JPH11149146A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material containing a developing agent capable of efficiently developing color by reaction with a properly selected known coupler to form an image sufficient in color density by incorporating at least one kind of specified compound in at least one layer formed on a support. SOLUTION: At least one of layers formed on the support of the silver halide photographic sensitive material contains at least one kind of compound represented by the formula in which each of R<1> and R<2> is an H atom or an alkyl, cycloalkyl, alkenyl, aryl, or heterocyclic group; R<3> is an H atom or an alkyl, aryl, or heterocyclic group; each of R<4> -R<7> is an H atom or a substituent; and X is a -CO- or -SO2 - group. This silver halide photographic sensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an interlayer, an antihalation layer, a backing layer, or the like when needed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material containing a developing agent.

[0002]

2. Description of the Related Art A photographic method using silver halide is superior to other photographic methods, such as electrophotography and diazo photographic methods, in terms of photographic characteristics such as sensitivity and gradation control. Has been used for 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, the image forming method of a photosensitive material using silver halide has been changed from a conventional wet processing to an instant photographic system incorporating a developing solution, and a dry thermal development processing by heating or the like, so that the image can be formed easily and quickly. Have been developed. In particular, the content of photothermographic materials is described in “Basics of Photographic Engineering (Non-Silver Photography), Corona”, p. 242 and thereafter. Only the image forming method. Recently, as photothermographic color photosensitive materials, products such as Pictrography and Pictrostat have been marketed by Fuji Photo Film Co., Ltd.
In the above-described simple and rapid processing method, a color image is formed using a redox coloring material to which a preformed die is connected.

The most common method 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. A heat-developable color light-sensitive material employing this method is also disclosed in the United States. Patent No. 3,76
Nos. 1,270 and 4,021,240;
Many ideas have been filed, such as 231538 and 60-128438.

When designing a silver halide photographic light-sensitive material aiming at simple and quick processing as described above, it is necessary to incorporate a developing agent into the light-sensitive material so as not to use a processing solution such as a developing solution. Required. Usually, since the developing agent is a reducing agent, compounds which are easily oxidized by oxygen molecules in the air are generally used, but such compounds are not endurable for such uses.

In order to solve this problem, p-sulfonamidophenols described in US Pat. No. 4,021,240 and JP-A-60-128439 are known as developing agents which can be incorporated in the art.
P-aminophenylsulfamic acid described in
8-227131 described sulfonyl hydrazine, JP-A-8-2020
Sulfonylhydrazone described in No. 02, EP 0772770
Carbamoyl hydrazine according to 8A1, JP-A-8-23439
No. 0 carbamoylhydrazone, JP-A-2-230143
Many ideas have been proposed, such as a solid dispersion addition method of the 1-phenyl-3-pyrazolidinone derivative described in the above publication.

As a result of the inventors of the present invention diligently examining a silver halide photographic light-sensitive material containing a developing agent, p
-When an aminophenol derivative or a p-phenylenediamine derivative was used as a developing agent, it was found that a dye giving a very good hue can be formed usually in combination with a coupler used in the art. . In particular, U.S. Pat. No. 4,021,240, JP-A-60-1
It has been found that sulfonamide phenols described in No. 28438 and the like are compounds excellent in discrimination and raw preservability when incorporated in a photosensitive material.

However, it has been found that p-sulfonamidophenol has extremely low color-forming efficiency when used in combination with a so-called 2-equivalent coupler, which is commonly used in the art. This is because, in this compound, the coupling site is substituted by a sulfonyl group, and at the time of coupling, the sulfonyl group is released as sulfinic acid, so that the leaving group on the coupler side must be released as a cation. For this reason, it reacts with a 4-equivalent coupler capable of releasing a proton as a leaving group at the time of coupling to form a color, but in the case of a 2-equivalent coupler whose leaving group is an anion, it reacts but color hardly occurs.

Due to the property of being difficult to react with a 2-equivalent coupler, a developing agent such as p-sulfonamidophenol can release a functional compound from the coupling site of the coupler or substitute a ballast at the coupling site. Then, it is difficult to construct a system such as forming a diffusible dye by separation. It is also known that 4-equivalent couplers have a problem in formalin gas resistance. Therefore, the inventors of the present invention have a leaving group at such a coupling site, so that a developing agent using an aminophenol-type and phenylenediamine-type developing agent can efficiently form a color reaction with a 2-equivalent coupler. Has been eagerly examining what options are available.

As a result, the above conventional problems can be solved by using a p-aminophenol derivative or a p-phenylenediamine derivative having a structure having a nucleophilic group in the molecule, and the type of coupler used is limited. However, it was found that a color was formed by reacting with an appropriately selected known coupler (particularly, a 2-equivalent coupler). However, as the silver halide light-sensitive material, the higher the color density, the better, and improvement of the color density has been desired for higher image quality.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and has as its object to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides a silver halide photographic light-sensitive material containing a developing agent capable of efficiently performing a color-forming reaction with a known coupler (particularly, a 2-equivalent coupler) appropriately selected and obtaining an image having a sufficient color density. The purpose is to:

[0012]

Means for solving the above problems are as follows. That is, <1> at least one layer of the following general formula (I) on the support
A silver halide photographic material comprising at least one compound represented by the formula: General formula (I)

[0013]

Embedded image

In the general formula (I), R ¹ and R ² represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ³ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ⁴ , R ⁵ ,
R ⁶ and R ⁷ represent a hydrogen atom or a substituent. X is-
CO- or -SO ₂ - represents a.

<2> The silver halide photographic material as described in <1>, wherein the compound represented by the formula (I) has at least one group having a ballast property.

<3> The silver halide photographic light-sensitive material according to <1> or <2>, further comprising a 2-equivalent coupler.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The silver halide photographic light-sensitive material of the present invention will be described in detail below. The silver halide light-sensitive material of the present invention contains at least one compound represented by formula (I) in at least one layer on a support.

