JPH0980677A - Silver halide emulsion, and silver halide photographic sensitive material using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion which is small in fogging because of its high sensitivity, and deteriorates little in photographic property after exposure with the lapse of time by containing a plurality of specified compounds. SOLUTION: This silver halide emulsion contains at least one kind each of compounds represented by the formula I and compounds represented by the formula II. In the formula I, Ra1 represents alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, carbamoyl group, sulfamoyl group, alkoxycarbamoyl group or aryloxycarbonyl group, Ra2 represents hydrogen atom or the same as Ra1 . In the formula II, Ra1 , Ra2 , which may be the same of different, each represent alkyl group, aryl group, heterocyclic group, amino group or the like. This silver halide emulsion is preferably reduction-sensitized. This silver halide photographic material has at least one silver halide emulsion layer containing this silver halide emulsion one a base, and the pH on the film surface is 6.3 or more and 7.5 or less.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion and a silver halide photographic light-sensitive material using the same, and in particular, it has high sensitivity and little fog, and the stability of photographic properties after exposure with time is improved. The present invention relates to an improved silver halide emulsion and a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the demand for higher sensitization of silver halide emulsions for photography has become stronger and stronger with the small format of films and diversification of photographing conditions. For this reason, various emulsion techniques have been studied and produced results, but in many of these techniques, there are many cases in which the fog is increased and the storage performance of the light-sensitive material is deteriorated, and a countermeasure technique therefor has long been desired. Numerous methods have been used to minimize the appearance of this fog. U.S. Pat. No. 2,440,206
Thiosulphonic acid salts and thiosulphonic acid esters have been used, such as the compounds described in U.S. Pat. Nos. 2,934,198, 3,047,393 and 4,960,689. In addition, it is disclosed in US Pat. Nos. 5,219,721 and 5,346,754 that dichalcogenide compounds are effective. Although this method was certainly a useful invention, it was still insufficient and further improvement was desired. Further, reduction sensitization has been attempted for a long time in order to achieve high sensitivity. Carroll
1 (Carroll) is a tin compound in US Pat. No. 2,487,850, and Lowe et al.
No. 2,925, the polyamine compound is
ns (Farence) et al. disclosed in British Patent 789,823 that thiourea dioxide compounds are useful as reduction sensitizers. Collier is also a Photographic Science and Engineering 2
Volume 3, page 113 (1979) compares the properties of silver nuclei made by various reduction sensitization methods. She adopted the methods of dimethylamine borane, stannous chloride, hydrazine, high pH aging, low pAg aging. The method of reduction sensitization is further described in U.S. Patent Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, and 3,930, No. 867. Regarding the improvement of the reduction sensitization method as well as the selection of the reduction sensitizer, JP-B-57-33572 and 5
8-1410. However, the increase in sensitivity due to reduction sensitization is accompanied by an increase in fog and deterioration in storage stability of the light-sensitive material. Therefore, a technique for suppressing fog has been particularly desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion and a silver halide photographic light-sensitive material, which have high sensitivity, less fog, and less change in photographic property after exposure with time.

[0004]

As a result of intensive studies, the object of the present invention could be achieved by the following means.

(1) A silver halide emulsion containing at least one compound represented by the following general formula (A) and at least one compound represented by the following general formula (S1).

[0006]

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In the general formula (A), R _a1 is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group,
It represents a sulfamoyl group, an alkoxycarbamoyl group or an aryloxycarbonyl group, and R _a2 represents a hydrogen atom or the group represented by R _a1 . However, R _a1 is an alkyl group,
When it is an alkenyl group or an aryl group, R _a2 is a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1 and R _a2
May combine with each other to form a 5- to 7-membered ring.

[0008]

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In the general formula (S1), in the formula, R _s1 and R _s2 may be the same or different and each is an alkyl group,
It represents an aryl group, a heterocyclic group, an amino group or a group shown below.

[0010]

[Chemical 6]

In the formula, R _s3 and R _s5 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R _s4 represents an alkyl group, an aryl group or a heterocyclic group. X ₁ and X ₂ may be the same or different and each represents S, Se or Te. R ₁ ,
R ₂ , X ₁ and X ₂ may together form a ring. (2) The silver halide emulsion according to (1), wherein the silver halide emulsion is subjected to reduction sensitization. (3) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a silver halide emulsion produced by the method described in (1) on a support. (4) In (3), the film surface pH of the photosensitive material is 6.3.
A silver halide photographic light-sensitive material characterized in that it is not less than 7.5.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. First, the compound represented by formula (A) will be described in detail. In the general formula (A), R _a1 is an alkyl group (for example, methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-).
Octyl, decyl, dodecyl, hexadecyl, benzyl), alkenyl groups (eg allyl, 2-butenyl,
Isopropenyl, oleyl, vinyl), aryl groups (eg, phenyl, naphthyl), heterocyclic groups (5- to 7-membered heterocyclic ring having at least one of nitrogen atom, sulfur atom, oxygen atom or phosphorus atom as a ring-constituting atom) A group formed, for example, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridin-2
-Yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuranyl, morpholinyl), an acyl group (for example, Acetyl, benzoyl, pivaloyl, α- (2,4-di-tert-
Amylphenoxy) butyryl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl, isonicotinoyl), sulfonyl group (eg methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl group (eg methanesulfinyl, benzenesulfinyl), carbamoyl group (For example, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-
Phenylcarbamoyl), sulfamoyl group (eg N
-Methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), alkoxycarbonyl group (for example, Methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or an aryloxycarbonyl group (eg phenoxycarbonyl, naphthoxycarbonyl). R _a2 represents a hydrogen atom or the group represented by R _a1 . R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring, and examples thereof include a succinimide ring, a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring.

R _a1 and R _a2 represented by the general formula (A)
The group may be further substituted with a substituent. Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group, Arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include an acyloxy group and a hydroxyamino group.

Among the compounds represented by the general formula (A),
R _a1 is preferably a heterocyclic group. More preferably, R _a1 is a heteroaromatic ring group (including a heterocyclic group that can formally form a heteroaromatic ring in the equilibrium structure; hereinafter used in this sense). More preferable ones are represented by the following general formula (AI).

[0015]

[Chemical 7]

In the general formula (AI), _R'a2 represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. Z represents a heteroaromatic ring group.

Of the compounds represented by formula (AI), those in which _R'a2 is a hydrogen atom or an alkyl group are preferred. Further, Z is preferably such that the ring-constituting atom is a carbon atom or a nitrogen atom. Most preferably, the following general formula (A
-II) is a compound.

[0018]

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In the general formula (A-II), _R'a2 represents the same group as _R'a2 in the general formula (AI). R _a3 and R _{a4, which} may be the same or different, each represents a hydrogen atom or a substituent. In the compound represented by formula (A-II), R _a3 and R _a4 are hydroxyamino group, hydroxyl group, amino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, alkylthio group, arylthio group. Particularly preferred is an alkyl group or an aryl group. Hereinafter, the general formula (A) of the present invention will be described.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

[Chemical 12]

[0024]

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These compounds of the present invention are described in J. Org. Chem.,
27, 4054 ('62), J. Amer. Chem. Soc., 73,2981 ('51),
It can be easily synthesized by the method described in JP-B-49-10692 or the like.

In the method of the present invention, the compound represented by the formula (A) may be added after being dissolved in water, alcohol, ester, ketone or a mixed solvent thereof. In the case of being dissolved in water, if the solubility is increased by increasing or decreasing the pH, the compound may be dissolved by increasing or decreasing the pH and then added. The oil-soluble compound represented by the formula (A) may be added in the form of being dispersed in an aqueous gelatin solution. The compound represented by the formula (A) can be added at any time during grain formation and before the end of chemical sensitization, but it is preferable to add it after grain formation is completed. Preferably, it is added before the start of chemical sensitization. In the present invention, before the chemical sensitization is started, before the chalcogen sensitizer or gold sensitizer is added, and after the chemical sensitization is ended, the temperature after the chemical sensitization is lowered. The addition amount of the compound represented by the formula (A) of the present invention is 1 mol per mol of silver halide to be added.
The range of x10 ^-6 to 1 x 10 ^-2 mol is preferable, the range of 1 x 10 ^{-5 to} 5 x 10 ^-3 mol is more preferable, and the range of 5 x 10 ^{-5 to} 5 x 10 ^-3 mol is more preferable.

In the present invention, R in the general formula (S1) is
_s1 , R _s2 , R _s3 , R _s4 , R _s5 , X ₁ and X ₂ will be described in detail below. R _s1 and R _{s2, which} may be the same or different, each represents an alkyl group, an aryl group, a heterocyclic group, an amino group or a group shown below.

[0028]

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In the formula, R _s3 and R _s5 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R _s4 represents an alkyl group, an aryl group or a heterocyclic group. When R _s1 and R _s2 are each an alkyl group, an aryl group or a heterocyclic group, these groups may further have a substituent. When R _s1 and R _s2 are each an alkyl group, examples of the substituent include a halogen atom, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a hydroxyl group, a carboxy group, a sulfo group, An alkoxy group, an aryloxy group,
Acylamino group, amino group, alkylamino group, anilino group, ureido group, thioureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl It is a base. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good.

When R _s1 and R _s2 are each an aryl group or a heterocyclic group, examples of the substituent include a halogen atom,
Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, nitro group, hydroxyl group, carboxy group, sulfo group, alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group , A ureido group, a thioureido group, a sulfamoylamino group, an alkylthio group, an arylthio group,
Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide Group, heterocyclic thio group, sulfinyl group, phosphonyl group,
An aryloxycarbonyl group and an acyl group. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good. When R _s1 and R _s2 are each an amino group, the amino group is a —NH ₂ group or represents an amino group substituted with at least one of an alkyl group, an aryl group or a heterocyclic group. At this time, the details of the alkyl group, aryl group and heterocyclic group are the same as those described for R _s1 and R _s2 .

More specifically, examples in which R _s1 and R _s2 are each an alkyl group, an aryl group, a heterocyclic group or an amino group are shown. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, preferably 1 to 16 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, 3-hydroxypropyl and benzyl. , 2-methanesulfonamidoethyl, 2-methanesulfonylethyl, 3-methoxypropyl, cyclopentyl, 4-acetamidobutyl, 2-carboxyethyl,
3-carbamoylpropyl, 3,4-dihydroxybutyl, n-hexyl, 2-hydroxypropyl, hexadecyl, 3-carbamoylaminopropyl, 4-carbamoylbutyl, 2-carbamoyl 1-methylethyl, 4-
It is nitrobutyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 16 carbon atoms, for example, phenyl, naphthyl, 4-methoxyphenyl, 4-acetamidophenyl, 3-hydroxyphenyl, 3-methylphenyl, 4-carboxyphenyl, 3-diethylaminophenyl, 3-acetamidophenyl, 4-carbamoylphenyl, 4-sulfophenyl, 2-carboxyphenyl, 2-acetamidophenyl, 3-formamidophenyl, 2,3-dichlorophenyl, 5-hydroxynaphthyl , 2-methanesulfonamidophenyl, 2-trifluoroacetamidophenyl, 3-benzoylamidophenyl, 4-ethoxycarbonylaminophenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocyclic ring containing 1 or more oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. And the number of kinds of elements may be one or more, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-pyridyl, 5-benzotriazolyl, 2
-Imidazolyl, 4-pyrazolyl, 5-quinolyl. When R _a1 and R _a2 are each a heterocyclic group, X ₁ and X ₂ are linked to the carbon atom forming the heterocyclic group.

Examples of the amino group include amino, methylamino, hydroxyethylamino, diethylamino, pyrrolidino, piperazino, morpholino, anilino, 4-methoxyanilino, 2,5-dichloroanilino, 3-pyridylamino, 2-imidazolylamino. , 5-quinolylamino, 3-methylpyrazolyl-5-amino, 3-tetrahydrofurylamino and the like. R _s3 and R _s5 may be the same or different and each is a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group, the details of which are the same as those described for R _s1 and R _s2 .
However, when each of R _s3 and R _s5 is a heterocyclic group, it is bonded to a carbon atom constituting the heterocycle of the heterocyclic group. R _s4 represents an alkyl group, an aryl group or a heterocyclic group, and the details are the same as those described for R _s1 and R _s2 . However, when R _s4 is a heterocyclic group, it is bonded to a carbon atom forming the heterocycle of the heterocyclic group.
X ₁ and X ₂ may be the same or different and each is S,
Represents Se or Te.

R _s1 , R _s2 , X ₁ and X ₂ may together form a ring. More specifically, the following general formula (S2)
Is represented by General formula (S2)

[0035]

[Chemical 15]

In the formula, X ₁ and X ₂ may be the same or different and each represents S, Se or Te. Z'represents a non-metal atomic group necessary for forming a ring. The number of ring members consisting of X ₁ , X ₂ and Z ′ is 4 to 16. However, X ₁
And the element bonded to X ₂ is a carbon atom. The element constituting Z ′ may have a substituent as much as possible, and the details are the same as those described as the substituent that may be possessed when R _s1 is an aryl group.

Among the compounds represented by the general formula (S1), the compound represented by the general formula (S2) or the compound represented by the following general formula (SS1) is preferable. General formula (SS1)

[0038]

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In the formula, R _s6 represents an aryl group or a pyridyl group. When R _s6 is a pyridyl group, it also includes those having a substituent on the pyridine ring. X ₃ represents a sulfur atom or a selenium atom. As a more preferable compound, a compound represented by the general formula (SS
The compound represented by 2) can be mentioned. General formula (SS2)

[0040]

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In the formula, R _s7 represents a substituent. Here, the substituent has the same _{meaning as} that described when R _s1 is an aryl group. p represents an integer of 0 to 2. General formula (SS2)
With respect to R _s7 and p therein, preferable combinations thereof will be described below. R _s7 is a halogen atom, an alkyl group,
Aryl group, cyano group, nitro group, hydroxyl group, carboxyl group, sulfo group, alkoxy group, acylamino group, amino group, alkylamino group, ureido group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl It is preferably a group, a sulfonyl group, an alkoxycarbonyl group, an acyloxy group, a carbamoyloxy group, an acyl group, and p is 1 or 2. Here, these substituents include those substituted by other substituents. Next, specific examples of the compound represented by formula (S1) in the present invention are shown, but the invention is not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

[Chemical 21]

[0046]

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[0047]

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[0048]

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[0049]

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The compound represented by the general formula (S1) can be obtained by the method described in, for example, New Chemical Chemistry, Volume 14, edited by The Chemical Society of Japan, "Synthesis and Reaction of Organic Compounds III", page 1735 (1978, Maruzen). Can be easily synthesized.

In the method of the present invention, the compound represented by the formula (S1) may be added after being dissolved in water, alcohol, ester, ketone or a mixed solvent thereof. In the case of being dissolved in water, if the solubility is increased by increasing or decreasing the pH, the compound may be dissolved by increasing or decreasing the pH and then added. The compound represented by the formula (S1) can be added at any time from the start of grain formation to the end of chemical sensitization, but it is preferably added before the start of chemical sensitization. Is preferably added after the grain formation is completed.
The addition amount of the compound represented by the formula (S1) of the present invention is 1 × 10 ⁻⁷ to 2 × 10 1 per mol of silver halide to be added.
^-3 mol range is preferable, and more preferably 1 x 10 ^-6.
To 5 × 10 ⁻⁴ mol, more preferably 1 × 10 ⁻⁶ to 1 × 1
It is 0 ^-4 mol.

Next, the reduction sensitization will be described.

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

The reduction sensitization of the present invention is a method of adding a known reducing agent to a silver halide emulsion, pA called silver ripening.
a method of growing or ripening in an atmosphere of low pAg of g1-7, a high p of pH8-11 called high pH ripening
Either a method of growing in an atmosphere of H or a method of ripening can be selected. Also, two or more methods can be used in combination.

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

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

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

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

[0059] Formula _{^{(B) R 3 -SO 2 S}} -M Formula _{^{(C) R 3 -SO 2 S}} -R 4 formula _{^{(D) R 3 -SO 2 S}} -L m -SSO 2 -R
^Five

The compounds of the general formulas (B), (C) and (D) will be explained in more detail. When R ³ , R ⁴ and R ⁵ are aliphatic groups, preferably an alkyl group having 1 to 22 carbon atoms. , An alkenyl group and an alkynyl group each having 2 to 22 carbon atoms, which may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl,
Examples thereof include cyclohexyl, isopropyl and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups for R ³ , R ⁴ and R ⁵ are:
It preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. These may be substituted.

The heterocyclic group of R ³ , R ⁴ and R ⁵ is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium,
For example, pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, tellurazole ring, triazole ring. , Benzotriazole ring, tetrazole ring,
An oxadiazole ring and a thiadiazole ring are exemplified.

Substituents for R ³ , R ⁴ and R ⁵ include, for example, alkyl groups (eg methyl, ethyl, hexyl),
Alkoxy groups (eg methoxy, ethoxy, octyloxy), aryl groups (phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms (eg fluorine, chlorine, bromine, iodine), aryloxy groups (eg phenoxy), alkylthio groups (eg Methylthio, butylthio), arylthio groups (eg phenylthio), acyl groups (eg acetyl, propionyl, butyryl, valeryl), sulfonyl groups (eg methylsulfonyl, phenylsulfonyl), acylamino groups (eg acetylamino, benzamino), sulfonyl amino acids (eg Examples thereof include methanesulfonylamino, benzenesulfonylamino), acyloxy groups (eg acetoxy, benzoxy), carboxyl groups, cyano groups, sulfo groups, amino groups and the like. L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include-(C
_{H 2) n - (n =} 1~12), - CH 2 -CH = CH
_{-CH 2 -, - CH 2 ≡CCH} 2 -,

[0066]

[Chemical formula 26]

Examples thereof include a xylylene group. Examples of the divalent aromatic group of L include phenylene and naphthylene.

These substituents may be further substituted with the above-mentioned substituents.

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

Specific examples of the compounds represented by formula (B), (C) or (D) are shown below, but the invention is not limited thereto.

