JP2001324773A - Silver halide photographic emulsion and silver halide photographic sensitive material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion which suppresses a change of fog due to oxygen in storage without impairing sensitivity and a silver halide photographic sensitive material containing the emulsion. SOLUTION: The silver halide photographic emulsion is prepared in the presence of at least one oxo acid salt of halogen represented by the formula M(XOn)m (where M is an alkali metal ion or an alkaline earth metal ion; X is a halogen atom; (n) is 2 or 3; and (m) is 1 or 2).

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. The present invention particularly relates to a silver halide photographic emulsion containing silver halide grains improved in deterioration by oxygen, and a silver halide photographic light-sensitive material containing the same.

[0002]

2. Description of the Related Art In silver halide photographic emulsions, sensitivity /
Improving granularity is the most important issue. The use of tabular grains to increase the light absorption efficiency as a method of improving the sensitivity / granularity ratio of silver halide photographic emulsions is disclosed in U.S. Pat.
No. 6,269, for example. In such tabular grains, the sensitivity can be improved by increasing the aspect ratio and increasing the spectral sensitizing dye. As a method for further increasing the quantum sensitivity, a reduction sensitization method is known.

[0003] However, improving the sensitivity often impairs the resistance of the photosensitive material to deterioration during storage. In particular, it is known that oxygen is involved in the increase in fog during storage. Wanted.

[0004] As a method of improving the fog increase caused by oxygen,
A method using oxygen or a radical scavenger for inactivating organic radicals in a photosensitive material generated by oxygen is described in, for example, phenolic compounds described in JP-A-7-72599, JP-A-8-76311 and US Pat. No. 5,719,007. And the like. General formulas (AI) to (A-III) described in JP-A-10-10668, general formula (S2) described in JP-A-11-15102, and general formula (S1) described in JP-A-11-15102. No. 10-90819 discloses a hydroxyamine compound represented by the general formula (S1) and the like.

The present invention intends to remove fine silver nuclei on the surface or inside of the emulsion grains, which are presumed to be the cause of fogging caused by oxygen, in advance by using an oxidizing agent.

JP-A-9-96883, 11-153
No. 840 discloses a method for producing tabular grains in the presence of an oxidizing agent for silver, but nothing can be predicted with respect to the reduction of fogging by the halogen oxo acid salt of the present invention. JP-B-52-14625 discloses a method of intensifying a dye image in the presence of chlorite, but does not disclose any method used in the production of an emulsion as in the present invention.

The present inventors have assiduously studied means for maintaining the improvement in sensitivity and suppressing an increase in fog due to oxygen.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion in which fog change due to oxygen during storage is remarkably improved without impairing sensitivity, and a silver halide photographic light-sensitive material containing the same. It is assumed that.

[0009]

The object of the present invention has been attained by the following silver halide emulsion and silver halide photographic material using the same.

(1) A silver halide photographic emulsion produced in the presence of at least one halogen oxoacid salt represented by the following general formula (I). In the general formula _{(I) M (XO n)} m formula, M represents an alkali metal ion or alkaline earth metal ion, X represents a halogen atom, n represents 2 or 3, m represents 1 or 2 .

(2) The silver halide photographic emulsion according to the above (1), wherein the halogen oxo acid salt is a chlorite.

(3) The silver halide photographic emulsion is
The parallel main plane is the (111) plane, and the aspect ratio is 5
The tabular silver halide grains described above were subjected to 50 times the total projected area.
% Or more of the above (1) or (2).
The photographic silver halide emulsion described in 1 above.

(4) The silver halide photographic emulsion of the above (1) or (3) comprises (a) thiourea dioxide, (b) hydroxyamines and derivatives thereof, and (c) dihydroxybenzenes and derivatives thereof. A silver halide photographic emulsion characterized by being reduction sensitized with at least one selected reducing agent.

(5) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer may be provided with the above (1) to (4).
A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion of any one of the above.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The oxoacid salt of a halogen represented by the general formula (I) of the present invention will be described in detail.

The halogen atom represented by X is preferably chlorine, bromine or iodine, more preferably chlorine. As the oxoacid salt of halogen, chlorite, bromate and iodate are preferred, and chlorite is most preferred.

The alkali metal ion or alkaline earth metal ion represented by M is preferably a potassium ion, a sodium ion, a magnesium ion, or a calcium ion, and more preferably a sodium ion.

Specific examples of the halogen oxoacid salt of the present invention include, but are not limited to, sodium chlorite, potassium chlorite, potassium iodate, sodium bromate and the like.

The oxoacid salt of halogen of the present invention can be used in any of the steps for producing silver halide grain emulsions, and can be used in a plurality of steps. During the formation of silver halide grains, the oxoacid salt of halogen
It is preferable to add the compound after the formation of the particles before the start of the desalting step, before the desalting step, before the start of chemical ripening, and in at least one of the chemical ripening steps. More preferably, it is added during the grain formation, before the start of chemical ripening, during the chemical ripening step, and at least one of after the chemical ripening.
In the case where a silver halide emulsion is subjected to reduction sensitization using a reducing agent as described later, it is preferable to add a halogen oxoacid salt. It is not preferable to add it when preparing a coating solution using a silver halide emulsion which has undergone the chemical ripening step after grain formation, since the effects of the present invention are impaired.

The concentration of the halogen oxoacid salt used in the step of use is 1 × 1 with respect to 1 mol of silver halide.
It is preferably present in an amount of from 0 ^-6 to 1 × 10 ^-3 mol, and 5 × 1
More preferably, it is present in an amount of 0 ^{-6 to} 2 × 10 ^-4 mol. Two or more halogen oxoacid salts of the present invention may be used in combination.

The oxoacid salt of halogen of the present invention is preferably added in the form of an aqueous solution or an aqueous gelatin solution. When used in an aqueous solution, it is preferable to adjust the pH with a known buffer or the like. The pH is preferably from 6 to 10, more preferably from 7 to 9.5.

The silver halide emulsion of the present invention will be described in detail. The shape of the grains contained in the silver halide emulsion of the present invention is cubic, octahedral, those having regular crystals such as tetradecahedron, spherical, irregular crystals such as tabular. One having a crystal defect such as a twin plane, or a composite form thereof. In particular, tabular grains are more preferable.

In the emulsion of the present invention, 50% or more of the total projected area is preferably occupied by tabular grains having an aspect ratio of 5 or more (hereinafter, emulsions satisfying such requirements are also referred to as "tabular grain emulsions"). . Here, the projected area and the aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method shadowed with a latex sphere for reference. When viewed from a direction perpendicular to the main plane, the tabular grains usually have a hexagonal, triangular or circular shape, but have a diameter (circle equivalent diameter) corresponding to a circle having an area equal to the projected area. The value divided by the thickness is the aspect ratio. The shape of the tabular grains is preferably as high as the ratio of hexagons, and the ratio of the lengths of adjacent sides of the hexagons is preferably 1: 2 or less.

In the effect of the present invention, the higher the aspect ratio, the better the photographic performance can be obtained. Therefore, the emulsion of the present invention more preferably has an aspect ratio of at least 50% of the total projected area.
Occupied by the above particles, and more preferably an aspect ratio of 1
2 or more. If the aspect ratio is too large, the variation coefficient of the particle size distribution tends to increase, so that the aspect ratio is usually preferably 50 or less.

The average grain diameter of the silver halide grains contained in the emulsion of the present invention is 0.2 to 1 as an average circle equivalent diameter.
0.0 μm, preferably 0.5 to 5.0 μm
Is more preferable. The equivalent circle diameter is the diameter of a circle having an area equal to the projected area of the parallel main plane of the particle. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification. Moreover, it is preferable that it is 0.1-5.0 micrometers in average sphere equivalent diameter, and it is more preferable that it is 0.6-2.0 micrometers. These ranges have the best sensitivity / granularity ratio for photographic emulsions. In the case of tabular grains, the average thickness is preferably 0.05 to 1.0 μm. Here, the average circle equivalent diameter is defined as 1 sample arbitrarily collected from a uniform emulsion.
It means the average value of the equivalent circle diameter of 000 or more particles. The same applies to the average thickness. The silver halide grains contained in the emulsion of the present invention may have a monodisperse or polydisperse grain size distribution, but are preferably monodisperse.

The tabular grains preferably comprise an opposing (111) main plane and side faces connecting the main planes. It is preferable that at least one twin plane exists between the main planes. Preferably, two twin planes are usually observed in the tabular grains used in the present invention. The distance between the two twin planes can be less than 0.012 μm as described in US Pat. No. 5,219,720. Further, as described in JP-A-5-249585, (111)
A value obtained by dividing the distance between the main planes by the twin plane spacing may be 15 or more.

In the present invention, opposing tabular grains (11
1) 75% or less of the side surfaces connecting the main planes are (1)
11) It is extremely preferable to be composed of planes. Here, that 75% or less of all the side surfaces are composed of the (111) plane means that one tabular grain has a crystallographic plane other than the (111) plane at a ratio higher than 25% of the whole side surface. That's what it means. Usually, the plane can be understood as the (100) plane, but other planes, that is, the (110) plane
Planes and higher index planes. In the present invention, the effect is remarkable when 70% or less of all side surfaces are constituted by (111) planes.

Whether or not 70% or less of all side surfaces are composed of (111) planes can be easily determined from electron micrographs of the tabular grains obtained by shadowing the carbon replica method. Usually, when 75% or more of the side surfaces are composed of (111) planes, (1)
11) The six side surfaces directly connected to the main plane are connected to each other at an acute angle and an obtuse angle with respect to the (111) main plane. On the other hand, when 70% or less of all side surfaces are composed of (111) planes, in hexagonal tabular grains, all six side surfaces directly connected to the (111) main plane are obtuse angles to the (111) main plane. Connect with. By applying shadowing at an angle of 50 ° or less, the obtuse angle and the acute angle of the side surface with respect to the main plane can be determined. Preferably, shadowing at an angle of 30 ° or less and 10 ° or more facilitates determination of an obtuse angle and an acute angle. Furthermore, a method using adsorption of a sensitizing dye is effective as a method for obtaining the ratio between the (111) plane and the (100) plane. Using the method described in The Chemical Society of Japan, 1984, vol. 6, pages 942-947 (11)
The ratio between the 1) plane and the (100) plane can be quantitatively determined. The ratio of the (111) plane on all side surfaces can be calculated and obtained using the ratio and the above-described circle equivalent diameter and thickness of the tabular grains. In this case, it is assumed that the tabular grain is a cylinder using the equivalent circle diameter and thickness. With this assumption, the ratio of the side surface to the total surface area can be determined.
The value obtained by dividing the ratio of the (100) plane obtained by the above-described adsorption of the sensitizing dye by the ratio of the above-described side surface and multiplying by 100 is the ratio of the (100) surface in all the side surfaces. By subtracting the value from 100, the ratio of the (111) plane on all side surfaces can be obtained. In the present invention, (1)
11) It is more preferable that the ratio of the surface is 65% or less.

In the present invention, 75% of all sides of tabular grains
A method for setting the (111) plane below will be described. Most commonly, the ratio of the (111) face of the side face of the silver iodobromide or silver chloroiodobromide tabular grains is determined by the pBr at the time of preparing the tabular grain emulsion.
Can be determined. Here, pBr is the logarithm of the reciprocal of the Br ^- ion concentration of the system. Assuming that the total silver content of the tabular grain emulsion is 100, the ratio of the (111) faces on the side faces decreases, that is, the proportion of the (100) faces on the side faces increases, preferably after at least 70% of the total silver content has been added. PBr like
Set to. Most preferably at least 90% of the total silver
The pBr is set so that the ratio of the (100) side surface increases after the above addition.

Prior to the addition of 70% of the total silver amount, the pBr such that the ratio of the (100) side faces increases.
Is not preferred because the aspect ratio of tabular grains is reduced. Further, the p ratio is such that the ratio of the (100) side surface increases after 98% or more of the total silver is added.
When it is set to Br, it is difficult to achieve the (100) face ratio of the side face for obtaining the effect of the present invention. Therefore, it is most preferable that the ratio of the (100) side surface is increased after at least 90% or more of the total silver is added and before 98% or less of the total silver is added.
When it is set to Br, the effect of the invention can be remarkably obtained. However, as another method, it is also possible to increase the ratio by setting the pBr such that the ratio of the (100) side surface increases after the total silver amount is added and then ripening.

The pBr such that the ratio of the (100) side surface increases is defined as the temperature of the system, the pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, the type, and the like.
Its value can vary widely depending on the concentration and the like. Usually, it is preferably pBr 2.0 or more and 5 or less. More preferably, it is pBr2.5 or more and 4.5 or less. However,
As described above, the value of pBr can be easily changed by the presence of, for example, a silver halide solvent. Preferably, no silver halide solvent is used in the present invention.

Examples of the silver halide solvent usable in the present invention include US Pat. Nos. 3,271,157, 3,531,289 and 3,574,628, and JP-A-54-1019. (A) Organic thioethers described in JP-A-53-824 and JP-A-54-158917.
(B) thiourea derivatives described in JP-A Nos. 08-55-77737 and 55-2982;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-4319, (d) imidazoles described in JP-A-54-100717, e) ammonia, (f) thiocyanate and the like.

Particularly preferred solvents include thiocyanate, ammonia and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferred amount is
It is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol.

As a method for changing the plane index of the side surface of the tabular grain emulsion, European Patent No. 515894 A1 can be referred to. Further, polyalkylene oxide compounds described in U.S. Pat. No. 5,252,453 can also be used. An effective method is disclosed in US Pat. No. 4,680,2.
54, 4,680,255, 4,680,256 and 4,684,607 can be used. Ordinary photographic spectral sensitizing dyes can also be used as modifiers having the same plane index as described above.

In the present invention, it can be prepared by various methods as long as the above requirements are satisfied. The preparation of a tabular grain emulsion usually comprises basically three steps of nucleation, ripening and growth. No. 4,713,320 and U.S. Pat.
Use of gelatin having a low methionine content described in JP-A-2,120, and high pB described in JP-A-4,914,014.
Performing nucleation with r and performing nucleation in a short time described in JP-A-2-222940 are extremely effective in the nucleation step of the tabular grain emulsion used in the present invention. In the aging step, US Pat.
Performing in the presence of a low-concentration base described in JP-A No. 6-64, and carrying out at a high pH described in JP-A No. 5,013,641 may be effective in the ripening step of the tabular grain emulsion used in the present invention. In the growth step, the growth is performed at a low temperature as described in US Pat. No. 5,248,587, US Pat. Nos. 4,672,027 and 4,693,9.
Use of the silver iodide fine grains described in No. 64 is particularly effective in the growth step of the tabular grain emulsion used in the present invention. Further, it is also preferable to use a silver bromide, silver iodobromide, silver chloroiodobromide fine grain emulsion to be added and ripened for growth. The fine grain emulsion can be supplied by using a stirring device described in JP-A-10-43570.

The emulsion used in the present invention preferably introduces a hole-capturing silver nucleus by intentional reduction sensitization. The intentional reduction sensitization means reduction sensitization performed by adding a reduction sensitizer. The hole-capturing silver nucleus means a small silver nucleus having a small developing activity, and the silver nucleus can prevent recombination loss in a photosensitive process and increase sensitivity. The method of introducing hole-capturing silver nuclei can be achieved by intentionally performing reduction sensitization in the grain formation of the silver halide emulsion.

Stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, thiourea dioxide, silane compounds, borane compounds, dihydroxybenzenes and their derivatives, hydroxyamines and their derivatives as reduction sensitizers Etc. are effective.
These reduction sensitizers can be selected for use in the reduction sensitization used in the present invention, and two or more compounds can be used in combination. Preferred reduction sensitizers in the present invention are thiourea dioxide, hydroxyamines and derivatives thereof, and dihydroxybenzenes and derivatives thereof. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount.
The range of ^0-7 to ^10-3 mol is suitable. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides, and added during grain growth.

In the present invention, a hole-capturing silver nucleus is preferably formed by adding a reduction sensitizer after 50% of the total silver amount required for grain formation is added. More preferably, a hole-capturing silver nucleus is formed by adding a reduction sensitizer after adding 70% of the total silver amount required for grain formation. It is also possible in the present invention to add a reduction sensitizer after the completion of grain formation to introduce hole-capturing silver nuclei on the grain surface.

When a reduction sensitizer is added during grain formation, some of the formed silver nuclei can remain inside the grains, but partly exude to form silver nuclei on the grain surfaces. In the present invention, it is preferable to use the exuded silver nuclei as hole-capturing silver nuclei.

Preferred dihydroxybenzenes and their derivatives as reduction sensitizers are represented by the compound of the formula (V-1) and / or the formula (V-2).

[0041]

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In the general formulas (V-1) and (V-2), W ₅₁ and W ₅₂ each independently represent a sulfo group or a hydrogen atom. However, at least one of W ₅₁ and W ₅₂ represents a sulfo group. The sulfo group is generally an alkali metal salt such as sodium or potassium, or a water-soluble salt such as an ammonium salt. Specific preferred compounds are 4,5-
Disodium dihydroxybenzene-1,3-disulfonate, 4-sulfocatecholammonium salt, 2,3-
Dihydroxy-7-sulfonaphthalene sodium salt,
2,3-Dihydroxy-6,7-disulfonaphthalene potassium salt and the like. The most preferred compounds are 4,5
-Disodium dihydroxybenzene-1,3-disulfonate. The preferred addition amount is the temperature of the system to be added, p
It may vary depending on the type and concentration of the protective colloid agent such as Br, pH and gelatin, the presence or absence of the silver halide solvent, the type and concentration, etc., but is generally 0.000.00 per mol of silver halide.
From 05 mol to 0.5 mol, more preferably from 0.003 mol to 0.05 mol is used.

Hydroxyamines and their derivatives which are preferable as the reduction sensitizer are represented by the general formula (A).

Formula (A) Ra-N (Rb) OH wherein Ra is an alkyl group, an alkenyl group, an aryl group,
Represents an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a heterocyclic group, and Rb represents a hydrogen atom or a group represented by Ra.

Ra 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,
Examples include a halogen atom, a cyano group, a nitro group, a sulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, and a hydroxyamino group. Ra is preferably a heterocyclic group, for example, 1,3,5-triazin-2-yl, 1,2,4
-Triazin-3-yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, thiazolyl, oxazolyl, 1,2,4-triazol-3-yl, benzimidazol-2-yl, benzothiazolyl, benzoxa Represents zolyl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl.

Rb is preferably a hydrogen atom or an alkyl group,
A hydrogen atom and a methyl group are more preferred.

Specific examples of the compound represented by the general formula (A) include the following RS-I to RS-X.

[0048]

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The emulsion of the present invention is preferably silver iodobromide, silver iodochloride, silver bromochloride or silver iodochlorobromide. More preferably, it is composed of silver iodobromide or silver iodochlorobromide. Silver iodochlorobromide may contain silver chloride, but preferably has a silver chloride content of 8 mol% or less, more preferably 3 mol% or less or 0 mol%. Regarding the silver iodide content, the coefficient of variation of the grain size distribution is preferably 25% or less, and thus the silver iodide content is preferably 20 mol% or less. By reducing the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion can be easily reduced. In particular, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less. Regardless of the silver iodide content, the coefficient of variation of the silver iodide content distribution between grains is preferably 20% or less, particularly preferably 10% or less.

The emulsion of the present invention preferably has a structure within the grains with respect to the silver iodide distribution. In this case, the structure of the silver iodide distribution may be a double structure, a triple structure, a quadruple structure, or even a higher structure.

The silver iodide content on the grain surface of the emulsion used in the present invention is preferably 10 mol% or less.
More preferably, it is at most mol%. The silver iodide content on the grain surface specified in the present invention is XPS (X-ray).
Photoelectron Spectrosco
py). Regarding the principle of the XPS method used for analyzing the silver iodide content near the surface of a silver halide grain, see Aihara et al., “Electron spectroscopy” (Kyoritsu library 1).
6, Kyoritsu Shuppan, published in 1978). The standard method of measuring XPS is to use Mg as excited X-rays.
Using -Kα, the intensity of photoelectrons (usually I-3d5 / 2, Ag-3d5 / 2) of iodine (I) and silver (Ag) emitted from silver halide in an appropriate sample form is observed. Is the way. In order to determine the iodine content, iodine (I) and silver (A) were obtained using several types of standard samples whose iodine content was known.
A calibration curve of the intensity ratio (intensity (I) / intensity (Ag)) of the photoelectrons in g) is prepared, and the calibration curve can be obtained from this calibration curve. In a silver halide emulsion, XPS must be measured after gelatin adsorbed on the surface of silver halide grains is decomposed and removed by a protease or the like. The tabular grain emulsion having a silver iodide content of 5 mol% or less on the grain surface used in the present invention is one in which the emulsion grains contained in one emulsion have a silver iodide content of 5 mol% or less when analyzed by XPS. Point out. In this case, when two or more types of emulsions are clearly mixed, it is necessary to perform an appropriate pretreatment such as a centrifugal separation method or a filtration method and then analyze the same type of emulsion.

The structure of the emulsion of the present invention is preferably a triple structure grain composed of, for example, silver bromide / silver iodobromide / silver bromide, or a higher-order structure thereof. The boundary of the silver iodide content between the structures may be clear or may be continuously and gradually changing. Normally, the measurement of the silver iodide content using the powder X-ray diffraction method does not show two distinct peaks having different silver iodide contents, and the skirt is shifted toward the high silver iodide content. Such an X-ray diffraction profile is shown.

In the present invention, the silver iodide content of the inner phase is preferably higher than the silver iodide content of the surface. The silver iodide content of the inner phase is preferably at least 5 mol%, more preferably at least 7 mol%, higher than the silver iodide content of the surface.

The emulsion grains of the present invention are preferably subjected to spectral sensitization with a known cyanine dye. The cyanine sensitizing dye may be added at any stage of the emulsion production process, but it is preferable that the cyanine dye is added at or before chemical sensitization and spectrally sensitized.

Examples of the cyanine dye useful in the present invention include a dye represented by the following general formula (II).

[0056]

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Z ₁ and Z ₂ each independently represent an atom group necessary for forming a heterocyclic nucleus usually used for a cyanine dye.
For example, thiazole, thiazoline, benzothiazole,
Naphthocyanazole, xazole, oxazoline, benzoxazole, naphthoxazole, tetrazole, pyridine, quinoline, imidazoline, imidazole, benzimidazole, naphthimidazole, selenazoline,
Selenazole, benzoselenazole, naphthoselenazole or indolenine and the like can be mentioned. These heterocyclic nuclei include, for example, lower alkyl groups such as methyl, halogen atoms, phenyl groups, hydroxyl groups,
May be substituted by an alkoxy group, carboxyl group, alkoxycarbonyl group, alkylsulfamoyl group, alkylcarbamoyl group, acetyl group, acetoxy group, cyano group, trichloromethyl group, trifluoromethyl group, or nitro group.

L ₁ and L ₂ each independently represent an unsubstituted methine group or a substituted methine group. Examples of the substituted methine group include a lower alkyl group such as methyl and ethyl, and a methine group substituted by phenyl, substituted phenyl, methoxy, and ethoxy. When L ₁ and L ₂ are both substituted methine groups, these substituents can be bonded to each other to form a ring.

R ₁ and R ₂ are each independently an alkyl group having 1 to 5 carbon atoms; a substituted alkyl group having a carboxy group: for example, carboxymethyl, 3-carboxybutyl; a substituted alkyl group having a sulfo group: for example, , Β-sulfoethyl, γ-sulfopropyl, δ-sulfobutyl, γ-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-
[2- (3-sulfopropoxy) ethoxy] ethyl, 2
Represents a substituted alkyl group having a sulfo group such as -hydroxysulfopropyl, an allyl group, and other substituted alkyl groups commonly used for N-substituents of cyanine dyes. X ₁ ^- represents an acid anion group, for example iodide, bromide, p- toluenesulfonate ion,
Represents perchlorate ion. n ₁ represents 1 or 2,
When taking a betaine structure, n ₁ is 1. m ₁ is 1, 2
Or 3 is represented.

Representative compounds of effective spectral sensitizing dyes usable in the present invention are shown below, but the present invention is not limited to these compounds.

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These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862 and 4,026,707, British Patent Nos. 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-5
Nos. 2-110618 and 52-109925.

In the present invention, two or more kinds of cyanine dyes selected from the cyanine dyes represented by the general formula (II) may be added. The cyanine dye represented by the general formula (II) of the present invention is more preferably a monomethine cyanine dye.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4225666, spectral sensitization may be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of the sensitizing dye added to the silver halide grains used in the present invention is 5 × / mol of silver halide.
It is preferably used in an amount of 10 ^-4 mol or more, and when the average silver halide particle diameter is 1.0 to 3.0 μm, about 2 × 10 ^{-4 to} 5
× 10 ^-3 mol is more effective.

The emulsion of the present invention is preferably produced in the presence of a water-soluble radical scavenger. The radical scavenger in the present invention, measuring the time variation of the absorbance at a 2.5Mmoldm ^-3 ethanol solution of 0.05Mmoldm ^-3 ethanol solution and the test compound of galvinoxyl under 25 ° C., were mixed by stopped-flow method 430nm And substantially decolorize galvinoxyl (4
It is a compound that reduces the absorbance at 30 nm) (If the compound does not dissolve at the above concentration, it may be measured at a lower concentration.)

The radical scavenging rate of the radical scavenger which can be used in the present invention is a rate constant of decolorization of galvinoxyl determined by the method described above. Preferably the radical scavenging rate to have radical scavengers, 0.01mmols ^-1 dm ³ or more, more preferably 0.1~10mmols ^-1 dm ^3. A method for determining the rate of radical scavenging using galvinoxyl is described in Micr
ochemical Journal 31, 18-21 (1985)
Regarding the stopped flow method, for example,
Vol. No. 6 (1970), paragraph 321.

The water solubility of the radical scavenger is represented by a partition coefficient in an n-octanol / water system defined by the following formula: logP = log [(Rs) octanol / (Rs) water].

In the above formula, (Rs) is the radical scavenger concentration, and (Rs) octanol and (Rs) water represent the concentrations in n-octanol and water, respectively. Being water-soluble means that the logP value is smaller than 1. The partition coefficient was determined according to the Journal of Medicinal Chemitry, Vol.
18, No. 9, 865-868 (1975).