First, in the present invention, a group containing the following substituent group is defined by the name "R ⁴⁰ ". That is, examples of the substituent group include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), an alkyl group (preferably a linear or branched alkyl group having 1 to 40 carbon atoms, for example, a methyl group and an ethyl group. Propyl group, isopropyl group, butyl group, t-butyl group, 1-octyl group, tridecyl group), cycloalkyl group (preferably having 3 to 4 carbon atoms).
0 cycloalkyl groups such as cyclopropyl group, 1
-Ethylcyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably an alkenyl group having 2 to 40 carbon atoms, for example, vinyl group, allyl group, 3-butene-
1-yl group), aryl group (preferably having 6 to 32 carbon atoms)
Aryl group, for example, a phenyl group, a 1-naphthyl group,
2-naphthyl group), heterocyclic group (preferably having 1 to 3 carbon atoms)
2, a 5- to 8-membered heterocyclic group, for example, a 2-thienyl group, 4-
Pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-
Pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-2-yl group), cyano group, silyl group (preferably having 3 to 4 carbon atoms)
0 silyl group, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, carboxyl group, nitro group, alkoxy group (preferably having 1 carbon atom) To 40 alkoxy groups such as a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a t-butoxy group and a dodecyloxy group, a cycloalkyloxy group (preferably having 3 carbon atoms).
To 8 cycloalkyloxy groups, for example, a cyclopentyloxy group, a cyclohexyloxy group), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms,
For example, a phenoxy group, a 2-naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 40 carbon atoms,
For example, a 1-phenyltetrazole-5-oxy group, 2
-Tetrahydropyranyloxy group, 2-furyloxy group), silyloxy group (preferably a silyloxy group having 1 to 40 carbon atoms, for example, trimethylsilyloxy group, t
-Butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably having 2 carbon atoms)
To 40 acyloxy groups, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 40 carbon atoms, for example, an ethoxycarbonyloxy group, t -Butoxycarbonyloxy group), a cycloalkyloxycarbonyloxy group (preferably a cycloalkyloxycarbonyloxy group having 4 to 40 carbon atoms, for example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably having a carbon number of 7 to 40) An aryloxycarbonyloxy group of 40, for example, a phenoxycarbonyloxy group), a carbamoyloxy group (preferably having 1 to 4 carbon atoms)
0 carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group), sulfamoyloxy group (preferably having 1 to 1 carbon atoms)
40 sulfamoyloxy groups, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), alkanesulfonyloxy group (preferably alkanesulfonyloxy group having 1 to 40 carbon atoms, for example, A methanesulfonyloxy group, a hexadecanesulfonyloxy group), an arenesulfonyloxy group (preferably an arenesulfonyloxy group having 6 to 40 carbon atoms, for example, a benzenesulfonyloxy group), an acyl group (preferably an acyl group having 1 to 40 carbon atoms) For example, a formyl group,
Acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 40 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group), cycloalkyloxy A carbonyl group (preferably a cycloalkyloxycarbonyl group having 4 to 40 carbon atoms, for example, cyclohexyloxycarbonyl group), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 40 carbon atoms, for example,
Phenoxycarbonyl group), carbamoyl group (preferably a carbamoyl group having 1 to 40 carbon atoms, for example, carbamoyl group, N, N-dibutylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N-propylcarbamoyl group), amino Groups (preferably amino groups having 32 or less carbon atoms, for example, amino groups, methylamino groups, N, N-dioctylamino groups, tetradecylamino groups, octadecylamino groups), anilino groups (preferably having 6 to 40 carbon atoms)
Anilino group, for example, anilino group, N-methylanilino group), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 40 carbon atoms, for example, 4-pyridylamino group), a carbonamide group (preferably 2 carbon atoms) ~ 40 carbonamido groups, for example, acetamido, benzamido,
A ureido group (preferably a ureido group having 1 to 40 carbon atoms, for example, a ureido group, N, N
-Dimethylureido group, N-phenylureido group), imide group (preferably imide group having 10 or less carbon atoms, for example, N-succinimide group, N-phthalimido group), alkoxycarbonylamino group (preferably having 2 to 4 carbon atoms)
An alkoxycarbonylamino group such as methoxycarbonylamino group, ethoxycarbonylamino group, t
-Butoxycarbonylamino group, octadecyloxycarbonylamino group), cycloalkyloxycarbonylamino group (preferably cycloalkyloxycarbonylamino group having 4 to 40 carbon atoms, for example, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group ( An aryloxycarbonylamino group having preferably 7 to 40 carbon atoms, such as a phenoxycarbonylamino group, a sulfonamide group (preferably having 1 to 4 carbon atoms)
0, for example, a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 40 carbon atoms, for example, , An N, N-dipropylsulfamoylamino group, an N-ethyl-N-dodecylsulfamoylamino group), an azo group (preferably an azo group having 1 to 40 carbon atoms, such as a phenylazo group), and an alkylthio group (preferably Is an alkylthio group having 1 to 40 carbon atoms, for example, an ethylthio group, an octylthio group), a cycloalkylthio group (preferably a cycloalkylthio group having 3 to 40 carbon atoms,
For example, a cyclohexylthio group), an arylthio group (preferably an arylthio group having 6 to 40 carbon atoms, for example, a phenylthio group), a heterocyclic thio group (preferably having a carbon number of 1 to 40)
40 heterocyclic thio groups, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 40 carbon atoms, for example, dodecane) Sulfinyl group), arene sulfinyl group (preferably arene sulfinyl group having 6 to 40 carbon atoms, for example,
A benzenesulfinyl group), an alkanesulfonyl group (preferably an alkanesulfonyl group having 1 to 40 carbon atoms, for example, a methanesulfonyl group, an octanesulfonyl group), an arenesulfonyl group (preferably an arenesulfonyl group having 6 to 40 carbon atoms, for example, Benzenesulfonyl group, 1
-Naphthalenesulfonyl group), an alkoxysulfonyl group (preferably an alkoxysulfonyl group having 1 to 40 carbon atoms, for example, a methoxysulfonyl group or an ethoxysulfonyl group), a cycloalkyloxysulfonyl group (preferably a cycloalkyloxy group having 3 to 40 carbon atoms) Sulfonyl group, for example, cyclopropyloxysulfonyl group, aryloxysulfonyl group (preferably having 6 to 40 carbon atoms)
Aryloxysulfonyl group, for example, phenoxysulfonyl group, p-methylphenoxysulfonyl group), sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, for example, sulfamoyl group, N, N-dipropylsulfamoyl group, N- Ethyl-N-dodecylsulfamoyl group), sulfo group, phosphonyl group (preferably a phosphonyl group having 1 to 40 carbon atoms, for example, phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphinoyl An amino group (preferably a phosphinoylamino group having 2 to 40 carbon atoms, for example, a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group) is exemplified.

