JPH1010693A - Silver halide photosensitive material and method for forming image by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an image small in light scattering like haze or the like and superior in storage stability by incorporating a specified compound in an emulsion layer or another hydrophilic colloidal layer. SOLUTION: The silver halide photosensitive material contains a 1-phenyl-3- pyrazolidone derivative represented by formula I and a 5-pyrazolone derivative in the emulsion layer or another hydrophilic binder layer, and in formula I, each of R<1> -R<4> is an H atom or a substituent, such as an alkyl group; R<5> is a substituent, such as the above group; and (n) is an integer of 0-5. The 5- pyrazolone derivative is represented by formula II in which each of R<1> -R<3> is an H atom or a group same as R<1> -R<3> in formula I, and R<6> is a phenyl or alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material and an image forming method using the same, and more particularly to a photothermographic material capable of obtaining a black-and-white image with high density and low fog and excellent storage stability in a short time. It is about.

[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 that it has superior photographic characteristics such as sensitivity, gradation control, and resolving power. Has been used for

At present, as image information, the amount of information and the ease of expression have largely changed from black-and-white images to color images. However, black-and-white images are preferred in specific fields, such as medical fields. It is used. Further, in the printing field, plate making materials for color images are also used as black and white images for each printing ink, and there is still a great demand mainly for industrial applications.

[0004] In recent years, the image formation processing method of a photosensitive material using silver halide has been simplified from the conventional wet processing to an instant system incorporating a developing solution, and a dry thermal development processing by heating or the like. A system that can obtain images has been developed from the viewpoint of environmental protection. Such photothermographic materials are described in “Basics of Photographic Engineering (Non-Silver Photography), Corona”, pages 242 to 25.
5 pages, JP-B-43-4921, JP-B-43-4924
No. etc.

[0005] For example, as a product, in a black-and-white system, 3
M company's dry silver sensitive material is on sale.

[0006] Like dry silver, silver halide,
Unused silver halide and organic silver salts remain in the heat-processed image of the monosheet photosensitive material comprising an organic base and a reducing agent. 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 of obtaining a black-and-white color image by dry processing is described in Research Disclosure Magazine (hereinafter abbreviated as RD), September 1978, pp. 49-51 (RD173).
No. 26), this method also has the same disadvantages as described above, since it is an unfixed type containing a silver salt in a color image.

In order to remedy these drawbacks, a movable (diffusible) dye is formed or released imagewise by heating, and the movable dye is converted to a dye-receptive substance by using various transfer solvents. For example, Japanese Patent Publication No. 3-78617 discloses a method for forming a black-and-white image having improved storability by transferring to a dye-fixing material containing a mordant, a heat-resistant organic polymer, or the like.
And No. 3-45820. 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 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. Sho 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 are problems that the film quality is reduced and the manufacturing cost is increased. In addition, there is a problem that applications are limited due to a decrease in sharpness due to transfer. Further, it is difficult to synthesize a black dye-donating compound, and it is also difficult to obtain a neutral gray color image by mixing yellow, magenta, and cyan dye-donating compounds.

A method of forming a silver image by thermal development silver salt diffusion transfer using a silver halide photosensitive material is described in JP-A-62-283332 and JP-A-63-19805.
No. 0, No. 60-194448 and the like,
These methods also use a transferred silver image, and it is difficult to obtain an image having a transmission density of 2 or more, low fog, and high sharpness in a short time, and improvement has been required. Japanese Patent Application Nos. 6-325350 and 7-169337 disclose an image forming method utilizing silver remaining on a photosensitive material by a heat-developable silver salt diffusion transfer method. High quality images could be obtained.

On the other hand, in a photosensitive material for plate making, light of 350 nm to 450 nm is generally used as a light source for printing on a PS plate, and a compound having light absorption in this spectral region in a Dmin part of an obtained image. Is not preferred because the amount of printing light decreases. From this viewpoint, when a 1-phenyl-3-pyrazolidone derivative is used as a developing agent, the compound itself and its oxidized form are desirable because of their low light absorption in this spectral region. However, if the oxidized form of the 1-phenyl-3-pyrazolidone derivative produced as a result of the development remains in the processed image, the surface becomes dusty during storage, causing a problem that haze increases.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a light-sensitive material and an image forming method capable of obtaining an image excellent in storability with little light scattering such as haze. Another object of the present invention is to provide a photosensitive material and an image forming method capable of obtaining an image with high density and low fog. Still another object of the present invention is to provide an image forming method for obtaining a black and white image having high sharpness in a short time.

[0014]

The object of the present invention is to provide at least one photosensitive silver halide emulsion layer on a support,
A silver halide photographic material characterized in that the emulsion layer or other hydrophilic binder layer contains a 1-phenyl-3-pyrazolidone derivative and a 5-pyrazolone derivative, and the silver halide photographic material is subjected to imagewise exposure. Subsequent or simultaneously with imagewise exposure, in the presence of a base (including a base precursor) and water, superimposed with a processing sheet containing a silver halide solvent and a physical development nucleus, heat-developed, and then peeling off the processing sheet Thus, a method for forming an image on a photosensitive material was achieved.

Hereinafter, the present invention will be described in detail. In the present invention, 1-phenyl-3 used as a developing agent
Examples of the pyrazolidone derivative include a compound group represented by the general formula (I).

[0016]

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In the formula (I), R ^{1 to} R ⁴ represent a hydrogen atom or a substituent, and examples of the substituent of R ^{1 to} R ⁴ include an alkyl group (having 1 to 60 carbon atoms; ,
Methyl, ethyl, propyl, iso-butyl, t-butyl, 2-ethylhexyl, nonyl, undecyl, pentadecyl, n-hexadecyl, hydroxymethyl, hydroxyethyl), aryl group (1-30 carbon atoms such as phenyl, naphthyl, p -Methoxyphenyl), an acylamino group (2 to 60 carbon atoms, for example, acetylamino, n
-Butanoylamino, octanoylamino, 2-hexadecanoylamino, 2- (2 ', 4'-di-t-amylphenoxy) butanoylamino, benzoylamino, nicotinoylamino), an alkoxy group (having 1 carbon atom) ~ 60.
For example, methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, 2-methoxyethoxy), an aryloxy group (having 6 to 60 carbon atoms, for example, phenoxy, 2,4-t-amylphenoxy, 4-t-) Butylphenoxy, naphthoxy), alkylthio group (1 to 60 carbon atoms, for example, methylthio, ethylthio, butylthio, hexadecylthio), arylthio group (6 carbon atoms)
~ 60. For example, phenylthio, 4-dodecyloxyphenylthio), an acyl group (1 to 60 carbon atoms, for example, acetyl, benzoyl, butanoyl, dodecanoyl), a sulfonyl group (1 to 60 carbon atoms, for example, methanesulfonyl, butanesulfonyl, toluene) Sulfonyl), sulfonylamino group (1 to 60 carbon atoms; methanesulfonylamino, phenylsulfonylamino), cyano group, carbamoyl group (1 to 60 carbon atoms, for example, N, N-dicyclohexylcarbamoyl) or sulfamoyl group (carbon Number 0
~ 60. For example, N, N-dimethylsulfamoyl),
Sulfo group (including its salt), carboxyl group (including its salt), halogen atom (for example, chlorine, bromine, fluorine),
Examples include an amino group, an alkoxycarbonyl group (for example, ethoxycarbonyl), a heterocyclic group (for example, 2-pyridyl), and a hydroxyl group.

These substituents may be further substituted with these substituents, and if possible, these substituents may be linked to each other to form a ring.

Examples of the substituent of R ⁵ include the substituents represented by R ^{1 to} R ⁴ , wherein n represents an integer of 0 to 5,
When n is 2 or more, two or more R ⁵ may be the same or different.

