JPH11202458A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material superior in discriminability and raw preservation stability. SOLUTION: This photographic sensitive material contains at least one of compounds represented by formula I and II in which each of R1 -R9 is an H or halogen atom or a substituent having <=4C or an I/O value of >>=1; in formula I, R2 and/or R4 , and R5 and/or R9 are each a substituent except a halogen atom, (a substituent having <=4C or an I/O value of >=1), and in formula II, R4 and R5 and/or R9 are each an atom except an H atom (a substituent having <=4C car an IO value of >=1), and each of R1 and R2 , R3 , and R4 , R5 and R6 , R6 and R7 , R7 and R8 , and R8 and R9 may combine, independently, with each other to from a ring, in the case of each being a substituent except a hydrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material excellent in image discrimination and raw storability.

[0002]

2. Description of the Related Art A photographic method using silver halide has been used most widely since it has superior photographic characteristics such as sensitivity and gradation control as compared with other photographic methods such as electrophotography and diazo photography. I have been. In particular, since the best image quality can be obtained as a color hard copy, it has been energetically studied more recently.

[0003] In recent years, image forming processing methods for photosensitive materials using silver halide have been simplified from conventional wet processing to instant photographic systems incorporating a developing solution, and dry thermal development processing by heating or the like. Systems have been developed that can rapidly obtain images. Photothermographic materials are described in “Basics of Photographic Engineering (Non-Silver Photography), Corona”, p.242-, but the content is black-and-white image formation such as dry silver. Stays in the law.

[0004] Recently, as photothermographic color photosensitive materials, products such as Pictrography and Pictrostat have been marketed by Fuji Photo Film Co., Ltd. In the above-described simple and rapid processing method, a color image is formed using a redox coloring material to which a preformed die is connected. The most common method for forming a color image of a photographic light-sensitive material is a method utilizing a coupling reaction between a coupler and an oxidized developing agent. A heat-developable color light-sensitive material employing this method is also disclosed in U.S. Pat. No. 3,761,270. , And 4,021,240
Many ideas have been filed, for example, JP-A-59-231539 and JP-A-60-128438. In addition, JP-A-9-146247,
Japanese Patent Application Nos. 9-146248 and 9-204031 disclose color photographic light-sensitive materials for photography which are subjected to heat treatment in the presence of a small amount of water using a processing material containing a base precursor.

[0005] In the photothermographic material as described above, the processing time is long, and it takes time from exposure to output.
There were points to be improved, such as an increase in the size of the processing machine. Also,
There was still room for improvement in image discrimination. Generally, in a photothermographic material, an image forming reaction takes place with the first step of reducing a silver halide by a reducing agent (or a developing agent) incorporated in a developing process. In order to speed up this, first, a method of promoting the reaction with silver halide in the aqueous phase by making the reducing agent hydrophilic can be considered. However, if this method is used with a normal photothermographic material, the reducing agent moves between layers during processing, causing undesired reactions such as color mixing. In order to avoid this, a method of using a hydrophilic reducing agent as an auxiliary developing agent and performing electron transfer between the two in combination with a lipophilic reducing agent may be used to increase the developing speed. This idea is known in the art, and its application to a photothermographic material is described in JP-A-1-138556.

However, a reducing agent having improved hydrophilicity and improved silver developability generally has poor stability, is oxidized by oxygen in the air, and has a problem that it is reduced during raw storage. Was. In particular, a 1-phenyl-3-pyrazolidinone derivative is known in the art as an auxiliary developing agent excellent in silver developability, but this compound also did not have sufficient stability as a built-in developing agent. The inventors have searched for a compound that meets this purpose. inside that,
U.S. Pat.No. 4,021,240, JP-A-60-128438,
Sulfonamidophenols described in 8-220717 and the like were found to be compounds excellent in discrimination and raw preservability when incorporated in a photosensitive material. As a result of various studies on the performance of this sulfonamide phenol as a reducing agent, this compound is a compound having sufficient raw preservability even if it increases hydrophilicity as a built-in developing agent and improves silver developability. I understand. However, sulfonamide phenol has poor stability of the oxidized base agent after silver development, so that the oxidized base agent is hydrolyzed in the developing section, and a developed amount of developed silver is exceeded. For this reason, it turned out that there exists a problem that color turbidity arises by a silver image.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in discrimination and raw preservability.

[0008]

The object of the present invention has been attained by a silver halide photographic material comprising at least a compound represented by the following general formula (1) or (2). .

General formula (1)

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General formula (2)

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In the formula, R _{1 to} R _{9 each} represent a hydrogen atom, a halogen atom, or a carbon atom of 4 or less or I / R
O represents one or more substituents. Note that R in the general formula (1)
₂ and / or R ₄ , and R ₅ and / or R
₉ is a substituent other than a hydrogen atom (halogen atom or carbon number
And R ₄ , R ₅ and / or R ₉ in the general formula (2) are substituents other than a hydrogen atom (halogen atom or C 4 or less or I / O value represents one or more substituents). R ₁ and R _2, R ₃ and R _4, R ₅ and R _6, R ₆ and R _7, R ₇ and R
_{In the case where 8} , R ₈ and R ₉ are each a substituent other than a hydrogen atom, in the combination of each group, they may be independently bonded to form a ring.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail. First, general formulas (1) and (2)
The compound represented by is described in detail. The compounds represented by the general formulas (1) and (2) represent a reducing agent (developing agent) generally called sulfonamidophenol. In the formula, R _{1 to} R _{9 each} represent a hydrogen atom, a halogen atom, or a substituent having a carbon number of 4 or less or an I / O value of 1 or more. The I / O value is a parameter indicating a measure of lipophilicity and hydrophilicity of a compound or a substituent, and is described in detail in "Organic Conceptual Diagram" (Yoshio Koda, Sankyo Publishing, 1984). I stands for inorganic, O stands for organic, I / O
The higher the value, the higher the inorganicity. Where I / O
A specific example of the value will be described. The O value is 20 per carbon number. Typical values of I are 200 for -NHCO- group, -N
For an HSO ₂ -group, it is 240, and for a -COO- group, it is 60. For example, -N
In the case of HCOC ₅ H ₁₁ , the carbon number is 6, and the O value is 20 × 6 = 120
Becomes Since I = 200, I / O ≒ 1.67 and I / O> 1
Becomes