Next, the compound represented by formula (I) will be described in detail below. R ¹ and R ² represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and preferred carbon numbers and specific examples thereof include the alkyl group in R ⁴⁰ described above.
It is the same as the cycloalkyl group, alkenyl group, aryl group and heterocyclic group. R ¹ and R ² may be the same as or different from each other. R ¹ and R ² are
It may have a substituent, and the substituent may be the aforementioned R
Same as shown as ⁴⁰ . R ¹ and R ² may be bonded to each other to form a 5- or 6-membered nitrogen-containing ring.

Among them, R ¹ and R ² are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group or an aryl group, more preferably a substituted or unsubstituted alkyl group, and have 10 or less carbon atoms. And a substituted or unsubstituted alkyl group is particularly preferred.

R ³ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the preferred number of carbon atoms and specific examples thereof are the same as those of the alkyl group, the aryl group and the heterocyclic group described above as R ^40. Is the same. R ³ may have a substituent, and the substituent is the same as the above-described R ⁴⁰ .

Among them, R ³ is preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and particularly preferably a hydrogen atom. When R ³ represents a substituted or unsubstituted alkyl group, the number of carbon atoms is preferably 15 or less, more preferably 5 or less.

R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a hydrogen atom or a substituent, and the substituents are the same as those described above for R ⁴⁰ . R ⁴ , R ⁵ , R ⁶ and R ⁷ are
They may be the same or different.
R ⁴ , R ⁵ , R ⁶ and R ⁷ may further have a substituent, and the substituent is the same as the above-mentioned R ⁴⁰ .

Among these, R ⁴ , R ⁵ , R ⁶ and R
⁷ as a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group,
Electron-donating groups such as an aryloxy group, an amino group, an anilino group, a carbonamide group, a ureido group, and an alkoxycarbonylamino group are preferred. The group having an electron donating property means a group having a Hammett sigma para value of 0 or less.

X represents -CO- or -SO _2- ;
It is preferably SO ₂ —.

Hereinafter, specific examples (D-1 to D-56) of the compound represented by formula (I) are shown, but the present invention is not limited to these specific examples. In the present invention, the compound represented by the general formula (1) is
It is a compound that functions as a developing agent.

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

The compound represented by the general formula (1) can be synthesized, for example, according to the method described in Japanese Patent Application No. 8-357191. Hereinafter, specific synthesis examples of the compound represented by the general formula (1) will be described.

--Synthesis Example 1 (Synthesis of Compound D-1)-The compound D-1 was synthesized according to the following reaction formula.

[0043]

Embedded image

-Synthesis of Intermediate (I-2)-Compound (I-1) (20.0 g) was mixed with acetonitrile (80 ml).
In a solution dissolved in pyridine, 5.3 ml of pyridine and 2-
11.2 g of sulfobenzoic anhydride were added sequentially. After removing the ice bath and stirring at room temperature for 1 hour, 9 ml of thionyl chloride was added to the reaction solution. The mixture was reacted for 1 hour while heating under reflux. Thereafter, the reaction solution was cooled on ice, and 100 ml of water was added.
Was added. The reaction mixture was extracted with ethyl acetate, and the organic layer was sequentially washed with water and saturated saline. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off to obtain 27 g of a crude product of Intermediate (I-2). This crude product was used for the next reaction without purification.

-Synthesis of compound represented by D-1- 27 g of the above-mentioned intermediate (I-2) was treated with acetonitrile 200
80 ml of 25% ammonia water was added to the solution dissolved in ml. After reacting at room temperature for 3 hours, the reaction solution was poured under vigorous stirring into dilute hydrochloric acid under ice-cooling. The precipitated crystals were collected by filtration under reduced pressure and washed with water. The obtained crude crystals were dried and then recrystallized from 200 ml of acetonitrile to obtain 20 g (yield: 71%) of the compound represented by D-1.
The structure of the compound represented by D-1 obtained at a melting point of 146 to 147 ° C. was confirmed by ¹ HNMR and mass spectrum.

¹ H NMR (CDCl ₃ , 300 MHz)
δ 0.90 (6H, t), 1.1-1.4 (12H,
m), 1.55 (4H, m), 2.09 (3H, s),
3.38 (4H, m), 6.33 (1H, br.s),
6.52 (1H, br.s), 6.80 (1H, d),
6.98 (1H, d), 7.36 (1H, m), 7.5
0 (2H, m), 7.61 (1H, m), 8.07 (1
H, s), 9.60 (1H, s), MS m / z 51
7 (M ⁺ )

--Synthesis Example 2 (Synthesis of Compound Represented by D-2)-The compound represented by D-2 was synthesized by the following reaction formula.

[0048]

Embedded image

Synthesis of Intermediate (II-1) To a solution of 26 g of the compound (I-1) in 100 ml of acetonitrile, 9.3 ml of pyridine and 12.1 g of phthalic anhydride were sequentially added under ice-cooling. After removing the ice bath and stirring at room temperature for 1 hour, the mixture was ice-cooled again and 100 ml of 2N hydrochloric acid was added. The reaction mixture was extracted with ethyl acetate, and the organic layer was sequentially washed with water and saturated saline. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off. Acetic acid 50ml in the residue
Was added and heated to reflux for 30 minutes. The reaction solution was poured into water, and the precipitated crystals were collected by filtration under reduced pressure and washed with water. The crystals collected by filtration were dried to obtain a crude product of intermediate (II-1)
5 g were obtained. This crude product was used for the next reaction without purification.

-Synthesis of compound represented by D-2- 35 g of the intermediate (II-1) was treated with 100 m of acetonitrile.
and 100 ml of THF were dissolved in a mixed solvent, and 15 ml of n-butylamine was added. After stirring at room temperature for 1 hour, the reaction solution was ice-cooled and 100 ml of 2N hydrochloric acid was added. The reaction mixture was extracted with ethyl acetate, and the organic layer was sequentially washed with water and saturated saline. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off. When 300 ml of acetonitrile was added to the residue, crystals precipitated, which were collected by filtration under reduced pressure. By recrystallizing the crude crystals with 200 ml of acetonitrile,
28 g (yield 69%) of Exemplified Compound D-2 was obtained. Melting point 1
12-113 ° C. The structure of the obtained exemplary compound D-2 is
Confirmed by ¹ H NMR and mass spectrum.

¹ H NMR (CDCl ₃ , 300 MHz)
δ 0.88 (9H, m), 1.2-1.4 (14H,
m), 1.50 (2H, m), 1.62 (4H, m),
2.25 (3H, s), 3.38 (2H, m), 3.4
2 (4H, m), 6.33 (1H, t), 7.23 (1
H, d), 7.48 (3H, m), 7.70 (1H,
d), 7.80 (1H, m), 9.24 (1H, s),
9.45 (1H, s), MS m / z 537 (M ⁺ ).

As a method for adding the compound represented by the above general formula (I) (developing agent) to a silver halide photographic light-sensitive material, first, a coupler, a developing agent and a high boiling organic solvent (for example, alkyl phosphate, Phthalic acid alkyl ester) 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.

When the compound represented by the general formula (I) is added by the emulsification dispersion method in the above addition method,
It is preferably an oil-soluble compound. For this purpose, it is preferable that at least one group having a ballast property is contained. The ballast group means an oil-solubilizing group, which usually has 8 to 80 carbon atoms, and preferably has 10 to 80 carbon atoms.
A group containing an oil-soluble partial structure of ４０40. Therefore, it is preferable that any one of R ^{1 to} R ⁷ be substituted with a ballast group having 8 or more carbon atoms. In particular, when the compound represented by the general formula (I) is used for a diffusion transfer type color photosensitive material, it is preferable that any one of R ^{3 to} R ⁷ is substituted with a ballast group. The number of carbon atoms of the ballast group is preferably from 8 to 80, and more preferably from 8 to 20.

The coating amount of the compound represented by formula (I) (developing agent) has a wide range,
1 to 1000 mmol / m ² is preferable, and 0.01 to 5
0 mmol / m ² is more preferred.

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. The compound (developing agent) represented by the general formula (1) can react with any coupler to form a dye.

As a specific example of the coupler, both the 4-equivalent coupler and the 2-equivalent coupler can be used in the theory of the photographic process (4th Ed.
H. Edited by James Macmilllan, 1977)
291 to 334, 354 to 361, JP-A-58-12353, 58-149046, 58
No.-149047, No.59-11114, No.59-1
No. 24399, No. 59-174835, No. 59-23
No. 1539, No. 59-231540, No. 60-129
No. 51, No. 60-14242, No. 60-23474
No. 60-66249, and the like.

Examples of the coupler preferably used in the present invention include compounds having structures represented by the following 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.

[0058]

Embedded image

[0059]

Embedded image

The compounds represented by formulas (2) to (5) are couplers called active methylene couplers. In these formulas, R ₂₄ may have a substituent. , An acyl group, a cyano group, a nitro group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group or an arylsulfonyl group. In the compounds represented by the general formulas (2) to (5), R ₂₅
Represents an alkyl group, an aryl group or a heterocyclic group which may have a substituent. In the general formula (5), R ₂₆
Represents an aryl group or a heterocyclic group which may have a substituent.

Examples of the substituent which R ₂₄ , 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, Examples include various substituents such as a halogen atom, an acylamino group, a sulfonamide 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. Preferred examples of R ₂₄ include an acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group.

In the compounds represented by the above general formulas (2) to (5), L is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized developing agent. Specific examples of L include a carboxyl group, a formyl group, a halogen atom (for example, bromine and iodine), a carbamoyl group, and a methylene group having a substituent (for the substituent, an aryl group, a sulfonamide group, a carbonamide group, an alkoxy group) Group, amino group, hydroxyl group, etc.), acyl group, sulfo group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, carbamoyloxy group,
Examples include a sulfamoyloxy group and an N-substituted heterocyclic group. Among these, a leaving group having a halogen atom, an S atom, or an O atom as the leaving atom is particularly preferable.

In the compounds represented by the general formulas (2) to (5), R ₂₄ and R ₂₅ may be bonded to each other to form a ring, and R ₂₄ and R ₂₆ may be bonded to each other. To form a ring.

The compound represented by the general formula (6)
A coupler called a pyrazolone-based magenta coupler. In the general formula (6), 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, an alkyl group,
Represents a phenyl group substituted by a cyano group, an alkoxy group, an alkoxycarbonyl group or an acylamino group. L is the same as the compounds represented by the general formulas (2) to (5).

In the 5-pyrazolone magenta coupler represented by the general formula (6), R ₂₇ is preferably an aryl group or an acyl group, and R ₂₈ is a phenyl group substituted by one or more halogen atoms. It is preferred that

Preferred examples of R ₂₇ include a phenyl group,
2-chlorophenyl group, 2-methoxyphenyl group, 2-
Chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl-1-succinimide)
An aryl group such as a phenyl group, a 2-chloro-5-octadecylsulfonamidophenyl group, or a 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group, or acetyl Group,
Pivaloyl group, tetradecanoyl group, 2- (2,4-di-t-pentylphenoxy) acetyl group, 2- (2,4
Acyl groups such as -di-t-pentylphenoxy) butanoyl group, benzoyl group and 3- (2,4-di-t-amylphenoxyacetoazide) benzoyl group. These groups may further have a substituent, and the substituent is an organic substituent linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, or a halogen atom.

Preferred examples of R ₂₈ include 2,4,6-
Trichlorophenyl group, 2,5-dichlorophenyl group,
And substituted phenyl groups such as 2-chlorophenyl group.

The compound represented by the general formula (7) is a coupler called a pyrazoloazole coupler.
In the general formula (7), R ₂₉ represents a hydrogen atom or a substituent. V represents a group of non-metallic atoms 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). L is the same as the compounds represented by the general formulas (2) to (5).

Among the pyrazoloazole-based couplers represented by the general formula (7), from the viewpoint of the absorption characteristics of the coloring dye,
The imidazo [1,2] described in U.S. Patent No. 4,500,630.
-B] pyrazoles, pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,654,654, and pyrazolo [5,1-c] [1] described in U.S. Pat. No. 3,725,067. , 2,4] triazoles are preferred. Of these, pyrazolo [1,5-
b] [1,2,4] triazoles are preferred.

For details of the substituents on the azole ring represented by R ₂₉ , L and V, see, for example, US Pat.
No. 54, second column, line 41 to eighth column, line 27
Listed on the line. Preferably, JP-A-61-652 is used.
No. 45, a pyrazoloazole coupler in which a branched alkyl group is directly bonded to the 2-, 3- or 6-position of a 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. 7 or 63-307453, pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, and pyrazolotriazole couplers having a carboxamide group in the molecule described in Japanese Patent Application No. 1-227979. Zolotriazole coupler.

The compound represented by the general formula (8) and the compound represented by the general formula (9) are couplers called phenol couplers and naphthol couplers, respectively. In these general formulas, 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 or -
It represents a group selected from NHSO ₂ NR ₃₂ R _33. R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. R ₃₁ represents a substituent. p represents an integer selected from 0 to 2. m is
Represents an integer selected from 0 to 4. L is the same as the compounds represented by the general formulas (2) to (5). R
The ₃₁ to R _33, include those mentioned as the substituent for the R ₂₄ to R _26.

Preferable examples of the phenolic coupler represented by the general formula (8) include US Pat.
No. 29, 2801171, 2772162
Nos. 2,895,826 and 377,2002, 2-alkylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162 and 3,758,308.
Nos. 4,126,396, 4,334,011, 4,327,173, and German Patent Publication 3,329,729.
2,5-diacylaminophenols described in U.S. Pat. No. 3,446,622 described in U.S. Pat.
2-phenylureido- described in Nos. 4,433,999, 4,451,559 and 4,427,767.
5-acylaminophenols and the like can be mentioned.

A preferred example of the naphthol coupler represented by the general formula (9) is described in US Pat.
No. 3, No. 4052212, No. 4146396,
2-carbamoyl-1-naphthols described in U.S. Pat. Nos. 4,228,233 and 4,296,200 and U.S. Pat.
And 2-carbamoyl-5-amide-1-naphthol described in JP-A-690889.

The compounds represented by formulas (10) to (13) are couplers called pyrrolotriazole. In these general formulas, R ₄₂ , R ₄₃ , and R
₄₄ represents a hydrogen atom or a substituent. L is the same as the compounds represented by the general formulas (2) to (5).
_Examples of the substituent of R ₄₂ , R ₄₃ and R ₄₄ include the aforementioned R _{24 to} R ₂₆
And the substituents described above. Preferable examples of the pyrrolotriazole-based couplers represented by the general formulas (10) to (13) include EP-A-488248.
A1, No. 491197A1, and No. 545300, in which at least one of R ₄₂ and R ₄₃ is an electron withdrawing group.

In the present invention, in addition to those described above, condensed phenol couplers, imidazole couplers, pyrrole couplers, 3-hydroxypyridine couplers, active methine couplers, 5,5-condensed heterocyclic couplers, Couplers having a structure such as a 5,6-fused heterocyclic coupler can be used.

The above-mentioned fused phenol couplers include
U.S. Pat. Nos. 4,327,173 and 4,564,586;
No. 4,904,575 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-based coupler, couplers described in JP-A-4-188137 and JP-A-4-190347 can be used.

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

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

As the 5,5-fused heterocyclic coupler, a pyrrolopyrazole coupler described in US Pat. No. 5,164,289, a pyrroleimidazole coupler described in JP-A-4-174429, and the like can be used.

Examples of the 5,6-fused heterocyclic coupler include pyrazolopyrimidine couplers described in US Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, and EP 556700.
And the like.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049, U.S. Pat. No. 329036, No. 354
No. 549A2, No. 374781A2, No. 3791
10A2, 386930A1, JP-A-63-1
No. 41055, No. 64-32260, No. 32261
JP-A-2-29747, JP-A-2-44340,
2-110555, 3-7938, 3-16
No. 0440, No. 3-172839, No. 4-17244
No. 7, 4-179949, 4-182645,
4-184337, 4-188138, 4-
Nos. 188139, 4-194847, 4-204
No. 532, No. 4-204731, No. 4-204732
The couplers described in the above publications can also be used.

Specific examples of the couplers usable in the present invention ("Y-1 to Y-12", "M-1 to M-14", "C
-1 to C-9 "," YY-1 to YY-10 "," MM-
1 to MM-14 "and" CC-1 to CC-14 ") are shown below. Note that the present invention is not limited to these specific examples.

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

The amount of the coupler to be added depends on its molar extinction coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, the amount of the dye formed by coupling must be ε.
Is about 5,000 to 500,000, the coating amount is about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ² , more preferably about 0.05 to 5 mmol / m ^2. Appropriate.

The silver halide photographic light-sensitive material of the present invention basically comprises a support having thereon a photosensitive silver halide and a coupler, a reducing agent and a binder as a dye-donating compound. An organic metal salt oxidizing agent 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, a blue-sensitive layer, a green-sensitive layer, and a three-layered green-sensitive layer,
There are three layers formed by a combination of 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 silver halide photographic 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, if necessary.
Further, various filter dyes can be added to improve color separation.

The silver halide emulsion which can be used in the silver halide photographic light-sensitive material of the present invention is not particularly limited, and may be silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide,
Any of 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. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and is described in JP-A-1-167743 and JP-A-4-223463.
A method of mixing monodisperse emulsions and adjusting the gradation as described in the above publication is preferably used. Particle size is 0.1-2μ
m, particularly preferably 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 spherical, high aspect ratio tabular, and twins. It may be one having a crystal defect such as a plane, or a combination 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. Glafkid)
es, Chemie et Phisique Photographique, Paul Monte
l, 1967), Duffin, Photographic Emulsion Chemistry, 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 producing the silver halide photographic light-sensitive material of the present invention, it is preferable to remove excess salt, that is, to perform so-called desalting. 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 (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrene sulfonic 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 emulsion in the silver halide photographic light-sensitive material 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 addition amount varies depending on the purpose of use and cannot be specified unconditionally, 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, Japanese Patent Laid-Open No. 2-2
No. 36542, No. 1-116637, No. 5-1812
The emulsion described in No. 46 or the like is preferably used.

In the present invention, in the step of forming the grains of the photosensitive silver halide emulsion, as a silver halide solvent, a rhodan salt, ammonia, a tetra-substituted thioether compound, an organic thioether derivative described in JP-B No. 47-11386, or an organic solvent disclosed in Sulfur-containing compounds described in JP-A-53-144319 can be used. For other conditions, see "Graduation of Physics and Chemistry of Photography", published by Paul Monte (P. Glafkides, Chemie et Phisique Photo).
graphique, Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, Focal Press (GF Duffin, Phot)
ographic Emulsion Chemistry, Focal Press, 1966),
"Manufacture and Coating of Photographic Emulsion", by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making and Coat
ing Photographic 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 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 (Japanese Patent Application Laid-Open Nos. 55-142329 and 55-142329).
-158124, U.S. Patent No. 3,650,757). Further, the method of stirring the reaction solution may be any known stirring method. The temperature of the reaction solution during the formation of silver halide grains,
The pH and the like may be set in any manner according to the purpose. The preferred pH range is 2.2 to 8.5, more preferably 2.
5 to 7.5.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. The chemical sensitization of the photosensitive silver halide emulsion in the present invention includes 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 photosensitive material. 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-3-110).
No. 555 and 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 anti-fogging agent described later can be added after completion of chemical sensitization. Specifically, JP-A-5-45833, JP-A-62-404
The method described in No. 46 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, and 5.5 to 5.5.
8.5 is more preferred. The pAg is 6.0 to 1
0.5 is preferable, and 6.8 to 9.0 is more preferable. The coating amount of the photosensitive silver halide emulsion used in the present invention is about 1 mg / m ^{2 to} 10 g / m ^{2 in} terms of silver.

In order to make the photosensitive silver halide used in the present invention have green sensitivity, red sensitivity and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. Is good. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Examples of the dye used include a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxonol dye.

Specifically, see US Pat. No. 4,617,25.
No. 7, JP-A-59-180550, 64-1354
And sensitizing dyes described in JP-A-5-45828 and JP-A-5-45834. These sensitizing dyes may be used alone or in combination of two or more. Combinations of sensitizing dyes are often employed, particularly for supersensitization and for adjusting the wavelength of spectral sensitivity.

Along with the sensitizing dye, a dye which has no 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. Patent Nos. 3,615,641 and JP-A-63-23145). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after chemical ripening, and US Pat. No. 4,183,756.
Nos. 4,225,566 before and after the nucleation of silver halide grains. 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 silver halide photographic light-sensitive material of the present invention include the above-mentioned RD Nos. 17643 and 187.
15 and No. 307105. The relevant locations are summarized below.

Type of Additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, 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 25-26 page 649 right column page 873 filter dye ６650 left column UV 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 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 27 pages 650 right column 876-877 Inhibitors 13. Matting agent 878-879

As the binder for the constituent layers of the silver halide photographic light-sensitive material, hydrophilic binders are preferably used. Examples thereof include those described in Research Disclosure and pages (71) to (75) of JP-A-64-13546. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and polyvinyl alcohol. And synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymers. No. 4,960,681.
No. superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer each other vinyl monomers having, Alternatively, a copolymer with another vinyl monomer (for example, 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 with a reduced content of calcium and the like according to various purposes. These gelatins may be used alone or in combination of two or more.

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 organic silver salt is used in an amount of 0.01 per mole of the 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.

The silver halide photographic light-sensitive material of the present invention includes
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, Nos. 51-5.
It is described in column 2. In addition, Japanese Patent Application No. 6-206331.
Compounds capable of fixing silver halide, such as those described in the above item, can also be used.

Examples of the hardener used in the constituent layers of the silver halide photographic light-sensitive material include the aforementioned Research Disclosure, US Pat. No. 4,678,739, column 41, and US Pat.
91,042, JP-A-59-116655, 62
245261, 61-18942, JP-A-42
Hardening agents described in -18044 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). The amount of these hardeners is 0.001-1 g / g of gelatin applied,
0.005 to 0.5 g is preferred. 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.

In the constituent layers of the silver halide photographic light-sensitive material,
Various antifoggants or photographic stabilizers and their precursors can be used. 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)-
(9), (57) to (71) and (81) to (97), U.S. Pat. Nos. 4,775,610 and 4,626,500
No. 4,983,494, JP-A-62-17474.
No. 7, No. 62-239148, No. 63-264747
No., JP-A-1-150135 and 2-110557
No. 2-178650, RD17643 (1978)
Compounds described on pages (24) to (25) are exemplified. The amount of these compounds is 5 × 10 ^-6 to 1 / mol silver.
× 10 ^-1 mol is preferable, and 1 × 10 ^-5 to 1 × 10 ^-2 mol is more preferable.

In the constituent layers of the silver halide photographic light-sensitive material,
Various surfactants can be used for the purpose of coating aid, improving peelability, improving slipperiness, preventing static charge, accelerating development, and the like. Specific examples of the surfactant are described in Research Disclosure, JP-A-62-173463, and 62-18-18.
No. 3457 and the like. The constituent layers of the silver halide photographic light-sensitive material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of the organic fluoro compound include Japanese Patent Publication No.
No. 9053, columns 8 to 17, fluorinated surfactants described in JP-A-51-20944, JP-A-62-135825, etc., or oily fluorinated compounds such as fluorinated oil or ethylene tetrafluoride resin, etc. And a hydrophobic fluorine compound such as a solid fluorine compound resin.

A matting agent can be used in the silver halide photographic light-sensitive material for the purpose of preventing adhesion, improving slipperiness, and giving a non-glossy surface. Examples of the matting agent include compounds described in JP-A-61-88256 (page 29) such as silicon dioxide, polyolefin and polymethacrylate, as well as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads. 63-274944
And No. 63-274952. In addition, the compounds described in the above 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 silver halide photographic 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 disclosed in
No. 88256, pages (26) to (32), JP-A-3-1133
No. 8, JP-B-2-51496, and the like.

In the silver halide photographic light-sensitive material of the present invention, an image formation accelerator can be used. 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-forming reaction, and from the physicochemical function, a base or a base precursor, a nucleophilic compound. , High boiling organic solvent (oil), thermal solvent, surfactant,
It is classified into compounds that interact with silver or silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. For further details on these, see US Pat. No. 4,678,
No. 739, columns 38-40.

In the silver halide photographic light-sensitive 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 development terminator is, after proper development, a compound that neutralizes a base immediately or reacts with the base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and a silver salt to suppress development. It is. 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).

Examples of a method for exposing and recording an image on a silver halide photographic material include a method for directly photographing a landscape or a person using a camera or the like, a reversal film or a negative film using a printer or a enlarger. Through a slit, a method of scanning and exposing the original image through slits, etc., using a copier exposure device, etc., emitting light from light emitting diodes and various lasers (laser diodes, gas lasers, etc.) through image information via electric signals Scanning exposure method (JP-A-2-129625, 5-
Nos. 176144, 5-199372, 6-127
No. 021 etc.), image information is transferred to a CRT, a liquid crystal display, an electroluminescence display,
There is a method of outputting to an image display device such as a plasma display and exposing directly or via an optical system.

As a light source for recording an image on a silver halide photographic 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 And light sources and exposure methods described in JP-A-2-53378 and JP-A-2-54672. Further, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as a laser beam are combined.

Here, the non-linear optical material is a material capable of exhibiting a nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, diphosphate, and the like. Inorganic compounds represented by potassium hydrogen (KDP), lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives such as 3-methyl-4
Nitropyridine-N-oxide derivatives such as -nitropyridine-N-oxide (POM);
Compounds described in JP-A Nos. 462 and 62-210432 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. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal generated using a computer represented by a signal, CG, or CAD can be used.

The silver halide photographic light-sensitive material of the present invention may have a form having a conductive heating element layer as a heating means for heat development. In this case, the heating element described in JP-A-61-145544 can be used.
The heating temperature in the step for heat development is about 80
C. to 180 C., and the heating time is 0.1 seconds to 60 seconds.

As a heating method in the developing step, a heated block or a 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 silver halide photographic light-sensitive material and a dye-fixing material is described in, for example, JP-A-62-253159.
And the method described in JP-A-61-147244 (page 27) can be applied.

[0134]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 <Preparation of Photosensitive Silver Halide Emulsion-1> A well-stirred aqueous gelatin solution (inert gelatin 3 in 1000 ml of water)
0 g, potassium bromide 2 g) and ammonia
Add ammonium nitrate as a solvent and keep the temperature at 75 ° C.
To this, 1,000 ml of an aqueous solution containing 1 mol of silver nitrate and 1000 ml of an aqueous solution containing 1 mol of potassium bromide and 0.03 mol of potassium iodide were simultaneously added over 78 minutes. After washing with water and desalting, the mixture was redispersed by adding inert gelatin to prepare a silver iodobromide emulsion having an equivalent sphere diameter of 0.76 μm and an iodine content of 3 mol%. The equivalent sphere diameter was measured with a Coulter Counter Model TA-3. To the photosensitive silver halide emulsion-1 prepared as described above, potassium thiocyanate, chloroauric acid, and sodium thiosulfate were added at 56 ° C. for optimal chemical sensitization. A sensitizing dye was added to this photosensitive silver halide emulsion-1 at the time of preparing a coating solution to give color sensitivity.

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

<Preparation of Emulsified Dispersion of Coupler> The oil phase component and the aqueous phase component having the compositions shown in Table 1 were dissolved respectively,
To make a homogeneous solution. Combine the oil phase component and the water phase component,
In a 1 l stainless steel container, the mixture was dispersed at 10,000 rpm for 20 minutes by a dissolver with a disperser having a diameter of 5 cm. To this, warm water in an amount shown in Table 1 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of the coupler was prepared. As the coupler (1), "MM-5" shown in the specific examples of the coupler was used.

[0138]

[Table 1]

[0139]

Embedded image

[0140]

Embedded image

A silver halide photographic light-sensitive material 101 having a multilayer structure as shown in Table 2 was prepared by using each of the materials thus obtained.

[0142]

[Table 2]

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

Next, a treated sheet R-1 having the contents shown in Tables 3, 4 and 5 was prepared. Table 4 shows a continuation of Table 3.

[0147]

[Table 3]

[0148]

[Table 4]

[0149]

[Table 5]

[0150]

Embedded image

[0151]

Embedded image

Next, as shown in Table 6, the coupler and / or developing agent of each layer was replaced with a silver halide photographic material 10
Silver halide photographic light-sensitive materials 102 to 120 having exactly the same composition as silver halide photographic light-sensitive material 101 except that the silver halide photographic light-sensitive material 101 was replaced with an equimolar amount to 1 were produced. The silver halide photographic light-sensitive materials 101 to 120 thus obtained are passed through a gray filter having a continuously changed density to 250.
It exposed for 0.01 second at 0 lux. 15 ml / m ² of 40 ° C. warm water was applied to the exposed photosensitive material surface, and the treated sheet and each film surface were overlapped with each other, and then heat-developed at 83 ° C. for 30 seconds using a heat drum.

After the processing, when the processed sheet was peeled off, a clear image was obtained corresponding to the filter exposed to the silver halide photographic material. Immediately after the processing, the transmission density of Dmax of the exposed part and Dmin of the white part of this sample were determined by X-rit.
Table 7 shows the results measured by the e-densitometer. In Table 7, the measurement filter is changed according to the color hue of the coupler. .

[0154]

[Table 6]

[0155]

[Table 7]

[0156]

Embedded image

From the results shown in Table 7, four-equivalent couplers were used in the silver halide photographic light-sensitive materials 101 to 103, and a dye image was formed in any of the developing agents. In the silver halide photographic light-sensitive materials 104 to 120 in which the coupler was changed to a 2-equivalent coupler, no color was formed when the developing agent (2) was used, and the compound represented by the formula (I) was used as the developing agent. It can be seen that in the case, the color developability is better than in the case where another developing agent is used.

Example 2 <Preparation of Photosensitive Silver Halide Emulsion-2> Solution (I) and solution (II) having the composition shown in Table 9 were added to an aqueous solution having the composition shown in Table 8 with good stirring. At the same time, it was added at an equal flow rate for 9 minutes. Part 5
One minute later, solution (III) and solution (IV) having the composition shown in Table 9 were simultaneously added at an equal flow rate for 32 minutes. After the addition of the solution (III) and the solution (IV), 60 ml of a methanol solution of the dye (including 360 mg of the sensitizing dye 1 and 73.4 mg of the sensitizing dye 2) was added all at once. After washing with water and desalting (using a precipitant a 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 and 180 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, and after optimal chemical sensitization at 60 ° C., 90 mg of antifoggant 3 And then cooled. In this way, the average particle size is 0.1 mm.
635 g of a 30 μm monodispersed cubic silver chlorobromide emulsion was obtained.

[0159]

[Table 8]

[0160]

[Table 9]

[0161]

Embedded image

Next, a silver halide photographic light-sensitive material 201 having the composition shown in Table 10 was prepared. In addition, coupler (24)
"Y-4" shown in the specific examples of the coupler was used.

[0163]

[Table 10]

[0164]

Embedded image

Further, the processing sheet R-
An image receiving sheet R-2 having exactly the same composition as the processing sheet R-1 was prepared except that palladium sulfide and potassium hydantoin were removed from Example 1.

Next, as shown in Table 11, except that the coupler and the developing agent in each layer were changed so as to be equimolar to the silver halide photographic material 201, the silver halide photographic material 201 was completely replaced. Silver halide photographic materials 202 to 220 having the same composition were prepared.

[0167]

[Table 11]

The silver halide photographic materials 201 to 220 thus obtained were exposed at 2500 lux for 0.01 second through a gray filter having a continuously changed density. 15 ml / m of 40 ° C warm water is applied to the exposed photosensitive material surface.
^{2 was applied,} and the image receiving sheet and the respective film surfaces were overlapped with each other, and then heat-developed at 83 ° C. for 17 seconds using a heat drum. After the processing, when the image receiving sheet was peeled off, a clear transfer dye image was obtained on the image receiving sheet corresponding to the filter exposed to the silver halide photographic material. Immediately after the treatment, the reflection density of Dmax of the exposed portion and Dmin of the white portion of this sample were measured with an X-rite densitometer, and the results are shown in Table 12. In Table 12, as in the case of Example 1, the measurement filter is changed according to the color hue of the coupler.

[0169]

[Table 12]

According to the results shown in Table 12, since the 2-equivalent coupler was used, no dye image was formed when the developing agent (2) was used. It can be seen that when the compound represented by formula (I) is used as a developing agent, a higher color density can be obtained as compared with the case where another developing agent is used.

[0171]

According to the present invention, the above-mentioned various problems in the prior art can be solved, and the color development reaction is efficiently performed with a well-known coupler (particularly, a 2-equivalent coupler) which is not limited by the kind of the coupler to be used. A silver halide photographic material incorporating a developing agent capable of obtaining an image having a sufficient color density can be provided.

Claims (3)

[Claims] 1. A silver halide photographic material characterized in that at least one layer on a support contains at least one compound represented by the following general formula (I). General formula (I) In the general formula (I), R ¹ and R ² represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ³ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ⁴ , R ⁵ , R ⁶ and R ⁷
Represents a hydrogen atom or a substituent. X is -CO- or-
Represents SO ₂ —. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by formula (I) has at least one group having a ballast property. 3. The silver halide photographic light-sensitive material according to claim 1, which contains a 2-equivalent coupler.