The radical scavenger used in the present invention is, for example, a phenolic compound described in JP-A-7-72599 or the like, and a general formula (AI) described in JP-A-8-76311 or US Pat. No. 5,719,007. ) To (A-III), general formula (S2) described in JP-A-10-10668, general formula (S1) described in JP-A-11-15102, and general formula (S) described in JP-A-10-90819. Among the hydroxyamine-based compounds represented by S1) and the like, water-soluble compounds can be mentioned.

Specific examples of the water-soluble radical scavenger are shown below, but are not limited thereto.

[0083]

Embedded image

The water-soluble radical scavenger is preferably added at the time of preparing an emulsion, and can be added at any time during the process. For example, the step of forming a silver halide grain, the step of desalting, Before the start of the step, desalting step, before the start of chemical ripening, the step of chemical ripening, the step before preparation of the finished emulsion, and the like. Further, it can be added in plural times during these steps. Preferably, it is added before, during or after chemical sensitization.

The preferred amount of the water-soluble radical scavenger to be added largely depends on the above-mentioned addition method and the kind of the compound to be added.
From 5 × 10 ^-6 mol to 0.5 mol, more preferably from 1 × 10 ^-5 mol to 0.005 mol per mol is used.
If the amount is larger than the above amount, adverse effects such as an increase in fog are undesirably exhibited. Two or more radical scavengers may be used in combination.

The radical scavenger may be added by dissolving in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof, or may be added by emulsification and dispersion. In the case of dissolving in water, if the solubility is increased by increasing or decreasing the pH, it may be dissolved by increasing or decreasing the pH, and then added, or a surfactant may be allowed to coexist.

In the present invention, tabular grains preferably have dislocation lines. Dislocation lines of tabular grains are described, for example, in J. Am. F. H
amilton, Photo. Sci. Eng. , 11,
57, (1967); Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
(1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines is preferably 10 or more on average per grain. More preferably, an average of 20 per particle
More than a book. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more.

Dislocation lines can be introduced, for example, near the outer periphery of tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but may not be a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The direction of the dislocation lines is approximately (211) crystallographically, but often meanders, and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, in the case of a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only near six vertices, or dislocation lines may be limited only near one of the vertices. Conversely, it is also possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

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

As described above, the position of the dislocation line may be limited to the outer periphery, the main plane, or a local position, or may be formed by combining these.
That is, they may be present simultaneously on the outer periphery and on the main plane.

In the present invention, dislocation lines are most preferably formed by adding a sparingly soluble silver halide emulsion to the above-mentioned silver bromide, silver chlorobromide, silver chloroiodobromide or silver iodobromide tabular grain emulsion. Introduce. Here, the sparingly soluble silver halide emulsion means that it is more sparingly soluble than a tabular grain emulsion in a halogen composition, and is preferably a silver iodide fine grain emulsion.

In the present invention, dislocation lines are preferably introduced by rapidly adding a silver iodide fine grain emulsion to the above-described tabular grain emulsion. This step is essentially composed of two steps: a step of rapidly adding a silver iodide fine grain emulsion to a tabular grain emulsion, and a step of growing silver bromide or silver iodobromide to introduce dislocation lines. is there. These two steps may be performed completely separately, or each may be performed at the same time with repetition. It is preferably performed separately. The step of rapidly adding a silver iodide fine grain emulsion to the first tabular grain emulsion will be described.

The rapid addition of the silver iodide fine grain emulsion means that:
Preferably, the silver iodide fine grain emulsion is added within 10 minutes. More preferably, it is added within 7 minutes. These conditions can vary depending on the temperature of the system to be added, pBr, pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, the type and the concentration, etc., but the shorter is preferable as described above. It is preferable that the addition of an aqueous solution of silver salt such as silver nitrate is not substantially performed during the addition.
The temperature of the system at the time of addition is preferably from 40 ° C to 90 ° C,
A temperature of 50 ° C or higher and 80 ° C or lower is particularly preferred. There is no particular limitation on pBr when the silver iodide fine grain emulsion is added.

The silver iodide fine grain emulsion only needs to be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. Silver iodide has β-form and γ-form in its crystal structure.
And α-isomer or α-isomer-like structure as described in US Pat. No. 4,672,026. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before addition as described in US Pat. No. 5,004,679 or may be subjected to a usual washing step, but is preferably used in the present invention. Is used after a normal washing step. The silver iodide fine grain emulsion is described in US Pat.
It can be easily formed by the method described in No. 26 or the like. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the grains are formed while the pI value during grain formation is kept constant, is preferred. Where pI is the logarithm of the reciprocal of the I ^- ion concentration of the system. Temperature, pI, pH, kind of protective colloid agent such as gelatin,
There is no particular limitation on the concentration, the presence or absence of the silver halide solvent, the type, the concentration, etc., but the grain size is preferably 0.1 μm or less, more preferably 0.08 μm or less, in the present invention. Although the particle shape cannot be completely specified because of the fine particles, the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when the content is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing silver iodide fine grains on a mesh for observation with an electron microscope and observing them directly by a transmission method instead of a carbon replica method. This is because the observation error by the carbon replica method becomes large due to the small particle size.
Particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined using the same projected area circle diameter. The most effective silver iodide fine grains in the present invention have a grain size of 0.07 μm.
And 0.02 μm or more, and the variation coefficient of the particle size distribution is 18% or less.

The silver iodide fine grain emulsion is preferably subjected to usual washing with water, adjustment of the concentration of a protective colloid agent such as pH, pI, gelatin and the like described in US Pat. The density adjustment is performed. pH
Is preferably 5 or more and 7 or less. The pI value is preferably set to a pI value at which the solubility of silver iodide is at a minimum or a pI value higher than that value. As the protective colloid, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It is sometimes convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The amount of silver in terms of silver atoms per kg of the emulsion is preferably from 10 g to 100 g. More preferably 20 g or more and 80 g
It is as follows. The amount of gelatin and / or silver is preferably selected to a value suitable for rapidly adding a silver iodide fine grain emulsion.

The addition amount of the silver iodide fine grain emulsion is preferably from 1 mol% to 10 mol% in terms of silver amount relative to the tabular grain emulsion. Most preferably, it is 2 mol% or more and 7 mol% or less. By selecting this addition amount, dislocation lines are preferably introduced, and the effect of the invention becomes remarkable. The silver iodide fine grain emulsion is usually dissolved and added beforehand, but at the time of addition, it is necessary to sufficiently increase the stirring efficiency of the system. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of foam during stirring. Specifically, an antifoaming agent described in Examples of US Pat. No. 5,275,929 is used.

After the silver iodide fine grain emulsion is rapidly added to the tabular grain emulsion, silver bromide or silver iodobromide is grown to introduce dislocation lines. The growth of silver bromide or silver iodobromide may be started before or simultaneously with the addition of the silver iodide fine grain emulsion, but preferably after the addition of the silver iodide fine grain emulsion, the growth of silver bromide or silver iodobromide is started. Start growing. The time from the addition of the silver iodide fine grain emulsion to the start of the growth of silver bromide or silver iodobromide is preferably within 10 minutes and 1 second or more. More preferably, it is 3 seconds or more within 5 minutes. More preferably, it is within one minute. This time interval is preferably as short as possible, but preferably before the start of silver bromide or silver iodobromide growth.

The growth after the addition of the silver iodide fine grain emulsion is preferably silver bromide. In the case of silver iodobromide, the silver iodide content is preferably within 3 mol% with respect to the layer. The amount of silver in the layer grown after the addition of the silver iodide fine grain emulsion is preferably 5 to 100 when the total silver content of the finished tabular grain emulsion is 100.
Not less than 50. Most preferably, it is 10 or more and 30 or less. Temperature, pH and pBr for forming this layer
Is not particularly limited, but the temperature is 40 ° C to 90 ° C, pH is
Is usually 2 or more and 9 or less. More preferably 50
The temperature ranges from 3 ° C to 80 ° C, and the pH ranges from 3 to 7.
Regarding pBr, in the present invention, it is preferable that pBr at the end of the formation of the layer be higher than pBr at the beginning of the formation of the layer. Preferably, pBr at the beginning of the formation of the layer is 2.9 or less, and pBr at the end of the formation of the layer is 1.7 or more. More preferably, the pBr at the beginning of the formation of the layer is 2.5 or less, and the pBr at the end of the formation of the layer is 1.9 or more. Most preferably, pBr in the initial stage of the formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is 2.1 or more and 4.5 or less. The dislocation lines in the present invention are preferably introduced by the above method.

The silver halide grains of the present invention are prepared by preparing at least one of chalcogen sensitization such as sulfur sensitization and selenium sensitization and noble metal sensitization such as gold sensitization and palladium sensitization to prepare a silver halide emulsion. It can be applied in any of the steps. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface.
In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose, but the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization alone or in combination, and is described by TH James, The Photographic Process, 4th Edition, Macmillan Company. Published, 197
7 years, (THJames, The Theory of the Photographic Pr
ocess, 4th ed, Macmillan, 1977), using active gelatin, as described in pages 67-76, and in Research Disclosure, Vol.
Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, and 3; 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,31.
PAg 5-10, pH as described in US Pat.
Sulfur, selenium at 5-8 and a temperature of 30-80 ° C.
It can be tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K_TwoPdCl_Four, (NH_Four)_TwoP
dCl₆, Na_TwoPdCl_Four, (NH_Four) _TwoPdCl_Four, Li_Two
PdCl_Four, Na_TwoPdCl₆Or K_TwoPdBr_FourIs preferred
New Gold compound and palladium compound are thiocyanic acid
Preferably used in combination with salt or selenocyanate
No.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,05
Sulfur-containing compounds described in US Pat. No. 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757;
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. The preferred range of the palladium compound is 1 × per mole of silver halide.
It is 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or the selenocyan compound is silver halide 1
It is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ per mole.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mole of silver halide.
10 ^-4 to 1 × 10 ^-7 mol, more preferably 1
It is from × 10 ^{-5 to} 5 × 10 ^-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

In the present invention, the thiocyanate is preferably added before the addition of the above-mentioned spectral sensitizing dye and chemical sensitizer. Preferably, it is added after particle formation, more preferably after the end of the desalting step. Preferably, the thiocyanate is added even during chemical sensitization, so that the thiocyanate is added twice or more. As the thiocyanate, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate and the like are used.

Usually, it is added after being dissolved in an aqueous solution or a water-soluble solvent. The addition amount is 1 × per mol of silver halide.
10 ⁻⁵ mol to 1 × 10 ⁻² mol, more preferably 5 × 1
It is from 0 ^-5 mol to 5 × 10 ^-3 mol.

It is advantageous to use gelatin as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; and sugar derivatives such as sodium alginate and starch derivatives. A variety of synthetic hydrophilic polymer substances such as homo- or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As gelatin, besides lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
No. 16, P30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzate or an enzyme-decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
Deionization step, chemical sensitization, metal ion salt before coating
It is preferable to perform the above depending on the purpose. Dope particles
In the case of grain formation, modification or chemical sensitization of the grain surface
When used as an agent, add after grain formation and before completion of chemical sensitization
Is preferred. Doping the whole grain and the grain
Core only, or shell only, or epi
Doping only the tangential portion or only the base particles
You can also choose a method. Mg, Ca, Sr, Ba, Al, S
c, Y, La, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals are ammonium
Salt, acetate, nitrate, sulfate, phosphate, hydroxide
Or six-coordinate complex salt, four-coordinate complex salt, etc.
It can be added in the form of a salt that can be For example, Cd
Br _Two, CdCl_Two, Cd (NO_Three)_Two, Pb (NO_Three)_Two, P
b (CH_ThreeCOO)_Two, K_Three[Fe (CN)₆], (NH_Four)_Four
[Fe (CN)₆], K_ThreeIrCl₆, (NH_Four)_ThreeRhC
l ₆, K_FourRu (CN)₆And so on. Coordination compound
Halo, aquo, cyano, cyanate, thiol as ligands
Cyanate, nitrosyl, thionitrosyl, oxo, mosquito
You can choose from among rubonil. These are metallized
Only one compound may be used, but two or three or more
May be used in combination.

The metal compound is preferably added by dissolving a suitable solvent such as water or methanol or acetone in a solvent.
In order to stabilize the solution, an aqueous solution of hydrogen halide (eg, HC
1, HBr, etc.) or alkali halides (eg KC
1, NaCl, KBr, NaBr, etc.). If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. Further, it can be added to a water-soluble silver salt (eg, AgNO ₃ ) or a water-soluble alkali halide (eg, NaCl, KBr, KI) and added continuously during silver halide grain formation. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogenide compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

In the emulsion of the present invention, it is preferable to use an oxidizing agent for silver in addition to the halogen oxoacid salt during the production process. However, the hole-capturing silver nuclei obtained by reduction sensitization on the surface of the grains need to remain so that the sensitivity / fogging ratio is optimal in terms of photographic performance. In particular, a compound that converts fine silver nuclei, which do not contribute to the increase in sensitivity in the process of forming silver halide grains and chemical sensitization and cause fog increase, into silver ions is effective. The silver ions generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide or silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. Preferred oxidizing agents are inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazain Dens, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers, such as 3,3a, 7) tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,9
No. 47 and JP-B No. 52-28660 can be used. One of the preferred compounds is disclosed in
There is a compound described in JP-A-3-212932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but other various additives can be used according to the purpose. These additives are
For more details, Research Disclosure Item 176
43 (December 1978), Item 18716 (19
November 1979) and Item 308119 (1989)
(December, 2012), and the relevant locations are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer page 649 right column 4 Brightener 24 page 998 right 5 Antifoggant page 24-25 page 649 right column 998 right to 1000 right and stabilizer 6 light absorber, page 25-26 page 649 right column 1003 Left to 1003 right Filter dye 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardening agent 26 page 651 left column 1004 right to 1005 left 10 Binder 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant page 27 650 page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left to 1006 left Surfactant 13 Static page 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left.

