JPH0954385A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the method for forming a black-and-white image low in Dmin and high in density and gradation and superior in sharpness and high in image quality in a short time without using any developing solution. SOLUTION: The silver halide photographic sensitive material contains at least a photosensitive silver halide emulsion and a hydrophilic binder and a basic metal compound hardly soluble in water on a support and a photosensitive silver halide emulsion layer has a binder to silver weight ratio of 0.25-2, and an amount of the binder in nonphotosensitive layers upper than the photosensitive silver halide emulsion layer is 0.1=1g/m<2> . A sheet containing a compound capable of forming a complex with a metal ion constituting the basic metal compound, physical development nuclei, and a silver halide solvent is superposed on this photosensitive material after imagewise exposure or at the same time as it and a silver image is formed by heat developing them in the presence of a reducing agent and water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide light-sensitive material. A black and white image can be obtained in a short time without using a developer, Dmin is low, high gradation and sharpness are obtained. The present invention relates to an image forming method which is high and the processed image is stable.

[0002]

2. Description of the Related Art A photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photography in photographic characteristics such as sensitivity, gradation control and resolution, and thus has been the most widely used. Has been used for

At present, image information has largely changed from monochrome images to color images because of the large amount of information and ease of expression. It is used. Further, regarding printing, character information is usually used as a black and white image.

In recent years, an image forming method for a photosensitive material using silver halide has been changed from a conventional wet processing to an instant system incorporating a developing solution, and a dry thermal developing processing by heating or the like. A system capable of easily and quickly obtaining an image without using a developer has been developed from the viewpoint of environmental protection. Regarding such a photothermographic material, "Basics of Photographic Engineering (Non-silver salt photography)" published by Corona Publishing Co., Ltd., pp. 242 to 255, JP-B-43-4921
And Japanese Examined Patent Publication No. 43-4924. As a product, 3M's dry silver sensitive material has been put on the market in black and white.

[0005] Like dry silver, silver halide,
In a mono-sheet photosensitive material comprising an organic silver salt and a reducing agent, unused silver halide and organic silver salt remain in the heat-developed image. Therefore, when exposed to intense light or stored for a long period of time, the remaining silver halide or organic silver salt is printed out and the white background is colored, and the contrast is lost.

A method for obtaining a black color image by a dry process is disclosed in Research Disclosure (hereinafter abbreviated as RD), September 1978, pages 49 to 51 (RD 17326).
However, since this method is also an unfixed type in which a silver salt is contained in the color image, it has the same drawbacks as described above.

In order to improve these drawbacks, a movable (diffusible) dye is formed or released imagewise by heating, and then the movable dye is converted to a dye-receiving substance by using various transfer solvents. For example, a method for forming a black-and-white image with improved storability by transferring to a dye fixing material containing a mordant, a heat-resistant organic polymer, or the like is disclosed in Japanese Patent Publication No. 3-78617.
No. 3,45,820. However, since these methods are methods of transferring after thermal development, the number of steps is large and the processing time is long.

Further, JP-A-3-260645 discloses that
Regarding a thermal development transfer type black-and-white image forming method using a coupling reaction, a method of transferring a dye formed by coupling after development and a method of simultaneously performing development and transfer are disclosed. However, this method also requires a high temperature and a long time for processing because it does not have an effective development transfer accelerator.

Japanese Patent Application Laid-Open No. 62-1219848 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. However, in order to obtain an image having a transmission density of 2 or more required for many black-and-white images in a short time by the dye transfer method, the thickness of the light-sensitive material, particularly the amount of the binder, must be reduced as much as possible, It is necessary to increase the amount. For this reason, there arises a problem that the film quality is reduced and the manufacturing cost is increased. Further, there is a problem that the use is limited because the sharpness is lowered by the transfer. Further, it is difficult to synthesize a black dye-donating compound, and it is also difficult to obtain a desired neutral gray color image by mixing yellow, magenta, and cyan dye-donating compounds.

On the other hand, a method of forming a silver image on an image receiving sheet by heat-developed silver salt diffusion transfer using a silver halide photosensitive material is described in JP-A-62-283332 and JP-A-63-283332.
No. 198050 and No. 60-194448, these methods also use a transferred silver image, and it is difficult to obtain an image with a transmission density of 2 or more and high sharpness in a short time. At that time, improvements were needed.

When the photographic light-sensitive material is applied as a photosensitive material for printing, one of the exposure methods is to scan the original image and perform exposure on the silver halide photographic light-sensitive material based on the image signal to obtain the image of the original image. There is known an image forming method by a so-called scanner method for forming a negative image or a positive image corresponding to the above. There are various types of recording apparatuses that use the scanner-type image forming method, and conventionally, glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, and the like have been used as recording light sources for these scanner-type recording apparatuses. However, each of these light sources has a practical defect that the output is weak and the life is short. To compensate for these drawbacks, He-
Recently, Ne lasers, Ar ion lasers, He-Cd lasers, and infrared and visible semiconductor lasers have been widely used.

He-Ne lasers, Ar ion lasers, infrared and visible semiconductor lasers are used for color scanners and imagesetters, especially in the field of printing, and photosensitive materials are spectrally adjusted to match the wavelengths of these lasers. The image which has been sensitized and chemically sensitized and which has been subjected to laser exposure is usually output in the form of halftone dots. On the other hand, there is also known a method in which halftone dots are formed by using a color separation filter or a contact screen by photographing with a plate making camera system.

Mainly in a photosensitive material for printing, a black and white image can be obtained in a short time without using a developing solution, and a high D
There has been a demand for an image forming method having high max, low Dmin, high gradation, high sharpness, and stable image after processing.

[0014]

SUMMARY OF THE INVENTION The first object of the present invention is to obtain a high-quality black and white image having a low Dmin, a high density, a high gradation and an excellent sharpness in a short time without using a developing solution. It is to provide an obtained image forming method. A second object of the present invention is to provide an image forming method for obtaining a stable image against light, temperature and humidity.

[0015]

The object of the present invention is to provide a silver halide light-sensitive material containing at least a light-sensitive silver halide emulsion, a hydrophilic binder and a basic metal compound which is hardly soluble in water on a support. After exposure or simultaneously with imagewise exposure
A sheet containing a complex-forming compound for the metal ion constituting the basic metal compound, physical development nuclei and a silver halide solvent is superposed and heat-developed in the presence of a reducing agent and water to give a light-sensitive material. In the method of forming a silver image, the weight ratio of the binder to silver in the photosensitive silver halide emulsion layer of the silver halide light-sensitive material is 0.25 or more and 2 or less, and a non-layer above the photosensitive silver halide emulsion layer is used. It is achieved by an image forming method characterized in that the amount of binder in the photosensitive layer is 0.1 g / m ² or more and 1 g / m ² or less.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the weight ratio of the binder to silver in the photosensitive silver halide emulsion layer (hereinafter referred to as silver binder ratio) is preferably 0.2 or more and 2 or less, and more preferably , 0.5 or more and 1.5 or less, and more preferably 0.75 or more and 1.25 or less. The silver in this case is the silver equivalent in the silver halide. When the number of photosensitive silver halide emulsion layers is two or more, the average value may be within the above range. When the number of photosensitive silver halide emulsion layers is two or more, they may be adjacent to each other or may be separated by a non-photosensitive intermediate layer.

The method of changing the silver binder ratio is to change the amount of binder added during the preparation of the coating solution for the photosensitive silver halide emulsion layer, or to re-process the silver halide grains after the desalting step of the silver halide emulsion. This is possible by changing the amount of binder (mainly gelatin) at the time of dispersion or changing the amount of protective colloid at the time of forming silver halide emulsion grains. The binder amount in the non-photosensitive layer above the uppermost photosensitive silver halide emulsion layer is preferably 0.1 g / m ² or more and 1 g / m ² or less, more preferably 0.15 g / m ² or more and 0.1. It is 5 g / m ² or less.

The non-light sensitive layer above the uppermost light sensitive silver halide emulsion layer is preferably a protective layer. Between the protective layer and the uppermost light-sensitive silver halide emulsion layer, there may be a layer containing a water-insoluble basic metal compound or a layer containing a reducing agent. The protective layer may contain a water-insoluble basic metal compound or a reducing agent. The amount of binder in the non-photosensitive layer above the uppermost photosensitive silver halide emulsion layer can be changed by the amount of binder added when preparing the coating solution or the amount of binder introduced when the other compound is a binder dispersion. .

The binder used in the present invention will be described later in detail, but gelatin is preferably used. The present inventors have found that when the binder amount and the silver binder ratio of the non-light-sensitive layer above the uppermost photosensitive silver halide emulsion layer are the above-mentioned combination, Dmin is not lowered and Dmin is lowered.
Is cut, the gradation of the foot of the characteristic curve becomes harder, and moreover,
It was found that there was little processing unevenness and the image stability after processing was good, but such effects were new and unexpected.

In the present invention, a water-insoluble basic metal compound used as a base precursor and a compound (complex forming compound or complexing agent) capable of undergoing a complex formation reaction with a metal ion constituting the hardly soluble metal compound Regarding the combination, JP-A-62-129848, European Patent Publication 210,660A2, and US Pat. No. 4,740,445.
And the like.

As a preferable hardly soluble base metal compound,
Zinc or aluminum oxides, hydroxides and basic carbonates, particularly preferably zinc oxide, zinc hydroxide and basic zinc carbonate. Metal compounds that are poorly soluble in water are disclosed in JP-A-59
As described in JP-A-174830, fine particles are dispersed in a hydrophilic binder for use. The average particle size of the fine particles is
0.001 to 5 μm, preferably 0.01 to 2 μm
m. The content in the photosensitive material is from 0.01 g / m ^{2 to} 5 g / m ^2.
a g / m ^2, preferably, is 0.05 to 2 g / m ^2.

