream) a contact portion with the film F at the uppermost point. The lower surface of the film F is immersed in the vortex.

The photosensitive material K101 produced as described above is
It is cut into a length of 10 mm and a length of 470 mm, and using a semiconductor laser having an output peak wavelength at 670 nm, one pixel (1
Exposure was performed while changing the amount of light at a rate of 1/1000 ^second per 100 μm ² ). Separately, the processed image-receiving material R101, which was formed into a roll having a width of 635 mm and a length of 76 m, was wound around a roll-shaped core (feeding side) having a diameter of 3 inches so that the application surface faced outward. Then, the tip of the processed image receiving material is
Partially wound around another winding core (winding side).

Next, the processed image receiving material was set so that the film surface of the processed image receiving material was in contact with the outer surface of the curved heater during the feeding and winding. Further, the exposed photosensitive material is heated to 50 ° C.
Immediately after being immersed in water kept for 3.2 seconds, the film surface of the photosensitive material and the film surface of the processed image receiving material are stuck so as to uniformly overlap with each other. Then, while moving the processed image receiving material and the photosensitive material on a curved heater, The processing was performed by adjusting the speed and the heater temperature so that the photosensitive material was heated at 85 ° C. for 17 seconds until the photosensitive material was separated from the processed image receiving material. Next, the photosensitive material was peeled from the processed image receiving material. Thereafter, the film surface of the photosensitive material was immersed in an aqueous solution using the immersion treatment apparatus described above.

The aqueous solution used for the immersion treatment was prepared and treated as shown in Table 9. However, the treatment 101 was dried without performing the immersion treatment.

Immediately after water was attached to the black portion (Dmax) of the dried image by spraying, the surface was rubbed, and the resulting pinholes were visually evaluated.
A pinhole was formed, but was practically usable, and a pinhole was not formed. The result and 40
Table 9 summarizes the amount of swelling in water at ° C. From the results shown in Table 9, when the swelling amount is 70% or less before immersion,
It can be seen that the occurrence of pinholes has been improved.

[0142]

[Table 9]

[0143]

According to the image forming method of the present invention, an image having excellent film quality after processing can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a configuration of an immersion section of an immersion treatment apparatus used in an example.

[Explanation of symbols]

 F film (silver halide photosensitive material) 200 immersion section 202 immersion tank 204 heater unit 206 circular hole 208 circular hole 210 piping 212 piping 214 U-shaped groove 216 immersion roller (washing roller) 218 rotating shaft 222 transport roller 224 guide plate 226 Guide Roller 228 Guide roller

Claims (5)

[Claims] 1. A photothermographic material having at least one light-sensitive silver halide emulsion layer on a support is superimposed on a processed image-receiving material after or simultaneously with imagewise exposure,
In the method of forming an image on the photothermographic material by peeling from the processed image-receiving material after thermal development in the presence of a reducing agent and water, the peeled photothermographic material contains a hardening agent An image forming method characterized by immersing in an aqueous solution. 2. The image forming method according to claim 1, wherein the amount of swelling of the photothermographic material after immersion in water is 70% or less of the amount of swelling before immersion. 3. A photothermographic material having at least one light-sensitive silver halide emulsion layer on a support is superimposed on a processed image-receiving material after or simultaneously with imagewise exposure.
In the method of forming an image on the processed image receiving material by heat-developing in the presence of a reducing agent and water and then peeling off the photothermographic material, the peeled processed image receiving material is treated with an aqueous solution containing a hardener. An image forming method characterized by immersing in an image. 4. The image forming method according to claim 3, wherein the swelling amount of the processed image receiving material after immersion in water is 70% or less of the swelling amount before immersion. 5. The photothermographic material contains a basic metal compound which is hardly soluble in water, and the processed image-receiving material contains a base precursor capable of chelating metal ions constituting the basic metal compound. The image forming method according to claim 1, wherein: