JPH08211539A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance latent image stability and stagnation restraint stability and pressure resistance without deteriorating photographic performance by incorporating a composite flocculation product of a specified compound. CONSTITUTION: The silver halide emulsion contains the composite flocculation product of the compound represented by the formula in which each of R1 -R4 is an H atom or an alkyl group or the like; each of R5 -R8 is a substituent; each of L1 and L2 is a methine group; Z1 is an 0 or S atom or the like; and each of R1 and R2 , R3 and R4 , R5 and R6 , and R7 and R8 may combine with each other to form a ring. This photosensitive material comprises >=2 silver halide emulsion layers the same as each other in photosensitivity and different from each other in sensitivity and the layer highest in sensitivity contains the compound of the formula, thus permitting the obtained silver halide emulsion to be enhanced in latent image stability and stagnation restraint stability and further, in pressure resistance without deteriorating photographic performance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material, more specifically, a silver halide photographic emulsion and a halogen having improved latent image stability, coating solution retention and pressure resistance. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, demands on silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) have become more and more strict, and one of them is stability over time, and in particular, stability from exposure to development. That is, latent image stability is an important item.

The latent image formed by the exposure of silver halide is unstable, and it regresses or is intensified due to the passage of time or heat, and the sensitivity is lowered or increased in terms of photographic performance. appear.

This latent image stability is determined by the method and structure of silver halide, surface treatment, chemical and spectral sensitization methods, binder properties such as gelatin, type of hardener, pH of coating solution.
It is greatly affected by the concentration of silver and silver ions.

Various methods have been proposed so far in order to increase the latent image stability. For example, a method using a benzothiazolium described in JP-A-50-94918 and a Schiff base described in JP-A-57-100425 is disclosed. However, even if these techniques are used, the improvement in latent image stability has not reached a sufficient level.

Another improvement technique is disclosed in Japanese Patent Laid-Open No. 5-75832.
And JP-A-5-13600 describe methods using styryl dyes known as supersensitizers. However, the conventional methods do not provide satisfactory latent image stability, such as a large latent image progress when stored at high humidity, or desensitization and pressure resistance over time when the coating solution is stagnant. Due to deterioration, further improvement techniques are desired.

[0007]

In view of the above problems, an object of the present invention is to provide a silver halide photographic emulsion and a halogenated photographic emulsion which are excellent in latent image stability, stagnation stability and pressure resistance without deteriorating photographic performance. It is to provide a silver photographic light-sensitive material.

[0008]

The above object of the present invention can be achieved by the following constitutions.

1. A silver halide photographic emulsion having a complex aggregate of a compound represented by the following general formula (I).

[0010]

[Chemical 4]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and Each R ₈ represents a substituent. L ₁ and L ₂ each represent a methine group,
Z ₁ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom,
_{-C (R 9) (R 10} ) - or -N (R ₉₎ - represents a. R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Also, R ₁ and R ₂ , R
₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , and R ₉ and R ₁₀ may combine with each other to form a ring.

2. The following general formula (II) and general formula (III)
A silver halide photographic emulsion containing a compound represented by:

[0013]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and R 4 Each ₈ represents a substituent. L ₁ and L ₂ each represent a methine group,
Z ₂ represents a sulfur atom, a selenium atom or a tellurium atom. Also, R ₁
And R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , and R ₇ and R ₈ may be bonded to each other to form a ring.

[0015]

[Chemical 6]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and Each R ₈ represents a substituent. L ₁ and L ₂ each represent a methine group,
Z ₃ is an oxygen _{atom, -C (R 9) (R} 10) - or -N (R ₉₎ - represents a.
R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , and R ₉ and R ₁₀ may be bonded to each other to form a ring.

3. The general formula (II) and the general formula (III)
The silver halide photographic emulsion according to claim ₂ , wherein Z ₂ in the formula is a sulfur atom and Z ₃ is an oxygen atom.

4. A silver halide photographic light-sensitive material containing the silver halide photographic emulsion described in 1, 2, or 3.

5. A silver halide photographic light-sensitive material containing the compound represented by the general formula (II) and the compound represented by the general formula (III).

6. The silver halide photographic light-sensitive material comprises two or more layers having the same color sensitivity but different sensitivities, and the highest-sensitivity layer contains the silver halide photographic emulsion described in 1, 2 or 3 above. .

7. A silver halide photographic light-sensitive material having a layer containing the compound represented by the general formula (II) and a layer containing the compound represented by the general formula (III).

8. The silver halide photographic light-sensitive material comprises two or more layers having the same color sensitivity but different sensitivities, the compound of the general formula (II) is contained in the highest sensitivity layer and the compound of the general formula (III) is contained in the lowest sensitivity layer. 7. The silver halide photographic light-sensitive material as described in 7 above, which comprises:

9. 6. The silver halide photographic light-sensitive material as described in 5 above, which comprises a silver halide photographic emulsion containing a compound of general formula (II) and a silver halide photographic emulsion containing a compound of general formula (III) in the same layer.

10. 10. The silver halide photographic light-sensitive material as described in 9 above, wherein the same layer is the highest sensitivity layer.

11. 11. The silver halide photographic light-sensitive material according to any one of the above 4 to 10, which has a photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer on a support.

The present invention will be described in more detail below.