The complex-forming compound used in the sheet containing a complex-forming compound for a metal ion of a basic metal compound which is poorly soluble in water (hereinafter referred to as a complexing agent sheet) is a chelating agent in analytical chemistry, and water softening in photographic chemistry. It is a known agent. For details, besides the above-mentioned patent specification,
A. Ringbomb, Translated by Nobuyuki Tanaka and Haruko Sugi "Complexation Reaction"
(Industrial books). Preferred complex-forming compounds for the present invention are water-soluble compounds, for example, aminopolycarboxylic acids (including salts) such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, aminotris (methylenephosphonic acid), ethylenediamine Examples thereof include aminophosphonic acids (salts) such as tetramethylenephosphonic acid, and pyridinecarboxylic acids (salts) such as 2-picolinic acid, pyridine-2,6-dicarboxylic acid, and 5-ethyl-2-picolinic acid. Among these, pyridinecarboxylic acid (salt) is particularly preferred.

In the present invention, the complex-forming compound is preferably used as a salt neutralized with a base. Particularly, salts with organic bases such as guanidines, amidines and tetraalkylammonium hydroxide and salts with alkali metals such as sodium, potassium and lithium are preferred. It may be a mixture of these. Specific examples of preferred complex-forming compounds include
JP-A-62-129848, European Patent Publication 21
No. 0,660A2 and the like. The content of the complex forming compound in the complexing agent sheet is 0.01 to 10 g / m ² , and preferably 0.05 to 5 g / m ² .

In the present invention, the complexing agent sheet contains physical development nuclei. The physical development nuclei reduce the soluble silver salt diffused from the light-sensitive material to convert it into physically developed silver, thereby forming the complexing agent. It is fixed to the seat. Physical development nuclei include zinc, mercury, lead, cadmium, iron, chromium, nickel,
Heavy metals such as tin, cobalt, copper, and ruthenium; or noble metals such as palladium, platinum, silver, and gold; and those known as physical development nuclei such as colloidal particles of chalcogen compounds such as sulfur, selenium, and tellurium are all included. Can be used. These physical development nuclei substances are prepared by reducing the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, hydroquinone to form a metal colloidal dispersion, or soluble sulfides, selenides or tellurides. Obtained by mixing the solutions to form a colloidal dispersion of water insoluble metal sulfide, metal selenide or metal telluride. These dispersions are preferably formed in a hydrophilic binder such as gelatin. A method for preparing colloidal silver particles is described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed.

The size of these physical development nuclei is 2 to 20.
Those having a particle size of 0 nm are preferably used. These physical development nuclei are usually contained in the complexing agent sheet at 10 ^{−3 to} 100 mg /
m ^2, preferably, 10 ^-2 ~10mg / m ² is contained. 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 a physical development nucleus,
Silver, silver sulfide, palladium sulfide and the like are preferably used.
When the physically developed silver transferred to the complexing agent sheet is used as an image, palladium sulfide, silver sulfide, etc. have a Dmin loss and Dm
It is preferably used because of high ax.

The silver halide solvent used in the present invention is
Known materials can be used. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, sulfites such as sodium sulfite and sodium hydrogensulfite, thiocyanates such as potassium thiocyanate and ammonium thiocyanate, and those described in JP-B-47-11386. Thioether compounds such as 8-di-3,6-dithiaoctane, 2,2'-thiodiethanol, 6,9-dioxa-3,12-dithiatetradecane-1,14-diol, Japanese Patent Application No. 6-325350. The compounds having a 5- or 6-membered imide ring such as the described uracil and hydantoin, and the compounds of the following general formula (I) described in JP-A-53-144319 can be used. Analytica
Chemica Acta Vol. 248 Volume 604 ~
Mesoionic thiolate compounds are also preferable for the trimethyltriazolium thiolate described on page 614 (1991). The compounds capable of fixing and stabilizing silver halide described in Japanese Patent Application No. 6-206331 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 group, an aryl group, a heterocyclic residue or an amino group.
R ³ represents an aliphatic or 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. The above silver halide solvents may be used in combination.

In the present invention, among the above compounds, compounds having a 5- or 6-membered imide ring such as sulfite, uracil and hydantoin are particularly preferable. Especially, when uracil and hydantoin are added as potassium salts,
It is preferable in that the deterioration of gloss during storage of the complexing agent sheet can be improved.

The content of the total silver halide solvent in the complexing agent sheet of the present invention is 0.01 to 50 mmol / m ² ,
It is preferably 0.1 to 30 mmol / m ² . More preferably, it is 1 to 20 mmol / m ² . The molar ratio to the coating silver amount of the light-sensitive material is 1/20 to 20 times, preferably 1/10 to 10 times, and more preferably 1/3 to 3 times.
It is twice. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropyl glycol or the like, or an alkaline or acidic aqueous solution, or may be dispersed in solid fine particles and added to the coating solution.

In the present invention, Japanese Patent Application No. 6-32535
By incorporating a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone described in No. 0 as a component in the complexing agent sheet, it is possible to increase the density of the silver image in the photosensitive material.

The photothermographic material used in the present invention basically comprises a photosensitive silver halide emulsion, a hydrophilic binder, a reducing agent and a water-insoluble basic metal compound on a support. Further, if necessary, an organic metal salt oxidizing agent, a dye donating compound and the like can be added.
These components are often added to the same layer, but they can also be added in separate layers. The reducing agent is incorporated in the photothermographic material, but may be supplied from outside by, for example, diffusing it from a complexing agent sheet. The silver halide emulsion light-sensitive layer may be divided into two or more layers as necessary.

In the photothermographic material, various non-photosensitive materials such as a protective layer, an undercoat layer, an intermediate layer, a filter layer and an antihalation layer are provided 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, an undercoat layer as described in US Pat. No. 5,051,335, JP-A Nos. 1-120553 and 5-34.
Reducing agents such as those described in No. 884 and No. 2-64634 and D
Interlayer with IR compound, US Pat. No. 5,017,4
54, 5,139,919, JP-A-2-2350.
An intermediate layer having an electron transfer agent as described in JP-A No. 44, a protective layer having a reducing agent as described in JP-A-4-249245, or a layer combining these may be provided. When the support is polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer preferably has an antistatic function and a surface resistivity of 10 ¹² Ω · cm or less. .

The silver halide grains that can be used in the present invention are
Silver chloride, silver iodochloride, silver chlorobromide, silver iodochlorobromide, silver iodobromide,
It is silver bromide. The silver iodide content is preferably at most 10 mol%, more preferably at most 1 mol%. More preferably, it is 0.5 mol% or less. .

The silver halide emulsion used in the present invention is
The surface latent image type or the internal latent image type may be used. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a multi-structure particle having a different halogen composition between the inside of the particle and the surface of the particle may be used. Further, silver halide emulsions having different compositions may be joined by epitaxial joining.

Particularly, in a silver chlorobromide emulsion having a silver chloride content of 80 mol% or more, a structure having a silver bromide localized phase in the inside and / or on the surface of the silver halide in the form of layer or non-layer is also included. Can be used. The halogen composition of the localized phase preferably has a silver bromide content of at least 20 mol%, and more preferably exceeds 30 mol%. The silver bromide content of the silver bromide localized phase is analyzed by an X-ray diffraction method or the like. For example, Sea Earl Berry, SJ Marino (C.
R. Berry, SJ Marino), Photographic Science and Technology (Potographic Scienc
e and Technology) Volume 2, Page 149 (1955) and Volume 4, Volume 22
Page (1957) describes the application of the X-ray diffraction method to silver halide. The silver bromide localized phase can be inside the grain, at the edge, corner, or on the surface of the grain, but a preferred example is one that is epitaxially bonded to the corner of the grain.

The shape of the silver halide grains is a normal crystal having no twin plane, a single twin having one twin plane, a parallel multiple twin having two or more parallel twin planes, and a non-parallel twin. It can be used depending on the purpose from non-parallel multi-twin crystals having two or more crystal planes, spheres, potatoes, flat plates having a high aspect ratio, and composite systems thereof. The shape of twinned grains is described on page 163, edited by The Photographic Society of Japan, Fundamentals of Photographic Industry-Silver Salt Photograph (Corona Publishing Co.). In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, or a dodecahedral particle having a (110) plane can be used. For dodecahedron grains, Japanese Examined Patent Publication No. 55-42737
And JP-A-60-222842. Furthermore, it is reported in Journal of Imaging Science, Vol. 30, p. 247 (1986). (Hll) plane, (hhl)
Face, (hk0) face and (hkl) face particles can also be used according to the purpose. A tetrahedron having (111) plane and (100) plane and a particle having (111) and (110) plane can also be used. If necessary, 38-sided, rhomboid 24
Polyhedral grains such as tetrahedrons, 46-hedrons, 68-hedrons can also be used. A flat plate having a high aspect ratio can also be preferably used. Tabular grains of high silver chloride emulsion grains having (111) planes are disclosed in U.S. Pat. Nos. 4,399,215 and 4,400,46.
3, No. 5,217,858, JP-A-2-32, and the like. In addition, the Journal of Photographic Sc
Ience 36, p. 182 (1988), also reports an empirical rule for forming silver chloride tabular grains. Tabular grains of high silver chloride emulsion grains having a (100) plane are disclosed in U.S. Pat. No. 4,946,772.
Nos. 5,275,930, 5,264,337
No. 6-59360, 6-308648,
It is described in European Patent 0,534,395A1 and the like.

Such a tabular grain having a high aspect ratio has a large surface area as compared with a normal crystal having the same volume, so that the adsorption amount of the sensitizing dye can be increased, which is advantageous in terms of color sensitization sensitivity. Further, since it is advantageous in terms of covering power, a high Dmax can be achieved with a small amount of silver. Since it has a large specific surface area, it has the feature of having high development activity.

The average grain size of silver halide grains is 0.05 μm.
m, or any size from fine particles having a projected area diameter of more than 10 μm to fine particles having a projected area diameter exceeding 10 μm. Preferably, it is 0.1 to 2 μm, particularly 0.1 to 0.9 μm. Monodisperse emulsions having a narrow grain size distribution may be used. The monodisperse emulsion is, for example, a silver halide emulsion having a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size in terms of the number or weight of grains. Polydisperse emulsions having a wide grain size distribution may be used. Also, JP-A-1-167743 and JP-A-4-22.
As described in No. 3463, two or more kinds of monodispersed silver halide emulsions having substantially the same color sensitivity and different grain sizes may be used in combination for the purpose of adjusting the gradation. Two or more emulsions may be mixed in the same layer or may constitute separate layers. Two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can also be used.

In the process of preparing the silver halide emulsion of the present invention, it is preferable to carry out a desalting step for removing excess salt. A Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (for example, sodium sulfate), an anionic surfactant, an anionic polymer (for example, sodium polystyrene sulfonate), Gelatin derivatives (aliphatic acylated gelatin,
A sedimentation method (flocculation) using aromatic acylated gelatin, aromatic carbamoylated gelatin, or the like may be used. Alternatively, U.S. Patent No. 4,758,505
No., JP-A-62-113137, and JP-B-59-437.
No. 27, U.S. Pat. No. 4,334,012, an ultrafiltration apparatus, a natural sedimentation method, or a centrifugation method may be used. Usually, the sedimentation method is preferably used.

A method for preparing a silver halide emulsion is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Gl.
afkides, Chimie et Physique Photographique Paul Mo
ntel, 1967) "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Che
mistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman et al. Makingand Coating Photographic Emuls
ion. Focal Press, 1964).

The method of preparation may be any of acid method, neutral method and ammonia method. To the extent that no overburden occurs,
High pH may be used. As a method of reacting the soluble silver salt and the soluble halogen salt, a one-side mixing method, a simultaneous mixing method, or a combination thereof can be used. Method of forming grains in the state of excess silver ion (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid layer in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal system and a nearly uniform grain size is obtained.

In the preparation of silver halide emulsion, it is preferable to adjust pAg and pH during grain formation. pAg
PH and pH adjustments are described in Photographic Science and Engineering.
and Engineering) Volume 6, 159-165 (1962);
Journal of Photographic Science (Jou
Rnal of Photographic Science), Volume 12, pp. 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Gelatin is preferably used as the protective colloid used in the preparation of the emulsion in the present invention, but other hydrophilic binders can also be used. The hydrophilic binder can be used alone or in combination with gelatin. As the hydrophilic binder, for example,
Gelatin derivatives, graft polymers of gelatin and other high polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose and cellulose sulfates, sodium alginate, starch derivatives, polysaccharides, carrageenan, polyvinyl alcohol and denatured alkyl Synthetic hydrophilic polymers such as homo- or copolymers such as polyvinyl alcohol, polyvinyl-N-pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole, US Pat. No. 3,615,624 The thioether polymer described in (1) can also be preferably used. As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin, gelatin derivatives such as decalcified gelatin and phthalated gelatin, and low-molecular gelatin can be used. Gelatin oxidized with an oxidizing agent such as hydrogen peroxide or gelatin treated with an enzyme can also be used. A hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

Examples of silver halide solvents include thiocyanates (US Pat. Nos. 2,222,264 and 2,44).
8,534, 3,320,069, each specification), thioether compound (US Pat. No. 3,271,15)
No. 7, No. 3,574,628, No. 3,704,130
Nos. 4,297,439 and 4,276,347), and thione compounds (JP-A-53-1443).
19, JP-A-53-82408, JP-A-55-77737) and imidazole compounds (JP-A-54).
No. 100717), benzimidazole (Japanese Patent Publication No. 60-54662), and amine compounds (described in JP-A No. 54-100717). Ammonia can be used in combination with a silver halide solvent within a range that does not cause adverse effects. Tokiko 46-77
81, JP-A-60-222842 and 60-122.
Nitrogen-containing compounds such as those described in No. 935 can be added to the step of forming silver halide grains. Details of specific examples of the silver halide solvent are described in JP-A-62-21527.
No. 2, pages 12-18.

In the process of grain formation or physical ripening of silver halide, a metal salt (including complex salt) may also be present. Examples of the metal salt include salts or complex salts of noble metals or heavy metals such as cadmium, zinc, lead, thallium, iridium, platinum, palladium, osmium, rhodium, chromium, ruthenium, and rhenium. These compounds may be used alone or in combination of two or more. The addition amount is about 10 ^-9 to 10 ^-3 mol per mol of silver halide. Complex ions and coordination compounds include bromine ion, chlorine ion, cyanide ion, nitrosyl ion, thionitrosyl ion,
Water, ammonia and the like and combinations thereof are preferably used. For example, yellow blood salt, K ₂ IrCl ₆ , K ₃ Ir
Cl ₆ , (NH ₄ ) ₂ RhCl ₅ (H ₂ 0), K ₂ RuCl ₅ (N
O) and K ₃ Cr (CN) ₆ are preferably used. The amount of addition depends on the purpose of use, but is in the range of 10 ^-9 to 10 ^-2 mol per mol of silver halide. The position to be incorporated in the silver halide grains may be uniform within the grains, or may be localized at the surface or inside of the grains, a localized phase of silver bromide, or a high silver chloride grain base. These compounds can be added by mixing the metal salt solution with an aqueous halide solution at the time of grain formation, by adding silver halide emulsion fine particles doped with the metal ion, or by adding the metal salt solution to the particles. During the formation, it can be added directly after the formation of the particles.

In order to increase the sensitivity and density of exposure under high illuminance, metal complex salts such as iridium and yellow blood salt having cyanide as a ligand, lead chloride, cadmium chloride and zinc chloride can be preferably used. In the case of spectral sensitization in the red or infrared region, it is preferable to use a metal complex salt such as a yellow blood salt having a cyanide as a ligand, lead chloride, cadmium chloride, or zinc chloride. Rhodium salt,
Ruthenium salts and chromium salts are preferably used.

When the silver halide grains are formed, the addition rate, addition amount or concentration of the silver salt solution (eg AgNO ₃ aqueous solution) and the halogen compound solution (eg KBr aqueous solution) to be added are increased to accelerate the grain formation rate. Good. As described above, a method for rapidly forming silver halide grains is as follows.
British Patent 1,335,925, US Patent 3,672,
900, 3,650,757, 4,242,4
45, each specification, JP-A-55-142329, 55
-158124, 58-113927, 58-
No. 113928, No. 58-111934, No. 58-1
It is described in each publication of No. 11936.

During or after grain formation, the surface of the silver halide grain may be replaced with a halogen that forms a hardly soluble silver halide grain (halogen conversion). The halogen conversion process is described in "Die Grundlagen der Photographische".
n Prozesse mit Silverhalogeniden) pp. 662-669 and "The Theory of Photographic Process"
(The Theory of Photographic Process) Fourth Edition 97-98
Page. In this method, the compound may be added in the form of a solution of a soluble halide or in the form of fine grain silver halide.

During grain formation and / or after grain formation,
Thiosulfonates, dichalcogen compounds described in US Pat. Nos. 5,219,721 and 5,364,754,
Inorganic metal complexes such as lipoic acid, cysteine, elemental sulfur, cobalt ammonia complexes may be added. The silver halide emulsion of the present invention can be used without chemical sensitization, but is usually used after chemical sensitization. The chemical sensitization method used in the present invention includes a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as tellurium sensitization method, a noble metal sensitization method and a reduction sensitization method using gold, platinum, palladium and the like. Can be used alone or in combination (for example, Japanese Patent Application Laid-Open No. 3-1
No. 10555, No. 5-241267, etc.). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). Further, an antifoggant described below can be added after the completion of chemical sensitization. Specifically, JP-A-5-45833 and JP-A-62-62
The method described in No. -40446 can be used.

An unstable sulfur compound is used as the sulfur sensitizer, and specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.). Well-known sulfur compounds such as allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanines, and mercaptos may be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion, and an appropriate amount is pH,
It varies depending on various conditions such as temperature, balance with other sensitizers, size of silver halide grains, etc., but as a guide, it is used in the range of 10 ^-9 to 10 ^-1 mol per mol of silver halide. Is preferred.

In the sensitization of selenium, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.) are used. ), Selenoketones, selenoamides, aliphatic isoselenocyanates (for example, allyl isoselenocyanate, etc.), selenocarboxylic acids and esters, selenophosates, diethyl selenides, diethyl selenides and other selenides. Can be used. The amount of addition varies depending on various conditions as in the case of the sulfur sensitizer, but it is preferably used in the range of 10 ^-10 to 10 ^-1 mol per mol of silver halide.

In the present invention, in addition to the chalcogen sensitization described above, sensitization with a noble metal can be performed. First, in gold sensitization, the valence of gold may be +1 or +3,
Various gold compounds are used. Representative examples include chloroauric acids, potassium chloroaurate, auric trichloride, potassium aurithiocyanate, potassium iodooleate, tetraauric acid, ammonium aurothiocyanate, pyridyl trichlorogold,
Gold sulfide, gold selenide, gold telluride and the like. The addition amount of the gold sensitizer varies depending on various conditions, but as a guide, it is preferable to use it in the range of 10 ^-10 to 10 ^-1 mol per mol of silver halide. The gold sensitizer may be added at the same time as sulfur sensitization, selenium sensitization, or tellurium sensitization, during, before, after, or after the sulfur or selenium / tellurium sensitization step. It is also possible to use.

The pAg and pH of the emulsion to be sulfur-sensitized, selenium-sensitized or tellurium-sensitized or gold-sensitized according to the present invention are not particularly limited, but the pAg is 5 to 11 and the pH is 3 to 10. Is preferred. More preferably, pAg
Is in the range of 6.8 to 9.0, and the pH is in the range of 5.5 to 8.5. In the present invention, noble metals other than gold can be used as the chemical sensitizer. As a noble metal other than gold, for example, a metal salt such as platinum, palladium, iridium and rhodium or a sensitizer based on a complex salt thereof can be used.

In the present invention, reduction sensitization can be further performed. Known reduction sensitizers used in the present invention include sulfites, ascorbic acid, stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like. In the present invention, one of these known compounds can be selected and used, and two or more compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide,
Dimethylamine borane, L-ascorbic acid and aminoiminomethanesulfinic acid are preferred compounds. Since the addition amount of the reduction sensitizer depends on emulsion conditions, it is necessary to select the amount, per mol of silver halide 10 ^-9 to 1
A range of 0 ^-2 mol is suitable.

In addition to the method of adding the reduction sensitizer described above, a method of growing or aging in a low pAg atmosphere of pAg1 to 7 called silver ripening, a high pH atmosphere of pH 8 to 11 called high pH ripening. It is also possible to select a method of growing or aging by, or a method of reducing and sensitizing by passing hydrogen gas or by hydrogen in the nascent stage by electrolysis. Further, two or more methods can be used in combination.
This reduction sensitization can be used alone, but can also be used in combination with the above-described chalcogen sensitization or noble metal sensitization.

The photosensitive silver halide emulsion is spectrally sensitized by the methine dye nucleus thereof in order to impart green-sensitive, red-sensitive and infrared-sensitive color sensitivity to the silver halide used in the present invention. Good. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of those generally used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is,
Pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; Benzindolenin nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, and a thiazolidine-2,4 are used.
-5- to 6-membered heterocyclic nuclei such as dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied. Specifically, U.S. Pat. No. 4,617,257, JP-A-59
JP-A-180550 and JP-A-64-13546;
No. 45828, No. 5-45834 and the like. These sensitizing dyes may be used alone,
A combination thereof may be used, and a combination of sensitizing dyes is often used particularly for the purpose of wavelength adjustment of supersensitization or spectral sensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that does not substantially absorb visible light, or a compound exhibiting supersensitization may be contained in the emulsion (for example, US Patent No. 3,61
5,641, JP-A-59-192242 and 59-
191032 and 63-23145).
In particular, JP-A-59-191032 and JP-A-59-19
No. 2242 is preferably used when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used.

The dye may be added to the emulsion at any stage of emulsion preparation. Most commonly, it is done after the completion of chemical sensitization and before coating, but U.S. Pat. Nos. 3,628,969 and 4,225,666.
No. 58-113928, it is also possible to add spectral sensitization at the same time as the chemical sensitizer, as described in JP-A No. 58-113928. It can also be performed prior to chemical sensitization. Further, it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, US Pat. No. 4,225,66
No. 6, to add these said compounds separately, ie to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization. It is also possible to do so according to US Pat. No. 4,183,7.
It may be at any time during silver halide grain formation, including the method taught in US Pat. The addition amount can be 9 × 10 ^{−9 to} 9 × 10 ⁻³ mol per mol of silver halide. These sensitizing dyes and supersensitizers can be used as a solution of a hydrophilic organic solvent such as methanol, an aqueous solution (which may be alkaline or acidic to enhance solubility), a dispersion such as gelatin, or a surfactant. What is necessary is just to add in a solution.

To enhance the adsorption of the sensitizing dye, a soluble Ca compound and a soluble B compound are added before and after the addition of the sensitizing dye.
An r compound, a soluble I compound, a soluble Cl compound, and a soluble SCN compound may be added. These compounds may be used in combination. Preferably CaCl ₂ , KI, K
Cl, KBr, KSCN. Further, fine grains of silver bromide, silver chlorobromide, silver iodobromide, silver iodide, and silver rhodane emulsion may be used.

There are no particular restrictions on other additives to the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure 176.
Volume, Item 17643 (RD-17643), ibid. 187
Vol., Item 18716 (RD-18716) and ibid.
The description of Volume 307, Item 307105, etc. can be referred to.

Additives used in such steps and known photographic additives usable in the light-sensitive material and complexing agent sheet of the present invention can be used as various additives in RD-17643, RD-18716 and RD-307105. Listed below are the locations of description. Additive type RD17643 RD18716 RD307105 1 Chemical sensitizer page 23, page 648 right column 866 page 2 Sensitivity enhancer Same as above 3 Spectral sensitizer 23 to 24 page 648 right column to 866 to 868 Supersensitizer page 649 right Column 4 Brightener page 24 page 648 right column to page 868 5 Antifoggant page 24-25 page 649 right column to 868 to 870 and stabilizer 6 Light absorber, f 25 to 26 page 649 right column to 873 Page filter 650 left column infrared absorber 7 antistain agent 25 page right column 650 page left to right column 8 dye image stabilizer page 25 650 page left column 872 9 hardening agent page 26 651 page left column 874 to 875 Page 10 Binders 26 pages Same as above 873-874 11 Plasticizers and lubricants 27 pages 650 right column 876 pages 12 Coating aids and interfaces 26-27 Same as above 875-87 Page 6 Activator 13 Static page 27 Same as above pages 876 to 877 Inhibitor 14 matting agent pages 878 to 879

Further, the compounds shown below can also be used. Item 1) Silver halide emulsion and JP-A-2-97937, page 20, lower right column 12, its production line to page 21, left lower column, line 14 and JP-A-2-12236. Page 7, upper right column, line 19 to page 8, lower left column, line 12, JP-A-4-330430 and JP-A-5-11389. 2) Spectral sensitizing dye JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8; JP-A 2-39042, page 7, lower right column, line 8 to Page 13, lower right column, line 5; JP-A-2-12236, page 8, lower left column 1, line 3 to same, lower right column, line 4; and JP-A 2-103536, page 16, lower right column, line 3 Spectral sensitizing dyes described on page 17, lower left column, line 20, and further described in JP-A Nos. 1-112235, 2-124560, 3-7928, and 5-11389.

3) Surfactant / Antistatic Prevention JP-A-2-12236, page 9, upper right column, line 7 From the stopping agent to the same, lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 From the same page, page 4, lower right column, line 18 4) Antifoggant / stability JP-A-2-103536, page 17, lower right column, 1 agent, line 9 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; A thiosulfinic acid compound described in 1-237538. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 and JP-A 2-5 5349, page 8, lower right column, line 13 From the same page, page 1, upper left column, line 8

7) Polyhydroxyben JP-A-2-55349, page 11, upper left column, line 9 zen to the same lower right column, line 17 8) Matting agent / slipping agent / JP-A-2-103536, page 10, upper left column 1, plasticizer, line 5 to page 19, upper right column, line 15 9) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 of the same. 10) Dyes, JP-A-2-103536, page 17, lower right column, lines 1 to 18; and JP-A 2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5. 11) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 12) Developer and developing method JP-A-2-55349, page 13, lower right column, line 1 to page 16, upper left column, line 10; JP-A-2-03536, page 19, upper right column, line 16 To page 21, upper left column, line 8 13) Black spot inhibitor The compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832.

14) Redox Compounds Compounds represented by formula (I) of JP-A-2-301743 (particularly compound examples 1 to 50), and described in JP-A-3-174143, pages 3 to 20. General formulas (R-1), (R-2), (R-3), compounds 1 to 75, and compounds described in JP-A Nos. 5-257239 and 4-278939. 15) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 16) Hydrazine nucleating agent JP-A-2-12236, page 2, upper right column, line 19 to page 7, upper right column, line 3, line 3-17 4143, page 20, lower right column, line 1 To page 27, upper right column, line 20, general formula (II) and compound examples II-1 to II-54. 17) Nucleation accelerators JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) and compound example II- 1 No. II-22, the compounds described in JP-A-1-179939.

Of the above additives, antifoggants and stabilizers include azoles (eg, benzothiazolium salt,
Nitroimidazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles,
Aminotriazoles, etc.); Mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole and its derivatives), mercapto) Pyrimidines, mercaptotriazines and the like); thioketo compounds such as oxadrinethione; azaindenes {eg, triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene), pentaazaindenes and the like); benzenethiosulfones; benzenesulfinic acid; benzenesulfonic acid amide and the like can be preferably used.

A hydrophilic binder is preferably used as the binder of the constituent layers of the photothermographic material and the complexing agent sheet. Examples thereof include those described in the aforementioned Research Disclosure and pages (71) to (75) of JP-A-64-13546. Specifically, a transparent or semi-transparent hydrophilic binder is preferable, and examples thereof include proteins such as gelatin and gelatin derivatives, or cellulose derivatives, agar, starch, gum arabic, dextran, pullulan, furceleran, and European Patent Publication 443,529. Polysaccharides such as carrageenan, locust bean gum, xanthan gum and pectin, natural compounds such as polysaccharides described in JP-A-1-221736, polyvinyl alcohol, Japanese Patent Application No. 5-
Synthetic polymer compounds such as modified alkyl polyvinyl alcohol, polyvinyl pyrrolidone, and acrylamide polymer described in 339155. U.S. Pat.
960,681, JP-A-62-245260, etc., that is, a superabsorbent polymer such as -COOM or -S
A homopolymer of a vinyl monomer having O ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of these vinyl monomers or a copolymer with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Co., Ltd. ) Sumikagel L-5H) manufactured by M.K. These binders can be used in combination of two or more. Combinations of gelatin and the above binders are preferred. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer.

Gelatin is preferably used as the binder, but when the gelatin content is low, hydrophilic polymers other than gelatin can be used in combination with carrageenan described in European Patent Publication 443,529 in terms of settability at the time of application. The modified alkyl polyvinyl alcohol described in Japanese Patent Application No. 5-339155 and the polysaccharide described in JP-A-6-67330 are preferably used.

The coating amount of all binders on the side of the light-sensitive material containing the light-sensitive silver halide emulsion layer is preferably 12 g / m ² or less, particularly 5 g / m ² or less, and further 4 g / m ² or less. Appropriate. The total amount of the binder coated on the side opposite to the side including the photosensitive silver halide emulsion layer is in the range of 50 to 100% of the total amount of the binder coated on the side including the photosensitive silver halide emulsion layer. It is preferable to have
More preferably, it is around 70%.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 4,839,272, 4,330,617, 4,590,152, 5,017,454, 5 139, 919, JP-A-60-140335, pages (17) to (18), JP-A-57-40245, and JP-A-56-13.
Nos. 8736, 59-178458 and 59-538
No. 31, No. 59-182449, No. 59-18245.
No. 0, No. 60-119555, No. 60-128436
No. 60-128439, No. 60-198540
No. 60-181742, No. 61-259253.
No. 62-2014434, No. 62-244044.
No. 62-131253, No. 62-131256
No. 63-10151, No. 64-13546
(40)-(57), JP-A-1-20553, 2-32
No. 338, No. 2-35451, No. 2-234158.
No. 3-160443, European Patent No. 220,746.
There are reducing agents and reducing agent precursors described on pages 78 to 96 of the publication. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion resistant reducing agent is used, in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide, an electron transfer agent and / or
Alternatively, electron transfer agent precursors can be used in combination. Particularly preferably, said US Patent No. 5,139,
919, European Patent Publication No. 418,743,
Nos. 138556 and 3-102345 are used. Further, JP-A-2-230143 and 2-2
As described in No. 35044, a method of stably introducing it into the layer is preferably used.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3
-Pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the reducing agents described above, and preferably hydroquinone, Sulfonamide phenols, sulfonamide naphthols, JP-A No. 53-110827, US Pat. Nos. 5,032,487, and 5,026,634.
No. 4,839,272, and compounds described as electron donors, and dye-donor compounds having diffusion resistance and reducing property described later. In addition, Japanese Patent Laid-Open No. 3-1
An electron donor precursor as described in No. 60443 is also preferably used.

Further, the reducing agent can be used in the intermediate layer or the protective layer for various purposes such as preventing color mixture, improving color reproduction, improving white background, and preventing silver transfer to the dye fixing material. Specifically, European Patent Publication Nos. 524,649 and 357,04
0, JP-A-4-249245, JP-A-2-64633
, JP-A-2-46450 and JP-A-63-186240 are preferably used. In addition, 3-6
3733, JP-A-1-150135 and 2-110
557, 2-64634, 3-43735,
Development inhibitor releasing reducing compounds such as those described in EP 451 833 are also used. In the present invention, the total amount of reducing agents added is 0.01 to 20 mol, and particularly preferably 0.1 to 10 mol, per mol of silver.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in 00,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is 0.01 mol per mol of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.4 g / m ^2.

Various dyes can be used in the constituent layers of the photothermographic material of the present invention for the purpose of preventing halation and irradiation. The dye is disclosed in JP-A-3-7.
As disclosed in JP-A-931 and JP-A-2-308242, it is preferable to disperse the solid-state fine particles and incorporate them into a photosensitive material. Specifically, the compounds described in the above Research Disclosure and the compounds described in Japanese Patent Application No. 6-259805 can be used.

In the photothermographic material of the present invention, a compound capable of activating development and stabilizing an image at the same time can be used. Specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In the present invention, the image forming substance is mainly developed silver in the light-sensitive material. If necessary, a dye (dye donating compound) may be used for the image forming substance. In a photosensitive material for printing plate making which is a printing original on a PS plate, the PS plate has a spectral sensitivity in a wavelength range of 300 nm to 500 nm so that it can be handled in an ultraviolet-cut light room. It is sufficient that discrimination is provided in the wavelength range, and a dye (dye donating compound) having absorption in this wavelength range can be formed into an image together with the silver image. In addition, a dye donor that forms or releases at least two types of dyes having a color tone substantially different from each other, or a dye donor that forms or emits at least two types of dyes having a color tone substantially different from each other is used. A black-and-white image can be obtained with a dye together with silver by using a hydrophilic compound.

As an example of the dye-donating compound that can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developing agents and couplers include para-phenylenediamine reducing agents and phenolic or active methylene couplers in U.S. Pat. Japanese Patent No. 802,519 and Research Disclosure, September 31, 1975, p. 32, a sulfonamide phenol-based reducing agent is disclosed in US Pat. No. 4,02,1240.
JP-A No. 1989-242, proposes a combination of a sulfonamidephenol-based reducing agent and a 4-equivalent coupler. Examples of other color developers and couplers can be found in "The James" by The James.
Theory of the Photographic Process ”4th Edition 291-334
Pages and pages 354-361. In the coupling reaction, as the reducing agent capable of reacting with the coupler,
A hydrazone compound and a hydrazine compound can also be preferably used.

Another example of the dye-donating compound is a heterocyclic ring containing a nitrogen atom and a sulfur atom or a selenium atom in the presence of a silver ion or a soluble silver complex as described in JP-A-59-180548. The anti-diffusible dye-donating compound (thiazolidine-based compound) having the above-mentioned heterocyclic ring which undergoes a cleavage reaction to release a mobile dye can also be used. As another example of the dye-donating compound, a compound having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. This type of compound can be represented by the following general formula [LI]. ((Dye) _m -Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. Or (Dye) _m -Y) _n -Z to produce a difference in the diffusibility of the compound corresponding to or opposite to the photosensitive silver salt having a latent image, or (Dye) _m -Y
Releasing, released (Dye) _m -Y and ((Dye) _m -
Y) represents a group having a property of causing a difference in diffusibility from _n- Z, m represents an integer of 1 to 5,
n represents 1 or 2, and when either m or n is not 1, a plurality of Dyes may be the same or different. Specific examples of the dye-donating compound represented by the general formula [LI] are those which form a diffusible dye image in the opposite manner to the development of silver halide described in the following.

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972 and Japanese Patent Publication No. 3-68387. A dye developing agent in which a hydroquinone-based developing agent and a dye component are linked, as described in No. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

As described in US Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. . Examples thereof include compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and isoxazolone described in US Pat. No. 4,199,354. Compounds that release a diffusible dye by an intramolecular ring rewinding reaction are included.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783.
396, Open Technical Report 87-6199, Japanese Patent Laid-Open No. 64-13.
As described in Japanese Patent No. 546, etc., 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 intramolecular sought after reduction as described in U.S. Pat. Compounds that release diffusible dyes by nuclear substitution reaction, US Pat.
32,107, JP-A-59-101649, 61.
-88257, RD24025 (1984) and the like, compounds that release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,58
8A, JP-A-56-142530, U.S. Pat. No. 4,
Compounds described in U.S. Pat. No. 4,450,223, which release a diffusible dye by cleavage of a single bond after reduction described in U.S. Pat. Examples thereof include a nitro compound that releases a diffusible dye after accepting an electron and compounds described in US Pat. No. 4,609,610 that release the diffusible dye after accepting an electron.

Further, as more preferable ones, European Patent No. 220,746, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-201653.
Nos. 63-2016654, 64-13546 and the like, a compound having an N—X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule,
SO _{2 in} one molecule described in JP-A-1-26842
-X (where X is as defined above) and a compound having an electron-withdrawing group, a PO-X bond (where X is as defined above) and an electron-withdrawing group are contained in one molecule described in JP-A-63-271344. A compound having a C--X 'bond in one molecule described in JP-A-63-271341 (where X'is synonymous with X or --SO
_2- representing) and a compound having an electron-withdrawing group. In addition, JP-A-1-161237 and JP-A-1-1613
Compounds described in No. 42 in which a single bond is cleaved after reduction by a π bond conjugated with an electron-accepting group to release a diffusible dye can also be used. Among these, especially N-X in one molecule
A compound having a bond and an electron-withdrawing group is preferable.

When the colored dye-providing compound is present in the lower layer of the light-sensitive silver halide emulsion layer, the reduction in sensitivity can be prevented.

Hydrophobic additives such as dye-donor compounds and diffusion resistant reducing agents can be incorporated into the layer of the photothermographic material by known methods such as the method described in US Pat. No. 2,322,027. it can. In this case, US Pat.
Nos. 55,470, 4,536,466, 4,53
6,467, 4,587,206, 4,55
No. 5,476, 4,599,296;
No. 306439, No. 62-8145, No. 62-302
No. 47, Japanese Examined Patent Publication No. 3-62256 and the like can be used in combination with a low boiling organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling organic solvent is 10 g per 1 g of the hydrophobic additive used.
Or less, preferably 5 g or less, more preferably 1 g to 0.
1 g. Also, 1 cc or less for 1 g of binder,
Furthermore, 0.5 cc or less, particularly 0.3 cc or less is suitable.

Also, Japanese Patent Publication No. 51-39853 and Japanese Unexamined Patent Publication No.
The dispersion method using a polymer described in 1-59943 and the method of adding a fine particle dispersion described in JP-A No. 62-30242 can also be used. 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, JP-A-59-157
No. 636, pages (37) to (38), the surfactants described in Research Disclosure above can be used. Further, JP-A-7-56267, Japanese Patent Application No. 6-19247, and West German Laid-Open Patent No. 1,932,29.
The phosphate ester type surfactant described in No. 9A can also be used.

When a dye image is used in combination with the complexing agent sheet, a mordant known in the photographic field can be used.
A specific example thereof is U.S. Pat. No. 4,500,626.
Columns 58 to 59, JP-A-61-88256 (32) to (41)
Page and mordants described in JP-A-1-161236, pages (4) to (7), U.S. Pat. Nos. 4,774,162 and 4,
619,883, 4,594,308, etc. can be mentioned. Also, US Pat.
A dye-receptive polymer compound as described in 3,079 may be used.

The complexing agent sheet may be provided with auxiliary layers such as a protective layer, a peeling layer, an undercoat layer, an intermediate layer, a back layer and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

The hydrophilic binder is preferably used as the binder used in the complexing agent sheet of the present invention. Further, a combination of carrageenans and polysaccharides such as dextran as described in EP-A-443,529, and
It is desirable to use in combination latexes having a glass transition temperature of 40 ° C. or lower as described in JP-A-74820. Also, mordant polymers known in the photographic art and US Pat. No. 4,960,
It is preferably used in combination with a superabsorbent polymer described in JP No. 681, JP-A No. 62-245260 and the like. Further, polyvinylpyrrolidone, polyvinylimidazole,
A polymer such as a copolymer of pyrrolidone and imidazole can also be preferably used. The total amount of binder applied is 20
g / m ² or less, preferably 10 g / m ² or less, and more preferably 7 g / m ² or less.