[0071]

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[0072]

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[0073]

[Chemical 29]

[0074]

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[0075]

[Chemical 31]

[0076]

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[0077]

[Chemical 33]

[0078]

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[0079]

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[0080]

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The compounds of the general formulas (B), (C) and (D) are described in JP-A-54-1019 and British Patent 972,211.
Can be easily synthesized by the method described in. The compound represented by formula (B), (C) or (D) is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. 10 ^-6 to 10 ^-2 , especially 10 ^-5 to 1
An addition amount of 0 ⁻³ mol / mol Ag is preferable.

To add the compounds represented by the general formulas (B) to (D) during the production process, a method usually used when adding an additive to a photographic emulsion can be applied. For example, the water-soluble compound is an aqueous solution having an appropriate concentration, and the water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, such as alcohols, glycols, ketones,
Of the esters and amides, it can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

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

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

Among the compounds represented by the general formulas (B) to (D), the most preferred compound for the present invention is the compound represented by the general formula (B).

Next, the film surface pH will be described. In the present invention, the film surface pH of the light-sensitive material is preferably 6.3 or more and 7.5 or less, more preferably 6.3 or more and 7.0 or less,
Most preferably, it is 6.5 or more and 7.0 or less. The film surface pH is 6.
When it is less than 3, the fogging increases drastically over time after application, and when it is more than 7.5, the fresh performance (performance immediately after application) causes fog. This phenomenon is particularly remarkable in the emulsion subjected to reduction sensitization. The film surface pH value mentioned here is a value measured as follows. First, in a photosensitive material in which a photosensitive layer is coated on a support, the photosensitive layer is placed horizontally with the photosensitive layer side facing up. Next, 20 microliters of pure water is dropped on the sample surface with a micropipette.
After 1 minute, gently drop the pH meter electrode onto it.
The value is read after 1 minute. In order to adjust the film surface pH within the preferable range, an appropriate amount of acid (eg sulfuric acid, acetic acid etc.) or alkali (eg sodium hydroxide etc.) may be added to the coating solution.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH And so on. Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL starts from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8, as described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448 and 63-89850, are described.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as RL is disposed adjacent to or close to the main photosensitive layer.

The preferred silver halide for use in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than about 30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-2.
Page 3, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid N.
o.307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Gl).
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion usually used is one subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are RD No. 17643 and RD No. 17643.
8716 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat.
It is preferred to apply the internally fogged silver halide grains and colloidal silver described in 214852 to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm
, Particularly preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least the weight or the number of silver halide grains).
95% have a particle size within ± 40% of the average particle size)
It is preferred that

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868 5. Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column, pages 873 to 874 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page 876 Right columns 876-877 Inhibitors 10. Matting agents 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); A-4 -6 of EP 456,257
3 (p. 134), A-4 -73, -75 (p. 139); M-4, -6 in EP 486,965
(Page 26), M-7 (page 27); EP-571,959A M-45 (page 19);
5-204106 (M-1) (page 6); JP-A-4-362631, paragraph 0237 M-
twenty two. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (11 of JP-A-2-44345
P.).

Examples of couplers in which the coloring dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), the compound of formula (1) of EP 568,037A (especially (23) (page 11)), and the compounds of formulas (I), (II), Compounds represented by (III) (especially I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69-118
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29 SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII),
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention are
For example, the RD. Page 28 of No.17643, 6 of No.18716
From page 47, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Is defined. The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and T _1/2 is A Green (A.Gr
een) et al., Photographic Science and Engineering (Photogr.Sci.Eng.), 19 volumes, 2,124 ~
It can be measured by using a swellometer (swelling meter) of the type described on page 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, it is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention has the RD. No.176
No. 18716, No. 18716, left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and the representative and preferred examples thereof are the compounds described on page 28, lines 43 to 52 of EP556700A. Can be mentioned. Two or more of these compounds can be used in combination depending on the purpose. The color developer should have a pH such as alkali metal carbonate, borate or phosphate.
It is common to include a development inhibitor such as a buffer, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye formation Coupling agents, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids ,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,
N, N-trimethylenephosphonic acid, ethylenediamine-
Add N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

When the reversal processing is carried out, black and white development is usually carried out before color development. A known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone in the black-and-white developer. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Photographic treatment in the treatment tank The treatment effect of contact with air is the aperture ratio (= [contact area between treatment liquid and air cm ² ] / [volume of treatment liquid cm ³ ])
Can be evaluated at. The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.
05. As a method of reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033,
The slit development processing method described in JP-A-63-216050 can be mentioned. The aperture ratio is not limited to both the color development and black and white development steps, and the subsequent steps, for example,
It is preferable to reduce the amount in all steps such as bleaching, bleach-fixing, fixing, washing with water and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The time for the color developing process is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, a high pH and using a high concentration of the color developing agent.