The complex aggregate of the compound represented by the general formula (I) in the present invention means a complex formed by aggregating two or more kinds of compounds which are not the same.

In the above general formula (I), general formula (II) and general formula (III), the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ is, for example, methyl, ethyl, propyl,
Examples thereof include i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl and dodecyl groups. These alkyl groups further include a halogen atom (for example, an atom such as chlorine, bromine, or fluorine), an alkoxy group (for example, each group such as methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy),
Aryloxy groups (eg, groups such as phenoxy and naphthyloxy), aryl groups (eg, groups such as phenyl and naphthyl), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl,
2-ethylhexylcarbonyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl, naphthyloxycarbonyl, etc.), alkenyl groups (eg, vinyl, allyl, etc.), heterocyclic groups (eg, 2-pyridyl, Each group such as 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, pyrimidyl, pyrazolyl, furyl, etc.), alkynyl group (eg, propargyl group), amino group (eg, amino, N, N-dimethylamino, anilino, etc.) Group), a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) Good.

Examples of the alkenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include groups such as vinyl and allyl.

Examples of the alkynyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a propargyl group.

Examples of the aryl group represented by R ₁ , R ₂ , R ₃ and R ₄ include phenyl and naphthyl groups.

The heterocyclic group represented by R ₁ , R ₂ , R ₃ and R ₄ includes, for example, pyridyl group (for example, each group such as 2-pyridyl, 3-pyridyl, 4-pyridyl), thiazolyl group, oxazolyl group. Group, imidazolyl group, furyl group, thienyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group and the like.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group are all the same as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups shown as the substituents of the alkyl groups. It can be replaced by a group.

The substituents represented by R ₅ , R ₆ , R ₇ and R ₈ include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, halogen atoms, alkoxy groups, aryloxy groups and alkoxy groups. Carbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group, amide group, sulfonyl group, amino group, cyano group, nitro group, carboxyl group, hydroxyl group, hydrogen atom, etc. . These groups can be substituted by the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ , and R ₄ and the groups shown as the substituents of the alkyl groups.

Z ₁ is an oxygen atom, a sulfur atom, a selenium atom,
Tellurium _{atom, -C (R 9) (R} 10) - or -N (R ₉₎ - represents a. R ₉
And R ₁₀ have the same meanings as R ₁ , R ₂ , R ₃ and R ₄ described above. Z ₂
Represents a sulfur atom, a selenium atom, and a tellurium atom. It is preferably a sulfur atom. Z ₃ is an oxygen _{atom, -C (R 9) (R} 10) - or -N (R ₉₎ - represents a. It is preferably an oxygen atom. R ₉ and R ₁₀ have the same meanings as R ₁ , R ₂ , R ₃ and R ₄ , respectively.

The ring formed by R ₁ and R ₂ includes, for example, benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole,
Examples include rings such as pyrazine and indole.

Examples of the ring which can be formed by R ₃ and R ₄ include rings such as piperidine, pyrrolidine, morpholine, pyrrole, pyrazole and piperazine.

Examples of the ring formed by R ₅ and R ₆ and R ₇ and R ₈ include rings such as benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole, pyrazine and indole.

Examples of the ring formed by R ₉ and R ₁₀ include rings such as cyclopentane and cyclohexane.

The above rings can be substituted with the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups mentioned as the substituents of the alkyl groups.

The methine group represented by L ₁ and L ₂ may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group,
Examples thereof include an alkoxycarbonyl group and an aryloxycarbonyl group. These groups further include R ₁ , R ₂ , R ₃ ,
It can be substituted with the same groups as the alkyl group represented by R ₄ and the substituents of the alkyl group.

The general formula (I) and the general formula (I
Specific examples of the compound represented by formula (I) and the general formula (III) (hereinafter, also referred to as the compound of the present invention) will be given, but the present invention is not limited thereto.

[0043]

[Chemical 7]

[0044]

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[0045]

[Chemical 9]

[0046]

[Chemical 10]

[0047]

[Chemical 11]

[0048]

[Chemical 12]

[0049]

[Chemical 13]

[0050]

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[0051]

[Chemical 15]

Specific synthetic examples of the compound of the present invention will be shown below, but other compounds can be easily synthesized by the same method.

Synthesis Example 1 (Synthesis of Exemplified Compound I-4) 2-methylbenzothiazole (14.9 g), p-diethylaminobenzaldehyde (17.7 g), sodium hydride (hard oil 60)
%) 6 g and dimethylformamide 60 ml are added, and the mixture is allowed to stand at room temperature for 30%.
Reaction was carried out for a minute. The reaction solution was poured into water and the precipitated solid was filtered. The solid was dried and then recrystallized from methanol to obtain the desired product. Yield 19.4 g (63%).

The amount of the compound of the present invention added is preferably 2 × 10 ^-7 to 1 × 10 ^-2 mol, and more preferably 2 × 10 ^{-7 to} 5 × 10 ^-3, per mol of silver halide. Molar is preferred.

As a method for adding the compound of the present invention to the silver halide emulsion, a method well known in the art can be used. For example, the compound can be dispersed directly in the emulsion, or dissolved in a water-soluble solvent such as pyridine, methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide, or a mixture thereof, or diluted with water. Alternatively, it can be dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibration can also be used during the dissolution process.

The compounds of the present invention can also be prepared according to the method described in US Pat. No. 3,469,98.
No. 7, etc., dissolved in a volatile organic solvent, and a solution obtained by dispersing this solution in a hydrophilic colloid is added to the emulsion. Water-insoluble as described in Japanese Examined Patent Publication No. 46-24185. A method is also used in which the dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to the emulsion.

Further, the compound of the present invention can be added to the emulsion in the form of a dispersion prepared by an acid solution dispersion method.

The compound of the present invention may be added anywhere from during the formation of silver halide grains to the coating, but it is particularly preferable to add it before the completion of chemical sensitization.

In the present invention, the total coated silver amount coated on the support can be measured by a fluorescent X-ray method. The total amount of coated silver also includes silver halide and colloidal silver which have substantially no photosensitivity. The total coated silver amount of the silver halide photographic light-sensitive material in the present invention is 3.0 g / m ² or more and 5.0 g
/ M ² or less.

In order to make effective use of valuable silver resources, studies have been conducted to reduce the coated silver amount in silver halide photographic light-sensitive materials as much as possible.

In the light-sensitive material of the present invention, the total coated silver amount is preferably 3.0 to 4.5 g / m ² , and more preferably 3.5 to 4.0 g / m ² .

The silver halide grains useful in the present invention have a silver halide content of 3 mol% or more as an average halogen composition in all silver halide emulsion layers constituting the light-sensitive material. Good. Therefore, the silver iodide content of the light-sensitive material as a whole is sufficient, and the silver halide grains contained in a certain layer may be out of this range.

The present invention is characterized by having at least one layer of red-sensitivity, green-sensitivity and blue-sensitivity on the support. Each photosensitive layer may have any number of layers,
1 to 5 layers are preferable, and 2 layers and 3 layers are particularly preferable. When each photosensitive layer is composed of multiple layers, a high-sensitivity layer,
It is preferably composed of layers having substantially the same color sensitivity, but different photographic sensitivities, such as a medium-speed layer and a low-speed layer. The "substantially the same color sensitivity" as used herein may be the same in terms of blue photosensitivity, green photosensitivity, and red photosensitivity, and the spectral sensitivity characteristics need not be exactly the same. Further, either a so-called forward layer structure or a reverse layer structure may be used.

A layer having substantially no photosensitivity may be provided between the respective photosensitive layers.

The grain size of the silver halide used in the present invention is not particularly limited, but it is preferably 0.1 to 3 μm in view of image characteristics such as graininess and processability due to the difference in developability depending on the grain size of the grains. And more preferably 0.2 to 2
μm. Further, the structure of the silver halide grains is preferably core / shell type silver halide grains. The core / shell type is a silver halide grain having different silver halide compositions between the inside and the surface.

Further, monodisperse grains are preferable, and the ratio S of the standard deviation (S) of the grain size to the average grain size (r) of the entire silver halide grains contained in each silver halide photographic emulsion layer.
The coefficient of variation defined by / r is preferably 0.4 or less, 0.33
The following is more preferable, 0.25 or less is further preferable, and 0.20 or less is particularly preferable.

The average grain size (r) is the grain size (in the case of cubic silver halide grains, the length of one side thereof, or in the case of grains other than cubic grains, converted to cubic grains having the same volume). When the number of particles of (length of one side) ri is ni, it is defined by the following formula 1. The standard deviation (S) of the particle size (ri) is expressed by the following equation 2.

[0068]

[Equation 1]

The monodisperse core / shell type silver halide emulsion used in the present invention as described above is described in JP-A-59-17735.
No. 3, No. 60-138538, No. 59-52238, No. 60-143331,
It can be produced by a known method disclosed in Nos. 60-35726 and 60-258536.

Tabular grains can also be used in the present invention.

In the silver halide emulsion according to the present invention, pAg and pH in the liquid phase for producing and growing silver halide grains, temperature and stirring are controlled in a predetermined pattern, sodium chloride, potassium bromide and iodide. Halides such as potassium,
It is produced by an emulsion producing apparatus by the double jet method, which controls the addition of silver nitrate. Further, a substantially non-photosensitive fine grain emulsion having silver halide grains having a diameter of 0.01 to 0.2 μm can be prepared in the same manner and used for the protective layer and the intermediate layer.

The term “substantially non-photosensitive” means a sensitivity of 1/50 or less of the lowest sensitivity grains in the photosensitive emulsion layer.

In the present invention, in order to obtain a wide exposure latitude, silver halide emulsions having different grain sizes or different silver halide compositions can be mixed and used in the same constituent layer.

The silver halide grains having different grain sizes to be mixed and used include silver halide grains having an average grain size of 0.2 to 2.0 μm and a minimum average grain size of 0.05 to 1.0 μm. A combination of silver halide grains having a different diameter is preferable, and one or more kinds of silver halide grains having an average particle diameter in the middle may be combined. The average grain size of the silver halide grains having the maximum average grain size is preferably 1.5 to 40 times the average grain size of the silver halide grains having the minimum average grain size.

The light-sensitive material of the present invention can be applied to various color light-sensitive materials represented by general color negative films and color positive films.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 24 μm or less, more preferably 20 μm or less, still more preferably 18 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. Film thickness is 25 ° C and relative humidity is 55
% Means the film thickness measured under humidity control (2 hr), and the film swelling rate T _1/2 can be measured according to a method known in the art.

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

The substantially water-insoluble spectral sensitizing dye for use in the present invention has a solubility of 1 × 10 ^-4 to 27 ° C. in an aqueous system in which an organic solvent and / or a surfactant is not present.
4 × 10 ^-2 mol / liter, preferably 2 × 10 ^-4 to 4 × 10
^A spectral sensitizing dye of ^-2 mol / liter was added in an amount exceeding the solubility and mechanically dispersed in solid fine particles of 1 μm or less.

In contrast to the technique disclosed in the above-mentioned JP-A-3-288842, the present invention has been made for uniformly and effectively adsorbing a photographic spectral sensitizing dye on the surface of silver halide grains, The above-mentioned technique for merely adding in a dispersed manner is different from the intended effect.

In the present invention, the above-mentioned conventionally used organic solvent is not substantially contained. Further, as described above, it does not substantially contain the surfactant which has been conventionally used as a dispersant for sensitizing dyes.

In the present invention, the aqueous system in which substantially no organic solvent and / or surfactant is present is water containing impurities at a level that does not adversely affect the silver halide photographic emulsion, more preferably ion exchange. Refers to water.

[0082] solubility in water of the spectral sensitizing dye in the present invention is a 2 × 10 ^-4 ~4 × 10 ^-2 mol / liter, more preferably 1 × 10 ^-3 ~4 × 10 ^-2 mol / It is a liter.

That is, if the solubility is lower than this range, the dispersed particle size becomes very large and non-uniform, so that the dispersion may precipitate after the dispersion is completed or the dispersion may be added to the silver halide emulsion. It was found that when this occurs, the process of adsorbing the dye on the silver halide is hindered.

When the solubility is higher than this range, the viscosity of the dispersion is increased more than necessary, air bubbles are entrapped, and the dispersion is hindered. At higher solubility, dispersion becomes impossible. However, it has become clear from the research conducted by the present inventors.

The spectral sensitizing dye in the present invention means a compound which causes electron transfer to the silver halide when it is photoexcited when adsorbed on the silver halide and does not include an organic dye.

The spectral sensitizing dye used in the present invention may be any one as long as it has a solubility in water in the range of 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / liter, and is preferably a cyanine dye. More preferably a hydrophilic group (eg -SO ₃ H, -CO
OH etc.) is a cyanine dye.

Specific examples and solubilities in water will be listed below, but the present invention is not limited thereto.

[0088]

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[0089]

[Chemical 17]

[0090]

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In the present invention, various dispersers are effectively used for mechanically pulverizing and dispersing the spectral sensitizing dye in an aqueous solvent. Specifically, a high speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser or the like is used. A high speed stirrer is preferred in the present invention.

The high-speed stirring type disperser may have a dissolver having a plurality of impellers mounted on the vertical axis or a multi-axis dissolver having a plurality of vertical axes. In addition to the dissolver alone, a high-speed stirring type disperser having anchor blades is more preferable.

As a concrete working example, after water is put into a temperature-controllable tank, a certain amount of powder of the spectral sensitizing dye is put into the tank, and the mixture is stirred with a high-speed agitator for a certain time under temperature control. Then, crush and disperse. The pH and temperature at which the spectral sensitizing dye is mechanically dispersed are not particularly limited, but the desired particle size cannot be reached even after long-term dispersion at low temperature, and reaggregation or decomposition occurs at high temperature. Occurs, and desired photographic performance cannot be obtained, and there is a problem that the efficiency of pulverization and dispersion of solids is greatly reduced because the viscosity of the solution system is lowered when the temperature is raised. Therefore, the dispersion temperature is 15 ~
It is more preferably 50 ° C. Further, the stirring rotation speed during dispersion requires a long time to obtain a desired particle size at low rotation speeds, and at high rotation speeds, bubbles are entrained and the dispersion efficiency is reduced, so dispersion is performed at 1000 to 6000 rpm. More preferably.

The fact that the solid fine particles of the spectral sensitizing dye dispersed by the method of the present invention are 1 μm or less means that the particle size according to the volume average diameter of spheres is 1 μm or less, which is measured by a general method. it can.

The dispersion used in the present invention means a suspension of the spectral sensitizing dye, and preferably, the weight ratio of the spectral sensitizing dye in the suspension is 0.2% to 5.0%. Used.

The dispersion of the spectral sensitizing dye prepared according to the present invention may be added directly to the silver halide emulsion,
Water may be used as the diluting solution at this time, although it may be appropriately diluted before addition.

In the case of constituting the light-sensitive material of the present invention, a silver halide emulsion which has been physically ripened and spectrally sensitized is generally used. Additives used in such processes are Research Disclosure No.17643, No.1
8716 and No.308119 (respectively RD17643, RD18
716 and RD308119).

The description is given below.

(Item) (Page of RD308119) (RD17643) (RD18716) Chemical sensitizer 996 III-A item 23 648 Spectral sensitizer 996 IV-A, B, C, 23-24 648-9 D, H , I, J items Supersensitizer 996 IV-AE, J items 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Chemical sensitization of emulsions used in the present invention The feeling is more specifically a sulfur-containing chemical that can react with silver ions, a sulfur sensitizing method using active gelatin, a selenium sensitizing method using a selenium compound, a reduction sensitizing method using a reducing substance, and gold. The noble metal sensitization method using other noble metal compounds can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizing method can be used as the chemical sensitizer, and among them, a sulfur sensitizer and a selenium sensitizer are preferable.

