JPH0836236A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material capable of reducing fog and having high image quality and high sensitivity by incorporating a compd. represented by a specified formula. CONSTITUTION:A spectral sensitizer represented by the formula is incorporated into a silver halide emulsion layer contg. silver halide particles subjected to reduction sensitization on a substrate. In the formula, Z is a heterocyclic group contg. two or more hetero atoms, X1 is a group of nonmetallic atoms required to form a 5 or 6-membered hetero ring of a benzo condensed ring, R1 is alkyl, (p) is 0 or 1 and Q is methylene or polymethylene having a hetero-cyclic group or an arom. group as a substituent. The objective silver halide photographic sensitive material inhibiting fog and having high image quality and high sensitivity is obtd. This material is stable even to a change of performance with the lapse of time.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. In particular, it relates to a silver halide photographic light-sensitive material containing grains subjected to reduction sensitization.

[0002]

2. Description of the Related Art Attempts for reduction sensitization have been studied for a long time in order to increase the sensitivity of silver halide photographic light-sensitive materials. For example, tin compounds in US Pat. No. 2,487,850, polyamine compounds in US Pat. No. 2,512,925, and thiourea dioxide compounds in British Patent 789,823 are useful as reduction sensitizers. It is disclosed that there is. Furthermore, Photographic Sc
Ience and Engineering, Vol. 23, p. 113 (1979), compare the properties of silver nuclei produced by various reduction sensitization methods, such as dimethylamine borane, stannous chloride, hydrazine, high pH ripening, low pH aging.
The pAg aging method has been adopted.

The reduction sensitization method is further described in US Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, and US Pat.
No. 3,930,867 is also disclosed. Not only selection of reduction sensitizer but also devising of reduction sensitization method is described in JP-B Nos. 57-33572 and 58-1410.

However, studies conducted by the inventors have revealed that the fog is increased by adsorbing the sensitizing dye on the reduction-sensitized silver halide grains.

In order to prevent desorption of the sensitizing dye from the silver halide grains in the light-sensitive material (especially at high humidity),
The sensitizing dye may be adsorbed at a high temperature (50 ° C. or higher), but this operation also causes fogging. Further, as a method for increasing the sensitivity, there is a method of adsorbing a sensitizing dye before chemical sensitization, but this method also aggravates fog.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high image quality and high sensitivity with reduced fog.

[0007]

As a result of intensive studies, the object of the present invention could be achieved by the following means. That is, (1) A silver halide photographic light-sensitive material containing a compound represented by the following general formula (I). General formula (I)

[0008]

Embedded image

Where Z contains two or more heteroatoms.
Represents a heterocyclic group represented by X₁Is benzo-fused 5 or 6
Group of non-metal atoms required to form a member heterocycle
You R ¹Represents an alkyl group, p represents 0 or 1.
You Q is methine substituted with a heterocyclic group or an aromatic group
Represents a group or a polymethine group.

(2) In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers contains a spectral sensitizer represented by the above general formula (I). The silver halide photographic light-sensitive material as described in (1) above, wherein the silver halide grains in the emulsion layer are subjected to reduction sensitization. (3) In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers contains a spectral sensitizer represented by formula (I),
The silver halide grains in the emulsion layer have been subjected to reduction sensitization and contain at least one compound selected from the compounds represented by the following general formula (III), (IV) or (V). A silver halide photographic light-sensitive material as described in (1) or (2) above, which is characterized by: Formula _{(III) R-SO 2 S} -M Formula _{(IV) R-SO 2 S} -R 3 formula _{(V) R-SO 2 S-} (E) a -SSO 2
-R ₄

In the formula, R, R ₃ and R _{4, which} may be the same or different, each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation, and E represents a divalent linking group. And a is 0 or 1. (4) The silver halide photographic light-sensitive material according to (1), (2) or (3), wherein the general formula (I) is the following general formula (II). General formula (II)

[0012]

[Chemical 4]

In the formula, Z, X ₁ , R ₁ and p have the same meaning as in formula (I). X ₂ represents a 5- or 6-membered heterocycle, and R ₂ has the same meaning as R ₁ . L represents a methine group, q
Represents 0 or 1, and n represents an integer of 1 to 4. W represents a charge balancing counterion and m represents the number required to neutralize the charge of the molecule.

The present invention will be described in detail below. First, the compounds of the general formulas (I) and (II) of the present invention will be explained.

Z represents a heterocyclic group containing two or more heteroatoms. Examples of the heterocyclic group represented by Z are a pyrazolyl group, an isoxazolyl group, an isothiazolyl group,
Imidazolyl group, oxazolyl group, pyridazyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 1,2,4-triazolyl group, 1,2,3-triazolyl group, tetrazolyl group, β-carbolyl group, pryl Groups and the like. These heterocyclic groups form a bond with any atom which will be described later as X ₁ on any atom which constitutes the heterocyclic group. Z may have a substituent.

The substituent has, for example, 1 to 1 carbon atoms.
8, preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl, hydroxyethyl, trifluoromethyl, benzyl, phenethyl, etc.), Substituted or unsubstituted 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 1 carbon atoms.
A substituted or unsubstituted aryl group of 0 (eg phenyl,
Naphthyl etc.),

Heterocyclic groups having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 to 6 carbon atoms, which may be substituted (eg pyridyl, 5-methylpyridyl, thienyl, etc.), halogen atoms (eg chlorine). , Bromine, iodine, fluorine), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, amino group, nitro group,

An optionally substituted alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (eg methoxy, ethoxy,
2-methoxyethoxy, 2-phenylethoxy, etc.),
An aryloxy group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy, etc.), 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. , And more preferably an acyl group having 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl, etc.), 2 to 2 carbon atoms.
0, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms acylamino group (eg acetylamino, caproylamino, etc.), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably carbon A sulfonyl group of the numbers 1 to 8 (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.),

A sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino, etc.),

A substituted amino group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg methylamino, dimethylamino, benzylamino, etc.), 1 to 20 carbon atoms, preferably An alkyl or arylthio group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio,
Carboxyethylthio, sulfobutylthio, phenylthio, etc.), an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.). ) Represents.

The preferred heterocyclic group represented by Z is a 1-pyrazolyl group, a 3-isoxazolyl group, a 3-isothiazolyl group, a 1 or 2-imidazolyl group, a 2 or 4-oxazolyl group, a 2 or 4-thiazolyl group,
It is a 2- or 3-pyridazyl group, a 1- or 2-pyrimidyl group, or a 1- or 2-pyrazyl group, more preferably a 1-pyrazolyl group, a 2-imidazolyl group, a 2-thiazolyl group, or a 2-pyridazyl group. Preferred as the substituent on Z are the above-mentioned alkyl group, aryl group, halogen atom, acyl group, cyano group, nitro group and sulfonyl group, more preferably a halogen atom, an acyl group,
A cyano group, a nitro group and a sulfonyl group.

R ¹ and R ² are each an alkyl group. Examples of the alkyl group represented by R ¹ and R ² include an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (unsubstituted alkyl group (for example,
Methyl, ethyl, propyl, isopropyl, still, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups such as aralkyl groups (eg benzyl, 2-phenylethyl), hydroxyalkyl groups (eg 2-hydroxyethyl, 3 -Hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl) ), A sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-
Sulfobutyl, 2- [3-sulfopropoxy] ethyl,
2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (eg, 3-sulfatopropyl, 4-sulfatobutyl), heterocycle-substituted alkyl group (eg, 2- (pyrrolidine-2) -On-1-yl) ethyl, tetrahydrofurfuryl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl, allyl group and the like}.

The alkyl group for R ¹ and R ² is preferably the above-mentioned carboxyalkyl group and sulfoalkyl group, more preferably the sulfoalkyl group.