The compound of the present invention is a compound substituted with a substituent having an I / O value of 1 or more or a carbon number of 4 or less, and is characterized by being hydrophilic. Specific examples of the substituent include, for example, a halogen atom (for example, chloro group, bromo group), an alkyl group (for example, methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group), and an aryl group (for example, 3-methanesulfonylaminophenyl group), alkylcarboxamide group (eg, acetylamino group, propionylamino group, butyroylamino group), arylcarboxamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group) , Ethanesulfonylamino group), arylsulfonamide group (eg, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, 4-methanesulfonylaminophenoxy group), alkylthio Group ( For example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, 4-methanesulfonylaminophenylthio group), alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, Piperidinocarbamoyl group, morpholinocarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group,
Benzylphenylcarbamoyl group), carbamoyl group,
Alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidinosulfamoyl group, morpholinosulfamoyl group) , Arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group) , Ethanesulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxyca) Boniru group), an aryloxycarbonyl group (e.g. phenoxycarbonyl group), an alkylcarbonyl group (e.g. an acetyl group, a propionyl group,
Butyroyl group), an arylcarbonyl group (eg, benzoyl group, alkylbenzoyl group), or an acyloxy group (eg, acetyloxy group, propionyloxy group,
Butyroyloxy group).

In the general formula (1), R ₂ and / or R ₄ , and R ₅ and / or R ₉ represent a substituent other than a hydrogen atom (a halogen atom or a compound having 4 or less carbon atoms,
/ O value is 1 or more), and R _{4 in the} general formula (2)
And R ₅ and / or R ₉ represent a substituent other than a hydrogen atom (a halogen atom or a substituent having 4 or less carbon atoms or an I / O value of 1 or more). R ₁ and R ₂ , R ₃ and R ₄ ,
When R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈ , and R ₈ and R ₉ are each a substituent other than a hydrogen atom, in the combination of each group, they are independently bonded to form a ring May be.

The compounds represented by the general formulas (1) and (2) can be synthesized by stepwise combining methods widely known in the field of synthetic organic chemistry. The synthesis scheme of the exemplified compound described below is shown below, and an example of the stepwise synthesis method is described.

[0016]

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<< Synthesis of Exemplified Compound D-5 >> 1) Synthesis of Compound A In a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator, 766 g of 6-amino-m-cresol was added. 5mol), acetonitrile 2000ml
And stirred under room temperature conditions. At this time, the solution is a non-uniform slurry. Here, 791 g of isobutyric anhydride (5 m
ol) over 30 minutes, the temperature gradually rises and finally rises to 60 ° C. until the solution becomes homogeneous. When the temperature rise subsides, product crystals begin to precipitate in the flask. After stirring for an additional hour, the contents were reduced to 10%
The solution is poured into 15 liters of a saline solution, and the precipitated crystals are filtered under reduced pressure using a Nutsche. The crystals are further washed with 2 liters of distilled water and dried. The crystals have such a purity that they can be used as they are in the next step. Thus, 928 g of Compound A crystals were obtained (96% yield).

2) Synthesis of Compound B In a 10-liter beaker, 193 g (1 mol) of Compound A is charged, and an aqueous solution obtained by dissolving 500 ml of methanol and 120 g (3 mol) of sodium hydroxide in 500 ml of water is added. This solution is kept under 0 ° C. and stirred. On the other hand, 216 g of sulfanilic acid (1.2
5 mol) with an aqueous sodium hydroxide solution (sodium hydroxide 50
g in an aqueous solution of 400 ml of water). 300 ml of concentrated hydrochloric acid is added to make a slurry-like solution. The solution is stirred vigorously while maintaining the temperature at 0 ° C. or lower, and a solution prepared by dissolving 93 g (1.35 mol) of sodium nitrite in 200 ml of water is gradually added to form a diazonium salt. At this time, the temperature is set to 0
The reaction is carried out while appropriately adding ice so as to keep the temperature at or below ℃.
The diazonium salt thus produced is slowly added to the previously stirred solution of compound A. At this time, the reaction is also carried out while appropriately adding ice so as to keep the temperature at 0 ° C. or lower. As it is added, the solution takes on the red color of the azo dye. After completion of the addition, the reaction is further carried out at 0 ° C. or lower for 30 minutes. When the disappearance of the raw materials is confirmed, 750 g (4.5 mol) of sodium hydrosulfite is added as a powder thereto. When this solution is heated to 50 ° C., azo groups are reduced while vigorously foaming. When the bubbling stops and the liquid decolorizes and turns into a yellowish transparent liquid, the solution is gradually cooled to 10 ° C., and crystals gradually precipitate from the time cooling is started. The precipitated crystals were separated by filtration, and the crude crystals were crystallized from a mixed solvent of methanol and water to obtain 162 g of Compound B crystals (78% yield).

3) Synthesis of Compound C 833 g (4 mol) of Compound B and 2000 ml of acetonitrile are charged into a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel and a mechanical agitator, and stirred at room temperature. . At this time, the solution is a non-uniform slurry. Here, trifluoroacetic anhydride 840g (4mol)
Over 30 minutes, the temperature gradually rises. Cool in an ice bath as appropriate to raise the temperature to 45 ° C. After the addition, the solution becomes uniform. When the temperature rise subsides, product crystals begin to precipitate in the flask. After stirring for an additional hour, pour the contents into 15 liters of 10% saline,
The precipitated crystals are filtered under reduced pressure using a Nutsche. The crystals are further washed with 2 liters of distilled water and dried. The crystals have such a purity that they can be used as they are in the next step.
In this way, 1132 g of compound C crystals were obtained (yield 93).
%).

4) Synthesis of Compound D In a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel and a mechanical agitator, 913 g (3 mol) of compound C and 2500 ml of dichloromethane are charged and stirred at room temperature. . At this time, the solution is a non-uniform slurry. Here, sulfuryl chloride 540g (4mol)
Is added over 30 minutes, the temperature gradually rises, and gas is generated, and at the same time, reflux starts. After the completion of the dropwise addition, the reaction is further continued for 2 hours under reflux conditions, whereby the generation of gas stops. At this time, the solution also remains in a non-uniform state. After stirring for an additional hour, the internal temperature is lowered to room temperature, and the contents are poured into 10 liters of n-hexane. The precipitated crystals are filtered under reduced pressure using a Nutsche, further washed with 2 L of n-hexane, and dried. The crystals have such a purity that they can be used as they are in the next step. Thus, the crystal 90 of compound D
4 g was obtained (89% yield).

