JP2002105044A - Sulfonamidephenol or aniline-based compound and halogenated silver photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a halogenated silver photosensitive material having a high maximum concentration of its image and excellent in discrimination. SOLUTION: This photosensitive material is obtained by using a compound expressed by the following general formula (1) (wherein, A is hydroxyl, a substituted or non-substituted amino or the like; R1 to R4 are each H, a halogen atom, cyano, an alkyl, an aryl or the like; and R5 is a pseudo aromatic ring).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a sulfonamidophenol or aniline compound useful as a reducing agent and the like, and a silver halide photographic material using the same.

[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. Recently, as photothermographic color light-sensitive materials, products such as Pictrography and Pictrostat have been sold 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 of 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, and a heat-developable color light-sensitive material employing this method is also disclosed in U.S. Pat. No. 3,761,270. ,
4,021,240, JP-A-59-231539, JP-A-60-128438, etc.
Many ideas have been filed.

[0004]

The present inventors have also studied a photothermographic material of the type utilizing the above-described coupling reaction. The maximum density (Dmax) of the image was low and there was a point to be improved. Japanese Patent Application Laid-Open No. 9-90582 discloses a technique for examining the molecular design of a reducing agent to improve such a point. However, even with a photosensitive material using these reducing agents, a dye image could not be obtained with a sufficient coloring efficiency as can be seen from the molar extinction coefficient of the dye formed from the coupler. An object of the present invention is to develop a reducing agent that satisfies the above objects and to provide a silver halide photographic light-sensitive material having a high maximum image density and excellent discrimination.

[0005]

The object of the present invention has been attained by the following compounds and a silver halide photographic material. 1) A compound represented by the following general formula (1).

[0006]

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In the formula, A represents a hydroxyl group, a substituted or unsubstituted amino group, or a group capable of forming a hydroxyl group or an amino group by hydrolysis. R _{1 to} R ₄ are a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, Arylsulfonyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkoxycarbonyl group, aryl Represents an oxycarbonyl group, a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a ureido group, or a urethane group. R ₅ represents a pseudo aromatic ring group. 2) In a silver halide photographic photosensitive material having at least a photosensitive silver halide, a binder and a reducing agent on a support, at least one of the reducing agents is represented by the general formula (1)
A silver halide photographic material characterized by being a compound represented by the formula: (3) The silver halide photographic material as described in (2) above, wherein R ₅ in the general formula (1) is a group represented by the following general formula (2).

[0008]

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In the formula, R _{6 to} R ₁₂ represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an arylcarbonyl group. Carbonyl group, alkylsulfonyl group, arylsulfonyl group,
Alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Sulfamoyl group,
Represents an alkylsulfamoyl group, an arylsulfamoyl group, a ureido group, or a urethane group. Adjacent groups in the substituents of R _{6 to} R ₁₂ may be independently bonded to each other to form a ring. (4) The silver halide photographic material as described in (3) above, wherein R ₆ and / or R _{12 in the} general formula (2) is a substituent.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

First, the compounds represented by formulas (1) and (2) will be described in detail.

The compound represented by the general formula (1) is a sulfo
With amidophenol or sulfonamidoaniline
It represents a reducing agent (developing agent) generically. Where A is hydroxyl
Group, substituted or unsubstituted amino group, or hydrolysis
Therefore, it represents a group capable of generating a hydroxyl group or an amino group. A
In the case of a amino group, an alkylamino group or an arylamino group
Any substituted amino group is preferred, most preferably dialky
It is a ruamino group. Hydrolysis of hydroxyl or amino groups
The groups capable of forming a phenyl group include acyl groups, ureido groups, and uranium groups.
Rethane groups and the like can be mentioned. Most preferred as A
Or a hydroxyl group. In the present invention, R5 is a pseudoaromatic ring
Is a group that forms A pseudoaromatic ring is a π electron in a single ring
The number does not correspond to the formula of 4n + 2 according to the Huckel rule
Calculates the total number of π electrons in the condensed ring.
Represents a fused ring system in which the corresponding electron is present. Special among them
To a five-membered azulene ring represented by the general formula (2)
It is preferable that the compound is substituted with a sulfonyl group.
R₁~ R_FourAnd R of the general formula (2)₆~ R₁₂Is a hydrogen atom,
Halogen atom (for example, chloro group, bromo group), alkyl
Groups (eg, methyl, ethyl, isopropyl, n-
Butyl group, t-butyl group), aryl group (for example,
Tansulfonylaminophenyl group), alkyl carboxyl
Amido groups (eg, acetylamino, propionylamido
Group, butyroylamino group), arylcarbonamide
Group (for example, benzoylamino group), alkyl sulfone
Amide group (for example, methanesulfonylamino group, ethanesulfone
Honylamino group), arylsulfonamide group (for example,
Benzenesulfonylamino group, toluenesulfonylamino
Group), alkoxy group (for example, methoxy group, ethoxy
Group), an aryloxy group (for example, 4-methanesulfonyl
Minophenoxy group), alkylthio group (for example, methylthio group)
O group, ethylthio group, butylthio group), arylthio group
(For example, 4-methanesulfonylaminophenylthio group),
Alkylcarbamoyl groups (eg, methylcarbamoyl
Group, dimethylcarbamoyl group, ethylcarbamoyl group,
Diethylcarbamoyl, dibutylcarbamoyl,
Peridinocarbamoyl group, morpholinocarbamoyl
Group), arylcarbamoyl group (for example, phenylcarbamoyl group)
Moyl group, methylphenylcarbamoyl group, ethylphen
Nilcarbamoyl group, benzylphenylcarbamoyl
Group), carbamoyl group, alkylsulfamoyl group (eg
For example, methylsulfamoyl group, dimethylsulfamoyl
Group, ethylsulfamoyl group, diethylsulfamoyl
Group, dibutylsulfamoyl group, piperidinosulfamo
Yl group, morpholinosulfamoyl group), aryl sulf
Famoyl group (for example, phenylsulfamoyl group, methyl
Ruphenylsulfamoyl group, ethylphenylsulfa
Moyl group, benzylphenylsulfamoyl group), sulf
Famoyl group, cyano group, alkylsulfonyl group (for example,
Methanesulfonyl group, ethanesulfonyl group), aryl
Rusulfonyl group (for example, phenylsulfonyl group,
Lorophenylsulfonyl group, p-toluenesulfonyl
Group), an alkoxycarbonyl group (for example, methoxycarbo)
Nyl group, ethoxycarbonyl group, butoxycarbonyl
Group), aryloxycarbonyl group (for example, phenoxy
Carbonyl group), alkylcarbonyl group (for example, acetyl
Group, propionyl group, butyroyl group), arylcar
Bonyl group (for example, benzoyl group, alkylbenzoyl
Group) or an acyloxy group (eg, acetyloxy
Group, propionyloxy group, butyroyloxy group)
You. Especially R₁~ R_FourThen, in the Hammett rule of the substituent
The value R₁~ R_FourCombinations of groups such that the sum of
Is preferred. R in general formula (2)₆And / or
Or R₁₂Is preferably a substituent. With this substituent
Is R₁~ R_FourDescribed halogen atoms and various
Groups, of which alkyl and aryl groups are preferred.
New R₁~ R_Four, R ₆~ R₁₂Is each a substituent,
Independently bonded in combination of adjacent groups
To form a ring.

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

[0014]

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(Synthesis of Reducing Agent D-1) (Synthesis of Acid Chloride A) 39.6 g (0.2 mol) of guaiazulene and 300 ml of dichloromethane were charged into a 1000 ml three-necked flask equipped with a thermometer and a reflux condenser. While stirring the contents using a magnetic stirrer, the internal temperature was lowered to −5 ° C. using an ice-methanol bath. To this, 23 g (0.2 mol) of chlorosulfonic acid was gradually added dropwise so that the internal temperature did not exceed 5 ° C. The stirring was continued as it was, and after 1 hour, the cooling bath was removed, and the mixture was left until the internal temperature reached room temperature. Under reduced pressure,
The solvent was distilled off, and 200 ml of acetonitrile and 30 ml of N, N-dimethylacetamide were added thereto, followed by stirring at room temperature.
When 47 g (0.25 mol) of phosphorus oxychloride was gradually added dropwise, the internal temperature rose to 60 ° C. After stirring was continued for 1 hour, the reaction mixture was poured into 3 liters of cold water to precipitate crystals. The crystals were separated by filtration, washed with water, and dried under reduced pressure. Thus, 41 g of acid chloride A crystals were obtained. (Synthesis of reducing agent D-1) In a 500 ml three-necked flask equipped with a thermometer and a reflux condenser, 17.8 g (0.1 mol) of 2,6-dichloro-4-aminophenol and 120 ml of N, N-dimethylacetamide Was completely dissolved using a magnetic stirrer while stirring. An ice bath was attached here, and the internal temperature was reduced to 0 ° C. Here, 30 g of acid chloride A
(0.1 mol), the internal temperature rose to 10 ° C. The cooling bath was removed as it was, and the reaction was continued for about 2 hours. After completion of the reaction, the reaction mixture was poured into 3 liters of cold water to precipitate crystals. The crystals were separated by filtration and recrystallized from a mixed solvent of methanol and water to obtain 37 g of crystals of a reducing agent D-1. Examples of the reducing agents represented by the general formulas (1) and (2) are shown below. The present invention is of course not limited by this specific example.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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When the compound of the present invention is used in a silver halide photographic light-sensitive material, the coating amount in the light-sensitive material can take a wide range. 0.001 for high density images
~1000mmol / m ^2, preferably 0.01~100mmol / m ^2.
Further, the compound of the present invention may be used alone as a reducing agent, or several kinds of the compounds of the present invention may be mixed or used in combination with other kinds of reducing agents.

