JP2000066322A - Compound for silver halide photographic sensitive material and preparation of silver halide photographic emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a silver halide photographic emulsion excellent in sensitivity and graininess and to provide a silver halide photographic sensitive material using the emulsion. SOLUTION: This silver halide photographic emulsion is prepd. by using a compd. for a silver halide photographic sensitive material contg. a substituent capable of releasing a bromine or chlorine ion in the molecule. The compd. is preferably represented by formula X-(L1)n1}n2-L2-(SOL)m, wherein X is Cl or Br, each of L1 and L2 is a divalent combining group, SOL is a water-soluble group, n1 is 0 or 1 and each of m and n2 is an integer of 1-4. This method is a method for manufacturing the emulsion by using the compound. Further, this is the silver halide photographic material so as to make the emulsion use.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for a silver halide photographic light-sensitive material and a method for producing a silver halide photographic emulsion, and more particularly, to a method for producing a silver halide photographic emulsion having excellent sensitivity and granularity, and a method for producing the same. To a silver halide photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art Photographic equipment such as cameras has become increasingly popular in recent years, and opportunities for taking photographs using silver halide photographic materials (hereinafter simply referred to as "photosensitive materials") have been increasing. Accordingly, demands for higher sensitivity and higher image quality have been increasing.

One of the dominant factors for increasing the sensitivity and image quality of photosensitive materials is silver halide grains. The development of silver halide grains aimed at higher sensitivity and higher image quality has been developed. It has traditionally been advanced in the industry. However, as generally practiced, the sensitivity tends to decrease as the size of the silver halide grains is reduced to improve image quality.
There is a limit to achieving both high sensitivity and high image quality.

In order to achieve higher sensitivity and higher image quality, techniques for improving the sensitivity / grain size ratio per silver halide grain have been studied. As one of them,
A technique using tabular silver halide grains is disclosed in
No. 111935, No. 58-111936, No. 58-1
Nos. 11937, 58-113927, 59-99
No. 433, etc.

When these tabular silver halide grains are compared with so-called normal-crystal silver halide grains such as octahedral, tetradecahedral or hexahedral, the surface area increases when the silver halide grains have the same volume. Therefore, many sensitizing dyes can be adsorbed on the silver halide grain surface,
There is an advantage that the sensitivity can be further improved.

JP-A-6-230491, JP-A-6-235
988, 6-258745, 6-289516
Have examined using tabular silver halide grains having a higher aspect ratio than before.

Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside tabular silver halide grains, and JP-A-63-163541 discloses a technique of forming a core between twin planes. A technique using tabular silver halide grains having a ratio of grain thickness to long distance of 5 or more is disclosed.
The effects on sensitivity and granularity are shown, respectively.
JP-A-63-106746 discloses a tabular silver halide grain having a substantially layered structure in a direction parallel to two opposite main planes.
Has a layered structure separated by planes substantially parallel to two opposite main planes, and the average silver iodide content of the outermost layer is the average silver iodide content of the entire silver halide grains. It describes a technique for using tabular silver halide grains that are at least 1 mol% higher than the respective ratios.

[0008] In addition, JP-A-1-183644 discloses that
A technique using tabular silver halide grains, characterized in that the silver iodide distribution of silver halide containing silver iodide is completely uniform is disclosed.

Further, there is disclosed a technique for controlling carriers by metal doping, that is, a technique for improving photographic characteristics by mainly including a polyvalent metal oxide in silver halide grains.

JP-A-3-196135 and JP-A-3-189
No. 641 and the like disclose a silver halide photographic emulsion produced in the presence of an oxidizing agent for silver and the effect of using a light-sensitive material using the same on sensitivity and fog.

Japanese Patent Application Laid-Open No. Sho 63-220238 discloses a technique using a silver halide emulsion containing tabular silver halide grains in which the positions of dislocation lines are defined.
No. 0 discloses a technique using a silver halide photographic emulsion containing tabular silver halide grains in which dislocation lines are concentrated near the apex of the grain, and Japanese Patent Publication No. 3-18695 discloses a clear core / shell structure. A technology using silver halide grains having a silver halide grain is disclosed in Japanese Patent Publication No. 3-31245, which relates to a silver halide grain having a core / shell three-layer structure.