X ₁ represents a benzo-condensed 5- or 6-membered heterocyclic ring and has a benzothiazole nucleus (eg, benzothiazole, 4-chlorobenzothiar, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitro). Benzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5 -Carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-
6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, 5-styrylbenzothiazole),

Benzoxazole nuclei (eg benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole,
5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-
Nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6
-Nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6
-Dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole),
Benzoselenazole nuclei (eg, benzoselenazole,
5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole),
A benzoterrazole nucleus (eg, benzoterrazole,
5-methylbenzoterrazole, 5-methoxybenzoterrazole), 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyano) Indolenine, 3,3-dimethyl-6-nitroindolenine,
3,3-dimethyl-5-nitroindolenine, 3,3-
Dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine),

Benzimidazole nucleus {eg, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl -5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro -5-trifluoromethylbenzimidazole, 1-allyl-5,
6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole,
1-aryl-5,6-dichlorobenzimidazole,
1-aryl-5-methoxybenzimidazole, 1-
Aryl-5-cyanobenzimidazole,

The above-mentioned alkyl group has 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl and butyl, and a hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl). Etc. are particularly preferable, and a methyl group and an ethyl group are particularly preferable.
Represents an alkoxy (eg methoxy) substituted phenyl and the like. }, A quinoline nucleus (for example, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-
Fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-
Quinoline, isoquinoline, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline), imidazo [4,5-b] quinoxaline nucleus (eg 1,3-diethylimidazo). [4,5
-D] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline) and the like.

X ₁ is preferably a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus or a quinoline nucleus, and more preferably a benzoxazole nucleus or a benzothiazole nucleus.

Q represents a methine group or a polymethine group which may have a heterocyclic group or an aromatic group. General formula (I)
Various dyes can be obtained from the compound represented by by changing the atomic group represented by Q. Preferred examples include a cyanine dye forming an amidinium ion system represented by the following general formula (II), a merocyanine dye forming a dipolar amide system represented by the following general formula (VI), and a general formula (VII) below. These complex rhodacyanine dyes represented by can be mentioned. General formula (II)

[0030]

Embedded image

General formula (VI)

[0032]

[Chemical 6]

General formula (VII)

[0034]

[Chemical 7]

X ₂ represents a 5- or 6-membered heterocycle, and is represented by a thiazole nucleus (eg, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole. Nucleus (for example, benzothiazole, 4-chlorobenzothiar, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole,
6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5- Ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole , Tetrahydrobenzothiazole, 4-phenylbenzothiazole, 5-
Styrylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho [1,
2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7
-Ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole), thiazoline nucleus (eg thiazoline, 4-methylthiazoline, 4-nitrothiazoline),

Oxazole nucleus (eg oxazole,
4-methyloxazole, 4-nitrooxazole, 5
-Methyloxazole, 4-phenyloxazole,
4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (eg benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-
Fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5
-Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole , 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,2].
1-d] oxazole, oxazoline nucleus (eg, 4,
4-dimethyloxazoline),

Selenazole nucleus (eg 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (eg benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselena) Azole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d]). Selenazole, naphtho [1,2-d] selenazole), tellurazole nucleus (for example, benzoterrazole, 5-methylbenzoterrazole, 5-methoxybenzoterrazole, naphtho [1,2-d] telrazole), 3,3 A dialkyl indolenine nucleus (eg 3,
3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine,
3,3-Dimethyl-6-nitroindolenine, 3,3-
Dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine),

Imidazole nucleus {for example, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkylbenzimidazole, 1-alkyl-
5-chlorobenzimidazole, 1-alkyl-5,6
-Dichlorobenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl -6-chloro-5-
Cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-alkylnaphtho [1,2-d] imidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-
5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5
6-dichlorobenzimidazole, 1-aryl-5-
Methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1-arylnaphtho [1,2-
d] imidazole,

The above-mentioned alkyl group has 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl and butyl, and a hydroxyalkyl group (eg 2-hydroxyethyl, 3-hydroxypropyl). Etc.) are preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl and the like. }, A pyridine nucleus (eg, 2
-Pyridine, 5-methyl-2-pyridine), quinoline nuclei (e.g., 2-quinoline, 3-methyl-2-quinoline,
5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8- Chloro-2-quinoline, isoquinoline, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-isoquinoline), an imidazo [4,5-b] quinoxaline nucleus (eg 1, 3-Diethylimidazo [4,5-d] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5]
-B] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like.

X ₂ may have a substituent at any position. Examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms (for example, methyl, ethyl, propyl, butyl, hydroxyethyl, Trifluoromethyl, benzyl, phenethyl, p-chlorophenethyl, sulfopropyl, diethylaminoethyl,
Cyanopropyl, adamantyl, ethoxyethyl, ethylthioethyl, phenoxyethyl, carbamoylethyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, etc.), substituted or unsubstituted carbon number 6 to 20, preferably 6 to 15 carbon atoms, More preferably, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl, p-carboxyphenyl, 3,5-dicarboxyphenyl, m-sulfonylphenyl, p-acetamidophenyl, 3-caprylamidophenyl). , P-sulfamoylphenyl, m-hydroxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-anisyl, o-anisyl, p-cyanophenyl, p-N-methylureidophenyl, m-fluorophenyl, p-to Le etc.), from 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 carbon atoms
To 6 optionally substituted heterocyclic groups (eg pyridyl, 5-methylpyridyl, thienyl, etc.), halogen atoms (eg chlorine, bromine, iodine, fluorine), mercapto groups, cyano groups, carboxyl groups, sulfo groups, hydroxy groups, A carbamoyl group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl), 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and Preferably a sulfamoyl group having 2 to 5 carbon atoms (eg methylsulfamoyl, ethylsulfamoyl etc.), an amino group, a nitro group, a carbon number of 1 to 20, preferably a carbon number of 1 to 10, and more preferably a carbon number of 1 To 8 optionally substituted alkoxy groups (eg, methoxy, ethoxy, 2-methoxyethoxide) Shi, such as 2-phenylethoxy), 6 to 20 carbon atoms, preferably from 6 carbon atoms 1
2, more preferably an aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, p-methylphenoxy, p-
Chlorophenoxy, naphthoxy, etc.), 2 to 2 carbon atoms
0, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon acyl groups (eg acetyl, benzoyl, trichloroacetyl, etc.), 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably carbon. Number 2
To 8 acylamino groups (eg acetylamino, caproylamino etc.), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms sulfonyl groups (eg methanesulfonyl, ethanesulfonyl, benzene) Sulfonyl etc.), 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 carbon atom.
To 8 sulfonylamino groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino, etc.), 1 to 20 carbon atoms, preferably 1 carbon atoms
To 12, more preferably a substituted amino group having 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino, etc.), 1 to 20 carbon atoms, preferably 1 carbon atom
To 12, more preferably an alkyl or arylthio group having 1 to 8 carbon atoms (eg, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, phenylthio, etc.), 2 to 20 carbon atoms, preferably 2 carbon atoms.
To 12 and more preferably an alkoxycarbonyl group having 1 to 8 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.).
X ₂ is preferably a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus or a quinoline nucleus, and more preferably a benzoxazole nucleus or a benzothiazole nucleus.

X ₃ represents an atomic group necessary for forming an acidic nucleus. As the acid nucleus, 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazoline-5
-One, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine- 2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3- Oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxy Hmm 4,6-dione, barbituric acid, 2-thiobarbituric acid, Kuroman 2,
4-dione, indazoline-2-one, pyrido [1,2
-A] pyrimidine-1,3-dione and the like.

X ₃ is preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid, and more preferably hydantoin, 2 or 4-thiohydantoin, rhodanine, barbituric acid, and 2-thiobarbituric acid.