Techniques such as layer arrangement and the like which can be used for the emulsion of the present invention and photographic light-sensitive materials using the emulsion, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives, etc. And development processing are described in EP 056596 A1 (published October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14, 2. Intermediate layer: page 61, lines 36 to 40, 3. Multilayer effect imparting layer: page 62, lines 15 to 18, 4. Silver halide composition: page 62, lines 21 to 25; 5. Silver halide grain habit: page 62, lines 26 to 30, 6. Silver halide grain size: page 62, lines 31 to 34, 7. Emulsion production method: page 62, lines 35 to 40, Silver halide grain size distribution: page 62, 41 to 42
Row, 9. Tabular grains: page 62, lines 43 to 46,10. 10. Internal structure of particle: page 62, lines 47 to 53, Emulsion latent image forming type: page 62, line 54 to page 63, 5
Line, 12. 12. Physical ripening / chemical ripening of emulsion: p. 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: p. 63, lines 14 to 31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49 to 50; Photographic additives: Research Disclosure (R
D) Item 17643 (December 1978), Item 18
716 (November 1979) and Item 307105
(November, 1989), and each item and a description place related thereto are shown below.

Types of Additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23, page 648, right column, page 866 2 Sensitivity enhancer page 648, right column 3 Spectral sensitizer, page 23-24, page 648, right column 866-868 Color sensitizer ~ page 649 right column 4 Brightener 4 page 647 page right column 868 page 5 Antifoggant, 24-25 page 649 right column 868-870 page stabilizer 6 light absorber, 25-26 649 Page right column 873 Filter dye, ~ 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left column-right column 872 8 Dye image stabilizer 25 page 650 left column 872 9 Hardener 26 Page 651 Left column 874 to 875 10 Binder Page 26 651 Left column 873 to 874 11 Plasticizer, lubricant 27 Page 650 Right column 876 Page 12 Coating aid, 26-27 Page 650 Right column 875- Page 876 Surfactant 13 Static page 27 Page 650 right column Inhibitor 14 Matting agent 878-879.

18. Formaldehyde scavenger: 6
Page 4, lines 54-57; 20. Mercapto antifoggant: page 65, lines 1 and 2, Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, lines 7-10, 22. General color couplers: p. 65, lines 11 to 13, 23. Yellow, magenta and cyan couplers: page 65, 1
Lines 4 to 25, 24. Polymer coupler: page 65, lines 26 to 28, 25. Diffusible dye-forming couplers: p. 65, lines 29 to 31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39 to 44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49 to 53, 30. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row, 35. Back layer: page 67, lines 3 to 8, 36. Overall development processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12 to 30, 38. 39. Developer additive: page 67, lines 31 to 44, Reverse processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57 to page 68, line 12, 41. Developing time: page 68, lines 13 to 15, 42. Bleach-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32 to 40, 44. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70 pages 34-38, 48. Use for film with lens: page 70, lines 39-41.

Also, a bleaching solution described in European Patent No. 602600 containing a 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid, a ferric salt such as ferric nitrate, and a persulfate is also used. It can be used preferably. In the use of this bleaching solution, it is preferable to interpose a stopping step and a washing step between the color developing step and the bleaching step,
It is preferable to use an organic acid such as acetic acid, succinic acid, and maleic acid for the stop solution. In addition, this bleaching solution contains p
Organic acids such as acetic acid, succinic acid, maleic acid, glutaric acid, adipic acid, etc.
It is preferable to contain it in the range of 2 mol / liter.

[0126]

Examples of the present invention will be described below. However, it is not limited to this embodiment. (Example 1) In this example, in the photosensitive silver halide emulsion, the fog increase which occurs when a light-sensitive material containing the silver halide emulsion is aged in an oxygen atmosphere is remarkable by the means disclosed in the present invention. Is resolved.

Gelatins 1 to 4 used as dispersion media in the following emulsion preparations are gelatins having the following attributes.

Gelatin-1: Normal alkali-treated ossein gelatin made from bovine bone. -NH ₂ in the gelatin
No chemical modification of the group.

Gelatin-2: In an aqueous solution of gelatin-1,
A gelatin obtained by adding phthalic anhydride at 50 ° C. and a pH of 9.0 to cause a chemical reaction, removing residual phthalic acid, and drying. 95% of the number of —NH ₂ groups chemically modified in gelatin.

Gelatin-3: In an aqueous solution of gelatin-1,
Gelatin obtained by adding trimellitic anhydride under conditions of 50 ° C. and pH 9.0 to cause a chemical reaction, and then removing remaining trimellitic acid and drying. 95% of the number of —NH ₂ groups chemically modified in gelatin.

Gelatin-4: Gelatin obtained by reducing the molecular weight of gelatin-1 by the action of an enzyme to make the average molecular weight 15,000, inactivating the enzyme, and drying. No chemical modification of -NH ₂ groups in the gelatin.

After deionizing all of the above gelatin-1 to gelatin-4, the pH of a 5% aqueous solution at 35 ° C. was 6.
Adjustment was made so as to be zero.

(Production Method of Emulsion A-1) Phthalated low molecular weight gelatin having a molecular weight of 15,000 and a phthalation rate of 97% 3
42.2 liters of an aqueous solution containing 1.7 g, KBr and 31.7 g (hereinafter, also referred to as “L”) was kept at 35 ° C. and stirred vigorously. 1583 mL of an aqueous solution containing 316.7 g of AgNO ₃ , 221.5 g of KBr, and 1583 mL of an aqueous solution containing 52.7 g of the above gelatin-4 were added over 1 minute by the double jet method. Immediately after completion of the addition, 52.8 g of KBr was added, and 398.2 of AgNO ₃ was added.
2485 mL of an aqueous solution containing 29 g of KBr and 2581 mL of an aqueous solution containing 291.1 g of KBr were added over 2 minutes by a double jet method. Immediately after the addition was completed, 44.8 g of KBr was added. Thereafter, the temperature was raised to 40 ° C. and the product was aged. After ripening, 923 g of the above gelatin-2 and KBr, 79.
2 g, an aqueous solution 1 containing 5103 g of AgNO ₃
5947 mL and KBr aqueous solution were accelerated by the double jet method so that the final flow rate was 1.4 times the initial flow rate, and 1
Added over 0 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.90. After washing with water, the above-mentioned gelatin-1 was added, and pH 5.7, pAg, 8.8,
The seed emulsion was adjusted to a weight of 131.8 g in terms of silver and a weight of 64.1 g of gelatin per kg of the emulsion.

46 g of the above gelatin-2, KBr1.
1211 mL of an aqueous solution containing 7 g was kept at 75 ° C. and stirred vigorously. After adding 9.9 g of the seed emulsion described above, denatured silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.)
Was added in an amount of 0.3 g. After adjusting the pH to 5.5 by adding sulfuric acid, an aqueous solution containing 7.0 g of AgNO ₃ , 67.6.
mL and KBr aqueous solution were added over 6 minutes by double jet method with the flow rate accelerated so that the final flow rate was 5.1 times the initial flow rate. At this time, p of the bulk emulsion solution in the reaction vessel
Ag was kept at 8.15. After adding 2 mg of thiourea dioxide, an aqueous solution containing 105.6 g of AgNO ₃ , 32
8 mL and the aqueous KBr solution were added by a double jet method over a period of 56 minutes by accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 27 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.60. Was. AgN
121.3 mL of an aqueous solution containing 45.6 g of O ₃ and KBr
The aqueous solution was added by the double jet method over 22 minutes.
At this time, the pAg of the bulk emulsion solution in the reaction vessel was increased to 7.6.
It was kept at zero. The temperature was raised to 82 ° C., KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 8.80, and then the above AgI fine grain emulsion was converted to 6.3 in terms of KI weight.
3 g were added.

Immediately after the addition was completed, AgNO ₃ was added to 66.
206.2 mL of an aqueous solution containing 4 g was added over 16 minutes. During the initial 5 minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.80 with an aqueous KBr solution. After washing with water, the above-mentioned gelatin-1 was added, and the pH was adjusted to 40 at 40 ° C.
8. The pAg was adjusted to 8.7 (process). The temperature was raised to 60 ° C., and 4.2 × 10 ⁻⁴ mol of sensitizing dye Exs-1 was added per mol of silver halide (process), and then potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N
-Dimethylselenourea was added for optimal chemical sensitization.
Compound RS-1 was used in an amount of 1 × 10 ⁻³ per mol of silver halide.
The compound ExA-2 and the compound ExA-3 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that each compound is selected from the range of 10 ^-1 to 10 ^-8 mol per mol of silver halide.

The obtained emulsion had an average sphere equivalent diameter of 1.05 μm.
m, the average value of the aspect ratio is 10 and 60% of the total projected area of the grains has an aspect ratio of 9.0 or more and 12 or less;
The average value of the gI content is 15 mol%, and the parallel main plane is (1
11) Tabular silver halide grains as planes.

[0137]

Embedded image

[0138]

Embedded image

(Preparation of Emulsion A-2) The compound ExA-2 was prepared at the end of the chemical sensitization under the conditions for preparing Emulsion A-1.
And before addition of compound ExA-3 (process), sodium chlorite was added to 1 × 10
Emulsion A-2 was prepared in the same manner except that ^-5 mol was added.

(Preparation of Emulsions A-3 to A-10 and A-13) According to the preparation conditions of Emulsion A-2 described above, instead of sodium chlorite, the halogen oxo acid was used as shown in Table 1. It prepared similarly except adding a salt and an oxidizing agent.

[0141]

[Table 1]

(Preparation of Emulsion A-11) Emulsion A-1
At the end of grain formation (process), sodium chlorite was added in an amount of 1 × 10
Emulsion A-11 was prepared in the same manner except that ^-5 mol was added.

(Preparation of Emulsion A-12) Emulsion A-1
At the end of the spectral sensitization (process), sodium chlorite was added in an amount of 1 × 10
Emulsion A-12 was prepared in the same manner except that ^-5 mol was added.

For the emulsions A-1 and A-2, 40
Observation at a temperature of liquid nitrogen using a transmission electron microscope of 0 kV revealed that at least 10 dislocation lines existed in the fringe portion of the tabular grain in each grain.

Further, the emulsions A-1 to A-13 were subjected to reduction sensitization by adding thiourea dioxide in the emulsion preparation step.

The above-mentioned emulsions A-1 to A-13 were coated on a cellulose triacetate film support provided with an undercoat layer under the coating conditions shown in Table 2 below. The applied samples were designated as samples 101 to 112 and 114.

[0147]

[Table 2]

(Preparation of Sample 113) Sample 101 coated with Emulsion A-1 was prepared in the same manner as in Sample 101 except that sodium chlorite was added to the coating solution in an amount of 1 × 10 ⁻⁵ mol per mol of silver halide. 113 was created.

These samples were subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge through a gelatin filter SC-50 (a long wavelength light transmission filter having a cutoff wavelength of 500 nm) manufactured by Fuji Film Co., Ltd.
The development processing was performed in the same manner as in the development processing described on page 16 of 1-153840, except that the processing time of the color development step was changed to 2 minutes and 45 seconds. The photographic performance was evaluated by measuring the density of the processed sample with a green filter.
The sensitivity was represented by the relative value of the reciprocal of the exposure required to reach the density of fog density plus 0.2 (the sensitivity of emulsion A-1 was defined as 100).

(Evaluation test of increase in fog due to oxygen) The increase in fog with the lapse of time of the above coated sample due to oxygen was evaluated by the following method.

The samples 101 to 114 were placed in a stainless steel pressure vessel (autoclave) using nitrogen at 5 atm, relative humidity at 80% (elapsed time), oxygen at 5 atm, and relative humidity at 8 atm.
It was adjusted to two conditions of 0% (age) and left at 40 ° C. for 3 days. After that, the above-described exposure and development processing is performed,
The fog density was measured with a green filter in the same manner as described above, and the increase in fog density with time under oxygen relative to the fog density with nitrogen was determined, and the value was defined as an increase in fog with oxygen.

The results of evaluation by the above method are also shown in Table 2 above.

From the results shown in Table 2, it is apparent that the increase in fog due to oxygen can be significantly reduced by adding the halogen oxoacid salt of the present invention to prepare emulsion grains. Even if it is an oxidizing agent, the effects of the present invention cannot be seen with known hydrogen peroxide, sodium hypochlorite, and the like. Among the halogen oxo acid salts of the present invention, the fogging reduction effect of chlorite is extremely remarkable. The same effect is obtained not only at the end of chemical sensitization but also at the end of grain formation and at the end of spectral sensitization. In addition, the effect obtained when the halogen oxoacid salt is added during coating rather than during emulsion production is insufficient.

Although the details of the mechanism of action of the halogen oxoacid salt of the present invention are not clear, it is presumed that they react with and remove silver nuclei which cause fogging with time. At this time, the strong oxidizing agent reacts with the organic compound around the emulsion grains to obtain no effect, and the oxoacid salt of the halogen of the present invention assumes that the reaction rate between the silver nucleus and the organic compound is in an appropriate range. Estimated.

Example 2 The following shows that the halogen oxoacid salt of the present invention is effective for tabular grains having a large aspect ratio.

(Preparation of Emulsion B-1) An aqueous solution 1211 m containing 46 g of gelatin-2 of Example 1 and 1.7 g of KBr
L was kept at 75 ° C. and stirred vigorously. Emulsion A of Example 1
After adding 3.0 g of the seed emulsion used in Step No. 1, 0.1 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added.
3 g were added. After adjusting the pH to 5.5 by adding sulfuric acid, a flow rate of 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and a KBr aqueous solution by a double jet method so that the final flow rate is 5.1 times the initial flow rate. Accelerated and added over 6 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.15 (growth process 2).

Sodium benzenethiosulfonate 2 mg
And after addition of thiourea dioxide 2 mg, the AgNO ₃ 1
328 mL of an aqueous solution containing 05.6 g and an aqueous KBr solution were added by a double jet method over a period of 56 minutes while accelerating the flow rate so that the final flow rate was 3.7 times the initial flow rate. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 14 mol%, and the p of the bulk emulsion solution in the reaction vessel was added.
Ag was kept at 8.60 (growth step 3).

Aqueous solution 12 containing 45.6 g of AgNO ₃
1.3 mL and KBr aqueous solution were added by a double jet method over 22 minutes (growth process 4). At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.60. 82 ° C
After adjusting the pAg of the bulk emulsion solution in the reaction vessel to 8.80 by adding KBr, 6.33 g of the above-mentioned AgI fine grain emulsion was added in terms of KI weight. Immediately after the addition, an aqueous solution 20 containing 66.4 g of AgNO ₃ was added.
6.2 mL was added over 16 minutes. Initial 5 of addition
For a minute, p of the bulk emulsion solution in the reaction vessel with KBr aqueous solution
Ag was kept at 8.80 (growth step 5).

After washing with water, gelatin-1 was added and
And adjusted to pH 5.8, pAg and 8.7. Compound R
After S-1 was added in an amount of 1.times.10.sup.- ³ mol per mol of silver halide, the temperature was raised to 60.degree. After adding the sensitizing dye Exs-1, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimal chemical sensitization. Compound ExA-3 at the end of chemical sensitization
Was added. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are added at 10 ^-1 per mol of silver halide.
From 10 to ⁸ moles.

The obtained emulsion had a parallel principal plane of (11).
1) A tabular silver halide grain as a surface, having a sphere equivalent diameter of 1.05 μm, an average aspect ratio of 10, and an aspect ratio of 9.5 or more 1 of 60% of the total projected area of the grain.
It was 1.5 or less, and the average value of the AgI content was 15.1 mol%.

(Production Method of Emulsion B-2) In the production method of Emulsion B-1, except that the pAg in the growth step 3 was changed from 8.60 to 7.70,
Emulsion B-2 was prepared. However, the amount of Exs-1 was adjusted for optimal chemical sensitization. The resulting emulsion has an average aspect ratio of 3.0 and a total projected area of 6 grains.
0% had an aspect ratio of 2.5 or more and 4.5 or less.

(Production Method of Emulsion B-3) In the emulsion B-1, the pAg in the growing step 3 was changed from 8.60 to 8.
Emulsion B-3 was prepared in the same manner as Emulsion B-1, except that it was changed to 00. However, the amount of Exs-1 was adjusted for optimal chemical sensitization. The resulting emulsion had a sphere equivalent diameter of 1.05 μm, an average aspect ratio of 6.0, and 60% of the total projected area of the grains had an aspect ratio of 5.5 or more and 7.5 or less.

(Preparation of Emulsion B-4) Emulsion B-4 was prepared in the same manner as Emulsion B-1, except that (Growth Process 2) and (Growth Process 3) were changed as follows. Was prepared. However, RS-1, Exs used in chemical sensitization
The amount of -1 was varied and adjusted for optimal chemical sensitization.

(Growing process 2)
g, 1.71 g of KBr in an aqueous solution at 75 ° C.
And stirred vigorously. After adding 3.0 g of the seed emulsion described above, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. After adjusting the pH to 5.5 by adding sulfuric acid, a flow rate of 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and a KBr aqueous solution by a double jet method so that the final flow rate is 5.1 times the initial flow rate. Accelerated and added over 6 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.80.

(Growth Process 3) After adding 2 mg of sodium benzenethiosulfonate and 5 mg of thiourea dioxide,
An aqueous solution containing 105.6 g of AgNO ₃ , 328 mL, and an aqueous KBr solution were added by a double jet method over a period of 56 minutes while the flow rate was accelerated so that the final flow rate was 3.7 times the initial flow rate. At this time, AgI having a particle size of 0.037 μm was used.
The fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content became 14.4 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.80.

The obtained emulsion had a parallel principal plane of (11).
1) A tabular silver halide grain which is a plane, having a sphere equivalent diameter of 0.50 μm, an average aspect ratio of 10, and an aspect ratio of 9.5 or more 1 of 60% of the total projected area of the grain.
It was 1.5 or less, and the average value of the AgI content was 9.2 mol%.

(Preparation of Emulsion C-1) In the preparation of Emulsion B-1, sodium chlorite was added to 1 mol of silver halide before the addition of compound ExA-3 at the end of chemical sensitization. Emulsion C was prepared in the same manner except that 1 × 10 ^-5 mol was added.
-1 was prepared.

(Preparation of Emulsion C-3) In contrast to the preparation of Emulsion B-3, sodium chlorite was added to 1 mol of silver halide before the addition of compound ExA-3 at the end of chemical sensitization. Emulsion C was prepared in the same manner except that 1 × 10 ^-5 mol was added.
-3 was prepared.

(Preparation of Emulsion C-4) In contrast to the preparation of Emulsion B-4, sodium chlorite was added to 1 mol of silver halide before adding the compound ExA-3 at the end of chemical sensitization. Emulsion C was prepared in the same manner except that 1 × 10 ^-5 mol was added.
-4 was prepared.

In the same manner as in Example 1, the emulsions B-1 to B-
4 and C-1, C-3 to C-4 were applied. The applied samples were designated as samples 201 to 207.

An experiment for evaluating sensitivity and an increase in fog due to oxygen was also performed in the same manner as in Example 1. The sensitivity of Sample 202 of Emulsion B-2 was set to 100. The results obtained are shown in Table 3 below.
Shown in

[0172]

[Table 3]

The following is clear from the results in Table 3. Higher sensitivity can be achieved by increasing the aspect ratio of the silver halide tabular grains and increasing the amount of the spectral sensitizing dye added per mole of silver halide. Significantly worsens. Addition of a halogen oxoacid salt to an emulsion having a large aspect ratio can improve sensitivity and increase fog due to oxygen.

The average equivalent spherical diameter of the particles is 0.5 μm.
In the following, although the effect of reduction by the addition of a halogen oxoacid salt is present, the sensitivity is insufficient, which is not preferable.

Example 3 The effectiveness of a silver halide color photographic light-sensitive material using the emulsion of the present invention will be described.

According to the following production method, silver halide emulsion D-
a, Db, Ea, Eb, Fa, Fb, G-
a, Gb, and H to R were prepared.

(Preparation of Emulsion Da) Emulsion B- of Example 2
1, the sensitizing dye has an E content per mole of silver halide
2.75 × 10 ⁻⁴ mol of xs-1 and 2.2 of Exs-2
It was prepared in the same manner as Emulsion B-1, except that 5 × 10 ^-4 mol was added.

(Preparation of Emulsion Db) The compound ExA-2 was prepared at the end of the chemical sensitization under the above conditions for preparing Emulsion Da.
Emulsion D-b was prepared in the same manner except that sodium chlorite was added at 1 × 10 ⁻⁵ mol per mol of silver halide before adding Compound ExA-3.

(Preparation of Emulsion Ea) An aqueous solution 11 containing 0.96 g of gelatin-4 of Example 1 and 0.9 g of KBr
92 mL was kept at 40 ° C. and stirred vigorously. AgN
37.5 mL of an aqueous solution containing 1.49 g of O ₃ and 37.5 mL of an aqueous solution containing 1.05 g of KBr were added over 30 seconds by a double jet method. After adding 1.2 g of KBr, the temperature was raised to 75 ° C. to ripen. After ripening, 35 g of gelatin-3 of Example 1 was added to adjust the pH to 7. 6 mg of thiourea dioxide were added. 116 mL of an aqueous solution containing 29 g of AgNO ₃ and an aqueous KBr solution were added by double jet method at an accelerated flow rate such that the final flow rate was three times the initial flow rate. At this time, p of the bulk emulsion solution in the reaction vessel
Ag was kept at 8.15. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over a period of 30 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, emulsion A-
AgI fine grain emulsion used in Preparation 1 was simultaneously added at an accelerated flow rate such that the silver iodide content became 15.8 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 7.
It was kept at 85.

Aqueous solution 9 containing 24.1 g of AgNO ₃
6.5 mL and KBr aqueous solution were added by the double jet method over 3 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.85. After adding 26 mg of sodium ethylthiosulfonate, the temperature was lowered to 55 ° C., and KB
rAqueous solution and pA of the bulk emulsion solution in the reaction vessel
g was adjusted to 9.80. 8.5 g of the above-mentioned AgI fine grain emulsion was added in terms of KI weight. Immediately after completion of the addition, 228 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 5 minutes. At this time, an aqueous KBr solution was used so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.75. The emulsion was washed with water in substantially the same manner as in the emulsion Da, and subjected to spectral sensitization and chemical sensitization. Compound RS-1, ExA
-2 and ExA-3 were also added in substantially the same manner as Emulsion Da.

(Preparation of Emulsion Eb) The compound ExA-2 was prepared at the end of the chemical sensitization under the above conditions for preparing Emulsion Ea.
Emulsion Eb was prepared in the same manner except that sodium chlorite was added in an amount of 7.times.10.sup.- ⁶ mol per mol of silver halide before adding Compound ExA-3.

(Preparation of Emulsion Fa) An aqueous solution 119 containing 1.02 g of gelatin-2 of Example 1 and 0.9 g of KBr
2 mL was kept at 35 ° C. and stirred vigorously. AgNO ₃ ,
Aqueous solution containing 4.47 g, 42 mL and KBr, 3.16
g of an aqueous solution, 42 mL, was added by a double jet method over 9 seconds. After adding 2.6 g of KBr, the temperature was raised to 63 ° C. to ripen. After ripening, gelatin-3 of Example 1 was used.
Was added to 41.2 g of NaCl and 18.5 g of NaCl. pH
Was adjusted to 7.2, dimethylamine borane, 8 mg
Was added. 203m of aqueous solution containing 26g of AgNO ₃
L and KBr aqueous solution were added by the double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.65. A
440.6 mL of an aqueous solution containing 110.2 g of gNO ₃ and an aqueous KBr solution were added over a period of 24 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Emulsion A-1 was simultaneously added at an accelerated flow rate such that the silver iodide content became 2.3 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was reduced to 8%. .50.

10. 1N aqueous potassium thiocyanate solution
After adding 7 mL, 153.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 2 minutes and 30 seconds. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.05. The aqueous KBr solution was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.25. The AgI fine grain emulsion described above was used for KI
6.4 g in terms of weight was added. Immediately after addition is complete, Ag
404 mL of an aqueous solution containing 57 g of NO ₃ was added over 45 minutes. At this time, an aqueous KBr solution was used so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 8.65. It was washed with water in almost the same manner as in Emulsion D, and subjected to spectral sensitization and chemical sensitization. Compounds RS-1, ExA-2 and ExA-3 were also added in substantially the same manner as in emulsion Da.

(Preparation of Emulsion Fb) The compound ExA-2 was prepared at the end of the chemical sensitization under the conditions for preparing Emulsion Fa.
Emulsion Fb was prepared in the same manner except that sodium chlorite was added in an amount of 7.times.10.sup.- ⁶ mol per mol of silver halide before adding Compound ExA-3.

(Preparation of Emulsion Ga) In the preparation of emulsion Fa, the amount of AgNO ₃ added during nucleation was changed to 2.3 times. Then, an aqueous solution 4 containing 57 g of the final AgNO ₃
It was changed so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition of 04 mL was adjusted to 6.85 with an aqueous KBr solution. Other than that, it was prepared almost in the same manner as the emulsion Fa.

(Preparation of Emulsion Gb) The compound ExA-2 was prepared at the end of the chemical sensitization under the above conditions for preparing Emulsion Ga.
Emulsion Gb was prepared in the same manner except that sodium chlorite was added in an amount of 7 × 10 ⁻⁶ mol per mol of silver halide before adding Compound ExA-3.

(Production method of emulsion H) 1300 mL of an aqueous solution containing 1.0 g of KBr and 1.1 g of gelatin-4 of Example 1
Was kept at 35 ° C. and stirred (1st liquid preparation). Ag-
38 mL of 1 aqueous solution (containing 4.9 g of AgNO ₃ in 100 mL) and an X-1 aqueous solution (KBr in 100 mL)
29 mL) and 8.5 mL of an aqueous G-1 solution (containing 8.0 g of the above gelatin-4 in 100 mL) were added by a triple jet method at a constant flow rate over 30 seconds. Thereafter, 6.5 g of KBr
Was added and the temperature was raised to 75 ° C. After an aging step for 12 minutes after the temperature rise, 300 mL of an aqueous G-2 solution (containing 12.7 g of gelatin-3 of Example 1 in 100 mL)
, Followed by 4,5-dihydroxybenzene-
2.1 g of disodium 1,3-disulfonate were added.