JP-A-5-323487 and JP-A-6-117
No. 81, No. 6-11772, No. 6-27564, No. 6-250309, No. 6-250310, No. 6-2
Nos. 50311, 6-250313, 6-2425
No. 27 and the like realize high sensitivity and improved fog / pressure resistance by using an iodide ion releasing compound in forming silver halide grains.

However, these conventional techniques have a limit in achieving both high sensitivity and high image quality, and are insufficient to satisfy recent demands on photosensitive materials. Was rare.

[0014]

An object of the present invention is to provide a method for producing a silver halide photographic emulsion. More specifically, a halide other than iodine ion is uniformly distributed between silver halide grains on the surface and inside of the silver halide grains. A method for producing a silver halide photographic emulsion having excellent sensitivity and granularity, and a method for producing a silver halide photographic emulsion having excellent sensitivity and granularity. An object of the present invention is to provide a silver halide photographic material.

[0015]

The above object is achieved by the following means. (1) A compound for a silver halide photographic material having a substituent capable of releasing a bromine ion or a chlorine ion in the molecule. (2) The compound represented by the general formula (I) (1)
4. The compound for a silver halide photographic light-sensitive material according to item 1. (3) The compound for a silver halide photographic light-sensitive material according to (2), wherein L ₁ in the general formula (I) has a structure represented by the general formula (II). (4) The compound for a silver halide photographic light-sensitive material according to any one of (1) to (3) is converted into the amount of silver in forming silver halide grains in the step of producing a silver halide photographic emulsion. At least 40% by weight. (5) The compound for a silver halide photographic light-sensitive material is added in an amount of 40% or more in terms of silver in the formation of silver halide grains in the production process of a silver halide photographic emulsion, and before the formation of silver halide grains is completed. (4) The method for producing a silver halide photographic emulsion according to (4).

Hereinafter, the present invention will be described specifically.

The compound for a light-sensitive material according to the present invention can reduce the non-uniformity in the content of silver bromide and silver chloride among silver halide grains, and can improve the sensitivity-granularity relationship. Compared with the case where silver iodide is formed by using an iodide ion-releasing compound, the effect on photographic performance such as development suppression is small, and it can be widely applied to silver halide photographic emulsions having a high silver chloride content.

In the present invention, the step of producing a silver halide photographic emulsion refers to a step from the formation of silver halide grains to the step before coating, specifically, the formation of silver halide grains, desalting,
This is a process from color sensitization, chemical sensitization, preparation of a coating solution to before coating.

In the present invention, the formation of silver halide grains means that after the nuclei of silver halide grains in the photographic emulsion according to the present invention have begun to form, the silver halide grains have been subjected to crystal growth and physical ripening, and then desalted. This is the previous process.

The compound of the present invention can be used in any step of the production of a silver halide photographic emulsion.
It is preferable to add at 0% or more. Particularly preferably, the amount of silver in the formation of silver halide grains is 4%.
It is preferably added from 0% to the end of silver halide grain formation.

When the compounds of the present invention are added in the step of preparing a silver halide photographic emulsion, they may be directly dispersed in the emulsion or may be used alone or in a mixture of solvents such as water, methanol and ethanol. A solution may be added, and a method of adding a compound to a silver halide emulsion generally in the art can be applied.

The addition amount of the compound of the present invention is preferably 1 × 10 ⁻⁷ to 30 mol% based on silver halide, and 1 × 10 ⁻⁷ mol%.
^{-5 to} 5 mol% is more preferred.

The compound of the present invention can be used in addition to a silver halide photographic emulsion by a method generally used in the art, or, if necessary, after addition, by reaction with a base or / and a nucleophile. It can be used by releasing bromine ions or chloride ions.

In the present invention, a nucleophile and a base can be used in combination.

Examples of the nucleophile that can be used include hydroxide ion, sulfite ion, hydroxylamine, hydroxamic acids, metabisulfite ion, thiosulfate ion, oximes, mercaptans, sulfinate, carboxylate, and the like. There are acid salts, ammonium compounds, amine compounds, phenols, alcohols, thioureas, ureas, hydrazines, sulfides, phosphines and the like, with preference given to alkali metal hydroxide compounds.

