JP2000035625A - Silver halide photographic emulsion, its manufacture and sliver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion high in sensitivity and elapsed storage stability and low in fog and superior in rapid processibility and to provide its manufacturing method and a silver halide photographic sensitive material using this photographic emulsion. SOLUTION: The silver halide photographic emulsion having a silver chloride content of >=50 mol.% based on the total silver halides and containing planar silver halide grains having an aspect ratio of >=2 and occupying >=50% of the projection areas of the total silver halide grains is manufactured by the method characterized by having the process in which silver halide grains are grown in the presence of at least one of organic polyhalocompounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide photographic emulsion, and more particularly, to a silver halide photographic emulsion containing tabular high silver chloride grains excellent in rapid processing, low in fog and high in sensitivity, and halogen. It relates to a silver halide photographic material.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials have extremely excellent characteristics, such as high sensitivity and excellent gradation, as compared with other light-sensitive materials. It is widely used. Among them, a light-sensitive material using silver halide grains having a high silver chloride content is preferred from the viewpoint of processing speed. In such silver halide grains having a high silver chloride content, studies on tabular silver halide grains have been actively conducted in recent years with the aim of further increasing sensitivity, sharpening, improving graininess, and speeding up processing. It is.

[0003] Such tabular silver halide grains having a high silver chloride content include grains having a (111) major plane (hereinafter also referred to as (111) tabular grains) and (100).
Particles having a main plane (hereinafter also referred to as (100) tabular particles) are known.

Among these, as a method for forming tabular grains having a (111) plane as a main plane, the grains are formed in the presence of a crystal habit controlling agent such as aminoazaindene, pyrimidine, aminoazine, thiourea, or xanthoidoid. Methods are known. However, in general, the (100) plane is stable in silver halide grains having a high silver chloride content, and these crystal habit controlling agents are desorbed when salts formed during the formation of silver halide grains are removed. The shape of the particles changes (1)
11) It has been difficult to stably obtain tabular grains having a plane as a main plane. Further, many of such crystal habit control agents are known as so-called inhibitors, and there has been a problem that chemical sensitization cannot be performed well in the presence of these compounds.

On the other hand, methods for forming tabular grains having a (100) plane as a main plane are described in JP-A-5-204073, US Pat. Nos. 5,264,337, 5,275,930 and JP-A-6-275930. No. 301131, No. 6-308648, No. 6
-337489, 6-337490, 6-33
No. 7507 and the like. These tabular silver halide grains having the (100) plane as the main plane are (111)
Compared to tabular silver halide grains having a major surface as a plane, the shape is more stable, and there is an advantage that spectral chemical sensitization is easily performed since no crystal habit controlling agent is particularly required.

[0006] As a method for introducing anisotropic growth into grains for growing them into (100) tabular grains, imidazole,
There are a method of adding a (100) plane formation accelerator such as 3,5-diaminotriazole, and a method of forming a gap in the halogen composition or causing a strain on the crystal plane under conditions such as high temperature and high pressure. The former method using a (100) plane formation accelerator has a problem that, similarly to the (111) plane formation accelerator, chemical sensitization cannot be performed well in the presence of these compounds. Since it cannot be neglected, a method utilizing a halogen composition gap surface by a silver iodide phase and a silver bromide phase is preferably used. As a typical example of the method utilizing the gap of the halogen composition, there is known a method in which silver iodide and silver bromide are present to cause nuclei to be distorted due to the difference in the size of the crystal lattice from silver chloride.

However, tabular grains produced in this manner have higher sensitivity than conventional normal crystal grains, but usually have higher fog. In particular, fog was remarkable in tabular grains having a high silver chloride content.
Although the mechanism of fogging formation is not clear, the fog is already seen in the emulsion which has not been subjected to chemical sensitization, and it is considered that the fogging formation is related to the crystal plane distortion caused by the growth of tabular grains. The fog seen here can be suppressed to some extent by adding a so-called development inhibitor, but it is re-amplified by chemical sensitization, which is a major drawback of tabular grains.

US Pat. No. 5,663,041 describes the addition of mercuric chloride during the growth of tabular high silver chloride grains. Japanese Patent Application Laid-Open No. 9-15773
Nos. 9-2262285 and 9-281620 describe the addition of disulfides and thiosulfonates during the growth of tabular high silver chloride grains.

In any of the methods, a compound acting as an oxidizing agent is added to the fog nucleus to be formed, but the reduction of fog is insufficient in each case, and further improvement has been demanded. In addition, when these compounds are added, the increase in fog can be prevented to some extent during storage over time,
There was a problem that desensitization increased, and a solution was awaited.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion having high sensitivity, low fog, high storage stability over time, and excellent rapid processing, a method for producing the same, and a silver halide photographic light-sensitive material. Is to provide.

[0011]

The above objects of the present invention have been attained by the following constitutions.

(1) The silver chloride content is 50 mol% of the total silver.
As described above, in the method for producing a silver halide photographic emulsion in which tabular grains having an aspect ratio of 2 or more occupy 50% or more of the total grain projected area, the grains grow in the presence of at least one polyhalogen organic compound. A method for producing a silver halide photographic emulsion, comprising the steps of:

(2) The method for producing a silver halide photographic emulsion as described in (1) above, wherein the polyhalogen organic compound is a compound represented by the following general formula (I).

[0014]

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(Wherein Q represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. X ¹ and X ² each represent a halogen atom. Y represents a carbonyl group, a sulfinyl group or a sulfonyl group. Represents a hydrogen atom or an electron-withdrawing group, n represents 0 or 1.) (3) The polyhalogen organic compound is a compound represented by the following general formula (II): Or the method for producing a silver halide photographic emulsion according to (2).

[0016]

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(In the formula, Q represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, Y represents a carbonyl group, a sulfinyl group or a sulfonyl group. N represents 0 or 1.) (4) Poly The method for producing a silver halide photographic emulsion according to the above (1), wherein the halogen organic compound is a compound represented by the following general formula (III).

[0018]

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(Wherein, P represents a group of atoms necessary for forming a 5- to 7-membered heterocyclic group). (5) Produced by the method described in any of (1) to (4) above. Silver halide photographic emulsion.

(6) In a silver halide photographic material having at least one photosensitive layer on a support, any one of the photosensitive layers contains the silver halide photographic emulsion according to claim 5. A silver halide photographic light-sensitive material comprising:

(7) In a silver halide photographic material having at least one photosensitive layer on a support, silver halide grains contained in at least one of the photosensitive layers are:
Tabular grains having a silver chloride content of 50 mol% or more of the total silver and an aspect ratio of 2 or more are 5% of the total grain projected area.
0% or more, and at least one of the compounds represented by formulas (I) to (III) is contained in at least one of the photosensitive layer and the non-photosensitive layer. A silver halide photographic material.

Hereinafter, the present invention will be described in detail.

<Silver halide grains which are tabular grains having a silver chloride content of at least 50 mol% of the total silver and an aspect ratio of at least 2 in at least 50% of the total projected area> Aspect ratio referred to herein Means the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes. In the present invention, the aspect ratio is 2 or more, preferably 3 or more and less than 25, and particularly preferably 4 or more and less than 20.

The tabular grains of the present invention preferably have a thickness (distance between main planes) of 0.3 μm or less. More preferably, it is 0.25 μm or less. In addition, the distribution of tabular grains is calculated by using the coefficient of variation (standard deviation S of the distribution of the diameter of a circle when the projected area is approximated by a circle) to the average diameter D.
(100 times the value S / D divided by the ratio) is preferably 30% or less.

One preferred form of the tabular silver halide grains according to the present invention is that the parallel principal plane is constituted by (100) planes. The principal plane referred to here is a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains. The average particle diameter of the main plane can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times and measuring the projected area of the particles on the print (the number of measured particles is zero). 1000 discrimination
There must be more than one. ). The particle thickness can also be obtained by actually measuring an electron micrograph.

Another preferred form is tabular silver halide grains having (111) as a main plane.

The principal plane is (100) plane or (111) plane
The plane can be determined by an electron diffraction method or an X-ray diffraction method. In observation of electron micrographs, (10
0) Particles having a main plane can be examined because the main plane is an orthogonal square (square or rectangular) plane.

The composition of the tabular silver halide grains is Ag
Cl, AgClBr, AgClI, AgClBrI, etc. can be used arbitrarily, but it is preferable that AgCl is a high silver chloride grain having 90 mol% or more. More preferably, Ag of 95 mol% or more and AgI of 1 mol% or less is used.
Cl, AgClBr, AgClI or AgClBrI. From the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing 97 mol% or more of AgCl is more preferable.
AgC with gCl of 98 mol% or more and AgI of 1 mol% or less
1, AgClBr, AgClI or AgClBrI is particularly preferred.

Tabular grains are disclosed in US Pat. No. 4,439,520.
Nos. 4,425,425 and 4,414,304, etc., and tabular grains can be easily obtained according to the description. A silver halide having a different composition can be epitaxially grown or shelled on a specific surface portion. In order to control the photosensitive nucleus, dislocation lines may be provided on the surface or inside of the tabular grains.

<Tabular silver halide emulsion> A method for producing tabular silver halide grains having a (100) major plane according to the present invention will be described below.

<Silver halide grain nucleus> It is preferable that the nucleus of the grain of the present invention is a normal crystal substantially containing no iodine, and further having no twinning and dislocation lines. It is preferable that 70% or more of the total number of nuclear particles is 0.2 μm or less, and more than 70% of the total number of nuclear particles is 0.1 μm or less and 0.005 μm or more. Is most preferred. The coefficient of variation of the core particle size is preferably 30% or less, and most preferably 15% or less.

<Heterogeneous Halogen> Subsequent to the nucleation or after the addition of the nucleus particles, a halogen ion of a type different from the halogen composition of the nucleus particles is added. It is preferably a halogen ion forming silver. Here, as an example of the solubility of silver halide, AgCl> AgB
r> AgI. When the composition is two or more, the solubility decreases as the composition having a low solubility alone is contained. For example, Ag
In ClBr, the higher the Br content, the more I
The higher the content, the less soluble.

<Maturation and Growth Process> Physical ripening is performed subsequent to the heterogeneous halogen mixing process. The aging temperature is 50-90
C is preferable, and 60 to 80C is preferable. Aging time is p
It is preferable to experimentally determine the aging speed because the aging speed varies depending on conditions such as Cl.

In order to control the growth of the grains during the formation of tabular grains, for example, ammonia, a thioether compound, a thione compound or the like can be used as a silver halide solvent. In addition, metal salts such as zinc, lead, thallium, iridium, and rhodium can coexist during physical ripening or chemical ripening.

The grain growth process is preferably carried out by a double jet method. One type of the double jet method is a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double method. The jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the tabular silver halide grains of the present invention, some or all of the steps during grain formation may be grain forming steps by supplying fine silver halide grains. Since the particle size of the fine particles supports the supply rate of halide ions, the preferred particle size varies depending on the size and the halogen composition of the silver halide grains of the host, but those having an average equivalent spherical diameter of 0.3 μm or less are preferably used. . More preferably, it is 0.1 μm or less. In order for the fine particles to be deposited on the host particles by recrystallization, the size of the fine particles is desirably smaller than the equivalent sphere diameter of the host particles, and more preferably 1/5 of the equivalent sphere diameter.
It is as follows.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention can be obtained by removing soluble salts after the completion of the growth of the silver halide grains and removing pAg suitable for chemical sensitization.
To obtain an ion concentration, a Nudel washing method, a flocculation sedimentation method, or the like may be used. As a preferred washing method, for example, an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086 is used. Or a desalting method using G-3, G-8 or the like which is a polymer flocculant described in JP-A-2-7037. In addition, Research Disclosure (R
D) Vol. 102, 1972, October issue, Item
10208 and Vol. 131, 1975, March, I
Desalting may be performed using the ultrafiltration method described in tem 13122.

<Compound of the Present Invention> In one embodiment of the present invention, a polyhalogen organic compound or a compound represented by any of the general formulas (I) to (III) may be used in any of the processes for producing tabular silver halide grains. To be added. The polyhalogen organic compound is an organic compound having two or more halogen atoms, and the compound according to the present invention may be added at any time in the above-mentioned production process. It is preferable until the growth process is completed. Especially the aging temperature is 50
It is preferable that the compound of the present invention be present in the process of raising the temperature to at least ° C.

Next, the compounds represented by formulas (I) and (II) will be described in detail.

The aliphatic hydrocarbon group represented by Q is a straight-chain,
A branched or cyclic alkyl group (preferably having 1 to 3 carbon atoms)
0, more preferably 1 to 20, even more preferably 1 to 12
And for example, methyl, ethyl, iso-propyl, te
rt-butyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl and the like, and an alkenyl group (preferably having 2 to 30, more preferably 2 to 20, more preferably 2 to 12 carbon atoms). ,
For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 carbon atoms)
~ 30, more preferably 2 ~ 20, still more preferably 2 ~ 2
12, for example, propargyl, 3-pentenyl and the like), and may have a substituent.

Examples of the substituent include a carboxy group, acyl group, acylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, oxycarbonylamino group and ureido group. The aliphatic hydrocarbon group is preferably an alkyl group, and more preferably a chain alkyl group.

The aryl group represented by Q is preferably a monocyclic or condensed aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.), and more preferably a phenyl group. The aryl group may have a substituent. Examples of the substituent include an alkyl group (eg, methyl, ethyl, iso-propyl, tert-butyl, n
-Octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (for example, vinyl, allyl, 2-butenyl, 3-
Pentenyl and the like), an aryl group (for example,
Phenyl, p-tolyl, naphthyl, etc.), alkoxy groups (eg, methoxy, ethoxy, butoxy, etc.), acyloxy groups (eg, acetoxy, benzoyloxy, etc.), acyl groups (eg, acetyl, propionyl, benzoyl, naphthoyl, etc.), Acylamino group (for example,
Acetylamino, benzoylamino, etc.), sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), halogen atom, trihalomethyl group (eg, trifluoromethyl) , Tribromomethyl, trichloromethyl, etc.), carbamoyl group, sulfamoyl group, nitro group and the like.

The substituent is more preferably an alkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonylamino group, a halogen atom, a trihalomethyl group, an acyl group, or an alkoxycarbonyl group.

The heterocyclic group represented by Q is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, and is a monocyclic ring or a condensed ring with another ring. May be formed. Preferably 5 to 6 as a heterocyclic group
Membered heterocyclic ring, and more preferably an unsaturated heterocyclic ring containing at least one nitrogen atom. More preferably, it is a 5-6 membered unsaturated heterocycle containing 2-4 nitrogen atoms.

Examples of the heterocyclic group represented by Q include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, Quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole,
Benzoxazole, benzothiazole, indolenine, pyrimidine, tetrazine, pyrazolopyrazine, triazolopyridazine, triazolopyrazine, benzotriazine, tetraazaindene, pyridopyridazine, pyrazolotriazole, pyrrolotriazole, and the like,
Preferably pyridine, triazole, triazine, thiadiazole, oxadiazole, quinoline, tetrazole, thiazole, oxazole, benzimidazole,
Benzoxazole, benzthiazole, indolenine, pyrazine, pyrimidine, phthalazine, quinoxaline, quinazoline and pyridazine, more preferably triazine, thiadiazole, quinoline, benzothiazole, pyrazine, pyrimidine, pyridazine, triazole and tetrazole.

The heterocyclic group represented by Q may have a substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
A sulfonylamino group, a sulfamoyl group, a carbamoyl group, a ureido group, a phosphoric acid amide group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, and a heterocyclic group.

The halogen atoms represented by X ₁ and X ₂ may be the same or different from each other, and are preferably a chlorine atom and a bromine atom, particularly preferably a bromine atom.

Y represents a carbonyl group, a sulfinyl group or a sulfonyl group, and is preferably a sulfonyl group. n
Represents 0 or 1, and is preferably 1 when Y is a sulfonyl group.

The electron-withdrawing group represented by A is preferably a substituent having a Hammett's substituent constant σ _p value of 0.01 or more, more preferably 0.1 or more. Regarding the Hammett's substituent constant, Journal of M
edininal Chemistry, 1973, V
ol. 16, No. 11, 1207 to 1216 can be referred to. Examples of the electron-withdrawing group such as halogen atom (fluorine atom (sigma _p: 0.06), chlorine atom (sigma _p: 0.23), bromine atom (sigma _p: 0.23), iodine (sigma _p: 0.18)), trihalomethyl group (tribromomethyl (σ _p : 0.29), trichloromethyl (σ _p : 0.33), trifluoromethyl (σ _p : 0.5
4)), a cyano group (σ _p : 0.60), a nitro group (σ _p :
0.78), an aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ _p : 0.7
2)), aliphatic aryl or heterocyclic acyl group (e.g., acetyl (sigma _P: 0.50), benzoyl (sigma _P:
0.43)), an alkynyl group (for example, C ₃ H ₃ (0.0
9)), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σ _P : 0.4
5), phenoxycarbonyl (σ _P : 0.45)), carbamoyl group (σ _P : 0.36), sulfamoyl group (σ _P : 0.57) and the like.

More preferably, they are a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl group, and particularly preferably a halogen atom. Among the halogen atoms, a chlorine atom and a bromine atom are preferable, and a bromine atom is particularly preferable. When X ¹ , X ² and A in the general formula (I) are a bromine atom, they represent the general formula (II).

The specific examples of the compounds represented by formulas (I) and (II) are shown below, but it should not be construed that the invention is limited thereto.

[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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The compounds represented by formulas (I) and (II) of the present invention are described in, for example, JP-B-54-165,
9-57234, JP-A-6-340611, and 7-57234
No. 2781, No. 7-5621, No. 9-244178
Nos. 9-258367 and 9-319022; U.S. Pat. Nos. 3,874,946 and 5,340,712.
No. 5,369,000 and 5,374,514
No. 5,460,938 and 5,464,737
And European Patent Nos. 6059881, 622666, 631176 and the like.

In the general formula (III), P represents an atom group necessary for forming a 5- to 7-membered heterocyclic group. Specifically, it is selected from C, S, N, Se and O, and more preferably selected from C, N and O. The heterocyclic group may be a single ring or a polycyclic fused with a benzene ring or the like.
This heterocyclic group may be unsubstituted or substituted with an alkyl group, an alkoxy group, an aryl group, a halogen atom, a hydroxy group, a cyano group, a nitro group, or the like. Examples of preferred heterocyclic groups include pyridine, pyrrolidone, pyrrolidinone,
Pyrrolidine, phthalazone and phthalazine are mentioned.

Specific examples of the compound represented by formula (III) are shown below, but it should not be construed that the invention is limited thereto.

[0060]

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[0061]

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Here, each R is independently selected from hydrogen, halogen atom, alkyl group, alkoxy group, aryl group, nitro group, cyano group and the like. n is an integer of 1 to 4.

The presence of the above compound in the process of producing a tabular silver halide emulsion can suppress the formation of fog. The effect can be confirmed by coating the emulsion, which has completed the growth and undergoing the desalting step, on a support without chemical sensitization, and developing the emulsion without exposure. As will be described in detail in Examples below, the fogging prevention effect of the above compound was remarkable.

In another embodiment, the compound of the present invention can be directly added to a light-sensitive layer or a non-light-sensitive layer of a silver halide photographic material after the preparation of the emulsion.

<Silver halide photographic light-sensitive material> At least one photosensitive silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention contains tabular silver halide grains. Tabular grains having an aspect ratio of 2 or more account for 50% or more of the total projected area of all silver halide grains in the emulsion layer.
Particularly, as the proportion of tabular grains increases to 70% and further to 80%, more favorable results are obtained.