Next, an aqueous solution of Ag-2 (A
Gno ₃ which contained 22.1 g) and 157 mL, X-2
Aqueous solution (containing 15.5 g of KBr in 100 mL)
Was added by the double jet method over 14 minutes. At this time, the final flow rate of addition of the Ag-2 aqueous solution is 3.
The flow rate was accelerated so as to be four times, and the addition of the X-2 aqueous solution was performed so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.30. Then, an Ag-3 aqueous solution (100 m
329 mL containing 32.0 g of AgNO ₃ in L)
And an X-3 aqueous solution (21.5 KBr in 100 mL).
g, KI containing 1.2 g) by the double jet method.
Added over 7 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.30. I went to keep it. Further, an Ag-4 aqueous solution ( ₃ mL of AgNO ₃ in 100 mL) was added.
156 mL containing 2.0 g) and an X-4 aqueous solution (10
(Containing 22.4 g of KBr in 0 mL) by the double jet method over 17 minutes. At this time, Ag-4
The aqueous solution was added at a constant flow rate, and the X-4 aqueous solution was added such that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 7.52 (addition 1).

Thereafter, 0.0025 g of sodium benzenethiosulfonate and 125 mL of an aqueous G-3 solution (containing 12.0 g of the above gelatin-1 in 100 mL)
Were added sequentially at one minute intervals. Then KB
of the bulk emulsion solution in the reaction vessel.
After adjusting the Ag to 9.00, the AgI fine grain emulsion (100
12. AgI fine particles having an average particle size of 0.047 μm in g.
03.9 g) and 2 minutes later,
249 mL of the Ag-4 aqueous solution and X-4 aqueous solution were added by the double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 9 minutes, and the X-4 aqueous solution was added only for the first 3.3 minutes so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.00, and the remaining was added. Was added for 5.7 minutes, so that the pAg of the bulk emulsion solution in the reaction vessel finally reached 8.4.

Thereafter, desalting is carried out by a usual flocculation method, and then water, NaOH and the above-mentioned gelatin-1 are added with stirring, and at pH 6.4, pA at 56 ° C.
g was adjusted to 8.6.

Subsequently, the sensitizing dye was added in an amount of 1 mole of silver halide.
Or Exs-3 is 5.50 × 10 ^-FourMol, Exs-4
Is 1.30 × 10^-Four4.65 x 10 mol, Exs-5
^-FiveBefore the chemical sensitization, the compound ExA-1
2 × 10 5 per mole of silver halide^-3Mole was added.
Potassium thiocyanate, chloroauric acid, sodium thiosulfate
And N, N-dimethylselenourea are added sequentially to optimize
After chemical sensitization, compound RS-1 was replaced with silver halide 1
2 × 10 per mole^-3Mol (addition 2). Then the following water
Soluble mercapto compounds MER-1 and MER-2
A total of 3.6 per mole of silver halide in a ratio of 4: 1
× 10^-FourChemical sensitization is terminated by adding
Was.

[0192]

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(Preparation of Emulsion I) Gelatin-4 of Example 1
Aqueous solution containing 0.75 g of KBr and 0.9 g of KBr
The mL was kept at 39 ° C., the pH was adjusted to 1.8 and stirred vigorously. An aqueous solution containing 1.85 g of AgNO ₃ and 1.5 m
An aqueous KBr solution containing ol% KI was added over 16 seconds by a double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After aging,
20 g of gelatin-2 of Example 1 was added. pH 5.
After adjusting to 9, KBr, 2.9 g was added. AgN
288 mL of an aqueous solution containing 27.4 g of O ₃ and an aqueous KBr solution were added over 53 minutes by a double jet method. At this time, an AgI fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was increased to 9.4.
It was kept at zero. After adding 2.5 g of KBr, AgNO
_{3. An} aqueous solution containing 87.7 g and an aqueous KBr solution were added over 63 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the AgI fine grain emulsion was adjusted to have a silver iodide content of 10.5 mol%
And the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.50.

AgNO_Three, Aqueous solution 13 containing 41.8 g
2mL and KBr aqueous solution in 25 minutes by double jet method
Migrated. Dissolve the bulk emulsion in the reaction vessel at the end of the addition
Add KBr aqueous solution so that pAg of the solution becomes 8.15
Was adjusted. Adjust the pH to 7.3 and add KBr
Adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.50
After that, the above AgI fine grain emulsion was converted to KI weight in 5.
73 g was added. Immediately after the addition is completed, AgNO_Three, 6
Add 609 mL of an aqueous solution containing 6.4 g over 10 minutes
did. During the initial 6 minutes of the addition, an aqueous KBr solution was
The pAg of the bulk emulsion solution was kept at 9.50. Washed
Thereafter, gelatin-1 of Example 1 was added, and the mixture was adjusted to pH 6 at 40 ° C.
Adjusted to 5, pAg, 8.2. Almost same as Emulsion H
I was sensitized. Compound RS-1 was also used in an amount of 1 mol per silver halide.
2 × 10^-3Mole was added. The amount of sensitizing dye used
Is 1.08 for Exs-3 per mole of silver halide.
× 10 ^-32.56 x 10 mol, Exs-4^-FourMol, e
xs-5 is 9.16 × 10^-FiveIs a mole.

(Preparation of Emulsion J) Gelatin-4 of Example 1
0.70 g, KBr, 0.9 g, KI, 0.175
g, an aqueous solution (1200 mL) containing 0.2 g of the modified silicone oil used in the preparation of Emulsion A-1 was kept at 33 ° C.
H was adjusted to 1.8 and stirred vigorously. AgNO ₃
Aqueous solution containing 8 g and KBr containing 3.2 mol% KI
The aqueous solution was added over 9 seconds by the double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 62 ° C. and ripened. After ripening, 2 parts of gelatin-3 of Example 1 were added.
7.8 g were added. After adjusting the pH to 6.3, KB
r, 2.9 g were added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes by the double jet method. At this time, the aqueous solution of gelatin-4, the aqueous solution of AgNO _{3, and the} aqueous solution of KI of Example 1 were mixed in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570, immediately before the addition, to prepare. The AgI fine grain emulsion having a grain size of 0.008 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.15.

After adding 2.6 g of KBr, AgNO was added.
_An aqueous solution containing 87.7 g of ₃ and an aqueous KBr solution were added by a double jet method over a period of 49 minutes while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time, the AgI fine grain emulsion prepared by mixing immediately before the addition was accelerated simultaneously so that the silver iodide content became 7.9 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was increased to 9.3.
It was kept at zero. After adding 1 mg of thiourea dioxide, A
Gno _3, an aqueous solution containing 41.8 g 132 mL of KBr
The aqueous solution was added by the double jet method over 20 minutes.
The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition was 7.90.
After the temperature was raised to 78 ° C. and the pH was adjusted to 9.1, KBr was added to increase the pAg of the bulk emulsion solution in the reaction vessel to 8.7.
It was set to 0. The AgI fine grain emulsion used in the preparation of Emulsion D was added in an amount of 5.73 g in terms of KI weight. Immediately after the addition, 321 mL of an aqueous solution containing 66.4 g of AgNO _{3 was} added to 4 parts of the solution.
Added over minutes. During the first two minutes of the addition, the pAg of the bulk emulsion solution in the reaction vessel was kept at 8.70 with an aqueous KBr solution.

The emulsion was washed with water and chemically sensitized almost in the same manner as in Emulsion H. Compound RS-1 was used in an amount of 2 × 1 per mol of silver halide.
0 ^-3 mol was added. The amount of the sensitizing dye used was 1.25 × 10 ⁻³ mol for Exs-3, 2.85 × 10 ⁻⁴ mol for Exs- ⁴ , and 3.29 for Exs-5 per mol of silver halide. × 10 ^-5 mol.

(Preparation of Emulsion K) Gelatin-1 of Example 1
And an aqueous solution containing 17.8 g, KBr, 6.2 g, KI and 0.46 g was kept at 45 ° C. and stirred vigorously. AgN
An aqueous solution containing 11.85 g of O ₃ and an aqueous solution containing 3.8 g of KBr were added by a double jet method over 45 seconds. After the temperature was raised to 63 ° C, gelatin-1 of Example 1 was added to 24.
1 g was added and the mixture was aged. After aging, AgNO ₃ , 13
An aqueous solution containing 3.4 g and an aqueous KBr solution were added by a double jet method over 20 minutes so that the final flow rate was 2.6 times the initial flow rate. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 7.60. Ten minutes after the start of the addition, 0.1 mg of K ₂ IrCl ₆ was added. NaCl 7
g of an aqueous solution containing 45.6 g of AgNO ₃ and K
The aqueous Br solution was added by the double jet method over 12 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 6.90. Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of the addition. KB
After adding 14.4 g of r, 6.3 g of the AgI fine grain emulsion used in the preparation of Emulsion A-1 was added in terms of KI weight. Immediately after the addition was completed, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 11 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 6.90.

The emulsion was washed with water in almost the same manner as in Emulsion H and chemically sensitized. Compound RS-1 was also 2 × 1 per mole of silver halide.
0 ^-3 mol was added. The amount of the sensitizing dye used was 5.79 × 10 ⁻⁴ mol for Exs-3, 1.32 × 10 ⁻⁴ mol for Exs- ⁴ , and 1.52 for Exs-5 per mol of silver halide. × 10 ^-5 mol.

(Preparation of Emulsion L) Emulsion K was prepared in substantially the same manner except that the temperature during nucleation was changed to 35 ° C. Compound RS-1 was also added in an amount of 2 × 10 ⁻³ mol per mol of silver halide. The amount of the sensitizing dye used is
9.66 × 1 Exs-3 per mole of silver halide
0 ^-4 mol, Exs-4 2.20 × 10 ^-4 mol, Exs
-5 is 2.54 × 10 ^-5 mol.

(Preparation of Emulsion M) Gelatin-4 of Example 1
Aqueous solution 1200 containing 0.75 g of KBr and 0.9 g of KBr
The mL was kept at 39 ° C., the pH was adjusted to 1.8 and stirred vigorously. Aqueous solution containing 0.34 g of AgNO ₃ and 1.5 m
An aqueous KBr solution containing ol% KI was added over 16 seconds by a double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 54 ° C. and ripened. After aging,
20 g of the gelatin-2 of Example 1 was added. After adjusting the pH to 5.9, 2.9 g of KBr was added. A
gNO ₃ , 288 mL of an aqueous solution containing 28.8 g of KBr and KBr
The aqueous solution was added by the double jet method over 58 minutes.
At this time, an AgI fine grain emulsion having a grain size of 0.03 μm was simultaneously added so that the silver iodide content became 4.1 mol%, and the pAg of the bulk emulsion solution in the reaction vessel was adjusted to 9.
It was kept at 40. After adding 2.5 g of KBr, AgN
An aqueous solution containing 87.7 g of O ₃ and an aqueous KBr solution were added over a period of 69 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the above AgI fine grain emulsion was mixed with a silver iodide content of 10.5 mol.
% While simultaneously increasing the flow rate and maintaining the pAg of the bulk emulsion solution in the reaction vessel at 9.50. A
Gno _3, an aqueous solution containing 41.8 g 132 mL of KBr
The aqueous solution was added by the double jet method over 27 minutes.
The addition of the KBr aqueous solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition became 8.15.

2 mg of sodium benzenethiosulfonate
Was added, and KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.50.
5.73 g of the fine grain emulsion was added in terms of KI weight. Immediately after the addition, an aqueous solution 6 containing 66.4 g of AgNO ₃
09 mL was added over 11 minutes. During the initial 6 minutes of the addition, the pA of the bulk emulsion solution in the reaction vessel was treated with an aqueous KBr solution.
g was kept at 9.50. After washing with water, gelatin was added and the pH was adjusted to 6.5, pAg, and 8.2 at 40 ° C. Thereafter, the compound RS-1 was added in an amount of 2 × 1 per mol of silver halide.
0 ^-3 mole was added and heated to 56 ° C.. Sensitizing dye Exs-
3 and Exs-6 were added, and then potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added and ripened for optimal chemical sensitization.
At the end of chemical sensitization, compounds ExA-2 and ExA-3 were added. The amount of the sensitizing dye used was 1 silver halide.
3.69 × 10 ⁻⁴ mol of Exs-3 per mol, Ex
s-6 is 8.19 × 10 ^-4 mol.

(Preparation of Emulsion N) Gelatin-2 of Example 1
Solution containing 0.38 g of KBr and 0.9 g of KBr
L was maintained at 60 ° C., the pH was adjusted to 2, and the mixture was stirred vigorously.
An aqueous solution containing 1.03 g of AgNO ₃ and 0.8% of KBr
An aqueous solution containing 8 g and 0.09 g of KI was added by a double jet method over 30 seconds. After completion of the ripening, 12.8 g of gelatin-3 of Example 1 was added. After adjusting the pH to 5.9, KBr, 2.99 g, NaCl, 6.2 g
Was added. An aqueous solution containing 27.3 g of AgNO ₃ 60.
7 mL and an aqueous KBr solution were added by the double jet method over 39 minutes. At this time, the pAg of the bulk emulsion solution in the reaction vessel was kept at 9.05. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were accelerated by a double jet method so that the final flow rate was 2.1 times the initial flow rate, and 46
Added over minutes. At this time, the AgI fine grain emulsion used in the preparation of Emulsion A-1 was changed to a silver iodide content of 6.5 mol.
%, And the pAg of the bulk emulsion solution in the reaction vessel was maintained at 9.05.