R ^{1 to} R ⁴ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a methyl group or a hydroxymethyl group as the alkyl group, and further preferably a phenyl group as the aryl group.

As R ⁵ , a hydrogen atom, a halogen atom (eg, chlorine and bromine), an alkyl group (having 1 to 1 carbon atoms)
An alkyl group of 0, such as methyl, ethyl, t-butyl,
2-ethylhexyl) or an alkoxy group (alkoxy group having 1 to 10 carbon atoms, for example, methoxy, iso-propoxy, 2-ethylhexyloxy) is preferable.

N is preferably 0 or 1. Hereinafter, specific examples of the 1-phenyl-3-pyrazolidone derivative that can be used in the present invention will be described.

[0023]

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[0024]

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The 5-pyrazolone derivatives used in the present invention include compounds represented by the general formula (II).

[0026]

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In the formula (II), R ^{1 to} R ³ are each a hydrogen atom or a substituent similar to R ^{1 to} R ^{3 in the} formula (I), and R ⁶ is a substituted or unsubstituted phenyl group. Or an alkyl group. When R ⁶ is a substituted phenyl group or alkyl group, examples of the substituent are the same as R ^{1 to} R ³ .

R ⁶ is preferably a substituted or unsubstituted phenyl group, and R ^{1 to} R ³ are preferably an alkyl group (particularly a methyl group or an ethyl group), a substituted or unsubstituted phenyl group, and a hydrogen atom.

Specific examples of the 5-pyrazolone derivative which can be used in the present invention are shown below, but the invention is not limited thereto.

[0030]

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[0031]

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In the present invention, by using a 5-pyrazolone derivative in combination with a 1-phenyl-3-pyrazolidone derivative, it is possible to suppress dusting generated during image storage and suppress an increase in haze. The amount of the 1-phenyl-3-pyrazolidone derivative used in the photosensitive material is as follows:
The molar ratio with respect to silver halide is 0.1 to 1.0, preferably 0.3 to 0.6. Furthermore, 5-
The amount of the pyrazolone derivative used in the photosensitive material is from 0.02 to 0.5, preferably from 0.05 to 0.3, in a molar ratio to the 1-phenyl-3-pyrazolidone derivative.

In the present invention, the reducing agent is 1-phenyl-
The 3-pyrazolidone derivative alone (including a plurality of combinations) may be used, or the following compounds known in the field of photosensitive materials may be used in combination. Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. Examples of the reducing agent used in the present invention include US Pat.
Columns 49-50 of 00,626, 4,839,27
No. 2, 4,330,617, 4,590,152
No. 5,017,454 and 5,139,919
No. (17)-(1) of JP-A-60-140,335.
8) pp. 57-40, 245, 56-138, 7
No. 36, 59-178, 458, 59-53, 8
Nos. 31, 59-182, 449 and 59-182,
No. 450, No. 60-119, 555, No. 60-12
No. 8,436, No. 60-128,439, No. 60-1
98,540, 60-181,742, 61-
No. 259, 253, No. 62-201, 434, No. 62
-244,044, 62-131,253, 6
2-131, 256, 63-10, 151, 6
Nos. 4-13,546, pp. (40)-(57), JP-A-1-120,553, JP-A-2-32,338, JP-A-2-132,338.
No. 35,451, No. 2-234,158, No. 3-16
0,443, EP 220,746, 78-.
There are reducing agents and reducing agent precursors described on page 96 and the like.

In the present invention, a reducing agent together with a 1-phenyl-3-pyrazolidone derivative is disclosed in Japanese Patent Application No. 7-279.
By using the dihydroxybenzene derivative described in No. 210 in combination, a high-contrast, high-density, low-fogging image can be obtained, which is preferable as a photosensitive material for plate making. Of the dihydroxybenzene derivatives, catechol derivatives are particularly preferred. In this case, the amount of the dihydroxybenzene derivative to be used is from 0.02 to 1.0 in terms of a molar ratio to the 1-phenyl-3-pyrazolidone derivative, preferably from 0.05 to 1.0.
Or 0.4.

The 1-phenyl-3-pyrazolidone derivative, the above-mentioned reducing agent and the 5-pyrazolone derivative are added to any constituent layers such as a photosensitive layer (emulsion layer), an antihalation layer, an intermediate layer and a protective layer of the photosensitive material. can do. Moreover, you may divide and add to several layers. The 1-phenyl-3-pyrazolidone derivative and the reducing agent having high solubility in water are preferably added to a layer different from the silver halide emulsion layer from the viewpoint of production stability.

The addition of the 1-phenyl-3-pyrazolidone derivative and the above-mentioned reducing agent and 5-pyrazolone derivative may be carried out in a state of being dissolved in an organic solvent such as methanol, ethanol or DMF, or in a state of a known emulsified dispersion (for example, And the method described in U.S. Pat. No. 2,322,027), and further dispersed in solid fine particles (for example, JP-A-62-302).
No. 42 etc.).

As the base or base precursor used in the present invention, various known compounds can be mentioned. Preferred bases are hydroxides, carbonates, bicarbonates, borates, phosphates, carboxylates of alkali metals such as sodium and potassium; hydroxylation of quaternary alkyl ammoniums such as tetramethylammonium and tetraethylammonium , Carbonate, bicarbonate, borate, phosphate, carboxylate, etc .; amidines, cyclic amidines, guanidines, cyclic guanidines, aliphatic amines, aromatic amines, heterocyclic amines, etc. And their carbonates, bicarbonates, borates, phosphates, carboxylate and the like. These bases can be added to the treated sheet at 0.05-
It is desirable to use 5 g / m ² or 1 to 100 g / l in treated water.

As the base precursor, a compound which decomposes or reacts under heat or alkali conditions to generate a base (for example, a compound described in JP-A-62-65038 or US Pat. No. 4,511,493) is also available. Can be used,
Particularly preferred are JP-A-62-129848, EP-A-210,660A2, and U.S. Pat.
No. 445 and the like, and a combination of a basic metal compound which is hardly soluble in water and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound or a complexing agent).

Preferred poorly soluble metal compounds are zinc or aluminum oxides, hydroxides and basic carbonates, and particularly preferred are zinc oxide, zinc hydroxide and basic zinc carbonate.

The metal compound which is hardly soluble in water is disclosed in JP-A-59-1.
It is preferable that fine particles are dispersed and used in a hydrophilic binder as described in No. 74830 or the like and contained in a photosensitive material. The average particle size of the fine particles is 0.001 to 5 μm, preferably 0.01 to 2 μm. The content in the light-sensitive material is 0.01 to 5 g / m ² , preferably 0.1 to 5 g / m ² .
05 to ² g / m ² .

The complex forming compound for the metal ion of the basic metal compound which is hardly soluble in water is preferably contained in the treated sheet. Complexing compounds are known as chelating agents in analytical chemistry and water softeners in photographic chemistry. The details thereof are described in A.I. Ringbomb, Translated by Nobuyuki Tanaka and Haruko Sugi “Complexation Reaction” (Sangyo Tosho)
It is also described in 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. Specific examples of preferred complex forming compounds are described in JP-A-62-129848.
And European Patent Publication No. 210,660A2. The content of the complex forming compound in the treated sheet is 0.0
1 to 10 g / m ² , preferably 0.05 to 5 g / m ²
a m ^2.