In the present invention, the timing and rate of bromine ion or chloride ion release can be controlled by the method of adding the nucleophile or base, the concentration, and the reaction temperature.

In the present invention, the concentration of the base and / or nucleophile is preferably 1 × 10 ^{−7 to} 50 M (molar concentration),
1 × 10 ^{−5 to} 10 M is more preferable, and 1 × 10 ^{−3 to 5} M
Is particularly preferred. The temperature at the time of addition is preferably from 20 to 90C, more preferably from 30 to 85C, even more preferably from 35 to 80C.

When a base is used to release bromine ions or chloride ions, the pH may be controlled. The pH at this time is 7
To 12 are preferable, and 8 to 11 are more preferable.

The bromine or chloride ions released are:
The content is preferably 0.001 to 30 mol%, more preferably 0.01 to 10 mol%, based on silver halide.

Compounds having a substituent capable of releasing an adsorbable group to silver halide and a halogen ion in the molecule may release all of the halogen atoms in the compound, and a part of the compound may remain without being decomposed. It may be.

The compounds of the present invention release bromine ions or chloride ions, but preferably release chloride ions. The compound of the present invention may be used alone,
Two or more kinds may be used in combination.

The compound of the present invention is disclosed in Japanese Patent Application No. 9-25206.
The compound described in No. 9 is preferably not a compound having both a group capable of releasing a halogen ion and a group capable of releasing a halogen ion in a molecule.

The compound according to the present invention, which has a substituent capable of releasing bromine ion or chloride ion in the molecule, is preferably represented by the following general formula (I).

General formula (I) {X- (L ₁ ) _n1 } _n2 −L ₂
— (SOL) _{m In the} formula, X represents a chlorine atom or a bromine atom, L ₁ and L ₂ each represent a divalent linking group, and SOL represents a water-soluble group. n
₁ represents 0 or 1, and n ₂ represents an integer of 1 to 4.

Further, it is preferable that L ₁ in the general formula (I) has a structure represented by the following general formula (II).

Formula (II) -C (R ₁ ) (R ₂ ) -C
(R ₃ ) (R ₄ ) -EWG- wherein R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and EWG represents —COO—, —OCO—, —SO ₂ —,
_{-SO 2 O -, - CON (} R 4) -, - N (R 4) CO
_{-, - CSN (R 4)} -, - N (R 4) CS -, - N (R
₄ )-, -O-, -S-, -CO-, -CS-, -CO
CO—, —SO ₂ N (R ₄ ) — or —N (R ₄ ) SO ₂ —, wherein R ₄ represents a hydrogen atom, an alkyl group or an aryl group.

First, the general formula (I) will be described in detail.

In the general formula (I), X represents a chlorine atom or a bromine atom, preferably a chlorine atom.

The divalent linking group represented by L1 includes an aliphatic group, an aromatic group, a heterocyclic group, and those groups and —COO
-, - OCO -, - SO 2 -, - SO 2 O -, - CON
(R ₄ )-, -N (R ₄ ) CO-, -CSN (R ₄ )-,
—N (R ₄ ) CS— is preferably a group obtained by arbitrarily bonding, and more preferably a divalent aliphatic group and —COO—,
_{-OCO -, - SO 2 -,} - SO 2 O -, - CON
(R ₄ )-, -N (R ₄ ) CO-, -CSN (R ₄ )-,
—N (R ₄ ) CS— is a group obtained by arbitrarily bonding, and particularly preferably adopts a structure represented by the general formula (II). n ₁ represents 0 or 1, but preferably 1
It is.

The divalent linking group represented by L ₂ is preferably an aliphatic group, an aromatic group or a heterocyclic group, more preferably an aromatic group, and particularly preferably a phenylene group.