Examples of the sulfur sensitizer include thiosulfate,
Examples thereof include allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, and rhodanine.

Others, US Pat. Nos. 1,574,944 and 2,410,6
89, 2,278,947, 2,728,668, 3,501,313
No. 3,656,955, West German Published Application (OLS) 1,422,869
The sulfur sensitizers described in JP-A Nos. 56-24937 and 55-45016 can also be used.

The addition amount of the sulfur sensitizer varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is about 1 mol per mol of silver halide. It is preferably about 10 ^-7 mol to about 10 ^-1 mol.

As the selenium sensitizer, there may be used aliphatic isocyanates such as allyl isoselenocyanate, selenoureas, selenoselenides, and selenides such as diethyl selenide. Specific examples thereof include US It is described in Japanese Patent Nos. 1,574,944, 1,602,592 and 1,623,499. Further, reduction sensitization can be used together.

Examples of the reducing agent include stannous chloride, thiourea dioxide, hydrazine and polyamine. Further, a noble metal compound other than gold, for example, a palladium compound or the like can be used together.

The silver halide grains of the emulsion used in the present invention preferably contain a gold compound.

The gold compound preferably used in the present invention may have a gold oxidation number of +1 valence or +3 valence, and various kinds of gold compounds are used.

As a typical example, chloroaurate is potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold. Examples include selenide.

The gold compound may be used to sensitize the silver halide grains, or may be used so as not to substantially contribute to the sensitization.

The addition amount of the gold compound varies depending on various conditions, but as a guide, from 10 ^-8 mol per mol of silver halide
It is 10 ^-1 mol, preferably 10 ^-7 mol to 10 ^-2 .

Further, these compounds may be added at any step of silver halide grain formation, physical ripening, chemical ripening and after chemical ripening.

Known photographic additives that can be used in the present invention are also described in the above Research Disclosure.

The following are the relevant locations.

(Item) (Page of RD308119) (RD17643) (RD18716) Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, 25-26 XIII-C Light absorber 1003 VIII 25-26 Light-scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricating oil 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI Developer 1011 XX-B (Contained in photosensitive material) Also, deterioration of photographic performance due to formaldehyde gas In order to prevent it, it is preferable to add to the light-sensitive material a compound capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the above-mentioned Research Disclosure (RD) No. 17643 and VII-C to G. .

Examples of yellow couplers include US Pat. Nos. 3,933,051, 4,022,620, 4,326,024 and 4,4.
01,752, 4,248,961, Japanese Patent Publication No. 58-10739, British Patent 1,425,020, 1,476,760, U.S. Patent 3,973,968
Nos. 4,314,023, 4,511,649 and European Patent 279,473.
Those described in No. A and the like are preferable.

As the magenta coupler, 5-pyrazolone type and pyrazoloazole type compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897, European Patent 73,636, US Pat. (June 1984), JP-A-60-33552
Issue, Research Disclosure No. 24230 (June 1984
Mon), JP-A-60-43659, 61-72238, 60-35730
No. 55-118034, No. 60-185951, U.S. Pat.
No. 0, 4,540,654, 4,556,630, international publication WO88 /
Those described in No. 04795 and the like are particularly preferred.

Examples of cyan couplers include phenol-based and naphthol-based couplers. US Pat. No. 4,052,21
No. 2, No. 4,146,396, No. 4,228,233, No. 4,296,200,
2,369,929, 2,801,171, 2,772,162, 2,8
95,826, 3,772,002, 3,758,308, 4,334,01
1, 4,327,173, West German Patent Publication 3,329,729, European Patent 121,365A, European Patent 249,453A, US Patent 3,446,622
No., No. 4,333,999, No. 4,775,616, No. 4,451,559,
4,427,767, 4,690,889, 4,254,212, 4,2
Those described in 96,199 and JP-A-61-242658 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No. 1
7643, Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
Those described in 9413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368 are preferable. US patent
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,774,181,
It is preferred to use the couplers described in U.S. Pat. No. 4,777,120 which have as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,570.
Those described in Japanese Patent No. 6, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820, 4,080,211 and 4,367.
282, 4,409,320, 4,576,910, British Patent 2,10
2, 173, etc.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention.
The DIR coupler that releases the development inhibitor is RD17 described above.
643, Patents described in Section VII-F, JP-A-57-151944
Nos. 57-154234, 60-184248, 63-37346, and US Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases an engraving agent or a development accelerator imagewise during development, there are described in British Patent 2,097,140.
No. 2,131,188, JP-A-59-157638, and 59-170840.
Those described in the above item are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,427 and 4,338,393.
No. 4,310,618, multi-equivalent coupler, JP-A-60-185950
No. 6, JP-A-62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR
A coupler releasing redox compound, or a DIR redox releasing redox compound, a coupler which releases a dye that recovers color after separation described in European Patent 173,302A, R.I. D.
No. 11449, 24241, bleaching accelerator releasing coupler described in JP-A No. 61-201247, ligand releasing coupler described in U.S. Pat. No. 4,553,477, releasing leuco dye described in JP-A-63-75747 And the couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

Further, various couplers can be used in the present invention, specific examples of which are described in the following RD. The relevant parts are shown below.

