JP3464578B2 - Silver halide photographic light-sensitive material and processing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image on a silver halide photographic light-sensitive material, and more particularly to a method for forming an ultrahigh contrast photographic image used in the field of graphic arts.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting super-high gradation (especially γ of 10 or more) is provided in order to improve reproduction of continuous tone images or line images by halftone dot images. is necessary. As a method for obtaining high-contrast photographic characteristics, a lithographic development method utilizing a so-called "infectious development effect" has been used for a long time, but it has a drawback that the developer is unstable and difficult to use. There is a demand for an image forming system which can be developed with a processing liquid having good storage stability to obtain photographic characteristics of ultra-high contrast, and one of them is US Pat. No. 4,166,74.
No. 2, No. 4,168,977, No. 4,221,8
No. 57, No. 4,224,401, No. 4,243,
No. 739, No. 4,269, 922, No. 4,27.
No. 2,606, No. 4,311,781, No. 4,3
No. 32,878, No. 4,618,574, No. 4,
Nos. 634,661, 4,681,836 and 5,650,746 are disclosed. These are obtained by processing a surface latent image type silver halide photographic light-sensitive material containing a hydrazine derivative with a stable MQ or PQ developer having a pH of 11.0 to 12.3 to obtain a super-high contrast negative image having a γ of more than 10. It is a system to obtain, by this method, photographic characteristics of ultra-high contrast and high sensitivity can be obtained, and since a high concentration of sulfite can be added to the developing solution, the stability of the developing solution against air oxidation is Greatly improved compared to lith developer.

Further, in the field of photoengraving, there is a demand for a photographic light-sensitive material having good original reproducibility, a stable processing solution, or easy replenishment in order to cope with the variety and complexity of printed matter. . Especially in the line drawing process,
Manuscripts are created by embedding typesetting letters, handwritten letters, illustrations, and half-tone dots. Therefore, images having different densities and line widths are mixed in the original document, and there is a strong demand for a plate-making camera, a photographic light-sensitive material, or an image forming method for finishing these original documents with good reproduction. On the other hand, for catalogs and plate making of large posters, enlarge halftone photographs (expand)
Alternatively, reduction (meshing) is widely performed, and in plate making in which halftone dots are enlarged and used, the number of lines becomes rough, and blurred points are photographed. In reduction, the number of lines / inch is larger than that of the original, and the image is taken at a thin point. Therefore, an image forming method having a wider latitude is required to maintain the reproducibility of halftone.

As a method for improving the original reproducibility, a layer containing a redox compound which releases a development inhibitor by oxidation in Japanese Patent Application Nos. 1-108215 and 1-240967, and a photosensitive halogen containing a hydrazine derivative. An ultrahigh-contrast silver halide light-sensitive material having a multilayer structure having a silver halide emulsion layer is disclosed. This greatly improves the original reproducibility. However, improving the original reproducibility is a permanent problem in graphic arts sensitive materials.

Further, in the above method, the stability of the developing solution can be increased by the high concentration of the sulfite preservative, but in order to obtain a super high contrast photographic image, the pH is relatively high.
It is necessary to use a value of developer, which makes the developer susceptible to air oxidation. Therefore, an ultra-high contrast photographic image forming system utilizing nucleation development of a hydrazine compound
Attempts have been made to realize a developer having a lower pH.

JP-A-1-179939 and JP-A-1-17939
-179940 is a process of developing with a developer having a pH of 11.0 or less using a photosensitive material containing a nucleation development accelerator having an adsorption group for silver halide emulsion grains and a nucleation agent also having an adsorption group. The method is described. However, when a compound having an adsorptive group is added to a silver halide emulsion, if it exceeds a certain limit, the photosensitivity may be impaired, the development may be suppressed, or the action of other useful adsorptive additives may be hindered. Therefore, the amount used is limited, and sufficient hardness cannot be achieved. JP-A-60-1403
No. 40 discloses that the addition of amines to a silver halide photographic light-sensitive material improves the contrast. However, in the case of developing with a developer having a pH of less than 11.0, sufficient contrast cannot be expressed. JP-A-56
-106244 discloses that an amino compound is added to a developer having a pH of 10 to 12 to promote contrast. However, when amines are used by adding them to a developing solution, there are problems such as odor of the solution and stains due to adhesion to equipment used, or environmental pollution due to waste solution, and it is desired to incorporate it into a light-sensitive material. It has not yet been found that it can be added to a light-sensitive material to obtain sufficient performance.

US Pat. No. 4,998,604, and US Pat.
No. 94365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However,
As is clear from these examples, the contrast is not sufficient, and it is difficult to obtain the contrast and the required Dmax under practical development processing conditions.

In order to obtain a super-high contrast image by using a stable developing solution having a pH of less than 11.0, various investigations have been conducted, and a specific hydrazine nucleating agent and a specific quaternary onium salt nucleation promoting agent are contained in a light-sensitive material. It has been found that a super-high contrast image can be obtained by using the agent together.

However, when a highly active hydrazine compound is used, there is a problem that fog called black spots is likely to occur in the unexposed area.

It is well known that the type of sensitizing dye used affects nucleation development, but a sensitizing dye which does not suppress nucleation development and has a small residual color is desired. Was there.

In recent years, environmental problems have been highlighted, and in order to reduce the developing waste liquid, there has been a strong demand for a light-sensitive material having a small variation in photographic property depending on the developer composition.

[0012]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a silver halide photographic light-sensitive material excellent in original reproducibility and having less residual color. A second object of the present invention is to provide a silver halide photographic light-sensitive material which has high contrast and hardly causes black spots. A third object of the present invention is to provide a silver halide photographic light-sensitive material having a small fluctuation in photographic performance even when a large amount of film is processed, and a processing method thereof.

[0013]

The first object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. The layer contains at least one compound represented by the general formula (S), and at least one layer of the emulsion layer or other hydrophilic colloid layer can release at least one development inhibitor by being oxidized. Achieved by a silver halide photographic light-sensitive material characterized by containing a redox compound. General formula (S)

[0014]

[Chemical 9]

In the formula, Z represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. R ₁ represents an alkyl group. R ₂ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₃ represents a nitrogen-containing 5-membered heterocyclic group or a pyrazyl group. L ₁ and L ₂ each represent a methine group. n represents an integer of 0 or more and 3 or less. A second object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one compound represented by formula (S) is contained in the silver halide emulsion layer, and at least one hydrazine derivative is contained in at least one layer of the emulsion layer and other hydrophilic colloid layers. Achieved by a characteristic silver halide photographic light-sensitive material.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The specific constitution of the present invention will be described in detail below. The general formula (S) will be described in more detail. R ₁ preferably has 1 to 18 carbon atoms,
Preferably an unsubstituted alkyl group having 2 to 10 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl,
n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl),
Alternatively, it is a substituted alkyl group. R ₁ may combine with the methine group in L to form a ring. Examples of the substituent include a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a hydroxy group, a carbon number of 2 to 10, preferably a carbon number of 2 to 8. An alkoxycarbonyl group of (for example,
Methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), 6 to 12 carbon atoms, preferably carbon An aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-tolyloxy), 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms
An acyloxy group (eg, acetyloxy, propionyloxy), a carbon number of 2 to 12, preferably an acyl group of 2 to 8 carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl), a carbon number of 1 to 10, a carbon number of 1 To 5 carbamoyl groups (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), 0 to 10 carbon atoms,
A sulfamoyl group having 0 to 5 carbon atoms (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), an aryl group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (eg, Phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) and the like. Particularly preferred as R ₁ are unsubstituted alkyl groups (eg, methyl, ethyl, n-propyl, n-butyl), carboxyalkyl groups (eg, 2-carboxyethyl, carboxymethyl), sulfoalkyl groups (eg, 2 -Sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-
Sulfobutyl), methanesulfonylcarbamoylmethyl group.

The 5- or 6-membered nitrogen-containing heterocycle completed by Z may be further condensed and may be saturated or unsaturated. In addition to nitrogen, an oxygen atom as a hetero atom, It may contain a sulfur atom, a selenium atom, or a tellurium atom. Preferred examples include benzothiazole nucleus, benzoxazole nucleus, benzoselenazole nucleus, benzoterrazole nucleus, 2-quinoline nucleus, 4-quinoline nucleus, isoquinoline nucleus, pyridine nucleus, indolenine nucleus, benzimidazole nucleus, naphthothiazole nucleus. , Naphthoxazole nucleus, naphthoselenazole nucleus, naphthotelrazole nucleus, naphthimidazole nucleus, oxazole nucleus, thiazoline nucleus,
Selenazoline nucleus, indoline nucleus, oxazoline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus,
Examples thereof include a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, an imidazo [4,5-b] quinoxaline nucleus and a pyrimidine nucleus, and more preferably an oxazole nucleus, a benzoxazole nucleus, a naphtho [1,2-d] oxazole nucleus, a naphtho. A [2,1-d] oxazole nucleus, a naphtho [2,3-d] oxazole nucleus, an oxazoline nucleus and a thiazoline nucleus are preferable, and a benzoxazole nucleus is particularly preferable. These nitrogen-containing heterocycles may have a substituent, and specific examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), and a carbon number of 1 to 1.
2, preferably an unsubstituted alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl), 1 to 6 carbon atoms,
Preferably an alkoxy group having 1 to 4 carbon atoms (for example,
Methoxy, ethoxy, propoxy, isopropoxy),
A hydroxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, preferably 2 to 5 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl), an alkylcarbonyloxy group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms (eg, , Acetyloxy, propionyloxy), phenyl group, hydroxyphenyl group, carbon number 3
To 15 and preferably 5 to 10 carbon atoms and groups having an amide group and an aromatic ring at the same time (for example, p-acetylaminophenyl, m-acetylaminophenyl, 2-pyrrolecarboxamide, m-hydroxybenzamide,
2,6-dihydroxybenzamide, 2-furancarboxamide, 2-thiophenecarboxamide), furyl group, pyrrolyl group and the like can be mentioned.

R ₂ is a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms (eg, allyl, 2-methylallyl), 5 to carbon atoms. 12 unsubstituted or substituted aryl groups (eg phenyl, tolyl,
m-cyanophenyl, p-hydroxyphenyl). Preferred examples of the unsubstituted alkyl group include methyl,
Examples thereof include ethyl, propyl, and butyl, with an ethyl group being more preferable. Examples of the substituted alkyl group have 3 to 12 carbon atoms, preferably 3 to 7 carbon atoms.
An alkoxycarbonylalkyl group of (eg, methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl), a hydroxyalkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (eg, 2
-Hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2,3-dihydroxypropyl),
A hydroxyalkoxyalkyl group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, (eg, hydroxymethoxymethyl, 2- (2-hydroxyethoxy) ethyl, 2-hydroxyethoxyethyl), 2 to 12 carbon atoms, preferably Is a carbamoylalkyl group having 2 to 8 carbon atoms (N-alkyl substituted, N, N-dialkyl substituted,
An N-hydroxyalkyl-substituted, N-alkyl-N-hydroxyalkyl-substituted or N, N-di (hydroxyalkyl) -substituted substituted carbamoylalkyl group and 5,
It includes a carbamoylalkyl group of a 6-membered cyclic amine.
For example, 2-carbamoylethyl, 2-N- (2-hydroxyethyl) carbamoylethyl, N, N-di (2-
Hydroxyethyl) carbamoylmethyl, N, N-di (2-hydroxyethyl) carbamoylethyl, N, N
-Dimethylcarbamoylmethyl, morpholinocarbamoylmethyl, piperidinocarbamoylmethyl), a hydroxyphenyl group (eg o-hydroxyphenyl, p-
Hydroxyphenyl, 2,6-dihydroxyphenyl), a hydroxyalkylphenyl group having 7 to 9 carbon atoms (for example, p- (2-hydroxyethyl) phenyl,
m- (1-hydroxyethyl) phenyl) may be mentioned, but particularly preferably, a hydroxyethyl group, 2
A-(2-hydroxyethoxy) ethyl group and a 2-hydroxyethoxyethyl group.

L ₁ and L ₂ each independently represent a substituted or unsubstituted methine group. Examples of the substituent include an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms (eg, methyl, ethyl, 2
-Carboxyethyl), a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, preferably 6 to 10 carbon atoms (eg phenyl, o-carboxyphenyl), 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. An alkoxy group (eg, methoxy, ethoxy), a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), amino group, 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms
4 substituted amino groups (eg, N, N-diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino), carboxy groups, alkylthio groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (eg, , Methylthio, ethylthio) and the like. Also,
L ₁ and L ₂ may form a ring with each other or with an auxiliary chromophore. Preferred as n are 0, 1, 2 and 3, and particularly preferred are 0, 1 and 2.

The nitrogen-containing 5-membered heterocycle in R ₃ may be further condensed, and may be saturated or unsaturated, which may contain, as a hetero atom, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom in addition to nitrogen. It is a nitrogen-containing 5-membered heterocycle. R ₃
Is preferably an unsaturated nitrogen-containing 5-membered heterocyclic group. R ₃
Examples of include a substituted or unsubstituted 2-pyrrolyl group, 3
-Pyrrolyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4
-Isoxazolyl group, 5-isoxazolyl group, 2-
Thiazolyl group, 4-thiazolyl group, 5-thiazolyl group,
3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 3-flazanyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 3-pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group,
1,2,4-triazolyl group, tetrazolyl group, 1,
2,3-thiadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, 1,2,4-dithiazolyl group, 2,1,3-thiadiazolyl group, 1,
2,4-oxadithiazolyl group, 1,3,4-oxadithiazolyl group, 2-pyrrolidinyl group, 2-imidazolidinyl group, 3-pyrazolidinyl group, 2-oxazolidinyl group, 3-isooxazolidinyl group , 2-thiazolidinyl group, 3-isothiazolidinyl group and the like, and preferably 2-thiazolyl group, 4-thiazolyl group, 2-imidazolyl group, 4-imidazolyl group, 3-pyrazolyl group, 4-pyrazolyl group. , 5-pyrazolyl group, 1,2,4
-Triazolyl group and tetrazolyl group, particularly preferably 2-thiazolyl group, 3-pyrazolyl group, 1,2,4
A triazolyl group. The substituent on the nitrogen-containing 5-membered heterocycle may be substituted on either the carbon atom or the nitrogen atom forming the heterocycle, and examples of the substituent on the carbon atom include a halogen atom (eg, fluorine, chlorine, bromine). ), An unsubstituted alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (eg, methyl, ethyl, propyl), an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms (eg, methoxy). , Ethoxy, propoxy, isopropoxy), a hydroxy group, an alkoxycarbonyl group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl), 2 to 8 carbon atoms, preferably 2 carbon atoms To 4 alkylcarbonyloxy groups (eg acetyloxy, propionyloxy), phenyl groups, tolyl groups, hydroxy A phenyl group, an amino group, a substituted amino group having 1 to 20 carbon atoms, preferably 1 to 14 carbon atoms (eg, N, N-dimethylamino group, N-methyl-N-phenylamino group), a cyano group and the like can be mentioned. However, a halogen atom (eg chlorine, bromine) or an unsubstituted alkyl group (eg methyl, ethyl) is particularly preferable. Examples of the substituent of the nitrogen atom include an unsubstituted alkyl group having 1 to 10 carbon atoms, preferably 2 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl), 1 to 10 carbon atoms, preferably carbon number A carboxyalkyl group having 2 to 6 (eg, 2-carboxyethyl, carboxymethyl), a sulfoalkyl group having 1 to 10 carbon atoms, preferably having 2 to 6 carbon atoms (eg, 2-sulfoethyl, 3-sulfopropyl, 4- Sulfobutyl, 3-sulfobutyl), methanesulfonylcarbamoylmethyl group, cyanoalkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (eg, cyanoethyl, cyanopropyl), 1 carbon atom
To 10, preferably C 1 to C 6 halogenated alkyl groups (eg, trifluoromethyl, 2,2,2
-Trifluoroethyl), a hydroxyalkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (eg, 2-hydroxyethyl, 2-hydroxypropyl), 3 to 16 carbon atoms, preferably 3 to 8 carbon atoms. An alkoxycarbonylalkyl group (for example, methoxycarbonylethyl, ethoxycarbonylmethyl), a C 2-16, preferably a C 2-8 alkoxyalkyl group (for example, methoxyethyl, ethoxyethyl), a C 3-12, Preferably, an acyl group having 3 to 8 carbon atoms (eg, acetyl, propionyl,
Benzoyl, mesyl), a carbamoyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), 1 to 1 carbon atoms.
0, preferably a sulfamoyl group having 1 to 6 carbon atoms (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms Examples thereof include groups (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) and the like. Particularly preferred are unsubstituted alkyl groups (eg, methyl, ethyl), sulfoalkyl groups (eg,
3-sulfopropyl, 4-sulfobutyl) and an acetyl group.