In the present invention, a compound (coupler) that forms a dye by an oxidative coupling reaction is used as the dye-donating compound. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler, but a 4-equivalent coupler is preferred in the present invention. First, in the present invention, the amino group, which is the coupling site of the reducing agent, is protected by a substituent, and if there is a substituent at the coupling site on the coupler side during the coupling, the reaction occurs due to steric hindrance. Is inhibited. Secondly, since this substituent leaves as an anion after coupling,
This is because the leaving group on the coupler side must be released as a cation, and such a leaving group cannot be obtained with a normal two-equivalent coupler.

A specific example of a coupler is the theory of the photographic process (4th Ed. TH James, edited by Macmillan, 1977) for both 4-equivalent and 2-equivalent.
291 to 334, 354 to 361, JP-A-58-12353, 58-149046, 58
No. 149047, No. 59 No. 11114, No. 59 No. 1
24399, 59-174835, 59-23
1539, 59-231540, 60-295
No. 1, No. 60-14242, No. 60-23474,
No. 60-66249, and the like.

Examples of the coupler preferably used in the present invention are listed below.

The couplers preferably used in the present invention include compounds having structures represented by the following general formulas [2] to [13]. These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0028]

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[0029]

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[0030]

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The general formulas [2] to [5] represent couplers referred to as active methylene couplers, wherein R ₂₄ represents an optionally substituted acyl, cyano, nitro or aryl group. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas [2] to [5], R ₂₅ is an optionally substituted alkyl group, aryl group or heterocyclic group. In the general formula [5], R ₂₆ is an aryl group or a heterocyclic group which may have a substituent. R ₂₄ ,
Examples of the substituent which R ₂₅ and R ₂₆ may have include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano group, a halogen atom, an acylamino group, a sulfone Various substituents such as an amide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, a hydroxyl group and a sulfo group can be exemplified. Preferred examples of R ₂₄ include an acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group.

In the general formulas [2] to [5], Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized developing agent. Examples of Y include a carboxyl group, a formyl group, a halogen atom, (eg, bromine, iodine),
A carbamoyl group, a methylene group having a substituent (as a substituent, an aryl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, an amino group, a hydroxyl group, etc.), an acyl group,
And a sulfo group. Among them, as described above, Y
Is preferably a hydrogen atom.

In the general formulas [2] to [5], R ₂₄ and R
₂₅ , R ₂₄ and R ₂₆ may combine with each other to form a ring.

The general formula [6] represents a coupler referred to as a 5-pyrazolone magenta coupler, wherein R ₂₇ represents an alkyl group, an aryl group, an acyl group or a carbamoyl group. R ₂₈ is a phenyl group or one or more halogen atoms,
Represents a phenyl group substituted by an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. Y is the same as in general formulas [2] to [5].

Among the 5-pyrazolone-based magenta couplers represented by the general formula [6], R ₂₇ is an aryl or acyl group, R ₂₈ is a phenyl group substituted by one or more halogen atoms, and Y is a hydrogen atom. Are preferred.

To describe these preferred groups in detail, R ₂₇ is phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3-octadecenyl-1-succinimide) Phenyl, 2-chloro-5-octadecylsulfonamidophenyl or 2-chloro-5- [2-
(4-hydroxy-3-t-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-di-t-pentylphenoxy) acetyl, 2- (2 , 4-
Acyl groups such as di-t-pentylphenoxy) butanoyl, benzoyl, and 3- (2,4-di-t-amylphenoxyacetoazide) benzoyl; these groups may further have a substituent; Is an organic substituent or a halogen atom connected by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.

R ₂₈ is 2,4,6-trichlorophenyl,
Substituted phenyl groups such as 2,5-dichlorophenyl and 2-chlorophenyl groups are preferred.

The general formula [7] represents a coupler called a pyrazoloazole-based coupler, wherein R ₂₉ represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).
Y is the same as in general formulas [2] to [5].

Among the pyrazoloazole couplers represented by the general formula [7], imidazo [1,2] described in US Pat.
- b] pyrazoles, U.S. Patent 4,540,654
No. 5,541,501.
5-b] [1,2,4] triazoles, U.S. Pat.
No. 725067, pyrazolo [5, 1-c] [1,
2,4] triazoles are preferable, and in terms of light fastness,
Of these, pyrazolo [1,5-b] [1,2,4] triazoles are preferred.

For details of the substituents on the azole ring represented by the substituents R ₂₉ , Y and Z, see, for example, US Pat.
No. 40,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2,3- or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
No. 9457 or No. 63-307453, pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position, and Japanese Patent Application No. 1-2227.
No. 9 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

The general formula [8],

[9] is a coupler called a phenol-based coupler or a naphthol-based coupler, wherein R ₃₀ is a hydrogen atom or —NHCOR ₃₂ ,
_{-SO 2 NR 32 R 33, -NHSO} 2 R 32, -NHCOR
₃₂ , —NHCONR ₃₂ R ₃₃ , and —NHSO ₂ NR ₃₂ R ₃₃ . R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. General formula [8],

In [9], R ₃₁ represents a substituent, p represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. About Y, general formula [2]-
Same as [5]. As R _{31 to} R ₃₃ , R _{24 to} R
The substituents described for ₂₆ are mentioned.

Preferred examples of the phenolic coupler represented by the general formula [8] include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-alkylamino-5-alkylphenols, U.S. Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729,
9,166,956 and the like, U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427. , 767, etc., and the like.

General formula

Preferred examples of the naphthol coupler represented by [9] include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,228,233, No. 4,296,
No. 200, etc., and 2-carbamoyl-1-naphthols described in US Pat. No. 4,690,889 and the like.
Carbamoyl-5-amide-1-naphthol and the like can be mentioned.

The general formulas [10] to [13] are couplers called pyrrolotriazole, and R ₄₂ , R ₄₃ and R ₄₄ each represent a hydrogen atom or a substituent. About Y, general formula [2]-
Same as [5]. _Examples of the substituent for R ₄₂ , R ₄₃ , and R ₄₄ include those described above as the substituent for R _{24 to} R ₂₆ . Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas [10] to [13] include European Patent No. 48
No. 8,248A1, No. 491,197A1, No. 5
Nos. 45,300 and 628,867,
A coupler in which at least one of R ₄₂ and R ₄₃ is an electron withdrawing group is exemplified.

In addition, fused ring phenol, imidazole,
Pyrrole, 3-hydroxypyridine, active methine, 5,
Couplers having a structure such as a 5-fused heterocycle and a 5,6-fused heterocycle can be used.

Examples of fused phenol couplers include US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used.

As the imidazole coupler, couplers described in US Pat. Nos. 4,818,672 and 5,051,347 can be used.

As the pyrrole coupler, JP-A-4-4-1
The couplers described in Nos. 88137 and 4-190347 can be used.

As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 can be used.

As active methine couplers, those described in US Pat. Nos. 5,104,783 and 5,162,196 can be used.

The 5,5-fused heterocyclic couplers include:
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289, pyrroloimidazole couplers described in JP-A-4-174429, and the like can be used.

The 5,6-fused heterocyclic couplers include:
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, EP 556,70.
The couplers described in No. 0 can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260 and 32261, JP-A No. 2
No. -297475, No. 2-44340, No. 2-110
555, 3-7938, 3-160440,
Nos. 3-172839, 4-172247, 4-
No. 179949, No. 4-182645, No. 4-184
Nos. 437, 4-188138, 4-188139
And couplers described in JP-A-4-194847, JP-A-4-204532, JP-A-4-204731, and JP-A-4-204732.

Specific examples of the coupler usable in the present invention are shown below, but the present invention is of course not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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The amount of the coupler to be added depends on the molar extinction coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, the ε of the dye formed by coupling is about 5,000 to 500,000. In the case of the coupler (1), the coating amount is about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ² , and more preferably 0.1 to 10 mmol / m ² .
An appropriate amount is from about 0.5 to 5 mmol / m ² .

The light-sensitive material of the present invention basically comprises a support having a light-sensitive silver halide and a coupler, a reducing agent and a binder as a dye-providing compound. Agents and the like can be contained. These components are often added to the same layer, but they can be added separately in separate layers if they can react.

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 having photosensitivity in 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.

The photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, various filter dyes can be added to improve color separation.

In general, a base is required in the processing of a photographic light-sensitive material. In the light-sensitive material of the present invention, various base supply methods can be adopted. For example, when a base generating function is imparted to the light-sensitive material side, it can be introduced into the light-sensitive material as a base precursor. Such base precursors include, for example, salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution, Lossen rearrangement or Beckmann rearrangement. This example is described in U.S. Patent Nos. 4,514,493 and 4,657,848.

When the photosensitive material and the processing sheet are superposed and processed, a method of introducing a base or a base precursor into the processing sheet can also be used.
As the base in this case, an organic base such as an amine derivative can be used in addition to the inorganic base.

Further, a reaction in which a base precursor is contained in each of the light-sensitive material side and the processing sheet side to generate a base by a reaction between the two can be used. Examples of such a two-agent reaction type base generation method include, for example, a method based on a reaction between a sparingly soluble basic metal salt and a chelating agent, and a method based on a reaction between a nucleophilic agent and an epoxy compound. This example is described in JP-A-63-198050 and the like.

The silver halide emulsion which can be used in the present invention is
Any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Also,
A so-called core-shell emulsion in which the inside of the grains and the surface layer of the grains have different phases may be used, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodisperse or polydisperse, and a method of adjusting the gradation by mixing monodisperse emulsions as described in JP-A-1-167743 and JP-A-4-223463 is preferably used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 1702
No. 9 (1978), No. 17643 (December 1978) 22-23
No. 18716 (November 1979), p. 648, p.
07105 (November 1989) pp. 863-865, JP-A-62-2
53159, 64-13546, JP-A-2-23
No. 6546, No. 3-110555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafk)
ides, Chemie et Phisique Photographique, Paul Mont
el, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Ch.
emistry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Focal Press (VL Ze)
likman et al., Making and Coating Photographic Emu
lsion, Focal Press, 1964), etc., any of which can be used.

In the process of preparing the photosensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting for removing excess salt. As a means for this, 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, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly contained in the particles, or may be localized inside or on the surface of the particles. Specifically, JP-A-2-236542, JP-A-1-116637, and JP-A-5-116637.
Emulsions described in 181246 and the like are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, a rhodan salt, ammonia, a tetra-substituted thioether compound, or a silver halide solvent may be used as a silver halide solvent.
Organic thioether derivatives described in 1386 or sulfur-containing compounds described in JP-A-53-144319 can be used.

Other conditions are described in “Graduation of the Physics and Chemistry of Photography” by Grafkid, published by Paul Monte, Inc. (P. Gla
fkides, Chemie et Phisique Photographique, Paul Mo
ntel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion)
Chemistry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions" by Zerikman et al., Published by Focal Press (VL
Zelikman et al., Making and Coating Photographic E
mulsion, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-5-142329).
No. 5-158124, U.S. Pat. No. 3,650,757). Further, the stirring method of the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type light-sensitive material, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, JP-A-3-110555).
No. 5-241267). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45833, JP-A-62-40446
Can be used. PH during chemical sensitization
Is preferably 5.3 to 10.5, more preferably 5.5.
To 8.5, and the pAg is preferably 6.0 to 10.
5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to give the photosensitive silver halide used in the present invention green, red, and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region.

The dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
Specific examples thereof include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828, and 5-45834. Can be These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,6
41, JP-A-63-23145).

These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,566. It may be before or after formation. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The additives used in such a step and the known photographic additives which can be used in the (heat-developable) light-sensitive material and the dye-fixing material of the present invention include the above-mentioned RDNo.
No. 18716 and No. 307105, and the corresponding portions are summarized in the following table.

Types of Additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866-868, super sensitizer ~ page 649, right column 4. Optical brightener page 24 page 648 right column page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer. 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, 頁 650, left column, ultraviolet absorbers. 7. Dye image stabilizer page 25 650 page left column page 872 8. Hardening agent page 26 page 651 left column 874-875 Binder page 26 page 651 left column pages 873 to 874 10. Plasticizer, lubricant page 27 page 650 right column page 876 11. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 12. Static, page 27, page 650, right column, pages 876-877 Inhibitors 13. Matting agent 878-879

(Heat development) A hydrophilic binder is preferably used for the constituent layer of the photosensitive material. Examples are the above-mentioned Research Disclosure and
Examples described on pages (71) to (75) of No. 4-13546 are mentioned. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also, superabsorbent polymers described in U.S. Pat. No. 4,960,681 and JP-A-62-245260,
That is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), a copolymer of the vinyl monomers, or a copolymer with another vinyl monomer (eg, sodium methacrylate, ammonium methacrylate) Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. The gelatin may be selected from lime-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 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.
Benzotriazoles, fatty acids and other compounds described in, for example, column Nos. 52 to 53 of 00,626. 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 salt is used in an amount of 0.01 per mole of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

In the (heat-developable) 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. Further, a compound capable of fixing a silver halide as described in JP-A-8-220694 can be used.

(Heat development) Examples of the hardening agent used in the constituent layers of the photosensitive material include the aforementioned Research Disclosure, US Pat. No. 4,678,739, column 41, and 4,791,0.
No. 42, JP-A-59-116655 and JP-A-62-245.
Nos. 261 and 61-18942, JP-A-42-180
No. 44 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), an N-methylol hardener (such as dimethylol urea), or a polymer hardener (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g per 1 g of gelatin applied.
g is used. The layer to be added may be any of the constituent layers of the light-sensitive material and the dye-fixing material, or may be added in two or more layers.

(Heat development) Various antifoggants or photographic stabilizers and precursors thereof can be used in the constituent layers of the photosensitive material. Specific examples thereof include the aforementioned Research Disclosure, US Pat.
9,378, 4,500,627, 4,61
No. 4,702, JP-A-64-13546 (7)-
Pages (9), (57)-(71) and (81)-(97),
U.S. Pat. Nos. 4,775,610 and 4,626,50
0, 4,983,494, JP-A-62-1747.
No. 47, No. 62-239148, No. 63-26474
7, JP-A-1-150135, JP-A-2-110557
No. 2-178650, RD17643 (1978)
Compounds described on pages (24) to (25) are exemplified. These compounds are preferably used in an amount of 5 × 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver.

(Heat development) Various surfactants can be used in the constituent layers of the photosensitive material for the purpose of coating aid, improvement of releasability, improvement of slipperiness, antistatic, acceleration of development, and the like. Specific examples of the surfactant are described in Research Disclosure, JP-A-62-173463, and 62-18345.
No. 7, etc. (Heat development) The constituent layers of the photosensitive material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-51-2094.
No. 4, 62-135825 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin. No.

(Heat development) A matting agent can be used in the photosensitive material for the purpose of preventing adhesion, improving slipperiness, and making the surface non-glossy. Matting agents such as silicon dioxide, polyolefin or polymethacrylate are disclosed in JP-A-61-88.
JP-A Nos. 63-274944 and 63-2, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads, in addition to the compounds described on page 256 (29).
No. 74952. 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. Others (thermal development)
The constituent layers of the light-sensitive material may contain a thermal 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 (26)-
(32) page, JP-A-3-11338, JP-B-2-514
No. 96, etc.

An image formation accelerator can be used in the (thermal development) photosensitive material of the present invention. The image formation accelerator has a function of accelerating a redox reaction between a silver salt oxidizing agent and a reducing agent, accelerating a dye formation reaction, and the like. From a physicochemical function, a base or a base precursor, a nucleophilic compound, It is classified into a boiling organic solvent (oil), a thermal solvent, a surfactant, a compound having an interaction with silver or silver ions, and the like. 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.

In the photothermographic material of the present invention, various development terminators can be used for the purpose of always obtaining 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 undergoes 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-62-253159 (31)-
It is described on page (32).

(Heat development) As a method of exposing and recording an image on a photosensitive material, for example, a method of directly photographing a landscape or a person using a camera or the like, a method of passing through a reversal film or a negative film using a printer or a enlarger, or the like. A method of exposing, a method of scanning and exposing an original image through a slit or the like by using an exposing device of a copying machine, a method of causing image information to emit a light emitting diode, various lasers (laser diode, gas laser, etc.) via an electric signal, etc. Scanning exposure method (JP-A-2-129625, 5-1761)
No. 44, No. 5-199372, No. 6-127022), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., directly or through an optical system. Exposure method.

(Heat development) As the light source for recording an image on a photosensitive material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., US Pat. No. 4,500,626, column 56 JP-A-2-
Light sources and exposure methods described in JP-A-53378 and JP-A-2-54672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate and potassium dihydrogen phosphate (KDP). ), Inorganic compounds such as lithium iodate, BaB ₂ O ₄ , urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivatives, JP-A-61-53462 and JP-A-62-2104
The compound described in No. 32 is preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. In addition, the image information includes an image signal obtained from a video camera, an electronic still camera, and the like, and the Nippon Television Signal Standard (NTT).
SC), an image signal obtained by dividing an original image into a large number of pixels such as a scanner, and an image signal created using a computer such as CG and CAD can be used.

The photothermographic material of the present invention may have a form having a conductive heating layer as a heating means for heat development. In this case, the heat generating element is disclosed in JP-A-61-1.
No. 45544 can be used. The heating temperature in the heat development step is about 80 ° C. to 180 ° C., and the heating time is 0.1 second to 60 seconds.

As a heating method in the developing step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heated roller, a heated drum, a halogen lamp heater, an infrared or far infrared lamp heater, or the like is contacted. Or passing through a high-temperature atmosphere. A method of superposing a photothermographic material and a dye fixing material is described in JP-A-62-253159 and JP-A-61-1472.
The method described on page 44 (27) can be applied.

As the support for the light-sensitive material of the present invention, those known in the art, in particular, as the support for the photothermographic material can be used. Examples of such a support include a paper support laminated with polyethylene, a polyester support represented by polyethylene terephthalate and polyethylene naphthalate, and the like. An example of such a support is disclosed in JP-A-63-18986.
No. 0 has a detailed description.

As the support for the light-sensitive material of the present invention, in addition to those described above, a support obtained by stretching a styrenic polymer having a syndiotactic structure can be preferably used. This polymer support is similar to that described above,
It may be a homopolymer or a copolymer. Such a polymer support is described in detail in JP-A-8-220694.

[0105]

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

Example 1 <Preparation of photosensitive silver halide emulsion> Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] A well-stirred gelatin aqueous solution (16 g of gelatin in 540 ml of water, Solution (1) and solution (2) in Table 1 were simultaneously added to 0.24 g of potassium, 1.6 g of sodium chloride and 24 mg of compound (a) and heated to 55 ° C.).
Add at an equal flow rate for minutes. Five minutes later, solution (3) and solution (4) in Table 1 were simultaneously added at an equal flow rate for 24 minutes. After washing with water and desalting by a conventional method, lime-treated ossein gelatin 17.
6 g and 56 mg of compound (b) were added to adjust the pH to 6.2 and p.
Ag was adjusted to 7.7, 0.41 g of ribonucleic acid degradation product and 1.02 mg of trimethylthiourea were added, and the mixture was optimally chemically sensitized at 60 ° C. Thereafter, 4-hydroxy-6-methyl-
0.18 g of 1,3,3a, 7-tetrazaindene, 64 mg of the sensitizing dye (c), and 0.41 g of potassium bromide were sequentially added, and the mixture was cooled. Thus, 590 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0107]

[Table 1]

[0108]

Embedded image

Photosensitive silver halide emulsion (2) [for green-sensitive emulsion layer] A well-stirred aqueous gelatin solution (20 g of gelatin, 0.30 g of potassium bromide, 2.0 g of sodium chloride and compound (a) in 600 ml of water) ) 30 mg was added and heated to 46 ° C).
Add at an equal flow rate for minutes. After 5 minutes, solutions (3) and (4) in Table 2 were simultaneously added at an equal flow rate for 30 minutes. Also,
One minute after the completion of the addition of the solutions (3) and (4), 60 ml of a methanol solution of the sensitizing dye (including 360 mg of the sensitizing dye (d ₁ ) and 73.4 mg of the sensitizing dye (d ₂ )) was added all at once. . After washing with water and desalting (using a precipitant (e) at pH 4.0) using a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and the pAg to 7.6. 1.8 mg of sodium thiosulfate, 4-hydroxy-6-methyl-
180 mg of 1,3,3a, 7-tetrazaindene was added,
Optimal chemical sensitization at 60 ° C. Next, 90 mg of antifoggant (f), 70 mg of compound (b) and 3 ml of compound (g) as preservatives were added, and the mixture was cooled. Thus, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0110]

[Table 2]

[0111]

Embedded image

[0112]

Embedded image

Photosensitive silver halide emulsion (3) [for blue-sensitive emulsion layer] A well-stirred aqueous gelatin solution (31.6 g of gelatin, 2.5 g of potassium bromide, and 13 mg of compound (a) in 584 ml of water) (Additionally heated to 70 ° C.), the addition of the liquid (2) in Table 3 was started first, and 10 seconds later, the addition of the liquid (1) was started. Thereafter, the liquids (1) and (2) were added over 30 minutes. (2) Five minutes after the addition of the solution,
Addition of solution (4) was started, and 10 seconds later, addition of solution (3) was started. (3) Liquid is 27 minutes and 50 seconds, (4) Liquid is 2
Added over 8 minutes. After washing with water and desalting (using a precipitant (j) at pH 3.9) according to a conventional method, 24.6 g of lime-treated ossein gelatin and 56 mg of the compound (b) were added to adjust the pH to 6.1. The pAg was adjusted to 8.5, 0.55 mg of sodium thiosulfate was added, and the mixture was optimally sensitized at 65 ° C. Next, 0.35 g of a sensitizing dye (h), 56 mg of an antifoggant (i), and 2.3 ml of a compound (g) as a preservative were added, followed by cooling. Thus, 582 g of a monodispersed octahedral silver bromide emulsion having an average grain size of 0.55 μm was obtained.

[0114]

[Table 3]

[0115]

Embedded image

<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, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained.

<Method for Preparing Emulsified Dispersion of Coupler> Table 4
The oil phase component and the water phase component having the compositions shown in
Make a homogeneous solution at 0 ° C. The oil phase component and the water phase component were combined, and in a 1-liter stainless steel container, a dissolver with a disperser having a diameter of 5 cm provided a 10,000 rp.
m for 20 minutes. To this, warm water in an amount shown in Table 4 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0118]

[Table 4]

[0119]

Embedded image

[0120]

Embedded image

Using the thus obtained materials, a heat-developable color light-sensitive material 101 having a multilayer structure shown in Table 5 was produced.

[0122]

[Table 5]

Next, as shown in Table 6, photosensitive materials 102 to 116 having exactly the same composition as the photosensitive material 101 were prepared except that the developing agents of the first and third layers were changed. These samples were mounted on a light-sensitive material magazine of FUJIX PICTROSTAT 200 (manufactured by Fuji Photo Film Co., Ltd.), and B, G, and R filters whose concentrations were continuously changed were mounted on a slide enlarging unit. Heat-processed (at this time, the image receiving material is disclosed in
No. 54, an image receiving material containing a base generator was used). When the image receiving material was peeled off after the processing, clear color images of cyan, magenta and yellow were obtained corresponding to the filters exposed on the light-sensitive material side. Immediately after the treatment, the highest density part (Dmax) and the lowest density part (Dmax)
Table 7 shows the results of the measurement of (min) with an X-rite densitometer.

[0124]

[Table 6]

[0125]

Embedded image

[0126]

[Table 7]

From the results shown in Table 7, it can be seen that Dmax of the photosensitive materials 107 to 116 using the main agent of the present invention is significantly higher than those of the samples 101 to 106 using the main agent of the comparative example. Understand. From the above, the effect of the present invention is clear.

Example 2 Silver benzotriazole emulsion [organic silver salt] 28 g of gelatin and 13.2 g of benzotriazole were added to water 3
Dissolved in 00 ml. This solution was kept at 40 ° C. and stirred.
A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution.
Minutes. The pH of the silver benzotriazole emulsion was adjusted, allowed to settle, and excess salts were removed. Then pH
Was adjusted to 6.30 to obtain 400 g of a silver benzotriazole emulsion.

Using the silver benzotriazole emulsion thus obtained, a heat-developable color light-sensitive material 20 shown in Table 8 was used.
1 was produced.

[0130]

[Table 8]

[0131]

Embedded image

Next, as shown in Table 9, photosensitive materials 202 to 212 having exactly the same composition as 201 except that the developing agents of the first layer and the third layer were changed, respectively, were prepared. The B, G, and R wedges having continuously changed densities are passed through the photosensitive materials 201 to 212 formed as described above to pass through the wedges.
Exposure was performed at 00 lux for 1 second. This exposed sample is
The substrate was heated for 10 seconds while being closely attached to a heat drum heated to 30 ° C. so that the back surface was in contact therewith. After the processing, when the light-sensitive material was peeled off from the heat drum, cyan, magenta, and yellow color images corresponding to the B, G, and R filters were clearly obtained on the light-sensitive material. Table 10 shows the results obtained by measuring the highest density part (Dmax) and the lowest density part (Dmin) of this sample with an X-rite densitometer immediately after the treatment.

[0133]

[Table 9]

[0134]

[Table 10]

From the results shown in Table 10, in the same manner as in Example 1, compared with the light-sensitive materials 201 to 205 using the main agent of the comparative example,
It can be seen that Dmax greatly increased in the light-sensitive materials 206 to 212 using the main agent of the present invention, as in Example 1.
The effect of the present invention is clear from this embodiment.

[0136]

According to the present invention, a silver halide photographic material having a high maximum density and excellent discrimination can be obtained.

Claims (4)

[Claims] 1. A compound represented by the following general formula (1). Embedded image In the formula, A represents a hydroxyl group, a substituted or unsubstituted amino group, or a group capable of generating a hydroxyl group or an amino group by hydrolysis. R _{1 to} R ₄ are a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, Arylsulfonyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkoxycarbonyl group, aryl Represents an oxycarbonyl group, a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a ureido group, or a urethane group. R ₅ represents a pseudo aromatic ring group. 2. A silver halide photographic photosensitive material having at least a photosensitive silver halide, a binder and a reducing agent on a support, wherein at least one of the reducing agents is represented by the above general formula (1). A silver halide photographic material, which is a compound. 3. The compound according to claim 2, wherein R ₅ in the general formula (1) is a group represented by the following general formula (2).
The silver halide photographic light-sensitive material as described above. Embedded image In the formula, R _{6 to} R ₁₂ are a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an arylcarbonyl group, Alkylsulfonyl group, arylsulfonyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, alkoxy Represents a carbonyl group, an aryloxycarbonyl group, a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a ureido group, or a urethane group. Adjacent groups in the substituents of R _{6 to} R ₁₂ may be independently bonded to each other to form a ring. 4. R ₆ and / or R _{12 in the} general formula (2)
Is a substituent. 4. The silver halide photographic material according to claim 3, wherein