(Item) (Page of RD308119) (RD17643) Yellow coupler 1001 VII-D item VII C-G item Magenta coupler 1001 VII-D item VII C-G item Cyan coupler 1001 VII-D item VII C-G item Colored coupler 1002 VII-G section VII G section DIR coupler 1001 VII-F section VII F section BAR coupler 1002 VII-F section Other useful residues Release coupler 1001 VII-F section Additives used in the present invention are RD308119XIV. It can be added by the dispersion method described.

In the present invention, the above-mentioned RD17643, 28th
The supports described on page RD 18716 647-8 and RD 308119 XIX can be used.

The light-sensitive material of the present invention includes the above-mentioned RD308119.
An auxiliary layer such as a filter layer or an intermediate layer described in the section VII-K can be provided.

The outermost surface of the photographic constituent layer of the light-sensitive material of the present invention
The pH is 5.0 to 7.0, preferably 5.5 to 6.5.
It can be measured by the method described in 245153.

Suitable supports which can be used in the present invention are, for example, RD. No. 17643, page 28 and No. 18716, page 647, right column to page 648, left column.

As a concrete support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate film or the like can be used. The thickness of the support is usually 50 to 200 μm.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that it be housed in a cartridge. The most common cartridges are
It is a 135 format Patrone. Other cartridges proposed in the following patents can also be used (Shokai 58-6
7329, JP-A-58-181035, JP-A-58-182634, Shoukai-sho 58
-195236, U.S. Pat.No. 4,221,479, Japanese Patent Application No. 63-57785
No. 63-183344, 63-325638, Japanese Patent Application No. 1-21862
No. 1, No. 1-25362, No. 1-30246, No. 1-20222, No. 1-218
63, 1-37181, 1-333108, 1-85198, 1-1
72595, 1-172594, 1-172593, U.S. Pat.
46,418, 4,848,693, 4,832,275).

Further, the present invention can be applied to Japanese Patent Application No. 4-16934, "Small photographic roll film cartridge and film camera".

To obtain a dye image using the light-sensitive material of the present invention, a generally known color development process can be carried out after exposure.

The light-sensitive material of the present invention is RD17643, 28-2.
Development processing can be carried out by a usual method described in page 9, RD18716, pages 647 and RD308119, XII.

[0136]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the following examples, the addition amount of each component of the silver halide color light-sensitive material is shown by the coating amount expressed in g / m ² . However, for silver halide, the coating amount in terms of silver is shown, and for the sensitizing dye, the coating amount per mol of silver halide in the same layer is shown in mol unit.

Example 1 Sample A, which is a multilayer color light-sensitive material composed of layers having the following compositions, was prepared on a cellulose triacetate film support having an undercoat.