Aqueous solution 13 containing 41.8 g of AgNO ₃
2 mL and an aqueous KBr solution were added over 16 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition became 7.70. Sodium benzenethiosulfonate 2mg
Was added, and KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.80. The above AgI fine grain emulsion was added in an amount of 6.2 g in terms of KI weight. Immediately after completion of the addition, an aqueous solution 300 containing 88.5 g of AgNO _{3 was} added.
mL was added over 10 minutes. The K is adjusted so that the pAg of the bulk emulsion solution in the reaction vessel at the end of the addition is 7.40.
It was adjusted by adding a Br aqueous solution. After washing with water, gelatin-1 of Example 1 was added and pH 6.5, pAg at 40 ° C.
Adjusted to 8.2. The compound RS-1 was added at 1 × 10 ⁻³ mol per mol of silver halide and then heated to 58 ° C. Sensitizing dyes Exs-7, Exs-8 and Exs-9
Was added, K ₂ IrCl ₆ potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimal chemical sensitization. At the end of the chemical sensitization, ExA-2 and compound ExA-3 were added.

(Preparation of Emulsion O)
The amount of AgNO ₃ added during nucleation is 1.96 g,
The amount of Br was changed to 1.67 g, the amount of KI was changed to 0.172 g, and the temperature at the time of chemical sensitization was changed from 58 ° C to 6 ° C.
The temperature was changed to 1 ° C. Other than that, it was prepared in substantially the same manner as in emulsion N. Compounds RS-1, ExA-2 and Ex
A-3 was added almost in the same manner as Emulsion N.

(Preparation of Emulsion P) Gelatin-4 of Example 1
Solution containing 4.9 g of KBr and 5.3 g of KBr
L was kept at 40 ° C. and stirred vigorously. AgNO_Three, 8.7
27 mL of aqueous solution containing 5 g and KBr, containing 6.45 g
Add 36mL of aqueous solution by double jet method over 1 minute
did. After the temperature was raised to 75 ° C., AgNO_Three, 6.9 g
21 mL of aqueous solution was added over 2 minutes. NH_FourN
O_Three, 26 g, 1N, NaOH, 56 mL were added sequentially.
After ripening. After ripening, adjust the pH to 4.8
Was. AgNO _Three438 mL of an aqueous solution containing 141 g and K
Double aqueous solution (458 mL) containing 102.6 g of Br
Add so that the final flow rate is four times the initial flow rate
Was. After cooling to 55 ° C, AgNO_ThreeContains 7.1 g
Dub an aqueous solution containing 240 mL of aqueous solution and 6.46 g of KI
It was added over 5 minutes by the Rujet method. 7.1 KBr
g of sodium benzenethiosulfonate,
mg and K_TwoIrCl₆, 0.05 mg were added. AgNO
_Three177 mL of an aqueous solution containing 57.2 g, KBr,
Add 223 mL of an aqueous solution containing 0.2 g over 8 minutes.
It was added by the Bulljet method. Washed almost the same as emulsion N
And chemically sensitized. Compounds RS-1, ExA-2 and
And ExA-3 were added almost in the same manner as Emulsion N.

(Preparation of Emulsions Q and R) Emulsions K and L were prepared in substantially the same manner. However, the chemical sensitization was carried out in substantially the same manner as for emulsion O. Compound RS-
1, ExA-2 and ExA-3 were also added in substantially the same manner as Emulsion N.

The emulsions Da, Db, Ea and E-
The structures of the sensitizing dyes used for b, Fa, Fb, Ga, Gb, and H to R are collectively shown.

[0209]

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[0210]

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The characteristic values of the silver halide emulsion are shown in Table 4. The above emulsions Da, Db, E
-A, Eb, Fa, Fb, Ga, Gb, H ~
Dislocation lines as described in JP-A-3-237450 are observed in the silver halide grains of R using a high-pressure electron microscope.

[0212]

[Table 4]

1) Support The support used in this example was:
Created by the following method. 100 parts by weight of polyethylene-2,6-naphthalate polymer and Tinuvin P. as an ultraviolet absorber. 326
2 parts by weight (Ciba-Geigy) were dried, melted at 300 ° C., extruded from a T-die, and longitudinally stretched 3.3 times at 140 ° C.
The film is stretched 3.3 times at 30 ° C. and further stretched at 250 ° C. for 6 times.
This was heat-set for 2 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye and a yellow dye (public technique: I-1, I- described in Japanese Patent Publication No. 94-6023).
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 winding core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV discharge treatment, and a glow discharge treatment on both surfaces, and then 0.1 g / g of gelatin was applied to each surface.
m ² , 0.01 g / m ^{2 of} sodium α-sulfodi-2-ethylhexyl succinate, 0.04 g of salicylic acid /
m ² , 0.2 g / m ^{2 of} p-chlorophenol, (CH ₂ =
CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ , 0.012 g
/ M ² , polyamide-epichlorohydrin polycondensate
An undercoat solution of 02 g / m ² was applied (10 mL / m ² , using a bar coater), and an undercoat layer was provided on the high-temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° 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 Tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm which is a dispersion of fine particle powder (secondary aggregated particle size of about 0.08 μm). .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 N
HCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g /
It was coated with m ² and resorcin.

3-2) Coating of Magnetic Recording Layer
Degree 15) Oxyethylene-propyloxytrimethoxy
Cobalt-γ coated with silane (15% by weight)
-Iron oxide (specific surface area 43 m^Two/ G, major axis 0.14 μm,
Uniaxial 0.03 μm, saturation magnetization 89 emu / g, Fe⁺²/
Fe⁺³= 6/94, the surface is aluminum oxide silicon oxide and iron oxide
0.06 g / m2^TwoThe zia
Cetyl cellulose 1.2 g / m^Two(The dispersion of iron oxide is
Pun kneader and sand mill), as a hardener
C_TwoH_FiveC (CH_TwoOCONH-C₆H_Three(CH_Three) NCO)
_Three 0.3g / m ^TwoWith acetone, methylethyl
Paint with a bar coater using luketone and cyclohexanone.
Then, a magnetic recording layer having a thickness of 1.2 μm was obtained. With matting agent
And silica particles (0.3 μm) and 3-poly (degree of polymerization 1)
5) Oxyethylene-propyloxytrimethoxysila
(15% by weight) coated abrasive aluminum oxide
(0.15 μm) at 10 mg / m^TwoSo that
Was added. Drying was performed at 115 ° C. for 6 minutes (drying zone).
All rollers and transport devices are 115 ° C). X-La
Of the magnetic recording layer at the site (blue filter)^BColor depth
The degree of increase is about 0.1, and the saturation magnetization
4.2 emu / g, coercive force 7.3 × 10 ^FourA /
m and the squareness ratio were 65%.

3-3) Adjustment of Sliding Layer Diacetylcellulose (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
A mixture of O (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) was applied. Note that this mixture is made of xylene / p
After melting at 105 ° C. in propylene monomethyl ether (1/1) and pouring and dispersing in propylene monomethyl ether (10-fold amount) at room temperature, it is dispersed in acetone (average particle size 0.01 μm). And then added. As a matting agent, silica particles (0.3 μm) and aluminum oxide (0.15 μm) coated with 3-poly (degree of polymerization 15) oxyethylenepropyloxytrimethoxysilane (15% by weight) as an abrasive are each 15 mg / m 2. ² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer is
Dynamic friction coefficient 0.06 (5mmφ stainless steel hard ball, load 100g, speed 6cm / min), static friction coefficient 0.07
(Clip method), and the coefficient of kinetic friction between the emulsion surface and the sliding layer described later was excellent at 0.12.

4) Coating of Photosensitive Layer (Sample 301) Next, on the opposite side of the back layer obtained above to the support, each layer having the following composition was applied in a multi-layered manner to obtain a color negative photosensitive material. 301 was created. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener (Specific compounds are described below, numbers are added after symbols, and chemical formulas are listed after the numbers.) The number corresponding to each component is the coating weight in g / m ^2. And for silver halide, the coating amount in terms of silver is shown.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.155 Silver Iodobromide Emulsion T Silver 0.01 Gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd-20 0.001 HBS-1 0.004 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.077 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid Disperse Dye ExF -2 0.014 solid disperse dye ExF-3 0.020.

Third layer (intermediate layer) Silver iodobromide emulsion S 0.020 ExC-2 0.022 polyethyl acrylate latex 0.085 gelatin 0.294.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion R silver 0.065 silver iodobromide emulsion Q silver 0.258 ExC-1 0.109 ExC-3 0.044 ExC-40 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver iodobromide emulsion P silver 0.21 silver iodobromide emulsion O silver 0.62 ExC-1 0.14 ExC-2 0.026 ExC-30 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion N silver 1.47 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY- 5 0.008 ExG-1 0.002 Cpd-2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 F-19 1.0 × 10 ^-5 F-20 1.0 × 10 ^-5 gelatin 2.12.

Seventh layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84.

Eighth Layer (Layer Which Gives Layered Effect to Red Sensitive Layer) Silver iodobromide emulsion M 0.560 Cpd-3 0.020 Cpd-4 0.030 ExM-2 0.096 ExM-30 028 ExY-1 0.031 ExG-1 0.003 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion L silver 0.39 silver iodobromide emulsion K silver 0.28 silver iodobromide emulsion J silver 0.35 ExM-2 0.36 ExM-3 0.045 ExG-1 0.005 Cpd-3 0.010 HBS-1 0.28 HBS-3 0.01 HBS-4 0.27 Gelatin 1.39.

Tenth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 0.45 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM- 4 0.028 ExG-1 0.005 Cpd-3 0.006 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44.

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I silver 0.25 silver iodobromide emulsion H silver 0.76 ExC-6 0.004 ExM-1 0.016 ExM-30 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 ExG-1 0.005 Cpd-3 0.004 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 F-19 1.0 × 10 ^-5 F-20 1.0 × 10 ^-5 gelatin 1.11.

Twelfth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.010 Cpd-1 0.16 Oil-soluble Dye ExF-5 0.010 Solid Dispersion Dye ExF-6 0.153 HBS-1 0.082 Gelatin 1 .057.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion Ea silver 0.20 Silver iodobromide emulsion Fa silver 0.07 Silver iodobromide emulsion Ga silver 0.18 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 ExG-1 0.001 Cpd-2 0.10 Cpd- 3 4.0 × 10 ⁻³ HBS-1 0.24 Gelatin 1.41.

Fourteenth Layer (High Sensitive Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion Da Silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 0.075 Cpd-3 1.0 × 10 ⁻³ HBS-1 0.10 Gelatin 0.91.

Fifteenth Layer (First Protective Layer) Silver Iodobromide Emulsion S Silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-180 0.0009 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3.

Sixteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-30 .05 S-1 0.20 gelatin 0.75.

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial property, antistatic property and coatability of each layer, W-1 to W-5, P-4 to P -6, F
-1 to F-9, F-11 to F-20, B-4 to B-6 and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, ruthenium salts, rhodium salts. I have. The coating solution for the eighth layer was 8.5 × 10 ^-3 g per mol of silver halide, and the coating solution for the eleventh layer was 7.9 × 10 ^-3 g / mol.
^A sample was prepared by adding ^-3 grams of calcium with an aqueous solution of calcium nitrate.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
5.0 g and zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.2
It was 4 μm.

Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the fine dye particles was 0.45 μm. E
xF-2 is disclosed in European Patent Application Publication (EP) 549,489.
Microprecipitation described in Example 1 of the specification of A (Microp
(recipitation) dispersion method.
The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method. ExF-6 wet cake 2 containing 18% water
In 800 g, 4.0 kg of water and a 3% solution of W-2 were added to 37 g.
6 g was added and stirred to obtain a slurry having a concentration of ExF-6 of 32%. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd.
Milling was performed for 8 hours at a discharge rate of 0.5 l / min at m / sec. The average particle size was 0.52 μm. The compounds used to form the above layers are as shown below.

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(Preparation of Sample 302) Sample 302 was prepared by making the following changes to Sample 301.

1) In the fourteenth layer, silver iodobromide emulsion Da was replaced with emulsion Db having an equal silver amount. 2) In the thirteenth layer, silver iodobromide emulsion Ea was replaced with emulsion Eb having the same silver amount, silver iodobromide emulsion Fa was replaced with emulsion Fb having the same silver amount, and Silver iodobromide emulsion G
-A was replaced with emulsion Gb of equal silver content.

These samples were subjected to a hardening treatment at 40 ° C. and a relative humidity of 70% for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge and a gelatin filter SC-39 (a long-wavelength light transmission filter having a cutoff wavelength of 390 nm) manufactured by FUJIFILM Corporation. The development was carried out using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd. in accordance with the processing steps and processing liquid compositions described in Item 42 of JP-A-11-153840. 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 Hatsumei Kyokai Disclosure Technique No. 94-4992.

