JP2002250982A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high contrast silver halide photosensitive material having low fog and high sensitivity, less liable to fog in long-term storage and causing a small sensitivity change with aging after exposure. SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer on the base, at least one kind of ultrafine particles of gold-containing material of the formula Au(0)Ln [where Au(0) is 0-valent gold; L is a compound which coordinates with the gold through a group other than a mercapto group; and (n) is a value of >=0 and may be a decimal fraction] is contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material. In particular, the present invention relates to a silver halide photographic material having high sensitivity, low fog generation and high contrast achieved by a gold-containing nanocrystal stabilized with a specific adsorptive compound.

[0002]

2. Description of the Related Art A silver halide emulsion used for a silver halide photographic light-sensitive material is usually subjected to chemical sensitization using various chemical substances in order to obtain desired sensitivity and gradation. As typical methods, sulfur sensitization, selenium sensitization, tellurium sensitization, sensitization of noble metals such as gold, reduction sensitization, and various sensitization methods using a combination thereof are known. In recent years, there has been a strong demand for high sensitivity, excellent graininess, high sharpness, and rapid processing in which development progress has been accelerated in silver halide photographic light-sensitive materials. Of these, the most widely used one is a gold-sulfur sensitization method using a so-called unstable low-sulfur compound and a gold compound, which can react with silver ions to generate silver sulfide. By P. Grafkies, “Chimie et Physiqu
e Photographique ”(Paul Montel, 1987, 5th
Edition), edited by TH James, “The Theory of the Photogr
aphic Process ”(published by Macmillan, 1977, 4th edition),
H. Frieser, “Die Grundlagen der Photographische
n Prozesse mit Silber-halogeniden ”(Akademische V
erlagasgeselshaft, 1968).

As a method of sensitizing a silver halide emulsion with gold-sulfur, a method of separately adding an unstable sulfur compound capable of reacting with silver ions to form silver sulfide and a gold compound, The method is described in the above-mentioned reference materials, as well as the Journal of the Photographic Society of Japan, Vol. 50, No. 2, p. 108 et seq. (1987);
ournal of the Optical Society of America, 39
Vol. 6, No. 6, 494 et seq. (1949). In these methods, chloroauric acid has been used as a gold compound, and thiourea compounds and thiosulfates have been used as unstable sulfur compounds. However, when these compounds are used, the degree of increase in sensitivity obtained is insufficient, fogging is likely to occur, the gradation is softened, and fog occurs when the photosensitive material is stored for a long period of time. There are various problems such as remarkable, and a solution to the problem has been strongly demanded.

On the other hand, gold sulfur sensitization using a gold compound other than chloroauric acid is described in JP-B-38-6447, JP-A-62-85239, and gold complexes of thioethers.
Gold complexes of rhodanines described in JP-A-1-47537, gold complexes of mesoions described in JP-A-4-267249, and golds of hydantoins disclosed in JP-A-4-268550 and the like Methods using a complex have been known. However, none of these compounds was sufficient to solve the above problems.

Further, JP-A-4-67032, JP-A-4-75053, JP-A-4-75053
No. 86649 describes a gold complex compound described as having an effect of improving fog when a photosensitive material is aged for a long period of time and accompanying deterioration of granularity. 266828 also discloses an example using a gold complex in which a tetra-substituted thiourea is coordinated to a trivalent gold ion,
All of these compounds did not show sufficient action to solve the above problems.

Further, JP-A-4-204724 discloses a method of sensitizing a silver halide emulsion to gold selenium by separately adding an unstable selenium compound which can react with silver ions to form silver selenide and a gold compound. However, in this case as well, the rise in fog is remarkable, and the above problem has not been solved.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned circumstances, and uses gold-containing ultrafine particles stabilized by a specific adsorptive compound.
It is an object of the present invention to provide a high-sensitivity silver halide light-sensitive material which has low fog and high sensitivity, reduces the occurrence of fog when stored for a long period of time, and has a small change in sensitivity over time after exposure.

[0008]

The above object has been achieved by the following silver halide photographic materials. [1] A silver halide photographic material having at least one silver halide emulsion layer on a support, characterized by containing at least one kind of ultrafine gold-containing particles represented by the following composition formula (1). Silver halide photographic light-sensitive material. Compositional formula (1) Au (0) L _n [In formula (1), L represents a compound other than a mercapto group that coordinates to gold. n represents a value of 0 or more, and may be a decimal number. [2] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has at least one of the following formulas (1): A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized by ultrafine gold-containing particles. Compositional formula (1) Au (0) L _n [In formula (1), Au (0) represents zero-valent gold, and L represents a compound other than a mercapto group that coordinates to gold. n represents a value of 0 or more, and may be a decimal number. [3] The halogenation according to (1) or (2), wherein in the composition formula (1), L is a compound which coordinates to gold via a sulfur atom, a selenium atom or a tellurium atom. Silver photographic photosensitive material. [4] The silver halide photographic material as described in (1) or (2), wherein in the composition formula (1), L is a compound which coordinates to gold via a nitrogen atom or a phosphorus atom. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The gold-containing ultrafine particles represented by the composition formula (1) used in the present invention will be described in detail below. In the present invention, the ultrafine particles containing gold are zero-valent gold atoms.
Ultrafine particles containing Au (0), which have an average particle size of 500 nm or less (preferably 0.5 nm or more) as an equivalent sphere diameter.

In the formula (1), L represents a compound other than a mercapto group that coordinates to gold. Compounds that coordinate to gold other than a mercapto group include, specifically, a thioether group, a selenoether group, a telluroether group, a disulfide group, a diselenide group, a ditelluride group, a thioamide group, a selenoamide group, a telluramide group, an amino group, and a phosphino group. Compounds having a 5- or 6-membered nitrogen-containing heterocyclic group, etc., each of which coordinates to gold via a sulfur atom (excluding a mercapto group), a selenium atom, a tellurium atom, a nitrogen atom or a phosphorus atom in the molecule It is.

The compound having a thioether group represented by L in the formula (1) is a thioether compound in which an alkyl group, an aryl group and a heterocyclic group are bonded to a sulfur atom.
It may be symmetrical or asymmetrical to the sulfur atom, and specifically includes dialkylthioethers, diarylthioethers, diheterocyclic thioethers, alkyl-arylthioethers, alkyl-heterocyclic thioethers, aryl -Heterocyclic thioethers and the like.

In the formula (1), the alkyl group of the thioether compound represented by L is a substituted or unsubstituted, straight-chain, branched or cyclic one having 1 to 30 carbon atoms. -20 alkyl groups.

In the formula (1), the aryl group of the thioether compound represented by L is a substituted or unsubstituted, monocyclic or condensed aryl group having 6 to 30 carbon atoms, such as phenyl and naphthyl. Group. Preferably, it is a substituted or unsubstituted phenyl group.

In the formula (1), the heterocyclic group of the thioether compound represented by L is a nitrogen atom, an oxygen atom,
It is a 5- or 7-membered, substituted or unsubstituted, saturated or unsaturated heterocyclic ring containing at least one of sulfur atoms. These may be a single ring, or may form a condensed ring with another aryl ring or hetero ring.
The heterocyclic group is preferably a 5- to 6-membered heterocyclic group.
Examples include quinolyl group, isoquinolyl group, indolyl group, indazolyl group, benzimidazolyl group, pyranyl group, chromenyl group, thienyl group, oxazolyl group, thiazolyl group, benzooxazolyl group, benzothiazolyl group, morpholino group, and morpholinyl group.

Preferred thioether compounds in the present invention are symmetric or asymmetric dialkylthioethers, diarylthioethers, and alkyl-arylthioethers.

In the formula (1), the alkyl group, aryl group and heterocyclic group of the thioether compound represented by L may be substituted, and typical substituents include a halogen atom and an alkyl group (cycloalkyl group). Group, bicycloalkyl group), alkenyl group (including cycloalkenyl group, bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy Group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, Aryloxycarbonyl Amino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group,
Examples include an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl and heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. More specifically, a halogen atom (eg, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [linear,
Represents a branched or cyclic substituted or unsubstituted alkyl group.
Alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl),
A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably substituted with 5 to 30 carbon atoms) Or an unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptane-2-yl, bicyclo [ 2,
2,2] octan-3-yl), and a tricyclo structure having more ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) among the substituents described below also represents an alkyl group having such a concept. And an alkenyl group [which represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. Alkenyl group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted alkenyl group such as vinyl,
Allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms) For example, 2-cyclopenten-1-yl,
2-cyclohexen-1-yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, bicycloalkene having one double bond) It is a monovalent group with one hydrogen atom removed.
For example, bicyclo [2,2,1] hept-2-ene-1
-Yl, bicyclo [2,2,2] oct-2-ene-4
-Yl)], an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group,
An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl,
Naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 or 6
A monovalent group in which one hydrogen atom has been removed from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms Is a heterocyclic group.

For example, 2-furyl, 2-thienyl, 2-
Pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t- Butoxy, n-octyloxy, 2-
Methoxyethoxy), an aryloxy group (preferably,
A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy,
-T-butylphenoxy, 3-nitrophenoxy, 2-
Tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted heterocyclic oxy group,
1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylcarbonyloxy group having 6 to 30 carbon atoms, or An unsubstituted arylcarbonyloxy group, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) A carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n
-Octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxy) Carbonyloxy, n-octylcarbonyloxy),
Aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn
-Hexadecyloxyphenoxycarbonyloxy),
An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) Group,

For example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, an aminocarbonylamino group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted aminocarbonylamino such as carbamoylamino,
N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino,
Ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-
Methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn- Octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N −
n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methyl Sulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n
-Hexadecylthio), an arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms,
For example, phenylthio, p-chlorophenylthio, m-
Methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group ( A substituted or unsubstituted sulfamoyl group preferably having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N
-(3-dodecyloxypropyl) sulfamoyl,
N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N ′
-Phenylcarbamoyl) sulfamoyl), a sulfo group,

Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl) , P-
Methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, Phenylsulfonyl,
p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl, Pivaloyl, 2-chloroacetyl, stearoyl,
Benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl group (preferably substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitro Phenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxy Carbonyl), carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl,
N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted having 6 to 30 carbon atoms) A substituted arylazo group, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, phenylazo,
p-chlorophenylazo, 5-ethylthio-1,3,4
-Thiadiazol-2-ylazo), imide group

(Preferably, N-succinimide, N-
Phthalimide), phosphino group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted phosphino groups such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino) and phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl , Dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyl) Oxyphosphinyloxy), phosphinylamino group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl group (preferably
A substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl,
Phenyldimethylsilyl).

Among the above functional groups, those having a hydrogen atom may be removed and further substituted with the above group.

In the formula (1), among the substituents which the thioether compound represented by L may have, preferably a halogen atom, an alkyl group, an alkenyl group, Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino Group, acylamino group,
Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfonyl group, acyl group,
An aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, and more preferably a halogen atom, an alkyl group, or an alkenyl group. , Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, Amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group,
Examples include a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl and arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, a phosphinyl group, and a phosphinyloxy group.

In formula (1), when the alkyl group, aryl group or heterocyclic group of the thioether compound represented by L has a substituent, the substituent is preferably a water-soluble group. In the present invention, the water-soluble group is an acidic functional group or a salt thereof, and the acidic functional group is preferably a functional group forming a Bronsted acid, and more preferably a functional group having a pKa value in water of 7 or less. Examples of preferred acidic functional groups in the present invention include a carboxyl group, a sulfo group, and an acidic functional group containing phosphorus, and a carboxyl group and a sulfo group are particularly preferred. In the case of having a salt of an acidic functional group, an alkali metal salt (eg, Na salt, K salt, etc.), an alkaline earth metal salt (eg, Ca salt, Mg salt, Ba salt, etc.), ammonium salt of the above acidic functional group , Phosphonium salts and sulfonium salts are preferred.
Further, when the salt of the acidic functional group is an ammonium salt, a phosphonium salt, or a sulfonium salt, it is also preferably an internal salt.

In the formula (1), the selenoether compound represented by L is a selenoether compound having an alkyl group, an aryl group and a heterocyclic group bonded to a selenium atom. It may be asymmetrically substituted, and specifically, dialkyl selenoethers, diarylselenoethers, diheterocyclic selenoethers, alkyl-arylselenoethers, alkyl-
Examples include heterocyclic selenoethers and aryl-heterocyclic selenoethers. Preferred selenoether compounds in the present invention are symmetric or asymmetric dialkylselenoethers, diarylselenoethers or alkyl-arylselenoethers.

In the formula (1), the alkyl group, aryl group or heterocyclic group of the selenoether compound represented by L has the same meaning as when L is a thioether compound, and the preferred range is also the same.

In the formula (1), the telluroether compound represented by L is a telluroether compound in which an alkyl group, an aryl group, and a heterocyclic group are bonded to a tellurium atom. It may be asymmetrically substituted, specifically, dialkyl telluroethers, diaryltelluroethers, diheterocyclic telluroethers, alkyl-aryltelluroethers, alkyl-
Examples include heterocyclic telluroethers and aryl-heterocyclic telluroethers. Preferred telluroethers in the present invention are symmetrical or asymmetrical dialkyltelluroethers, diaryltelluroethers or alkyl-aryltelluroethers.

In the formula (1), the alkyl group, aryl group or heterocyclic group of the telluroether compound represented by L has the same meaning as when L is a thioether compound, and the preferred range is also the same. .

The compound having a disulfide group represented by L in the formula (1) is a disulfide compound in which an alkyl group, an aryl group or a heterocyclic group is bonded to a sulfur atom. It may be asymmetrically substituted, and specific examples include dialkyl disulfides, diaryl disulfides, diheterocyclic disulfides, alkyl-aryl disulfides, alkyl-heterocyclic disulfides, and aryl-heterocyclic disulfides. Preferred disulfides in the present invention are symmetric or asymmetric dialkyl disulfides, diaryl disulfides or alkyl-aryl disulfides.

In formula (1), the alkyl group, aryl group or heterocyclic group of the disulfide compound represented by L has the same meaning as when L is a thioether compound, and the preferred range is also the same.

The compound having a diselenide group represented by L in the formula (1) is a diselenide compound in which an alkyl group, an aryl group or a heterocyclic group is bonded to a sulfur atom. It may be asymmetrically substituted, specifically, dialkyl diselenides, diaryl diselenides, diheterocyclic diselenides, alkyl-aryl diselenides, alkyl-heterocyclic diselenides, aryl-heterocyclic diselenides And the like. Preferred diselenides in the present invention are symmetric or asymmetric dialkyl diselenides, diaryl diselenides or alkyl-aryl diselenides.

In formula (1), the alkyl group, aryl group or heterocyclic group of the diselenide compound represented by L has the same meaning as when L is a thioether compound, and the preferred range is also the same.

The compound having a ditelluride group represented by L in the formula (1) is a ditelluride compound in which an alkyl group, an aryl group or a heterocyclic group is bonded to a sulfur atom. It may be asymmetrically substituted, specifically, dialkyl ditellurides, diaryl ditellurides, diheterocyclic ditellurides, alkyl-aryl ditellurides, alkyl-heterocyclic ditellurides, aryl-heterocyclic ditellurides And the like. Preferred ditellurides in the present invention are symmetric or asymmetric dialkylditellurides, diarylditellurides or alkyl-arylditellurides.

In the formula (1), the alkyl group, aryl group or heterocyclic group of the ditelluride compound represented by L has the same meaning as when L is a thioether compound, and the preferred range is also the same.

In the formula (1), when L is a compound having a thioamide group, the thioamide group may be a part of a ring structure or an acyclic thioamide group.
Useful thioamide groups include, for example, U.S. Pat.
0,925, 4,031,127, 4,08
Nos. 0,207, 4,245,037, 4,25
5,511, 4,266,031 and 4,2
No. 76,364 and Research Disclosure, Volume 151, November 1976
Mon., 15162, Vol. 176, Dec. 1978
Months can be selected from those disclosed in section 17626. When L represents a compound having a thioamide group,
Preferred thioamide compounds are thiourea, thiourethane,
Dithiocarbamic acid ester, 4-thiazoline-2-thione, thiazolidine-2-thione, 4-oxazoline-
2-thione, oxazolidine-2-thione, 2-pyrazolin-5-thione, 4-imidazoline-2-thione, 2
-Thiohydantoin, rhodanine, isorhodanine, 2
-Thio-2,4-oxazolidinedione, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-thiadiazoline-
2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione and the like, which may be further substituted. Good.

When L in the formula (1) is a compound having a selenoamide group or a telluramide group, examples of L include compounds in which the sulfur atom of the thioamide compound is replaced by a selenium atom or a tellurium atom.

In the formula (1), when L is a compound having a 5- or 6-membered nitrogen-containing heterocyclic group, the heterocyclic ring is a 5- or 6-membered nitrogen-containing heterocyclic group comprising a combination of nitrogen, oxygen, sulfur and carbon. And heterocycles. When L has a nitrogen-containing heterocyclic group, L is preferably benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole,
Benzoxazoline, oxazole, thiadiazole,
Oxadiazole, triazine, pyrrole, pyrrolidine, imidazolidine, morpholine, and the like.
These may further have a suitable substituent. More preferred are benzotriazole, triazole, tetrazole and indazole, and most preferred is benzotriazole.

In the formula (1), when L is a compound having an amino group, the amino group is preferably an unsubstituted amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, or a 6 to 30 carbon atoms. And a substituted or unsubstituted anilino group.

In the formula (1), when L is a compound having a phosphino group, substituents of the phosphino group include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a substituent having 1 to 20 carbon atoms. An alkoxy group having 6 to 30 carbon atoms
An aryloxy group, an alkylamino group having 1 to 20 carbon atoms, or an arylamino group having 6 to 30 carbon atoms is preferable.

In the equation (1), n represents a value of 0 or more, and may be a decimal number. The value of n varies depending on the individual gold-containing ultrafine particles, but is preferably larger than 0, more preferably larger than 0 and 100 or less, particularly preferably larger than 0 and 10 or less.

In the present invention, L is preferably a thioether group, a selenoether group, a telluroether group, a thioamide group, a selenoamide group, a telluroamide group, an amino group,
Compounds having a phosphino group, a 5- to 6-membered nitrogen-containing heterocyclic group, more preferably a thioamide group, a selenoamide group, a telluroamide group, a phosphino group,
It is a compound having a nitrogen-containing heterocyclic group of 5 members, most preferably a phosphino group and a compound having a heterocyclic group of 5 to 6 members.

Various sizes of gold-containing ultrafine particles can be used. The average particle size of the gold-containing ultrafine particles preferably used in the present invention is 0.5 n
m to 500 nm, more preferably 0.5 nm to 50 nm, particularly preferably 0.5 nm to 10 nm, and most preferably 0.5 nm to 5 nm.

Next, specific examples of L in the present invention are shown in Tables 1-4.
Table 5 shows specific examples of the gold-containing ultrafine particles represented by the composition formula (1). However, the present invention is not limited to these.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

The gold-containing ultrafine particles represented by the composition formula (1) of the present invention are selected from the most suitable one for each composition. For example, the following documents already known,
Langmuir, vol. 15, p. 1075 (1
999). Next, a typical method for synthesizing the gold-containing ultrafine particles of the present invention will be described with reference to synthetic examples.

(Synthesis of gold-containing ultrafine particles represented by composition formula G-2) To 206 mg of chloroauric acid tetrahydrate, 4 ml of water was added, and 150 mg of L-3 was added to 100 ml of methanol.
Add solution. This solution contains sodium borohydride 19
A solution of 0 mg in 25 ml of water is slowly added dropwise. The solution is centrifuged to remove the supernatant, 25 ml of an aqueous solution of 20% methanol is added, and the mixture is subjected to ultrasonic waves for 30 minutes, and then the supernatant is removed by a centrifuge. This operation was repeated twice more to obtain 320 mg of gold-containing ultrafine particles. The ultrafine particles containing gold were analyzed by elemental analysis to find that AuL _0.30
It turned out that it has the composition.

[0050] As may vary in a wide range of silver halide per mole gold amount depending on the case the addition amount of the gold-containing ultrafine particles represented by the composition formula (1) of the present invention 1 × 10 ^-6 to 5 × 1
It is 0 ^-1 mol, preferably 5 × 10 ^{-6 to} 5 × 10 ^-3 mol.

The gold-containing ultrafine particles represented by the compositional formula (1) of the present invention include water, alcohols (eg, methanol and ethanol), ketones (eg, acetone), amides (eg, dimethylformamide), and glycols. (Eg, methyl propylene glycol) and esters (eg, ethyl acetate) may be added as a solvent or a dispersion medium. As for the gold-containing ultrafine particles which are insoluble in various solvents, solids themselves can be used.

The gold-containing ultrafine particles represented by the composition formula (1) of the present invention can be added at any stage during the production of the emulsion. Is preferably added.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and silver chloride, silver chlorobromide, silver bromide, silver iodochloride, and silver iodobromide are used. However, an emulsion containing bromide ions or iodide ions is more preferable. The size of silver halide grains is not limited, but is equivalent to 0.01 to 3 μm
Is preferred. The shape of silver halide grains is
A regular crystal system (normal crystal grains) or an irregular crystal system may be used. Normal crystal grains include cubic, octahedral, dodecahedral, tetradecahedral, icosahedral, and forty-octahedral. Irregular crystal forms include spherical and potato-like. In addition, grains having one or more twin planes may be used, and hexagonal tabular grains and triangular tabular grains having two or three parallel twin planes are preferably used. Further, in the case of tabular grains, it is more preferable that the grain size distribution be monodisperse (coefficient of variation: 10 to 20%). For the preparation of monodisperse tabular grains, see JP-A-63-11928.
There is a description in the publication. Monodisperse hexagonal tabular grains are described in JP-A-63-151618. Circular monodisperse tabular grain emulsions are described in JP-A-1-131.
No. 541. JP-A-2-838 discloses that at least 95% of the total projected area is occupied by tabular grains having two twin planes parallel to the main plane, and the size distribution of the tabular grains is small. Emulsions that are monodisperse are disclosed. EP 514 742 A discloses a tabular grain emulsion prepared using a polyalkylene oxide block polymer and having a grain size variation coefficient of 10% or less. By using these techniques, it is possible to prepare monodisperse particles preferred in the present invention. Further, the coefficient of variation of the particle thickness is preferably 20% or less, particularly preferably 5 to 15%.

The tabular grains have a principal plane of (10).
Nos. 0) and (111) are known, and the former is described in U.S. Pat. No. 4,063,951 and JP-A-5-281640 regarding silver bromide.
Silver chloride is described in EP 0534395 A1 and US Pat. No. 5,264,337. The latter tabular grains are grains having various shapes having one or more twin planes described above. Silver chloride is disclosed in U.S. Pat. Nos. 4,399,215, 4,983,508 and 5,183. 732, JP-A-3-13763.
Nos. 2 and 3-116113 can be referred to. The present invention can be preferably applied to both (100) and (111) tabular grains. The tabular emulsion preferably used in the invention has an aspect ratio (equivalent circle diameter / grain thickness) of 2 or more and 1 or more.
An emulsion in which silver halide grains of not more than 00 exist in an amount of 50% or more (area) of all silver halide grains in the emulsion. The emulsion is preferably one in which silver halide grains having an aspect ratio of 5 or more, more preferably 8 or more, are present in an amount of 50% (area) or more of all silver halide grains in the emulsion, preferably 60% or more, and particularly preferably. Is an emulsion present in 85% or more. The equivalent circle diameter of the tabular grains is 0.2 to 5.
0 μm, preferably 0.5 to 3.0 μm, particularly preferably 0.6 to 2.0 μm. The thickness of the tabular grains is preferably 0.02 to 0.3 μm, and 0.03 to 0.2 μm.
m is particularly preferred. In the case of an internal latent image type direct positive silver halide emulsion, the same range as that of the above-mentioned tabular emulsion is preferable, but the average grain diameter (equivalent circle diameter) is 0.3.
μm or more (preferably 0.3 to 10 μm, more preferably 0.5 to 5.0 μm, and still more preferably 0.5 to 3.
0 μm) and an aspect ratio of 2 or more, more preferably 5 or more, and still more preferably 8 or more (preferably 100 or less).
Is 5% of the total silver halide grains in the emulsion.
Emulsions having 0% (area) or more (preferably 70% or more, more preferably 85% or more) are preferable.

The silver halide grains may have dislocation lines in the grains. With respect to the technique of introducing dislocations into silver halide grains while controlling the dislocations, see JP-A-63-22023.
No. 8 can be referred to. Dislocation can be introduced by providing a specific high iodine phase inside a tabular grain having an average aspect ratio of 2 or more and covering the outside thereof with a phase having a lower iodine content than the high iodine phase. By introducing the dislocation, effects such as an increase in sensitivity, an improvement in storage stability, an improvement in latent image stability, and a reduction in pressure fog can be obtained. Thereby, dislocations are mainly introduced at the edge portions of the tabular grains. The tabular grains having dislocations introduced at the center are described in US Pat. No. 5,238,796. The present invention
The effect is obtained when 50% or more of the silver halide grains contain 10 or more dislocation lines per grain.

In the preparation of the silver halide emulsion, there are no particular restrictions on the additives that can be added from the time of grain formation to the time of coating. A silver halide solvent can be used to promote growth during the crystal formation process, and to effectively enhance chemical sensitization during grain formation and / or chemical sensitization. As preferred silver halide solvents, water-soluble thiocyanates, ammonia, thioethers and thioureas can be used. Examples of silver halide solvents include thiocyanates (U.S. Pat. No. 2,222,264).
No. 2,448,534 and No. 332,069), ammonia, thioether compound (US Pat.
No. 271157, No. 3574628, No. 370413
0, 4297439 and 4276347), thione compounds (JP-A-53-144319,
JP-A-53-82408 and JP-A-55-77737, amine compounds (described in JP-A-54-100717), thiourea derivatives (described in JP-A-55-2982), imidazoles (described in JP-A-55-2982). 54-100717) and substituted mercaptotetrazole (Japanese Unexamined Patent Publication No.
2020531).

The method for producing a silver halide emulsion is not particularly limited. Generally, a silver salt aqueous solution and a halogen salt aqueous solution are added to a reaction solution having an aqueous gelatin solution with efficient stirring. As a specific method, P. Glafk
by ides Chimie et PhysiquePhtographique (Paul Mont
el, 1967), GF Dufin, PhotographicEmu
lsion Chemistry (The Forcal Press, 1966), V.
Making and Coating Photographi by L. Zelikman etal
c It can be prepared using the method described in Emulsion (The Forcal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-sided mixing method, a double-mixing method, a combination thereof and the like. good. A method of changing the addition rate of silver nitrate or an aqueous alkali halide solution in accordance with the grain growth rate (British Patent No. 153016, Japanese Patent Publication No. Sho 4)
8-36890 and 52-16364) and a method of changing the concentration of an aqueous solution (US Pat. No. 424).
It is preferable to use the method described in Japanese Patent No. 2445 and Japanese Patent Application Laid-Open No. 55-158124) to grow the material quickly within a range not exceeding the critical supersaturation degree. These methods can be preferably used because silver halide grains grow uniformly without generating renucleation.

Instead of adding a silver salt solution and a halogen solution to a reaction vessel, a method in which fine particles prepared in advance are added to the reaction vessel to cause nucleation and / or grain growth to obtain silver halide grains. It is also preferred to use This technique is disclosed in Japanese Patent Laid-Open No. 1-183644.
Nos. 1-183645, 2-44335, and 2
References can be made to JP-A-43534 and JP-A-2-43535 and U.S. Pat. No. 4,879,208. According to this method, the distribution of halogen ions in the crystal of the emulsion grains can be made completely uniform, and favorable photographic characteristics can be obtained. Further, in the present invention, emulsion grains having various structures can be used. A so-called core / shell double-structured particle comprising a particle inside (core portion) and an outside (shell portion), and a triple structure particle (JP-A-60-2)
No. 22844) or a multi-layered particle having more than that is used. When giving a structure inside the emulsion grain,
Particles having not only the above-described wrapping structure but also a so-called bonding structure can be produced. Examples thereof are described in JP-A-58-108526, JP-A-59-16254, JP-A-59-133540, JP-B-58-24772, and European Patent 199290A2. The crystal to be bonded can be grown by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure. In the case of a joint structure,
Naturally, silver halides can be combined with each other, but any silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, may be used in combination with silver halide to form a bonding grain. In the present invention, it is most preferable to use core-shell type double structure particles.

In the case of silver iodobromide particles having these structures, for example, in core-shell type particles, even if the silver iodide content in the core portion is high and the silver iodide content in the shell portion is low, Conversely, grains having a low silver iodide content in the core portion and a high silver iodide content in the shell portion may be used. Similarly, particles having a bonding structure may be particles having a high silver iodide content in the host crystal and a relatively low silver iodide content in the bonding crystal, or vice versa. Further, in the grains having these structures, the boundary portion having different halogen composition may be a clear boundary, or may be an unclear boundary by forming a mixed crystal due to a composition difference, and may be continuously connected. It may have a structural change. The silver halide emulsion is preferably of a surface latent image type. However, JP-A-59-1335
As disclosed in JP-A-42, an internal latent image type emulsion can be used by selecting a developing solution or conditions for development. Also, a shallow internal latent image type emulsion covered with a thin shell can be used according to the purpose. In the present invention, the chemical sensitization of at least one of the above-mentioned core and shell chemical sensitizations is preferably performed using the compound of the above composition formula (1), preferably with a pAg of 5 to 10, a pH of 4 to 8 and a temperature of 30 to 30. Performed at 80 ° C. Together with the compound of the above formula (1), L 1 in the above formula (1), a gold sensitizer,
Further, another chemical sensitizer may be used in combination. A typical example of the gold sensitizer is chloroauric acid or an alkali salt thereof. Preferably, chemical sensitization of the core is performed using a compound of the composition formula (1). It is not necessary that both the core and the shell are chemically sensitized with the compound of the composition formula (1), in which case the other is a combination of L in the composition formula (1) and a gold sensitizer. Or other chemical sensitizers are applied. Regarding the production method of the silver iodobromide tabular emulsion preferably used in the present invention, U.S. Pat. Nos. 4,439,520, 4,434,226, 4,443,048, 44
Nos. 14310 and 5334495 can be referred to. For ultra-thin tabular emulsions having a grain thickness of 0.1 μm or less, reference can be made to US Pat. Nos. 5,460,928, 5,418,853 and 5,418,125. When the present invention is applied to a high silver chloride tabular emulsion, the emulsion preferably used is described in European Patent No. 7
No. 23187, No. 615517, No. 534395
And No. 584644 can be referred to.

The silver halide emulsion is usually spectrally sensitized. It is usually preferable to use a methine dye as the spectral sensitizing dye. Methine dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
Any of rings generally used for cyanine dyes as basic heterocycles can be applied to these dyes. Examples of the basic hetero ring include a pyrroline ring, an oxazoline ring, a thiazoline ring, a pyrrole ring, an oxazole ring, a thiazole ring, a selenazole ring, an imidazole ring, a tetrazole ring, and a pyridine ring. Also,
Rings in which a cyclic hydrocarbon ring or an aromatic hydrocarbon ring is fused to a hetero ring can also be used. Examples of the condensed ring include an indolenine ring, a benzindolenin ring, an indole ring, a benzoxadol ring, a naphthoxazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a benzimidazole ring and a quinoline ring. Can be done. Substituents may be bonded to carbon atoms of these rings. A 5- or 6-membered heterocycle having a ketomethylene structure can be applied to the merocyanine dye or the composite merocyanine dye. Examples of such heterocycles include pyrazolin-5-one ring, thiohydantoin ring, 2-thiooxazolidine-2,4-dione ring, thiazolidine-2,4-dione ring, rhodanine ring and thiobarbitur. Acid rings can be mentioned.

The sensitizing dye is preferably added in an amount of 0.001 to 100 mmol per mol of silver halide, preferably 0.1 to 100 mmol.
More preferably, it is from 01 to 10 mmol. The sensitizing dye is preferably added during or before chemical sensitization (for example, during grain formation or physical ripening).

A dye which does not exhibit spectral sensitization itself or a substance which does not substantially absorb visible light and exhibits supersensitization together with a sensitizing dye can be added to a silver halide emulsion. Good. Examples of such dyes or substances include aminostil compounds substituted with a nitrogen-containing heterocyclic group (US Pat. Nos. 2,933,390 and 3,635,721).
Described in each specification), an aromatic organic acid formaldehyde condensate (described in US Pat. No. 3,743,510), a cadmium salt and an azaindene compound. For the combination of a sensitizing dye and the above dye or substance, see US Pat. Nos. 3,615,613 and 3,61.
Nos. 5,641, 3,617,295 and 3,6
No. 35,721.

The silver halide emulsion is generally used after chemical sensitization. As chemical sensitization, chalcogen sensitization (sulfur sensitization, selenium sensitization, tellurium sensitization), noble metal sensitization (eg, gold sensitization), and reduction sensitization are performed alone or in combination. In the present invention, chemical sensitization combining sulfur sensitization and gold sulfur sensitization is preferably used, but selenium sensitization and tellurium sensitization are also preferably used. In sulfur sensitization,
Unstable sulfur compounds are used as sensitizers. For unstable sulfur compounds, see P. Glafkides, Chimie et Physique
Photographeque (Paul Montel, 1987, 5th
Edition), Research Disclosure Magazine, Volume 307, 307105
No., edited by THJames, The Theory of the Photographic
Process (Macmillan, 1977, 4th edition), H. Frie
by ser, Die Grundlagender Photographischen Prozess
mit Silver-halogeniden (AkademischeVerlags- gesel
bshaft, 1968). Examples of the sulfur sensitizer include thiosulfates (eg, sodium thiosulfate, p-toluenethiosulfonate), thioureas (eg, diphenylthiourea, triethylthiourea, N-ethyl-N′-).
(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide, N-phenylthioacetamide), rhodanines (eg, rhodanine, N-ethylrhodanine, 5
-Benzylidene rhodanine, 5-benzylidene-N-ethyl-rhodanine, diethyl rhodanine), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidin-2-thiones, dipolysulfide (E.g., dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (e.g., cysteine), polythionates and elemental sulfur. Activated gelatin can also be used as a sulfur sensitizer.

In selenium sensitization, an unstable selenium compound is used as a sensitizer. Unstable selenium compounds are described in JP-B-43-13489 and JP-B-44-15748.
No., JP-A-4-25832, JP-A-4-109240,
It is described in JP-A-4-271341 and JP-A-5-40324. Examples of selenium sensitizers include colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenourea) Acetamide, N, N-diethylphenylselenoamide), phosphine selenides (eg, triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg, tri-p-) Tolyl selenophosphate, tri-n-butylselenophosphate), selenoketones (eg, selenobenzophenone) isoselenocyanates, selenocarboxylic acids, selenoesters, and diacyl selenides. In addition, relatively stable selenium compounds such as selenous acid, potassium selenocyanide, selenazoles and selenides (Japanese Patent Publication No.
Nos. 4553 and 52-34492)
Can also be used as a selenium sensitizer.

In the tellurium sensitizer, an unstable tellurium compound is used as a sensitizer. Unstable tellurium compounds are described in Canadian Patent No. 800,958;
Nos. 295,462 and 1,396,696, JP-A-4-204640 and 4-271341.
No. 4,333,033 and 5-303157. Examples of tellurium sensitization include telluroureas (eg, tetramethyltellurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylenetellurourea), phosphine tellurides (eg, butyl- Diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride,
Ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (eg, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride , Bis (ethoxycarbonyl) telluride), isotellurocyanates (eg, allyl isotellurocyanate), telluroketones (eg, telluroacetone, telluroacetophenone), telluramides (eg, telluroacetamide, N, N-dimethyltellurobenzamide) , Tellurohydrazides (eg, N, N ', N'
-Trimethyltellurobenzhydrazide), telluroesters (eg, t-butyl-t-hexyltelluroester), colloidal tellurium, (di) tellurides and other tellurium compounds (eg, potassium telluride, sodium telluropentathionate) Salt).

In the noble metal sensitization, a salt of a noble metal such as gold, platinum, palladium or iridium is used as a sensitizer. For precious metal salts, see P. Grafkides, Chimie et P
hysique Photographique (Paul Montel, 1987,
5th edition), Research Disclosure, Vol. 307, 307105
There is a description in the issue. Gold sensitization is particularly preferred. Examples of gold sensitization include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide. In addition, U.S. Pat.
The gold compounds described in the specifications of JP-A-49,484 and JP-A-5,049,485 can also be used. As one form of gold sensitization, U.S. Pat.
No. 5,568,841 and JP-A-3-266828.
It is also preferable to use the gold complexes described in JP-A Nos. 4-67032 and 8-69074.

In the present invention, reduction sensitization can be used in combination. In reduction sensitization, a reducing compound is used as a sensitizer. For reducing compounds, see P. Grafkides, Chi
mie et Physique Photographique (Paul Montel, 1
987, 5th edition), Research Disclosure 307, 30
No. 7105. Examples of reduction sensitizers include aminoiminomethanesulfinic acid (thiourea dioxide), borane compounds (eg, dimethylamine borane), hydrazine compounds (eg, hydrazine, p-tolylhydrazine), polyamine compounds (eg, diethylenetriamine, Triethylenetetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds and hydrogen. Further, reduction sensitization can be carried out in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening).

The chemical sensitization may be performed by combining two or more kinds. As the combination, a combination of chalcogen sensitization and gold sensitization is particularly preferable. Further, reduction sensitization is preferably performed at the time of forming silver halide grains. The amount of sensitizer used is
It is determined by the type of silver halide grains generally used and the conditions of chemical sensitization. The amount of the chalcogen sensitizer used is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide,
It is preferably ^-7 to 5 × 10 ^-3 mol. The use amount of the noble metal sensitizer is preferably 10 ^-7 to 10 ^-2 mol per mol of silver halide. There are no particular restrictions on the conditions for chemical sensitization. The pAg is 6 to 11, preferably 7 to 10. Preferably, the pH is between 4 and 10. Temperature is 40 ~ 95 ℃
And more preferably 45 to 85 ° C.

The layer constitution of the silver halide photographic material is not particularly limited. However, in the case of color photographic materials, blue,
It has a multilayer structure to record green and red light separately. Each silver halide emulsion layer may be composed of two layers, a high-speed layer and a low-speed layer. Examples of practical layer configurations are listed in (1) to (6) below.

(1) BH / BL / GH / GL / RH / RL / S (2) BH / BM / BL / GH / GM / GL / RH / R
M / RL / S (3) BH / BL / GH / RH / GL / RL / S (4) BH / GH / RH / BL / GL / RL / S (5) BH / BL / CL / GH / GL / RH / RL / S (6) BH / BL / GH / GL / CL / RH / RL / S

B is a blue-sensitive layer, G is a green-sensitive layer, R is a red-sensitive layer, H is the highest sensitivity layer, M is an intermediate sensitivity layer, L is a low sensitivity layer, S is a support, and CL is a multilayer effect. Layer. Non-photosensitive layers such as a protective layer, a filter layer, an intermediate layer, an antihalation layer and an undercoat layer are omitted. The high-sensitivity layer and the low-sensitivity layer having the same color sensitivity may be arranged in reverse.
(3) is described in US Pat. No. 4,184,876. For (4), Research Disclos
ure, Vol. 225, No. 22534, JP-A-59-177551
And JP-A-59-177552.
Further, (5) and (6) are described in JP-A-61-345.
No. 41 discloses this. Preferred layer constitutions are (1)
(2) and (4). The silver halide photographic material of the present invention can be applied not only to color photographic materials but also to X-ray photographic materials, black-and-white photographic materials, plate-making photographic materials and photographic paper.

Various additives of the silver halide emulsion (eg, binder, chemical sensitizer, spectral sensitizer, stabilizer, gelatin, hardener, surfactant, antistatic agent, polymer latex, matting agent, colorant For couplers, ultraviolet absorbers, anti-fading agents, dyes), photographic material supports and photographic material processing methods (eg, coating methods, exposure methods, development processing methods), Research Disclosure 176, 17643 (RD- 17643), 187, 18716 (RD-18716),
Reference can be made to the description of Vol. 225, No. 22534 (RD-22534). The following table shows the descriptions in these Research Disclosure magazines.

種類 Additive type RD-17643 RD-18716 RD-22534 ─ ───────────────────────────────── 1 Chemical sensitizer Page 23 648 Right column Page 24 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24 page 648, right column 24-28 page Supersensitizer 〜 page 649 right column 4 Brightening agent page 24 5 Anti-fogging agent, page 24-25 page 649 right column page 24 , Page 31 Stabilizer 6 Light absorber, pages 25 to 26, page 649, right column Filter dye, 650 page 650, left column UV absorber Stain inhibitor, page 25, right column, page 650, left column to right column 8 Dye image stabilizer 25 Page 32 9 Hardener 26 Page 651 Left column 32 Page 10 Binder 26 Same as above 28 Page 11 Plasticizers and lubricants 27 Page 650 Right column 12 Coating aids, pages 26 to 27 Same as above Surfactants 13 Static prevention Agent page 27 Same as above 14 Color coupler page 25 page 649 page 31 ───── ─────────────────────────────

As the gelatin hardener, for example, an active halogen compound (2,4-dichloro-6-hydroxy-
1,3,5-triazine and its sodium salt, etc.)
And active vinyl compounds (such as 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane or a vinyl-based polymer having a vinylsulfonyl group in the chain) can rapidly convert hydrophilic colloids such as gelatin. It is preferred because it cures and provides stable photographic properties. N-carbamoylpyridinium salts ((1
-Morpholinocarbonyl-3-pyridinio) matansulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) can be preferably used because of their high curing rate.

Color photographic materials are available from Research Disclosure
The development can be carried out by a usual method described in Journal Nos. 176, 17643 and 187, 18716.
The color photographic light-sensitive material is usually subjected to a washing treatment or a stabilizer treatment after development, bleach-fixing or fixing. In the rinsing step, two or more tanks are generally countercurrently washed to save water. A typical example of the stabilizing treatment is a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543, instead of the washing step.

In addition to the above, the color coupler used in the present invention is described in JP-A-11-65007, paragraphs 0019 to 0024, and the chemical sensitization is described in paragraphs 0041 to 0053 in JP-A-11-65007. For the agent, paragraph No. 0057 of the same publication, for sensitizing dyes and the like, paragraphs 0058 to 0060 of the same publication, for development processing, paragraphs 0080 to 999 of the same publication, and for the application to the APS system, paragraphs 0100 to 0100 of the same publication. 01
26 can be referred to.

The present invention can be preferably applied to a color diffusion transfer photosensitive material using an internal latent image type direct positive silver halide emulsion. As for the internal latent image type direct positive silver halide emulsion, there are a type fogged with light and a type fogged chemically using a nucleating agent, and the type fogged chemically is preferred. Examples of the nucleating agent include hydrazines, hydrazides, heterocyclic quaternary salt compounds, thiourea-bonded acylhydrazine compounds, and hydrazine compounds in which a heterocyclic group such as a thioamide ring or triazole or tetrazole is bonded as an adsorbing group. Compounds are preferred. Preferred internal latent image type direct positive silver halide emulsions are described in US Pat. No. 3,206,313.
Nos. 3761266, 4035185, 43
No. 95478, No. 4504570, No. 4434226
And Nos. 4,414,310 and 4,439,520.

The compound represented by the composition formula (1) of the present invention is
When used for internal latent image type direct positive silver halide emulsion
Is 5 × 10 5 per mol of silver halide in the core grains.^-Five
~ 1 × 10^-7It is preferably used in a molar ratio, more preferably
Or 1 × 10^-Five~ 1 × 10 ^-6Used in moles. composition
L in the composition formula (1) which may be used in combination with the formula (1);
The sensitizer and the other chemical sensitizer are each represented by the formula (I)
Use 100-fold to 1 / 100-fold (molar ratio) the compound.
Preferably, it is used 10 times to 1/10 times (molar ratio)
More preferably, it is used. In addition, shell particles
When silver halide is used for shell sensitization
Preferably, however, the abovementioned amounts are used.

Color diffusion transfer to which the present invention can be preferably applied
The photosensitive material will be described. Dye used in the present invention
The imaging substance is a diffusible dye (dye preform) associated with silver development.
Non-diffusible compounds that release
Or its own diffusivity changes,
The Theory of the Photograp
hic Process) 4th edition. These compounds
Can be represented by the following general formula (3). General formula (3) (DYE-Y^')_p-Z^' Ｄ In the formula (3), DYE is a dye group, which is temporarily shortened.
Represents a dye group or a dye precursor group, Y^'Is just a bond or
Represents a linking group, Z^'Is related to silver development (specifically,
Corresponds to or opposite to photosensitive silver salts with latent images in image form
T) (DYE-Y ^')_p-Z^'Diffusion of the compound represented by
Gender differences or release DYE and release
DYE and (DYE-Y^')_p-Z^'Diffusing between
Represents a group having a property that causes a difference in,
p represents 1 or 2, and when p is 2, two DYE-Y^'
May be the same or different. Ｚ Z in general formula (3)^'Diffusibility in silver developing part
Negative compound to become positive and positive to become diffusible in undeveloped area
They are roughly divided into compounds.

Specific examples of the negative type Z ^′ include those which oxidize as a result of development and are cleaved to release a diffusible dye. Specific examples of Z are described in U.S. Pat. Nos. 3,928,312, 4,055,428, 4,179,291, 4,149,892, 4,183,753, and 4,142. Nos. 4,891,355, 4,135,929, JP-A-53-50736, JP-A-57-4043, JP-A-54-130927, and 56-
164342, 57-119345 and the like.

The negative dye-releasing redox compound Z ^′
Among them, a particularly preferred group is an N-substituted sulfamoyl group (an example of the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). Specific examples include compounds (dye developing agents) which are initially diffusible under alkaline conditions but are oxidized by development to become non-diffusible. As the effective Z ^′ for this type of compound, those described in US Pat. No. 2,983,606 are representative.

Another type is one that releases a diffusible dye by, for example, self-ring closure under alkaline conditions, but substantially does not release the dye when oxidized during development. Specific examples of Z ^' having such a function are described in JP-A-53-69033 and JP-A-54-130927.
No. 3,421,964, 4,199,3
No. 55, etc.

Another type does not release the dye itself, but releases the dye when reduced.
Compounds of this type are used in combination with an electron donor,
The diffusible dye can be released imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, see, for example, U.S. Patent Nos. 4,183,753 and 4,278,750.
No. 4,218,368, 4,358,535
JP-A-53-110827 and JP-A-54-13092.
7, No. 56-164342, published technical report 87-619
No. 9, EP-A-220746A2 and the like.

When a compound of this type is used, it is preferably used in combination with a diffusion-resistant electron donating compound (known as an ED compound) or a precursor thereof. Examples of ED compounds include, for example, US Pat.
Nos. 63,393 and 4,278,750;
No. 138736. Specific examples of other types of dye image-forming substances include US Pat.
No. 89 and 4,098,783.

On the other hand, specific examples of the dye represented by DYE of the above general formula are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930 and JP-A-56-71072: Rese
arch Disclosure 17630 (1978), 164
75 (1977).

Examples of magenta dyes: US Pat.
No. 2,380, No. 4,233,237, No. 4,25
0,246, 4,207,104, 4,28
No. 7,292: JP-A-55-36804 and JP-A-56-7
Nos. 3057 and 55-134.

Examples of cyan dyes: US Pat. No. 3,482,9
No. 72, No. 4,171, 220, No. 4, 142, 89
Nos. 1 and 4,148,642; British Patent 1,551,
No. 138; JP-A-52-8827 and JP-A-53-4782.
Nos. 3 and 56-71061; European Patent (EP)
53,037, 53,040; Research Disclos
ure 17,630 (1978) and 16,475
(1977).

[0088]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Example 1 (Production method of Em-1) 1200 ml of an aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously. 30 ml of an aqueous solution containing 1.9 g of AgNO ₃ , 1.5 g of KBr and a molecular weight of 15,000
30 ml of an aqueous solution containing 0.7 g of low molecular weight gelatin was added by a double jet method over 30 seconds to form nuclei.
At this time, the excess concentration of KBr was kept constant. 5 KBr
0 g was added, and the temperature was raised to 75 ° C. to ripen. After aging, 1
Molecular weight 10 containing 35 μmol methionine per gram
35 g of phthalated gelatin having a phthalation rate of 97% and 0000
Was added. The pH was adjusted to 5.6. AgNO ₃ 30
g of an aqueous solution containing g and a KBr aqueous solution were added over 16 minutes by a double jet method (growth step 1). At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. Further, an aqueous solution containing 110 g of AgNO ₃ and 3.8
A KBr aqueous solution (15% by mass) containing mol% KI was added over 15 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate (growth step 2). At this time, the silver potential was kept at -20 mV. Further, the number of rotations of the stirring solution was returned to 132, and an aqueous solution 132 containing 35 g of AgNO ₃ was added.
ml and an aqueous KBr solution were added over 7 minutes by the double jet method. KB so that the potential at the end of addition becomes +20 mV
The addition of the r aqueous solution was adjusted. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to −20 mV, and an aqueous solution 1 containing 6.8 g of AgNO ₃ was added.
900 ml of an aqueous solution containing 00 ml and 7.1 g of KI were added by the double jet method over 10 minutes. Immediately after the addition, 250 ml of an aqueous solution containing 70 g of AgNO ₃ and KBr5
170 ml of an aqueous solution containing 0 g was added over 20 minutes. After washing with water, 45 g of gelatin was added and the mixture was adjusted to pH 5.
8, pAg was adjusted to 8.7.

From observation by transmission electron microscopy of Em-1 at the temperature of liquid nitrogen, dislocation lines were observed at a high density in the fringe portions of the particles, and each particle clearly had 20 or more dislocation lines. The proportion of particles of Em-1 having an aspect ratio of 8 or more occupied 61%, the average aspect ratio was 9.0, the coefficient of variation in iodine distribution between particles was 17, and the average iodine content was 4.3 mol%. .

(Chemical sensitization and spectral sensitization) (Preparation of solid fine dispersion of sensitizing dye) Solid fine dispersions of sensitizing dyes 1 to 3 were prepared as follows. As shown in the preparation conditions in Table 1, after dissolving the inorganic salt in ion-exchanged water, adding a sensitizing dye, and dispersing at 2000 rpm for 20 minutes using a dissolver blade at 60 ° C.,
Solid fine dispersions of sensitizing dyes 1 to 3 were prepared. Sensitizing dye 1

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Sensitizing dye 2

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Sensitizing dye 3

[0095]

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[0096]

[Table 6]

(Preparation of Em-1AR to Em-15AR)
Em-1 was heated to 56 ° C. Sensitizing dyes 1, 2, and 3 were added in a molar ratio of 58: 36: 1, respectively, and in the form of a fine solid dispersion. Thereafter, 1800 ppm of calcium nitrate was added to the emulsion. Thereafter, the gold compound of the present invention, a sulfur sensitizer, potassium thiocyanate (1.5 × 10 ⁻³ mol / mol Ag), chloroauric acid, and N, N-dimethylselenourea shown in Table 7 were added, followed by aging. Optimal chemical sensitization. 1- (p-carboxyphenyl) at the end of chemical sensitization
Em-1AR to Em-15AR were prepared by adding the disodium salt of -5-mercaptotetrazole.

[0098]

[Table 7]

[0099]

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A sample was prepared by applying the above chemically sensitized emulsion to the protective layer on a cellulose triacetate film support provided with an undercoat layer under the coating conditions shown in Table 8 below to prepare a sample.

[0101]

[Table 8]

These samples were left under the conditions of 40 ° C. and 70% relative humidity for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge with a gelatin filter SC-50 manufactured by FUJIFILM Corporation. Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., the following method was used (the cumulative replenishment amount of the solution was 3% of the mother liquor tank capacity).
(Until doubled).

(Processing method) Process Processing time Processing temperature Replenishment amount Color development 3 min. 15 sec. 38 ° C. 45 ml Bleaching 1 min. 00 sec. 38 ° C. 20 ml. 30 ° C water washing (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Water washing (2) 1 minute 00 seconds 35 ° C 30 ml Stable 40 seconds 38 ° C 20 ml Drying 1 minute 15 seconds 55 ° C * The replenishment amount is 35mm width 1.1m per length (24Ex. 1 bottle).

Next, the composition of the processing solution will be described. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] 2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.10

(Bleach) Common to tank liquid and replenisher (unit: g) Ferric ammonium ammonium diaminetetraacetate dihydrate 20.0 Disodium ethylenediaminetetraacetate 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching Promoter 0.005 mol (CH ₃ ) ₂ N-CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -N (CH ₃ ) ₂ .2HCl ammonia water (27%) 15.0 ml 0 liter pH (adjusted with aqueous ammonia and nitric acid) 6.3

(Bleaching / fixing solution) Tank solution (g) Replenisher (g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0-Disodium ethylenediaminetetraacetate 5.0 2.0 Sodium sulfite 12.0 20 6. Ammonium thiosulfate aqueous solution (700 g / L) 240.0 mL 400.0 mL Ammonia water (27%) 6.0 mL-Add water 1.0 L 1.0 L pH (adjusted with ammonia water and acetic acid) 2 7.3

(Washing solution) Common to tank liquid and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) The mixture was passed through a mixed-bed column filled with to treat the calcium and magnesium ion concentrations at 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water 1.0 liter pH 8.5

The concentration of the treated sample was measured with a green filter. The sensitivity was indicated by a relative value of the reciprocal of the exposure required to give a density of fog plus 0.2. In addition, the following experiment was performed to evaluate the storage stability. Unexposed samples were stored at 50 ° C. and 60% relative humidity for 2 weeks. The same sample stored at 5 ° C. for 2 weeks was subjected to a color temperature of 4800 °
A sensitometric exposure was given for 1/100 second through a continuous wedge at K to perform the above color development processing. Next, the concentration was measured, and the difference (Δfog) between the fog value of the sample stored at 50 ° C. and the fog value of the sample stored at 5 ° C. was determined. The larger the plus value, the higher the density. The results are shown in Table 7 above.

As is clear from Table 7, when the ultrafine particles containing gold of the present invention are used, the sensitivity tends to be higher and the fog tends to be lower than when chloroauric acid is used. It was found that the increase in fog was significantly suppressed. Also, as compared with the present invention,
In the case of using the compound HK-1 described in (1), an increase in fog during storage could not be suppressed.

Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: sensitizing dye ExF: dye The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Sample 101) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion P Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-2 0.001 HBS-1 0.004 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid disperse dye ExF-2 0.015 Solid disperse dye ExF-3 0.020 Third layer (intermediate layer) Silver iodobromide emulsion O 0.020 ExC-2 0.022 Polyethyl acrylate latex 0.085 gelatin 0.294 4th layer (low-speed red-sensitive emulsion layer) silver iodobromide emulsion A silver ^{0.323 ExS-1 5.5 × 10 -4} ExS-2 1.0 × 1 ^{-5 ExS-3 2.4 × 10 -4} ExC-1 0.109 ExC-3 0.044 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd- 4 0.025 HBS-1 0.17 Gelatin 0.80 Fifth layer (Medium sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion B Silver 0.28 Silver iodobromide emulsion C Silver 0.54 ExS-1 0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 2.0 × 10 ^-4 ExC-1 0.14 ExC-2 0.026 ExC-3 0.020 ExC-4 0.12 ExC -5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18 6th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.47 ExS-1 3.7 × 10 ^-4 ExS-2 1 × 10 ^-5 ExS-3 1.8 × 10 ^-4 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY-5 0.008 Cpd-2 0.046 Cpd- 4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12 7th layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl Acrylate latex 0.83 Gelatin 0.84 Eighth layer (layer giving an overlay effect to red-sensitive layer) Silver iodobromide emulsion E Silver 0.560 ExS-6 1.7 × 10 ^-4 ExS-10 4.6 × 10 ^-4 Cpd-4 0.030 ExM-2 0.096 ExM-3 0.028 ExY-1 0.031 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58 9th layer (low sensitivity green) Emulsion layer) Silver iodobromide emulsion F silver 0.39 silver iodobromide emulsion G silver 0.28 silver iodobromide emulsion H silver 0.35 ExS-4 2.4 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 3.9 × 10 ^-4 ExS-7 7.7 × 10 ^-5 ExS-8 3.3 × 10 ^-4 ExM-2 0.36 ExM-3 0.045 HBS-1 0.28 HBS- 3 0.01 HSB-4 0.27 Gelatin 1.39 10th layer (Medium speed green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.45 ExS-4 5.3 × 10 ^-5 ExS-7 5 × 10 ^-4 ExS-8 6.3 × 10 ^-4 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM-4 0.028 HBS-1 064 HBS-3 2.1 × 10 ^-3 gelatin 0.44 11th layer (high sensitivity green-sensitive emulsion layer) silver iodobromide emulsion I silver 0. 9 iodobromide emulsion J silver ^{0.80 ExS-4 4.1 × 10 -5} ExS-7 1.1 × 10 -4 ExS-8 4.9 × 10 -4 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 Cpd-3 0.004 Cpd-4 0.007 HBS-1 18 polyethyl acrylate latex 0.099 gelatin 1.11 12th layer (yellow filter layer) yellow colloidal silver silver 0.047 Cpd-1 0.16 solid disperse dye ExF-5 0.020 solid disperse dye ExF-6 020 Oil-soluble dye ExF-7 0.010 HBS-1 0.082 Gelatin 1.057 13th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion K silver 0.18 Silver iodobromide emulsion L Silver 0.20 silver iodobromide emulsion M silver 0.07 ExS-9 4.4 × 10 ^-4 ExS-10 4.0 × 10 ^-4 ExC-1 0.041 ExC-8 0.012 ExY-1 035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.24 Gelatin 1.41 Layer 14 (high Sensitive blue-sensitive emulsion layer) Silver iodobromide emulsion N silver 0.75 ExS-9 3.6 × 10 ^-4 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.91 15th layer (first protective layer) Silver iodobromide emulsion O silver 0.30 UV-1 21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-18 009 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 Gelatin 2.3 16th layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.75 Furthermore, each layer may have a suitable storage property, processing property, pressure resistance, and antifungal property.
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-5, B-4 to B-6, F-1 to F
-18 and iron, lead, gold, platinum, palladium, iridium, ruthenium, and rhodium salts. The coating solution for the eighth layer was 8.5 × 10 ^-3 g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 10 ^-3 g / mol.
^A sample was prepared by adding ^-3 grams of calcium with an aqueous solution of calcium nitrate.

Table 4 below shows the AgI content, grain size, surface iodine content and the like of the emulsions represented by the above-mentioned abbreviations. The surface iodine content can be determined by XPS as follows. The sample was transferred to -115 in a 1x10 torr transfer vacuum.
C., and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 8 kV and an X-ray current of 20 mA.
2, measured for Br3d and I3d5 / 2 electrons, the integrated intensity of the measured peak was corrected by a sensitivity factor, and the iodine content of the surface was determined from the intensity ratio.

[0113]

[Table 9]

In Table 9, (1) Emulsions L to O were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Emulsions A to O are described in JP-A-3-23745.
According to the example of No. 0, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer.

(3) The preparation of tabular grains is described in
According to the example of 58 426, low molecular weight gelatin is used.

(4) Tabular grains are disclosed in JP-A-3-2374.
Dislocation lines as described in No. 50 have been observed using a high voltage electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were placed in a 700 ml pot mill. , Dye ExF-
2 and 5.0 g of zirconium oxide beads (diameter 1 mm)
500 milliliters were added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin 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 is 0.4
It was 4 μm.

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

The compounds used for forming the above layers are as shown below.

[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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(Preparation of Samples 102 to 104) Em-1A prepared in Example 1 instead of the silver iodobromide emulsion D of the sixth layer
R, Em-2AR, Em-3AR, Em-4AR, Em
Samples using -8AR, Em-10AR, and Em-14AR were prepared, and samples 102, 103, 104, and 10, respectively.
5, 106, 107 and 108.

Next, a method of developing each sample will be described.

[0140] Next, the composition of the treatment liquid will be described. (Color developing solution) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) 4.5 amino] -2-methylaniline sulfate 1.0 liter by adding water pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 (bleach-fix solution) (g) Ethylenediaminetetraacetic acid Ferric 100.0 Sodium trihydrate Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH (ammonia 6.0 (Fixing solution) Ethylene Amine tetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / L) 295.0 mL Acetic acid (90%) 3.3 Add water to 1.0 L pH (adjusted with ammonia water and acetic acid) 6.7 (Stabilized solution) (Unit g) ) P-Nonylphenoxy polyglycidol (glycidol average polymerization degree 10) 0.2 ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 hydroxyacetic acid 0.02 Hydroxyethylcellulose 0.1 (Daicel Chemical HEC SP-2000) 1,2-benzisothiazolin-3-one 0.05 Add water and add 1.0 liter pH 8.5

The density of the processed sample was measured with a red filter, and the fogging value, sensitivity, and increase in fogging during storage were evaluated in the same manner as in Example 1. Table 10 shows the results. Emulsions of the invention (Em-3AR, Em-4AR, Em-8AR, Em-
10AR and Em-14AR), it was confirmed that high sensitivity and low fogging were achieved even with a multilayer color light-sensitive material, and that the increase in fogging during storage was small.

[0142]

[Table 10]

Example 3 In the sample of Example 2, instead of the cellulose triacetate film of the support, the support used for the sample 104 in Example 1 of US Pat. The undercoat layer and the back layer were provided by the method described in column 21, line 54 to column 23, line 29,
A heat treated PEN support was used. Further, these samples were loaded into a packaging unit having a photographing function, and evaluated in the same manner as in Example 2.

As a result, the same result as in Example 2 was obtained. Example 4 Sample 102 of Example 1 in JP-A-7-333782
A color diffusion transfer photosensitive material was prepared in the same manner as described above.
However, instead of Em-D7 of the eighth, fifteenth, and twenty-second layers of the same sample, Em-7R, which is the emulsion of Example 1 of the present application, was used. A cover sheet was prepared in the same manner as in the example of JP-A-7-337378, and treated in the same manner as in the example. The obtained photographic properties (highest density, gradation) were all good.

[0145]

By using the gold-containing ultrafine particles represented by the composition formula (1) of the present invention, the sensitivity tends to be higher and the fog tends to be lower than when the other gold sensitizer is added.
An increase in fog when stored for a long time can also be suppressed. Also,
In the photographic light-sensitive material using the internal latent image type direct positive silver halide emulsion, the gold-containing ultrafine particles represented by the composition formula (1) of the present invention have a middle point which is lower than that in the case where another gold sensitizer is added. Both sensitivity and foot sensitivity could be improved.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, comprising at least one kind of ultrafine gold-containing particles represented by the following composition formula (1). Characteristic silver halide photographic material. Compositional formula (1) Au (0) L _n [In formula (1), Au (0) represents zero-valent gold, and L represents a compound other than a mercapto group that coordinates to gold. n represents a value of 0 or more, and may be a decimal number. ] 2. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has at least one kind represented by the following composition formula (1). A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized by ultrafine gold-containing particles. Compositional formula (1) Au (0) L _n [In formula (1), Au (0) represents zero-valent gold, and L represents a compound other than a mercapto group that coordinates to gold. n represents a value of 0 or more, and may be a decimal number. ] 3. The silver halide according to claim 1, wherein in the composition formula (1), L is a compound which coordinates to gold via a sulfur atom, a selenium atom or a tellurium atom. Photosensitive material. 4. A silver halide photographic light-sensitive material according to claim 1, wherein in the composition formula (1), L is a compound which coordinates to gold via a nitrogen atom or a phosphorus atom. .