In the present invention, the processing sheet contains a physical development nucleus. The physical development nucleus converts the soluble silver salt diffused from the light-sensitive material into physical development silver and fixes it on the processing sheet. Things. As physical development nuclei, zinc,
Heavy metals such as mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt and copper, or precious metals such as palladium, platinum, silver and gold, or colloidal particles of chalcogen compounds such as sulfur, selenium and tellurium Any known physical development nuclei can be used. These physical development nuclei substances reduce the corresponding metal ions with a reducing agent such as ascorbic acid or sodium borohydride to form a metal colloidal dispersion or a soluble sulfide, selenide or telluride solution. Mix,
Obtained by making 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.

These physical development nuclei are usually added to the processing sheet in an amount of 10 ^{-3 to} 100 mg / m ² , preferably 10 ^-2 to 40.
mg / m ² . Physical development nuclei can be separately prepared and added to a coating solution, but in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or gold chloride and a reducing agent are reacted. May be created.

As physical development nuclei, silver, silver sulfide, palladium sulfide and the like are preferably used. When the physically developed silver transferred to the processing sheet is used as an image, palladium sulfide, silver sulfide, and the like are preferably used because Dmin is cut off. The physical development nuclei are preferably contained in the outermost layer of the processing sheet (the layer in contact with the emulsion surface of the light-sensitive material).

Known silver halide solvents can be used for the processing sheet of the present invention. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sulfites such as sodium sulfite;
Organic thioether compounds such as 1,8-dihydroxy-3,6-dithiaoctane, 2,2-thiodiethanol, 6,9-dioxa-3,12-dithiatetradecane-1,14-diol described in JP-A-1386; Hei 6-325
No. 350, compounds having a 5- or 6-membered imide ring, such as uracil and hydantoin, Analytica Chemica Acta, 248 vol.
Meso-ion thiolate compounds such as trimethyl thiolate described on page 614 and compounds of the following general formula described in JP-A-53-144319 can be used.

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 group or an amino group.
R ³ represents an aliphatic group or an aryl group. R ¹ and R ²
Alternatively, R ² and R ³ may combine with each other to form a 5- or 6-membered heterocyclic ring.

In the present invention, among the above compounds, compounds having a 5- or 6-membered imide ring such as uracil and hydantoin are particularly preferred.

The content of the silver halide solvent in the processed sheet is 0.01 to 5 g / m ² , preferably 0.05 to 5 g / m ^2.
2.5 g / m ² . The molar ratio is 1/20 to 20 times, preferably 1/10, with respect to the amount of silver applied to the light-sensitive material.
It is 10 times. The silver halide solvent may be dissolved in a solvent such as water, methanol, ethanol, acetone or DMF or an aqueous alkali solution such as sodium hydroxide or potassium hydroxide and added to the coating solution, or dispersed in solid fine particles. It may be added to the coating solution.

In the present invention, Japanese Patent Application No. Hei 6-32535
The density of the silver image on the photosensitive material can be increased by incorporating a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone described in No. 0 as a constituent component in the processing sheet.

The light-sensitive material used in the present invention is basically composed of a light-sensitive silver halide, a hydrophilic binder,
It has a phenyl-3-pyrazolidone derivative and a 5-pyrazolone derivative, and may further contain other reducing agents, organic metal salt oxidizing agents, dye-donating compounds, and the like, if necessary. These components can be added to the same layer or can be added separately to different layers. The silver halide emulsion light-sensitive layer may be divided into two or more layers as necessary.

In the light-sensitive material, various non-light-sensitive layers 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 on the uppermost layer and the lowermost layer. Various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, an undercoat layer as described in U.S. Pat. No. 5,051,335, JP-A-1-120,553 and JP-A-5-34,8.
Nos. 84 and 2-64,634, and reducing agents such as
Interlayer with IR compound, US Pat. No. 5,017,4
No. 54, 5-139, 919, JP-A-2-235,
An intermediate layer having an electron transfer agent as described in JP-A-044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer obtained by combining them can be provided. The back layer is preferably designed to have an antistatic function and to have a surface resistivity of 10 ¹² Ω · cm or less.

In the present invention, the photosensitive silver halide is
Various materials such as silver chloride, silver bromide, silver iodochloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide can be used, and preferably, silver chloride having a silver chloride content of 80 mol% or more, Silver iodochloride, silver chlorobromide, and silver iodochlorobromide. More preferably, the silver chloride content is 90 mol% or more. The silver iodide content is preferably 2 mol% or less, more preferably 1 mol% or less, and furthermore,
0.5 mol% or less.

The silver halide used in the present invention may be a surface latent image type or an internal latent image type. 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.

In particular, in the high silver chloride emulsion used in the present invention, as described above, the silver bromide localized phase has a layered or non-layered structure having silver halide inside and / or on the surface. Things can also 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 Arlberg, S.J.Marino
(CRBerry, SJMarino) Photographic Science and Technology
ce and Technology, Vol. 2, p. 149 (1955) and Vol. 4, p. 22 (1957), describe methods of applying X-ray diffraction 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 shapes of silver halide grains include 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. Non-parallel multiple twins containing two or more crystal planes, spheres, potatoes, high aspect ratio flat plates, and composites thereof can be used according to the purpose. Regarding the shape of twin grains, see Photographic Society of Japan, Basics of the Photographic Industry-Silver Halide Photo Edition (Corona), Chapter 16
It is described on page 3.

In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, or (11)
Dodecahedral particles composed of the 0) plane can be used. 1
The dihedral particles are described in JP-B-55-42737 and JP-A-60-222842. Further, it is reported in Journal of Imaging Science, Vol. 30, p. 247 (1986). (Hl1) plane, (hh
1) plane, (hk0) plane, and (hk1) plane 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, polyhedral particles such as 38-hedron, rhombohedral 24-hedron, 46-hedron, and 68-hedron 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 comprising (111) planes are described in U.S. Pat. Nos. 4,399,215 and 4,400,463;
No. 5,217,858 and JP-A-2-32, and tabular grains of high silver chloride emulsion grains having a (100) plane are described in U.S. Pat. Nos. 4,946,772 and 5,275,930.
No. 5264337, Japanese Patent Application No. 4-214109,
Japanese Patent Application No. 5-96250, European Patent 0534395A1
No. etc. Such tabular grains having a high aspect ratio have a larger surface area than normal crystals having the same volume, so that the amount of sensitizing dye adsorbed 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 the 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, and particularly preferably 0.1 to 0.9 μm. The grain size distribution is, for example, ± 30% of the average grain size in terms of the number or weight of grains of the silver halide emulsion.
A monodisperse emulsion having a grain size distribution such that 80% or more of all grains fall within the range may be used, or a polydisperse emulsion having a wide grain size distribution may be used. Preferably,
Monodisperse emulsions are used.

Further, JP-A-1-167743 and JP-A-4-167743.
As described in Japanese Patent No. 223463, 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 addition, two different heavy metal contents described later are used.
At least one kind of monodispersed silver halide emulsion may be used in combination,
Two or more monodispersed silver halide emulsions having different chemical ripening may be used in combination.

In the process of preparing the silver halide emulsion in the present invention, it is preferable to carry out a desalting step for removing excess salts. A Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, 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. Pat. No. 4,758,505, JP-A-62-111137, and JP-B-59-43727.
Or an ultrafiltration apparatus disclosed in U.S. Pat. No. 4,334,012, or a natural sedimentation method or a centrifugal separation method. Usually, the sedimentation method is preferably used.

The preparation method of the silver halide emulsion is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P.Gl.
afkides, Chemie et Physique Photographique, Paul M
ontel, 1967), Duffin's "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Che)
mistry (Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VLZelikm)
an et al., Making and Coating Photographic Emulsio
n, Focal Press, 1964).

The preparation method may be any of an acidic method, a neutral method and an ammonia method. 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. A method of forming grains in a state where silver ions are excessive (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 can be obtained.