In the silver halide photographic light-sensitive material according to the present invention, non-tabular silver halide grains can be used in combination. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat.
No. 56, 4,225,666, JP-A-55-265.
No. 89, Japanese Patent Publication No. 55-42737, and The Journal of Photographic Science (J. Pho
togr. Sci. ) Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). Further, particles having a twin plane may be used.

The composition of silver halide grains other than tabular grains is not particularly limited, and the preferred range is the same as that of the above-mentioned tabular grains. The particle size is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm, in consideration of other photographic properties such as rapid processing property and sensitivity.
It is in the range of 2 to 1.0 μm. Here, the particle size is represented by the length of one side of a cube when the silver halide grains are converted into a cube having the same volume.

The particle size distribution of the non-tabular silver halide grains is preferably a monodispersed silver halide grain having a variation coefficient of 22% or less, more preferably 15% or less.

Various methods known in the art can be used for preparing silver halide emulsions other than tabular ones.

The non-tabular silver halide emulsion may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523, JP-A-57-92523 and
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

In the present invention, regardless of whether the silver halide grains are tabular or not, when AgBrCl or AgBrClI grains of high silver chloride are used, the silver halide grains having a portion containing silver bromide at a high concentration are used. Silver particles are particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

It is advantageous that silver halide grains contain heavy metal ions. Heavy metal ions that can be used for such purposes include iron, iridium, platinum,
Group 8-10 metals such as palladium, nickel, rhodium, osmium, ruthenium, cobalt and cadmium,
Group 12 transition metals such as zinc and mercury, lead, rhenium,
Examples include molybdenum, tungsten, gallium, and chromium ions. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand may be a cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, ammonia And the like. Among them, cyanide ion, thiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to allow the silver halide grains to contain heavy metal ions, the heavy metal compound is added during the physical ripening before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion to be added is at least 1 × 10 ⁻⁹ mol per mol of silver halide and 1 × 10 ⁻² mol or more.
Mol or less, more preferably 1 × 10 ⁻⁸ mol or more and 5 × or less.
It is preferably at most 10 ^-5 mol.

In the silver halide emulsion layer of the silver halide color photographic light-sensitive material according to the present invention, a silver halide emulsion composed of single-shaped grains is preferably used. These may be added to the same layer.

The silver halide emulsion according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of the silver halide emulsion to be applied and the size of the expected effect. ^In the range of ^{-10 to} 5 × 10 ^-5 mol,
Preferably it is in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

The gold sensitizer according to the present invention can be added as various gold complexes such as chloroauric acid and gold sulfide. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ per mol of silver halide.
Preferably it is molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

The chemical sensitization of the silver halide emulsion according to the present invention may be a reduction sensitization.

The silver halide emulsion according to the present invention is intended to prevent fogging that occurs during the preparation process of the silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fogging that occurs during development. And known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include JP-A-2-146.
No. 036, page 7, the lower column, compounds represented by the general formula (II) can be mentioned. More preferred specific compounds are (IIa-) described on page 8 of the same publication.
1) to (IIa-8), (IIb-1) to (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5
Compounds such as mercaptotetrazole can be mentioned. These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ^-6 mol to 1 mol per mol of silver halide is used.
An amount of about × 10 ⁻² mol is preferable, and 1 × 10 ⁻⁵ mol to 5
× 10 ^-3 mol is more preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻¹ mol per mol of silver halide, and more preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁵ mol. 1 × 10 ^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used. In particular, dyes having absorption in the visible region include AI-1 described in JP-A-3-251840, page 308.
To 11 and the dyes described in JP-A-6-3770 are preferably used.
Compounds represented by general formulas (I), (II), and (III) described in the lower left column of page 2, page 280750 have preferable spectral characteristics, do not affect the photographic characteristics of silver halide photographic emulsions, and It is also preferable because there is no contamination due to residual color. Specific examples of preferred compounds are described in the same publication, page 3, lower left column to 5
Exemplary compounds (1) to (45) listed in the lower left column of the page
Can be mentioned.

For the purpose of improving sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is more preferably 0.7 or more, and even more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to a silver halide photographic light-sensitive material using the reflective support according to the present invention, since whiteness can be improved. Preferred examples of the compound include a compound represented by formula II described in JP-A-2-232652.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any of the known compounds can be used.
BS-1 to 8 described on page 28 of 51840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-
1 to 5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye.
IRS described on pages 6 to 8 of JP-A-4-285950
-1 to 11 dyes are preferably used. These infrared, red, green, and blue sensitizing dyes are disclosed in JP-A-4-285.
Supersensitizers SS-1 to S described in No. 950, pages 8 to 9
It is preferable to use a combination of S-9 and compounds S-1 to S-17 described in JP-A-5-66515, pp. 15-17.

These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

As the coupler used in the silver halide photographic light-sensitive material of the present invention, a coupling reaction with an oxidized form of a color developing agent is performed to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Any compound that can be used can be used, and particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material according to the present invention, a water-insoluble emulsion having a boiling point of 150 ° C. or higher is usually used. In the boiling point organic solvent, if necessary, dissolve in combination with a low boiling point and / or water-soluble organic solvent,
It is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, and phosphates such as trioctyl phthalate, Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a preferred compound as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A-1 to A-1 described in JP-A-64-26854.
1 is mentioned. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion,
It is better that the time from dispersion to addition to the coating solution and the time from addition to coating after the addition to the coating solution are shorter, and preferably 10 hours or less, and more preferably 3 hours or less and 20 minutes or less, respectively.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include compounds of the general formula I described in page 3 of JP-A-2-66541.
And phenyl ether compounds represented by II
A phenolic compound represented by the general formula IIIB described in JP-A-174150; an amine-based compound represented by the general formula A described in JP-A-64-90445;
Metal complexes represented by general formulas XII, XIII, XIV and XV described in No. 741 are particularly preferable for magenta dyes. Further, the compound represented by the general formula I 'described in JP-A-1-19649 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound (A'-1) described in the lower left column of page 10 of the same publication are disclosed. And the like. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

The silver halide light-sensitive material according to the present invention includes:
It is preferable to add a compound that reacts with the oxidized developing agent to a layer between the photosensitive layers to prevent color turbidity, or to add a compound to the silver halide emulsion layer to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17. .

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or to improve the light fastness of a dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-66646.
A compound represented by the general formula III described in
UV-1L to UV-27L described in JP-A-187240, compounds represented by the general formula I described in JP-A-4-1633, compounds represented by the general formula (I) described in JP-A-5-165144,
The compound shown by (II) is mentioned.

It is advantageous to use gelatin as a binder in the silver halide photographic light-sensitive material according to the present invention. If necessary, other gelatins, gelatin derivatives, graft polymers of gelatin and other high polymers, gelatin Other than these, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

As the hardener of these binders, it is preferable to use a vinylsulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-249
It is preferable to use the compounds described in JP-A Nos. 054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. In order to improve the physical properties of the surface of the light-sensitive material or the sample after processing, a protective layer is disclosed in
It is preferable to add a slip agent or a matting agent described in JP 18543 or JP-A-2-73250.

As the reflective support used in the silver halide photographic light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, or a paper support made of natural pulp or synthetic pulp. ,
A vinyl chloride sheet, polypropylene which may contain a white pigment, a polyethylene terephthalate support, baryta paper, and the like can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina,
Examples include alumina hydrate, titanium oxide, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support is preferably at least 13% by weight, more preferably at least 15% by weight, in order to improve sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.

Also, the center plane average roughness (SR
It is more preferable that the value of a) is 0.15 μm or less, and more preferably 0.12 μm or less, because the effect of good gloss can be obtained. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the reflective support, if necessary, and then to the direct or undercoat layer (adhesion of the support surface). , One or more subbing layers to improve antistatic properties, dimensional stability, rub resistance, hardness, antihalation properties, friction properties and / or other properties) Is also good.

In the present invention, various kinds of transparent supports can be used. Examples of the support that can be used include polyester films such as polyethylene terephthalate and polyethylene naphthalate, cellulose triacetate films, cellulose diacetate films, polycarbonate films, polystyrene films, and polyolefin films.

Examples of the polyester support include, but are not limited to, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, and the like. Condensation polymers with alkylene glycols such as, for example, polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate and the like, and copolymers thereof.

In particular, Japanese Patent Application Laid-Open Nos. 1-244446, 1-291248, 1
-298350, 2-89045, 2-936
It is preferable to use a polyester having a high water content as described in JP-A Nos. 41, 2-181749, 2-214852 and JP-A-2-291135.

These polyesters may have a polar group and other substituents. In the present invention, the support is preferably polyethylene terephthalate or polyethylene naphthalate.

The polyester is preferably stretched in an area ratio of 4 to 16 times in order to satisfy the mechanical strength and dimensional stability of the film support. Further, it is preferable to perform a heat treatment (annealing treatment) as described in JP-A-51-16358 after film formation.

On the transparent support, there are provided a matting agent, an antistatic agent, a lubricant, a surfactant, a stabilizer, a dispersant, a plasticizer, an ultraviolet absorber, a conductive substance, a tackifier, a softener, and a fluidizer. , A thickener, an antioxidant, and the like.

The purpose of the transparent support is to neutralize the tint of the minimum density portion, to prevent the light piping phenomenon (edge fogging) that occurs when light enters the film coated with the photographic constituent layer from the edge, and to prevent halation. Can contain a dye.

The type of the dye is not particularly limited, but when a polyester film is used as the transparent support, it is preferable that the film has excellent heat resistance in the film forming step, and examples thereof include an anthraquinone-based chemical dye. As for the color tone, when the purpose is to prevent light piping, gray dyeing is preferable as seen in general photosensitive materials. The dyes may be used alone or in combination of two or more. Diaresin, Bayer manufactured by Mitsubishi Chemical Corporation
The target can be achieved by using a dye such as MACROLEX manufactured by the company alone or in a suitable mixture.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-(Β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-
N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature for color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable. Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds. A known developer component compound can be added to the color developing solution in addition to the above color developing agent. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing tank, or a belt. An endless belt system that fixes and transports the photosensitive material may be used,
A processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and a photosensitive material is transported. A spray method is used to spray the processing liquid. A web method is used to contact a carrier impregnated with the processing liquid. Alternatively, a method using a viscous treatment liquid may be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. In the form of adding a treating agent.
The method described in No. 5 is most preferred.

[0124]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 <Preparation of tabular silver halide emulsion Em-a> The following solutions were prepared.

Solution G1 Ossein gelatin 31.45 g NaCl 1.26 g Make up 1534.5 ml with distilled water Solution Ag1 1.18 N aqueous silver nitrate solution X1 1.21 N aqueous NaCl solution X2 0.06 N KI aqueous solution Solution Ag2 2.94 N silver nitrate Aqueous solution Solution X3 3.01 N NaCl aqueous solution.

The total amount of the solution G1 was placed in a reaction vessel at 40 ° C.
The pH was adjusted to 4.3. While sufficiently stirring, the solution Ag1
And the same amount of solution X1 as 17.98 ml was simultaneously added over 15 seconds. After stirring for 3 minutes, 65 ml of solution X2 was added into the reaction vessel at 186 ml / min. After stirring for 9 minutes, 53.95 ml of solution Ag1 and the same amount of solution X1 were simultaneously added over 45 seconds. 9.6% hydrogen peroxide solution 1
After adding 2.6 ml, the mixture was adjusted to pH 6.5 and stirred for 30 minutes. The pCl was adjusted to 1.75, the temperature was raised to 70 ° C. and the mixture was aged for 20 minutes, and the same amount of solution X3 as 211.22 ml of solution Ag2 was added simultaneously over 20 minutes. 30 more
After ripening, the temperature was lowered to 40 ° C., a flocculant was added, washed with water, gelatin was added and dispersed to obtain a tabular silver halide emulsion Em-a.

<Tabular silver halide emulsion Em-b1 to Em-b
Preparation of 23> Exactly the same as Em-a except that the compounds shown in Table 1 were added in the preparation of the tabular silver halide emulsion Em-a before the temperature was raised to 70 ° C. in the amounts shown in Table 1. Thus, tabular silver halide emulsions Em-b1 to Em-b23 were obtained.

Each of the obtained silver halide grains was all (1)
(00) in the main plane. Table 1 shows the measurement results of the characteristic values of the respective particle shapes. In Table 1, R1: ratio of tabular grains having an aspect ratio of 2 or more in the total projected area R2: average thickness of tabular grains having an aspect ratio of 2 or more [μ]
m] R3: Average aspect ratio of tabular grains having an aspect ratio of 2 or more R4: Particle size distribution of tabular silver halide grains having an aspect ratio of 3 or more and a thickness of 0.3 μm or less (the particle size is a cube of the same volume as the grains) It is expressed by the length of one side, and the particle size distribution is represented by a value obtained by multiplying the number obtained by dividing the standard deviation of the particle size distribution by the average particle size by 100.)

[0130]

[Table 1]

[0131]

Embedded image

Em-b1-b8 and Em-b20-b23 to which the compound of the present invention and a comparative compound were added,
No significant difference was found in the characteristic values of the particle shapes, which could affect the evaluation results of this example. In the case of Em-b9 to Emb-b19, the measurement of the characteristic value of the grain shape was not performed. However, observation with an electron microscope confirmed that a tabular silver halide emulsion having the same grain shape as Em-a was obtained. .

<Preparation of Coated Samples (1) to (24)> Coated samples were prepared using the tabular silver halide emulsion obtained above.

High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side on which the emulsion layer was applied, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. After subjecting this reflective support to corona discharge treatment, a gelatin undercoat layer is provided,
Further, each layer having the following configuration was applied, and samples (1) to (2)
4) was produced. In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-2) was added as a hardener. Surfactants (SU-1), (SU-2) and (SU-3) are added as coating aids,
The surface tension was adjusted. The coating amount of each layer is shown below. still,
The amount of silver halide applied was shown as a value converted to silver.

H-2: 2,4-Dichloro-6-hydroxy-s-triazine sodium SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate ・
Sodium salt SU-3: sulfosuccinic acid di (2,2,3,3,4
4,5,5-octafluoropentyl) sodium salt STAB-1: 1- (3-acetamidophenyl) -5
- mercaptotetrazole layer configuration amount (g / m ²⁾ a second layer (protective layer) Gelatin 1.30 The first layer (green-sensitive layer) Gelatin 1.70 tabular silver halide emulsion 0.18 stabilizer STAB- 1 0.0001 Magenta coupler (M-1) 0.26 Dye image stabilizer (ST-3) 0.26 Dye image stabilizer (ST-4) 0.22 DIDP 0.17 DBP 0.13 Support Polyethylene laminated paper

[0136]

Embedded image

<Evaluation of Fog> The coating samples (1) to (24) thus produced were subjected to a developing treatment by the following developing treatment steps without exposure.

Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 90 seconds or 180 seconds 80 cc Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank liquid and replenisher tank liquid Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Sodium pentaacetate 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. = 10.10, replenisher is pH Adjusted to 10.60.

Bleach-fixer tank solution and replenisher diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Fluorescent whitening agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Using the obtained sample, the green density of fog was measured using a PDA-65 densitometer (manufactured by Konica Corporation).
Table 2 shows the results.

[0143]

[Table 2]

As shown in Table 2, the fogging of the tabular silver halide emulsion could be suppressed by using the emulsion produced by the method of the present invention.

Example 2 <Preparation of Tabular Silver Halide Emulsions Em-c1 to Em-c23>
In the preparation of the tabular silver halide emulsion Em-a, the compounds shown in Table 2 were added to the compounds shown in Table 2 before adding the solutions Ag2 and X3.
The tabular silver halide emulsions Em-c1 to Em-c23 were obtained in exactly the same manner as Em-a except that the amounts described in (1) and (2) were added.

Each of the obtained silver halide grains was all (1
(00) on the main plane. Table 3 shows the measurement results of the characteristic values of each particle shape. In Table 3, R1: ratio of tabular grains having an aspect ratio of 2 or more to the total projected area R2: average thickness of tabular grains having an aspect ratio of 2 or more [μ]
m] R3: Average aspect ratio of tabular grains having an aspect ratio of 2 or more R4: Particle size distribution of tabular silver halide grains having an aspect ratio of 3 or more and a thickness of 0.3 μm or less (the particle size is a cube of the same volume as the grains) It is expressed by the length of one side, and the particle size distribution is represented by a value obtained by multiplying the number obtained by dividing the standard deviation of the particle size distribution by the average particle size by 100.)

[0147]

[Table 3]

In the case of Em-c1 to Em-c10 to which the compound of the present invention and the comparative compound were added, no significant difference was found in the characteristic values of the particle shapes, which could affect the evaluation results of this example. In Em-c11 to Em-c23, the measurement of the characteristic value of the grain shape was not performed. However, observation with an electron microscope confirmed that a tabular silver halide emulsion having the same grain shape as Em-a was obtained. .

<Preparation of Coated Samples (101) to (123) and Evaluation of Fog> Coated samples were prepared in the same manner as in Example 1 with respect to the tabular silver halide emulsions Em-c1 to c23 obtained above. It was prepared and fog was evaluated. Table 4 shows the results.

[0150]

[Table 4]

As shown in Table 4, the fog of the tabular silver halide emulsion could be suppressed by using the emulsion produced by the method of the present invention.

Example 3 <Blue-sensitive tabular silver halide emulsions (Em-aB, Em-aB)
Preparation of b1B to c23B)> Em-a and Em-b1 above
~ C23 (Em-b series includes Em-b
1, b2, b4, b5, b7, b10, b14, b1
8, b20 and b22 are selected, and Em-c1, c3, c5, c7, c11 and c1 are selected from the Em-c series.
3, c15, c19 and c21 were selected. Table 5), the following compounds were optimally chemically sensitized at 60 ° C. to obtain blue-sensitive silver halide tabular emulsions Em-aB and Em-b.
1B to c23B were obtained.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-2: 1-phenyl -5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0154]

Embedded image

<Preparation of Coated Samples (201) to (220) and Evaluation of Photographic Properties> The blue-sensitive tabular silver halide emulsions (Em-b1B to c23B) obtained above were used.
A coated sample was produced in the same manner as in Example 1. The thus-prepared sample was designated as 101, exposed to a light wedge by a conventional method, and then subjected to a developing process in the following developing process. The development time was 45 seconds.

The characteristic curve of green density of the obtained sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation).
The lowest concentration, sensitivity and γ were measured. Sensitivity is 0.75
Is defined based on the reciprocal of the exposure amount, and the relative value is represented by setting the sensitivity of the comparative sample 202 as 100. In addition,
γ is the exposure amount that gives a density of fog +0.3, and fog +
A slope connecting two points on a sensitometry curve (a characteristic curve in which the logarithm of the exposure is plotted on the horizontal axis and the density is plotted on the vertical axis) at an exposure that gives a density of 1.3 is a comparative sample 202. Was expressed as a relative value with γ as 100.

The sensitivity and γ of the sample 201 using Em-aB were not measured because the fog was extremely high.

The coated sample was treated at 40 ° C. and 80% RH for 14 hours.
After storage for days, the same exposure and development treatment as above was performed, and the minimum density, sensitivity, and γ were measured.

Table 5 shows the results. As is clear from Table 5, the sample using the tabular silver halide emulsion according to the present invention has a low minimum density and a high γ, and further has an improved minimum density and decreased sensitivity with storage over time. You can see that there is.