R ₅ is a substituted or unsubstituted C 1 to C 2
0, preferably 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms alkyl group (eg, methyl, ethyl, phenethyl, naphthoxyethyl, cyanoethyl, carboxymethyl, carboxyethyl, sulfoethyl, sulfopropyl, sulfobutyl, etc.), a substituent An aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms (for example, phenyl, p-chlorophenyl, o-hydroxyphenyl, etc.) or 1 to 20 carbon atoms. A heterocyclic group having 2 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (eg, pyridyl, pyrazolyl, isoxazolyl, isothiazolyl, imidazolyl, oxazolyl, thiazolyl,
Pyridazyl, pyrimidyl, pyrazyl, 1,3,5-triazolyl, 1,2,4-triazolyl, tetrazolyl and the like).
Preferred as R ₅ are methyl, ethyl, sulfoethyl, sulfopropyl, sulfobutyl, carboxyethyl, phenyl, pyridyl and thiazolyl, more preferably sulfoethyl, sulfopropyl, sulfobutyl, phenyl, pyridyl and thiazolyl.

L is a methine group (substituted or unsubstituted 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl 2-carboxyethyl, etc.), substituted Alternatively, an unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl, etc.), a halogen atom (eg, chlorine, bromine, fluorine, iodine). ), Carbon number 1 to 1
5, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon alkoxy groups (eg, methoxy, ethoxy, etc.), 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms.
0 more preferably an alkylthio group having 1 to 5 carbon atoms (eg methylthio, ethylthio etc.), an arylthio group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably an arylthio group having 6 to 10 carbon atoms (eg phenylthio etc.), etc. May be replaced with. }, And may form a ring with another methine group, or an auxiliary chromophore may form a ring.

W represents a charge balancing counterion. W may be a cation or an anion, and examples of the cation include alkali metal ions such as sodium ion, potassium ion and lithium ion, and organic ions such as tetraalkylammonium ion and pyridinium ion. The anion may be either an inorganic anion or an organic anion, a halogen anion (eg, fluorine ion,
Chlorine ion, bromine ion, iodine ion), substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion, etc.), aryl disulfonate ion (eg, 1,3-benzene disulfonate ion, 1 5, naphthalene disulfonate ion, 2, 6 naphthalene disulfonate ion, etc.), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picric acid Ion, acetate ion, trifluoromethanesulfonate ion and the like. Furthermore, an ionic polymer or another dye having an opposite charge to the dye may be used as the charge-balancing counter ion, and a metal complex ion is also possible.

W is preferably ammonium ion,
Alkali metal ions, halogen anions, and substituted arylsulfonate ions are more preferable, and triethylammonium ion, pyridinium ion, sodium ion, potassium ion, iodine ion, and p-toluenesulfonate ion are more preferable. p and q represent 0 or 1. n, a and b represent an integer of 1 to 4. m represents the number required to neutralize the charge of the molecule.

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto. {Includes general formulas (II), (VI) and (VII) which are subordinate concepts of (I). } Specific examples of the compound represented by formula (I)

[0048]

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[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

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The compound represented by the general formula (I) of the present invention is described in "Heterocyclic Compounds-Cy" by FM Harmer, "Heterocyclic Compounds-Cyanide-and Related Compounds".
anine Dyes and Related Compounds ", John Wiley & Sons-New York, London, 1964, DMSturmer," Heterocyclic Compounds Special Topics. " In Heterocyclic Compounds-Special
topics in heterocyclic chemistry ", Chapter 18, Section 14, 482-515, John Wiley & Sons, Inc.-New York,
London, 1977, "Rodd's Chemistry of Car Compounds"
bon Compounds) "2nd.Ed.vol.IV, partB, 1977, Chapter 15, Chapters 369-422, Elsevier Scienc.
e Publishing Company Inc.), published by New York, and the like.

The synthesis examples of compound I-10 are shown below. Two
-Methyl-5- (2-pyrimidyl) benzoxazole
21 g and 12.1 g of propane sultone and 100 ml of nitrobenzene
The mixture was stirred at 100 ° C for 12 hours. The crystals precipitated in the reaction solution were collected by filtration and 2-methyl-5- (2-pyrimidyl) -3
-(3-Sulfopropyl) benzoxazolium quaternary salt
Obtained 10.1 g. 10.0 g of the quaternary salt was dissolved in a mixed solvent of 25 ml of 2,6-lutidine and 20 ml of acetic acid, 30 ml of triethylorthopropionate was added, and the mixture was stirred at 140 ° C. for 1 hour. After cooling the reaction solution to room temperature, 500 ml of diethyl ether was added to obtain a red oily residue. The supernatant was removed, 75 ml of methanol was added to the oily residue and dissolved, 2.5 g of sodium acetate was added, and the mixture was stirred for 1 hour under ice cooling to precipitate crude crystals of I-10. The crude crystals were collected by filtration and recrystallized twice with methanol to obtain I-10. Yield: 0.3 g Other compounds can be similarly synthesized.

The saturated adsorption amount of the sensitizing dye can be determined from the adsorption isotherm by centrifuging the emulsion adsorbing the dye. Spectral sensitizer represented by general formula (I) (sensitizing dye)
The preferred addition amount of is 40% or more of the saturated adsorption amount,
More preferably 40-120%, even more preferably 70%
~ 100%. The sensitizing dye may be added in the process of forming silver halide grains or in the process of chemical sensitization, or may be added at the time of coating.

Particularly, a method of adding a sensitizing dye during the formation of silver halide emulsion grains is described in US Pat. No. 4,225,666.
No. 4,828,972, JP-A-61-103,1.
No. 49 can be referred to. Further, as a method of adding a sensitizing dye in the desalting step of a silver halide emulsion, European Patent 291,339-A, JP-A 64-52,
No. 137 can be referred to. The method of adding a sensitizing dye in the chemical sensitization step is described in JP-A-59-4.
Reference can be made to No. 8,756.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, an aminostill compound substituted with a nitrogen-containing heterocyclic group (for example, US Pat. Nos. 2,933,390 and 3,3,390).
635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,51).
No. 0), cadmium salt, azaindene compound and the like. US Patent 3,615,613
No. 3,615,641, No. 3,617,295
No. 3,635,721, the combination is particularly useful.

The steps for producing a silver halide emulsion are roughly classified into steps such as grain formation, desalting and chemical sensitization. Particle formation is divided into nucleation, ripening and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. The fact that reduction sensitization is performed during the production process of a silver halide emulsion basically means that it may be performed at any process. The reduction sensitization may be carried out during nucleation which is an initial stage of grain formation, during physical ripening, during growth, or before chemical sensitization other than reduction sensitization or after this chemical sensitization. . When chemical sensitization is performed in combination with gold sensitization, it is preferable to carry out reduction sensitization prior to chemical sensitization so that unfavorable fog does not occur. Most preferred is a method of reduction sensitization during growth of silver halide grains. The term "during growth" here also refers to a method in which the silver halide grains are physically ripened or subjected to reduction sensitization while they are growing by the addition of a water-soluble silver salt and a water-soluble alkali halide, and the growth is temporarily stopped during the growth. It means that the method also includes a method of performing reduction sensitization in the above state and then further growing.

The reduction sensitization of the present invention means a method of adding a known reducing agent to a silver halide emulsion, pAg called silver ripening.
Either a method of growing or aging in a low pAg atmosphere of 1 to 7 or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, amines and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. In the present invention, these known compounds can be selected and used, and two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide and dimethylamine borane are preferred compounds. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the addition amount, but 10 ^-7 to 10 ^-3 per mol of silver halide
A molar range is suitable.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention.

Ascorbic acid and its derivatives (hereinafter
It is called "ascorbic acid compound". Specific examples of () include the following. (A-1) L-ascorbic acid (A-2) L-sodium ascorbate (A-3) L-ascorbate potassium (A-4) DL-ascorbic acid (A-5) D-ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6 -Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is used in a large amount as compared with the addition amount in which a reduction sensitizer is conventionally used preferably. Is desirable. For example, Japanese Patent Publication No. 57-33572
"The amount of reducing agent is usually 0.75 x per g of silver ion"
Do not exceed 10 ^-2 milliequivalents (8 x 10 ^-4 mol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (10 ^-7 to 10 ^-5 mol / AgX mol as ascorbic acid) is often effective. (The converted value is by the inventors). US Pat. No. 2,487,850 states that "a tin compound can be used as a reduction sensitizer in an amount of 1
× 10 ^{−7 to} 44 × 10 ⁻⁶ mol ”. Further, in JP-A-57-179835, it is appropriate that the addition amount of thiourea dioxide is about 0.01 mg to about 2 mg per mol of silver halide and the addition amount of stannous chloride is about 0.01 mg to about 3 mg. It has been described. The amount of the ascorbic acid compound used in the present invention depends on factors such as the grain size of the emulsion, the halogen composition, the temperature for emulsion preparation, pH and pAg, but the preferred addition amount depends on 5 × 10 ^-5 to 1 per mol of silver halide.
It is desirable to select from the range of × 10 ^-1 mol. More preferably, it is selected from the range of 5 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol. Particularly preferred is 1 × 10 ^-3 mol-
It is to select from the range of 1 × 10 ^-2 mol.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. It may be added at any stage of the emulsion production process, but the method of addition during grain growth is particularly preferred. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for particle formation. It is also possible to add a reduction sensitizer to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance and use these aqueous solutions to form grains. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

The silver halide photographic light-sensitive material of the present invention preferably contains at least one compound selected from the compounds represented by formula (III), (IV) or (V).

Compounds of the general formulas (III), (IV) and (V)
Explaining in more detail, R, R ₃And R_FourIs aliphatic
In the case of a group, it is preferably alkyl having 1 to 22 carbon atoms.
Group, alkenyl group having 2 to 22 carbon atoms, alkynyl group
And these may have a substituent. Archi
Group, for example, methyl, ethyl, propyl, buty
Ru, pentyl, hexyl, octyl, 2-ethylhexyl
Le, decyl, dodecyl, hexadecyl, octadecyl,
Cyclohexyl, isopropyl, t-butyl can be mentioned.
It

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups for R, R ₃ and R ₄ include
It preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. These may be substituted.

The heterocyclic group for R, R ₃ and R ₄ includes
3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium, for example, pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole Examples thereof include a ring, a benzothiazole ring, a benzoxazole ring, a benzimidazole ring, a selenazole ring, a benzoselenazole ring, a tellurazole ring, a triazole ring, a benzotriazole ring, a tetrazole ring, an oxadiazole ring and a thiadiazole ring.

The substituents of R, R ₃ and R ₄ include, for example, an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyloxy), an aryl group (phenyl, naphthyl, tolyl). ,
Hydroxy group, halogen atom (eg fluorine, chlorine, bromine, iodine), aryloxy group (eg phenoxy), alkylthio group (eg methylthio, butylthio), arylthio group (eg phenylthio), acyl group (eg acetyl, propionyl, butyryl, valeryl) ), A sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), an acylamino group (eg, acetylamino, benzamino), a sulfonylamino acid (eg, methanesulfonylamino, benzenesulfonylamino), an acyloxy group (eg, acetoxy, benoxy), a carboxyl group,
Examples thereof include a cyano group, a sulfo group and an amino group.

E is preferably a divalent aliphatic group or a divalent aromatic group. The divalent aliphatic group E for example _{- (CH 2) n - (} n = 1~12), - CH 2 -CH
= CH-CH ₂ -,

[0075]

[Chemical 15]

Examples thereof include a xylylene group. Examples of the divalent aromatic group of E include phenylene and naphthylene. These substituents may be further substituted with the above-described substituents.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions.
Examples of the organic cation include ammonium ion (for example, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), guanidine group and the like.

Specific examples of the compound represented by formula (III), (IV) or (V) are shown below, but the invention is not limited thereto.

[0079]

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[0080]

[Chemical 17]

[0081]

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[0082]

[Chemical 19]

[0083]

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[0084]

[Chemical 21]

[0085]

[Chemical formula 22]

[0086]

[Chemical formula 23]

[0087]

[Chemical formula 24]

[0088]

[Chemical 25]

Compounds of general formula (III), JP-A-54-10
19 and British Patent 972,211 for easy synthesis. General formula (III), (IV) or (V)
The compound represented is 10 ^-7 per mol of silver halide.
It is preferable to add from 10 to ¹ mol. Further, the addition amount of 10 ⁻⁶ to 10 ⁻² , particularly 10 ⁻⁵ to 10 ⁻³ mol / mol Ag is preferable.

To add the compounds represented by the general formulas (III), (IV) and (V) during the production process, a method usually used for adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a compound that is insoluble or hardly soluble in water is a suitable organic solvent that is miscible with water, for example, alcohols, glycols, ketones, esters, amides and the like. Among them, it can be dissolved in a solvent that does not adversely affect the photographic properties and added as a solution.

The compound represented by formula (III), (IV) or (V) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization.
Preferred is a method of adding the compound before or during the reduction sensitization. Particularly preferred is the method of addition during grain growth.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for grain formation. Alternatively, the compound of the general formula (III), (IV) or (V) may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. Further, with the formation of particles, general formulas (III) and (I
It is also a preferable method to add the solution of the compound V) or (V) in several times or continuously for a long time.

Among the compounds represented by the general formula (III), (IV) or (V), the most preferred compound for the present invention is the compound represented by the general formula (III).

The emulsion of the present invention preferably has an aspect ratio of 3 or more, more preferably an average aspect ratio of 3 or more 8
Less than tabular silver halide grains. Here, the tabular grains are a general term for grains having one twin plane or two or more parallel twin planes. In this case the twin plane is (111)
This refers to the (111) plane when ions at all lattice points on both sides of the plane have a mirror image relationship. When viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded circular shape.The triangular shape is a triangular shape, the hexagonal shape is a hexagonal shape, and the Have circular outer surfaces parallel to each other.

The aspect ratio of the tabular grains in the present invention means a value obtained by dividing the grain diameter of each tabular grain having a grain diameter of 0.1 μm or more by the thickness. The thickness of the particles is measured by evaporating the metal from the oblique direction of the particles together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. You can easily.

The grain diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the grain.

The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The tabular grains have a diameter of 0.15 to 5.
It is preferably 0 μm. The thickness of the tabular grains is preferably 0.05 to 1.0 μm.

The average aspect ratio is obtained as the arithmetic mean of the aspect ratios of each grain for at least 100 silver halide grains. It can also be obtained as the ratio of the average diameter to the average thickness of the particles.

The emulsion of the present invention contains tabular silver halide grains having an aspect ratio of 3 or more, preferably tabular silver halide grains having an average aspect ratio of 3 or more and less than 8, and preferably 60 of the total projected area. % Or more is occupied by such tabular silver halide grains.

The proportion of tabular grains is preferably 60% or more and particularly preferably 80% or more of the total projected area.

Further, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-1516.
According to the description of No. 18, etc., but its shape is simply stated, 70% or more of the total projected area of the silver halide grains is such that The hexagonal tabular silver halide grains have a hexagonal ratio of 2 or less, and are occupied by tabular silver halide having two parallel outer surfaces, and the hexagonal tabular silver halide grains have a grain size distribution. Has a monodispersity of 20% or less (a value obtained by dividing the variation (standard deviation) in particle size represented by the circle-converted diameter of the projected area by the average particle size).

Further, the emulsion of the present invention preferably has dislocation lines. Dislocations of tabular grains are described, for example, in J. F. Ha
milton, Photo. Sci. Eng. , 11, 5
7, (1967) and T.S. Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
It can be observed by a direct method using a transmission electron microscope at low temperature described in (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation, and the sample is placed so as to prevent damage (printout etc.) due to electron beams. Observation is carried out by the transmission method in the cooled state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass through. Therefore, it is possible to observe more clearly by using a high-pressure type (200 kV or more for a particle having a thickness of 0.25 μm) electron microscope. . From the photograph of the grain obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

The average number of dislocation lines is 10 or more per grain. More preferably, the average number of particles is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, about 10
It is possible to count as many as 20 or 30, which is clearly distinguishable from the case where there are only a few. The average number of dislocation lines per grain is 100.
The number of dislocation lines is counted for particles or more, and the number is determined as a number average.

Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of tabular grains. In this case, the dislocations are almost perpendicular to the outer circumference, and dislocation lines are generated starting from the position of x% of the length of the distance from the center of the tabular grain to the side (outer circumference) and reaching the outer circumference. The value of x is preferably 10 or more and 100
Less than, more preferably 30 or more and less than 99,
Most preferably, it is 50 or more and less than 98. At this time, the shape formed by connecting the positions where the dislocations start is similar to the particle shape, but it is not a perfect shape and may be distorted. This type of dislocation is not found in the central region of the grain. The dislocation lines are crystallographically in the (211) direction, but they are often meandering and may intersect with each other.

Further, the dislocation lines may be almost uniformly distributed over the entire outer circumference of the tabular grain, or may be locally located on the outer circumference. That is, taking a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only in the vicinity of the six vertices, or dislocation lines may be limited in the vicinity of one of the vertices. . On the contrary, it is possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grain.
When dislocation lines are formed over the entire main plane, the direction of the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane, but (110) or In some cases, they are randomly formed, and the length of each dislocation line is also random. In some cases, they are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer periphery). is there. Dislocation lines are often straight or meandering. Also, they often intersect with each other.

The position of the dislocation may be limited to the outer periphery, the main plane, or the local position as described above.
These may be formed in combination. That is, they may exist on the outer circumference and the main plane at the same time.

Introduction of dislocation lines on the outer periphery of tabular grains can be achieved by providing a specific high silver iodide layer inside the grains. Here, the high silver iodide layer includes the case where discontinuous high silver iodide regions are provided. Specifically, it can be obtained by preparing a base grain and then providing a high silver iodide layer and covering the outside thereof with a layer having a lower silver iodide content than the high silver iodide layer. The silver iodide content of the base tabular grains is lower than that of the high silver iodide layer, preferably 0 to 20 mol%, more preferably 0 to 15%.
Mol%.

The high silver iodide layer inside the grain means a silver halide solid solution containing silver iodide. The silver halide in this case is preferably silver iodide, silver iodobromide or silver chloroiodobromide, but is silver iodide or silver iodobromide (silver iodide content of 10 to 40 mol%). More preferable. In order to selectively cause the high silver iodide layer inside the grain (hereinafter referred to as the internal high silver iodide layer) to be present on any side or corner of the base grain, the generation condition of the base grain and the internal It can be controlled by the production conditions of the high silver iodide layer. As the conditions for forming the base silver grains, pAg (logarithm of reciprocal of silver ion concentration), presence / absence of silver halide solvent, type and amount, and temperature are important factors. By setting the pAg during the growth of the base grains to be 8.5 or less, more preferably 8 or less, the internal high silver iodide layer can be made to selectively exist near the apexes of the base grains. On the other hand, the internal high silver iodide layer can be made to exist on the sides of the base grains by setting the pAg during the growth of the base grains to be 8.5 or more, more preferably 9 or more. These pAg
The threshold of changes up and down depending on the temperature and the presence, type, and amount of silver halide solvent. When thiocyanate is used as the silver halide solvent, the pAg
The threshold of shifts toward higher values. The most important pAg during growth is the pAg at the end of the growth of the base grain.
Is. On the other hand, even when the pAg during growth does not satisfy the above value, it is possible to control the selected position of the internal high silver iodide layer by adjusting the pAg to the pAg after the growth of the base grain and ripening. is there. At this time, ammonia, amine compounds and thiocyanate salts are effective as silver halide solvents. The so-called conversion method can be used to form the internal high silver iodide layer. This method includes a method of adding a halogen ion having a smaller solubility of a salt forming silver ion than a halogen ion forming the particle or the surface vicinity of the particle at the time of grain formation. In the present invention, it is preferable that the amount of halogen ion having a small solubility to be added with respect to the surface area of the particle at that time is a certain value (related to the halogen composition) or more. For example, during particle formation, AgB at that time
It is preferable to add a certain amount or more of KI with respect to the surface area of the r particles. Specifically, it is 8.2 × 10 ^-5 mol / m ^2.
It is preferable to add the above iodide salts.

A more preferable method of forming an internal high silver iodide layer is a method of adding an aqueous silver salt solution at the same time as adding an aqueous halide salt solution containing an iodide salt.

For example, at the same time as the addition of the KI aqueous solution, AgNO
₃ Add aqueous solution with double jet. At this time, the addition start time and the addition end time of the KI aqueous solution and the AgNO ₃ aqueous solution may deviate from each other. The addition molar ratio of the AgNO ₃ aqueous solution to the KI aqueous solution is preferably 0.1 or more, more preferably 0.5 or more. More preferably, it is 1 or more. The total added molar amount of the AgNO ₃ aqueous solution may be in the silver excess region with respect to the halogen ions and the added iodine ions in the system. It is preferable that pAg at the time of the addition of the halide aqueous solution containing these iodine ions and the addition of the silver salt aqueous solution by the double jet is decreased with the addition time of the double jet. PAg before start of addition
Is preferably 6.5 or more and 13 or less. It is more preferably 7.0 or more and 11 or less. The pAg at the end of addition is most preferably 6.5 or more and 10.0 or less.

In carrying out the above method, it is preferable that the solubility of the mixed silver halide is as low as possible. Therefore, the temperature of the mixed system for forming the high silver iodide layer is preferably 30 ° C. or higher and 70 ° C. or lower, more preferably 30 ° C. or higher and 5 ° C. or higher.
It is 0 ° C or lower.

Most preferably, the formation of the internal high silver iodide layer is fine grain silver iodide (fine silver iodide, hereinafter the same).
Alternatively, fine grain silver iodobromide, fine grain silver chloroiodobromide or fine grain silver chloroiodobromide can be added. It is particularly preferable to add fine grain silver iodide. These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm, but fine particles having a particle size of 0.01 μm or less or 0.1 μm or more can also be used. Regarding the preparation method of these fine silver halide grains, Japanese Patent Application No. 63-785
1, No. 63-195778, No. 63-7852,
Reference can be made to the descriptions relating to 63-7853, 63-194861 and 63-194862. An internal high silver iodide layer can be provided by adding and ripening these fine grain silver halides.
When dissolving the fine particles by ripening, it is also possible to use the above-mentioned silver halide solvent. It is not necessary that all of the added fine particles dissolve and disappear immediately, and it is sufficient that the fine particles dissolve and disappear when the final particles are completed.

The outer layer covering the internal high silver iodide layer is lower than the silver iodide content of the high silver iodide layer, preferably the silver iodide content is 0 to 30 mol%, more preferably 0 to 20 mol%. Mol%
Most preferably, it is 0 to 10 mol%. The position of this internal high silver iodide layer is measured from the center of the projected hexagon or the like of the grain, and is 5 mol% to 100 mol% with respect to the total silver amount of the grain.
It is preferably present in the range of less than 20% by mole, more preferably 20% by mole or more and less than 95% by mole, particularly 50% by mole or more and 9% by mole or more.
It is preferably within the range of less than 0 mol%. The amount of silver halide forming these internal high silver iodide layers is 50 mol% or less, and more preferably 20 mol% or less, based on the total silver amount of the grains in terms of silver amount. These high silver iodide layers are prescribed values for producing a silver halide emulsion, and are not values obtained by measuring the halogen composition of final grains by various analytical methods. The internal high silver iodide layer often disappears in the final grain due to the recrystallization process or the like, and the above is all about the manufacturing method thereof.

Therefore, in the final grain, the dislocation line can be easily observed by the above-mentioned method, but the internal silver iodide layer introduced for introducing the dislocation line cannot be confirmed as a clear layer in many cases. In some cases, for example, the entire peripheral area of the tabular grains may be observed as a high silver iodide layer. X-ray diffraction and EP
MA (also called XMA) method (a method of scanning silver halide grains with an electron beam to detect the silver halide composition), ESCA (also called XPS) method (irradiated with X-rays and emitted from the grain surface It can be confirmed by combining the method of separating the coming photoelectrons).

The temperature at the time of forming the outer layer covering the internal high silver iodide layer, pAg, is arbitrary, but the preferred temperature is 30.
The temperature is not less than 0 ° C and not more than 80 ° C. Most preferably, it is 35 ° C. or higher and 70 ° C. or lower. Preferred pAg is 6.5 or more 11.5
It is the following. It may be preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt.

To introduce dislocation lines on the main surface of tabular grains, after preparing the base grains, silver halochloride is deposited on the main surface, and the silver halochloride is subjected to conversion to obtain high silver bromide or high silver iodide. A layer may be formed and a shell may be further provided on the outside thereof. Examples of the halosilver chloride include silver chloride or silver chlorobromide having a silver chloride content of 10 mol% or more, preferably 60 mol% or more, or silver chloroiodobromide. Deposition of these halosilver chloride base grains on the principal plane can be carried out by adding an aqueous solution of silver nitrate and an appropriate alkali metal salt (eg, potassium chloride) separately or simultaneously, or an emulsion comprising these silver salts. It is also possible to deposit by adding and aging. Deposition of these silver halochlorides is possible in all pAg regions, but most preferably between 5.0 and 9.5. In this method, tabular grains are mainly grown in the thickness direction. The amount of this halosilver chloride layer is 1 mol% or more and 80 mol% or less in terms of silver mol based on the base grains. It is more preferably 2 mol% or more and 60 mol% or less. By converting this halosilver chloride layer with an aqueous solution of a halide capable of forming a silver salt having a solubility lower than that of halosilver chloride, dislocation lines can be introduced on the principal planes of the tabular grains. After conversion of this silver halochloride layer, for example with an aqueous solution of KI, it is possible to grow the shell and obtain the final grains. The halogen conversion of these halosilver chloride layers does not mean that all of them are replaced with silver salts having a lower solubility than halosilver chloride, but preferably 5% or more, more preferably 10% or more, most preferably 20% or more, It replaces the low-solubility silver salt. By controlling the halogen structure of the base grain on which the halosilver chloride layer is provided, it is possible to introduce dislocation lines into local sites on the principal plane. For example, when a base grain having an internal high silver iodide structure is used by laterally displacing the base tabular grain, dislocation lines can be introduced only into the peripheral main planes excluding the central portion of the main plane. When the base grains having an outer silver iodide-rich structure are displaced in the lateral direction of the base tabular grains, dislocation lines can be introduced only into the central portion excluding the peripheral portion of the main plane. Further, it is also possible to deposit a halosilver chloride only on a site limited in area by using a locally dominant substance for epitaxial growth of halosilver chloride, for example, iodide, and introduce a dislocation line only to the site. The temperature during the deposition of silver halochloride is 30 ° C or higher, 70
℃ or less is preferable, more preferably 30 ℃ or more 50 ℃
It is the following. It is possible to carry out conversion after the deposition of these silver halochlorides and then grow the shell, but it is also possible to carry out halogen conversion while the growth of the shells is carried out after the deposition of the silver halochloride.

The position of the internal halosilver chloride layer formed substantially parallel to the principal plane may be in the range of 5 mol% or more and less than 100 mol% with respect to the total amount of silver in the grains on both sides from the center of the grain thickness. It is more preferably 20 mol% or more and less than 95 mol%, and particularly preferably 50 mol% or more and less than 90 mol%.

The silver iodide content of the shell is preferably 0-3.
It is 0 mol%, more preferably 0 to 20 mol%. The temperature at the time of shell formation and pAg are arbitrary, but the preferred temperature is 30 ° C or higher and 80 ° C or lower. Most preferably 35 ° C
It is above 70 ° C. Preferred pAg is 6.5 or more 1
It is 1.5 or less. It may be preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt. In the final grain, the internal halosilver chloride layer that has undergone halogen conversion may not be confirmed by the above-described method for analyzing halogen composition, depending on conditions such as the degree of halogen conversion. However, dislocation lines can be clearly observed.

A method of introducing a dislocation line at an arbitrary position on the principal plane of the tabular grain and a method of introducing a dislocation line at an arbitrary position on the outer periphery of the tabular grain described above are appropriately combined and used. It is also possible to introduce dislocation lines.

Any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used in the silver halide emulsion usable in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide.

The tabular grains of the present invention are described in "Theory and Practice of Photography" by Cleeve (Cleve, Photography).
Theory and Practice (193
0)), page 131; Gaft, Photographic Science and Engineering (Gutoff, Ph.
otographic Science and En
Gineering), Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,1
It can be easily prepared by the method described in No. 57, etc.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, H. H. Frieser, Di Grundragel
Dell Photography Shen Plotse Mitt Gilberhalogeniden (Die Grundlagen)
der Photographischen Proz
ess mit Silberhalogenide
n) (Academia Michel Ferragus Gezel Shackt 1
968) The method described on pages 675 to 734 can be used.

That is, compounds containing sulfur capable of reacting with active gelatin or silver (eg, thiosulfates, thioureas,
Sulfur sensitization method using mercapto compounds, rhodanins); Reduction sensitization method using reducing substances (eg, primary tin salt, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); noble metal compounds (eg, , Gold complex salts, complex salts of metals of Group VIII such as Pt, Ir, Pd), and selenium sensitization methods using selenium compounds (selenoureas, selenoketones, selenides, etc.) Etc. can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; such as carboxyl group and sulfone group The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazoline thione; azaindenes such as tetraazaindene (particularly 4-hydroxy-substituted (1, 3, 3
a, 7) Tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers can be added.

The antifoggant or stabilizer is usually added after chemical sensitization, but more preferably during the chemical ripening or before the start of the chemical ripening. That is, in the process of forming silver halide emulsion grains, during the addition of the silver salt solution, after the addition until the start of chemical ripening, during the chemical ripening (during the chemical ripening time, preferably within 50% from the start, More preferably within 20% of the time).

The addition amount of the above-mentioned compounds used in the present invention cannot be uniquely determined by the addition method or the amount of silver halide, but is preferably 10 ^-7 mol to 10 ^-2 mol per mol of silver halide. , And more preferably 10
^{It is -5} to 10 ^-2 mol.

As the preservative (bound or protective colloid) of the photographic emulsion of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

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 and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinyl imidazole and polyvinyl pyrazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Pho
t. Japan. No. The enzyme-treated gelatin as described in pages 16 and 30 (1966) may be used, or a hydrolyzate or an enzymatic hydrolyzate of gelatin may be used.
As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used.

As the dispersion medium used in the present invention, specifically, Research Disclosure (RESEARCH)
DISCROSURE) Volume 176, No. 17643
(December 1978) Section IX.

The present invention can be used for a color photographic light-sensitive material. It suffices that at least one layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer is provided on the support, and a silver halide emulsion layer and a non-light-sensitive layer can be provided. There is no particular limitation on the number of layers and the order of layers. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as usual.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
It can be installed in the order of.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

As described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a lower layer than the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

Also, in the case of four or more layers, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. Particularly preferred is about 2 mol%
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% of silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and Id. No. 187.
16 (November 1979), p.648, ibid. 3071
05 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by P. Glafkides, Chemie et Ph.
isique Photographie, Pau
L Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,499,520, and British Patent No. 2,112,157, and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image in both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and No.
No. 307105, and the corresponding portions are summarized in Table 1 below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553, and the inside of the grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498,
It is described in JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of circle equivalent diameters of projected areas) of 0.01 to 0.5 μm, more preferably 0.02 to 2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in Table 1 below.

[0161]

[Table 1]

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add to the photographic material a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503. The light-sensitive material of the present invention can be incorporated into U.S. Pat. Nos. 4,740,454 and 4,788,132.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
No. 52, it is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

In the light-sensitive material of the present invention, the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 be contained.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and N
o. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in the above item are preferred. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 which has a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, section VII-F and ibid. 307105, VII-
Patents described in section F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Patents 4,248,962 and 4,782,012 are preferable.

A coupler capable of releasing a nucleating agent or a development accelerator imagewise during development is described in British Patent 2,093.
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. R.K. D. No.
11449, 24241, JP-A-61-201247.
Bleach accelerator releasing couplers described in U.S. Pat.
Examples thereof include ligand releasing couplers described in US Pat. No. 555,477, couplers releasing a leuco dye described in JP-A-63-75747, couplers releasing a fluorescent dye described in US Pat. No. 4,774,181, and the like. To be

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-di-ethylpropyl) phthalate), phosphoric acid Or esters of phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-
2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoic acid esters (eg 2-ethylhexyl benzoate, dodecyl benzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g. N, N-diethyldodecane amide, N,
N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl)) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate nad), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-).
tert-octylaniline) and hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-125747.
272248, and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid. 18
716, page 647, right column to page 648, left column, and the same No.
307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gre
en) et al. in Photographic Science and Engineering (Photogr. Sci. En.
g. ), Vol. 19, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 minutes 15 seconds processing 90% of the maximum swollen film thickness reached when
It is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film-hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid. 1
8716, 651 left column to right column, and the same No. 30710
No. 5, 880-881 can be developed.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Examples thereof include N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--1,
1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-
Hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. A known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone in the black-and-white developer. Alternatively, they can be used in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below.

That is, aperture ratio = {contact area between treatment liquid and air (cm ² )} ÷ volume of treatment liquid (cm ³ ). The above aperture ratio is preferably 0.1 or less, more preferably It is 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set within a range from 2 to 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration. it can.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH may be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-51-140129; JP-B-45-8506 and JP-A-52-20832.
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivative described in No. 61; West German Patent 1,127,
715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,43.
Polyoxyethylene compounds described in No. 0; JP-B-45
Polyamine compounds described in JP-A-8836;
9-40,943, 49-59,644, 53
-94,927, 54-35,727, 55-
26,506 and 58-163,940; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,85
No. 8, West German Patent No. 1,290,812, JP-A-53-
The compounds described in No. 95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,884 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid,
Propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts, but the use of thiosulfates is preferred. It is common and in particular ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the agitation improving means described above is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the amount of the bleaching agent or eliminate the fixing inhibiting action by the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows: Journalof the Society
of Motion Picture and Tel
edition Engineers, Vol. 64, P.P. Two
48-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances produced to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. In addition, JP-A-57
No. 8,542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Technology Society, "Microbial sterilization, sterilization, and antifungal technology" (1982)
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society (1986).

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58
All known methods described in Nos. 14834 and 60-220345 can be used.

In some cases, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizer containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Research Disclosure
No. 14,850 and the same No. Examples of the Schiff base type compounds described in JP-A No. 15,159, 15, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A No. 53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-23805.
It is also applicable to the photothermographic materials described in No. 6, European Patent No. 210,660A2, and the like.

[0212]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of Emulsion An aqueous solution prepared by dissolving 6 g of potassium bromide and 30 g of inactive gelatin having an average molecular weight of 15,000 in 3.7 l of distilled water was stirred well, and 14% of bromide was brominated by the double jet method. An aqueous potassium solution and a 20% aqueous silver nitrate solution were added at a constant flow rate over 1 minute at 55 ° C. and pBr 1.0 (this addition consumed 2.4% of the total silver amount).

An aqueous gelatin solution (17%, 300 cc) was added, and after stirring at 55 ° C., a 20% aqueous silver nitrate solution was added at a constant flow rate until pBr reached 1.4 (this addition of 5. 0% consumed). Furthermore, 20%
Potassium iodobromide solution (KBr _1-x I _x : x = 0.0
4) and 33% aqueous silver nitrate solution were added over 43 minutes by the double jet method (with this addition, 5% of the total silver amount was added).
0% consumed). Here, after adding an aqueous solution containing 8.3 g of potassium iodide, 0.001 / wt% of K ₃ I was added.
14.5 ml of an aqueous rCl ₆ solution was added, and a 20% potassium bromide solution and a 33% aqueous silver nitrate solution were added by the double-bet method over 39 minutes (this addition consumed 42.6% of the total silver amount). The amount of silver nitrate used in this emulsion was 425 g. Then, after desalting by a usual flocculation method, pAg was adjusted to 8.2 and pH was adjusted to 5.8 at 40 ° C. A tabular silver iodobromide emulsion having an average aspect ratio of 6.5, a coefficient of variation of 18% and a sphere equivalent diameter of 0.8 μm (Em-
1) was prepared. Observation with a 200 kV transmission electron microscope at a liquid N ₂ temperature revealed that, on average, 50 or more dislocation lines per grain exist near the outer periphery of the tabular grain. On the other hand, p
After Br reached 1.4, Emulsion E was prepared in the same manner as Emulsion Em-1 except that thiourea dioxide was added to the reaction vessel in an amount of 1.2 × 10 ^-5 mol per mol of silver to form grains.
m-2 was produced. An emulsion Em-3 was prepared in the same manner as the emulsion Em-2 except that thiourea dioxide was changed to L-ascorbic acid 2.5 × 10 ^-3 mol / mol Ag.

When grains were formed in the same manner as Emulsion Em-2, Emulsion Em-2 was used except that Compound III-2 was added in an amount of 1.2 × 10 ⁻⁴ mol per mol of silver 10 minutes after the final shell formation. Emulsion Em-4 was prepared in exactly the same manner.

Emulsions Em-1 to 4 thus prepared
The sensitizing dye A shown in Table 2 was added to 4 × 10 ^-FourMol / mol Ag,
Sensitizing dye B 2 × 10^-FiveMol / mol Ag, sensitizing dye C
6 x 10^-FourAfter adding mol / mol Ag, sodium thiosulfate is added.
Um, chloroauric acid, N, N-dimethylselenourea and thio
Optimum gold-selenium-sulfur sensitization using potassium cyanate
Then, emulsions 101 to 104 were prepared.

[0216]

[Table 2]

Emulsions 105-10 were prepared in the same manner as Emulsions 101-104 except that Sensitizing dye A was changed to I-19 and Sensitizing dye C was changed to I-16.
8 was produced. A triacetyl cellulose support provided with an undercoat layer was coated with the emulsion layer and the protective layer in the coating amounts shown in Table 3, and emulsions 101 to 108 were used to prepare Sample 1
001 to 1008 were produced.

[0218]

[Table 3]

These samples were exposed to sensitometry for 1/100 seconds through a continuous wedge at a color temperature of 4800 ° K and subjected to the following color development processing.

The development processing used here is 38 under the following conditions.
Performed at ° C.