Sample A First layer: Antihalation layer Black colloidal silver 0.15 Ultraviolet absorber (UV-1) 0.30 High boiling point solvent (Oil-1) 0.16 Gelatin 1.64 Second layer: Intermediate layer Gelatin 0.80 Third layer: Low sensitivity Red-sensitive layer Silver iodobromide emulsion (1) 0.29 Silver iodobromide emulsion (3) 0.073 Sensitizing dye (SD-1) 2.6 × 10 ^-5 Sensitizing dye (SD-2) 2.6 × 10 ^-5 Sensitizing Dye (SD-3) 3.1 × 10 ^-4 Sensitizing dye (SD-4) 2.3 × 10 ^-5 Sensitizing dye (SD-5) 2.8 × 10 ^-4 Cyan coupler (C-1) 0.35 Colored cyan coupler (CC -1) 0.065 Compound (GA-1) 2.0 x 10 ^-3 High boiling point solvent (Oil-1) 0.33 Gelatin 0.73 Fourth layer: Medium-sensitive red photosensitive layer Silver iodobromide emulsion (3) 0.26 Sensitizing dye (SD -1) 1.3 × 10 ^-4 sensitizing dye (SD-2) 1.3 × 10 ^-4 sensitizing dye (SD-3) 2.5 × 10 ^-4 sensitizing dye (SD-4) 1.8 × 10 ^-5 cyan coupler (C-1) 0.24 Colored cyan coupler (CC-1) 0.040 DIR compound (D-1) 0.025 Compound (GA-1) 1.0 × 10 ⁻³ High boiling point solvent (Oil-1) 0.30 Gelatin 0.59 Fifth layer: High Sensitive red photosensitive layer Silver iodobromide emulsion (4) 0.56 Sensitizing dye (SD-1) 8.5 × 10 ^-5 Sensitizing dye (SD-2) 9.1 × 10 ^-5 Sensitizing dye (SD-3) 1.7 × 10 ⁻⁴ Sensitizing dye (SD-4) 2.3 × 10 ⁻⁵ Sensitizing dye (SD-6) 1.1 × 10 ⁻⁵ Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.014 DIR compound (D -1) 7.5 x 10
^-3 Compound (GA-1) 1.4 × 10 ^-3 High boiling point solvent (Oil-1) 0.12 Gelatin 0.53 Sixth layer: Intermediate layer Gelatin 1.14 Seventh layer: Low sensitivity green photosensitive layer Silver iodobromide emulsion ( 2) 0.21 Silver iodobromide emulsion (3) 0.49 Sensitizing dye (SD-7) 5.5 × 10 ⁻⁴ Sensitizing dye (SD-1) 5.2 × 10 ⁻⁵ Sensitizing dye (SD-12) 4.8 × 10 ^{− 5} Magenta coupler (M-1) 0.15 Magenta coupler (M-2) 0.37 Colored magenta coupler (CM-1) 0.20 DIR compound (D-2) 0.020 Compound (GA-1) 4.0 × 10 ^-3 High boiling solvent (Oil -2) 0.65 gelatin 1.65 8th layer: high sensitivity green-sensitive layer silver iodobromide emulsion (5) 0.45 sensitizing dye (SD-8) 1.4 × 10 -4 sensitizing dye (SD-9) 1.5 × 10 - ⁴ sensitizing dye (SD-10) 1.4 × 10 -4 sensitizing dye (SD-12) 7.1 × 10 -5 magenta coupler (M-2) 0.065 magenta coupler (M-3) 0.025 Lard magenta coupler (CM-2) 0.025 DIR compound (D-3) 7.0 × 10 -4 Compound (GA-1) 1.8 × 10
^-3 High boiling point solvent (Oil-2) 0.15 Gelatin 0.46 9th layer: Yellow filter layer Yellow colloidal silver 0.10 Compound (SC-1) 0.14 Compound (FS-1) 0.20 High boiling point solvent (Oil-2) 0.18 Gelatin 1.20 Layer 10: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion (2) 0.18 Silver iodobromide emulsion (3) 0.21 Sensitizing dye (SD-11) 5.4 × 10 ^-4 Sensitizing dye (SD-12) 2.0 × 10 ^-4 Yellow coupler (Y-1) 0.62 Yellow coupler (Y-2) 0.31 Compound (GA-1) 4.5 × 10 ^-3 High boiling point solvent (Oil-2) 0.20 Gelatin 1.27 11th layer: High sensitivity blue Photosensitive layer Silver iodobromide emulsion (5) 0.38 Sensitizing dye (SD-11) 2.8 × 10 ^-4 Sensitizing dye (SD-12) 1.1 × 10 ^-4 Yellow coupler (Y-1) 0.10 Compound (GA- 1) 2.0 × 10 ^-3 high boiling solvent (Oil-2) 0.04 gelatin 0.57 12th layer: first protective layer silver iodobromide emulsion (average particle size 0.04μm , A silver iodide content of 4.0 mol%) 0.30 UV absorber (UV-2) 0.03
0 UV absorber (UV-3) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV-5) 0.015 UV absorber (UV-6) 0.10 Compound (FS-1) 0.25 High boiling solvent (Oil- 1) 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin 1.04 13th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid S
u-2, viscosity modifier, hardener H-1, H-2, stabilizer S
T-1, antifoggant AF-1, dye AI-1, AI-
2, two kinds of AF-2 having a molecular weight of 10,000 and 20,000, and a preservative D
I-1 was added.

The emulsions used for the above samples are as follows. The average particle diameter is shown as the particle diameter converted into the diameter of a sphere having the same volume. The above emulsions were optimally subjected to gold and sulfur sensitization.

Emulsion name Average grain size AgI Average grain size Crystal habit Diameter / thickness ratio Content (mol%) (μm) Emulsion (1) 2.0 0.27 Normal crystal tetrahedron 1 Emulsion (2) 2.0 0.30 Normal crystal tetrahedral 1 emulsion (3) 8.0 0.38 twin octahedron 1.5 emulsion (4) 8.0 0.55 twin octahedron 1.5 emulsion (5) 8.0 0.65 twin octahedron 1.5 For emulsions F to N, emulsions (2), (3), It was prepared by adding compounds I-4 and I-21 to (5) as follows.

[0142]

[0143]

[Chemical 19]

[0144]

Embedded image

[0145]

[Chemical 21]

[0146]

[Chemical formula 22]

[0147]

[Chemical formula 23]

[0148]

[Chemical formula 24]

[0149]

[Chemical 25]

[0150]

[Chemical formula 26]

[0151]

[Chemical 27]

(Treatment process) Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780cc Bleach 45 seconds 38 ± 2.0 ℃ 150ml fixation 1 minute 30 seconds 38 ± 2.0 ℃ 830ml stability 60 Second 38 ± 5.0 ℃ 830ml Dry 1 minute 55 ± 5.0 ℃ － * Replenishment amount is the value per 1m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer and color replenisher developer Replenisher Replenisher Water 800cc 800cc Potassium carbonate 30g 35g Sodium hydrogencarbonate 2.5g 3.0g Potassium sulfite 3.0g 5.0g Sodium bromide 1.3g 0.4g Potassium iodide 1.2mg-hydroxylamine sulfate Salt 2.5g 3.1g Sodium chloride 0.6g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0g 3.0g Potassium hydroxide 1.2g 2.0 g Water is added to make 1 liter, and the color developer is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using potassium hydroxide or 20% sulfuric acid.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700cc 700cc 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125g 175g Ethylenediaminetetraacetic acid 2g 2g Sodium nitrate 40g 50g Ammonium bromide 150g 200g Glacial acetic acid 40g 56g Water To 1 liter, and adjust the bleaching solution to pH 4.4 and the replenisher to pH 4.0 using aqueous ammonia or glacial acetic acid.

Further, the emulsions of the 10th and 11th layers were changed to prepare Samples 101 to 107 below. The pH of the outermost surface of the photographic constituent layers of all samples was adjusted to 5.9.

Samples 101 to 107 were each divided into two samples to obtain samples I and II, and the following treatments were performed. Sample I was subjected to wedge exposure according to a conventional method, and immediately subjected to development processing according to the following processing steps. Sample II was exposed to a wedge, left standing for 7 days under the conditions of 30 ° C. and 80% RH, and then subjected to the same development processing. After development, the sensitivity of each sample was evaluated.

Regarding the sensitivity of each sample, the blue sensitivity is the fog density +
Expressed as the reciprocal of the exposure dose giving an optical density of 0.15, Sample 101
It was shown as a relative value with sample I of No. 1 as 100.

[0159] The evaluation results are shown below.

[0160] From the above results, it can be seen that the sample of the present invention is excellent in latent image stability without deteriorating the sensitivity.

Example 2 Sample 10 prepared in Example 1 for evaluating pressure resistance.
For 1 to 107, the change in the density of the pressed portion due to bending was evaluated. Specifically, at the density point where the blue sensitivity becomes the fog density +0.50, the density of the pressed part and the density of the unpressurized part are measured with a microdensitometer, and the density change of the sample is obtained by the following formula, The value in the case of bending, exposing and treating was set as 100, and the relative value was evaluated.

Relative Density of Pressurized Portion (%) = [(Pressurized Portion Density−
The density of unpressurized part) /0.5] × 100 The evaluation results are shown below.

[0163] From the above results, it can be seen that the samples of the present invention have a small change in the concentration of the pressure portion and are excellent in pressure resistance.

Example 3 Sample 101 prepared in Example 1 was used to evaluate stagnation.
Nos. 107 to 107, except that the coating solutions for the 10th and 11th layers were stagnant while stirring at 38 ° C. for 20 hours,
07a was created.

The samples 101 to 107 and 101a to 107a were exposed, developed and processed in the same manner as in Example 1 to evaluate the sensitivity.

Regarding the sensitivity of each sample, the blue sensitivity is the fog density +
Expressed as the reciprocal of the exposure dose that gives an optical density of 2.0, sample 101
The relative value was set to 100.

The evaluation results are shown below.

[0168] From the above results, it is understood that the sample of the present invention does not suffer from the sensitivity decrease due to the stagnant coating liquid.

[0169]

According to the present invention, a silver halide photographic emulsion and a silver halide photographic light-sensitive material which are excellent in latent image stability and stagnation stability and are excellent in pressure resistance without deteriorating photographic performance are provided. be able to.

Claims (11)

[Claims] 1. A silver halide photographic emulsion having a complex aggregate of a compound represented by the following general formula (I). Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ Each represents a substituent, L ₁ and L ₂ each represent a methine group, and Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C (R ₉ ) (R
₁₀₎ - or -N (R ₉₎ - represents a. R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Also, R ₁ and R ₂ , R ₃ and R ₄ ,
R ₅ and R ₆ , R ₇ and R ₈ , and R ₉ and R ₁₀ may be bonded to each other to form a ring. ) 2. A silver halide photographic emulsion containing compounds represented by the following general formulas (II) and (III). Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ represent Each represents a substituent, L ₁ and L ₂ each represent a methine group, Z ₂ represents a sulfur atom, a selenium atom, or a tellurium atom, and R ₁ and R ₂ or R ₃
And R ₄ , R ₅ and R ₆ , R ₇ and R ₈ may be bonded to form a ring. ) [Chemical 3] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ represent Each represents a substituent, L ₁ and L ₂ each represent a methine group, Z ₃ represents an oxygen atom, —C (R ₉ ) (R ₁₀ ) — or —N (R ₉ ) —, R ₉ and R ₁₀
Each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , and R ₉ and R ₁₀ may be bonded to each other to form a ring. ) 3. A silver halide photographic emulsion containing the compounds represented by the general formulas (II) and (III), wherein Z ₂ in the formula is a sulfur atom and Z ₃ is an oxygen atom. The silver halide photographic emulsion according to claim 2. 4. A silver halide photographic light-sensitive material containing the silver halide photographic emulsion according to claim 1, 2. 5. A silver halide photographic light-sensitive material containing the compound represented by the general formula (II) and the compound represented by the general formula (III). 6. The silver halide photographic light-sensitive material comprises two or more layers having the same color sensitivity but different sensitivities, and the highest sensitivity layer contains the silver halide photographic emulsion according to claim 1, 2. Silver halide photographic light-sensitive material. 7. A silver halide photographic light-sensitive material having a layer containing a compound represented by the general formula (II) and a layer containing a compound represented by the general formula (III). 8. The silver halide photographic light-sensitive material is composed of two or more layers having the same color sensitivity but different sensitivities, wherein the highest sensitivity layer contains the compound of the general formula (II) and the lowest sensitivity layer comprises the general formula The silver halide photographic light-sensitive material according to claim 7, which contains the compound (III). 9. The halogenated composition according to claim 5, which comprises a silver halide photographic emulsion containing a compound of general formula (II) and a silver halide photographic emulsion containing a compound of general formula (III) in the same layer. Silver photographic light-sensitive material. 10. The silver halide photographic light-sensitive material according to claim 9, wherein the same layer is the highest sensitivity layer. 11. A silver halide photographic light-sensitive material according to claim 4, which has a photographic constituent layer comprising a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer and a non-photosensitive layer on a support. .