5) Synthesis of Compound E In a 3-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, a nitrogen inlet tube, and a mechanical agitator, 224 g of potassium hydroxide and 1200 ml of water are charged and completely dissolved. . While passing nitrogen here, 678 g of compound D
(2 mol) is added slowly as powder, and after the addition, the internal temperature is reduced to 60
Increase to ° C. At this time, the solution changes from a non-uniform slurry state to a uniform solution. After continuing stirring for 2 hours, the internal temperature is lowered to room temperature, and 200 ml of acetic acid is added thereto to precipitate crystals. The precipitated crystals are filtered under reduced pressure using a Nutsche. The crystals were further washed with cold distilled water, and then recrystallized from a mixed solvent of methanol and water to give Compound E.
(403 g) was obtained (yield 83%).

6) Synthesis of Exemplified Compound D-5 In a 5 liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator, compound E 971 g (4 mol) and acetonitrile 2800 ml were charged. And stir. At this time, the solution is a non-uniform slurry. Here, mesitylenesulfonyl chloride 87
When 5g (4mol) is added as a powder over 10 minutes, the temperature gradually rises. Cool in an ice bath as needed to raise the temperature to 30 ° C. After completion of the addition, the mixture is cooled in an ice bath so that the internal temperature becomes 15 ° C. or lower, and 324 ml (4 mol) of pyridine is added dropwise thereto over 10 minutes. After dropping, stir at room temperature
Let react for 2 hours. After some time, product crystals begin to precipitate in the flask. After completion of the reaction, the content is poured into 20 liters of 3% aqueous hydrochloric acid, and the precipitated crystals are filtered under reduced pressure using a Nutsche. After the crystals were further washed with 4 liters of distilled water, the crystals were recrystallized from a mixed solvent of acetonitrile and water to obtain 1564 g of crystals of Exemplified Compound D-5 (yield 92%).

<< Synthesis of Exemplified Compound D-9 >> 1) Synthesis of Compound F In a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator, 153 g of 4-nitro-m-cresol ( 1 mol) and 1000 ml of methanol, and the mixture is stirred at room temperature. At this time, the solution is a non-uniform slurry. To this, 2 liters of an aqueous solution of sodium hypochlorite (effective chlorine amount: 5%) is added dropwise while taking care that the internal temperature does not exceed 50 ° C. Upon addition, the color of the solution changes to reddish brown. After the completion of the dropping, 500 g (3 mol) of sodium hydrosulfite is gradually added thereto in powder form, and the nitro group is reduced while vigorously foaming. At this time, care should be taken that the internal temperature does not exceed 60 ° C and that the foaming does not become excessive. When foaming stops and the solution decolorizes and turns into a yellowish transparent liquid, slowly add this solution to 10
When cooled to ° C., crystals are gradually precipitated from the beginning of cooling. The precipitated crystals were separated by filtration, and the crude crystals were crystallized from a mixed solvent of methanol and water to give 142 g of Compound F crystals.
Was obtained (yield 74%).

2) Synthesis of Exemplified Compound D-9 In a 5-liter three-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a mechanical agitator, 768 g (4 mol) of Compound F, 1500 ml of acetonitrile, N, N-dimethyl Charge 1100 ml of acetamide (DMAc) and stir at room temperature. At this time, the solution becomes uniform. Here, 1212 g (4 mol) of triisopropylbenzenesulfonyl chloride
Is added over 10 minutes as a powder, the temperature gradually rises. Cool in an ice bath as needed to raise the temperature to 30 ° C. After completion of the addition, the mixture is cooled in an ice bath so that the internal temperature becomes 15 ° C. or lower, and 324 ml (4 mol) of pyridine is added dropwise thereto over 10 minutes. After completion of the dropwise addition, the mixture is further reacted at room temperature with stirring for 2 hours. After completion of the reaction, the content is poured into 20 liters of 3% aqueous hydrochloric acid, and the precipitated crystals are filtered under reduced pressure using a Nutsche.
After the crystals were further washed with 4 liters of distilled water, the crystals were recrystallized from a mixed solvent of methanol and water to obtain 1669 g of crystals of Exemplified Compound D-9 (yield: 91%).

Specific examples of the compounds represented by formulas (1) and (2) are listed below, but the present invention is not limited by them.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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When the compounds represented by the general formulas (1) and (2) are used in a silver halide photographic light-sensitive material, these compounds can perform rapid silver development for the purpose of the present invention. Images by reduced silver generated by the reduction reaction of these compounds alone can be used, or the difference between different types of reducing agents and oxidized compounds of the compounds represented by formulas (1) and (2) can be used. It is also possible to form an image using a cross-oxidation reaction. The reducing agents used in combination with the compounds represented by formulas (1) and (2) to form an image by performing a cross-oxidation reaction are shown below.

1) A color developing agent capable of forming a dye image in combination with a coupler. Examples of such compounds include, for example, JP-A-8-110608
No. 9-34081, sulfonamide phenol, sulfonyl hydrazine, sulfonyl hydrazone, carbamoyl hydrazine, carbamoyl hydrazone described in JP-A-8-267839, and aminoantipyrine derivatives described in JP-A-9-120132. it can. 2) DD capable of releasing a diffusible dye by coupling
R-coupler. Examples of this are, for example, U.S. Pat.
Nos. 4,474,867 and 4,483914, and the like. 3) A dye-donating compound (DRR compound) that releases a diffusible dye when oxidized. Examples of this compound include, for example, JP-A-59-65839,
Compounds described in Nos. 59-69839 and 53-3819 can be exemplified. 4) Dye-donating compound [ROSET compound (Journal of the Photographic Society of Japan 5
5, No. 3, p. 185, 1992), and a reducing agent used in combination with a BEND compound or the like (US Pat. No. 4,139,379). In this image forming method, a positive image can be formed by the reducing agent remaining without being oxidized by silver development. Examples of the dye-donating compound include, for example, JP-A-1-2684
No. 2, compounds described in JP-A-63-201653, JP-A-63-201654 and the like.