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

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specifications: US 3,893,858, DE 1,290,81.
2, same 2,059,988, JP-A-53-32736,
53-57831, 53-37418, 53-7
2623, the same 53-95630, the same 53-95631,
53-104232, 53-124424, 53
-141623, 53-28426, RD No. 171
29 (July 1978), a compound having a mercapto group or a disulfide group; JP-A-50-14012.
The thiazolidine derivative according to item 9; JP-B-45-850.
6, JP-A-52-20832, JP-A-53-32735, U
Thiourea derivative described in S3,706,561; DE
No. 1,127,715, iodide salts described in JP-A-58-16,235; DE966,410, and JP2,748,43.
0 polyoxyethylene compounds; Japanese Patent Publication No. 45-
8836 described polyamine compounds; Others JP-A-49-
40, 943, 49-59, 644, 53-94,
927, 54-35, 727, 55-26, 50.
6, compounds described in 58-163, 940; bromide ions can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US 3,893,858, DE 1,290,8.
12, compounds described in JP-A-53-95,630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. Yes, especially ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, or thiourea. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP294769A are preferable. Furthermore, aminopolycarboxylic acids or organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixer or the bleach-fixer has a pKa of 6.0 to 9 for adjusting the pH.
0 compounds, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole at 0.1 per liter.
It is preferable to add 10 to 10 moles.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 minute to 3
Minutes, more preferably 1 minute to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, Japanese Patent Laid-Open No. 62-
No. 183460, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using a rotating means of JP-A-62-183461, and a wiper blade and emulsion provided in the solution. Examples include a method of moving the light-sensitive material while bringing the surfaces into contact with each other to make the emulsion surface turbulent to further improve the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is
It is preferable to have the photosensitive material conveying means described in JP-A-60-191257, 60-191258 and 60-191259. The above-mentioned JP-A-60-191257.
As described above, such a transporting means can significantly reduce the carry-in of the treatment liquid from the front bath to the post-bath, and is highly effective in preventing the deterioration of the performance of the treatment liquid. It is especially effective in reducing the amount of replenishment.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the intended use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of t
he Society of MotionPicture and Television Enginee
rs vol. 64, p. 248-253 (May 1955)
Can be obtained by the method described in (1). According to the multi-stage counterflow method described in this document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bagteria propagate and the suspended matter generated adheres to the photosensitive material. Problem arises. As a solution to this, JP-A-62-2
The method of reducing calcium ion and magnesium ion described in 88,838 is extremely effective. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles,
Hiroshi Horiguchi, "The Chemistry of Antibacterial and Antifungal Agents" (1986), Sankyo Publishing, edited by Hygiene Technology Society "Sterilization, sterilization and antifungal technology of microorganisms"
(1982) The sterilizing agents described in "Technological Society of Japan", "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents (1986) can also be used. The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be set depending on the characteristics and use of the light-sensitive material, but generally, the range is 20 to 10 minutes at 15 to 45 ° C., preferably 30 seconds to 5 minutes at 25 to 40 ° C. . Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing treatment, JP-A-57-8543 and 58-1
Known methods described in 4834 and 60-220345 can be applied. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing. You can Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use a precursor of a color developing agent. For example US3
342, 597 described indoaniline compounds,
342, 599, Research Disclosure No. 1
4,850 and Schiff base type compounds described in Nos. 15 and 159, aldol compounds described in 13,924, U
Metal complexes described in S3,719,492, JP-A-53-1
The urethane type compound described in 35628 can be mentioned. The light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-6.
4339, 57-144547, and 58-11.
5438. The processing liquid used for processing the light-sensitive material of the present invention is used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C. to 38 ° C. is standard, but it is possible to raise the temperature to accelerate the treatment to shorten the treatment time, or to lower the temperature to improve the image quality and the stability of the treatment liquid. it can.

[0104]

The present invention will be described in more detail with reference to the following examples, but it goes without saying that the present invention is not limited to these examples. Example 1 Preparation of emulsion Z-1 (Preparation of seed emulsion a) Aqueous solution 1 containing 0.85 g of gelatin
500 ml was kept at 35 ° C. and stirred. The silver potential was adjusted to -10 mV against saturated calomel electrode and pH was adjusted to 2.0. AgNO ₃ (0.85g) aqueous solution and KBr
An aqueous solution (0.59 g) was added by the double jet method over 15 seconds. After heating to 62 ° C, gelatin 7.6g
Was added. After adjusting the pH to 5.5, the silver potential was adjusted to -20 mV with respect to the saturated calomel electrode. AgNO
₃ (235.0 g) aqueous solution and KBr aqueous solution were added over 48 minutes while accelerating the flow rate by the double jet method.
At this time, the silver potential was set to -25 mV against the saturated calomel electrode.
Kept at. After desalting, add 55 g of gelatin and add 40
The pH was adjusted to 5.8 and pAg 8.8 at 0 ° C to prepare a seed emulsion. This seed emulsion contains 1 mol of Ag and 75 g of gelatin per 1 kg of emulsion, has a mean equivalent circle diameter of 0.69 μm, a coefficient of variation of equivalent circle diameter of 19%, an average thickness of 0.08 μm, and an average aspect ratio of 8.6. It was a particle.

(Formation of Core) 130 g of the above seed emulsion a,
Aqueous solution 1230 containing 1.9 g of KBr and 41 g of gelatin
The ml was kept at 70 ° C. and stirred. AgNO ₃ (43.0g)
The aqueous solution and the KBr aqueous solution were added over 25 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode.

(Formation of First Shell) After the formation of the core particles, KB containing the AgNO ₃ (43.9 g) aqueous solution and KI is formed.
The r aqueous solution was added over 40 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode.

(Formation of Second Shell) After the formation of the first shell, an AgNO ₃ (43.0 g) aqueous solution and a KBr aqueous solution were added over 12 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at +30 mV against the saturated calomel electrode.

(Formation of Third Shell) After the formation of the second shell, an aqueous KBr solution was added to adjust the silver potential to −80 mV. A silver iodide fine grain emulsion having an average equivalent circle diameter of 0.025 μm and a coefficient of variation of equivalent circle diameter of 16% was added to AgNO within 5 seconds.
7.8 g in terms of ₃ was rapidly added.

(Formation of Fourth Shell) 30 seconds after the above silver iodide fine grain emulsion was added, AgNO ₃ (68.3) was added.
g) The aqueous solution was added over 4 minutes at a reduced flow rate. Iridium potassium hexachloride was added on the way. The silver potential after the addition was -20 mV. Do normal washing,
Add gelatin, pH 5.8 at 40 ° C, pAg 8.8
Adjusted to. This emulsion was designated as emulsion Z-1. Emulsion Z-1
Is the average equivalent circle diameter of 1.37 μm, and the variation coefficient of equivalent circle diameter is 20
%, Average thickness 0.156 μm, average aspect ratio 8.
8 was a tabular grain having an average equivalent spherical diameter of 0.77 μm. Particles with an aspect ratio of 8 or more account for about 90% of the total projected area.
Was occupied. The characteristics of emulsion Z-1 are shown in Table 1.

[0110]

[Table 1]

Preparation of Emulsion Z-2 (Formation of Core) 130 g of the above seed emulsion a and KBr1.9.
1230 ml of an aqueous solution containing g and 41 g of gelatin was kept at 70 ° C. and stirred. AgNO after addition of thiourea dioxide
₃ (43.0 g) aqueous solution and KBr aqueous solution were added over 25 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode.

(Formation of First Shell and Second Shell) Emulsion Z
A first shell and a second shell were formed in the same manner as in -1.