When R ₃ is an unsubstituted or substituted pyrazyl group, R ₃ may be further condensed. The substituent on the pyrazine ring may be substituted on either the carbon atom or the nitrogen atom forming the ring, and examples of the substituent on the carbon atom include a halogen atom (eg fluorine, chlorine, bromine) and the number of carbon atoms. 1 to 6, preferably 1 to 3 carbon atoms
An unsubstituted alkyl group (eg, methyl, ethyl, propyl) having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms
An alkoxy group (eg, methoxy, ethoxy, propoxy, isopropoxy), a hydroxy group, an alkoxycarbonyl group having 2 to 8 carbon atoms, preferably an alkoxycarbonyl group having 2 to 5 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl), 2 to 8, preferably an alkylcarbonyloxy group having 2 to 4 carbon atoms (eg, acetyloxy, propionyloxy), a phenyl group, a tolyl group,
Hydroxyphenyl group, amino group, 1 to 2 carbon atoms
0, preferably a substituted amino group having 1 to 14 carbon atoms (for example, N, N-dimethylamino group, N-methyl-N-phenylamino group), cyano group, and the like, and more preferably none. Substituted alkyl groups (eg, methyl, ethyl) and alkoxy groups (eg, methoxy, ethoxy).

As an example of the substituent of the nitrogen atom, the number of carbon atoms is 1.
To C10, preferably C2 to C4 unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, butyl), C1 to C10, preferably C2 to C6 carboxyalkyl groups (e.g., 2-carboxy). Ethyl, carboxymethyl), a sulfoalkyl group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms (eg,
2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl), methanesulfonylcarbamoylmethyl group, 1 to 6 carbon atoms, preferably 1 carbon atom
To 4 cyanoalkyl groups (eg, cyanoethyl,
Cyanopropyl), a halogenated alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (eg, trifluoromethyl, 2,2,2-trifluoroethyl),
A hydroxyalkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (eg, 2-hydroxyethyl,
2-hydroxypropyl), an alkoxycarbonylalkyl group having 3 to 16 carbon atoms, preferably 3 to 8 carbon atoms (eg, methoxycarbonylethyl, ethoxycarbonylmethyl), 2 to 16 carbon atoms, preferably 2 to 8 carbon atoms An alkoxyalkyl group (eg, methoxyethyl, ethoxyethyl), having 3 to 12 carbon atoms,
Preferably, an acyl group having 3 to 8 carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl), 1 carbon atom
To 10, preferably carbamoyl group having 1 to 6 carbon atoms (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms (For example, sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl,
Piperidinosulfonyl), an aryl group having 6 to 18 carbon atoms, preferably 6 to 10 carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) and the like, and more preferable ones. ,
It is an unsubstituted alkyl group (for example, methyl, ethyl), a sulfoalkyl group (for example, 3-sulfopropyl, 4-sulfobutyl), and an acetyl group. Particularly preferred as R ₃ are pyrazyl group and 5-methylpyrazyl group.

A preferred combination of the substituents represented by R ₁ , R ₂ and R ₃ , the group of atoms represented by Z and n is 0, 1 and 2, and Z forms a benzoxazole nucleus. A combination, more preferably, R ₁ is a sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl), and R ₂ is a hydroxyalkoxyalkyl group (for example, Hydroxymethoxymethyl, 2-hydroxyethoxyethyl) or hydroxyalkyl groups (eg 2-hydroxyethyl, 2-hydroxypropyl)
And a particularly preferred one is R ₃ is 2.
-Thiazolyl group, 3-pyrazolyl group (e.g., 3-pyrazolyl, 3- (5-methyl-pyrazolyl), 3- (4-
Chloro-5-methylpyrazolyl), 3- (1,2,4-
(Triazolyl) an unsubstituted pyrazyl group or a 5-methylpyrazyl group in combination. Specific examples of the compound represented by formula (S) are shown below, but the invention is not limited thereto.

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

[0033]

[Chemical 19]

[0034]

[Chemical 20]

[0035]

[Chemical 21]

[0036]

[Chemical formula 22]

[0037]

[Chemical formula 23]

[0038]

[Chemical formula 24]

[0039]

[Chemical 25]

[0040]

[Chemical formula 26]

[0041]

[Chemical 27]

[0042]

[Chemical 28]

[0043]

[Chemical 29]

In the present invention, the synthesis of the methine compound represented by the general formula (S) can be carried out with reference to the following references and the synthesis examples described in the references cited therein. a) Dokradi Academia Nauk SSSR (Do
kl. Akad. Nauk SSSR), 177, 869 (19)
67 years). b) "Heterocyclic Compounds-Cyanine Die and." by FM Harmer.
Related Compounds (Heterocyclic compound
s-Cyanine dyes and related compounds-) '' (John Wiley & Sons),
New York London, 1964). c) by DM Starmer,
"Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry
(Heterocyclic Compounds-Special topics in hetero
cyclic chemistry ", pp. 482-515 (John Wiley & Sons, NY, London, 1977). d) Japanese Patent Publication No. 47-4085, Japanese Patent Publication No. 46-549,
US Patent 3,625,698, US Patent 3,567,
No. 458.

The compound represented by formula (S) of the present invention can be present in any layer in a silver halide photographic light-sensitive material, but in a hydrophilic colloid layer containing light-sensitive silver halide grains. In the above, it is preferable that the photosensitive silver halide grains are present in a state of being adsorbed. In order to incorporate the compound represented by formula (S) of the present invention into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol and acetone. , Methyl cellosolve, 2, 2, 3, 3
-Tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3
It may be added to the emulsion by dissolving it in a solvent such as -methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide or the like alone or as a mixed solvent.
Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is placed in an emulsion. A method of adding, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion as described in JP-B-46-24,185 and the like.
JP-B-44-23,389, JP-B-44-27,55
No. 5, JP-B-57-22,091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an aqueous solution is prepared by coexisting an acid or a base and added to the emulsion. As described in US Pat. No. 3,822,135, US Pat. No. 4,006,026, etc., an aqueous solution or colloidal dispersion containing a surfactant is added to the emulsion. Method, JP-A-53-102,7
33, JP-A-58-105,141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, JP-A-51-74,624.
It is also possible to use a method in which a dye is dissolved using a compound that causes red shift and the solution is added to the emulsion, as described in No. Ultrasonic waves can also be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention in any step of emulsion preparation which has been found to be useful so far. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat. No. 4,183,756.
No. 4,225,666, JP-A-58-18.
No. 4,142, JP-A-60-196749, and the like, as disclosed in the specification of the silver halide grain formation step or / and before desalting, during the desalting step and / or desalting step. From the time after salting to before the start of chemical aging, JP-A-58-1
As disclosed in the specification of No. 13,920, etc., it may be added at any time or step immediately before or during the chemical ripening, at any time before the emulsion is coated until after the chemical ripening and before the coating. May be. US Pat. No. 4,225,6
66, JP-A-58-7,629 and the like, the same compound alone or in combination with a compound having a different structure, for example, during the grain forming step and the chemical ripening step. Alternatively, it may be added in divided portions such as after completion of chemical aging or before or after chemical aging or after completion of the step, and the type of compound or combination of compounds added in division may be changed. May be added. The amount of the compound represented by formula (S) used in the present invention varies depending on the shape and size of silver halide grains, but is 0.1 to 4 mmol, preferably 0.2 to 2 per 1 mol of silver halide. It is 0.5 mmol and may be used in combination with other sensitizing dyes.

The redox compound capable of releasing the development inhibitor by being oxidized according to the present invention will be described. The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinone groups, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones, and more preferably hydrazines. The hydrazines used as the redox compound capable of releasing the development inhibitor by being oxidized in the present invention are preferably represented by the general formula (R-1), the general formula (R-2) and the general formula (R-3). Be done. The compound represented by formula (R-1) is particularly preferable.

[0048]

[Chemical 30]

In the formula, R ₁ represents an aliphatic group or an aromatic group. G ₁ is a -CO- group, a -COCO- group, a -CS- group,
_{-C (= NG 2 R 2)} - represents the group - group, -SO- group, -SO ₂ - group or _{-P (O) (G 2 R} 2). G ₂ is a mere bond, —O— group, —S— group or —N (R ₂ ) —
Represents a group, R ₂ represents a group having the same definition as R ₁ or a hydrogen atom, and when plural R ₂ are present in the molecule, they may be the same or different. A ₁ and A ₂ are hydrogen atoms,
It represents an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. General formula (R-
In 1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is synonymous with A ₁ or -CH ₂ CH (A ₄ )-(Time) _t -PUG
Represents A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfonyl group or -G ₁ -G ₂ -R ₁ (in this case, two -G ₁ -G ₂ -R ₁ in the molecule is different even with the same Is also good). Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor.

General formulas (R-1), (R-2), (R-
3) will be described in more detail. General formula (R-
In 1), (R-2) and (R-3), the aliphatic group represented by R ₁ is preferably one having 1 to 30 carbon atoms, particularly straight chain or branched one having 1 to 20 carbon atoms. Alternatively, it is a cyclic alkyl group. This alkyl group may have a substituent. In the general formulas (R-1), (R-2) and (R-3), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group and a substituted group. Amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group,
Examples thereof include a halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a carboxyl group, and a phosphoric acid amide group. Chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), aralkyl group (preferably having 7 to 30 carbon atoms), alkoxy group (preferably having 1 to 30 carbon atoms), substituted amino Group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), acylamino group (preferably 2 to 4 carbon atoms)
0), sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms), phosphoric acid amide group (preferably having 1 to 40 carbon atoms) ) And so on.

General formulas (R-1), (R-2), (R-
As G ₁ in 3), a —CO— group and a —SO ₂ — group are preferable, and a —CO— group is most preferable. A ₁ and A ₂ are preferably hydrogen atoms, A ₃ is a hydrogen atom, —CH _{2
-CH (A 4) - (Time} ) t -PUG are preferred.

General formulas (R-1), (R-2), (R-
In 3), Time represents a divalent linking group and may have a timing adjusting function. The divalent linking group represented by Time represents a group capable of releasing PUG from Time-PUG released from the oxidized product of the redox mother nucleus through a reaction in one step or more steps. Tim
Examples of the divalent linking group represented by e include U.S. Pat. No. 4,248,962 (JP-A-54-145,135).
Releasing PUG by an intramolecular ring closure reaction of the p-nitrophenoxy derivative described in U.S. Pat.
310,612 (JP-A-55-53,330) and 4,358,525, which release PUG by an intramolecular ring closure reaction after ring cleavage; US Pat. No. 4,330,617. Nos. 4,446,216, 4,483,919, JP-A-59-121,328, and the like, acid anhydrides by the intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or its analogs. Release of PUG with the formation of a product; US Pat. No. 4,40
9,323, 4,421,845, Research Disclosure No. 21,228 (December 1981)
U.S. Pat. No. 4,416,977 (JP-A-57-57).
135,944), JP-A-58-209,736,
No. 58-209,738, etc., which produces quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG; US Pat. 4,420,5
54 (JP-A-57-136,640) and JP-A-57.
-135,945, 57-188,035, 5
8-98,728 and 58-209,737, which release PUG from the γ-position of the enamine by electron transfer of the portion having the enamine structure of the nitrogen-containing heterocycle; JP-A-57-56, No. 837, which releases PUG by an intramolecular ring-closing reaction of an oxy group formed by electron transfer to a carbonyl group conjugated with a nitrogen atom of a nitrogen-containing heterocycle; U.S. Pat. No. 4,146,396. 52-90932), JP-A-59-93,442,
JP-A-59-75475, JP-A-60-249148
Releasing PUG with the formation of aldehydes described in JP-A No. 60-249149;
146, 828, 57-179, 842, 59
-O-COOCR _a R _b- PUG which releases PUG with decarboxylation of the carboxyl group described in -104,641;
(R _a and R _b represent a monovalent group) and release PUG with decarboxylation and subsequent formation of aldehydes; JP-A-60-7,429 Examples thereof include those releasing PUG with the formation of isocyanate; those releasing PUG by a coupling reaction with an oxidized product of a color developing agent described in US Pat. No. 4,438,193 and the like. Specific examples of these divalent linking groups represented by Time are described in JP-A-61-23.
6,549, Japanese Patent Application No. 63-98,803, Japanese Patent Application No. 2
It is also described in detail in, for example, No. -93487.

General formulas (R-1), (R-2), (R-
In 3) PUG is a development inhibitor. PUG has a heteroatom, the general formula (R-1) via the heteroatom,
It is bonded to the other part of the compound represented by (R-2) or (R-3). An example of a commonly known development inhibitor is, for example, "The Theory of the Photographic Process" by TH James.
Theory of the Photographic Process) "4th Edition, 19
1977, Macmillan, 396-39.
Page 9 and Japanese Patent Application No. 2-93,487, pages 56 to 69. These development inhibitors may have a substituent. Examples of useful substituents include mercapto group, nitro group, carboxyl group, sulfo group, phosphono group, hydroxy group, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, amino group. , Acylamino group, sulfonylamino group, ureido group, urethane group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, An acyloxy group, a carbonamido group, a sulfonamide group, a phosphonamido group, etc. are mentioned, and these groups may be further substituted.