When the compounds represented by the general formulas (1) and (2) are used in a light-sensitive material, the coating amount can be selected from a wide range. In particular, the amount used differs depending on whether these compounds are used alone or in combination with other reducing agents as described above. First, when used alone, preferably 0.001 ~1000mmol / m ^2, more preferably 0.05~50mm
ol / m ² . When used in combination with other reducing agents, the reducing agent used for image formation is preferably 0.001 to 10 depending on the molar absorption coefficient of the dye to be formed.
00mmol / m ^2, more preferably from 0.05~50mmol / m ^2. On the other hand, the compounds represented by the general formulas (1) and (2) used as auxiliary developing agents are used in an amount of 0.001 to 1000 times, preferably 0.01 to 100 times, more preferably 0.01 to 100 times the reducing agent. Is suitably added at 0.05 to 10 mole times.

As a method for adding the compounds represented by the general formulas (1) and (2), first, an oil-soluble compound used for other components such as a coupler, and a high-boiling organic solvent (eg, alkyl phosphate, alkyl phthalate) Ester and the like can be mixed, dissolved in a low boiling organic solvent (eg, ethyl acetate, methyl ethyl ketone, etc.), dispersed in water using an emulsification dispersion method known in the art, and then added. In addition, Japanese Unexamined Patent Publication
Addition by the solid dispersion method described in 3-271339 is also possible.

The compounds of the present invention can be used for monochromatic silver halide photographic materials and also for color photographic materials. In the following examples, color photographic materials using the compound (1) or (2) of the present invention will be described.

In order to obtain a wide range of colors on the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. . For example, there are three layers of a blue sensitive layer, a green sensitive layer, and a red sensitive layer, and a combination of a green sensitive layer, a red sensitive layer, and an infrared sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

After forming a color image by thermal development,
The remaining silver halide and / or developed silver may or may not be removed. In addition, as a method of outputting to another material based on the image information, normal projection exposure may be used, or image information may be photoelectrically read by measuring the density of transmitted light, and output using the signal. The material to be output need not be a photosensitive material, and may be, for example, a sublimation type thermosensitive recording material, an inkjet material, an electrophotographic material, a full-color direct thermosensitive recording material, or the like. An example of a preferred embodiment of the present invention is that after forming a color image by thermal development, the image information is transmitted by using a diffused light and a CCD image sensor without performing an additional process of removing the remaining silver halide and developed silver. It is read photoelectrically by density measurement, converted into a digital signal, image-processed, and output with a heat development color printer, for example, "Pictrography 3000" of Fuji Photo Film Co., Ltd. In this case, a good print can be obtained quickly without using any processing liquid used in conventional color photography. In this case, the digital signal can be processed and edited arbitrarily.
It can be transformed, processed and output.

The photosensitive material may have at least one photosensitive layer on a support and an antihalation layer thereunder. The photosensitive layer may be a photosensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities, or the photosensitive layer may be a blue light, a green light, And a unit light-sensitive layer having color sensitivity to any of red light, the arrangement of the unit light-sensitive layers is, in order from the support side, a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer It is also a preferred embodiment to be installed in order. Further, depending on the purpose, the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These include the aforementioned couplers,
It may contain a developing agent, a DIR compound, a color mixing inhibitor, a dye, and the like. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are DE 1,121,470 or GB 923,0
As described in No. 45, it is preferred that two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer are arranged so that the sensitivity gradually decreases toward the support. Also, JP-A-57-112751,
No. 62-200350, No. 62-206541 and No. 62-206543, a low-speed emulsion layer on the side away from the support,
A high-sensitivity emulsion layer may be provided on the side close to the support.

The silver halide may be any of silver iodobromide, silver chloroiodobromide, silver bromide, silver chlorobromide, silver iodochloride and silver chloride. These compositions are selected according to the properties to be imparted to the photosensitive silver halide. For example, when high sensitivity is required as in a photographic material, a silver iodobromide emulsion is mainly used. Further, silver chloride is often used in print materials in which quickness and simplification of development processing are important. Nevertheless, recently, there have been reports of attempts to consider the use of silver chloride for the purpose of speeding up processing of photographic materials.

The size of the silver halide grains constituting the photosensitive emulsion is 0.1 to 2 μm in terms of the diameter of a sphere having the same volume.
m, particularly preferably 0.2 to 1.5 μm. In addition, the shape of silver halide grains has a shape composed of normal crystals such as cubic, octahedral or tetradecahedral, those having irregular shapes such as spheres, and hexagonal or rectangular flat shapes. Can be arbitrarily used. In the photographic material, it is preferable to use so-called high aspect ratio tabular grains having a large projected area diameter with respect to the grain thickness in order to impart high sensitivity. Here, the aspect ratio is a value obtained by dividing the diameter of a circle equivalent to the projected area of a grain by the grain thickness. The silver halide emulsion used for the photographic material preferably has an aspect ratio of 2 or more, more preferably 5 or more, still more preferably 8 or more, and most preferably 20 or more.
With the above tabular grains, the projected area of all grains in the emulsion was 50%.
% Or more, preferably 80% or more, more preferably 90%
It is composed of the above. For particles having a small particle size (approximately 0.5 μm or less in diameter of a volume equivalent sphere), particles having an aspect ratio further divided by the particle thickness and having a tabularity of 25 or more are preferable.

By increasing the aspect ratio, a large projection area can be obtained even with the same volume, so that the spectral sensitization rate can be increased. In the case where the photographic sensitivity is proportional to the grain projection area, the amount of silver halide required to obtain the same sensitivity can be reduced. On the other hand, when preparing grains with a constant grain projected area, increasing the aspect ratio makes it possible to increase the number of grains even with the same amount of silver halide, thereby improving graininess. it can. Further, when high aspect ratio particles are used, the scattered light component having a large scattering angle with respect to the incident optical path is reduced, so that the sharpness can be increased.

The techniques and characteristics of using these high aspect ratio flat plates are disclosed in US Pat. Nos. 4,433,048, 4,434,226, 4,439,520 and the like. Further, the technology of ultra-high aspect ratio tabular grains having a grain thickness of less than 0.07 μm is disclosed in US Pat.
No. 789, No. 5,503,970, No. 5,503,971
No. 5,536,632, EP 0699945
Nos. 0699950, 0699948, 0699944, 0701165, and 0699946. The high aspect ratio tabular grains described in these specifications are mainly composed of silver bromide or silver iodobromide, and the frequency of hexagonal tabular grains whose main plane is composed of (111) planes is high. Particles having such a shape generally have two twin planes parallel to the (111) plane. In order to prepare tabular grains having a high aspect ratio and a small grain thickness, it is a technical point to form the two twin planes with a narrow interval. For this purpose, it is important to control the binder concentration, temperature, pH, excess halogen ion species and the same ion concentration at the time of nucleation, and the supply rate of the reaction solution. The selective growth of the formed tabular nuclei not in the thickness direction but in the peripheral direction of the tabular plate is also a point of forming the high aspect ratio tabular grains. To this end, it is important to control the rate of addition of the reaction solution for particle growth and to select the most suitable binder as a binder in the growth process from the time of particle formation. The above specification states that gelatin having a low methionine content is advantageous for increasing the aspect ratio.

On the other hand, a technique of forming tabular grains using high silver chloride having a high silver chloride content is also disclosed. For example, U.S. Patent Nos. 4,400,463 and 4,713,323.
No. 5,217,858 and European Patent No. 0423840.
No. 0647877 and the like describe techniques of high silver chloride tabular grains having a (111) plane as a main plane.

On the other hand, US Pat. Nos. 5,264,337, 5,292,632, 5,310,635, and 527
5932, EP 0534395, EP 061
No. 7320, International Publication WO94 / 22054, etc. disclose techniques of high silver chloride tabular grains having a (100) plane as a main plane. These are all techniques useful for preparing a high-sensitivity emulsion using silver chloride having excellent development speed and optical characteristics.

The silver halide grains are prepared so as to have various structures in the grains in addition to devising the above shapes. A commonly used method is to form grains into a plurality of layers having different halogen compositions. Silver iodobromide grains used for photographic materials preferably have layers having different iodine contents. So-called internal high iodine-type core-shell particles are known in which a layer having a high iodine content is covered with a shell having a low iodine content for the purpose of controlling developability. Conversely, externally high iodine type core-shell particles covered with a shell having a high iodine content are also known. This is effective for enhancing the stability of the shape when the thickness of the tabular grains becomes small. There is also known a technique in which a nucleus having a low iodine content is covered with a first shell having a high iodine content, and a second shell having a low iodine content is deposited thereon to thereby provide high sensitivity. In this type of silver halide grain, a shell deposited on a high iodine layer (corresponding to a fringe portion on the outer edge of the grain in tabular grains)
Is formed with dislocation lines based on crystal irregularities, which contributes to obtaining high sensitivity.

Further, a technique of epitaxially growing crystals having different halogen compositions at the localized portions of the formed host grains is also preferably used for obtaining high sensitivity. For example, a technique is known in which a crystal having a high iodine content is epitaxially grown on a part of the surface of a host grain rich in silver bromide (at the top or ridge of the grain or on the surface). On the contrary, there is also known a technique in which a host grain of silver bromide or silver iodobromide is epitaxially grown with a higher solubility (for example, a crystal having an increased silver chloride content).
The latter is preferably used for imparting high sensitivity particularly to tabular grains having a small grain thickness.

Even in high silver chloride tabular grains having a high silver chloride content, it is preferable to form a localized phase having a high silver bromide or silver iodide content inside or on the surface of the grains. In particular, it is preferable to epitaxially grow these localized phases on the vertices and ridges of the particle surface. These epitaxial crystal sites serve as effective photosensitive nucleation sites and provide high sensitivity.

For the purpose of improving the photographic characteristics of the photosensitive silver halide emulsion, it is also preferable to dope a metal salt or complex salt into the grains. These compounds act as transient or permanent traps of electrons or holes in the silver halide crystal to obtain high sensitivity and high contrast, improve the illuminance dependence during exposure, or improve the exposure environment. This is useful for improving (temperature, humidity) dependence and suppressing a change in performance when pressure is applied before and after exposure. These dopants may be uniformly doped into silver halide grains, may be locally localized at specific sites inside the grains, or may be locally localized on subsurfaces or surfaces.
Various methods can be selected according to the purpose, and doping can be localized in the above-mentioned epi portion.

Preferred metals are iron, ruthenium,
Examples include first to third transition metal elements such as rhodium, palladium, cadmium, rhenium, osmium, iridium, and platinum, and amphoteric metal elements such as thallium and lead. These metal ions are doped in a suitable salt or complex salt form. Among these, a hexacoordinate halogeno complex or cyano complex using a halide ion or cyanide ion as a ligand is preferably used. Further, a complex having an organic ligand such as a nitrosyl ligand, a carbonyl ligand, a thiocarbonyl ligand, a dinitrogen ligand, or a bipyridyl ligand, a cyclopentadienyl ligand, a 1,2-dithioenyl ligand, or the like may be used. Can be. These techniques are disclosed in
No. 36542, No. 1-116637, Japanese Patent Application No. 4-12
No. 6629 and the like.

Further, it is also preferable to dope a so-called chalcogen element divalent anion such as sulfur, selenium or tellurium. These dopants are also effective for obtaining high sensitivity and improving the dependence on exposure conditions.

The method of preparing silver halide grains is known in the art, that is, "Physics and Chemistry of Photography" by Grafkid, published by Paul Montesha (P.GLAFKIDES, C.
HIMIE ET PHISIQUE PHOTOGR
APHIQUE, PAUL MONTEL, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF DUFFIN, PHOTOGRAPHHI)
C EMULSION CHEMISTRY, FOCA
L PRESS, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZ).
EILKMAN ETAL. , MAKING AND
COATING OF PHOTOGRAPHICE
MULSION, FOCAL PRESS, 1964)
And the like. That is,
It can be prepared in various pH ranges such as an acidic method, a neutral method, and an ammonia method. In addition, as a method for supplying a water-soluble silver salt and a water-soluble halogen salt solution as a reaction solution, a one-side mixing method, a simultaneous mixing method, or the like can be used alone or in combination. Further, it is also preferable to use a controlled double jet method for controlling the addition of the reaction solution so as to keep the pAg during the reaction at a target value. Further, a method of maintaining a constant pH value during the reaction is also used. In forming the grains, a method of controlling the solubility of silver halide by changing the temperature, pH or pAg value of the system can be used, but thioethers, thioureas, rhodan salts and the like can also be used as the solvent. Examples of these are described in JP-B-47-11386,
It is described in JP-A-53-144319.