(Formation of Third Shell) After the formation of the second shell, benzenethiosulfonic acid was added and an aqueous KBr solution was added to adjust the silver potential to −80 mV. A silver iodide fine grain emulsion having an average equivalent circle diameter of 0.025 μm and a variation coefficient of equivalent circle diameter of 16% was rapidly added within 5 seconds in terms of AgNO _{3 in} terms of AgNO ₃ .

(Formation of Fourth Shell) 30 seconds after the above silver iodide fine grain emulsion was added, AgNO ₃ (68.3) was added.
g) The aqueous solution was added over 4 minutes at a reduced flow rate. Iridium potassium hexachloride was added on the way. The silver potential after the addition was -20 mV. Do normal washing,
Add gelatin, pH 5.8 at 40 ° C, pAg 8.8
Adjusted to. This emulsion was designated as emulsion Z-2. Emulsion Z-2
Is the average equivalent circle diameter of 1.37 μm, and the variation coefficient of equivalent circle diameter is 20
%, Average thickness 0.156 μm, average aspect ratio 8.
8 was a tabular grain having an average equivalent spherical diameter of 0.77 μm. Particles with an aspect ratio of 8 or more account for about 90% of the total projected area.
Was occupied. The grain shape was almost the same as that of the emulsion Z-1.

Preparation of Emulsion Z-3 Emulsion Z-1 was prepared except that the compound (S1-3) was added in an amount of 1.34 × 10 ⁻⁵ 1 minute before the end of AgNO ₃ addition when the fourth shell was formed. An emulsion prepared by the same method as Z
-3.

Preparation of Emulsion Z-4 Emulsion Z-2 was prepared except that the compound (S1-3) was added in an amount of 1.34 × 10 ⁻⁵ mol 1 minute before the end of the addition of AgNO ₃ in the formation of the fourth shell. An emulsion prepared by the same method as Z
It was set to -4.

Emulsions Z-1 to 4 were heated to 56 ° C., sensitizing dyes I, II and III shown below were added, and after 20 minutes, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N,
N-Dimethylselenourea was added and chemically sensitized to optimize the 1/100 ″ sensitivity.

[0118]

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Preparation of Emulsions Z-5 to 7 Grain formation, washing and dispersion were carried out in the same manner as in Emulsion Z-3, followed by sensitization before the start of chemical sensitization, specifically by raising the temperature to 56 ° C. 1x A-3, A-4, A-19 before dye addition
Emulsion Z- was prepared by adding 10 ^-3 mol / mol Ag.
5, Z-6, and Z-7. The addition of the sensitizing dye and the chemical sensitization were performed in the same manner as in the emulsion Z-3, and the chemical sensitization was performed so that the 1/100 ″ sensitivity was also optimum.

Preparation of Emulsions Z-8 to 10 Grain formation, washing and dispersion were carried out in the same manner as in Emulsion Z-4, and before the start of chemical sensitization, specifically, after raising the temperature to 56 ° C., sensitization 1x A-3, A-4, A-19 before dye addition
Emulsion Z- was prepared by adding 10 ^-3 mol / mol Ag.
8, Z-9, and Z-10. The addition of the sensitizing dye and the chemical sensitization were performed in the same manner as in the emulsion Z-4, and the chemical sensitization was performed so that the 1/100 ″ sensitivity was also optimum.

On the cellulose triacetate film support provided with an undercoat layer, the above-mentioned chemically sensitized emulsions Z-1 to 10 were coated under the coating conditions shown in Table 2 below with a protective layer provided, Sample Nos. 101 to 110 were prepared.

[0122]

[Table 2]

Fuji Photo Film Co., Ltd. was used for these samples.
It was exposed for 1/100 seconds through a gelatin filter SC-50 manufactured by Kanamoto and a continuous wedge.

Negative Processor F, Fuji Photo Film Co., Ltd.
P-350 was treated in the manner described below (until the cumulative replenishment rate of the solution was three times its mother liquor tank capacity). (Processing method) Process Processing time Processing temperature Replenishment amount ^* Color development 3 minutes 15 seconds 38 ° C 45 ml Bleach 1 minute 00 seconds 38 ° C 20 ml Bleach solution overflows into bleach-fixing tank 3 minutes 15 seconds 38 ° C 30 ml Washing with water (1) 40 seconds 35 ℃ Countercurrent piping system from (2) to (1) Washing with water (2) 1 minute 00 seconds 35 ℃ 30 ml Stability 40 seconds 38 ℃ 20 ml Drying 1 minute 15 seconds 55 ℃ * Replenishment amount is 35 mm width 1.1 m length (equivalent to 24 Ex. 1) Next, the composition of the treatment liquid is described.

(Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 1.0 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodine Potassium iodide 1.5 mg-hydroxyamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Water was added to 1.0 liter 1.0 liter pH (potassium hydroxide 10.05 10.10 (bleaching solution) Common tank solution and replenisher solution (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mole _{(CH 3) 2 N-CH} 2 -CH 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 1.0 liter by adding water (pH adjusted with ammonia water and nitric acid) 6.3 (bleach-fixing solution) tank solution (g) replenishing solution (g) ferric ethylenediaminetetraacetate ammonium dihydrate 50.0-ethylenediaminetetraacetate Sodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 240.0 ml 400.0 ml Ammonia water (27%) 6.0 ml-1.0 liter with water added 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.2 7.3 ( Washing liquid) Common to tank liquid and replenishing liquid Tap water mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Calcium and magnesium ion concentration by passing water through the floor column Treated below 3 mg / liter, followed by the addition of sodium isocyanurate dichloride 20mg / liter and sodium 0.15 g / l of sulfuric acid. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing Solution) Common to Tank Solution and Replenishing Solution (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Disodium salt of ethylenediaminetetraacetic acid 0.05 1, 2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added and 1.0 liter pH 8.5 A sample that had been treated was measured for concentration with a green filter.

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

The aging stability of photographic properties after exposure was evaluated by the following method. After exposing samples 101 to 110 for sensitometry, the samples were stored under forced conditions of 50 ° C. and 80% relative humidity for 3 days, and then subjected to the above color development treatment,
The processed sample was evaluated for sensitivity and fog when the density was measured with a green filter. The above results are shown in Table 3.

[0129]

[Table 3]

As is clear from Table 3, the general formula (S1)
When the compound represented by the formula (1) is added, it has an effect of suppressing fogging immediately after coating, but it is still insufficient, and in particular, it has an insufficient effect of suppressing the increase of fogging with the passage of time after coating. However, it is understood that the combined use of the compound (S1) and the compound (A) has a remarkable effect of suppressing fogging immediately after coating and suppressing an increase in fogging with time after coating. Further, as is clear from a comparison between the effects of the present invention samples 105 to 107 on the sample Nos. 101 and 103 and the effects of the present invention samples 108 to 110 on the sample Nos. 102 and 104, the effect of the present invention is , Especially in the emulsion subjected to reduction sensitization.

Example 2 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P.326 (Ciba
2 parts by weight of Ciba-Geigy)
After melting at 300 ℃, extrude from T-die, 140 ℃
, And then stretched 3.3 times at 130 ° C.
Double stretching was performed twice, and the film was heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. This PEN
The film has a blue dye, a magenta dye and a yellow dye (public technical report: I- described in Japanese Patent Publication No. 94-6023).
1, I-4, I-6, I-24, I-26, I-27,
II-5) was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support with which a winding habit was not easily formed.

2) Coating of Undercoat Layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione were applied to each side. 2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² ,
_{(CH 2 = CHSO 2 CH 2} CH 2 NHCO) 2 CH 2 0.012g / m 2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, using a bar coater ), An undercoat layer was provided on the high-temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 1
15 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of Antistatic Layer A dispersion of fine particles of tin oxide-antimony oxide having an average particle size of 0.005 μm and a specific resistance of 5 Ω · cm (secondary agglomerated particle size of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02
g / m ^2, it was coated with poly (polymerization degree 10) oxyethylene -p- nonylphenol 0.005 g / m ^2, and resorcin. 3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g; Long axis 0.
14 μm, single axis 0.03 μm, saturation magnetization 89 emu / g,
Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (of iron oxide Dispersion was carried out with an open kneader and sand mill), as a curing agent
C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent, and a film thickness of 1.2 μm Of the magnetic recording layer was obtained. Silica particles (0.3μ
m) and 3-poly (degree of polymerization: 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) coated and coated with an aluminum oxide (0.15 μm) as an abrasive so as to be 10 mg / m ^2. did. Drying is 115 ° C, 6
(All rollers and conveying devices in the drying zone are at 115 ° C.). X- write saturation magnetization moment 4.2 emu / g to about 0.1, and the magnetic recording layer color density increment of D ^B of the magnetic recording layer in the (blue filter), the coercive force 7.
3 × 10 ⁴ A / m, and the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀
H ₂₀ COOC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH
₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. This mixture was prepared by melting it in xylene / propylene monomethyl ether (1/1) at 105 ° C. and pouring and dispersing it in propylene monomethyl ether (10 times the volume) at room temperature. Average particle size 0.01μ
m) and then added. Silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15) as an abrasive.
Aluminum oxide (0.15 μm) coated by weight% was added to a concentration of 15 mg / m ² . 115 for drying
C., 6 minutes (115.degree. C. for all rollers and conveyors in the drying zone). The sliding layer has a dynamic friction coefficient of 0.06 (5
mmφ stainless steel ball, load 100g, speed 6cm /
Min), the coefficient of static friction was 0.07 (clip method), and the coefficient of dynamic friction between the emulsion surface and the sliding layer described later was 0.12.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multilayer coated to form a color negative film.
These are designated as sample Nos. 201 to 210.

(Photosensitive Layer Composition) 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 hardening agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver Silver 0.08 Gelatin 1.57 ExM-1 0.12 ExF-1 2.5 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.16 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.072 ExC-2 0.05 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.27 Silver iodobromide emulsion B Silver 0.28 ExS-1 7.2 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.2 × 10 ^-4 ExC-1 0.16 ExC-3 0.030 ExC-4 0.10 ExC-5 0.022 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.67 ExS-1 3.3 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 4.9 × 10 ^-4 ExC-1 0.11 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.092 ExC-5 0.014 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.72

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.42 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.6 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.022 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.24 HBS-2 0.050 Gelatin 1.15

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.033 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.20

Seventh Layer (Low-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion 0.15 Silver iodobromide Emulsion F Silver 0.08 Silver iodobromide Emulsion G Silver 0.13 ExS-4 3.0 × 10 ^-5 ExS-5 2.3 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.10 ExY-1 0.015 HBS-1 0.32 HBS-3 0.010 Gelatin 0.70

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.72 ExS-4 3.2 × 10 ^-5 ExS-5 1.5 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.033 ExY-1 0.010 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.72

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion used in Example 1 Silver 1.33 (Z-1 to 10) ExC-1 0.013 ExM-1 0.020 ExM-4 0.020 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.23 Polyethyl acrylate latex 0.15 Gelatin 1.35

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.014 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.55

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.11 Silver iodobromide emulsion J Silver 0.11 ExS-7 8.9 × 10 ^-4 ExC-8 7.7 × 10 ^-3 ExY-1 0.050 ExY-2 0.17 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.08 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.15

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion K Silver 0.95 ExS-7 4.0 × 10 ^-4 ExY-2 0.08 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.066 Gelatin 0.72

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.085 UV-3 0.065 HBS-1 5.2 × 10 ^-2 HBS-4 4.6 × 10 ^-2 gelatin 1.84

Fourteenth layer (second protective layer) Silver iodobromide emulsion L Silver 0.10 H-1 0.50 B-1 (diameter 1.7 μm) 6.2 × 10 ^-2 B-2 (diameter 1.7 μm) 0.13 B-3 0.05 S-1 0.22 Gelatin 67

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-15 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0152]

[Table 4]

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

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP549,489A. The average particle size was 0.06 μm.

[0155]

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[0156]

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[0157]

[Chemical 40]

[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0164]

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[0166]

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[0167]

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[0168]

[Chemical 51]

[0169]

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[0170]

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The photosensitive material prepared as described above is used for 24 mm
The photosensitive material is cut to a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. I made a set of these two sets with a 32mm interval, and US 5,296,88
7 FIG. 1 to FIG. 7 was housed in a plastic film cartridge. For this sample, an FM signal was sent from the coated surface side of the magnetic recording layer at a feed speed of 1,000 / s during the above-mentioned perforation of the photosensitive material by using a head having a head gap of 5 μm and a turn count of 2,000. Recorded. After the FM signal was recorded, the emulsion surface was exposed uniformly over the entire surface for 1,000 cms, and each processing was performed by the methods described below, and then the emulsion was stored again in the original plastic film cartridge. This sample 10
1 was cut into 35mm width and photographed with a camera 1m ² per day
The following treatments were performed for 15 days each. (Running process) Each process is an automatic processor FP-3 manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using 60B. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992. The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 ml 11.5 liter Bleaching 50 seconds 38.0 ℃ 5 ml 5 liter Fixing (1) 50 seconds 38.0 ℃ -5 liter Fixing (2) 50 seconds 38.0 ℃ 8 ml 5 liters Water wash 30 seconds 38.0 ℃ 17 ml 3 liters Stable (1) 20 seconds 38.0 ℃ −3 liters Stable (2) 20 seconds 38.0 ℃ 15 milliliters 3 liters Dry 1 minute 30 60 ° C / s * Replenishment amount per 1.1 m of width 35 mm of photosensitive material (equivalent to 24 Ex. 1) Stabilizer and fixer are countercurrent method from (2) to (1), and overflow solution of washing water is all It was introduced into the fixing bath (2). The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the water washing process were 2.5 ml and 2.0 ml, respectively, per 35 mm width of the light-sensitive material of 1.1 mm. They were milliliter and 2.0 milliliter. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 c for color developer.
m ² , 120cm ^{2 for} bleaching solution, about 100c for other processing solutions
It was m ² .

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium salt 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2 -Sulfonatoethyl) hydroxylamine 1.5 2.0 potassium bromide 1.3 0.3 potassium iodide 1.3 mg-4-hydroxy-6-methyl-1,3,0.05-3a, 7-tetrazaindene hydroxylamine sulfate 2.4 3.3 2-methyl- 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.5 1.0 liter by adding water 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropanetetraacetic acid Ferric ammonium ammonium monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.6 4.0

(Fixing (1) Tank Solution) A 5:95 (volume ratio) mixed solution of the above bleaching tank solution and the following fixing tank solution. (PH
6.8) (Fixer solution (2)) Tank solution (g) Replenisher solution (g) Ammonium thiosulfate aqueous solution 240 ml 720 ml (750 g / l) Imidazole 7 21 Ammonium methanethiosulfonate 5 15 Ammonium methanesulfinate 10 30 Ethylenediamine Tetraacetic acid 13 39 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR manufactured by Rohm and Haas Company).
-120B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust calcium and magnesium ion concentrations to 3
Treatment to less than mg / liter, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 15
0 mg / l was added. The pH of this solution is 6.5
It was in the range of 7.5.

(Stabilizer) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 1,2-Benzisothiazoline-3- on. Sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

When the same experiment as in Example 1 was carried out on the multilayer color light-sensitive material as in this example, the effect of the present invention was similarly confirmed.

Example 3 A cellulose triacetate film support having an undercoat layer was coated with a protective layer under the coating conditions as shown in Table 5 below, and sample Nos. 301 to 315 as shown in Table 6 below. It was created. The pH of the film surface was adjusted by adding sulfuric acid or sodium hydroxide to the protective layer. The aging stability of the photographic properties after exposure was evaluated by the same method as in Example 1.

[0180]

[Table 5]

[0181]

[Table 6]

As is apparent from Table 6, according to the present invention,
It can be seen that the effect of suppressing fogging in the fresh performance and the effect of suppressing increase in fogging with time after application are most remarkable at the film surface pH of 6.6. More specifically, the film surface p
Samples 301 and 304 of H6.2 show a significant increase in fog after the passage of time. However, when looking at Samples 307, 310 and 313, the effect of suppressing the increase in fog according to the present invention is certainly seen. However, in contrast to this, the sample 30 with a membrane surface pH of 6.6
The present invention samples 308, 311, 314 against 2,305
It can be seen that the improvement effect is much larger by comparing In addition, the samples 303 and 306 having a film surface pH of 7.6 are
The fogging immediately after coating was particularly high, and the increase in fogging with time after coating was large, but the samples 309, 312, 315 of the present invention were used.
Has been improved by. On the other hand, when the samples 302 and 305 of the present invention were compared with the samples 302 and 305 having the pH of the film surface of 6.6, the improvement effect was much greater both in the fogging immediately after coating and in the increase in the fogging with time. I understand.

Example 4 When the same experiment as in Example 3 was carried out on the same multilayer color light-sensitive material as in Example 2, the effect of the present invention was similarly confirmed.

[0184]

As described above, according to the present invention, it is possible to provide a silver halide emulsion and a silver halide photographic light-sensitive material with less fog and improved aging stability of photographic properties after exposure. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 7/392 G03C 7/392 A

Claims (4)

[Claims] 1. A compound represented by the following general formula (A):
A silver halide emulsion comprising at least one compound represented by the following general formula (S1). Embedded image In formula (A), R _a1 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbamoyl group or an aryloxycarbonyl group, and R _a2 represents a hydrogen atom or a group represented by R _a1 . However, when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. _Ra1 and _Ra2 may combine with each other to form a 5- to 7-membered ring. Embedded image In the general formula (S1), in the formula, R _s1 and R _s2 may be the same or different and each is an alkyl group, an aryl group,
It represents a heterocyclic group, an amino group or a group shown below. Embedded image In the formula, R _s3 and R _s5 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R _s4 represents an alkyl group, an aryl group or a heterocyclic group. X ₁ and X ₂ may be the same or different and each represents S, Se or Te. R ₁ , R ₂ , X ₁
And X ₂ may together form a ring. 2. The silver halide emulsion according to claim 1, wherein the silver halide emulsion is subjected to reduction sensitization. 3. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing the silver halide emulsion according to claim 1 on a support. 4. The film surface p of the photosensitive material according to claim 3.
A silver halide photographic light-sensitive material, wherein H is 6.3 or more and 7.5 or less.