The photographic performance was evaluated by measuring the density of the processed sample with a blue filter. The sensitivity is represented by the relative value of the reciprocal of the exposure necessary for the yellow density to reach the fog density plus the density of 0.2 (sample 301).
Was set to 100. ).

The increase in fog of the samples 301 and 302 due to oxygen was evaluated in the same manner as in Example 1.
The results obtained are shown in Table 5 below.

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[Table 5]

As can be seen from Table 5, the silver halide color photographic light-sensitive material containing tabular grains having a high aspect ratio using the halogen oxo acid salt of the present invention significantly improved the increase in fog due to oxygen without deteriorating the sensitivity. can do.

Example 4 (Preparation of Emulsion H-2) In Emulsion H of Example 3, after adding Compound RS-1 (Addition 2), sodium chlorite was added at a ratio of 2 to 1 mol of silver halide. Emulsion H-2 was prepared in the same manner except that × 10 ^-5 mol was added.

(Preparation of Emulsion H-3) In Emulsion H of Example 3, except that sodium chlorite was added in an amount of 2 × 10 ⁻⁵ mol per mol of silver halide in “Addition 1” during grain formation. Emulsion H-3 was prepared in the same manner.

(Preparation of Samples 401 and 402) The same procedure as in Sample 3 of Example 3 was carried out except that silver iodobromide emulsion H was replaced by emulsion H-2 or H-3 having the same silver content in the eleventh layer. Thus, samples 401 and 402 were prepared.

(Evaluation of photographic performance) The photographic performance was evaluated by measuring the density of the hardened, exposed and processed samples in the same manner as in Example 3 with a green filter. Sample 4 was evaluated for sensitivity and increase in fog due to oxygen in the same manner as in Example 3.
01 and 402 obtained good results. Accordingly, the addition after the completion of the chemical sensitization is effective also in the green-sensitive emulsion, and excellent results can be obtained even when the addition is performed during grain formation.

Example 5 (Preparation of Emulsion N-2) In the emulsion N of Example 2, after adding the compound RS-1, sodium chlorite was added to 1.5 × 10 ⁻ mol per mol of silver halide. Emulsion N-2 was prepared in the same manner except that ⁵ mol was added.

(Preparation of Sample 501) Sample 30 of Example 3
Sample 501 was prepared in the same manner as in Example 1, except that silver iodobromide emulsion N was replaced with emulsion N-2 having an equal silver amount in the sixth layer.

(Evaluation of photographic performance) The photographic performance was evaluated by measuring the density of the hardened, exposed, and processed samples in the same manner as in Example 3 using a red filter. The sensitivity and the increase in fog due to oxygen were evaluated in the same manner as in Example 3, and good results were obtained. Therefore, even in a red-sensitive emulsion, excellent results can be obtained by adding it after completion of grain formation.

Example 6 (Preparation of Emulsion S-1) 1300 mL of an aqueous solution containing 1.0 g of KBr and 1.1 g of gelatin-4 of Example 1 was heated at 35 ° C.
And stirred (preparation of 1st liquid). Ag-1 aqueous solution (containing 4.9 g of AgNO ₃ in 100 mL) 38
mL and an X-1 aqueous solution (5.2 mL of KBr in 100 mL).
g-1) and G-1 aqueous solution (100 m
L contains 8.0 g of the above gelatin-4) 8.5
mL was added by the triple jet method at a constant flow rate over 30 seconds. Thereafter, 6.5 g of KBr was added,
The temperature was raised to 75C. After an aging step for 12 minutes after the temperature was raised, sodium benzenethiosulfonate was added in an amount of 0.00
25 g and 300 mL of an aqueous G-2 solution (containing 12.7 g of gelatin-3 of Example 1 in 100 mL) were added.

Next, an aqueous solution of Ag-2 (A in 100 mL)
Gno ₃ which contained 22.1 g) and 157 mL, X-2
Aqueous solution (containing 15.5 g of KBr in 100 mL)
Was added by the double jet method over 14 minutes. At this time, the final flow rate of addition of the Ag-2 aqueous solution is 3.
The flow rate was accelerated so as to be four times, and the addition of the X-2 aqueous solution was performed so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.30. Then, an Ag-3 aqueous solution (100 m
329 mL containing 32.0 g of AgNO ₃ in L)
And an X-3 aqueous solution (21.5 KBr in 100 mL).
g, KI containing 1.2 g) by the double jet method.
Added over 7 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.30. I went to keep it. Further, an Ag-4 aqueous solution ( ₃ mL of AgNO ₃ in 100 mL) was added.
156 mL containing 2.0 g) and an X-4 aqueous solution (10
(Containing 22.4 g of KBr in 0 mL) by the double jet method over 17 minutes. At this time, Ag-4
The aqueous solution was added at a constant flow rate, and the X-4 aqueous solution was added such that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 7.52.

Next, 4,5-dihydroxybenzene-
Reduction sensitization was performed by adding 6.9 g of disodium 1,3-disulfonate. Then, G-3 aqueous solution (100 mL
125 g of the above gelatin-1)
mL was added sequentially at one minute intervals. Next, 43.7 g of KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.00, and then the AgI fine grain emulsion (1
AgI fine particles having an average particle size of 0.047 μm
73.9 g (containing 3.0 g) was added, and two minutes later, 249 mL of an Ag-4 aqueous solution and an X-4 aqueous solution were added by a double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 9 minutes, and the X-4 aqueous solution was added for only the first 3.3 minutes to the pAg of the bulk emulsion solution in the reaction vessel.
Was added so as to keep it at 9.00, and was not added for the remaining 5.7 minutes so that the pAg of the bulk emulsion solution in the reaction vessel finally reached 8.4.

Thereafter, desalting was carried out by a usual flocculation method, and then water, NaOH and the above-mentioned gelatin-1 were added with stirring, and pH 6.4, pA at 56 ° C.
g was adjusted to 8.6.

Subsequently, spectral sensitization and chemical sensitization were carried out in the same manner as in Emulsion H of Example 3. Exs-3 was 5.50 × 10 ^-4 mol per mol of silver halide and Exs
-4 is 1.30 × 10 ^-4 mol, Exs-5 is 4.65 ×
^10-5 mol was added and compound ExA was added before chemical sensitization.
-1 was added in an amount of 2.times.10.sup.- ³ mol per mol of silver halide. After optimal addition of potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea for optimal chemical sensitization, compound RS-1 was added at 2 × 10 ⁻³ mol per mol of silver halide. . Next, the chemical sensitization was terminated by adding a total of 3.6 × 10 ^-4 mol of the water-soluble mercapto compounds MER-1 and MER-2 in a ratio of 4: 1 per mol of silver halide.

(Preparation of Emulsion S-2) In Emulsion S-1, before the start of ripening, when the temperature was raised to 75 ° C., sodium chlorite was added in an amount of 5 × 10 ⁻⁵ to 1 mol of silver halide.
Emulsion S-2 was prepared in the same manner except that mol was added.

(Preparation of Emulsion S-3) In the emulsion S-1, sodium chlorite was added at 5 × with respect to 1 mol of silver halide after adding the AgI fine grain emulsion and before adding the Ag-4 and X-4 solutions. Emulsion S- was prepared in the same manner except that ^10-5 mol was added.
3 was prepared.

(Preparation of Emulsions S-4 to S-6) Emulsion S-1
4,5 used as a reduction sensitizer in S-3
Emulsions S-4, S-5 and S-6 were prepared in the same manner except that 0.020 g of compound RS-1 was added instead of disodium dihydroxybenzene-1,3-disulfonate.

(Preparation of Emulsion S-7) 1.0 g of KBr was prepared.
Aqueous solution 1300 containing 1.1 g of gelatin-4 of Example 1
mL was kept at 35 ° C. and stirred (1st liquid preparation). A
38 mL of an aqueous g-1 solution (containing 4.9 g of AgNO ₃ in 100 mL) and an aqueous X-1 solution (K in 100 mL)
29 mL of Br (containing 5.2 g) and 8.5 mL of an aqueous G-1 solution (containing 8.0 g of the above gelatin-4 in 100 mL) were added by a triple jet method at a constant flow rate over 30 seconds. Then, KBr 6.5
g was added and the temperature was raised to 75 ° C. After an aging step for 12 minutes after the temperature was raised, an aqueous G-2 solution (containing 12.7 g of gelatin-3 of Example 1 in 100 mL) 300 m
L was added. Then, 4,5-dihydroxybenzene-
Reduction sensitization was performed by adding 6.9 g of disodium 1,3-disulfonate.

Next, an aqueous solution of Ag-2 (A in 100 mL)
Gno ₃ which contained 22.1 g) and 157 mL, X-2
Aqueous solution (containing 15.5 g of KBr in 100 mL)
Was added by the double jet method over 14 minutes. At this time, the final flow rate of addition of the Ag-2 aqueous solution is 3.
The flow rate was accelerated so as to be four times, and the addition of the X-2 aqueous solution was performed so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.30. Then, an Ag-3 aqueous solution (100 m
329 mL containing 32.0 g of AgNO ₃ in L)
And an X-3 aqueous solution (21.5 KBr in 100 mL).
g, KI containing 1.2 g) by the double jet method.
Added over 7 minutes. At this time, the addition of the Ag-3 aqueous solution accelerates the flow rate so that the final flow rate becomes 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution reduces the pAg of the bulk emulsion solution in the reaction vessel to 8.30. I went to keep it. Further, an Ag-4 aqueous solution ( ₃ mL of AgNO ₃ in 100 mL) was added.
156 mL containing 2.0 g) and an X-4 aqueous solution (10
(Containing 22.4 g of KBr in 0 mL) by the double jet method over 17 minutes. At this time, Ag-4
The aqueous solution was added at a constant flow rate, and the X-4 aqueous solution was added such that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 7.52.

Next, 0.0025 g of sodium benzenethiosulfonate was added, and a G-3 aqueous solution (100 mL) was added.
125 g of the above gelatin-1)
mL was added sequentially at one minute intervals. Next, 43.7 g of KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.00, and then the AgI fine grain emulsion (1
AgI fine particles having an average particle size of 0.047 μm
73.9 g (containing 3.0 g) was added, and two minutes later, 249 mL of an Ag-4 aqueous solution and an X-4 aqueous solution were added by a double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate over 9 minutes, and the X-4 aqueous solution was added for only the first 3.3 minutes to the pAg of the bulk emulsion solution in the reaction vessel.
Was added so as to keep it at 9.00, and was not added for the remaining 5.7 minutes so that the pAg of the bulk emulsion solution in the reaction vessel finally reached 8.4. Thereafter, desalting was carried out by a normal flocculation method, and then water, NaOH and the above-mentioned gelatin-1 were added with stirring, and the mixture was adjusted to pH 6.4 and pAg 8.6 at 56 ° C. Subsequently, the same spectral sensitization and chemical sensitization as in emulsion S-1 were performed.

(Preparation of Emulsion S-8) In Emulsion S-7, after adding the AgI fine grain emulsion, and before adding the Ag-4 and X-4 solutions, sodium chlorite was added in an amount of 5 × with respect to 1 mol of silver halide. Emulsion S- was prepared in the same manner except that 10 ^-6 mol was added.
8 was prepared.

(Preparation of Samples 601 to 608) The same procedure as in Sample 301 of Example 3 was carried out except that silver iodobromide emulsion H was replaced by emulsions S-1 to S-8 having the same silver content in the eleventh layer. Thus, samples 601 to 608 were prepared.

(Evaluation of Photographic Performance) The photographic performance was evaluated by measuring the density of the hardened, exposed and processed samples in the same manner as in Example 3 using a green filter. The sensitivity and the increase in fog due to oxygen were evaluated in the same manner as in Example 3 (the sensitivity of Sample 601 was set to 100). Table 6 shows the results.

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[Table 6]

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According to the present invention, it is possible to provide a silver halide photographic emulsion and a silver halide photographic material having high sensitivity and improved fog increase by oxygen.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kiyoshi Morimoto 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (72) Inventor Hirotomo Sasaki 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film F Term (reference) 2H023 BA01 BA04 CA03

Claims (5)

[Claims] 1. A silver halide photographic emulsion produced in the presence of at least one oxoacid salt of a halogen represented by the following general formula (I). M (XO _n ) _m (I) In the formula, M represents an alkali metal ion or an alkaline earth metal ion, X represents a halogen atom, n represents 2 or 3, and m represents 1 or 2. 2. The silver halide photographic emulsion according to claim 1, wherein the oxo acid salt of the halogen is a chlorite. 3. The silver halide photographic emulsion contains tabular silver halide grains whose parallel main plane is a (111) plane and whose aspect ratio is 5 or more, 50% or more of the total projected area. The silver halide photographic emulsion according to claim 1 or 2, wherein 4. The silver halide photographic emulsion according to claim 1, wherein the silver halide photographic emulsion is at least one selected from (a) thiourea dioxide, (b) hydroxyamines and derivatives thereof, and (c) dihydroxybenzenes and derivatives thereof. A silver halide photographic emulsion characterized by being reduction sensitized with various kinds of reducing agents. 5. A silver halide photographic material having at least one silver halide emulsion layer on a support,
5. The silver halide emulsion layer according to claim 1, wherein
13. A silver halide photographic light-sensitive material, comprising the silver halide photographic emulsion described in item 8.