The development inhibitor represented by PUG used in the present invention is preferably a compound which inhibits nucleated infectious development. Nucleating infectious development is a new development chemistry used in the image forming method of the Fuji Film GRANDEX system (Fuji Photo Film Co., Ltd. and Kodak Ultratec system (Eastman Kodak Co., Ltd.). Ordinary development of exposed silver halide grains, as described in The Journal of the Photographic Society of Japan, Vol. 52, No. 5, 390-394 (1989) and "Journal of Photographic Science", Vol. 35, 162 (1987). Nucleating active species are generated based on the cross-oxidation between the developing process of the main agent and the oxidation product of the developing agent and the nucleating agent, and the surrounding unexposed to weakly exposed halogenation by the active species. 2 of nucleation and development process of silver particles
It consists of two processes. Therefore, the whole development process is
Since it consists of the sum of the normal development process and the nucleation development process, in addition to the conventional development inhibitor conventionally known as a development inhibitor, a compound that newly inhibits the nucleation-infectious development process has an inhibitory effect. It can be demonstrated. The latter is referred to herein as a nucleation development inhibitor. The development inhibitor represented by PUG used in the present invention is preferably a nucleation development inhibitor. As a compound acting as a nucleation development inhibitor, conventionally known development inhibitors are effective, but particularly useful compounds. Is a compound having at least one nitro group or a nitroso group, a nitrogen-containing heterocyclic skeleton such as pyridine, pyrazine, quinoline, quinoxaline, or phenazine, particularly a compound having a 6-membered nitrogen-containing heteroaromatic ring skeleton, N -Compounds having a halogen bond, quinones, tetrazoliums, amine oxides, azoxy compounds, coordination compounds having an oxidizing ability, and the like. Among them, a compound having a nitro group and a compound having a pyridine skeleton are particularly effective.

These nucleation development inhibitors may have a substituent, and the properties of the substituent, such as electron withdrawing property, electron donating property, hydrophobicity, hydrophilicity, charge, and adsorptivity to silver halide. It is possible to control various characteristics such as strength of development inhibition and easiness of diffusion by such properties. Examples of useful substituents are those listed above as examples of common development inhibitor substituents. Specific examples of these nucleation development inhibitors useful in the present invention are described in detail in JP-A-4-13639, 4-136840 and the like, as well as JP-A-4-136841 and Japanese Patent Application No. No. 15648, No. 3-70411, No. 3-7
It is also described as Ind in 0388. Further, as another series of nucleation development inhibitors, an adsorptive compound to a silver halide grain having an anionic charged group or a dissociative group capable of dissociating in a developing solution to generate anionic charge is also effective. .

The general formulas (R-1), (R-2) and (R
-3), R ₁ or Time is a ballast group or a general formula (R-1), (R-2), (R-3) commonly used in a non-moving photographic additive such as a coupler. A group that promotes the adsorption of the compound represented by the formula (1) to silver halide may be incorporated. The ballast group is an organic compound giving a molecular weight sufficient to prevent the compounds represented by the general formulas (R-1), (R-2) and (R-3) from substantially diffusing into another layer or the treatment liquid. The group is a group consisting of one or more of an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, an amide group, a ureido group, a urethane group, a sulfonamide group and the like. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the adsorption promoting group for silver halide include 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine,
Thiobarbituric acid, tetrazoline-5-thione, 1,
2,4-triazoline-3-thione, 1,3,4-oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3- Cyclic thioamide group such as imidazoline-2-thione, chain thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (If the carbon atom next to the -SH group is a nitrogen atom, this It has the same meaning as a cyclic thioamide group in a tautomeric relationship, and specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benz Imidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oki A 5- to 6-membered nitrogen-containing heterocyclic group consisting of a combination of nitrogen, oxygen, sulfur and carbon such as sol, oxazoline, thiadiazole, oxathiazole, triazine and azaindene, and a heterocyclic quaternary group such as benzimidazolinium Examples include salt. These may be further substituted with appropriate substituents. Examples of the substituent include those mentioned as the substituent of R ₁ . Specific examples of the compound used in the present invention are listed below, but the present invention is not limited thereto.

[0059]

[Chemical 31]

[0060]

[Chemical 32]

[0061]

[Chemical 33]

[0062]

[Chemical 34]

[0063]

[Chemical 35]

[0064]

[Chemical 36]

[0065]

[Chemical 37]

[0066]

[Chemical 38]

[0067]

[Chemical Formula 39]

[0068]

[Chemical 40]

[0069]

[Chemical 41]

[0070]

[Chemical 42]

[0071]

[Chemical 43]

[0072]

[Chemical 44]

[0073]

[Chemical formula 45]

[0074]

[Chemical formula 46]

[0075]

[Chemical 47]

As the redox compound used in the present invention, in addition to the above compounds, for example, JP-A-61-213,8 can be used.
No. 47, No. 62-260, 153, Japanese Patent Application No. 1-10
No. 2,393, No. 1-102, 394, No. 1-10
No. 2,395, No. 1-114,455, No. 1-290
No. 563, No. 2-62337, No. 2-64717,
No. 2-258927, No. 2-258928, No. 2-
258929, 3-15648, 3-7041
No. 1 and No. 3-70388 can be used. The method for synthesizing the redox compound used in the present invention is described in the above-mentioned materials, and for example, US Pat. No. 4,684,604, Japanese Patent Application No. 63-98,803.
U.S. Pat. Nos. 3,379,529 and 3,620,
No. 746, No. 4,377, 634, No. 4,332, 8
78, JP-A-49-129,536 and JP-A-56-15.
3, 336, 56-153, 342, etc.

The redox compound of the present invention is used in the range of 1 × 10 ^{-6 to} 5 × 10 ^-2 mol, and more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver halide. . The redox compound of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving in dimethyl sulfoxide, methyl cellosolve and the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The redox compound of the present invention is added to a silver halide emulsion layer or other hydrophilic colloid layer. Further, it may be added to at least one of a plurality of silver halide emulsion layers. Although some constitutional examples are given, the present invention is not limited to these. Structural Example 1) A silver halide emulsion layer containing the redox compound of the present invention and a protective layer are provided on a support. These emulsion layers or protective layers may contain the hydrazine derivative of the present invention as a nucleating agent. Structural Example 2) A first silver halide emulsion layer and a second silver halide emulsion layer are sequentially provided on a support, and the first silver halide emulsion layer or the adjacent hydrophilic colloid layer is provided. , The hydrazine derivative, and the redox compound in the second silver halide emulsion layer or the adjacent hydrophilic colloid layer. Structure Example 3) In Structure Example 2), the order of the two emulsion layers is reversed. In the constitution examples 2) and 3), an intermediate layer containing gelatin or a synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the two photosensitive emulsion layers. Structural Example 4) A silver halide emulsion layer containing the hydrazine derivative is provided on a support, and the hydrophilic layer containing the redox compound is provided on the emulsion layer or between the support and the silver halide emulsion layer. Having an organic colloid layer. A particularly preferred configuration is configuration example 2) or 3).

The hydrazine derivative used in the present invention will be described. In the present invention, the compound of general formula (I) described in Japanese Patent Application No. 6-47961 is used. Specifically, the compounds represented by I-1 to I-53 described in the same specification are used.

The following hydrazine derivatives are also preferably used. The compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically the compounds described on pages 3 and 4 of the publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, pages 8 to 1 of the publication;
1 to 38 compounds described on page 8. JP-A-6-23049
Compounds represented by the general formula (4), the general formula (5) and the general formula (6) described in No. 7, specifically, page 25 of the same publication;
Compounds 4-1 to 4-10 described on page 26, Compounds 5-1 to 5-42 described on pages 28 to 36, and 39
Compound 6-1 to compound 6-7 described on page 40. Compounds represented by the general formula (1) and the general formula (2) described in JP-A-6-289520, specifically, from page 5 of the same publication.
Compounds 1-1) to 1-17) and 2-described on page 7
1). The compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically the compounds described on pages 6 to 19 of the same. The compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically the compounds described on pages 3 to 5 of the publication. Compounds represented by formula (I) described in JP-A-7-5610, specifically compounds I-1 to I-38 described on pages 5 to 10 of the same; Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the publication. Compounds represented by formula (H) and formula (Ha) described in JP-A-7-104426, specifically compound H described on pages 8 to 15 of the same;
-1-H-44.

The hydrazine derivative particularly preferably used in the present invention is a compound characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group and a general formula ( It is the compound of 1).

First, the former will be described.

Specific examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means that an atom 2 to 5 selected from at least one of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom is present between the nitrogen atom close to the anionic group of hydrazine and the anionic group.
It means that there is an intervening bond chain formed by individuals. More preferably as a neighborhood, there is an intervening bond chain formed of 2 to 5 atoms selected from at least one of carbon and nitrogen atoms, and even more preferably a bond chain formed of 2 to 3 carbon atoms. This is when intervening. The nonionic group forming an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and contains at least an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following general formulas (A), (B) and (C). General formula (A)

[0084]

[Chemical 48]

(In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine, and Represents a nonionic group forming an intramolecular hydrogen bond.) General formula (B)

[0086]

[Chemical 49]

(Wherein R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (C)

[0088]

[Chemical 50]

(Wherein X ³ represents a group capable of substituting on a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (A), (B) and (C) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, t-butyl, Allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl. Is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferable as R ¹ and R ² .
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amido group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphorus amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

[0093] alkyl groups R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Is a linear, branched or cyclic alkoxy group, and is, for example, methoxy, isopropoxy or benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group or an alkynyl group. n ³ =
When 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group of R ³ has a Hammett σm value of 0.2 or more, preferably 0.3.
Examples of the above include halogen atoms (fluorine, chlorine, bromine), cyano groups, sulfonyl groups (methanesulfonyl, benzenesulfonyl), sulfinyl groups (methanesulfinyl), acyl groups (acetyl, benzoyl), oxycarbonyl groups (methoxycarbonyl). ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, and -O-, -S-,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-butene-1,4-yl, 2
-Butyn-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene-, -NH-arylene are preferable,
-NH-alkylene and -O-alkylene- are more preferable.

Examples of the electron-withdrawing group possessed by L ¹ include R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). The nonionic group is a group having at least one of an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. As Y ¹ to Y ³ , an anionic group is preferable, and a carboxylic acid and its salt are more preferable.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable groups include those mentioned as the substituents of R ^{1 in the} general formula (A). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler, or may have an adsorption promoting group for silver halide. The diffusion resistant group has 8 to 30 carbon atoms, preferably 12 to 25 carbon atoms. The adsorption promoting group for silver halide is preferably a thioamide (eg thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
Is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorbing group is protected and the protecting group is removed during the development processing to enhance the adsorptivity to silver halide.

In the general formulas (A), (B) and (C),
The radicals from which the hydrogen atoms of the two compounds are removed may combine with each other to form a bis type. In the general formulas (A), (B), and (C), the general formulas (A) and (B) are preferable, and the general formula (A) is more preferable. Further, in the general formulas (A), (B) and (C), the following general formulas (D), (E) and (F) are more preferable, and the general formula (D) is most preferable. General formula (D)

[0101]

[Chemical 51]

(In the formula, R ⁴ , X ⁴ and m ⁴ are respectively synonymous with R ³ , X ³ and m ^{3 of the} general formula (C), and L ⁴ , Y ^{4 and}
Is synonymous with L ¹ and Y ¹ of the general formula (A). ) General formula (E)

[0103]

[Chemical 52]

(In the formula, R ⁵ , X ⁵ and m ⁵ have the same meanings as R ³ , X ³ and m ^{3 in} formula (C), respectively, and L ⁵ , Y ^{5 and}
Is synonymous with L ² and Y ^{2 in} the general formula (B). ) General formula (F)

[0105]

[Chemical 53]

(In the formula, R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ ,
Y has the same meaning as R ³ , X ³ , m ³ , n ³ and Y ³ in the general formula (C). )

Specific examples of the nucleating agent used in the present invention are shown below, but the present invention is not limited thereto.

[0108]

[Chemical 54]

[0109]

[Chemical 55]

[0110]

[Chemical 56]

[0111]

[Chemical 57]

[0112]

[Chemical 58]

[0113]

[Chemical 59]

Next, the hydrazine derivative represented by the general formula (1) will be described in detail. General formula (1)

[0115]

[Chemical 60]

In the formula, R ₀ represents a difluoromethyl group or a monofluoromethyl group, and A ₀ represents an aromatic group.
However, at least one of the substituents possessed by A ₀ is a diffusion resistant group, a silver halide adsorption promoting group, an alkylthio group, an arylthio group, a heterocyclic thio group, a quaternary ammonium group,
A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a saturated heterocyclic group containing a sulfide bond or a disulfide bond, or at least one of these groups It is a substituent containing.

Among the compounds represented by the general formula (1), preferable compounds are represented by the following general formula (1-a). General formula (1-a)

[0118]

[Chemical formula 61]

In the formula, R1 represents a difluoromethyl group or a monofluoromethyl group, A1 represents a divalent aromatic group, R2 and R3 represent a divalent aliphatic group or an aromatic group, and L1 and L2 are It represents a divalent linking group, and m2 and m3 each independently represent 0 or 1. X1 is a diffusion resistant group, a silver halide adsorption promoting group, an alkylthio group, an arylthio group, a heterocyclic thio group, a quaternary ammonium group, and a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom,
It represents an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a saturated heterocyclic group containing a sulfide bond or a disulfide bond.

Among the compounds represented by the general formula (1-a), preferred compounds are represented by the following general formula (1-b). General formula (1-b)

[0121]

[Chemical formula 62]

In the formula, X11, R11, R21, R31, L21, m21
And m31 are each X1 in the general formula (1-a).
, R2, R3, L2, m2 and m3 have the same meanings, Y represents a substituent and n represents an integer of 0 to 4. Next, the compound represented by formula (D) will be described in detail. The aromatic group represented by A ₀ in the general formula (D) is a monocyclic or bicyclic aryl group and an aromatic heterocyclic group. Specifically, a benzene ring, a naphthalene ring,
Examples thereof include a pyridine ring, quinoline ring, isoquinoline ring, pyrrole ring, furan ring, thiophene ring, thiazole ring and indole ring. A ₀ preferably contains a benzene ring, and particularly preferably a benzene ring. A ₀ may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, an acyloxy group, an acyl group, an oxycarbonyl group, a carbamoyl group, N-sulfonylcarbamoyl group, carboxyl group, substituted amino group, acylamino group, sulfonamide group, ureido group, urethane group, sulfonylureido group,
Alkylthio group, arylthio group, sulfonyl group, sulfamoyl group, acylsulfamoyl group, carbamoylsulfamoyl group, sulfo group, cyano group, halogen atom, phosphinyloxy group, phosphinylamino group, sulfamoylamino group , Oxamoylamino group and the like. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an acylamino group, a carbamoyl group, an alkoxy group, a substituted amino group, an alkyl group and an oxycarbonyl group are preferable, and a sulfonamide group and a ureido group are particularly preferable. Next, the specific group which the substituent of A ₀ should have will be described in detail.
The diffusion resistant group means a diffusion resistant group in a photographic coupler or the like, a so-called ballast group, which is used when the compound of the present invention is added to a specific silver halide emulsion layer. Is a group that can easily prevent diffusion to other layers, or a group that can be prevented from being easily eluted in a developing solution during development. Specifically, it is a group having 8 or more total carbon atoms, preferably 8 to 16 carbon atoms in total, and as a ballast group, preferably an alkyl group, an aryl group, an alkoxy group, an aryl group having 8 or more total carbon atoms. Examples thereof include an oxy group, an oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a carbonyloxy group, a ureido group, a sulfamoyl group, and a group consisting of a combination thereof. When A ₀ has a ballast group, the total number of carbon atoms of A ₀ including the ballast group is 14 or more.