In the preparation of silver halide grains, a solution of a water-soluble silver salt such as silver nitrate and a solution of a water-soluble halide salt such as an alkali halide are usually controlled in a solution in which a water-soluble binder such as gelatin is dissolved. It is performed by supplying under the conditions described above. After the silver halide grains are formed, it is preferable to remove excess water-soluble salts. This step is called a desalting or washing step, and various means are used. For example, a gelatin solution containing silver halide grains is gelled, cut into strings, and washed with cold water to remove water-soluble salts, such as the Nudel water washing method, inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactant Agent, anionic polymer (eg, sodium polystyrene sulfonate),
Alternatively, a precipitation method may be used in which a gelatin derivative (for example, an aliphatic acylated gelatin, an aromatic acylated gelatin, an aromatic carbamoylated gelatin, etc.) is added to agglomerate the gelatin to remove excess salts. Above all, the sedimentation method is preferably used because the removal of excess salts is quickly performed.

In the present invention, it is usually preferable to use a chemically sensitized silver halide emulsion. Chemical sensitization imparts high sensitivity to the prepared silver halide grains and contributes to imparting exposure condition stability and storage stability. For chemical sensitization, generally known sensitization methods can be used alone or in various combinations.

As a chemical sensitization method, a chalcogen sensitization method using a sulfur, selenium or tellurium compound is preferably used. As these sensitizers, compounds that release the above-described chalcogen elements to form silver chalcogenides when added to a silver halide emulsion are used. further,
It is also preferable to use these in combination in order to obtain high sensitivity and to suppress fog to a low level.

Further, a noble metal sensitization method using gold, platinum, iridium or the like is also preferable. In particular, a gold sensitization method using chloroauric acid alone or in combination with a thiocyanate ion serving as a gold ligand can provide high sensitivity. When gold sensitization and chalcogen sensitization are used together, higher sensitivity can be obtained.

A so-called reduction sensitization method in which a compound having an appropriate reducing property is used during grain formation to obtain high sensitivity by introducing a reducing silver nucleus is also preferably used. A reduction sensitization method in which an alkynylamine compound having an aromatic ring is added during chemical sensitization is also preferable.

When performing chemical sensitization, it is also preferable to control the reactivity of the compound by using various compounds having adsorptivity to silver halide grains. In particular, a method in which a nitrogen-containing heterocyclic compound, a mercapto compound, or a sensitizing dye such as a cyanine or a merocyanine is added prior to the chalcogen sensitization or the gold sensitization is particularly preferable.

The reaction conditions for chemical sensitization vary depending on the purpose, but the temperature is 30 ° C. to 95 ° C., preferably 40 ° C.
~ 75 ° C, pH 5.0 ~ 11.0, preferably 5.5.
8.5 to 8.5, pAg 6.0 to 10.5, preferably 6.0.
5 to 9.8. Regarding chemical sensitization technology,
No. 110555, Japanese Patent Application No. 4-75798, Japanese Unexamined Patent Publication No.
No. 2,253,159, JP-A-5-45833, JP-A-62-40446, and the like.

In the present invention, it is preferable that the photosensitive silver halide emulsion is subjected to so-called spectral sensitization for imparting sensitivity to a desired light wavelength range. In particular, in a color photographic light-sensitive material, a light-sensitive layer having photosensitivity to blue, green and red is incorporated in order to reproduce colors faithfully to the original. These sensitivities are provided by spectrally sensitizing silver halide. For spectral sensitization, a so-called spectral sensitizing dye is used, which is adsorbed on silver halide grains and has sensitivity in its own absorption wavelength range.

Examples of these dyes include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Examples of these are described in US Pat. No. 4,617,257.
No. JP-A-59-180550, JP-A-64-13546
And JP-A-5-45828 and JP-A-5-45834.

The spectral sensitizing dye is used alone,
A plurality of dyes are used in combination. This is performed for the purpose of adjusting the wavelength distribution of spectral sensitivity and for supersensitization. With a combination of dyes exhibiting supersensitization, a sensitivity that greatly exceeds the sum of the sensitivities that can be achieved alone can be obtained.

It is also preferable to use a dye which does not have a spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits a supersensitizing effect. Diaminostilbene compounds and the like can be mentioned as examples of the supersensitizer. Examples of these are disclosed in U.S. Pat. No. 3,615,641 and JP-A-63-231.
No. 45, etc.

These spectral sensitizing dyes and supersensitizers can be added to the silver halide emulsion at any time during the preparation of the emulsion. It is added to the emulsion after chemical sensitization is completed at the time of preparation of the coating solution, added at the end of chemical sensitization, added during chemical sensitization, added before chemical sensitization, and added after grain formation is completed and before desalting. Various methods such as addition during the formation of particles or addition prior to the formation of particles can be used alone or in combination. It is preferable to add in a step before chemical sensitization in order to obtain high sensitivity.

The amount of the spectral sensitizing dye or supersensitizer to be added varies widely depending on the shape and size of the grains or the photographic properties to be imparted, but generally ranges from 1 to 1 per mole of silver halide.
The range is 0 ^-8 to 10 ^-1 mol, preferably 10 ^-5 to 10 ^-2 mol. These compounds can be added in a state of being dissolved in an organic solvent such as methanol or fluorine alcohol, or in a state of being dispersed in water together with a surfactant or gelatin.

It is preferable to add various stabilizers to the silver halide emulsion for the purpose of preventing fog and improving the stability during storage. Preferred stabilizers include azaindenes, triazoles, tetrazoles, nitrogen-containing heterocyclic compounds such as purines, mercaptotetrazole, mercaptotriazoles, mercaptoimidazoles, and mercapto compounds such as mercaptothiadiazole. Can be. Details of these compounds can be found in James, "Theory of Photographic Processes", published by Macmillan, Inc. (TH JAMES, THE THEORY OF).
THE PHOTOGRAPHIC PROCESS,
MACMILLAN, 1977), pp. 396-399 and references cited therein.

These antifoggants or stabilizers can be added to the silver halide emulsion at any time during the preparation of the emulsion. It is added to the emulsion after chemical sensitization is completed at the time of preparation of the coating solution, added at the end of chemical sensitization, added during chemical sensitization, added before chemical sensitization, and added after grain formation is completed and before desalting. Various methods such as addition during the formation of particles or addition prior to the formation of particles can be used alone or in combination.

The addition amount of these antifoggants or stabilizers varies depending on the halogen composition and purpose of the silver halide emulsion, but is generally about 10 ^-6 per mol of silver halide.
It is in the range of 10 ^-1 mol, preferably 10 ^-5 to 10 ^-2 mol. The photosensitive silver halide used in the light-sensitive material is 0.05 to ²⁰ g / m ² , preferably 0.1 to 10 g / m ^{2 in} terms of silver.
m ² is appropriate.

Organic metal salts, binders, high-boiling organic solvents, surfactants, hardeners, antifoggants, photographic stabilizers and precursors thereof, coating aids, antistatic agents, and the like which can be used in the present invention. Development accelerator, organic fluoro compound, slip agent, polymer latex, matting agent,
For the support, film patrone, etc.
No. 762201A1. In addition, the following compounds can also be used effectively.

Dispersion medium for oil-soluble organic compound: JP-A-62-215
272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,
93 (pp. 140-144); Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidized developing agent scavenger: Represented by formula (I) in column 2, lines 54 to 62 of US Pat. No. 4,978,606. Compounds (especially I-,
(1), (2), (6), (12) (columns 4-5), US Pat. No. 4,923,787, column 5 lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP 298321A) Formula (I) on page 4, lines 30-33
To (III), especially I-47,72, III-1,27 (pages 24 to 48); anti-fading agent: A-6,7,20,21,23,24,25,26, of EP 298321A
30,37,40,42,48,63,90,92,94,164 (pp.69-118), US
No. 5,122,444 column 25-38 II-1 to III-23, especially III-1
0, I-1 to III-4 on pages 8 to 12 of EP 471347A, especially II-2,
US Pat. No. 5,139,931 A-1 to 48 of columns 32 to 40, especially A-39,
42; a material for reducing the amount of a color-enhancing agent or a color-mixing inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin Scavenger: EP 477932A, pp. 24-29
SCV-1 to 28, especially SCV-8; hardener: H-1,4,6,8,14, US on page 17 of JP-A-1-214845
Compounds (H-1 to 54) represented by formulas (VII) to (XII) in columns 13 to 23 of 4,618,573; compounds represented by formula (6) on the lower right of page 8 of JP-A-2-214852 (H -1 to 76), especially H-14, US
Compound described in claim 1 of 3,325,287; Development inhibitor precursor: P-24,3 of JP-A-62-168139
7,39 (pages 6-7), the compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; preservatives and fungicides: I-1 of columns 3 to 15 of US Pat. No. 4,923,790
~ III-43, especially II-1,9,10,18, III-25; stabilizers, antifoggants: columns 6 to 16 of US 4,923,793
I-1 to (14), especially I-1,60, (2), (13), compounds 1 to 65, especially 36 in columns 25 to 32 of US Pat. No. 4,952,483; Chemical sensitizer: triphenylphosphine selenium Nido, JP
Compound 50 of No. 5-40324; Dye: A-1 to B-20 on pages 15 to 18 of JP-A-3-156450, particularly
A-1,12,18,27,35,36, B-5,27-29 V-1 to 23, especially V-
1, FI-1 to F-II-43 on pages 33 to 55 of EP 445627A, especially
FI-11, F-II-8, III-1 on pages 17 to 28 of EP 457153A
36, especially III-1,3, Dye-1 to 124 of 8-26 of WO 88/04794
Microcrystal dispersion of compound 1 on page 6 to 11 of EP 319999A
22, particularly compound 1, compounds D-1 to 87 (pages 3 to 28) represented by formulas (1) to (3) in EP 519306A, compounds 1 to 22 represented by formula (I) in US 4,268,622. Columns 3-10),
Compounds (1) to (3) represented by formula (I) of US Pat. No. 4,923,788
1) (columns 2 to 9); UV absorber: compounds (18B) to (18R), 101 to 427 (pages 6 to 9) represented by formula (1) in JP-A-46-3335, EP 520938A The compounds (3) to (66) (pages 10 to 44) represented by the formula (I) and the compounds HBT-1 to 10 (page 14) represented by the formula (III), E
Compounds (1) to (31) represented by Formula (1) of P 521823A
(Columns 2-9).

The silver halide photographic light-sensitive material of the present invention can be processed with a processing solution such as a developing solution containing a developing agent and an activator solution composed of an aqueous alkali solution, or can be subjected to thermal development processing. Further, as described in JP-A-9-127670, a method for forming an image in a silver halide photographic light-sensitive material, after image exposure, is heated in close contact with a processing layer of a processing member having a processing layer. Can also be used.

The treatment layer of the treatment member preferably used in the present invention contains at least a base and / or a base precursor. As the base, an inorganic or organic base can be used. Examples of the inorganic base include:
Hydroxide, phosphate, carbonate, borate, organic acid salt of alkali metal or alkaline earth metal described in JP 09448, acetylide of alkali metal or alkaline earth metal described in JP-A-63-25208, And the like.

As the organic base, ammonia,
Aliphatic or aromatic amines (eg, primary amines, secondary amines, tertiary amines, polyamines, hydroxylamines, heterocyclic amines), amidines,
Bis or tris or tetraamidine, guanidines, water-insoluble mono or bis or tris or tetraguanidines, quaternary ammonium hydroxides and the like can be mentioned.

As the base precursor, decarboxylation type, decomposition type, reaction type, complex salt forming type and the like can be used. In the present invention, European Patent Publication 210,660
As described in U.S. Pat. No. 4,740,445, a basic metal compound which is hardly soluble in water as a base precursor and a complex formation reaction with a metal ion constituting the basic metal compound and water as a medium. It is effective to adopt a method of generating a base by a combination of compounds that can be used (referred to as complex forming compounds). In this case, it is desirable that the basic metal compound which is hardly soluble in water is added to the light-sensitive material and the complex-forming compound is added to the processing member, and vice versa.

The amount of base or base precursor used is
It is 0.1 to 20 g / m ^2, preferably 1 to 10 g / m ² . As the binder of the processing layer, a hydrophilic polymer similar to the photosensitive member can be used. In addition, materials and other configurations that can be used for processing members are also described in EP 0762.
201A1.

In a preferred embodiment of the present invention, as a method of developing a photosensitive member photographed by a camera or the like, the amount required for maximally swelling the entire coating film excluding the back layer of both the photosensitive member and the processing member is from 0.1 to 1%. The photosensitive member and the processing member are overlapped with the photosensitive layer and the processing layer facing each other in the presence of twice as much water, and heated at a temperature of 60 ° C. to 100 ° C. for 5 seconds to 60 seconds.

The water mentioned here may be any water that is generally used. Specifically, distilled water, ion exchange water, tap water, well water, mineral water, and the like can be used. A method in which a small amount of a preservative is added to these waters for the purpose of preventing generation of scale and decay, and circulating and filtering the water with an activated carbon filter, an ion exchange resin filter or the like is also preferably used.