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[Table 5]

Example 4 The following composition was applied on a cellulose triacetate film support provided with an undercoat layer to prepare a sample 301 as a multilayer color photosensitive material.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material was 1 m ² unless otherwise specified.
Indicates the number of grams per unit. Silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is silver halide 1
It was shown in moles per mole.

First layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-11) 0.30 High boiling organic solvent (Oil-2) 0.17 Gelatin 1.59 Second layer: Intermediate layer High Boiling point organic solvent (Oil-2) 0.01 Gelatin 1.27 Third layer: Low-sensitivity red-sensitive layer Emulsion (Em-2) 0.80 Sensitizing dye (SD-1) 5.0 × 10 ^-5 sensitization Dye (SD-2) 9.0 × 10 ^-5 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitizing dye (SD-4) 2.0 × 10 ^-4 sensitizing dye (SD-5) ) 2.8 × 10 ^-4 cyan coupler (C-11) 0.42 colored cyan coupler (CC-1) 0.02 high-boiling organic solvent (Oil-1) 0.35 gelatin 1.02 fourth layer: medium sensitivity red-sensitive layer emulsion (Em-1) 0.40 sensitizing dye (SD-3) 1.8 × 10 -5 sensitizing dye ( D-4) 2.4 × 10 ^-4 Sensitizing dye (SD-5) 4.5 × 10 -4 Cyan coupler (C-11) 0.26 Colored cyan coupler (CC-1) 0.05 DIR compound ( D-1) 0.01 High boiling organic solvent (Oil-1) 0.31 Gelatin 0.78.

Fifth layer: High-sensitivity red-sensitive layer Emulsion (Em-3) 1.51 Sensitizing dye (SD-3) 1.8 × 10 ^-5 Sensitizing dye (SD-4) 3.1 × 10 ^{− 4} Sensitizing dye (SD-5) 2.7 × 10 ^-4 Cyan coupler (C-12) 0.11 Colored cyan coupler (CC-1) 0.02 DIR compound (D-2) 0.04 High boiling organic Solvent (Oil-1) 0.17 Gelatin 1.15 6th layer: Intermediate layer Gelatin 0.80 7th layer: Low sensitivity green-sensitive layer Emulsion (Em-2) 0.21 Sensitizing dye (SD-1) 5 0.9 × 10 ^-5 sensitizing dye (SD-6) 3.1 × 10 ^-4 sensitizing dye (SD-9) 1.8 × 10 ^-4 sensitizing dye (SD-11) 5.6 × 10 ^{− 5} magenta coupler (M-11) 0.20 colored magenta coupler (CM-1) 0.05 DIR compound (D-1) 0.02 high boiling Organic solvent (Oil-2) 0.27 Gelatin 1.34.

Eighth layer: middle-sensitivity green-sensitive layer Emulsion (Em-2) 0.82 Sensitizing dye (SD-1) 5.0 × 10 ⁻⁵ Sensitizing dye (SD-6) 2.7 × 10 ^{− 4} Sensitizing dye (SD-9) 1.7 × 10 ^-4 Sensitizing dye (SD-11) 4.8 × 10 ^-5 Magenta coupler (M-11) 0.21 Colored magenta coupler (CM-1) 0 0.05 DIR compound (D-4) 0.02 High boiling organic solvent (Oil-2) 0.33 Gelatin 0.89 Ninth layer: Highly sensitive green-sensitive layer Emulsion (Em-3) 0.99 Sensitizing dye ( SD-6) 3.6 × 10 ^-4 sensitizing dye (SD-7) 7.0 × 10 ^-5 sensitizing dye (SD-8) 4.8 × 10 ^-5 sensitizing dye (SD-11) 6 .2 × 10 ^-5 magenta coupler (M-11) 0.05 magenta coupler (M-12) 0.06 colored magenta coupler (CM-2) 0.03 High boiling organic solvent (Oil-2) 0.25 Gelatin 0.88 10th layer: Intermediate layer High boiling organic solvent (Oil-1) 0.25 Gelatin 0.50 11th layer: Yellow filter layer Yellow colloid Silver 0.11 Color stain inhibitor (SC-1) 0.12 High boiling organic solvent (Oil-2) 0.16 Gelatin 1.00.

Layer 12: Intermediate layer Gelatin 0.36 Layer 13: Low-sensitivity blue-sensitive layer Emulsion (Em-2) 0.37 Sensitizing dye (SD-10) 5.6 × 10 ^-4 sensitizing dye ( SD-11) 2.0 × 10 ^-4 sensitizing dye (SD-13) 9.8 × 10 ^-5 Yellow coupler (Y-11) 0.39 Yellow coupler (Y-12) 0.14 DIR compound (D -5) 0.03 High boiling organic solvent (Oil-2) 0.11 Gelatin 1.02 Fourteenth layer: Medium-sensitivity blue-sensitive layer Emulsion (Em-2) 0.46 Emulsion (Em-1) 0.10 increase Sensitizing dye (SD-10) 5.3 × 10 ^-4 sensitizing dye (SD-11) 1.9 × 10 ^-4 sensitizing dye (SD-13) 1.1 × 10 ^-5 Yellow coupler (Y-11) ) 0.28 Yellow coupler (Y-12) 0.10 DIR compound (D-5) 0.05 High boiling organic solvent Agent (Oil-2) 0.08 Gelatin 1.12.

15th layer: high-sensitivity blue-sensitive layer Emulsion (Em-3) 0.04 Emulsion (Em-4) 0.28 Sensitizing dye (SD-11) 8.4 × 10 ^-5 sensitizing dye (SD -12) 2.3 × 10 ^-4 yellow coupler (Y-11) 0.04 yellow coupler (Y-12) 0.12 high boiling point organic solvent (Oil-2) 0.03 gelatin 0.85 16th layer: First protective layer Emulsion (Em-5) 0.30 UV absorber (UV-12) 0.03 UV absorber (UV-13) 0.015 UV absorber (UV-14) 0.015 UV absorber ( UV-15) 0.015 Ultraviolet absorber (UV-16) 0.10 High boiling organic solvent (Oil-1) 0.44 High boiling organic solvent (Oil-3) 0.07 Gelatin 1.35 17th layer: Second protective layer Alkali-soluble matting agent (PM-1, flat 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.54 In addition to the above-mentioned composition, compounds SU-11 and SU-12 ,
SU-13, SU-14, viscosity modifier V-1, hardener H
-11, H-12, stabilizer ST-11, antifoggant A
F-1 and AF-2, two types of AF- having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000
3. Dyes AI-11, AI-12, AI-13, compounds FS-1, FS-2 and preservative DI-1 were appropriately added to each layer.