The adsorption promoting group for silver halide is preferably a thioamide group, a mercapto group, a group having a disulfide bond or a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption promoting group is a divalent group represented by -CS-amino- and may be a part of the ring structure or may be an acyclic thioamide group.
Useful thioamide adsorption promoting groups are described, for example, in US Pat.
No. 30,925, No. 4,031,127, No. 4,08
0,207, 4,245,037, 4,25
5,511, 4,266,013, and 4,2
76, 364, and "Research Disclosure," Vol. 151, No. 1.
5162 (November 1976), and Vol. 176, N
o. 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione and 4-thiazoline-2-thione group. Imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3.
4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione and the like can be mentioned. It may be substituted. As the mercapto group, an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the —SH group is bonded is a nitrogen atom next to the carbon atom, a cyclic thioamide group having a tautomeric relationship therewith) Are synonymous, and specific examples of this group are the same as those listed above).

Examples of the 5- to 6-membered nitrogen-containing heterocyclic group include 5- to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like.
These may be further substituted with appropriate substituents.
Preferred as the adsorption promoting group is a cyclic thioamide group (that is, a mercapto-substituted nitrogen-containing heterocycle, for example, 2
-Mercaptothiadiazole group, 3-mercapto-1,
2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or a nitrogen-containing heterocyclic group forming iminosilver (for example, , A benzotriazole group, a benzimidazole group, an indazole group, etc.). In the present invention, the adsorption promoting group includes its precursor. The precursor is an adsorption promoting group with a precursor group, which is released by the developing solution for the first time during development, and reacts with hydroxide ion or sulfite ion in the developing solution or with a developing agent. It is disassembled as a scratch. Specifically, a carbamoyl group, a 1,3,3a, 7-tetrazainden-4-yl group, a uracil group, an alkoxycarbonyl group, or the 4-position is substituted with an ureido group, a sulfonamide group, or an amide group. 4-substituted-2,5-dihydroxyphenyl group and the like can be mentioned.

The alkylthio group is a substituted or unsubstituted, branched, cyclic or linear chain having 1 to 18 carbon atoms in total.
The alkylthio group of is preferably a substituent thereof,
An aryl group, an alkoxy group (including an alkoxy group containing repeating ethyleneoxy or propyleneoxy units), a carboxyl group, a carbonyloxy group, an oxycarbonyl group, an acylamino group, a quaternary ammonium group,
Examples thereof include an alkylthio group, a heterocyclic group, a sulfonamide group, and a ureido group. Specific examples of the alkylthio group include the following groups.

[0127]

[Chemical formula 63]

The arylthio group is a substituted or unsubstituted arylthio group having a total of 6 to 18 carbon atoms, and as the substituent, the substituent which A ₀ of the general formula (D) may have has been described. The same thing as is mentioned. The arylthio group is preferably a substituted or unsubstituted phenylthio group, specifically, a phenylthio group and 4-τ.
-Butylphenylthio group, 4-dodecylphenylthio group and the like.

The heterocyclic thio group is a substituted or unsubstituted, saturated or unsaturated heterocyclic thio group having 1 to 18 carbon atoms and contains at least one oxygen atom, nitrogen atom or sulfur atom. It is a 5- or 6-membered monocyclic heterocycle or a condensed heterocycle. Specifically, a benzothiazolylthio group, a 1-phenyl-5-tetrazolylthio group, 2
-Mercaptothiadiazolyl-4-thio group, pyridyl-
2-thio group and the like can be mentioned.

The quaternary ammonium group represents a quaternary aliphatic ammonium cation or a quaternary aromatic ammonium cation, and their counter anions. It may be a cyclic quaternary ammonium group, and the total carbon number of the quaternary ammonium cation is preferably 3 to 24. As the counter anion, specifically, chloro anion, bromo anion,
Examples thereof include iodo anion, sulfonate anion, and carboxylate anion. When the compound represented by the general formula (D) has a sulfo group, a carboxyl group, or the like, an inner salt may be formed.

When X represents a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, specific examples thereof include pyridinium group, quinolinium group, isoquinolinium group, phenanthrinium group, triazolinium group and imidazoli group. And a benzothiazolinium group. These groups may be further substituted with a substituent, but the substituent is preferably an alkyl group, an aryl group, an alkoxy group, an alkylcarbamoyl group, an amino group, an ammonium group or a heterocyclic group.

An alkoxy group containing an ethyleneoxy or propyleneoxy unit is specifically R ₄ -O- (CH ₂ CH ₂
O) _p- , R ₄ -O- {CH ₂ CH (CH ₃ ) O} _p- , or R ₄ -O-
It is an alkoxy group represented by {CH ₂ CH (OH) CH ₂ O} _p − and the like. Here, p represents an integer of 1 or more, and R ₄
Represents an aliphatic group or an aromatic group. R ₄ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Specifically, CH ₃ O (CH ₂ CH ₂ O) ₃ −, C ₆ H ₁₃ O
(CH ₂ CH ₂ O) ₂ −, C ₄ H ₉ O − (CH ₂ CH ₂ CH ₂ O) ₂ −, C ₈ H ₁₇ OCH _{2
CH (OH) CH 2 O -} , C 12 H 25 O- {CH 2 CH (CH 3) O} 2 -, C 2 H
_And groups such as ₅ O (CH ₂ CH ₂ O) ₆ − and the like.

The saturated heterocyclic group containing a sulfide bond or a disulfide bond is specifically -S- or -S-.
It represents a 5- or 6-membered saturated heterocycle containing an S-bond and is preferably a group shown below.

[0134]

[Chemical 64]

Next, the compound represented by formula (1-a) will be described. In the general formula (1-a), A ₁ represents a divalent aromatic group, which is the same as the general formula (1-a) except that the substituent that A ₀ should have is more limited. It is a group having almost the same meaning as A _{0 in} (D), and its preferable range is also the same. That is, the divalent aromatic group represented by A ₁ in the general formula (1-a) is preferably
It is a monocyclic arylene group, more preferably a phenylene group. When A ₁ represents a phenylene group, this may have a substituent. Examples of the substituent of the phenylene group include those described for the substituent of A _{0 in} the general formula (1), and preferably an alkyl group, an alkoxy group, a hydroxy group, an amino group, an alkylamino group, an acylamino group. , Sulfonamide group, ureido group,
It is a halogen atom, a carboxyl group, a sulfo group, etc., and the total number of carbon atoms in these groups is 1 to 12, particularly preferably 1
~ 8. When A ₁ represents a phenylene group, particularly preferably when A ₁ represents an unsubstituted phenylene group.

In the general formula (1-a), R2 and R3 are 2
Represents a valent aliphatic group or aromatic group. The divalent aliphatic group is a substituted or unsubstituted, linear, branched or cyclic alkylene group, alkenylene group or alkynylene group, and the aromatic group is a monocyclic or bicyclic arylene group. R2 and R3 are preferably an alkylene group or an arylene group, and most preferably R2 is a phenylene group and R3 is a phenylene group or an alkylene group. These are A in the general formula (1).
_It may have the same substituent as described for the substituent of ₀ .

In the general formula (1-a), the divalent linking group represented by L1 and L2 means --O--, --S--, --N.
(R _N) - (R _N represents a hydrogen atom, an alkyl group or an aryl group,.), - CO -, - SO 2 -, group alone etc., or a group composed of a combination of these groups.
The group consisting of a combination here specifically means -CO.
_{N (R N) -, -} SO 2 N (R N) -, - COO -, -
_{N (R N) CON (R} N) -, - SO 2 N (R N) CO
_{-, - SO 2 N (R} N) CON (R N) -, - N
_{(R N) COCON (R N} ) -, - N (R N) SO 2 N
(R _N )-and the like. In the general formula (1-a), L
1 is preferably -SO ₂ NH -, - NHCONH-,
-O -, - S -, - N (R N) - a, and most preferably -SO ₂ NH -, - it is -NHCONH-. L2 is _{preferably, -CON (R N) -,} - SO 2 NH -, - N
_{HCONH -, - N (R N} ) CONH -, - is COO-. Here L ₂ is -CON (R _N) - or -N
When representing the (R _N) CONH-, as R _N is a substituted alkyl group, it may be a represent the -R ₃ -X groups in Formula (1-a).

In the general formula (1-a), X1 is a diffusion resistant group, an adsorption promoting group on silver halide, an alkylthio group,
It represents an arylthio group, a heterocyclic thio group, a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a heterocyclic group containing a disulfide bond. These are the same as those described above as the substituent of A ₀ in the general formula (1) or the group contained in the substituent. In the general formula (1-a), X1 is an alkylthio group,
When representing an arylthio group, a heterocyclic thio group, a quaternary ammonium group, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a heterocyclic group containing a disulfide bond, R3 is preferably an alkylene group,
m3 represents 1. In the general formula (1-a), when X1 represents a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, the nitrogen-containing heterocyclic group is quaternized by the bond between the nitrogen atom and R3. In some cases, the quaternized nitrogen-containing heterocyclic group originally bonded to L2 or L1 without R3. In the former, m3 is 1, R3 is preferably an alkylene group, and in the latter, m3 represents 0.

Among the compounds represented by the general formula (1-a), more preferable compounds are represented by the general formula (1-b). In the formula, X11, R11, R21, R31, L21, m21 and m
31 is X1, R1 in the general formula (1-a),
R2, R3, L2, m2 and a group having the same meaning as m3,
Y represents a substituent, and n represents an integer of 0 to 4. The substituent represented by Y has the same meaning as the substituent which A1 may have in the general formula (1-a), and the preferred range is also the same. n is preferably 0 or 1, and more preferably n is 0.

In the compound represented by the general formula (1-b), when X11 represents an alkylthio group, more preferable ones are those represented by the following general formula (1-c). General formula (1-c)

[0141]

[Chemical 65]

In the formula, R ₁₂ is R ₁₁ in the general formula (1-b).
And R ₅ represents an alkylene group. L ₃₂
Represents an acylamino group, a carbamoyl group, a ureido group, an oxycarbonyl group or a sulfonamide group in connection with a benzene ring. When L ₃₂ represents an acylamino group, an oxycarbonyl group or a sulfonamide group, m ₄ represents 1, and when L ₃₂ represents a carbamoyl group or an ureido group, m ₄ represents 1 or 2. When m ₄ is 1,
R ₆ represents an unsubstituted alkyl group having a total carbon number of 7 or more, a substituted alkyl group having a total carbon number of 1 to 18, a cycloalkyl group having a total carbon number of 3 or more, and when m ₄ is 2, R ₆ is a total carbon number. Number 1
~ 18 substituted or unsubstituted alkyl groups, total carbon number 3
It represents the above cycloalkyl group.

The compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0144]

[Chemical formula 66]

[0145]

[Chemical formula 67]

[0146]

[Chemical 68]

[0147]

[Chemical 69]

[0148]

[Chemical 70]

[0149]

[Chemical 71]

[0150]

[Chemical 72]

The hydrazine nucleating agent of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, It can be used by dissolving it in methyl cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The hydrazine nucleating agent of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent of the present invention is 1 × 10 ⁻⁶ to 1 × per mol of silver halide
10 ⁻² mol is preferable, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferable, and 2 × 10 ^{−5 to} 5 × 10 ⁻³ mol is most preferable.

The nucleation accelerator used in the present invention includes:
Examples thereof include amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. The examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically compounds A-1) to A-73), described on pages 49 to 58. JP-A-7-84
No. 331 (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 2)
The compounds represented by 3), specifically the compounds described on pages 6 to 8 of the same publication. Compounds represented by the general formula [Na] and the general formula [Nb] described in JP-A-7-104426, specifically Na-1 described on pages 16 to 20 of the publication.
-The compound of Na-22 and the compound of Nb-1 to Nb-12. General formula (1) described in Japanese Patent Application No. 7-37817,
Compounds represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7). 1-1 to 1-19
Compound, 2-1 to 2-22 compound, 3-1 to 3-3
6 compounds, 4-1 to 4-5 compounds, 5-1 to 5-4
1 compound, 6-1 to 6-58 compound and 7-1 to
Compounds 7-38.

Nucleation accelerators preferably used in the present invention are onium salt compounds represented by the general formulas (2), (3), (4) and (5). The details will be described below.

First, the general formula (2) will be described in detail.

[0156]

[Chemical formula 73]

In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. . m represents an integer, L represents an m-valent organic group which is bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X is linked to L. You may have. Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s
an aralkyl group such as a linear or branched alkyl group such as an ec-butyl group, a tert-butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group or an octadecyl group, a substituted or unsubstituted benzyl group; Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, aryl groups such as phenyl group, naphthyl group, phenanthryl group; alkenyl groups such as allyl group, vinyl group, 5-hexenyl group; cyclopentenyl group,
Cycloalkenyl groups such as cyclohexenyl group; heterocyclic residues such as pyridyl group, quinolyl group, furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzotriazolyl group, benzothiazolyl group, morpholyl group, pyrimidyl group, pyrrolidyl group Is mentioned. Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁ , R ₂ and R ₃ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, 1 ,
A secondary or tertiary amino group, an alkyl or aryl ether group,
Alkyl or aryl thioether group, carbonamido group, carbamoyl group, sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group,
Examples thereof include a carboxyl group, a sulfonic acid group, a cyano group or a carbonyl group. Examples of the group represented by L include R
_In addition to the groups synonymous with ₁ , R ₂ and R ₃ , trimethylene group, tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group, polymethylene group such as dodecamethylene group, phenylene group, biphenylene group, naphthylene group, etc. Divalent aromatic group, trimethylenemethyl group, polyvalent aliphatic group such as tetramethylenemethyl group, phenylene-
1,3,5-toluyl group, phenylene-1,2,4,5
-A polyvalent aromatic group such as a tetrayl group may be mentioned.
Examples of the anion represented by X include halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion,
Carboxylate ion such as benzoate ion, p
-Toluene sulfonate, methane sulfonate, butane sulfonate, benzene sulfonate and other sulfonate ions, sulfate ions, perchlorate ions, carbonate ions,
An example is nitrate ion. In the general formula (2),
R ₁ , R ₂ and R ₃ are preferably groups having 20 or less carbon atoms, and aryl groups having 15 or less carbon atoms are particularly preferred. m is preferably 1 or 2, and when m is 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, and further, these groups and a -CO- group. ,
—O— group, —NR ₄ — group (wherein R ₄ represents a hydrogen atom or a group having the same meaning as R ₁ , R ₂ and R ₃ and when a plurality of R _4's are present in the molecule, they are the same. Or different, and may be bonded to each other), -S
- is a divalent group formed by combining groups - group, -SO- group, -SO _2. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less, which is bonded to a P atom at that carbon atom. When m represents an integer of 2 or more,
There are a plurality of R ₁ , R ₂ and R _{3 in the} molecule,
The plurality of R ₁ , R ₂ and R ₃ may be the same or different. n is preferably 1 or 2 and m is preferably 1 or 2. X may combine with R ₁ , R ₂ , R ₃ or L to form an inner salt. Many of the compounds represented by the general formula (2) of the present invention are known and are commercially available as reagents. As a general synthetic method, there is a method of reacting a phosphinic acid with an alkylating agent such as an alkyl halide or a sulfonate: or a method of exchanging a counter anion of a phosphonium salt by a conventional method. Specific examples of the compound represented by the general formula (2) are shown below. However, the present invention is not limited to the following compounds.

[0158]

[Chemical 74]

[0159]

[Chemical 75]

[0160]

[Chemical 76]

[0161]

[Chemical 77]

General formulas (3) and (4) will be described in more detail.

[0163]

[Chemical 78]

In the formula, A represents an organic group for completing the heterocycle, and may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. . As a preferred example, A can be a 5- or 6-membered ring, and a more preferred example is a pyridine ring. B, 2 divalent group represented by C is an alkylene, arylene, alkenylene, -SO ₂ -, -
SO -, - O -, - S -, - N (R 5) - those constituted alone or in combination are preferred. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. As particularly preferable examples, B and C are alkylene, arylene, and -O.
-, -S- may be used alone or in combination. R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms and may be the same or different. A substituent may be substituted on the alkyl group, and as the substituent,
Halogen atom (eg, chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl) Group), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, etc.), It represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group and an arylthio group. As a particularly preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. R ₃ and R ₄ represent a hydrogen atom or a substituent, and examples of the substituent are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. X represents an anion group, but in the case of an inner salt, X
Is not necessary. Examples of X include chlorine ion, bromine ion,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. Next, specific compounds of the present invention will be described, but the present invention is not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163 (1
962). )

Specific compounds of the general formulas (3) and (4) are shown below, but the invention is not limited thereto.

[0166]

[Chemical 79]

[0167]

[Chemical 80]

General formula (5) will be described in more detail.

[0169]

[Chemical 81]

The nitrogen-containing heteroaromatic ring represented by Z may contain a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom in addition to the nitrogen atom, and the benzene ring may be condensed. The heteroaromatic ring formed is preferably a 5- or 6-membered ring, more preferably a pyridine ring, a quinoline ring, or an isoquinoline ring. R ₅ is preferably an alkyl group having 1 to 20 carbon atoms, and may be a straight chain, branched chain, or cyclic alkyl group. More preferred is an alkyl group having 1 to 12 carbon atoms, and 1 to 8 carbon atoms.
Is most preferred. X ⁻ represents an anion group, but in the case of an intramolecular salt, X ⁻ is not necessary. Examples of X ⁻ include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

The groups represented by Z and R ₅ may be substituted and preferred substituents include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg, phenyl group, Tolyl group, p-chlorophenyl group, etc.), substituted or unsubstituted acyl group (for example, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group,
Represents an alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, unsubstituted or alkyl-substituted amino group, cyano group, nitro group, alkylthio group, arylthio group . Examples of particularly preferable substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. Other examples of the substituent of A include a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.) and a substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.). preferable. Next, specific compounds of the present invention will be described, but the present invention is not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163 (196
2). ) Specific compounds of the general formula (5) are shown below, but the present invention is not limited thereto.

[0172]

[Chemical formula 82]

[0173]

[Chemical 83]

Amino compounds are also preferably used as the nucleation accelerator, and the following compounds are particularly preferably used.

[Chemical Formula 2] described in JP-A-7-84331
1), (Chemical Formula 22) and (Chemical Formula 23), specifically the compounds described on pages 6 to 8 of the same publication. Compounds represented by the general formula [Na] described in JP-A-7-104426, specifically, compounds Na-1 to Na-22 described on pages 16 to 20 of the same. Japanese Patent Application No. 7-37817
Compounds represented by general formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (6) and general formula (7) Specifically, the compounds 1-1 to 1-19 described in the same specification, 2-1 to 2-
22 compounds, 3-1 to 3-36 compounds, 4-1 to 4
-5 compound, 5-1 to 5-41 compound, 6-1 to 6
Compounds of -58 and 7-1 to 7-38.

The nucleation accelerator of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl. It can be used by dissolving it in cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the powder of the nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The nucleation accelerator of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × 10 with ^respect to 1 mol of silver halide.
^-2 mol is preferable, 1 x 10 ^-5 to 2 x 10 ^-2 mol is more preferable, and 2 x 10 ^-5 to 1 x 10 ^-2 mol is most preferable.

The halogen composition of the silver halide emulsion used in the present invention is not particularly limited, but silver chlorobromide or silver iodochlorobromide having a silver chloride content of 50 mol% or more is preferable.
The silver iodide content is 3 mol% or less, more preferably 0.5.
It is not more than mol%. The silver halide emulsion in the present invention is preferably a monodisperse emulsion, and the coefficient of variation is 20% or less, particularly preferably 15% or less. Here, the coefficient of variation (%) is a value obtained by dividing the standard deviation of the particle diameter by the average value of the particle diameter and multiplying by 100. The average grain size of the grains in the monodisperse silver halide emulsion is 0.5 μm or less, particularly preferably 0.
It is 1 μm to 0.4 μm. As the method for preparing the monodisperse silver halide emulsion, various methods known in the field of silver halide photographic light-sensitive materials are used. For example, P.Gl
afkides) "Chimie et Physique Photographique" (1967, published by Paul Montel), GFDuffin's "Photographic Emulsion Chemistry" Photographic Emu
lsion Chemistry) (The Focal Press)
Cal Press), 1966), by VLZelikman et al, "Making and Coating Photographic Emulation (Ma.
king and Coating Photographic Emulsion) "(The Focal Press, 1964)
And the like.

The method of reacting the water-soluble silver salt (for example, silver nitrate aqueous solution) with the water-soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used.
Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. Tetrasubstituted thiourea compounds are more preferred, and JP-A-53-82408 and JP-A-55-77737.
No. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The control double jet method and the grain formation method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is an effective means. Monodisperse emulsions are cubic, octahedral,
It is preferable to have a regular crystal form such as a tetradecahedron, and a cube is particularly preferable. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention contain at least one metal selected from rhodium, rhenium and ruthenium. This content is at least 5 × 10 with respect to 1 mol of silver.
^-6 mol or more, preferably 5 × 10 ^-6 to 1 × 10 ^-4
It is a mole. Two or more of these metals may be used in combination.
These metals can be uniformly contained in the silver halide grains, and they are disclosed in JP-A-63-29603 and JP-A-2 / 1983.
-306236, 3-167545, 4-76
No. 535, Japanese Patent Application No. 4-68305, and No. 4-25818.
As described in No. 7 or the like, it may be contained in the particles with a distribution.

Rhodium, rhenium and ruthenium are described in JP-A-63-2042, JP-A-1-285941 and JP-A-2-285941.
It is added in the form of a water-soluble complex salt described in Nos. 20852 and 2-20855. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] ^-n Here, M represents Rh, Ru or Re, L represents a bridge coordination, and n represents 0, 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Moreover, as a preferred coordination, a halide ligand, a cyanide ligand,
Examples thereof include a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, and an aco ligand.

The silver halide photographic light-sensitive material of the present invention preferably contains an iridium compound in order to achieve high contrast. Various compounds can be used as the iridium compound, for example, hexachloroiridium,
Hexaammine iridium, trioxalato iridium, hexacyano iridium and the like can be mentioned. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or alkali halides (eg KCl, NaCl, K
Br, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The total addition amount of the iridium compound is 1 × 10 ^{-8 to} 5 × per mol of the finally formed silver halide.
10 ^-6 mol is suitable, and preferably 5 × 10 ^-8 to 1 ×.
It is 10 ^-6 mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. .

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper and lead. The above metal is 1 × 10 ^-9 per mol of silver halide.
It is preferably 1 × 10 ⁻⁴ mol. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide emulsion of the present invention is gold-sensitized, and it is preferably combined with chalcogen sensitization. Specifically, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are used in combination with gold sensitization. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, etc. Is preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. Can be used.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻² mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
The compounds described in No. 121798 and the like can be used. Especially, the general formula (VIII) in Japanese Patent Application No. 3-121798.
And compounds represented by (IX) or Japanese Patent Application No. 6-250
It is preferable to use the general formulas (I) and (II) in No. 156.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride presumed to serve as a sensitizing nucleus on the surface or inside of silver halide grains. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Pat. Nos. 1,623,493, 3,320,069, 3,772,031, British Patents 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980),
ibid 1102 (1979), ibid 645 (197)
9), Journal of Chemical Society Perkin Transaction (J. Chem. Soc. Perkin.Tra
ns.) 1, 191 (1980), S. Patai
Hen, The Chemistry of Organic Selenium and Tellurium Companies (The Chemistry
of Organic Sereniun and Tellunium Compounds), Vol
1 (1986) and the same Vol 2 (1987) can be used. In particular, the general formulas (II) (III) (IV) in Japanese Patent Application No. 4-146739 and Japanese Patent Application No. 6-2501
The compounds represented by formulas (III) to (V) in No. 56 are preferable.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C.

Although gelatin is used as the binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, other hydrophilic colloids can be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. Use of various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. In the present invention, the coating amount of gelatin as a binder is such that the total hydrophilic colloid layer on the side having the silver halide emulsion layer has a gelatin amount of 3 g / m ² or less (preferably 3 g / m ² to 1.
0 g / m ² ), and the total amount of gelatin in the total hydrophilic colloid layer on the side having the silver halide emulsion layer and the total hydrophilic colloid layer on the opposite side is 6 g / m ² or less, preferably 2. It is 0 to 6.0 g / m ² .

The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is 80.
To 150% is preferable, and 90% to 90% is more preferable.
It is in the range of 140%. The swelling ratio of the hydrophilic colloid layer in the present invention is the thickness (d) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic light-sensitive material.
₀ ) was measured, the silver halide photographic light-sensitive material was immersed in distilled water at 25 ° C. for 1 minute, and the swollen thickness (Δd) was measured,
The swelling ratio (%) = Δd ÷ d ₃ × 100.

The processing agents and processing methods such as the developing solution and the fixing solution in the present invention will be described below, but needless to say, the present invention is not limited to the following description and specific examples.

The developer used for processing the light-sensitive material in the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffer, preservative, chelating agent). Any known method can be used for the development processing of the present invention, and a known development processing solution can be used.

The developing agent used in the developing solution used in the present invention is not particularly limited, but dihydroxybenzenes,
It is preferable to include an ascorbic acid derivative and a hydroquinone monosulfonate, and from the viewpoint of developing ability, a combination of a dihydroxybenzene or an ascorbic acid derivative and 1-phenyl-3-pyrazolidone, or a dihydroxybenzene or an ascorbic acid derivative and p. A combination of aminophenols is preferred. Hydroquinone as a dihydroxybenzene developing agent used in the present invention,
Chlorohydroquinone, isopropylhydroquinone,
There are methylhydroquinone and the like, but hydroquinone is particularly preferable. Ascorbic acid derivative developing agents include ascorbic acid, isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferable from the viewpoint of material cost.

The developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4. -Methyl-
4-hydroxymethyl-3-pyrazolidone and the like.
N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine and the like as the p-aminophenol-based developing agent used in the present invention However, N-methyl-p-aminophenol is preferable among them.

The dihydroxybenzene type developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 mol / liter to 0.6 mol / liter, preferably 0.23 mol / liter. ˜0.5 mol / liter, the latter is preferably used in an amount of 0.06 mol / liter or less, preferably 0.03 mol / liter to 0.003 mol / liter.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / liter to 0.5 mol / liter, and preferably 0.05 mol / liter or more.
0.3 mol / liter is more preferable. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the amount of the ascorbic acid derivative is 0.01 mol / liter or more.
It is preferable to use 0.5 mol / liter, 1-phenyl-3-pyrazolidones or p-aminophenols in an amount of 0.005 mol / liter to 0.2 mol / liter.

As a buffering agent used in a developing solution (hereinafter, both the developing starting solution and the developing replenishing solution are collectively referred to as a developing solution) at the time of developing the light-sensitive material in the present invention, a carbonate is used, and JP 62-186259, boric acid, saccharides (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid) and tertiary phosphate (for example, sodium salt) described in JP-A-60-93433. , Potassium salt) and the like, and preferably carbonate and boric acid. Buffer,
In particular, the amount of carbonate used is preferably 0.5 mol / liter or more, and particularly 0.5 to 1.5 mol / liter. The developer preferably used in the present invention is a liquid having a property that the pH rise when 0.25 mol of sodium hydroxide is added to 1 liter of the developer is 0.25 or less.

The developer of the present invention may contain various additives (for example, preservatives and chelating agents), if desired. As the preservative used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Formaldehyde sodium bisulfite and the like. The sulfite is used in an amount of 0.2 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.2 mol / liter. Is desirable. Particularly preferably 0.35
~ 0.7 mol / l. As a preservative for the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with sulfite. Of these, sodium erythorbate is preferably used from the viewpoint of material cost. The addition amount is preferably in the range of 0.03 to 0.12, and particularly preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Additives other than those mentioned above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide,
Alkanolamines such as diethanolamine and triethanolamine, development accelerators such as imidazole and its derivatives, heterocyclic mercapto compounds (for example, 3-
(5-Mercaptotetrazol-1-yl) benzenesulfonate sodium salt, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A No. 62-212651 may be added as a physical development unevenness preventing agent. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound is used as an antifoggant or a black pepper.
It may be contained as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2- Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4 -Thiadiazole-2
-Thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these additives is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution.

Further, in the developer of the present invention, various organic compounds,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate, etc. can be used. On the other hand, as the organic chelating agent, mainly organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, acieleic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid,
Undecane dicarboxylic acid, maleic acid, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

Examples of aminopolycarboxylic acids include:
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediamine monohydroxyethyl triacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-Diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and others, JP-A-52-25632 and 5
5-67747, 57-102624, and the compounds described in JP-B-53-40900 can be mentioned.

Examples of the organic phosphonic acid include hydroxyalkylidene groups described in US Pat. Nos. 3,214,454 and 3,794,591 and West German Patent Publication 2,227,369.
Diphosphonic Acid and Research Disclosure No. 181
Vol., Item 18170 (May 1979 issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. Others include Research Disclosure 18170 and JP-A-57-20855.
4, ibid 54-61125, ibid 55-29883, ibid 56
The compounds described in -97347 and the like can be mentioned.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726, 53-42730, 54-112127, 55-4024 and 55-40.
25, the same 55-126241, the same 55-65955, the same 55-69556 and the compounds described in the above-mentioned Research Disclosure 18170 and the like.

These organic and / or inorganic chelating agents are not limited to those mentioned above. Also,
You may use it in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol, per liter of the developing solution.

Further, as a silver stain preventing agent in the developer,
For example, JP-A-56-24347 and JP-B-56-465.
85, JP-B-62-2849, JP-A-4-362942.
In addition to the compounds described in 1., triazines having one or more mercapto groups (for example, Japanese Patent Publication No. 6-23830, JP-A-3-
282457, compounds described in JP-A-7-175178), and the same pyrimidines (for example, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercapto). Pyrimidine, 2,4,6-trimercaptopyrimidine, etc.), the same pyridine (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, Such as the compound described in Kaihei 7-248587) and the same pyrazine (for example, 2-mercaptopyrazine, 2,6-
Dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc., and pyridazine (for example, 3-mercaptopyridazine, 3,4)
-Dimercaptopyridazine, 3,5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177, polyoxyalkylphosphonates described in US Pat. be able to. These silver stain inhibitors can be used alone or in combination of two or more, and the addition amount is preferably 0.05 to 10 mmol, and more preferably 0.1 to 5 mmol per liter of the developing solution. Further, the compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color toning agent, a surfactant, a defoaming agent, a hardener and the like may be contained.

The preferred pH of the developer is 9.0 to 12.0.
And particularly preferably in the range of 9.5 to 11.0. As the alkali agent used for pH adjustment, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

The replenishing amount of the developing solution is 390 ml or less per square meter of the light-sensitive material, preferably 225 ml, and most preferably 180 to 120 ml. The development replenisher may have the same composition and / or concentration as the development starter, or may have a different composition and / or concentration from the starter.

Ammonium thiosulfate, sodium thiosulfate and ammonium ammonium thiosulfate can be used as the fixing agent of the fixing processing agent in the present invention. The amount of the fixing agent used can be changed as appropriate, but generally about 0.7 to
It is about 3.0 mol / liter.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt which acts as a hardening agent, and the water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, aluminum lactate and the like. These are 0.01 to 0.1 as the aluminum ion concentration in the used liquid.
It is preferably contained at 5 mol / liter. When the fixer is stored as a concentrated solution or a solid agent, it may be composed of a plurality of parts including a hardener or the like as a separate part, or may be a one-part type composition containing all components.

Preservatives (for example, sulfite, bisulfite, metabisulfite, etc.) may be added to the fixing treatment agent if desired.
15 mol / liter or more, preferably 0.02 mol / liter to 0.3 mol / liter, and a pH buffering agent (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc.). 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / l to 0.7 mol / l), a compound capable of stabilizing aluminum and softening water (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid) , Maleic acid, glycolic acid, benzoic acid, salicylic acid, Tyrone, ascorbic acid, glutaric acid, aspartic acid,
Glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, sugars,
0.001 mol / liter to 0.5 mol / boric acid
Liter, preferably 0.005 mol / liter to 0.
3 mol / liter).

In addition, the compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene-based surfactants, and JP-A-57-6840.
Examples of the amphoteric surfactants described above include known antifoaming agents. Wetting agents include alkanolamines and alkylene glycols. Examples of fixing accelerators include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B-45-35754, JP-A-58-122535, and JP-A-58-125535.
-122536 described thiourea derivative, alcohol having a triple bond in the molecule, thioether compound described in U.S. Pat. No. 4,126,459, JP-A-64-4739, JP-A-1
-4739, 1-115645 and 3-1017
The mercapto compound described in No. 28, the mesoionic compound described in No. 4-170539, and thiocyanate can be included.

The pH of the fixing solution in the present invention is 4.0 or higher, preferably 4.5 to 6.0.

The replenishing amount of the fixing solution is 500 ml or less per square meter of the light-sensitive material, preferably 390 ml or less, more preferably 320 to 80 ml.

The fixing solution can be recycled and used by a known fixing solution recycling method such as electrolytic silver recovery. Examples of the reproducing device include Reclaim R-60 manufactured by Fuji Hunt.

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. The water used for the washing or stabilizing bath may be tap water, ion-exchanged water or distilled water. The replenishing amount of these varies depending on the tap water pressure, and is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but a replenishing amount less than that can also be used. In particular, when the replenishment amount is 3 liters or less (including 0. That is, washing with water), not only the water saving process becomes possible, but also the pipe for installing the automatic processor can be eliminated. When the washing with water is carried out with a small amount of water, JP-A 63-18350 and 62-62
It is more preferable to provide a washing tank for the squeeze roller and the crossover roller described in US Pat. In addition, in order to reduce the pollution load that becomes a problem when washing with a small amount of water, addition of various oxidants (eg ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) and filters You may combine filtration.

As a method of reducing the replenishment amount of washing water,
A multi-stage counter-current method (for example, two-stage, three-stage, etc.) has been known for a long time, and the replenishing amount for washing is 200 to ⁵ per 1 m ² of light-sensitive material.
0 ml is preferred. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing will gradually move in the normal direction,
That is, since the treatment liquid which is not contaminated with the fixing liquid is sequentially contacted and processed, the water washing can be performed more efficiently. This effect can be similarly obtained by an independent multi-stage system (a method of replenishing a multi-stage washing tank or a stabilizing bath with a new solution without countercurrent flow).

Further, the method of the present invention may be provided with a scale preventive means in the washing or stabilizing bath. Any known means can be used as the scale preventing means, but the method is not particularly limited, but a method of adding an antifungal agent (so-called scale preventing agent) to the washing water or the stabilizing solution, or applying electricity to the washing water or the stabilizing solution Method, irradiation with ultraviolet rays or infrared rays or far infrared rays, method of applying magnetic field, method of ultrasonic treatment, method of applying heat, and method of emptying tank when not in use.
These water stain preventing means may be carried out according to the processing of the light-sensitive material, may be carried out at a constant interval regardless of the use condition, or may be carried out only during a non-working period such as at night. Further, it is also preferable to carry out different scale preventive means at regular intervals in order to suppress the generation of resistant bacteria. The antifungal agent is not particularly limited and known ones can be used. For example, glutaraldehyde, chelating agent such as aminopolycarboxylic acid, cationic surfactant, oxidizing agent (eg ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.), Mercaptopyridine oxide (eg 2-
Mercaptopyridine-N-oxide, etc.),
They may be used alone or in combination of two or more. The antibacterial agent may be added to the washing or stabilizing bath depending on the treatment, or may be added to the washing water or stabilizing solution in advance and replenished. The replenishment of the antibacterial agent may be carried out according to the processing of the light-sensitive material, may be carried out at a constant interval regardless of the use condition, or may be carried out only during a non-processing time such as at night. Furthermore, it is also preferable to use different antifungal agents at regular intervals in order to suppress the development of resistant bacteria. As a method of energizing, there are JP-A-3-224685, JP-A-3-224687, and JP-A-4-162.
80, 4-18980, etc. can be used.

In order to prevent unevenness of water bubbles, which is likely to occur at the time of washing with a small amount of water, and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film,
A known water-soluble surfactant or antifoaming agent may be added. Further, the dye adsorbent described in JP-A-63-163456 may be installed in a water washing tank to prevent contamination by dyes eluted from the light-sensitive material.

A part or the whole of the overflow liquid from the washing or stabilizing bath can be mixed and used in a processing liquid having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (for example, sulfur-oxidizing bacteria, activated sludge treatment, treatment with a filter supporting microorganisms on a porous carrier such as activated carbon or ceramics), or oxidization treatment with electricity or an oxidant to obtain biochemical oxygen demand Amount (BOD), chemical oxygen demand (COD), iodine consumption, etc. are reduced before draining or forming a sparingly soluble silver complex such as a filter or trimercaptotriazine using a polymer having an affinity for silver. It is also preferable from the viewpoint of conservation of the natural environment to reduce the silver concentration in the waste water by adding the compound described above to precipitate silver and filter it with a filter.

There is also a case where a stabilizing treatment is carried out after the water washing treatment, and examples thereof include JP-A-2-201357 and JP-A-2-201357.
-132435, 1-102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, antifungal agents, alkanolamines and surface active agents. Agents can also be added.

Additives such as antifungal agents and stabilizers to be added to the washing and stabilizing baths may be solid agents like the above-mentioned developing and fixing processing agents.

Waste liquids of the developing solution, fixing solution, washing water, and stabilizing solution used in the present invention are preferably burned and disposed. Also, these waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.
It is also possible to dispose after concentrating and liquefying with a concentrating device such as described in S5439560.

When the replenishment amount of the processing agent is reduced, it is preferable to prevent the liquid from evaporating and oxidizing by reducing the contact area of the processing tank with the air. A roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,779 and 3,545,971, and is simply referred to as a roller-conveying type processor in this specification.
The roller transport type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. Instead of the washing step, four stable steps may be used.

In the developing treatment of the present invention, the developing and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each solution is preferably 25 to 50 ° C, preferably 30 to 40 ° C. The temperature and time of the washing or stabilizing bath are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the light-sensitive material that has been developed, fixed and washed (or stabilized) may be dried by squeezing the washing water, that is, passing through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the ambient conditions. Any known method can be used as the drying method, and the method is not particularly limited.
6, drying by a heat roller as disclosed in the same 5-289294, drying by far infrared rays, etc.,
You may use a some method together.

When the developing and fixing processing agents used in the present invention are stored in a liquid form, for example, JP-A-61-731.
It is preferable to store in a packaging material having low oxygen permeability as described in 47. Further, when these solutions are supplied as a concentrated solution, they are diluted with water so as to have a predetermined concentration when used, and are diluted at a ratio of 0.2 to 3 parts of water to 1 part of the concentrated solution.

The development processing agent and the fixing processing agent in the present invention may be in the form of a bath, even if they are solid, in a known form (powder, granular, granular,
Lumps, tablets, compactors, briquettes, plates, crushed products, rods, pastes, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or a coating film in order to separate the components that react with each other when they come into contact with each other. Alternatively, these may be used in combination.

In the case of forming a plurality of layers, the components which do not react even when they come into contact with each other may be sandwiched between the components which react with each other and processed into tablets or briquettes. It may be packaged in the same layer structure. Examples of these methods include, for example, JP-A-61-25992.
1, No. 4-16841, No. 4-78848, and the like.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferred, especially tablets are 1.0-5.0 g / cm ³
Is preferred, and the granules are preferably 0.5 to 1.5 g / cm ³ .

As a method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, and JP-A-4-7884.
8, same 5-93991, JP-A-4-85533, same 4-
85534, 4-85535, 5-134362,
5-1997070, 5-204098, 5-22
4361, 6-138604, 6-138605,
It can be used with reference to Japanese Patent Application No. 7-89123.

More specifically, rolling granulation method, extrusion granulation method, compression granulation method, crushing granulation method, stirring granulation method, spray drying method, dissolution coagulation method, briquetting method, roller compaction method. The Ting method or the like can be used.

The particle size and shape of the granulated product suitable for the present invention will vary depending on the desired characteristics, but in the case of granules, the sphere-converted particle size is about 0.5 to 50 mm, preferably 1 to 15 mm.
The shape is cylindrical, spherical, cubic, rectangular parallelepiped, etc., more preferably spherical or cylindrical. Roller compacting processed may be crushed,
Further, it may be sieved to have a diameter of about 2 mm to 1 cm. Similarly, in the case of briquettes and tablets, the particle size and shape are different depending on the desired characteristics, but a diameter of about 2 mm to 5 cm is preferable, and the shape is cylindrical, spherical, cubic, rectangular parallelepiped, etc.,
More preferably, it is spherical or cylindrical. In addition, the solubility can be adjusted by partially changing the thickness, making a hollow donut shape, or changing the surface condition (smoothness, porosity, etc.). Further, it is possible to take a plurality of shapes in order to give different solubilities to a plurality of granules or to adjust the solubilities of materials having different solubilities. Further, a multi-layer granulated product having different compositions on the surface and inside may be used.

The packaging material for the solid processing agent is preferably a material having low oxygen and water permeability, and the packaging material may have a known shape such as a bag, a cylinder or a box. Also,
JP-A-6-242585, 6-242588, 6-
247432, 6-247448, and Japanese Patent Application No. 5-306.
64, JP-A-7-5664, and 7-5666 to 7-5.
The foldable shape as disclosed in 669 is also preferable in order to reduce the storage space of the waste packaging material. These packaging materials may be provided with a screw cap, a pull top, an aluminum seal at the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and there is no particular limitation. do not do. In addition, recycling or waste of the waste packaging material is preferable for environmental protection.

The method of dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. Examples of these methods include a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, a method of dissolving with a dissolving device having a dissolving portion and a portion for stocking a finished liquid, and replenishing from a stock portion. 5-119
454, 6-19102, 7-261357, and a method of adding a processing agent to the circulation system of an automatic developing machine to dissolve and replenish it, and processing a photosensitive material with an automatic developing machine having a dissolution tank. Depending on the method, a treatment agent may be added and dissolved, and any other known method may be used. Further, the treatment agent may be charged manually, or may be automatically opened and automatically charged by a dissolving device having an opening mechanism or an automatic processor, and the latter is preferable from the viewpoint of working environment. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting, a method of pushing off, and
102, 6-95331, and the like.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention and the development processing method. For example, those described in the following sections can be preferably used. Item 1) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to right lower column, line 7 and JP-A-2-18542, page 2, lower left column 13 From line 4 to page 4, lower right column, line 18. 2) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A 1-237538. Thiosulfinic acid compounds described in the public notice. 3) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 4) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 5) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 7) Dyes Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-187573. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot inhibitor The compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Monomethine compound Compounds of general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 11) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12 lower left column, and EP452772A.

[0236]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 <Preparation of silver halide photographic light-sensitive material> (Image forming layer formulation) 0.37 M silver nitrate aqueous solution, and silver 1
0.16M potassium bromide and 0.02M chloride containing 1 × 10 ^-7 moles of K ₂ Rh (H ₂ O) Cl ₅ and 2 × 10 ^-7 moles of K ₃ IrCl ₆ per mole. An aqueous solution of halogen salt containing sodium was mixed with 0.08M sodium chloride and 1,3
-Silver chlorobromide grains having an average grain size of 0.20 µm and a silver chloride content of 55 mol% were added to a 2% aqueous gelatin solution containing dimethyl-2-imidazolithion by stirring with a double jet method at 38 ° C for 12 minutes while stirring. Nucleation was performed by obtaining. Subsequently, similarly, a 0.63 M silver nitrate aqueous solution and a halogen salt aqueous solution containing 0.23 M potassium bromide and 0.43 M sodium chloride were added over 20 minutes by the double jet method. Then, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver for conversion, followed by washing with water by a flocculation method according to a conventional method.
40 g of gelatin was added per 1 mol of silver, pH 6.0, p
After adjusting to Ag 7.3, and further adding 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid and 5 mg of sodium thiosulfate per 1 mol of silver, and heating at 60 ° C. for 45 minutes for chemical sensitization , 4-hydroxy-6-methyl-1,3,3a as a stabilizer,
150 mg of 7-tetrazaindene and proxel as preservative were added. The particles obtained have an average particle size of 0.2.
The silver chlorobromide cubic grains had a grain size of 7 μm and a silver chloride content of 60 mol%. (Variation coefficient 10%)

To the emulsion thus obtained, the compounds shown in Table 1 and comparative compounds as sensitizing dyes were added in an amount of 7 × 10 ⁻⁴ mol per mol of silver, and further 4 × per mol of silver.
10 ⁻⁴ mol of the short-wave cyanine dye represented by the following structural formula (A), 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 4 × 10 ⁻⁴ mol of the following structural formula (B) Mercapto compound, 3 × 10 ⁻⁴ mol of a mercapto compound represented by the following structural formula (C), 4 × 10 ⁻⁴ mol of a triazine compound represented by the following structural formula (D), 2
X 10 ^-3 mol of 5-chloro-8-hydroxyquinoline,
1 × 10 ⁻³ mol of the nucleation accelerator represented by the following structural formula (a), the hydrazine derivative N-2 of the present invention is 1.5 × 10 ⁻⁴ mol per mol of silver, and further N-oleoyl- N-Methyltaurine sodium salt was added to be coated at 30 mg / m ² . Add to this a dispersion of polyethyl acrylate (50
0 mg / m ² ) 1,2-bis (vinylsulfonylacetamido) ethane 30 mg / m ² was added as a hardening agent.