The photosensitive member and / or the processing member are stuck together in a state of being swollen with water and heated. The state of the film at the time of swelling is unstable, and it is important to limit the amount of water to the above range in order to prevent local uneven coloring.

The amount of water required for maximum swelling is determined by immersing a photosensitive member or a processing member having a coating film to be measured in water to be used, measuring the film thickness when the swelling is sufficient, and calculating the maximum swelling amount. It can be obtained by reducing the weight of the coating film afterwards. Further, an example of a method for measuring the degree of swelling is described in Photographic Science Engineering, Vol. 16, No. 449.
It is also described on page (1972).

[0082]

EXAMPLES Hereinafter, the effects of the present invention will be described in detail with reference to examples. Example 1 <Method for Preparing Photosensitive Silver Halide Emulsion-1> A well-stirred aqueous gelatin solution (30 ml of inert gelatin in 1000 ml of water)
g, 2 g of potassium bromide), add ammonia / ammonium nitrate as a solvent as a solvent, keep the temperature at 75 ° C, and add 1000 ml of an aqueous solution containing 1 mol of silver nitrate and an aqueous solution containing 1 mol of potassium bromide and 0.03 mol of potassium iodide. 1000 ml were added simultaneously over 78 minutes. After washing with water and desalting, re-disperse by adding inert gelatin, and the iodine content of a sphere equivalent diameter 0.76μ 3mol
% Silver iodobromide emulsion was prepared. The sphere equivalent diameter was measured using a model TA-3 manufactured by Coulter Counter. 56 in the above emulsion
At room temperature, potassium thiocyanate, chloroauric acid, and sodium thiosulfate were added for optimal chemical sensitization. A sensitizing dye was added to this emulsion at the time of preparing the coating solution to give color sensitivity.

<Preparation method of zinc hydroxide dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm, 1.6 g of carboxymethylcellulose and 0.4 g of sodium polyacrylate as dispersants, 8.5 g of lime-treated ossein gelatin g,
158.5 ml of water was mixed, and this mixture was dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

<Method for Preparing Emulsified Dispersion of Coupler> Table 1
Dissolve the oil phase component and the aqueous phase component of the composition shown in
Make a homogeneous solution at ℃. Combine the oil phase component and the water phase component,
In a 1 liter stainless steel container, the mixture was dispersed at 10,000 rpm for 20 minutes by a dissolver with a disperser having a diameter of 5 cm. Warm water in the amount shown in Table 1 was added to this dispersion as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of the coupler was prepared.

[0085]

[Table 1]

[0086]

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[0087]

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[0088]

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Using the thus obtained materials, photothermographic materials 101 having a multilayer structure as shown in Tables 2 and 3 were produced.

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

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[0093]

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[0094]

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Further, the processing member R-1 having the contents shown in Table 4
Was prepared.

[Table 4]

[0096]

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Next, as shown in Table 5, photosensitive materials 102 to 115 having exactly the same composition as 101 except that the developing agent and the reducing agent of the third layer (magenta coloring layer) were changed from 101.
Were prepared respectively. Photosensitive material 10 made in this way
Exposure was performed at 2500 lux for 0.01 second through B, G, R, and gray filters of continuously changing density from 1 to 115. 15 ml / m of 40 ° C. warm water is applied to the exposed photosensitive material surface, and the processing member and the respective film surfaces are overlapped with each other.
Heat development was performed at 30 ° C. for 30 seconds. When the treated member is peeled off after the treatment,
Clear images were obtained corresponding to the filters exposed on the light-sensitive material side. Immediately after the treatment, the transmission density of Dmax of the exposed portion and Dmin of the white portion of this sample were measured by an X-rite densitometer, and the results are shown in Table 6. In addition, this sample was stored at 45 ° C and 80% relative humidity.
Table 7 shows the results of the same treatment after storage for 7 days under the conditions of%.

[0098]

[Table 5]

[0099]

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[0100]

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[0101]

[Table 6]

[0102]

[Table 7]

Summarizing the results in Tables 6 and 7, first, no significant improvement in photographic properties was observed in Comparative Samples 101 to 104 even though the developing agents were changed. In Comparative Samples 105 to 107, the effect of using the main drug having a small molecular weight is recognized, but the density of the silver image is increased in each color. In Comparative Samples 108 and 109 using the 1-phenyl-3-pyrazolidinone derivative as the reducing agent, the effect of addition was completely lost after storage. On the other hand, in the light-sensitive materials 110 to 115 of the present invention, although the increase in the density of the silver image was extremely small, a large increase in the color image density was recognized.
Further, it can be seen that this effect is effective even after storage.

Next, after setting these photosensitive materials in a camera and photographing, the same processing is performed, and the image obtained on the photosensitive materials is read by a digital image reading / reproducing apparatus frontier.
Output with SP-1000 (Fuji Photo Film Co., Ltd.).
Among the photosensitive materials 101 to 104, for which sufficient color formation cannot be obtained, the photosensitive materials 105 to 107 having a high silver image density, and the photosensitive materials 108, 109 after storage under high-temperature and high-humidity conditions, the photosensitive materials 110 to 115
And the image quality was inferior, for example, the graininess was conspicuous.

[0105]

According to the present invention, it is possible to provide a silver halide photographic material excellent in image discrimination and raw storage stability.

Claims (1)

[Claims] (1) At least the following general formula (1) or (2)
A silver halide photographic material comprising a compound represented by the formula: General formula (1) General formula (2) In the formula, R _{1 to} R _{9 each} represent a hydrogen atom, a halogen atom, or a substituent having a carbon number of 4 or less or an I / O value of 1 or more. In the general formula (1), R ₂ and / or R ₄ , and R ₅ and / or R ₉ are a substituent other than a hydrogen atom (a halogen atom or a substituent having 4 or less carbon atoms or an I / O value of 1 or more) ), And R in the general formula (2)
₄ , and R ₅ and / or R ₉ are substituents other than a hydrogen atom (halogen atom or C 4 or less or I / O
A substituent having a value of 1 or more). R ₁ and R _2, R ₃ and R _4, R ₅ and R _6, R ₆ and R _7, R ₇ and R _8, R ₈ and R
_When each of ₉ is a substituent other than a hydrogen atom, in the combination of each group, they may be independently bonded to form a ring.