(Processing step) Step Processing time Processing temperature Color development 45 seconds 38 ° C Bleach 30 seconds 38 ° C Fixing 45 seconds 38 ° C Stable (1) 20 seconds 38 ° C Stable (2) 20 seconds 38 ° C Stable (3) 20 seconds 38 ° C. Drying 30 seconds 60 ° C. * Stability was a countercurrent system from (3) to (1).

The composition of the treatment liquid is shown below. (Color developer) Ethylene dian tetraacetic acid 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid 2-sodium salt 0.3 g Potassium carbonate 30.0 g Sodium chloride 5.0 g Disodium N, N-bis (sulfonate ethyl) ) Hydroxylamine 6.0 g 4- [N-ethyl-N- (β-hydroxylethyl) amino] -2-methylaniline sulfate 5.0 g Water was added to 1.0 liter pH (with potassium hydroxide and sulfuric acid. Preparation) 10.00

(Bleaching Solution) 1,3-Diaminopropanetetraacetic acid ammonium ferric acid monohydrate 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 80 g Ammonium nitrate 15 g Hydroxyacetic acid 25 g Acetic acid (98%) 40 g Water was added. 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 4.3

(Fixer) Ethylenediaminetetraacetic acid disodium salt 15 g Ammonium sulfite 19 g Imidazole 15 g Ammonium thiosulfate (70 WT%) 280 ml Water was added to 1.0 liter pH (prepared with ammonia water and acetic acid) 7.4

(Stabilizing Solution) Sodium p-toluenesulfinate 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 g Ethylenediamon tetraacetic acid disodium salt 0.05 g 1,2 4-triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g Water was added to 1.0 liter pH (prepared with ammonia water and acetic acid) 8.5 Treatment The concentration of the sample of the agent was measured with a green filter.

The obtained sensitivity and fog were evaluated.
Regarding the sensitivity, the relative value of the reciprocal of the exposure amount required for the optical density to be higher than the fog by 0.2 is shown as the sensitivity.

Table 4 shows the results thus obtained.

[0228]

[Table 4]

As is clear from Table 4, Sample 10 of the present invention
Nos. 06 to 1008 are highly sensitive to the comparative sample and have low fog and high sensitivity to the comparative samples 1002 to 1004 subjected to reduction sensitization, and the effect of the present invention is remarkable. Further, the effect is particularly remarkable in the sample 1008 using thiosulfonic acid.

Example 2 The sensitizing dyes used in the emulsions 101 to 104 of Example 1 are shown in Table 5.
Sensitizing dye D5 × 10 ⁻⁴ mol / mol Ag, E2 × 1
Emulsions 201 to 204 were prepared in the same manner except that the content was changed to 0 ^-4 mol / mol Ag and F2 × 10 ^-4 mol / mol Ag. Sensitizing dye E in Emulsions 105 to 106 of Example 1
Is I-13, 5 × 10 ⁻⁴ mol / mol Ag, and F is I-1
Emulsions 205 to 208 were prepared in the same manner except that the amount was changed to 5, 2 × 10 ⁻⁴ mol / mol Ag.

[0231]

[Table 5]

Emulsions 201-208 as in Example 1
Is applied to prepare samples 2001 to 2008, and the same evaluation as in Example 1 is performed. Table 6 shows the results.

[0233]

[Table 6]

As is clear from Table 6, Sample 20 of the present invention
Nos. 06 to 2008 are highly sensitive to the comparative sample and have low fog and high sensitivity to the comparative samples 2002 to 2004 subjected to reduction sensitization, and the effect of the present invention is remarkable. Further, the effect is particularly remarkable in the sample 2008 using thiosulfonic acid.

Example 3 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition)
The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.30 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS -0.02 Second layer (intermediate layer) ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsions 101 to 108 Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC- 3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion A Silver 0.15 Emulsion B Silver 0.15 Emulsion C Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion 201 to 208 Silver 1.20 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM- 2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.88

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.00

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.70

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion A Silver 0.08 Emulsion B Silver 0.07 Emulsion F Silver 0.07 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.73 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.32 Gelatin 1.20

12th Layer (High Sensitivity Blue Sensitive Emulsion Layer) Emulsion G Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.2

14th layer (second protective layer) Emulsion I Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

Preparation of Dispersion of Organic Solid Disperse Dye
ExF-2 was dispersed by the following method. That is, 21.7 ml of water, 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethane sulfonate, and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) were added to a 700 ml pot mill. Then, 5.0 g of the dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

The contents of the emulsion used are shown in Table 7, and the structural formulas of the compounds are shown in Chemical formulas 26 to 42.

[0252]

[Table 7]

[0253]

[Chemical formula 26]

[0254]

[Chemical 27]

[0255]

[Chemical 28]

[0256]

[Chemical 29]

[0257]

Embedded image

[0258]

[Chemical 31]

[0259]

Embedded image

[0260]

[Chemical 33]

[0261]

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[0262]

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[0263]

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[0264]

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[0265]

[Chemical 38]

[0266]

[Chemical Formula 39]

[0267]

[Chemical 40]

[0268]

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[0269]

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Emulsions 101 to 101 prepared in Example 1 were used in the seventh layer.
No. 108 was used as the eleventh layer to prepare emulsions 201 to 201 prepared in Example 2.
Samples 3001 to 3008 were prepared using 208, and exposed and processed in the same manner as in Example 1. However, the color development time of the processing was changed to 3 minutes and 15 seconds.

Emulsions of the Invention 106-108 and 206
The samples using ~ 208 had high sensitivity and low fog, as in Examples 1 and 2.

The sample was tested at 50 ° C., relative humidity of 30% and 60%.
The sample was stored at 80% and 80% for 1 month, and the same exposure and treatment were performed to measure the change in fog density. Table 8 shows the obtained results.

[0273]

[Table 8]

Emulsions of the Invention 106-108 and 206
It was revealed that Samples 3006 to 3008 using Samples No.-208 not only have high sensitivity and little fog, but also have very little change in fog density at high temperature.

[0275]

According to the present invention, a high-quality and high-sensitivity silver halide photographic light-sensitive material in which fogging is suppressed can be obtained. It is also stable against changes in performance over time.

Claims (4)

[Claims] 1. A compound represented by the following general formula (I):
A silver halide photographic light-sensitive material characterized by having. General formula (I)In the formula, Z is a heterocyclic group containing two or more heteroatoms.
Represents X₁Is a benzo-fused 5- or 6-membered heterocycle
It represents a group of non-metal atoms necessary for formation. R ¹Is al
Represents a kill group, and p represents 0 or 1. Q is a heterocycle
Group or polymethyi substituted with a radical or an aromatic group
Represents a group. 2. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of said emulsion layers contains a compound represented by the above general formula (I), 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains therein are subjected to reduction sensitization. 3. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the emulsion layers contains a spectral sensitizer represented by formula (I), The silver halide grains in the emulsion layer have been subjected to reduction sensitization and contain at least one compound represented by the following general formula (III), (IV) or (V). The silver halide photographic light-sensitive material according to claim 1 or 2. Formula _{(III) R-SO 2 S} -M Formula _{(IV) R-SO 2 S} -R 3 formula _{(V) R-SO 2 S-} (E) a -SSO 2
-R _{4 In the} formula, R, R ₃ and R ₄ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a cation and E is a divalent linking group. And a is 0 or 1. 4. The compound represented by the general formula (I) is a compound represented by the following general formula (II):
2. A silver halide photographic light-sensitive material as described in 2 or 3. General formula (II) In the formula, Z, X ₁ , R ₁ and p have the same meaning as in formula (I). X ₂ represents a 5- or 6-membered heterocycle, R ₂ is R ₁
Is synonymous with L represents a methine group, q represents 0 or 1, and n represents an integer of 1 to 4. W represents a charge balancing counterion and m represents the number required to neutralize the charge of the molecule.