[0238]

[Chemical 84]

[0239]

[Chemical 85]

(Redox compound-containing layer formulation) 1.0M
And a halogen salt solution containing 0.3M potassium bromide and 0.74M sodium chloride containing (NH ₄ ) ₃ RhCl ₅ corresponding to 3 × 10 ⁻⁷ mol per mol of silver. 0.08M sodium chloride and 1,3-dimethyl-
To a 2% gelatin aqueous solution containing 2-imidazoline thione, the mixture was added by a double jet method at 45 ° C. for 30 minutes while stirring to obtain silver chlorobromide grains having an average grain size of 0.30 μm and a silver chloride content of 70 mol%. It was Then, 1 × 10 ⁻³ mol of KI solution was added per mol of silver for conversion, followed by washing with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per mol of silver to give a pH of 6.
0, pAg 7.6, and further, per mol of silver, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid and 5 parts of sodium thiosulfate.
After adding mg and heating for 60 minutes at 60 ° C. for chemical sensitization, 4-hydroxy-6-methyl-1, as a stabilizer,
350 mg 3,3a, 7-tetrazaindene and proxel as preservative were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.30 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%)

Each of the emulsions thus obtained contained 5 × 10 ⁻⁴ mol of 5- [3-mol as a sensitizing dye per mol of silver.
(4-Sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin potassium salt was added, and the following structural formula (J) was added. 10 mg / m ^{2 of the} dye represented by the formula ( ¹ ), a dispersion of polyethyl acrylate (250 mg / m ² ) and the redox compound of the present invention (100 mg / m ² ) were added as shown in Table 1.

[0242]

[Chemical 86]

[0243] (Intermediate layer Formulation) to the gelatin solution, ethanethiolate of sodium 5 mg / m ^2, dye 100 mg / m ² expressed by (K), hydroquinone 100 mg / m ^2,
The triol compound represented by (L) was added in an amount of 50 mg / m ² and the polyethyl acrylate dispersion was added in an amount of 350 mg / m ² to prepare an intermediate layer coating solution.

[0244]

[Chemical 87]

On the polyethylene terephthalate film undercoated with gelatin, a layer of gelatin 0.2 g / m ² containing 40 mg / m ² of bis (vinylsulfonyl) ethane was used as the lowermost layer and an image forming layer (Ag 3.4 g / m ² ). ^2, gelatin 1.6 g / m ^2), via an intermediate layer (gelatin 0.8 g / m ^2), redox compound-containing layer (Ag0.2g / m ^2,
Gelatin 0.2 g / m ² ), and further thereon 0.3 g / m ² of gelatin as a protective layer, 60 mg / m ^{2 of} amorphous SiO ₂ matting agent having an average particle size of about 3.5μ, 0.1 g of methanol silica / m ² , liquid paraffin 50 mg / m ² , fluorosurfactant 5 mg represented by the following structural formula (F) as a coating aid
/ M ² and sodium dodecylbenzene sulfonate 20mg /
m ² was applied to prepare a sample as shown in Table 1.

[0246]

[Chemical 88]

The back layer was coated according to the following formulation. (Back layer formulation) Gelatin 3.2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 40 mg / m ² Gelatin hardening agent 1,3-Divinylsulfonyl- 2-propanol 200 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 300 mg / m ² dyes of the following dyes (M), (H), (I), (J) Mixture Dye (M) 20 mg / m ² Dye (H) 50 mg / m ² Dye (I) 20 mg / m ² Dye (J) 30 mg / m ²

[0248]

[Chemical 89]

(Back protective layer) Gelatin 1.3 g / m ² polymethylmethacrylate fine particles (average particle size 2.5 μm) 20 mg / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² dihexyl-α-sulfosuccinate sodium Salt 15 mg / m ² Sodium acetate 60 mg / m ²

The swelling ratio (H ₂ O, 25 ° C.) of each sample was 125%, and the film surface pH was 6.2. <Evaluation> The light-sensitive material shown in Table 1 was exposed with a tungsten light of 3200 ° K through an optical wedge and a contact screen (Fuji Film, 150 L chain dot type), and then exposed with the following developer A to obtain an FG-680AG automatic developing machine (Fuji. Photographic Film Co., Ltd.) was used for treatment at 35 ° C. for 30 seconds. GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as the fixing solution.

[0251] Composition of developer A per liter of used solution   Potassium hydroxide 40.0 g   Diethylenetriamine / pentaacetic acid 2.0 g   Potassium carbonate 60.0 g   Sodium metabisulfite 70.0 g   Potassium bromide 7.0 g   Hydroquinone 40.0 g   5-methylbenzotriazole 0.35 g   4-hydroxymethyl-4-methyl-1-phenyl-3-     Pyrazolidone 1.5 g   2-Mercaptobenzimidazole-5-sulfonic acid     0.3 g of sodium   3- (5-mercaptotetrazol-1-yl) benzene     Sodium sulfonate 0.1 g   Sodium erythorbate 6.0 g   Diethylene glycol 5.0 g   pH 10.65

The pH of the developer A was 0.2 when 0.1 mol of sodium hydroxide was added to 1 liter of the developer.

Gamma is expressed by the following equation. The larger this value, the harder the photographic characteristics. * Gamma = (3.0-0.3) / [log (exposure amount giving density 3.0) -log (exposure amount giving density 0.3)]

The halftone is expressed by the following equation. The larger this value, the better the original reproducibility. * Amount of exposure that gives a halftone dot area ratio of halftone = 95% (logE95
%)-Exposure amount giving a dot area ratio of -5% (log E5%)

The residual color was evaluated as follows. The coated sample was developed without exposing it under the same conditions as in the evaluation of photographic characteristics. The evaluation is carried out in five stages. "5" indicates that there is almost no color remaining, and "1" indicates that the remaining color is the largest. "5" or "4" is practical, "3" is barely practical with residual color, and "2" or "1" is not practical.

The results are shown in Table 1.

[0257]

[Table 1]

<Results> By comparing the experiment numbers 1-1 to 1-3 with the experiment numbers 1-4 to 1-12, the original reproducibility was excellent and the residual color was observed only when the sensitizing dye of the present invention was used. It can be seen that a sample with less number of samples is obtained.

Example 2 An emulsion was prepared by the following method. An aqueous solution of 0.13 M silver nitrate and 1.5 × 10 ^-7 mol per mol of silver (N
H ₄ ) ₂ Rh (H ₂ O) Cl ₅ and K ₃ IrCl equivalent to 2 × 10 ^-7 mol
_An aqueous solution of halogen salt containing ₆ and 0.04M potassium bromide and 0.09M sodium chloride was added to a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione at 38 ° C. with stirring. In 12
Nucleation was carried out by adding by a double jet method for minutes to obtain silver chlorobromide grains having an average grain size of 0.14 μm and a silver chloride content of 70 mol%. Then 0.8
7M silver nitrate aqueous solution and 0.26M potassium bromide,
A halogen salt aqueous solution containing 0.65 M sodium chloride was added by the double jet method over 20 minutes.

Thereafter, 1 × 10 ⁻³ mol of KI solution was added to each emulsion for conversion, and the emulsion was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per 1 mol of silver, pH 5.9, pAg 7.5. 3. The temperature was adjusted to 65 ° C., and sodium benzenethiosulfonate (4 mg), sodium benzenesulfinate (1 mg), chloroauric acid (6 mg) and triphosphine selenide were added per mol of silver (3).
After 0 mg and 2 mg of sodium thiosulfate were added and chemical sensitization was performed to obtain the optimum sensitivity, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. Proxel 1 as a preservative
00 mg was added. After that, adjust the temperature to 55 ℃,
5,5'-dichloro-9-ethyl-3,3'-bis (3
-Sulfopropyl) oxacarbocyanine sodium salt was added to 100 mg and stirred for 15 minutes, containing silver chloride 69.9 mol% and having an average size of 0.25 μm.
A silver chloroiodobromide cubic emulsion A was prepared.

(Preparation of Coating Sample) The layer structure of the coating sample is from the upper layer to the protective layer upper layer, the protective layer lower layer, the emulsion layer, the support, the conductive layer and the back layer. <Protective layer upper layer> (Gelatin 0.5 g / m ² ) Unshaped SiO ₂ matting agent with an average particle size of about 3.5 μm 30 mg / m ² Colloidal silica (Nissan Chemical Co., Ltd. Snowtex C) 100 mg / m ² Polyacrylamide 100 mg / m ² Liquid paraffin (gelatin dispersion) 20 mg / m ² Fluorosurfactant (a) 5 mg / m ² Sodium dodecylbenzene sulfonate 100 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Preservative (b) 10 mg / m ² <Protective layer lower layer> (Gelatin 0.6 g / m ² ) Polyethyl acrylate latex 300 mg / m ² Surfactant (c) 5 mg / m ² 1,5-dihydroxy 2-Benzaldoxime 10 mg / m ² Hydroquinone 100 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Dye represented by the following structural formula (d) 60 mg / m ² Preservative (b) 10 mg / m ²

[0262]

[Chemical 90]

<Emulsion layer> (Gelatin: 1.4 g / m ² , Ag: 3.4 g / m ² ) The compound of the general formula (I) of the present invention and the comparative compound (Table 2) 5 × 10 ⁻⁴ mol / molAg Hydrazine derivative of the present invention (Table 2) 1.5 × 10 ⁻⁴ mol / molAg N-oleyl-N-methyltaurine Na salt 29 mg / m ² Ethylthiosulfonic acid 4 mg / m ² Compound represented by the following structural formula ( e) 2 mg / m ² 〃 (f) 6 mg / m ² 〃 (g) 8 mg / m ² 〃 (h) 10 mg / m ² 〃 (A) 15 mg / m ² Ethyl acrylate / acrylic acid (98 / 2) Latex 750 mg / m ² (particle size 0.1 μ) 1,2-bis (vinylsulfonylacetamide) ethane 80 mg / m ²

[0264]

[Chemical Formula 91]

[0265]

[Chemical Formula 92]

<Back Layer> (Gelatin 3.16 g / m ² ) ・ Compound (i) represented by the following structural formula (38.9 mg / m ² ) ・ Dye represented by the following structural formula A 18.4 mg / m ² 〃 B 13.9 mg / m ² · 〃 C 25.3mg / m ² · 〃 D 53.1mg / m ² · sodium dodecylbenzenesulfonate 38.9mg / m ² · 1,3- vinylsulfonyl-2-propanol 146 mg / m ²

[0267]

[Chemical formula 93]

[0268]

[Chemical 94]

[0269] <back protective layer> (Gelatin 1.32g / m ²⁾ · Sodium dodecylbenzenesulfonate 13.8 mg / m ² · polymethyl methacrylate particles (particle size 2.8 μ) 15mg / m ² · sodium acetate 57.7 mg / m ² · Compound (i) 16mg / m ²

Swelling rate of each sample (H ₂ O, 25 ° C.)
Was 100% and the film surface pH was 5.6. <Evaluation> The photosensitive materials shown in Table 1 were exposed with an optical wedge and a contact screen (Fujifilm, 150 L chain dot type) with tungsten light of 3200 ° K. After exposure, FG-680AG was automatically developed with the developer A of Example 1. Machine (Fuji Photo Film Co., Ltd.)
The treatment was performed for 0 seconds. GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as the fixing solution.

Gamma is expressed by the following equation. The larger this value, the harder the photographic characteristics. * Gamma = (3.0-0.3) / [log (exposure amount giving density 3.0) -log (exposure amount giving density 0.3)]

The residual color was evaluated as follows. The coated sample was developed without exposing it under the same conditions as in the evaluation of photographic characteristics. The evaluation is carried out in five stages. "5" indicates that there is almost no color remaining, and "1" indicates that the remaining color is the largest. "5" or "4" is practical, "3" is barely practical with residual color, and "2" or "1" is not practical.

The black spots were evaluated by microscopic observation using an unexposed sample developed for 45 seconds under the above conditions.
Graded. "5" represents the best level without black spots, and "1" represents the worst black spots and represents the worst quality. “3” is the limit level at which the generation of black spots is practically acceptable.

[0274]

[Table 2]

<Results> Comparison between Experiment Nos. 2-1 to 2-3 and Experiment Nos. 2-4 to 2-12 shows that black spots are less likely to occur and the residuals remain only when the sensitizing dye of the present invention is used. It can be seen that a sample with less color is obtained.

Example 3 The following running test was conducted using the sample prepared in Example 2. <Running test> The developer A of Example 1 was treated with FG-68.
It was filled with a 0AG automatic processor (Fuji Photo Film Co., Ltd.). After developing at 35 ° C for 30 seconds, the replenishment amount of developer is 17
It was set to 0 ml / m ² . This automatic developing machine develops 40 samples of each large size paper (50.8 x 61.0 cm) which is blackened 30% per day (3 sheets out of 10 sheets are exposed) for 6 days. There were 6 rounds of work, 1 day off and 1 day off. <Evaluation> Using the developer before running (new solution) and the developer after running, exposure and development were performed in the same manner as in Example 2.
Gamma was calculated by the method of Example 2. The results are shown in Table 3.

[0277]

[Table 3]

<Results> The sample of the present invention has less variation in photographic property before and after running.

Example 4 Even when the same experiment as in Examples 1 and 2 was conducted by using the following developer B instead of the developer A of Examples 1 and 2, a good result was obtained with the constitution of the present invention. Obtained.

Developer B is a solid developer having the following composition dissolved in water. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (bulk powder) 63.0 g Sodium sulfite (bulk powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) 40.0 g Diethylenetriamine pentaacetic acid 2.0 g 5-Methylbenzotriazole 0.35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.3 g 3- (5-Mercaptotetrazol-1-yl) Sodium benzenesulfonate 0.1 g Sodium erythorbate 6.0 g Potassium bromide 6.6 g Dissolve this in water to 1 liter. pH 10.65

Here, in the raw material form, the bulk powder was used as a general industrial product, and the beads of the alkali metal salt were commercial products. If the raw material is briquette, it is pressed and compressed using a briquetting machine to give an irregular length of 4 to 6
A rugby ball shape having a size of about mm was prepared, crushed and used. For minor components, each component was blended before briquetting.

Example 5 <Emulsion preparation> Emulsion A: 0.37 M silver nitrate aqueous solution, and K ₂ Rh (H ₂ O) Cl ₅ and 2 × 10 ^-7 corresponding to 1 × 10 ^-7 mol per mol of silver.
An aqueous solution of halogen salt containing 0.16M potassium bromide and 0.02M sodium chloride containing K ₃ IrCl ₆ in an amount of 0.08M sodium chloride and 1,3-dimethyl-2-imidazolithione. The mixture was added to a 2% aqueous gelatin solution at 38 ° C. for 12 minutes with stirring by a double jet method to give an average particle size of 0.20 μm and a silver chloride content of 5
Nucleation was performed by obtaining 5 mol% silver chlorobromide grains. Then, similarly, a 0.63 M silver nitrate aqueous solution and 0.2
A halogen salt aqueous solution containing 3M potassium bromide and 0.43M sodium chloride was added over 20 minutes by the double jet method. Then 1 × 10 ^-3 per mole of silver
A molar KI solution was added for conversion, followed by washing with water by a flocculation method according to a conventional method, 40 g of gelatin was added per 1 mol of silver, pH 6.0, pAg 7.3.
To 7 mol of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid, and 5 mg of sodium thiosulfate per mol of silver,
After 45 minutes of heating and chemical sensitization, 4 as a stabilizer
150 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and proxel as preservative were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 60 mol%.
(Variation coefficient 10%)

Emulsion B: 1.0 M silver nitrate aqueous solution and silver 1
An aqueous solution of halogen salt containing 0.3M potassium bromide and 0.74M sodium chloride containing (NH ₄ ) ₃ RhCl ₅ in an amount of 3 × 10 ^-7 mol per mol, and 0.08M sodium chloride , 2-dimethyl-2-imidazolinethione-containing 2% gelatin aqueous solution was added by stirring with a double jet method at 45 ° C. for 30 minutes to obtain a salty odor having an average particle size of 0.30 μm and a silver chloride content of 70 mol%. Silver halide grains were obtained. Then 1 × 10 ^-3 mol of K per mol of silver
Solution I was added for conversion, followed by washing with water by a flocculation method according to a conventional method, 40 g of gelatin was added per mol of silver to adjust pH to 6.0 and pAg of 7.6, and further sodium benzenethiosulfonate per mol of silver was added. 7 mg, benzenesulfinic acid 2 mg, chloroauric acid 8
mg and sodium thiosulfate 5 mg were added, and the mixture was added at 60 ° C.
After heating for a minute for chemical sensitization, 350 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and proxel as a preservative were added.
The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.30 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%)

<Preparation of Coated Sample> The layer structure of the coated sample is from the upper layer to the protective layer, the redox compound-containing layer, the intermediate layer, the image forming layer, the lowermost gelatin layer, the support, the back layer and the back protective layer. <Protective layer> (Gelatin (Ca ²⁺ content 2700 ppm) coating amount 0.15 g / m ² ) ・ SiO ₂ matting agent 60 mg / m ² (average particle diameter 3.6 μm amorphous, pore diameter 170 Å, surface area 300 m ² / G) ・ Snowtex C 61 mg / m ²・ Liquid paraffin (gelatin dispersion) 30 mg / m ²・ sodium p-dodecylbenzenesulfonate 19 mg / m ²・ N-perfluorooctanesulfonyl-N-propyl glycine potassium 2 .8mg / m ² · compound -A 0.5 mg / m ² · sodium polystyrenesulfonate 5.1 mg / m ² <redox compound-containing layer> · emulsion B silver: 0.32g / m ^2, gelatin: 0.35 g / m ² · redox compound (R-26) 132mg / m 2 · sensitizing dye (I-98) per mol of silver 4 × 10 ^-4 mol dye -B 11 mg / m ² · polystyrene sulfonic acid sodium of the present invention Arm 3.1 mg / m ² · polymer latex amount (Table 4) 260mg / m ² · Compound -C (hardener) 25 ° C. the emulsion surface side after coating, the 1 minute distilled water swelling ratio is 175% <intermediate layer> (gelatin (Ca ²⁺ content 2700 ppm) coating amount 0.95g / m ²⁾ · ethylthiomethyl sulfonate 4.3 mg / m ² · hydroquinone 172 mg / m ² · compound -A 1.5 mg / m ²・ Compound-D 5.0 mg / m ²・ Dye-E 67 mg / m ²・ Ethyl acrylate / acrylic acid (99/1 wt%) copolymer 200 mg / m ²

[0285]

[Chemical 95]

<Image forming layer> Emulsion A Silver: 3.60 g / m ² , gelatin: 1.76 g / m ² Sensitizing dye of the present invention (Table 4) 7 × 10 ⁻⁴ mol per mol of silver N-oleyl-N-methyltaurine sodium salt 61 mg / m ² · short-wave cyanine dye-F 4.2 mg / m ² · short-wave cyanine dye-G 4.2 mg / m ² · compound-H 2.5 mg / m ² · compound -I 7.9 mg / m ² · Compound-J 2.2 mg / m ² · Nucleating agent of the present invention-K 37 mg / m ² · Nucleating agent of the present invention-L 26 mg / m ² · Compound-M 13 mg / m ² · Sodium polystyrene sulfonate 8.7 mg / m ² · 3- (5-mercaptotetrazole) -benzene Sodium sulfonate 1.9 mg / m ² · Snowtex C 270 mg / m ² · Polymer latex (Table 4) 610 mg / m ² <gelatin lowermost> (gelatin (Ca ²⁺ content 2700 ppm) coating amount 0. g / m ²⁾ · Compound -A 0.9 mg / m ² · sodium polystyrenesulfonate 7.8 mg / m ² · ethyl acrylate / acrylic acid (99/1 wt%) copolymer 290 mg / m ² · Compound -N 40 mg / M ²

[0287]

[Chemical 96]

<Support and Undercoat Layer> The first and second undercoat layers having the following compositions on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were applied. -Styrene-butadiene rubber latex 10.6 g-Ethyl acrylate latex 0.05 g-2,4-dichloro-6-hydroxy-s-triazine 0.29 g-Compound-O 0.20 g-Polystyrene fine particles (average particle size 2. 5 μm) 0.11 g Water was added and 100 g This coating solution was applied at a drying temperature of 175 ° C. for 2 minutes so that the dry film thickness was 0.6 μm. <Second layer of undercoat layer> -Gelatin 1 g-Compound-A 0.04 g-Compound-P 0.02 g-Acetic acid 0.20 g Water was added to 100 g This coating solution was dried at 170 ° C for 2 minutes to give a dry film thickness. It was applied so as to have a thickness of 0.1 μm to prepare a support including an undercoat layer.

[0289]

[Chemical 97]

<Back Layer> (Gelatin (Ca ²⁺ content 3500 ppm) Coating amount 2.96 g / m ² ) Dye-Q 23 mg / m ² Dye-R 51 mg / m ² Dye-S 21 mg / m ² dye -T 14 mg / m ² · compound -O 6.9mg / m ² · p- sodium dodecylbenzenesulfonate 6.9 mg / m ² · compound -A 3.7 mg / m ² · sodium polystyrene sulfonate 8.5mg / M ² · Compound-C (hardener) Amount at which swelling rate of distilled water at 25 ° C for 1 minute on the emulsion surface side after coating is 145% <Back protective layer> (Gelatin (Ca ²⁺ content 3500ppm) Coating amount 1.12 g / m ² ) ・ Polymethylmethacrylate fine particles (average particle size 3.0 μm) ・ Compound-O 14 mg / m ²・ sodium p-dodecylbenzenesulfonate 12 mg / m ²・ Compound-A 1.4 mg / M ² · Sodium acetate 49mg / m ²

[0291]

[Chemical 98]

[0292]

[Chemical 99]

[0293]

[Chemical 100]

The film surface pH was 6.2. <Evaluation> The light-sensitive materials shown in Table 4 were exposed with a tungsten light of 3200 ° K through an optical wedge and a contact screen (Fuji Film, 150 L chain dot type), and then exposed with the following developer A to produce an FG-680AG automatic developing machine (Fuji Photographic Film Co., Ltd.) was used for treatment at 35 ° C. for 30 seconds. GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as the fixing solution.

Preparation of developer   Developer A     Sodium hydroxide 8.0g     Potassium hydroxide 90.0g     5-sulfosalicylic acid 23 g     N-n-butyldiethanolamine 14 g     N, N-dimethylamino-6-hexanol 0.2 g     p-Toluenesulfonate sodium 8g     Boric acid 24g     Ethylenediaminetetraacetic acid disodium 1g     Potassium bromide 10g     5-methylbenzotriazole 0.4 g     2-mercaptobenzimidazole-5-       Sodium sulfonate 0.3g     3- (5-mercaptotetrazole) benzenesulfonic acid       0.2 g of sodium     Sodium metabisulfite 65g     Hydroquinone 55g     N-methyl-p-aminophenol 0.5 g   1 liter with water   pH 11.92

Gamma is expressed by the following equation. The larger this value, the harder the photographic characteristics. * Gamma = (3.0-0.3) / [log (concentration 3.0
Exposure dose giving-) (exposure dose giving a density of 0.3)]

The halftone is expressed by the following equation. The larger this value, the better the original reproducibility. * Exposure amount that gives a halftone dot area ratio of halftone = 95% (log
E 95%)-Exposure dose giving a dot area ratio of -5% (log
E5%)

The residual color was evaluated as follows. The coated sample was developed without exposing it under the same conditions as in the evaluation of photographic characteristics. The evaluation is carried out in five stages. "5" indicates that there is almost no color remaining, and "1" indicates that the remaining color is the largest. "5" or "4" is practical, "3" is barely practical with residual color, and "2" or "1" is not practical. The results are shown in Table 4.

[0299]

[Table 4]

<Results> Comparison between Experiment Nos. 1-1 to 1-4 and Experiment Nos. 1-5 to 1-6 shows excellent original reproducibility and residual color only when the sensitizing dye of the present invention is used. It can be seen that a sample with less number of samples is obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03C 5/31 G03C 5/31 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/035 G03C 1/06 G03C 1/22 G03C 5/29

Claims (11)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein the compound represented by formula (S) is contained in the silver halide emulsion layer. A silver halide photograph containing at least one kind of redox compound capable of releasing a development inhibitor by being oxidized in at least one layer of the emulsion layer or other hydrophilic colloid layer Photosensitive material. General formula (S) In the formula, Z represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. R ₁ represents an alkyl group. R ₂
Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₃ represents a nitrogen-containing 5-membered heterocyclic group or a pyrazyl group. L ₁ and L ₂ each represent a methine group. n is 0
It represents an integer of 3 or more and 3 or less. 2. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the emulsion layer and the other hydrophilic colloid layer contains at least one hydrazine derivative. Photographic material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the redox compound has a general formula (R-1) or a general formula (R-2) as a redox group.
A silver halide photographic light-sensitive material represented by the general formula (R-3). [Chemical 2] In these formulas, R ₁ represents an aliphatic group or an aromatic group.
G ₁ is a —CO— group, a —CO—CO— group, a —CS— group, a —CO
_{C (= NG 2 R 2)} - represents a group - group, -SO- group, -SO ₂ - group or _{-P (O) (G 2 R} 2). G ₂ represents a mere bond, —O— group, —S— group or —N (R ₂ ) — group, R ₂ represents a group having the same definition as R ₁ or a hydrogen atom,
When plural R _2's are present in the molecule, they may be the same or different. A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ has the same meaning as A ₁ or -CH ₂ CH (A ₄ )-(Time)
Represents t-PUG. A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfonyl group or -G ₁ -G ₂ -R ₁ (in this case, two -G ₁ -G ₂ -R ₁ in the molecule is optionally substituted by one or more identical May be used). Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor. 4. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one compound represented by formula (S) is contained in the silver halide emulsion layer, and at least one hydrazine derivative is contained in at least one layer of the emulsion layer and other hydrophilic colloid layers. A characteristic silver halide photographic light-sensitive material. General formula (S) In the formula, Z represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. R ₁ represents an alkyl group. R ₂
Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₃ represents a nitrogen-containing 5-membered heterocyclic group or a pyrazyl group. L ₁ and L ₂ each represent a methine group. n is 0
It represents an integer of 3 or more and 3 or less. 5. The silver halide photographic light-sensitive material according to claim 2, 3, or 4, wherein the hydrazine derivative has an anion group near the hydrazine group or a hydrogen atom of hydrazine and an intramolecular group. A silver halide photographic light-sensitive material, which is a compound having a nonionic group forming a hydrogen bond or at least one compound selected from compounds represented by the following general formula (1). General formula (1) In the formula, R ₀ represents a difluoromethyl group or a monofluoromethyl group, and A ₀ represents an aromatic group. However, at least one of the substituents possessed by A ₀ is a diffusion resistant group, an adsorption promoting group on silver halide, an alkylthio group, an arylthio group,
A heterocyclic thio group, a quaternary ammonium group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an alkoxy group containing an ethyleneoxy or propyleneoxy unit, or a saturated heterocyclic group containing a sulfide bond or a disulfide bond. Or a substituent containing at least one of these groups. 6. The silver halide photographic light-sensitive material according to claim 2, claim 3, claim 4 or claim 5, wherein at least one of said emulsion layer and other hydrophilic colloid layer is at least one layer. 2. A silver halide photographic light-sensitive material containing the nucleation accelerator of. 7. The silver halide photographic light-sensitive material according to claim 6, wherein the nucleation accelerator is represented by general formula (2), general formula (3), general formula (4) or general formula (5). Silver halide photographic light-sensitive material, which is at least one compound selected from the compounds described above and amino compounds. General formula (2) In the formula, R ₁ , R ₂ and R ₃ are an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group,
Represents a heterocycle residue. m is an integer, L is an n-valent organic group which is bonded to the P atom by its carbon atom, and n is an integer of 1 to 3. General formula (3) General formula (4) In the formula, A represents an organic group for completing the heterocycle.
B, and C is an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, - S -, - N
(R ₅ )-represents one or a combination thereof. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. R ₁ and R ₂ each represent an alkyl group, and R ₃ and
Each R ₄ represents a substituent. X represents an anion group, but X is not necessary in the case of an inner salt. General formula (5) In the formula, Z represents an organic group for completing the heterocycle.
R ₅ represents an alkyl group. X represents an anion group, but X is not necessary in the case of an inner salt. 8. The silver halide photographic light-sensitive material according to claim 2, claim 3, claim 4, claim 5, claim 6 or claim 7, wherein the silver halide emulsion is
A silver halide photographic light-sensitive material having a silver chloride content of 50 mol% or more. 9. The silver halide photographic light-sensitive material according to claim 2, claim 3, claim 4, claim 5, claim 6, claim 7, or claim 8, wherein the silver halide is used. A silver halide photographic light-sensitive material characterized in that the emulsion is chemically sensitized. 10. A silver halide photographic light-sensitive material according to claim 2, claim 3, claim 4, claim 5, claim 6, claim 7, claim 8 or claim 9, A method for processing a silver halide photographic light-sensitive material, which comprises developing after image exposure with a developer having a pH of 9.5 or more and less than 11.0. 11. A silver halide photographic light-sensitive material according to claim 2, claim 3, claim 4, claim 5, claim 6, claim 7, claim 8 or claim 9, In a method of developing while replenishing a developing solution after imagewise exposure, a developing starter solution and a developing replenishing solution contain a dihydroxybenzene-based developing agent and an auxiliary developing agent exhibiting superadditivity with the dihydroxybenzene type developing agent. On the other hand, it is a liquid having a property that the pH increase when 0.1 mol of sodium hydroxide is added is 0.25 or less, and the pH of the development initiation liquid is 9.5 or more and less than 11.0, Developer replenishment amount is 225 ml /
A method for developing and processing a silver halide photographic light-sensitive material, which is characterized by being m ² or less.