In the constituent layers of the photothermographic material and the complexing agent sheet, a high boiling point organic solvent can be used as a plasticizer, a sliding agent, or an agent for improving the peelability between the photosensitive material and the complexing agent sheet. Specific examples thereof include those described in Research Disclosure and JP-A-62-245253. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in “Modified Silicone Oil” technical data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. Silicone oils described in JP-A Nos. 62-215953 and 63-46449 are also effective. Examples of the hardener used in the constituent layers of the photothermographic material and the complexing agent sheet include Research Disclosure, US Pat. No. 4,678,73.
No. 9, column 41, 4,791,042;
116655, 62-245261, 61-1.
The hardeners described in JP-A-8942, JP-A-4-218044 and the like can be mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardener (such as dimethylolurea), or polymer hardener (JP-A-62-23415).
Compounds described in No. 7 and the like). These hardeners are added in an amount of 0.001 per 1 g of the coated hydrophilic binder.
1 to 1 g, preferably 0.005 to 0.5 g is used. The layer to be added may be any of the layers constituting the photosensitive material or the complexing agent sheet, or may be added in two or more layers.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the photothermographic material and the complexing agent sheet. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. ), (57) to (71) and (81) to
(97) pages, U.S. Pat. Nos. 4,775,610 and 4,6.
26,500, 4,983,494, JP-A-62.
-174747, 62-239148, 63-
264747, JP-A-1-150135 and 2-1.
No. 10557, No. 2-178650, RD17643
(1978) (24)-(25), Japanese Patent Application No. 6-190529
The compounds described in No. etc. are mentioned. The amount of these compounds is preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver,
Further, 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol is preferably used.

In the constituent layers of the photothermographic material and complexing agent sheet, coating aids, improvement of peeling property, improvement of sliding property, antistatic property,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant include Research Disclosure, JP-A-62-173463 and JP-A-62-1.
No. 83457 and the like. The constituent layers of the photothermographic material and the complexing agent sheet may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57
-9053, columns 8 to 17, JP-A-61-29444,
Examples thereof include fluorine-based surfactants described in JP-A-62-135826, oil-based fluorine-based compounds such as fluorine oil, and hydrophobic fluorine-containing compounds such as solid fluorine-containing compound resins such as tetrafluoroethylene resin.

A matting agent can be used in the photothermographic material and the complexing agent sheet for the purpose of preventing adhesion, improving slipperiness, and providing a non-glossy surface. As the matting agent, various inorganic compound and organic compound particles, particularly polymer particles are used.
Inorganic matting agents include oxides such as silicon dioxide, colloidal silica, titanium oxide and aluminum oxide, alkaline earth metal salts such as barium sulfate, calcium carbonate and magnesium sulfate, and silicates, phosphates and borates. Glass particles. Examples of the organic matting agent include natural products such as corn starch, cellulose ester and cellulose ether and modified products thereof, alkyl acrylates, alkyl methacrylates, acrylamides, vinyl esters, synthetic resins such as styrenes, polyolefins or polymethacrylates. Japanese Patent Laid-Open No. 61-8
In addition to the compounds described in page 8256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, and other compounds described in JP-A-63-274944 and the above-mentioned Research Disclosure can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed.

In the present invention, the matting agents may be used alone or in combination of two or more kinds. The matting agent used in the present invention preferably has an average particle size of 0.1 μm to 20 μm. The amount of the matting agent added is preferably 1 to 40% by weight, more preferably 2 to 20%, based on the weight of the binder.

JP-A-3-109542 and JP-A-64-
As described in JP-A-31149 and JP-A-62-163047, those having a cavity or those having a porous surface may be used.

In addition, the heat-developable photosensitive material and the non-photosensitive separate sheet may contain a thermal solvent, an antifoaming agent, an antibacterial and antibacterial agent, etc. Specific examples of these additives are disclosed in Japanese Patent Laid-Open No.
1-88256, pages (26) to (32), JP-A-3-11
No. 338 and Japanese Patent Publication No. 2-51496.

In the present invention, an image forming accelerator can be used in the photothermographic material and / or the complexing agent sheet. From the physicochemical function, the image formation accelerator has an interaction with a base or the aforementioned base precursor, a nucleophilic compound, a high-boiling organic solvent (oil), a thermal solvent, a surfactant, silver or silver ions. Classified as compounds. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. For details of these, see US Pat. No. 4,678,739, No. 3,
It is described in columns 8-40.

In the present invention, various development stoppers may be used in the photothermographic material and / or the complexing agent sheet for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. it can. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. 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 more details, see
No. 2-253159, pages (31) to (32).

In the present invention, as the support for the photothermographic material and the complexing agent sheet, those capable of withstanding the processing temperature are used. Generally speaking, “Basics of Photographic Engineering: Silver Salt Photography” edited by The Photographic Society of Japan, published by Corona Publishing Co., Ltd.
54) Papers described on pages (223) to (240), photographic supports such as synthetic polymers (films). Specifically, polyethylene terephthalate, polyethylene naphthalate,
Polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, polyarylate, celluloses (eg triacetyl cellulose) or those films containing pigment such as titanium oxide,
In addition, film-processed synthetic paper made from polypropylene, etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast coated paper), metal, cloth,
Glasses and the like are used. The thickness of the support is from 10 μm
200 μm is preferably used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue and carbon black as required.

In addition to this, JP-A-62-253159, pages (29) to (31), JP-A-1-161236 (14) to
(17) page, JP-A-63-16848, JP-A-2-2
2651, 3-56955, US Pat. No. 5,00
The support described in No. 1,033 or the like can be used.
The back surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent. Specifically, the supports described in JP-A-63-220246 and the like can be used. It is also preferable to apply a water-resistant polymer to the back surface of the support of the photosensitive material from the viewpoint of improving the adhesion after processing. It is desirable to design so that the surface resistivity is 10 ¹² Ω · cm or less. The surface of the support is preferably subjected to various surface treatments or undercoating for the purpose of improving the adhesion to the hydrophilic binder.

The light-sensitive material of the present invention can be used in various applications of a light-sensitive material for printing, that is, not only as a film for a scanner, but also as a film for halftone shooting, a film for line drawing, and a contact (negative-positive / negative) film.
Type) film, for adhesion (reversal positive-positive type)
It can be used as a film or a bright room film.

As a method for exposing and recording an image on the photothermographic material of the present invention, for example, a printing original such as a reversal film is exposed with a contact screen or a color separation filter using a plate making camera, and a plate making printer. Scanning exposure by using a scanner, an image setter, a facsimile, etc. to emit image information through an electric signal to emit a xenon lamp, a light emitting diode, various lasers (laser diode, gas laser, etc.), etc. Kaihei No. 2-129625, No. 5-1761
No. 44, No. 5-199372, No. 6-127021, etc.)

As a light source for recording an image on the photothermographic material, a xenon lamp, a tungsten lamp, a halogen lamp, a metal halide lamp, a quartz lamp, a light emitting diode, a laser light source or the like can be used.

An example of the exposure apparatus in the present invention will be given below. Linoty, a commercially available Ar laser exposure system
pe-Hell DC series, Crossfield
Magnascan series, a commercial He-Ne laser exposure system Dainippon Screen's SG series, and a commercial laser exposure apparatus Fuji Photo Film's Lux Scan, Dainippon Screen MT
R and other color scanners and Agfa-Gevae
rt's Selectset (He-Ne), Avan
tra (Red-LD), Linotype-Hell
Herkules (Red-LD), Scitex
Dolev (He-Ne), Agfa-Gevae
An image setter such as Accuset (Red-LD) manufactured by rt, LuxSetter5600 manufactured by Fuji Photo Film Co., Ltd., or a facsimile exposure apparatus such as 240R manufactured by NEC can be used.

The following is an example of a plate-making printer that can be used in the exposure of the present invention. Fuji Photo Film FP
A740, FPA800, FPA800X, FPA80
0Hg, FPA800FX, Dainippon Screen P6
07 series, P617 series, P627 series,
P647 series, P648 series, P607 series, P607 series, IPB of Eye Graphics Inc.
1000SH, USHIO FL2M, FL3M, Kuramisha SK-16, Eastman-Kodak Ver.
salite Contact Printer 840
H, Contact2200Printer, Cont
act2200Printer, Agfa-Gevae
CDL2002Ri from rt, P-6 and P from Kitamura.
-4, P-2, P-8, OR30, THI from SACK
EMER VDM5, CONVAC RD7087
D can be used.

The following is an example of a plate-making camera that can be used in the exposure of the present invention. FCS8 of Fuji Photo Film
20, FCS820S, FGC100, FGC200,
FGC300, Fine Japan Screen's Fine Zoo
M880, ZOMACE800, Companica C-68
0, Companica C-690, P648 series, P60
7 series, P607 series, Imagemaker 540, Eastman-
Kodak's Opti-Copy 32, Opti-C
opy42, Opti-Copy23, image maker 5060A, image maker IM200, image maker IM400, image maker IM600, image maker IM800, Agfa-Gevaert.
The RPS camera manufactured by Mitsubishi Corporation, the repro master series, the Linearus 2000 manufactured by Izumiya, the DesignScope series, and the repro camera series manufactured by Mitsubishi Paper Mills can be used.

The photothermographic material and / or complexing agent sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development and silver salt diffusion transfer. The heat generating element in this case is described in JP-A-61-1455.
No. 44 etc. can be used. In the present invention,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238056 and the like, it is preferable to carry out development and transfer simultaneously or continuously by heating in the presence of a small amount of water. In this method, the heating temperature is preferably 50 ° C to 100 ° C.

As the water used in the present invention, any water can 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 heat developing apparatus using the photothermographic material and the complexing agent sheet of the present invention, water may be used up, or may be circulated for repeated use. In the latter case, water containing components eluted from the material will be used. Also, JP-A-63-144354 and JP-A-63-1.
44355, 62-38460, JP-A-3-21
You may use the apparatus and water described in 0555 etc. Further, it may be contained in a low-boiling solvent soluble in water, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, a fungicide, or a bactericide.

These solvents can be applied to the photothermographic material, the complexing agent sheet, or both, but are preferably applied to the light-sensitive material. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film.
As a method of applying the water, for example,
The methods described in JP-A-53159, page (5) and JP-A-63-85544 are preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in advance in the photothermographic material and / or dye fixing element in the form of a hydrate. The temperature of the applied water may be 30 ° C to 60 ° C as described in JP-A-63-85544 and the like. Especially for the purpose of preventing the growth of various fungi in water 4
A temperature of 5 ° C or higher is useful.

A hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature can be incorporated in the photothermographic material and / or the complexing agent sheet. The layer to be incorporated can be any of the photosensitive silver halide emulsion layer, the intermediate layer, and the protective layer of the photosensitive material,
Any layer of the complexing agent sheet may be used. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

As a heating method in the developing and / or transferring step, a heating block or plate is brought into contact with a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far infrared lamp heater. There is a method of contacting with, etc. or passing through in a high temperature atmosphere.

The method for superimposing the photothermographic material and the complexing agent sheet on each other is described in JP-A-62-253159 and JP-A-61-161.
The method described in page 147244 (27) can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
44, JP-A-6-130509, and JP-A-6-95338.
No. 6-95267 and the like are preferably used. As commercially available devices, Fuji Photo Film Co., Ltd. Pictrostat 100, Pictrostat 200, Pictrostat 300, Pictrograph 3000, and Pictrography 2000 are available.
Etc. can be used.

[0117]

The present invention will be described with reference to the following examples.
The present invention is not limited to these.

Example 1 A method for preparing the photosensitive silver halide emulsion (I) will be described. A well-stirred aqueous solution of gelatin having a composition shown in Table 1 having a pH of 6 was added simultaneously with the solutions (I) and (II) shown in Table 2 over 3 minutes, and 5 minutes later, the solution (III) was added. And (IV)
The liquids were added simultaneously over 15 minutes.

[0119]

[Table 1]

[0120]

[Table 2]

[0121]

Embedded image

After washing with water and desalting (using a precipitating agent and adjusting the pH to 4.1 with sulfuric acid) by a conventional method, 22 g of lime-processed gelatin was added to adjust the pH to 6.1 and pAg to 7.1, and then 50 Chemically sensitized at ℃. The compounds used for chemical sensitization were added sequentially as shown in Table 3. Sensitizing dye,
The chemical sensitization was terminated 20 minutes after the addition of the 4: 1 mixture. The emulsion was a silver chloride emulsion having an average grain size of 0.22 µm and a standard deviation of 0.02 µm. The yield of this emulsion is 630 g. The silver bromide fine grain emulsion (A) used in the chemical sensitization had a grain size of 0.05 μm and a silver amount of 5.
It was 5%.

[0123]

[Table 3]

[0124]

Embedded image

The sensitizing dye is 3,3'-di- (3-sulfopropyl) -9-ethyl-naphtho [1,2-d] thiacarbocyanine triethylamine salt, and the sensitizing dye is
5,5'-dichloro-3,3'-di- (3-sulfopropyl) -9-ethyl-thiacarbocyanine ethylpyridine salt. The preservative is phenoxyethanol.

Next, a method for preparing the silver bromide fine grain emulsion (A) will be described. The gelatin aqueous solution having the composition shown in Table 4 which was well stirred was cooled to 30 ° C.
Solution and (II) solution are added simultaneously over 3 minutes and 40 seconds, and 5 minutes after that, (III) solution and (IV) solution are simultaneously added over 13 minutes so that the silver potential becomes 50 mV. The flow rate was controlled and added.

[0127]

[Table 4]

[0128]

[Table 5]

After washing with water and desalting (adjusted to pH 4.1 with phosphoric acid using a precipitating agent) by a conventional method, 22 g of lime-processed gelatin was added to pH 6.1 and pAg 7.8 (K
Adjusted by Br). A preservative was used as a preservative. It was a silver bromide emulsion having a grain size of 0.05 μm. The yield of this emulsion is 630 g.

Next, a method for preparing a dispersion of the reducing agent 1,5-diphenyl-3-pyrazolidone will be described. 10 g of 1,5-diphenyl-3-pyrazolidone and 0.2 g of Demol manufactured by Kao were added to 90 cc of 5.7% lime-processed gelatin, and dispersed with 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.

Next, a solid state dispersion of the antihalation dye was also prepared according to the above method. A gelatin dispersion was obtained.

[0132]

Embedded image

Next, a method for preparing a zinc hydroxide dispersion will be described. 12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm were used. Dispersed in a mill for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Using the above, a light-sensitive material 101 shown in Table 6 was prepared. The stabilizer is 4,4′-bis [4,6-di (naphthyl-2-oxy) pyrimidine-2.
-Ylamino] stilbene-2,2'-disulfonic acid disodium salt, the polymer being a copolymer of methylmethacrylate-styrene-2-ethylhexylacrylate-methacrylic acid.

[0135]

[Table 6]

[0136]

Embedded image

Next, using the same material as the light-sensitive material 101 with the same coating silver amount, the light-sensitive material 102 shown in Table 7 is used.
~ 114 were created. The silver binder ratio of the photosensitive silver halide emulsion layer is such that the dispersed gelatin after desalting of the silver halide emulsion is lowered, or the dispersed gelatin is removed to reduce the gelatin amount in the gelatin aqueous solution, or the gelatin solution of the coating solution is used. Was added and adjusted. The amount of non-photosensitive gelatin above the uppermost photosensitive silver halide emulsion layer was adjusted by the amount of acid-treated gelatin in the protective layer.

[0138]

[Table 7]

Next, the complexing agent sheet R1 as shown in Table 8
It was created.

[0140]

[Table 8]

[0141]

Embedded image

Photosensitive materials 101 to 1 obtained as described above
14 was exposed with a semiconductor laser having a peak at 680 nm while changing the light amount at 1 / 10,000,000 seconds per pixel (100 μm ² ). Exposed photosensitive material is 40
After soaking in water kept at ℃ for 2.5 seconds, it was squeezed with a roller and immediately superposed so that the complexing agent sheet and the film surface were in contact with each other. Then, the complexing agent sheet R1 was peeled off by heating for 15 seconds using a heat drum whose temperature was adjusted so that the water-absorbed film surface temperature became 80 ° C., whereby a black and white silver image was obtained on the light-sensitive material. Using an automatic densitometer, a characteristic curve, which is the relationship between the blue density of the transmitted image and the exposure amount, was obtained. From this characteristic curve, the maximum density Dmax and the minimum density Dmin were measured. The tonality γ of the foot portion was obtained from the slope of the characteristic curve between Dmin +0.1 and 1.0. The light stability of the processed image was evaluated at the window on the south side. The results are shown in Table 9.

[0143]

[Table 9]

From the above results, in the present invention, Dmi
It can be seen that n is low, Dmax is high, the tonal gradation is high, the processing unevenness is small, and the processed image is stable.

Example 2 A method for preparing the photosensitive silver halide emulsions (II), (III) and (IV) will be described. For the photosensitive silver halide (I), a photosensitive silver halide emulsion (II) was prepared in the same manner as the photosensitive silver halide (I) except that Table 2 was changed to Table 10. For the photosensitive silver halide (I), Table 2 was changed as shown in Table 11, and the solutions (I) and (I
Solution I) was added simultaneously over 10 minutes and 48 seconds, and 5 minutes later, solution (III) and solution (IV) were added simultaneously over 5 minutes, in the same manner as for photosensitive silver halide (I). To prepare a photosensitive silver halide emulsion (III). With respect to photosensitive silver halide (I), Table 2 was changed to Table 12 and Table 3 was changed to Table 13, and solution (I) and solution (II) were simultaneously applied for 11 minutes and 24 seconds. Photosensitive silver halide emulsion (IV) in the same manner as photosensitive silver halide (I) except that solution (III) and solution (IV) were added simultaneously after 4 minutes. Was prepared.

[0146]

[Table 10]

[0147]

[Table 11]

[0148]

[Table 12]

[0149]

[Table 13]

[0150]

[Chemical 6]

The method for preparing the photosensitive silver halide emulsion (V) will be described. To the well-stirred aqueous gelatin solution having the composition shown in Table 14 and having a pH of 3, the solutions (I) and (II) shown in Table 15 were simultaneously added over 3 minutes, and after 5 minutes,
Solution (III) and solution (IV) were added simultaneously over 15 minutes.

[0152]

[Table 14]

[0153]

[Table 15]

After washing with water and desalting (adjusted to pH 3 with sulfuric acid using a precipitating agent) by a conventional method, 22 g of lime-processed gelatin was added to adjust pH 6.1 and pAg 7.4, and then 60 ° C. I chemically sensitized. The compounds used for chemical sensitization were sequentially added as shown in Table 16. Sensitizing dye,
The chemical sensitization was terminated 20 minutes after the addition of the 4: 1 mixture. It was a silver chlorobromide emulsion having a grain size of 0.22 μm and a silver bromide content of 5 mol%. The yield of this emulsion is 630
g.

[0155]

[Chemical 7]

[0156]

[Table 16]

[0157]

Embedded image

Photosensitive silver halide emulsions (VI), (VII),
The preparation method of (VIII) and (IX) is described. For the photosensitive silver halide (V), a pure silver chloride photosensitive silver halide emulsion (VI) was prepared in the same manner as the photosensitive silver halide (V) except that Table 14 was changed as shown in Table 17. Prepared. For the photosensitive silver halide (V), (NH ₄ ) in Table 14
₂ RhCl ₅ (H ₂ O) was added in the same manner as in Photosensitive silver halide (V) except that the addition position was changed from (II) solution to (IV) solution. A photosensitive silver halide emulsion (VII) of silver halide was prepared.

In the photosensitive silver halide (V), the first
The silver bromide content was 5 mol% in the same manner as in the photosensitive silver halide (V) except that the addition position of potassium hexachloryridium (III) in Table 4 was changed from the solution (IV) to the solution (II).
A photosensitive silver halide emulsion of silver chlorobromide (VIII) was prepared. In the photosensitive silver halide (V), the addition position of potassium hexachloroiridium (III) in Table 14 was changed from the solution (IV) to the solution (II), and (NH ₄ ) ₂ RhCl
Silver chlorobromide having a silver bromide content of 5 mol% in the same manner as the photosensitive silver halide (V) except that the addition position of ₅ (H ₂ O) was changed from the (II) solution to the (IV) solution. To prepare a light-sensitive silver halide emulsion (IX).

[0160]

[Table 17]

Next, a method for preparing the photosensitive silver halide (X) will be described. In the photosensitive silver halide (V),
Table 15 was changed as shown in Table 18, so that (I) solution and (II)
The liquid was added simultaneously for 2 minutes and 24 seconds, and 5 minutes later,
Solution (III) and solution (IV) were added simultaneously over 15 minutes, and 5 minutes later, solution (V) and solution (VI) were added simultaneously over 1 minute, and Table 16 was changed to Table 19. Except for the above, a photosensitive silver halide emulsion (X) of silver chlorobromide having a silver bromide content of 5 mol% was prepared in the same manner as in the photosensitive silver halide (V).

[0162]

[Table 18]

[0163]

[Table 19]

[0164]

Embedded image

Next, the method for preparing the photosensitive silver halide (XI) will be described. For photosensitive silver halide (X), bromination was carried out in the same manner as for photosensitive silver halide (X) except that Table 18 was changed to Table 20 and Table 19 was changed to Table 21. A photosensitive silver halide emulsion (XI) of silver chlorobromide having a silver content of 5 mol% was prepared.

[0166]

[Table 20]

[0167]

[Table 21]

[0168]

Embedded image

The above emulsion was used in the light-sensitive material 101.
In the same manner as the photosensitive material 101 except that the photosensitive silver halide (I) was replaced, the photosensitive silver halide (II) to
Using (XI), the light-sensitive material of the present invention 115-124
It was created. Using these photosensitive material and photosensitive material 101, a He-Ne that oscillates a semiconductor laser at 633 nm
Exposing was performed in the same manner as in Example 1 except that the laser was used.
Processing was performed. In any case, Dmin is 0.25 to 0.3
It was within the range of 2. Dmax was also in the range of 3.4 to 3.5, the toe gradation γ was 2.5 or more and 3.5 or less, and no processing unevenness was observed, and a good image was obtained. The processed image,
The sample was left for 3 days at the window on the south side, but no change in the concentration of Dmin and Dmax was observed.

Example 3 A method for preparing the photosensitive silver halide emulsion (XII) will be described. Solution (I) and solution (II) shown in Table 23 were simultaneously added over 6 minutes to an aqueous gelatin solution having a composition of pH 4 shown in Table 22, which was well stirred, and 5 minutes later, solution (III) was added. And (IV) solution were added simultaneously over 10 minutes. Solution (V) shown in Table 24 was added from 1 minute after the start of addition of solution (III) and solution (IV) to 1 minute after the end of addition of solution (III) and solution (IV). The concentration of the sensitizing dye gelatin dispersion used in these solutions (V) is 1%.

[0171]

[Table 22]

[0172]

[Table 23]

[0173]

[Table 24]

After washing with water and desalting (using a precipitating agent and adjusting the pH to 4 with sulfuric acid) by a conventional method, 22 g of lime-processed gelatin was added to adjust the pH to 6.1 and pAg to 7.4, and then 60 ° C. I chemically sensitized. The compounds used for chemical sensitization were sequentially added as shown in Table 25. Particle size 0.
It was a silver chlorobromide emulsion having a silver bromide content of 22 μm and 5 mol%. The yield of this emulsion is 630 g.

[0175]

[Table 25]

Photosensitive silver halide emulsions (XIII), (XI
V) will be described. In the photosensitive silver halide (XII), Table 23 was changed as shown in Table 26, and 30 seconds after the addition of the solutions (I) and (II) was completed, the solution (V) in table 24 was changed to 10 The salt having a silver bromide content of 5 mol% was added in the same manner as the photosensitive silver halide (XII) except that the addition of the solutions (III) and (IV) was started 4 minutes after the addition. A photosensitive silver halide emulsion of silver bromide (XIII) was prepared. In photosensitive silver halide (XII), Table 23 was changed to Table 26, and solution (V) in Table 26 was replaced with solution (III) and solution (IV).
A photosensitive silver halide emulsion of silver chlorobromide having a silver bromide content of 5 mol% was prepared in the same manner as the photosensitive silver halide (XII) except that the addition was carried out for 10 seconds 1 minute after the addition of the solution. X
IV) was prepared.

[0177]

[Table 26]

Photosensitive silver halide emulsion (XV), (XV
I) will be described. In the photosensitive silver halide (XII), Table 23 was changed to Table 27, and the solutions (I) and (II) shown in Table 27 were added simultaneously over 9 minutes,
Five minutes after that, silver chlorobromide having a silver bromide content of 5 mol% was prepared in the same manner as the photosensitive silver halide (XII) except that the solution (III) and the solution (IV) were simultaneously added over 5 minutes. To prepare a light-sensitive silver halide emulsion (XV). Photosensitive silver halide (XI
In I), Table 23 was changed to Table 28, and Solution (I) and Solution (II) shown in Table 28 were simultaneously added over 10 minutes and 48 seconds, and 5 minutes later, (III) Liquid and (IV) liquid 3
A salt having a silver bromide content of 5 mol% in the same manner as the photosensitive silver halide (XII) except that the solution (V) shown in Table 24 was added at the time of gelatin dispersion after washing with water. A photosensitive silver halide emulsion of silver bromide (XVI) was prepared.

[0179]

[Table 27]

[0180]

[Table 28]

The photosensitive silver halide emulsion (XVII) is described below. In the light-sensitive silver halide (XII), the 23rd
The table was changed as shown in Table 29, and the liquid (V) shown in Table 24 was added together with the wash water during the first settling and the second settling in the washing step over 10 seconds. In the same manner as the photosensitive silver halide (XII) except that the table is changed to Table 30,
A photosensitive silver halide emulsion (XVII) of silver chlorobromide having a silver bromide content of 5 mol% was prepared.

[0182]

[Table 29]

[0183]

[Table 30]

[0184]

Embedded image

The method for preparing the photosensitive silver halide emulsion (XVIII) will be described. In a well-stirred aqueous solution of gelatin having a composition shown in Table 31 at pH 9, shown in Table 32 (I)
Solution and solution (II) were added simultaneously over 3 minutes, and 5 minutes after that, solution (III) and solution (IV) were added simultaneously over 15 minutes.

[0186]

[Table 31]

[0187]

[Table 32]

After washing with water and desalting (using a precipitating agent and adjusting the pH to 4 with sulfuric acid) by a conventional method, 22 g of lime-processed gelatin was added to adjust the pH to 7.1 and pAg to 7.4, and then 50 ° C. I chemically sensitized. The compounds used for chemical sensitization were sequentially added as shown in Table 33. Particle size 0.
It was a 22 μm silver chloride emulsion. The yield of this emulsion is 6
30 g.

[0189]

[Table 33]

The method for preparing the photosensitive silver halide emulsion (XIX) will be described. In a well-stirred aqueous gelatin solution having the composition shown in Table 34, the solutions (I) and (II) shown in Table 35 were added.
The liquids were added simultaneously over 3 minutes, and after 5 minutes, liquids (III) and (IV) were added simultaneously over 15 minutes.

[0191]

[Table 34]

[0192]

[Table 35]

[0193]

[Chemical 12]

After washing with water and desalting (adjusted to pH 4 with sulfuric acid using a precipitating agent) by a conventional method, 22 g of lime-processed gelatin was added to adjust pH 6.1 and pAg 7.4, and then 50 ° C. I chemically sensitized. The compounds used for chemical sensitization were sequentially added as shown in Table 36. It was a silver chloride emulsion having a grain size of 0.22 μm. The yield of this emulsion is 630 g.

[0195]

[Table 36]

The above emulsion was used in a light-sensitive material 101.
In the same manner as the photosensitive material 101 except that the photosensitive silver halide (I) was replaced, the photosensitive silver halide (XII) to
(XIX) for use in the light-sensitive material 125-132 of the present invention.
It was created. These light-sensitive materials were used in Example 1 with an exposure device of Accuset manufactured by Agfa / Gevaert.
Exposure and treatment were carried out in the same manner as in Example 1 except that was used, and good images were obtained in each case.

Example 4 A silver iodochlorobromide emulsion having a silver bromide content of 30 mol% and a silver iodide content of 0.08 mol% described on pages 34 to 35 of Japanese Patent Application No. 7-58236 and JP-A No. 7-58236. The photosensitive silver halide emulsion (I) having an average silver bromide content of 83 mol% and a different silver bromide content in the core and the shell of Example 1 of 6-308696 was used as a photosensitive material of the photosensitive material 101 of the present invention. Silver halide emulsion (I)
Photosensitive materials 133 and 134 were prepared in the same manner as the photosensitive material 101 except that the photosensitive materials 133 and 134 were replaced. This photosensitive material 133
And 134 were exposed and processed in the same manner as in Example 1 except that the complexing agent sheet R3 or R4 of Example 2 in Japanese Patent Application No. 7-45018 was used. These photosensitive materials also
Dmax was about 2.8 to 3, and Dmin was about 0.2 to 0.1. The processed image was left for 3 days near the window on the south side, but no change in density was observed between the Dmin portion and the Dmax portion. With the gelatin amount and silver gelatin ratio of the present invention,
By using KSCN or sodium thiosulfate as the silver halide solvent of the complexing agent sheet, the silver bromide content is 30 mol%.
Even with the above, it is possible to achieve high Dmax, low Dmin and stable image storability after processing.

[0198]

According to the present invention, a high-quality black-and-white image having a low Dmin, a high density, a high gradation and an excellent sharpness can be obtained in a short time without using a developing solution. Further, it is possible to obtain a stable image against light, temperature and humidity.

Claims (1)

[Claims] 1. A silver halide light-sensitive material containing at least a light-sensitive silver halide emulsion, a hydrophilic binder, and a water-insoluble basic metal compound on a support, after imagewise exposure or simultaneously with imagewise exposure. A sheet containing a complexing compound for a metal ion constituting the basic metal compound, physical development nuclei and a silver halide solvent is superposed and heat-developed in the presence of a reducing agent and water. In the method for forming a silver image on the surface of the silver halide light-sensitive material, the weight ratio of the binder to silver in the light-sensitive silver halide emulsion layer of the silver halide light-sensitive material is 0.25 or more and 2 or less, The image forming method, wherein the amount of binder in the non-photosensitive layer is 0.1 g / m ² or more and 1 g / m ² or less.