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The emulsions used in the above samples are as follows. In addition, the average particle size was shown by the particle size converted into a cube. Each emulsion was optimally subjected to gold, sulfur, and selenium sensitization.

Emulsion name Average AgCl Average AgBr Crystal habit Side length Content (mol%) Content (mol%) (μm) Em-1 99 1 cubic 0.46 Em-299 1 cubic 0.30 Em- 399 1 Cube 0.70 Em-4 99 1 Cube 0.85 Em-5 50 50 Cube 0.07 Next, Em-4 in the sample 301 was converted to Em-aB, E
m-b1B, b4B, b5B, b7B, b10B, b1
4B, b18B, b20B, b22B, Em-c1B,
c3B, c5B, c7B, c11B, c13B, c15
Samples replaced with emulsions B, c19B and c21B were designated 302 to 320, respectively. The samples 301 to 320 obtained in this manner were subjected to white light wedge exposure and subjected to the following developing treatment to evaluate fog (Dmin) and sensitivity. The sensitivity is shown as a relative value with the sensitivity of the blue-sensitive layer of Sample 301 being 100.

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[Table 6]

However, the stabilization treatment was carried out in a three-tank counter current, in which the stabilizing solution was replenished to the last tank and overflowed into the preceding tank. Further, a part of the overflow of the stabilizing tank following the fixing tank (275 ml / m
² ) was poured into the fixing tank.

The compositions of the used color developing solution and its replenisher are as follows.

[Color developing solution] Potassium bromide 15 mg Potassium chloride 5.0 g Potassium sulfite 0.4 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylhydroxyl Amine 5.0 g Potassium carbonate 30 g Sodium diethylenetriamine pentaacetate 2.5 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Nitrilotri (methylenephosphonic acid) 2.0 g Hydrazinodiacetic acid 2.0 g Finished to 1 liter with water and hydroxylated Adjust the pH to 10.05 with potassium or 50% sulfuric acid.

[Color developing replenisher] 0.2 g potassium chloride 0.9 g potassium sulfite 0.9 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 6.2 g diethylhydroxylamine 7. 0 g Potassium carbonate 32 g Sodium diethylenetriamine pentaacetate 3.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.5 g Nitrilotri (methylenephosphonic acid) 2.5 g Hydrazinodiacetic acid 2.5 g Finished to 1 liter with water Potassium hydroxide or 50 Adjust to pH 10.40 with% sulfuric acid.

The composition of the bleaching solution used is as follows.

Ferric ammonium 1,3-diaminopropanetetraacetate 0.35 mol Disodium ethylenediaminetetraacetate 2 g Ammonium bromide 150 g Glacial acetic acid 40 ml Ammonium nitrate 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. Adjust to pH 4.5.

The composition of the bleaching replenisher used was as follows.

Ferric ammonium 1,3-diaminopropanetetraacetate 0.40 mol Disodium ethylenediaminetetraacetate 2 g Ammonium bromide 170 g Ammonium nitrate 50 g Glacial acetic acid 61 ml Add water to make 1 liter, and use ammonia water or glacial acetic acid. The pH is adjusted to 3.5, and the pH of the bleach tank solution is adjusted as appropriate.

The composition of the fixing solution and the fixing replenisher used is as follows.

Ammonium thiosulfate 100 g Ammonium thiocyanate 150 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Disodium ethylenediaminetetraacetate 1.0 g Water was added to 700 ml, and the pH was adjusted to 6.5 using glacial acetic acid and aqueous ammonia. I do.

The compositions of the stabilizing solution and the stabilizing replenisher used are as follows.

1,2-benzisothiazolin-3-one 0.1 g pn-octyl-decaethyleneoxy-phenol 50% aqueous solution 2.0 ml hexamethylenetetramine 0.2 g hexahydro-1,3,5-tris (2 -Hydroxyethyl) -5-triazine 0.3 g Water was added to make up to 1 liter, and pH 7.0 using potassium hydroxide and 50% sulfuric acid. Adjust to 0.

The coated sample was treated at 40 ° C. and 80% RH for 14 hours.
After storage for days, the same exposure and development treatment as described above was performed, and the minimum density and sensitivity were measured. Table 7 shows the results.

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[Table 7]

As shown in Table 7, even when rapid processing was performed in the color negative processing, the tabular silver halide emulsion according to the present invention was found to have high sensitivity and low fog.
The tabular silver halide emulsion of the present invention has good storage stability over time.

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According to the present invention, high sensitivity, low fog,
Thus, a silver halide photographic emulsion having high storage stability over time and excellent in rapid processing, a method for producing the same, and a silver halide photographic light-sensitive material were obtained.

Claims (7)

[Claims] 1. A method for producing a silver halide photographic emulsion in which tabular grains having a silver chloride content of 50 mol% or more of the total silver and an aspect ratio of 2 or more occupy 50% or more of the total grain projected area. 3. The method for producing a silver halide photographic emulsion according to claim 1, further comprising the step of growing grains in the presence of at least one polyhalogen organic compound. 2. The method for producing a silver halide photographic emulsion according to claim 1, wherein the polyhalogen organic compound is a compound represented by the following general formula (I). Embedded image (In the formula, Q represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group; X ¹ and X ² each represent a halogen atom; Y represents a carbonyl group, a sulfinyl group or a sulfonyl group; and A represents a hydrogen atom Alternatively, it represents an electron-withdrawing group.
n represents 0 or 1. ) 3. The method for producing a silver halide photographic emulsion according to claim 1, wherein the polyhalogen organic compound is a compound represented by the following general formula (II). Embedded image (In the formula, Q represents an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group, Y represents a carbonyl group, a sulfinyl group, or a sulfonyl group. N represents 0 or 1.) 4. The method for producing a silver halide photographic emulsion according to claim 1, wherein the polyhalogen organic compound is a compound represented by the following general formula (III). Embedded image (In the formula, P represents an atom group necessary to form a 5- to 7-membered heterocyclic group.) 5. A silver halide photographic emulsion produced by the method according to claim 1. Description: 6. A silver halide photographic material having at least one photosensitive layer on a support, wherein at least one of the photosensitive layers contains the silver halide photographic emulsion according to claim 5. Characteristic silver halide photographic material. 7. A silver halide photographic material having at least one photosensitive layer on a support, wherein silver halide grains contained in at least one of the photosensitive layers have a silver chloride content of total silver. Tabular grains having an aspect ratio of 2 or more account for 50% or more of the total grain projected area.
At least one of the compounds represented by the general formulas (I) to (III) is contained in at least one of the photosensitive layer and the non-photosensitive layer. A silver halide photographic light-sensitive material comprising: