JP2000310841A - Silver halide color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cyan picture which is excellent in discrimination and hue due to heat developing and to obtain the cyan picture which is also excellent in hue in the process with the conventional color negative film developer as well by incorporating a specific coupler. SOLUTION: The coupler, which is expressed in a formular as a coupler, is incorporated in a heat developing photosensitive material having photosensitive silver halide, a binder, the coupler and a developing agent on a support. In the formular, R1 to R3 denote hydrogen atoms or substituent, X denotes a group separatable due to a coupling reaction with hydrogen atoms or a developing agent oxidant, R11 and R13 denote alkali groups, R12, R14 and R15 denote hydrogen or alkyl groups. Thus, the cyan picture, which is excellent in discrimination and hue due to heat developing and is also excellent in hue in the process with the conventional color negative film developer as well, is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material, and more particularly to a heat-developable color light-sensitive material capable of obtaining a cyan image excellent in hue.

[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 is still being vigorously studied.

[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. As heat-developable color light-sensitive materials, products such as Pictrography and Pictrostat have been sold by Fuji Photo Film Co., Ltd. In this simple rapid processing method, a color image is formed using a redox compound (hereinafter, referred to as a coloring material) linked to a preformed dye. On the other hand, as a color image forming method for a photographic light-sensitive material, a method utilizing a coupling reaction between a coupler and an oxidized developing agent is the most common, and a heat-developable color light-sensitive material employing this method is disclosed in US Pat. No. 761,270, No. 4,021,240
And JP-A-59-231439 and JP-A-60-12.
No. 8438, and in these patents, p-sulfonamidophenol is used as a developing agent. Coupling-type photosensitive materials are advantageous in terms of sensitivity compared to photosensitive materials using color materials because the coupler does not absorb in the visible region before processing, and can be used not only as printing materials but also as photographic materials It is thought that there is an advantage that it can be done.

[0004]

SUMMARY OF THE INVENTION From such a viewpoint,
Research on p-sulfonamidophenol-type developing agents has been further advanced, and EP-A-0,764.
No. 876 discloses a p-sulfonamidophenol type developing agent which gives a color image excellent in discrimination when incorporated in a photosensitive material. However, in the process of studying the development of a color negative photographic material for thermal development, if a naphthol cyan coupler used in a conventional color negative photographic material is used to obtain a cyan dye image, the absorption position of the formed dye is too long. It was found that the cyan color density was insufficient. In order to solve this problem, a cyan coupler described in Japanese Patent No. 2779728 as a cyan coupler having excellent heat resistance and hue of a dye is used in a photothermographic material.
No. 94. On the other hand, a color negative film for thermal development is processed by a development process using a conventional developer for a color negative film (for example, C-41 processing by Eastman Kodak Company, CN-16 processing by Fujifilm Corporation). An attempt was made in Japanese Patent Laid-Open No. 9-27.
4295 is disclosed in the embodiment. However, when the photothermographic material using the coupler described in JP-A-8-122994 is treated with a conventional developing solution for a color negative film, the dye formed from the cyan coupler has a large side absorption in the blue light region. A problem arose.

[0005] Therefore, when used in combination with a p-sulfonamidophenol developing agent, a cyan image having a preferable hue is obtained at a high density, and when a developing process using a conventional developing solution for a color negative film is carried out, As a result of intensive studies on the molecular design of a cyan coupler that gives a cyan image having a preferable hue, it was found that the coupler represented by the following general formula (1) of the present invention is effective in solving this problem.

(Object of the Invention) It is an object of the present invention to provide a cyan image having excellent discrimination and excellent hue by heat development, and excellent hue even when processed with a conventional developing solution for a color negative film. An object of the present invention is to provide a heat-developable color light-sensitive material that gives a cyan image.

[0007]

The object of the present invention has been attained by the following means. [1] A silver halide color light-sensitive material comprising a coupler represented by the following general formula (1). General formula (1)

[0008]

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In the formula, R _{1 to} R ₃ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group which can be removed by a coupling reaction with an oxidized developing agent. R ₁₁ and R ₁₃ represent an alkyl group, and R ₁₂ , R ₁₄ and R ₁₅ represent a hydrogen atom or an alkyl group. [2] In a heat-developable color light-sensitive material having at least a photosensitive silver halide, a binder, a coupler and a developing agent on a support, the coupler contains a coupler represented by the general formula (1) as described in the above item 1 as the coupler. A heat-developable color light-sensitive material, comprising: [3] The heat-developable color light-sensitive material as described in [2] above, comprising a compound represented by the following general formula (2) as a developing agent. General formula (2)

[0010]

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In the formula, R _{21 to} R ₂₄ represent a hydrogen atom or a substituent, and represent a group having a total Hammett substituent constant σ _p value of 0 or more. R ₂₅ represents an aryl group.

The coupler represented by the general formula (1) will be described in detail below. In the coupler represented by the general formula (1), R ₁ represents a hydrogen atom or a substituent. Specifically, R ₁ represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group ( A straight-chain, branched or cyclic alkyl group preferably having 1 to 32 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl, tridecyl,
Cyclopropyl, cyclopentyl, cyclohexyl, 1
-Norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 32 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 32 carbon atoms) For example, phenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably a 5- to 8-membered heterocyclic group having 1 to 32 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2
-Benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), a cyano group, a silyl group (preferably a silyl group having 3 to 32 carbon atoms, for example, trimethylsilyl, triethylsilyl, tocibutylsilyl, t- Butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 32 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t -Butoxy, dodecyloxy,
A cycloalkyloxy group, for example, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 32 carbon atoms, for example, phenoxy, 2-naphthoxy),

A heterocyclic oxy group (preferably having 1 to carbon atoms)
32 heterocyclic oxy groups, for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy), silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, for example, trimethylsilyl Oxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy group (preferably an acyloxy group having 2 to 32 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), alkoxycarbonyloxy group (preferably Is an alkoxycarbonyloxy group having 2 to 32 carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), aryl An oxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms such as phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 32 carbon atoms such as N, N- Dimethylcarbamoyloxy,

N-butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy ), An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 32 carbon atoms, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), an arylsulfonyloxy (preferably an aryl having 6 to 32 carbon atoms) A sulfonyloxy group, for example, phenylsulfonyloxy), an acyl group (preferably an acyl group having 1 to 32 carbon atoms, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexylcarbonyl), alkoxycarbonyl (Preferably 2 carbon atoms
32 alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl),

An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms such as phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 32 carbon atoms such as carbamoyl, N, N -Dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having 32 or less carbon atoms, for example,
Amino, methylamino, N, N-dioctylamino, tetradecylamino, octadecylamino, cyclohexylamino), anilino group (preferably anilino group having 6 to 32 carbon atoms, for example, anilino, N-methylanilino), heterocycle An amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, for example, 4-pyridylamino);
A carbonamide group (preferably a carbonamide group having 2 to 32 carbon atoms, for example, acetamido, benzamido,
Tetradecanamide), a ureido group (preferably a ureido group having 1 to 32 carbon atoms, for example, ureido, N, N-
Dimethylureide, N-phenylureide), imide group (preferably an imide group having 10 or less carbon atoms, for example, N
-Succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 32 carbon atoms,

For example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino, an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms) , For example, phenoxycarbonylamino), a sulfonamide group (preferably having 1 carbon atom)
And sulfonic acid groups such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexylsulfonylamino) and sulfamoylamino group (preferably a sulfamoylamino group having 1 to 32 carbon atoms). So, for example,
N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms such as phenylazo), an alkylthio group (preferably having a carbon number of 1 to 32) 1 to 32 alkylthio groups such as ethylthio, octylthio,
Cyclohexylthio), an arylthio group (preferably an arylthio group having 6 to 32 carbon atoms, for example, phenylthio),

A heterocyclic thio group (preferably having 1 to 3 carbon atoms)
2 heterocyclic thio groups, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), alkylsulfinyl group (preferably having 1 to 1 carbon atoms)
32 alkylsulfinyl groups, for example, dodecanesulfinyl), arylsulfinyl (preferably 6 to 32 carbon atoms, for example, phenylsulfinyl), alkylsulfonyl groups (preferably 1 to 32 carbon atoms, alkylsulfonyl groups) So, for example,
Methylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably an arylsulfonyl group having 6 to 32 carbon atoms, for example, phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms) For example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to carbon atoms)
And 32 represents a phosphonyl group, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), and phosphinoylamino group (diethoxyphosphinoylamino, dioctyloxyphosphinoylamino group).

In the coupler represented by the formula (1), R ₂ and R ₃ represent groups having the same meaning as R ₁ . R _{1 to} R
_{When the} group represented by ₃ is a further substitutable group, R ₁
Groups represented by to R ₃ may further have a substituent, preferable substituent is a group having the same meaning as the substituent represented by R _1.

[0019] In general formula couplers represented by (1), R ₁₁ and R ₁₃ represents an alkyl group, preferably a carbon number and specific examples of the alkyl group represented by R ₁₁ and R ₁₃ are R ₁
Are the same as those described in the description of the alkyl group represented by. In the coupler represented by the general formula (1), R ₁₂ ,
R ₁₄ and R ₁₅ represent a hydrogen atom or an alkyl group,
The preferred number of carbon atoms and specific examples of the alkyl group represented by R ₁₂ , R ₁₄ or R ₁₅ are the same as those described for the alkyl group represented by R ₁ .

In the coupler represented by the general formula (1), X represents a hydrogen atom or a group which can be removed by a coupling reaction with an oxidized developing agent. Groups which can be removed by a coupling reaction with an oxidized developing agent include a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group, a cycloalkyloxycarbonyloxy group, and an aryloxycarbonyloxy group. A carbamoyloxy group, a sulfamoyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a carbonamide group, a sulfonamide group, a heterocyclic group, an arylazo group, an alkylthio group,
It represents an arylthio group, a heterocyclic thio group or the like, and the preferred carbon number and specific examples of these groups are the same as those described for the group represented by R ₁ .

X may be a bis-type coupler in which two equivalents of four-equivalent couplers are bonded via an aldehyde or ketone, and X may be a development accelerator, a development inhibitor,
It may be a photographically useful group such as a desilvering accelerator or a leuco dye or a precursor thereof. Preferred groups which can be removed by a coupling reaction with an oxidized developing agent are Research Disclosure Nos. 37038 (1995
And the leaving groups of the couplers described in pages 86 to 88 of the development inhibitor releasing coupler described on pages 80 to 84 of the same publication.

Next, a preferred range of the coupler represented by the general formula (1) will be described. R ₁ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group, and more preferably an aryl group and a heterocyclic group.
R ₂ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylsulfonyl group, and an aryl group. Sulfonyl groups are preferred, and amino groups, carbonamido groups, ureido groups, alkoxycarbonylamino groups, alkylthio groups, and arylthio groups are more preferred. R ₃ is preferably a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, and an arylsulfonyl group, and is preferably a hydrogen atom, a halogen atom, an alkyl group, or a carbamoyl group. Groups are more preferred. X is preferably a hydrogen atom, a halogen atom, a heterocyclic group, an aryloxy group, an alkylthio group, an arylthio group, and a heterocyclic thio group, and more preferably a hydrogen atom and a chlorine atom. R ₁₁ and R ₁₃ are preferably a methyl group, an isopropyl group, a t-butyl group, a s-butyl group, a t-amyl group, a cyclohexyl group, and a 1,1,3,3-tetramethylbutyl group, and a t-butyl group Is most preferred. R ₁₂ and R ₁₄ are preferably a hydrogen atom or a methyl group,
Hydrogen atoms are most preferred. R ₁₅ is a hydrogen atom, a methyl group,
Ethyl, isopropyl, t-butyl, s-butyl, t-amyl, cyclohexyl, and 1,1,
A 3,3-tetramethylbutyl group is preferred, and a methyl group is most preferred.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

[0024]

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[0025]

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[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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The coupler of the present invention represented by the general formula (1) can be synthesized according to the method described in JP-A-5-232648. Hereinafter, specific synthesis examples of the coupler of the present invention will be described. Synthesis Example 1 (Synthesis of Exemplified Compound C-9) Exemplified Compound C-9 could be synthesized according to the following scheme. (Synthesis of Intermediate A-2)

[0035]

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457 g (2.00 mol) of 2,6-di-tert-butyl-4-methylcyclohexanol (intermediate A-1) and 187 g of cyanoacetic acid described in JP-A-8-12609.
(2.20 mol) was added to 1300 ml of toluene and stirred at room temperature. After adding 174 ml of pyridine and stirring for 10 minutes, 622 ml of acetic anhydride was added dropwise over about 1.5 hours. After stirring for 1.5 hours, it was left overnight. To the reaction mixture, 500 ml of water was added dropwise over about 30 minutes, and then 200 g of sodium bicarbonate was added little by little over 1 hour. 1000 ml of ethyl acetate was added to the reaction mixture, and the mixture was washed twice with 1500 ml of water containing 150 g of sodium bicarbonate. The organic layer is concentrated under reduced pressure,
The residue was dissolved by adding 2000 ml of methanol. After adding seed crystals and stirring at room temperature for 1.5 hours, 400 ml of water was added and stirring was continued for 2 hours. The precipitated crystals are collected by filtration, washed with a mixed solvent of methanol and water (5/1), and air-dried.
76 g (yield 82%) of intermediate A-2 was obtained.

(Synthesis of Intermediate A-4)

[0038]

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Intermediates A-3, 4 obtained from commercially available 2,4'-dichloroacetophenone and potassium phthalimide
8.5 g (0.162 mol) and Intermediate A-2, 48.5 g (0.162 mol)
Was added to 150 ml of ethanol, and the mixture was stirred at room temperature under a nitrogen stream. After adding 13.0 g (0.325 mol) of sodium hydroxide dissolved in 40 ml of water, the mixture was heated on a steam bath for 4 hours. 200 ml of water was added to the reaction mixture, the mixture was cooled with stirring, and the precipitated crystals were collected by filtration. The crystals were dissolved in 300 ml of ethyl acetate, washed with 250 ml of a saline solution, and the organic layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. 400 ml of hexane was added to the residue to disperse the crystals, which was collected by filtration and dried to obtain 57.0 g (yield 79).
%) Of intermediate A-4.

(Synthesis of Intermediate A-6)

[0041]

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11.5 g (63 mmol) of an intermediate A-5 obtained by reacting ethanol and hydrochloric acid gas with cyanoacetic acid was added to 60 ml of chloroform, stirred at room temperature, and 7.0 g (69 mmol) of triethylamine was added. And stirred for 20 minutes. This solution was concentrated on a rotary evaporator. Ethyl acetate (40 ml) was added to the residue, and insolubles (triethylamine hydrochloride) were filtered off. To the filtrate, 20 g (45 mmol) of intermediate A-4 and 100 ml of ethanol were added, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was concentrated on a rotary evaporator, and 200 ml of acetonitrile was added to the residue to disperse the crystals. The crystals were collected by filtration, dried and 22.6 g (yield 98%, based on Intermediate A-4)
Intermediate A-6 was obtained.

(Synthesis of Exemplified Compound C-9)

[0044]

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Intermediate A-6, 20.5 g (50 mmol), 10.5 ml (75 mmol) of triethylamine and 1.83 g (15 mmol) of 4-dimethylaminopyridine were added to 60 ml of N, N-dimethylacetamide, and the mixture was heated at 60 ° C. With stirring. 9.76 g (60 mmol) of 2-ethylhexanoyl chloride are added,
Stirred at 60 ° C. for 3 hours. After cooling, the reaction mixture was poured into 150 ml of ethyl acetate and washed with 150 ml of water containing 5 ml of concentrated hydrochloric acid, followed by 120 ml of brine. After the organic layer was dried over anhydrous magnesium sulfate, it was concentrated with a rotary evaporator. Hexane (150 ml) was added to the residue and dissolved by heating. The mixture was stirred at room temperature for crystallization, collected by filtration, and dried to obtain 19.5 g.
Exemplified compound C-9 (yield 61%) was obtained. _{^{1 HNMR (CDCl 3) δ (}} ppm) 10.15 (s, 1H), 7.36 (d, 2H), 7.30 (d, 2H), 5.
96 (s, 1H), 5.60 (s, 1H), 2.39 (m, 1H), 1.8-0.4 (m, 43
H)

Synthesis Example 2 (Synthesis of Exemplified Compound C-13) Exemplified Compound C-13 could be synthesized according to the following scheme.

[0047]

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9.57 g (15 mmol) of Exemplified Compound C-9 was added to 60 ml of ethyl acetate, and the mixture was once heated to 40 ° C. and stirred to dissolve. 2.1 g of N-chlorosuccinimide (15 g
mmol) and stirred at room temperature for 2 hours. The reaction solution was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and then concentrated using a rotary evaporator. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 5/1) to obtain 7.2 g (yield 71%) of Exemplified Compound C-13. ¹ H NMR (CDCl ₃ ) δ (ppm) 13.56 (brs, 1H), 8.13 (brs, 1H), 7.38 (d, 2
H), 7.30 (d, 2H), 5.96 (s, 1H), 2.35 (m, 1H), 1.9-0.5
(m, 43H)

Synthesis Example 3 (Synthesis of Exemplified Compound C-33) Exemplified Compound C-33 could be synthesized according to the following scheme.

[0050]

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8.5 g (13 mmol) of Exemplified Compound C-9 was added to 50 ml of ethyl acetate, and the mixture was dissolved by heating to 40 ° C. once,
The mixture was stirred for 3 hours while adding 6.9 g (51.6 mmol) of chlorosuccinimide in portions. Add ethyl acetoacetate to this.
1 g (39 mmol) and 5.5 ml (39 mmol) of triethylamine were added and stirred for 1.5 hours. The reaction solution was washed with 50 ml of water containing 5 ml of concentrated hydrochloric acid, then with 50 ml of a saline solution, and the organic layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 5 /
After purification in 1), crystallization from hexane gave 6.2 g (yield 67%) of Exemplified Compound C-33. ¹ H NMR (CDCl ₃ ) δ (ppm) 13.6 (m, 1H), 8.07 (s, 1H), 7.42 (d, 2H), 7.2
3 (d, 2H), 5.94 (s, 1H), 2.34 (m, 1H), 1.85-0.35 (m, 42
H)

The amount of the coupler represented by the general formula (1) of the present invention is about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ² , more preferably 0.01 to 10 mmol / m ² , as a coating amount. It is suitably about 0.05 to 5 mmol / m ² .

Next, the developing agent represented by the formula (2) will be described in detail. The compound represented by the general formula (2) is
It represents a developing agent generally called sulfonamidophenol. In the formula, R _{21 to} R ₂₄ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonamide group, an alkane sulfonamide group, an arenesulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyl group. Represents an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or an acyloxy group, and R ₂₅ represents a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group. Represents a group. The preferred carbon number and specific examples of these groups are the same as those described for the group represented by R ₁ . Especially R ₂₁
To R ₂₄ are a hydrogen atom, a halogen atom, an alkyl group, a carbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an aryl Sulfonyl, acyl and alkoxycarbonyl groups are preferred. R ₂₁
Among to R _24, R ₂₂ and R ₂₄ are preferably hydrogen atoms. The sum of Hammett σ _P values of R _{21 to} R ₂₄ is 0
The sum of the Hammett σ _p values of R _{21 to} R ₂₄ is preferably 0.2 or more. The upper limit is preferably 1.2, and more preferably 0.8. When the group represented by R _{21 to} R ₂₄ is a substitutable group, it may further have a substituent, and preferred examples of the substituent are the same as those described as R ₁ .

R_{twenty five}Represents an aryl group, particularly
As represented by (3), R₂₆~ R ₃₀Substituted with a substituent
Aryl groups are preferred. General formula (3)

[0055]

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R _{26 to} R ₃₀ in the general formula (3) represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. Group, an arylthio group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an acyl group, and the preferred carbon number and specific examples of these groups are R ₁ Are the same as those described in the description of the group represented by. It is preferable that R ₂₆ and / or R ₃₀ have a substituent other than a hydrogen atom. R ₂₆
And R ₂₇ or R ₂₉ and R ₃₀ may combine with each other to form a ring. May further have a substituent group when the group represented by R ₂₆ to R ₃₀ is a substitutable group, preferred examples of the substituent are the same as those exemplified as R _1.

The compound represented by the general formula (2) is preferably an oil-soluble compound for use in the purpose of the present invention. Therefore, it is preferable that at least one group having a ballast property is included. The ballast group as used herein refers to an oil-solubilizing group, and is a group containing an oil-soluble partial structure having 8 to 80 carbon atoms, preferably 10 to 40 carbon atoms. Therefore, in the R ₂₁ to R _24, it is preferable either having 8 or more ballast group carbon, or the total number of carbon atoms of R ₂₆ to R ₃₀ is 8 or more. The total number of carbon atoms in R _{26 to} R ₃₀ is preferably from 8 to 80, more preferably from 8 to 20.
It is.

Hereinafter, specific examples of the compound represented by formula (2) are shown, but the compounds of the present invention are not limited thereto.

[0059]

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[0060]

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[0061]

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[0062]

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The developing agent represented by the general formula (2) can be synthesized by a known method described in JP-A-9-146248.

The addition amount of the developing agent represented by the general formula (2) has a wide range.
It is suitably from 0.1 to 100 mol times, more preferably from 0.1 to 10 mol times.

As a method for adding the coupler represented by the general formula (1) and the developing agent represented by the general formula (2), first, the coupler, the developing agent and a high-boiling organic solvent (for example, alkyl phosphate, phthalate, An acid alkyl ester, etc.) can be mixed and 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.
Further, addition by the solid dispersion method described in JP-A-63-271339 is also possible.

The couplers represented by the general formula (1) of the present invention are described in JP-A-8-286340, JP-A-9-152700, JP-A-9-152701, JP-A-9-152702, and JP-A-9-152702.
Nos. 52703, 9-152704, and 9-21
It may be used for a photosensitive material containing a hydrazine type developing agent described in No. 1818. When used in combination with these developing agents, the substituent X of the coupler represented by the general formula (1) of the present invention is preferably a removable group other than a hydrogen atom. Specific examples of typical hydrazine-type developing agents are shown below.

[0067]

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[0068]

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Further, the coupler represented by the general formula (1) of the present invention is a Research Disclosure No. 37038
(February 1995), pp. 103, 110, and 111 may be used as a photosensitive material for forming an image by developing with a developing solution containing a developing agent. The structure of a typical developing agent is shown below.

[0070]

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The heat-developable color light-sensitive material of the present invention basically comprises a support having a photosensitive silver halide, a coupler as a dye-providing compound, a reducing agent, and a binder. A metal oxidizing agent or 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. Examples of such a base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement. For this example, see U.S. Pat. Nos. 4,514,493 and 46.
No. 57848 and the like.

In the case of using a form in which 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. In this case, heating may be performed with a small amount of solvent (such as water) contained between the photosensitive material and the processing sheet. The method for applying the solvent will be described later. As the solvent, a polar liquid, particularly water, is preferred.

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 of the light-sensitive material of the present invention, in addition to those described above, a support obtained by stretching a styrene 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 Japanese Patent Application No. 7-45079.

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. Further, a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodisperse or polydisperse.
As described in JP-A Nos. 7,743 and 4-223,463, a method of mixing monodispersed emulsions and adjusting gradation is preferably used. The particle size is 0.1-2 μm, especially 0.2-
1.5 μm is preferred. 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 tabular shapes having a high aspect ratio, 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. 4,500,626 No. 50
No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,029 (1
No. 17,643 (December 1978)
Nos. 18,716 (November 11, 1979)
No. 307, 105 (November 1989)
Mon.) pp.863-865, JP-A-62-253,159.
No. 64-13,546, JP-A-2-236,54
No. 6, No. 3-110, 555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (F. Glafk)
ides, Chemie et Phisique Photographique, Paul Mont
el, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsio).
n 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 Photog).
Raphic Emulsion, Focal Press, 1964) and the like can be used.

Particularly for tabular silver halide grains,
Hexagonal and rectangular tabular grains can be used. Among them, the tabular grains having an aspect ratio of 2 or more, preferably 8 or more, more preferably 20 or more, which is a value obtained by dividing the grain projected diameter by the grain thickness, can be used. Is preferably 50% or more, preferably 8% or more of the projected area of all the grains in such tabular grains.
It is preferable to use an emulsion occupying 0% or more, more preferably 90% or more. The thickness of these tabular grains is preferably 0.3 μm or less, more preferably 0.2 μm or less,
Most preferably, it is 0.1 μm or less.

Also, US Pat. No. 5,494,789,
No. 5,503,970, No. 5,503,971, No. 5,536,632, etc., the particle thickness is smaller than 0.07 μm, and particles having a higher aspect ratio can also be preferably used. . Also, U.S. Pat.
00,463, 4,713,323, 5,21
No. 7,858, and the like, high silver chloride tabular grains having a (111) plane as a main plane, and US Pat.
Nos. 64,337, 5,292,632, 5,31
High silver chloride tabular grains having a (100) plane as a main plane described in JP-A-0,635 or the like can also be preferably used. Examples in which these silver halide grains are actually used are described in JP-A-9-274295, JP-A-9-319047 and JP-A-9-319047.
Nos. 0-115888 and 10-2221827. The silver halide grains are preferably so-called monodisperse grains having a uniform grain size distribution. As a measure of monodispersity, the coefficient of variation obtained by dividing the standard deviation of the particle size distribution by the average particle size is preferably 25% or less, and more preferably 20% or less. It is also preferable that the halogen composition is uniform among the grains. In the silver halide grains, the halogen composition in the grains may be made uniform, or a site having a different halogen composition may be intentionally introduced. Particularly, in order to obtain high sensitivity, grains having a laminated structure composed of a core (nucleus) and a shell (shell) having different halogen compositions are preferably used. It is also preferable to further grow the grains after introducing a region having a different halogen composition to intentionally introduce dislocation lines. Further, it is also preferable that guest crystals having different halogen compositions are epitaxially bonded to the apexes and ridges of the formed host grains.

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 water washing method in which gelatin is gelled may be used, and inorganic salts composed of polyvalent anions (for example, sodium sulfate), an anionic surfactant, and an anionic polymer (for example, polystyrene sulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. 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, the emulsions described in JP-A-2-236542, JP-A-1-116637 and JP-A-5-181246 are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a tetra-substituted thioether compound or JP-B-47-1
Organic thioether derivatives described in 1,386 or sulfur-containing compounds described in JP-A-53-144,319 can be used.

For other conditions, see the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (F.G.
lafkides, Chemie et Phisique photographique, Paul
Montel, 1967), Duffin's "Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emul)
sion 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 Phot).
For example, reference may be made to descriptions such as ographic Emulsion, 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 with a soluble halogen salt may be any of a one-side 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 the 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 concentration, amount and rate of silver salt and halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-158, JP-A-55-142329). 124, U.S. Pat. No. 3,650,575). Further, the stirring method of the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, 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, see JP-A-3-11055).
No. 5, No. 5-241267). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253,159). Further, a fogging inhibitor described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833, JP-A-62-40,
No. 446 can also be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 1.
0.5, more preferably 6.8 to 9.0. 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 impart green, red and infrared sensitivity to the photosensitive silver halide used in the present invention, 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. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat.
Sensitizing dyes described in JP-A-617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. 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. 615,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. 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 from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

The additives used in these steps and known photographic additives which can be used in the light-sensitive material and the processing sheet of the present invention are described in RD Nos. 17, 643 and 1 above.
No. 8,715 and Nos. 307, 105, 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 absorber, pages 25 to 26, page 649, right column, page 873, filter dye, 頁 650, left column, ultraviolet absorber 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 873-874 10. Plasticizer, lubricant page 27 page 650 right column page 876 11. Coating aid, page 26-27 page 650 right column pages 875-876 Surfactant 12. 12. Static prevention, page 27, page 650, right column, pages 876-877. Matting agent 878-879

As the binder for the constituent layers of the photosensitive material, hydrophilic binders are preferably used. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13 / 1988.
No. 546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, for example, gelatin, protein or cellulose derivative such as gelatin derivative, starch, gum arabic,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, and synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer. Also, U.S. Pat. No. 4,960,681,
No. 2-245260, etc., ie, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a vinyl monomer or another vinyl Copolymers with monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are 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 is preferably used 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.
There are benzotriazoles, fatty acids and other compounds described in 00,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above-mentioned organic silver 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 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 US Pat. No. 4,500,626, Nos. 51 to 51.
It is described in column 52. In addition, Japanese Patent Application No. 6-20633.
Compounds capable of fixing silver halide as described in No. 1 can also be used.

Examples of the hardener used in the constituent layers of the light-sensitive material include the aforementioned Research Disclosure, US Pat. No. 4,678,739, column 41, and 4,791,042.
JP-A-59-116,655 and JP-A-62-245,
No. 261, No. 61-18, 942, JP-A-4-21
Hardening agents described in JP-A-8,044 and the like can be mentioned. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), an N-methylol-based hardening agent (such as dimethylol urea), or a polymer hardening agent (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.001 g per g of gelatin applied.
5 to 0.5 g are used. The layer to be added may be any of the constituent layers of the light-sensitive material and the dye-fixing material.
It may be added in layers or more.

In the constituent layers of the light-sensitive material, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the aforementioned Research Disclosure, US Pat. No. 5,089,378.
Nos. 4,500,627 and 4,614,702
No., JP-A-64-13546, pages (7) to (9),
(57)-(71) and (81)-(97), U.S. Pat. Nos. 4,775,610 and 4,626,500.
No. 4,983,494, JP-A-62-174,7
No. 47, 62-239, 148, 63-264,
747, JP-A-1-150,135, 2-11
0,557, 2-178,650, RD17,6
43 (1978), pages (24) to (25). These compounds are present in 5 moles per silver mole.
X 10 ^-6 to 1 x 10 ^-1 mol is preferred, and 1 x 10
^-5 to 1 × 10 ^-2 mol is preferably used.

In the constituent layers of the photosensitive material, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, accelerating development and the like. Specific examples of surfactants are described in Research Disclosure,
2-173,463 and 62-183,457. The constituent layers of the photothermographic material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of the organic fluoro compounds include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, and JP-A-62-135826, and fluorine oils. And a hydrophobic fluorine compound such as a solid fluorine compound resin such as an tetrafluoroethylene resin.

The photosensitive material has anti-adhesion properties, improved slipperiness,
A matting agent can be used for the purpose of making a matte surface or the like. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 29, benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
No. 952. In addition, the compounds described in the aforementioned Research Disclosure can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, the constituent layers of the light-sensitive material may contain a heat solvent, an antifoaming agent, a germicide / antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3-11,338, and JP-B-2-51,496.

In the present invention, an image formation accelerator can be used in the light-sensitive material. The image formation accelerator has functions such as accelerating the oxidation-reduction reaction between the silver salt oxidizing agent and the reducing agent and accelerating the dye formation reaction. From the 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. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

In the present invention, various development terminators can be used in the photothermographic material 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 causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-253159 (3.
It is described on pages 1) to (32).

Examples of the method of exposing and recording an image on a photosensitive material include a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, Using a copier exposure device to scan and expose the original image through slits, etc., image information via electric signals, light emitting diodes, various lasers (laser diodes,
A method of performing scanning exposure by emitting light from a gas laser or the like (Japanese Unexamined Patent Application Publication No. 2-129625, 5-176144).
And the 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.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No. 4,500,626, column 56, natural light, tungsten lamp, light emitting diode, laser light source, CRT light source and the like, JP-A-2-53,37.
No. 8, No. 2-54, 672 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 expressing nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, potassium dihydrogen phosphate (K
DP), lithium iodate, BaB ₂ O _{4 and} other inorganic compounds, urea derivatives, nitroaniline derivatives,
For example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-53462 and JP-A-62-121032.
The compounds described in (1) are 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 Standards (NTS
A television signal represented by C), an image signal obtained by dividing an original image into a number of pixels such as a scanner, and an image signal created by using a computer represented by CG and CAD can be used.

When the light-sensitive material of the present invention is processed by heat development, the light-sensitive material may have a conductive heating layer as a heating means for heat development. In this case, the heat generating element described in JP-A-61-145544 can be used. The heating temperature in the thermal development process is about 80 ° C to 18 ° C.
0 ° C. and the heating time is 0.1 seconds 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 photosensitive material and a processing sheet is described in JP-A-62-253,159 and JP-A-61-147,244.
(27) can be applied.

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

[0104]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 Gelatin 0.74 having an average molecular weight of 15,000
930 ml of distilled water containing g and 0.7 g of potassium bromide
Was put into a reaction vessel, and the temperature was raised to 40 ° C. 30 ml of an aqueous solution containing 0.34 g of silver nitrate while vigorously stirring this solution
And 30 ml of an aqueous solution containing 0.24 g of potassium bromide
Added in 0 seconds. After maintaining the temperature at 40 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was raised to 75 ° C. Gelatin 2
After adding 7.0 g together with 200 ml of distilled water, silver nitrate 2
100 ml of an aqueous solution containing 3.36 g and potassium bromide 1
80 ml of an aqueous solution containing 6.37 g was added over a period of 36 minutes while increasing the addition flow rate. Then silver nitrate 8
The addition of 250 ml of an aqueous solution containing 3.2 g and an aqueous solution containing potassium iodide at a molar ratio of 3:97 to potassium bromide (concentration of potassium bromide: 26%) was accelerated, and the silver potential of the reaction solution was increased. It was added for 60 minutes so as to be -20 mV with respect to the saturated calomel electrode. Furthermore, silver nitrate 18.7
g and an aqueous solution of 21.9% potassium bromide were added over 10 minutes so that the silver potential of the reaction solution became 20 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 40 ° C. Next, 100 ml of an aqueous solution containing 10.5 g of sodium p-iodoacetamidobenzenesulfonate monohydrate was added to adjust the pH of the reaction solution to 9.0. Next, 50 ml of an aqueous solution containing 4.3 g of sodium sulfite was added. After completion of the addition, the temperature was maintained at 40 ° C. for 3 minutes, and then the temperature of the reaction solution was increased to 55 ° C. PH of reaction solution
Was adjusted to 5.8, 0.8 mg of sodium benzenethiosulfinate, 0.04 mg of potassium hexachloroiridate (IV) and 5.5 g of potassium bromide were added, and the mixture was kept at 55 ° C. for 1 minute. 0.3g
And 180 ml of an aqueous solution containing 34.0 g of potassium bromide and 8.9 mg of potassium hexacyanoferrate (II) were added over 30 minutes. The temperature was lowered and desalting was performed according to a standard method. After completion of desalting, gelatin was added so as to be 7% by weight, and the pH was adjusted to 6.2. The resulting emulsion was a hexagonal flat plate having an average particle size of 1.29 μm expressed as a diameter equivalent to a sphere, an average particle thickness of 0.27 μm, and an average aspect ratio, which is a ratio obtained by dividing the projected particle diameter by the particle thickness, of 8.5. This was an emulsion consisting of like particles. This emulsion was designated as emulsion A-1.

From the emulsion A-1, by changing the amounts of silver nitrate and potassium bromide added at the beginning of the grain formation and changing the number of nuclei formed, the average grain size represented by a diameter equivalent to a sphere was 0.75 μm. An emulsion composed of hexagonal tabular grains having an average grain thickness of 0.18 μm and an average aspect ratio of 6.9 was prepared by A-
2, and an average particle size of 0.52 expressed by a diameter equivalent to a sphere.
A-3, an emulsion composed of hexagonal tabular grains having an average grain thickness of 0.18 μm and an average aspect ratio of 4.0 was designated as A-3, and an average grain size of 0.44 μm represented by a diameter equivalent to a sphere,
Each emulsion was prepared as A-4, which was composed of hexagonal tabular grains having an average grain thickness of 0.18 μm and an average aspect ratio of 3.1. However, the addition amounts of potassium hexachloroiridate (IV) and potassium hexacyanoferrate (II) are inversely proportional to the particle volume, and the addition amount of sodium p-iodoacetamidobenzenesulfonate monohydrate depends on the particle circumference. It was changed in proportion.

Next, 930 ml of distilled water containing 0.37 g of gelatin having an average molecular weight of 15,000, 0.37 g of oxidized gelatin and 0.7 g of potassium bromide was placed in a reaction vessel, and the temperature was raised to 40 ° C. To this solution, 30 ml of an aqueous solution containing 0.34 g of silver nitrate and 30 ml of an aqueous solution containing 0.24 g of potassium bromide were added over 20 seconds with vigorous stirring. After maintaining the temperature at 40 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was raised to 75 ° C. After adding 27.0 g of gelatin whose amino group was modified with trimellitic acid together with 200 ml of distilled water, 100 ml of an aqueous solution containing 23.36 g of silver nitrate and 80 ml of an aqueous solution containing 16.37 g of potassium bromide were added for 36 minutes while accelerating the addition flow rate. Over a period of time. Then, 250 ml of an aqueous solution containing 83.2 g of silver nitrate and an aqueous solution containing potassium iodide at a molar ratio of 3:97 to potassium bromide (concentration of potassium bromide: 26%) were added at an accelerated flow rate, and the silver in the reaction solution was increased. It was added for 60 minutes so that the potential became -50 mV with respect to the saturated calomel electrode. Further, 75 ml of an aqueous solution containing 18.7 g of silver nitrate and a 21.9% aqueous solution of potassium bromide were added over 10 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 40 ° C. Then, sodium p-iodoacetamidobenzenesulfonate monohydrate 10.5
100 ml of an aqueous solution containing g was added to adjust the pH of the reaction solution to 9.0. Then 4.3 g of sodium sulfite
Was added. After completion of addition, 40 ° C
, And the temperature of the reaction solution was raised to 55 ° C. After adjusting the pH of the reaction solution to 5.8, 0.8 mg of sodium benzenethiosulfinate, 0.04 mg of potassium hexachloroiridate (IV), and 5.
5 g, and kept at 55 ° C. for 1 minute.
180 ml of an aqueous solution containing 4.3 g and potassium bromide
0 g and potassium hexacyanoferrate (II) 8.9 mg
160 ml of an aqueous solution containing was added over 30 minutes. The temperature was lowered and desalting was performed according to a standard method. After completion of desalting, gelatin was added so as to be 7% by weight, and the pH was adjusted to 6.2.

The obtained emulsion had an average grain size of 1.29 μm and an average grain thickness of 0.13 μm expressed by a diameter equivalent to a sphere.
The emulsion was composed of hexagonal tabular grains having an average aspect ratio of 25.4. This emulsion was designated as Emulsion A-5. Emulsion A-
By changing the amounts of silver nitrate and potassium bromide added at the beginning of the grain formation and changing the number of nuclei formed, the average grain size expressed as a sphere-equivalent diameter is 0.75 μm and the average grain thickness is 0.1. An emulsion composed of hexagonal tabular grains having an average aspect ratio of 14.0 and an average aspect ratio of 14.0 was designated as A-6. The average grain size was 0.52 μm, the average grain thickness was 0.09 μm, and the average aspect ratio was 11.3. The emulsion composed of hexagonal tabular grains of A-7 was designated as A-7, and had an average grain size of 0.44 μm and an average grain thickness of 0.04 expressed by a diameter equivalent to a sphere.
An emulsion composed of hexagonal tabular grains having an average aspect ratio of 10.5 and an average aspect ratio of 10.5 was designated as A-8, and each emulsion was prepared. However, the addition amounts of potassium hexachloroiridate (IV) and potassium hexacyanoferrate (II) are inversely proportional to the particle volume, and the addition amount of sodium p-iodoacetamidobenzenesulfonate monohydrate depends on the particle circumference. It was changed in proportion. After adding 5.6 ml of a 1% aqueous solution of potassium iodide to emulsion A-1 at 40 ° C., 6.1 × 10 ⁻⁴ mol of the following spectral sensitizing dye, compound I, potassium thiocyanate, chloroauric acid , Sodium thiosulfate and mono (pentafluorophenyl) diphenylphosphine selenide were added for spectral and chemical sensitization. After completion of the chemical sensitization, 1.2 × 10 ^-4 mol of a stabilizer S was added. At this time, the amount of the chemical sensitizer was adjusted so that the degree of chemical sensitization of the emulsion was optimized.

[0108]

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The blue-sensitive emulsion thus prepared was designated as A-1b. Similarly, each emulsion was subjected to spectral sensitization and chemical sensitization to prepare emulsions A-2b, A-3b, A-4b, A-5b and A-6b. However, the addition amount of the spectral sensitizing dye was changed according to the surface area of the silver halide grains in each emulsion. The amounts of each chemical used for chemical sensitization were also adjusted so that the degree of chemical sensitization of each emulsion was optimized. Similarly, green-sensitive emulsions A-1g and A-2 were obtained by changing the spectral sensitizing dye.
g, A-3g, A-4g, A-5g, A-6g, A-7
g and A-8g, red-sensitive emulsions A-1r, A-2r, A
-3r, A-4r, A-5r, A-6r, A-7r and A-8r were prepared.

[0110]

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[0111]

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Next, a dispersion of zinc hydroxide used as a base precursor was prepared. The particle size of the primary particles is 0.
31 g of 2 μm zinc hydroxide powder, 1.6 g of carboxymethylcellulose and 0.4 g of sodium polyacrylate as a dispersant, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed, and the mixture was mixed with glass beads. Dispersed in the mill for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

Further, an emulsified dispersion containing a coupler and a built-in developing agent was prepared. Yellow coupler (a)
8.95 g, developing agent (b) 7.26 g, (c) 1.4
7g, antifoggant (d) 0.17g, (e) 0.28
g, 18.29 g of a high boiling point organic solvent (d) and 50.0 ml of ethyl acetate were dissolved at 60 ° C. The above solution was mixed with 200 g of an aqueous solution in which 18.0 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and the solution was stirred at 10,000 rpm using a dissolver stirrer.
Emulsified and dispersed over 0 minutes. After the dispersion, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

[0114]

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[0115]

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Next, a dispersion of a magenta coupler and a cyan coupler was similarly prepared. 7.65 g of magenta coupler (g), 1.12 g of (h), developing agent (i)
8.13 g, (c) 1.05 g, antifoggant (d) 0.
11 g, 7.52 g of a high boiling point organic solvent (j) and 38.0 ml of ethyl acetate were dissolved at 60 ° C. The above solution was mixed with 150 g of an aqueous solution in which 12.2 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. After dispersion, the total amount is 300 g
And distilled water was added at 2,000 rpm for 10 minutes. 6.55 g of cyan coupler (k), 8.23 g of developing agent (i), 1.06 g of (c), 0.15 g of antifoggant (d), 8.27 g of high boiling organic solvent (j) and ethyl acetate. 0 ml was dissolved at 60 ° C. The above solution was mixed with 150 g of an aqueous solution in which 12.2 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved.
Emulsification and dispersion were performed at 00 rpm for 20 minutes. After the dispersion, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

[0117]

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[0118]

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Further, a dispersion of a dye for coloring the intermediate layer as a filter layer and an antihalation layer was prepared in the same manner. The dyes and the high-boiling organic solvents used to disperse them are shown below.

[0120]

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[0121]

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These dispersions and the previously prepared silver halide emulsion were combined and coated on a support with the composition shown in Table 1 to prepare a multilayer color negative photosensitive material of Sample 101.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

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Samples 102 to 110 were prepared in the same manner as in Sample 101, except that the coupler (k) in the cyan coloring layer of Sample 101 was replaced with the comparative coupler and the coupler of the present invention in equimolar amounts as shown in Table 4. did. Further, treatment materials P-1 and P as shown in Tables 2 and 3
-2 was created.

[0128]

[Table 4]

[0129]

[Table 5]

[0130]

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[0131]

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[0132]

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A sample piece was cut out from these photosensitive materials,
A 1/100 second wedge exposure was performed with 200 lux white light. After exposure, warm water of 40 ° C. is applied to the surface of the photosensitive material for 15 minutes.
ml / m ^2, and the processing material P-1 was overlaid on each other's film surfaces, and then heat-developed at 86 ° C. for 17 seconds using a heat drum. 10 cc on the surface of the photosensitive material from which P-1 was removed
/ M ² of water was applied, bonded to the processing material P-2, and further heated at 50 ° C. for 30 seconds. The transmission density of the obtained color sample was measured. These results are summarized in Table-4.

[0134]

[Table 6]

From the results, it was found that the sample using the coupler of the present invention had an excellent effect that the maximum R density was high and the fog density was the same as that of the conventional coupler. Example 2 Multilayer color photosensitive material 1 prepared in Example 1
200lux using a step wedge on 01-110
1/16 second wedge exposure with red light, CN-16S for conventional color negative film
Standard processing (manufactured by Fuji Photo Film Co., Ltd.) was performed. The film absorption of the obtained sample was measured using Shimadzu UV-26.
Measured using a 0-type spectrometer, the absorbance at the maximum absorption wavelength is 450 nm in the spectrum of 1.9 to 2.1.
Table shows the ratio of the absorbance at m to the absorbance at the maximum absorption wavelength.
5 is shown.

[0136]

[Table 7]

From the table, it was found that the light-sensitive material using the coupler of the present invention had a low absorbance at 450 nm and gave a favorable hue.

[0138]

By using the coupler of the present invention represented by the general formula (1), a cyan image having a low fog and a high maximum color density can be obtained, and the hue of the cyan image is good. Furthermore, a cyan image having an excellent hue can be obtained even in a process using a conventional developing solution for a color negative film.

Claims (3)

[Claims] 1. A silver halide color light-sensitive material comprising a coupler represented by the following general formula (1). General formula (1) In the formula, R _{1 to} R ₃ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized developing agent. R ₁₁ and R ₁₃ represent an alkyl group, and R ₁₂ , R ₁₄ and R ₁₅ represent a hydrogen atom or an alkyl group. 2. In a heat-developable color light-sensitive material having at least a photosensitive silver halide, a binder, a coupler and a developing agent on a support, the coupler represented by the general formula (1) according to claim 1 is used as the coupler. A heat-developable color light-sensitive material comprising: 3. The heat-developable color light-sensitive material according to claim 2, comprising a compound represented by the following general formula (2) as a developing agent. General formula (2) In the formula, R _{21 to} R ₂₄ represent a hydrogen atom or a substituent, and represent a group having a total Hammett substituent constant σ _p value of 0 or more. R ₂₅ represents an aryl group.