In the preparation of a 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.
ce and Engineering), Vol. 6, pp. 159-165 (19
62); Journal of Photographic Science, Vol. 12,
242-251 (1964), U.S. Pat.
No. 4 and British Patent 1413748.

By using a silver halide solvent during the formation of silver halide grains, a silver halide emulsion having a higher monodispersity can be produced. Examples of silver halide solvents include thiocyanates (U.S. Pat. No. 2,222,264).
No. 2,448,534 and No. 332,069), thioether compounds (US Pat.
Nos. 7, 3574628, 3704130, 4297439, and 4276347, and thione compounds (described in JP-A-53-144319, JP-A-53-82408, and JP-A-55-77737). ) And imidazole compounds (JP-A-54-100)
717), benzimidazole (JP-B-60-5)
No. 4662), and an amine compound (JP-A-54-10).
0717). Ammonia can be used in combination with a silver halide solvent within a range that does not cause adverse effects. Nitrogen-containing compounds described in JP-B-46-7781, JP-A-60-222842, JP-A-60-122935 and the like can be added to the silver halide grain formation stage. Details of specific examples of the silver halide solvent are described in JP-A-62-215272.
It is described on pages 2 to 18.

In the course of silver halide grain formation or physical ripening, a metal salt (including a complex salt) may be allowed to coexist. Examples of metal salts include salts or complex salts of noble metals or heavy metals such as iridium, rhodium, ruthenium, chromium, cadmium, zinc, lead, thallium, platinum, palladium, osmium, rhenium and the like. Among these, salts or complex salts of iridium, rhodium, ruthenium, and chromium are preferable. These compounds may be used alone or in combination of two or more. The addition amount is 10 ^-9 to 10 per mol of silver halide.
^{About -3} mol, particularly preferably 10 ^{-9 to} 5 × 10 ^-6 mol. As a complex ion and a coordination compound, a bromine ion, a chloride ion, a cyanide ion, a nitrosyl ion, a thionitrosyl ion, water, ammonia and the like and a combination thereof are preferably used. For example, yellow blood salt, K ₂
IrCl ₆ , K ₃ IrCl ₆ , (NH ₄ ) ₂ RhCl ₅ (H ₂ O), K ₂ RuCl ₅ (NO),
K ₃ Cr (CN) _{6 and the} like are preferably used. Further, the position to be incorporated into the silver halide grain may be uniform within the grain, or may be a localized position such as the surface or inside of the grain, a silver bromide localized phase, or a high silver chloride grain substrate. 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 high-intensity light exposure, metal complex salts such as iridium and yellow blood salt in which cyanide is used as a ligand, lead chloride, cadmium chloride, and zinc chloride can be preferably used. In the case of spectral sensitization as in the present invention, it is preferable to use a metal complex salt in which cyanide such as yellow blood salt is used as a ligand, lead chloride, cadmium chloride, or zinc chloride. An iridium salt, a rhodium salt, a ruthenium salt, and a chromium salt are preferably used for the purpose of increasing contrast.

During the formation of silver halide grains, the addition rate, amount or concentration of a silver salt solution (eg, an aqueous AgNO ₃ solution) and a halogen compound solution (eg, an aqueous KBr solution) are increased to increase the grain formation speed. Is also good. As described above, a method for rapidly forming silver halide grains is as follows.
UK Patent 1335925, US Patent 3672900
Nos. 3,650,575 and 4,424,445, JP-A-55-142329, and JP-A-55-15812.
No. 4, No. 58-113927, No. 58-113988
And Nos. 58-111934 and 58-111936.

During or after grain formation, the surface of the silver halide grains may be substituted with halogen which forms hardly soluble silver halide grains (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" 4th edition 9
It is described on pages 7 to 98 and the like. 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.

Although the silver halide emulsion of the present invention can be used without chemical sensitization, it is usually used after chemical sensitization. The chemical sensitization method used in the present invention includes a sulfur sensitization method,
Chalcogen sensitization methods such as selenium sensitization and tellurium sensitization,
Noble metal sensitization and reduction sensitization using gold, platinum, palladium or the like can be used alone or in combination (for example, JP-A-3-110555, Japanese Patent Application No. 4-75).
798). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25331).
No. 59). Further, an antifoggant described below can be added after the completion of chemical sensitization. Specifically, Japanese Patent Laid-Open No. 5-4
No. 5833 and JP-A-62-40446 can be used.

As the sulfur sensitizer, an unstable sulfur compound is used. Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.) A known sulfur compound 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 selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.) ), Selenoketones, selenoamides, aliphatic isoselenocyanates (eg, allyl isoselenocyanate), selenocarboxylic acids and esters, selenophosphates, diethyl selenides, diethyl diselenides, 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 above-described chalcogen sensitization, sensitization with a noble metal can also 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 amount of the gold sensitizer to be added varies depending on various conditions, but the standard is 10 ^-10 to 1 mol per mol of silver halide.
Preferably it is used in the range of 10 ^-1 mol. 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 subjected to sulfur sensitization, selenium sensitization, tellurium sensitization or gold sensitization in the present invention are not particularly limited, but pAg is in the range of 5 to 11 and pH is in the range of 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. As the reduction sensitizer used in the present invention, ascorbic acid, stannous salts, amines and polyamines,
Hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. In the present invention,
One of these known compounds can be selected and used,
Two or more compounds can be used in combination. As the reduction sensitizer, silver chloride, thiourea dioxide, dimethylamine borane, L-ascorbic acid, and aminoiminomethanesulfinic acid are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-9 to 10 ^-2 mol per mol of silver halide.

In addition to the above-described method of adding a reduction sensitizer, a method of growing or ripening in a low pAg atmosphere of pAg 1 to 7 called silver ripening, and a high pH atmosphere of pH 8 to 11 called high pH ripening. And a method of passing through hydrogen gas or a method of reducing and sensitizing by hydrogen generated during electrolysis. Further, two or more methods can be used in combination.

This reduction sensitization can be used alone or in combination with the above-described chalcogen sensitization or noble metal sensitization.

In the present invention, the amount of silver halide emulsion used in the light-sensitive material is 0.5 to 2.0 as silver.
Preferably 5 g / m ^2, particularly preferably used 0.8 to 2.0 g / m ^2.

As the protective colloid used in preparing the emulsion, gelatin is preferably used, but other hydrophilic binders can also be used. The hydrophilic binder can be used alone or in combination with gelatin. Examples of the hydrophilic binder include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose and cellulose sulfates,
Mono- or copolymers such as sodium alginate, starch derivatives, polysaccharides, carrageenan, polyvinyl alcohol and modified alkyl polyvinyl alcohol and polyvinyl-N-pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Such synthetic hydrophilic polymers, US Patent No. 36
The thioether polymer described in No. 15624 can also be preferably used.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin, gelatin derivatives such as demineralized 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 enzymatic hydrolyzate of gelatin can also be used.

The photosensitive silver halide emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. 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.

In addition to the sensitizing dye, the emulsion may contain a dye having no spectral sensitizing effect or a compound which does not substantially absorb visible light, or a compound which exhibits supersensitization.

The dye may be added to the emulsion at any stage during the preparation of the emulsion. Most commonly, it is performed after completion of chemical sensitization and before coating, but is added at the same time as the chemical sensitizer as described in US Pat. Nos. 3,628,969 and 4,225,666. Japanese Patent Application Laid-Open No. Sho 5 (1993) discloses that spectral sensitization is performed simultaneously with chemical sensitization.
As described in JP-A-8-113928 and JP-A-4-63337, it can be carried out prior to chemical sensitization. Further, it can be added before the completion of precipitation of silver halide grains to start spectral sensitization. Furthermore, as taught in US Pat. No. 4,225,666,
These compounds are added separately, that is,
Some of these compounds can be added prior to chemical sensitization, and the remainder can be added after chemical sensitization, including the methods taught in U.S. Pat. No. 4,183,756. It can be at any time during particle formation.

To enhance the adsorption of the sensitizing dye, a soluble Ca compound and a soluble B compound were added before, during 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 and 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 of the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure 17
6 volumes, item 17643 (RD-17643), 1
87, Item 18716 (RD-18716) and 307, Item 307105, etc. can be referred to.

The additives used in such a step and the various additives described in RD-17643, RD-18716 and RD-307105 are known additives for photographic iodine which can be used in the light-sensitive material and the processing sheet of the present invention. The locations are listed below. Additive type RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 right column 866 page 2 Sensitivity enhancer Same as above 3 Spectral sensitizer 23-23 24 page 648 right column 866-868 Super sensitizer page 649 Right column 4 Brightener page 24 page 648 right column to page 868 5 Antifoggant 24 to 25 page 649 right column to 868 to 870 and stabilizer 6 Light absorber, f 25 to 26 page 649 right column Page 873 Filter dye 650 Left column UV absorber 7 Stain inhibitor 25 Page Right column 650 Page Left-Right column 8 Dye image stabilizer Page 25 650 Page Left column 872 9 Hardener 26 Page 651 Left column 874- 875 p. 10 Binder 26 p. Pp. 873-874 11 Plasticizers and lubricants p. 27 650 p. Right column 876 p. 12 Coating aid, interface 26-27 p. Page 76 Activator 13 Static page 27 Same as above pages 876 to 877 Inhibitor 14 matting agent pages 878 to 879

Further, the following compounds and the like can be used. Item 1) Silver halide emulsion and page 12, lower right column, line 12 in JP-A-2-97937, page 14 and lower left column, line 14 in JP-A-2-97937, and from JP-A-2-2236. From page 19, upper right column, line 19 to page 8, lower left column, line 12, Japanese Patent Application No. 3-116573 and Japanese Patent Application No. 3-189532. 2) Spectral sensitizing dyes 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, Page 13, lower right column, line 5, JP-A-2-12236, page 8 lower left column, line 13 to lower right column, line 4; JP-A-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20; and further, spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and Japanese Patent Application No. 3-189532.2. 3) Surfactant and antistatic From page 7, upper right column, line 7 of JP-A-2-12236 or from the lower right column, line 7 in JP-A-2-18542 and page 13, lower left column, line 13 of JP-A-2-18542. Page 4, lower right column, line 18. 4) Antifoggant / stable JP-A-2-103536, page 17, lower right column, line 19 to line 18, page 18, upper right column, line 4 and lower right column, lines 1 to 5, and Thiosulfinic acid compounds described in JP-A-237538. 5) Polymer latex: JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound 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-2-55349, page 8, lower right column, line 13 From the eye, page 11, line 8 in the upper left column. 7) Polyhydroxyl JP-A-2-55349, page 11, upper left column, line 9, benzenes to lower right column, line 17, same. 8) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, 15 plasticizer line to page 19, upper right column, line 15 line. 9) Hardener JP-A-2-103536, page 18, upper right column, 5th line to 17th line. 10) Dyes JP-A-2-103536, page 17, upper right column, lines 1 to 18; JP-A-2-39042, page 4, upper right column, lines 1 to page 6, upper right column, line 5; 11) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 12) Black potting inhibitor A compound described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 13) Redox compound The compound represented by the general formula (I) of JP-A-2-301743 (especially, compound examples 1 to 50), and the general formula (3) of JP-A-3-174143, pages 3 to 20: R-1), (R-2), (R-3), Compounds 1 to 75, and compounds described in JP-A-5-257239 and JP-A-4-278939. 14) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 15) Hydrazine compounds JP-A-2-12236, page 2, upper right column, line 19 to page 7, upper right column, line 3; JP-A-3-174143, page 20, lower right column, line 1, line 1 General formula (II) and compound examples II-1 or II-54 on page 27, right upper column, line 20. 16) Nucleation accelerator 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 examples II- 1 to II-22, compounds described in JP-A-1-179939.

Among the above additives, azoles (for example, benzothiazolium salt,
Nitroimidazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles,
Mercapto compounds {eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole and derivatives thereof), mercapto Pyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg, triazaindenes, tetraazaindenes}, especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene, pentaazaindene, etc .; benzenethiosulfones, benzenesulfinic acid, benzenesulfonamide, and the like can be preferably used.

As the binder for the constituent layers of the photosensitive material and the processing sheet, hydrophilic binders are preferably used. Examples thereof include those described in the above-mentioned Research Disclosure and JP-A-64-13546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, for example, gelatin, a protein or a cellulose derivative such as a gelatin derivative, agar, starch, acacia, dextran, pullulan, furceleran, carrageenan described in European Patent Publication No. 443529, Polysaccharides such as locust bean gum, xanthan gum and pectin; natural compounds such as polysaccharides described in JP-A-1-221736; polyvinyl alcohol;
Synthetic polymer compounds such as modified alkyl polyvinyl alcohol, polyvinyl pyrrolidone, and acrylamide polymer described in 339155. U.S. Pat.
No. 960,681, JP-A-62-245260, etc., ie, the superabsorbent polymer, ie, -COOM or-.
Homopolymers of vinyl monomers having SO ₃ M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers or other vinyl monomers (eg, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Co., Ltd. Sumikagel L-5H), which is also available from These binders can be used in combination of two or more kinds. 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.

In the case where a system for performing thermal development by supplying a small amount of water is used, the use of the above superabsorbent polymer makes it possible to rapidly absorb water.

When the content of gelatin is low, hydrophilic polymers other than gelatin may be used in the form of carrageenan described in EP-A-443529 or Japanese Patent Application No. Hei.
Modified alkyl polyvinyl alcohol described in 339155 and polysaccharides described in JP-A-6-67330 are preferably used.

[0092] The coating amount of total binder in the light-sensitive material and the processing ^{sheet, 12g / m 2 ~0.5g / m} 2 are preferred, especially 5
g / m ² or less, more preferably 3 g / m ² or less.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include 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-mentioned organic silver salts can be used as photosensitive silver halide 1
0.01 to 10 mol, preferably 0.01 to 10 mol
１1 mol can be used in combination. The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is 0.05 to 10 in terms of silver.
g / m ^2, and preferably it is 0.4~5g / m ² suitably.

Dyes which can be used in the yellow filter layer and the antihalation layer are preferably those which do not contribute to the density after processing by decoloring at the time of development or transferring to a processing sheet. The fact that the dye of the yellow filter layer and the antihalation layer is erased or removed at the time of development means that the amount of the dye remaining after the processing is ３ or less, preferably 1/10 or less immediately before coating, The dye component may be transferred from the light-sensitive material to the processing sheet during development, or may be converted to a colorless compound by reacting during development.

As the dye that can be used in the light-sensitive material of the present invention, for example, a solid-dispersed dye as described in Japanese Patent Application No. 6-259805 can be used. This dye becomes soluble during heat development and is transferred and removed to the processing sheet. Further, as described in Japanese Patent Application No. 7-293765, a mordant and a binder may be mordanted with a dye. In this case, at the time of heat development, the dye is demorded and the dye is transferred and removed to the processing sheet. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the movable dye can be released with an alkali at the time of development, and transferred to and removed from a processing sheet. Specifically, US Patent No. 4,559,2
No. 90, 4,783, 396, European Patent No. 220,
746A2 and JP-A-87-6119, and paragraph No. 0080 of Japanese Patent Application No. 6-259805.
To 0081.

A decolorizable leuco dye or the like can be used. Specifically, a color is developed in advance with a developer of a metal salt of an organic acid as disclosed in JP-A-1-150,132 and Japanese Patent Application No. 7-204024. A silver halide light-sensitive material containing a leuco dye has been disclosed. Known leuco dyes can be used. Moriga, Yoshida, “Dyes and Chemicals”, page 9, page 84 (Chemical Products Industry Association), “New Edition Dye Handbook”, page 242 (Maruzen, 1970), R. Garner “Reports on the Progress
of Appl. Chem ", 56, 199 (1971)," Dyes and Chemicals ", 19, 230 (Chemical Products Association, 197).
4), “Coloring Materials” 62, 288 (1989), and “Dye Industry” 32, 208. As the developer, a metal salt of an organic acid is preferably used in addition to the acid clay-based developer and phenol formaldehyde resin. As metal salts of organic acids, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodan salts,
Metal salts of xanthates are useful, and zinc is particularly preferred as the metal. Of the above developers, oil-soluble zinc salicylate is disclosed in U.S. Pat.
No. 146, 4,046,941 and Japanese Patent Publication No. 52-1327 can be used.

In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used.
Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In the present invention, the image forming substance is mainly developed silver in the photosensitive material. If necessary, a dye (dye donating compound) can be used in combination. As an example, PS
The plate is 300nm so that it can be handled in an ultraviolet-cut light room
It has spectral sensitivity in the wavelength range between
The photosensitive material for printing plate making as an original printed on the S plate only needs to have a disc crimination in this wavelength region, and a dye (dye donating compound) having absorption in this wavelength region together with the silver image. Can be an 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.

Examples of the dye-donating compounds usable in the present invention include compounds (couplers) which form a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a polymer coupler in which a diffusion-resistant group forms a polymer chain is also preferable. Specific examples of color developing agents and couplers are described in U.S. Pat. No. 3,531,286, which includes a paraphenylenediamine-based reducing agent and a phenolic or active methylene coupler, U.S. Pat. No. 3,761,270, a para-aminophenol-based reducing agent, Belgian Patent 802519 and Research Disclosure. On September 31, 1975, p. 32, a sulfonamidophenol-based reducing agent is disclosed in US Pat.
No. 1240, a sulfonamide phenol-based reducing agent and 4
Combinations with equivalent couplers have been proposed. Other examples of color developers and couplers are available from TH Jame
s "The Theory of the Photographic Process" 4
It is also described in editions 291-334 and 354-361.

Examples of other dye-donating compounds include heterocycles 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. A diffusion-resistant dye-donating compound (thiazolidine-based compound) having a heterocyclic ring, which causes a cleavage reaction of the compound to release a mobile dye, can also be used. Further, as another example of the dye-donating compound, a compound having a function of releasing or diffusing a diffusible dye imagewise can be mentioned. This type of compound can be represented by the following general formula [LI].

[(Dye) mY] nZ [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z May cause a difference in the diffusivity of the compound represented by [(Dye) m-Y] n-Z, corresponding to a photosensitive silver salt having a latent image in an image form, or (Dye) m-Y (Dye) m-Y and [(n represents a group having a property to cause a difference in diffusibility between (n-Z), m represents an integer of 1 to 5, and n represents an integer of 1 to 5. 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] include the following.

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972, and JP-B-3-68. No. 3,387, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted 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, EP 220,746 A2, US Pat. No. 4,783,
No. 396, published technical report 87-6, 199, Japanese Unexamined Patent Publication No. 64-1
As described in US Pat. No. 3,546 or the like, 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 are U.S. Pat. Nos. 4,139,389 and 4,139,379,
JP-A-59-185333, 57-84,453
No. 4,232,107, compounds disclosed in US Pat. No. 4,232,107, and JP-A-59-101,649.
No. 61-88,257, RD24, 025 (19
1984) and the like, which release a diffusible dye by electron transfer reaction in the molecule after reduction, West German Patent No. 3,008,588A, JP-A-56-14253.
0, U.S. Pat. Nos. 4,343,893 and 4,61
No. 9,884 and the like, compounds which release a diffusible dye by cleavage of a single bond after reduction, US Pat.
Nitro compounds which release a diffusible dye after electron acceptance, described in US Pat.
9,610 and the like, which release a diffusible dye after electron acceptance.

[0107] More preferably, European Patent No. 220,746, published technical report 87-6,199, US Patent No. 4,783,396, and JP-A-63-201,664 are preferred.
No. 53, No. 63-201, 654, No. 64-13, 5
No. 46, etc., a compound having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, a single molecule described in JP-A 1-26,842 A compound having an SO ₂ —X (X is as defined above) and an electron-withdrawing group, and a PO—X bond (X is as defined above) in one molecule described in JP-A-63-271,344. And a compound having an electron-withdrawing group, JP-A-63-271341
The compounds having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in (1). Also, JP-A-1-161,237
And a compound capable of releasing a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group described in JP-A Nos.

Of these, compounds having an NX bond and an electron-withdrawing group in one molecule are particularly preferred.

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

A hydrophobic additive such as a dye-donating compound and a nondiffusible reducing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
470, 4,536,466, 4,536,4
Nos. 67, 4,587,206 and 4,555,47
No. 6,4,599,296, JP-A-63-3064
No. 39, No. 62-8145, No. 62-30247,
A high-boiling organic solvent as described in JP-B-3-62,256 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination.

The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the hydrophobic additive used. In addition, 1 cc or less, more preferably 0.5 cc or less, especially 0.1 cc, per 1 g of the binder.
3cc or less is appropriate. In addition, Japanese Patent Publication No. 51-39,853
And a dispersion method using a polymer described in JP-A-51-59,943 or a method of adding a fine particle dispersion described in JP-A-62-30242.

In dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, Japanese Patent Application Laid-Open No. 59-157,636 (37) to (3)
8) The surfactants described as the surfactants described in Research Disclosure described above can be used. Also,
JP-A-7-056267, Japanese Patent Application No. 6-19247,
Phosphate ester type surfactants described in West German Patent No. 1932299A can also be used.

The treatment sheet can be provided with auxiliary layers such as a protective layer, a release layer, an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer, if necessary.

In the constituent layers of the photosensitive material and the processing sheet,
A high-boiling organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability between the photosensitive material and the processing sheet. Specifically, there are those described in the above-mentioned Research Disclosure and JP-A-62-245253. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd.
22-3710) are effective.

Also, JP-A-62-215953, 6
The silicone oil described in 3-46,449 is also effective.

Examples of the hardening agent used in the constituent layers of the light-sensitive material and the processing sheet include the aforementioned Research Disclosure, US Pat. No. 4,678,739, column 41 and 4, 79.
1,042, JP-A-59-116,655, 62
And hardening agents described in JP-A Nos. 245,261, 61-18,942, and JP-A-4-218,044.
More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), an N-methylol-based hardening agent (such as dimethylol urea), or a polymer hardening agent (compounds described in JP-A-62-234157).

These hardeners are used in an amount of 0.001 to 1 g, preferably 0.1 to 1 g per 1 g of the applied hydrophilic binder.
005 to 0.5 g are used. The layer to be added may be any of the constituent layers of the photosensitive material or the processing sheet,
It may be added in two or more layers.

In the constituent layers of the light-sensitive material and the processing sheet, various antifoggants or photographic stabilizers and precursors thereof can be used. As a specific example,
The Research Disclosure, US Pat.
89,378, 4,500,627, 4,61
4,702, JP-A-64-13,546 (7)-
Pages (9), (57) to (71) and (81) to (9)
7), U.S. Pat. Nos. 4,775,610 and 4,62.
Nos. 6,500 and 4,983,494;
Nos. 174,747, 62-239,148, 63
-264,747, JP-A-1-150,135, 2-110,557, 2-178,650, RD
17, 643 (1978), pp. 24 to 25, and Japanese Patent Application No. 6-190529.
These compounds are used in an amount of 5 × 10 ⁻⁶ to 1 × 1 per mole of silver.
It is preferably 0 ^-1 mol, and more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol.

In the constituent layers of the light-sensitive material and the processing sheet, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and promoting development.
Specific examples of the surfactant are described in Research Disclosure, JP-A-62-173463, and JP-A-62-18383.
457, etc. The constituent layers of the photosensitive material and the processing sheet may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of the organic fluoro compound include JP-B-57-9053, columns 8 to 17, JP-A-61-20944, and JP-A-62-1.
Fluorinated surfactants described in 35826 and the like,
Or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin.

A matting agent can be used in the light-sensitive material and the processing sheet for the purpose of preventing adhesion, improving slipperiness, and giving a non-glossy surface. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
JP-A Nos. 63-274944 and 6
There is a compound described in 3-274952. In addition, the compounds described in the aforementioned 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 addition, the constituent layers of the light-sensitive material and the processing sheet may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3-11,338, and JP-B-2-51,496.

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the processing sheet. From the physicochemical function, the image formation accelerator has an interaction with the above-mentioned base or 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 promoting effects. For details of these, see U.S. Pat. No. 4,678,739, 38-40.
Column. By adding a high-boiling organic solvent to the processing sheet, the reduction in gloss of the processed light-sensitive material and the image of the processing sheet is remarkably improved.

In the present invention, various development terminators can be used in the photosensitive material and / or the processing sheet in order to always obtain a constant image with respect to fluctuations in processing temperature and processing time during development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. 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 further details, see JP-A-62-25
No. 3,159, pages (31) to (32).

In the present invention, it is desirable to include a mordant in the treated sheet. As the mordant, those known in the field of photography can be used. Specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59;
No.-88256, pages (32) to (41) and JP-A-1-1-1.
Mordants described in pages 61,236, pages (4) to (7); U.S. Patent Nos. 4,774,162 and 4,619,883.
And Nos. 4,594,308 and the like. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. The use of a mordant facilitates the diffusion and transfer of the reducing agent and its oxidized form, the dye released from the dye-providing substance, the AH dye, and the like in the photosensitive material to the processing sheet during thermal development, and thereby discriminates the image. Can be improved.

In the present invention, as a support of the photosensitive material or the processing sheet, a support that can withstand the processing temperature is used. Generally, The Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography", Corona Co., Ltd. (1979)
Photographic supports such as papers and synthetic polymers (films) described on pages (223) to (240). Specifically, pigments such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, polyarylate, celluloses (for example, triacetylcellulose), or pigments such as titanium oxide are contained in these films. 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.

These can be used alone,
It can also be used 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 necessary. In addition, Japanese Patent Application Laid-Open No. 62-253,159 (2)
9) to (31), JP-A-1-161,236 (1)
4) to (17), supports described in JP-A-63-316,848, JP-A-2-22,651, JP-A-3-56,955, U.S. Pat. No. 5,001,033, etc. Can be used.

The back surface of these supports may be coated with a hydrophilic binder, a metal oxide such as alumina sol, tin oxide, and antimony oxide, carbon black, and other antistatic agents. Specifically, JP-A-63-22024
No. 6, etc. can be used. Surface resistivity is 1
It is desirable to design so as to be 0 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 thickness of the support is from 20 μm
It can be arbitrarily selected within a range of 300 μm.

The light-sensitive material of the present invention can be used in a wide range of materials such as black-and-white light-sensitive materials for photography, medical light-sensitive materials (for direct radiography or for computed radiography), and printing light-sensitive materials. Applications of the photosensitive material for printing include not only a film for a scanner, but also a film for a net, a film for a line drawing, a film for a close contact (negative-positive type), a film for a close contact (reverse positive-positive type),
Alternatively, it can be used as a bright room film.

The method of exposing and recording an image on the photothermographic material of the present invention includes, for example, a method of exposing a printing original such as a reversal film using a plate making camera with a contact screen or a color separation filter, a plate making printer, or the like. Using a scanner, an image setter, a facsimile, or the like to scan and expose image information by emitting xenon lamps, color-forming diodes, various lasers (laser diodes, gas lasers, etc.) via electrical signals, etc. Kaihei 2-129625, 5-1761
Nos. 44, 5-199302 and 6-127012) can be used.

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 and the like can be used.

The following is an example of an exposure apparatus according to the present invention. Linotype-Hel, a commercial Ar laser exposure system
l series DC series, Crosfield Magnascan series, commercially available He-Ne laser exposure system Dainippon Screen SG series, and commercial laser exposure apparatus Fuji Photo Film Lux Scan, Dainippon Screen Color scanners such as MTR and Agfa
-Gevaert Selectset (He-Ne), Avantra (Re
d-LD), Herkules (Red-L) of Linotype-Hell
D), Docite (He-Ne) from Scitex, Accuset (Red-LD) from Agfa-Gevaert, Lux from Fuji Photo Film
Imagesetters such as Setter5600, NEC's 24
An exposure apparatus for facsimile such as 0R can be used.

The following are examples of plate making printers 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, IPB-1000SH from Eye Graphics, FL2M and FL3M from Ushio, SK-16 from Kuraminami, East
man-Kodak Versalite Contact Printer 840H, Cont
act 2200 Printer, Contact 2200 Printer, Agfa-Gevae
rt CDL2002Ri, Kitamura P-6, P-
4, P-2, P-8, SACK OR30, THIE
MER VDM5, CONVAC RD7087D
Can be used.

The following are examples of plate making cameras 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, Image maker of i-tech graphics company
540, Eastman-Kodak Opti-Copy 32, Opti-Copy 4
2, Opti-Copy 23, Image Maker 5060A, Image Maker IM200, Image Maker IM40
0, Image Maker IM600, Image Maker I
M800, an RPS camera from Agfa-Gevaert, a repro master series, a linears 2000, a design scope series from Izmiya, and a repro camera series from Mitsubishi Paper can be used.

The photothermographic material and / or processing sheet of the present invention may have a form having a conductive heating 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-61-14554.
No. 4, etc. can be used. In the present invention, U.S. Patent Nos. 4,704,345 and 4,740,445.
It is preferred that heating and development and transfer are carried out simultaneously or continuously in the presence of a small amount of water, as described in JP-A-61-238,056. In this method, the heating temperature is preferably from 50C to 100C.

As the water used in the present invention, any water that is generally used may be used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photosensitive material and the processing sheet of the present invention, water may be used up or may be circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. And JP-A-63-144,354 and JP-A-63-144,3.
No. 55, 62-38, 460, JP-A-3-210,
No. 555 or the like or water may be used. further,
Low-boiling solvents, surfactants, antifoggants,
A complex-forming compound with a hardly soluble metal salt, a water-soluble reducing agent, a fungicide, or a bactericide may be contained.

These solvents can be applied to the light-sensitive material, the processing sheet or both, but preferably 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. Specifically, it is ^{5 to} 30 cc, preferably 10 to 20 cc per 1 m ² . As a method of applying this water, for example,
253, 159 (5), JP-A-63-85,54.
The method described in No. 4, etc. is preferably used. Further, the solvent can be enclosed in microcapsules, or can be incorporated in the photographic material or the processing sheet or both in advance in the form of a hydrate.

The temperature of the water to be applied is determined by the method described in
The temperature may be 30 ° C. to 60 ° C. as described in US Pat. In particular, it is useful to raise the temperature to 45 ° C. or higher for the purpose of preventing the propagation of various bacteria in water.

A hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature can be incorporated in the photosensitive material and / or the processing sheet. The layer to be incorporated may be any of the photosensitive silver halide emulsion layer, the intermediate layer and the protective layer of the photosensitive material, or any of the layers of the processing sheet. Examples of hydrophilic thermal solvents include:
There are ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

As a heating method in the development and / or transfer step, a heating block, a plate, a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared and far-infrared lamp heater may be used. For example, or by passing through a high-temperature atmosphere. A method of superposing a photosensitive material and a processing sheet is described in JP-A-62-253,159,
No. 147,244 (page 27) can be applied.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
Nos. 5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, JP-A-6-130509, JP-A-6-130509
No. 95338, No. 6-95267 and the like are preferably used. As a commercially available device, there is a Pictrostat 100 manufactured by Fuji Photo Film Co., Ltd.
Pictrostat 200, Pictrostat 30
0, Pictography 3000, Pictography 2000, etc. can be used.

The speed (linear speed) at which these thermal developing devices convey a film may be low or high. If the size of the apparatus is to be reduced, the linear velocity may be, for example, 200 mm / min or less. If a large amount of film is to be processed in a short time, the linear velocity may be, for example, 1000 mm / min or more. Alternatively, a high linear velocity of 1500 mm / min or more may be used. Of course, an intermediate linear velocity may be used depending on the purpose.

[0143]

EXAMPLES The effects of the present invention will be described below in detail with reference to examples.

Example 1 A method for preparing a photosensitive silver halide emulsion (1) will be described. Solution (I) and solution (II) shown in Table 2 were simultaneously added to a well-stirred aqueous solution of gelatin having the composition shown in Table 1 over a period of 6 minutes, and 5 minutes later, a sensitizing dye ( k ₁ )
Was added to 15 ml of a methanol solution containing 150 mg of (k ₂ ) and 37.5 mg of (k ₂ ). Five minutes later, the solution (III) and the solution (IV) were simultaneously added over 10 minutes.

[0145]

[Table 1]

[0146]

[Table 2]

After washing with water and desalting (using a precipitant (d) and adjusting the pH to 3 with sulfuric acid using a conventional method), 22 g of lime-processed gelatin was added to adjust the pH to 6.1 and the pAg to 7.1. , Compound (b) was added, and the mixture was chemically sensitized at 60 ° C. The compounds used for chemical sensitization were added sequentially as shown in Table 3. The particle size is 0.22 μm on average side length,
It was a silver chloride cubic emulsion having a silver bromide content of 1.7 mol% with a standard deviation of 0.019 μm. The yield of this emulsion was 635
g.

[0148]

[Table 3]

Next, the preparation method of the silver bromide fine grain emulsion (2) used in Table 3 will be described. 4th stirring well
The gelatin aqueous solution having the composition shown in the table was cooled to 30 ° C., and the solution (I) and the solution (II) shown in Table 5 were simultaneously added over 3 minutes and 40 seconds, and 5 minutes later, the solution (III) was added. The solution (IV) was added over 2 minutes while controlling the flow rate of the solution (IV) so that the silver potential became 50 mV at the same time.

[0150]

[Table 4]

[0151]

[Table 5]

After washing with water and desalting (adjusted to pH 4.1 with phosphoric acid using a precipitant (e)) according to a conventional method, 22 g of lime-processed gelatin was added, and the pH was 6.1 and the pAg was 7.8.
Adjusted (by KBr). Compound (c) was used as a preservative. It was a silver bromide cubic emulsion having a grain size of 0.05 μm. The yield of this emulsion is 630 g.

100 g of photosensitive silver halide emulsion (1)
Then, 5 cc of a methanol solution containing 30 mg of sensitizing dye (k ₁ ) and 6 mg of (k ₂ ) was added, and after 5 minutes, 10 ml of sensitizing dye (k ₃ ) was added.
3 cc of a methanol solution containing 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidine-
0.25 cc of a 1% methanol solution of disodium 2-ylamino] stilbene-2,2'-disulfonate was added, and 0.2 g of surfactant (1) and 0.25 g of water-soluble polymer (2) were further added. Thus, a coating solution for an emulsion layer was prepared.

[0154]

Embedded image

[0155]

Embedded image

A photosensitive material 101 having the composition shown in Table 6 was prepared using these materials. In addition, 1,5-diphenyl-3-pyrazolidone, zinc hydroxide, and zinc thiosalicylate were respectively added as solid dispersions of fine particles, and the leuco dye and the developer were added as co-emulsions.

[0157]

[Table 6]

In this embodiment, a processing sheet having the structure shown in Table 7 was used.

[0159]

[Table 7]

[0160]

Embedded image

[0161]

Embedded image

As shown in Table 8, the first photosensitive material 101
Light-sensitive materials 102 to 106 were prepared by adding the 5-pyrazolone derivative of the present invention to the first to third layers.

[0163]

[Table 8]

The photosensitive materials 101 to 1 obtained as described above
No. 06 was exposed with a semiconductor laser having an exposure peak at 680 nm while changing the light quantity in 1/10000 ^second per pixel (40 μm ² ). Exposed photosensitive material is 40 ° C
Immersed in water kept warm for 2.5 seconds, squeezed with a roller,
Immediately, the treated sheet and the film surface were overlapped so that they contacted each other.
Then, using a heat drum whose temperature was adjusted so that the temperature of the film surface having absorbed water became 78 ° C., the sheet was heated for 20 seconds and the processing sheet was peeled off, whereby a black-and-white silver image (negative image) was obtained on the photosensitive material. (A positive silver image was obtained on the processed sheet.) Table 8 shows the results of measuring the maximum density Dmax and the minimum density Dmin of the transmitted image on the photosensitive material side using an automatic densitometer. Table 8 also shows the degree of dusting when the obtained image was stored at 30 ° C. and a relative humidity of 80% for 2 weeks.

Example 2 In place of 1,5-diphenyl-3-pyrazolidone (I-1) used in Example 1, (I-5) or (I-8)
When a light-sensitive material having the same constitution was prepared except that the compound was used in an equimolar amount, the combined use of a 5-pyrazolone derivative was examined in the same manner as in Example 1. As a result, the effects of lowering Dmin and improving dusting were also recognized.

[0166]

According to the black-and-white photosensitive material containing a 1-phenyl-3-pyrazolidone derivative as a developing agent, the use of a 5-pyrazolone derivative suppresses the occurrence of dusting in an image after development processing. Can be. In addition, using this photosensitive material, a base (including a base precursor)
And in the presence of water, superimpose with a processing sheet containing a silver halide solvent and a physical development nucleus, heat develop, and then peel off the processing sheet to obtain a high density and low fog image in a short time Can be.

Claims (3)

[Claims] 1. A support comprising at least one photosensitive silver halide emulsion layer on a support, wherein said emulsion layer or another hydrophilic binder layer contains a 1-phenyl-3-pyrazolidone derivative and a 5-pyrazolone derivative. A silver halide light-sensitive material, characterized in that: 2. The content of the 1-phenyl-3-pyrazolidone derivative in a molar ratio to the content of silver halide is 0.1%.
And a molar ratio of the 5-pyrazolone derivative to the 1-phenyl-3-pyrazolidone derivative is 0.02 to 0.5 with respect to the content of the 1-phenyl-3-pyrazolidone derivative. 3. The silver halide light-sensitive material according to item 1. 3. The photosensitive material according to claim 1 or 2,
After or at the same time as the imagewise exposure, in the presence of a base (including a base precursor) and water, the resultant is overlaid with a processing sheet containing a silver halide solvent and a physical development nucleus and heated and developed. A method in which an image is formed on a photosensitive material by peeling.