The SOL group represents a water-soluble group. The water-soluble group is a group that, when added to a compound, improves the hydrophilicity of the compound and further improves the solubility in water. Specific examples include a carboxyl group, a sulfo group, a hydroxyl group, and a quaternary ammonium group. Among them, preferred are a sulfo group, a carboxyl group and a hydroxyl group. The carboxyl group and the sulfo group are preferably in the form of a salt of an alkali metal atom (such as sodium or potassium) from the viewpoint of improving water solubility. m is 1
Represents an integer of 1 to 4, preferably 1 or 2, and particularly preferably 1.

Next, the general formula (II) will be described in detail.

Specific examples of the substituent represented by R _{1 to} R ₃ include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, a urethane group and an aryloxy group. Group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxyl group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy Groups, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoramide group, a diacylamino group, an imide group and the like. R _{1 to} R ₃ are preferably a hydrogen atom.

EWG is -COO-, -OCO-, SO _{2
-, - SO 2 O -,} - CON (R 5) -, - N (R 5) C
_{O -, - CSN (R 5} ) -, - N (R 5) CS -, - O
-, - S -, - N (R 5) -, - CO-. −CS −, −
_{COCO -, - SO 2 N (} R 5) - or -N (R ₅₎ SO ₂
And R ₅ represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.

Hereinafter, specific examples of the compound of the present invention will be listed, but the present invention is not limited thereto.

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Next, typical examples of the synthesis of the compounds of the present invention will be described. Synthesis Example 1 (Synthesis of Compound CL-8) After 27.5 g of 5-aminoisophthalic acid and 40.5 g of sodium hydrogen carbonate were dissolved in 330 ml of water, 29.8 g of chloroacetyl chloride was slowly added dropwise with ice cooling.
After completion of the dropwise addition, the reaction was allowed to proceed for 30 minutes.
ml was slowly added dropwise. The precipitated crystals were collected by filtration and dried to obtain the desired product (yield: 40 g). The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis. Synthesis Example 2 (Synthesis of Compound CL-20) 33 g of 2-aminoethane-1-sulfonic acid and 44.3 g of sodium hydrogen carbonate were dissolved in 390 ml of water, and 50 g of p-chloromethylbenzoyl chloride was slowly added dropwise at room temperature. After the dropwise addition, the mixture was reacted for 5 hours, filtered, and 40 g of sodium chloride was added to the filtrate. The precipitated crystals were collected by filtration and recrystallized from water to obtain the desired product (yield 4).
0 g). The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis. Synthesis Example 3 (Synthesis of Compound CL-26) 57.5 g of sodium hydrogen carbonate and 52 g of sulfanilic acid
Was dissolved in 450 ml of water, and 38.6 g of chloroacetyl chloride was slowly added dropwise while cooling with ice. After the completion of the dropwise addition, the mixture was allowed to react for 30 minutes, filtered, and the filtrate was cooled.
The precipitated crystals were collected by filtration and recrystallized from water to obtain the desired product (yield: 65 g). The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis. Synthesis Example 4 (Synthesis of Compound CL-61) 130 g of phenolsulfonic acid was dissolved in 1000 ml of water, and 140 g of sodium hydrogen carbonate was added little by little.
After completion of the addition, the mixture was cooled to 10 ° C., and 114 g of chloropropionic chloride was slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. After adding 30 g of activated carbon and further stirring, the activated carbon was filtered, the filtrate was distilled off under reduced pressure, and the residue was recrystallized from water to obtain 122 g of the desired product. Chemical structure is NMR
Confirmed by spectrum, MS spectrum, IR spectrum and elemental analysis. Synthesis Example 5 (Synthesis of Compound CL-91) 131.8 g of sulfanilic acid was dissolved in 1000 ml of water, and 143.2 g of sodium hydrogencarbonate was added little by little. After the addition was completed, the mixture was cooled to 10 ° C and 109 g of chloropropionic chloride was slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. After adding 30 g of activated carbon and further stirring, the activated carbon was filtered, the filtrate was distilled off under reduced pressure, and the residue was recrystallized from water to obtain 138 g of the desired product. The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis. Synthesis Example 6 (Synthesis of Compound CL-101) 50 g of β-chloroethylthiobenzene was dissolved in 250 ml of dichloromethane and cooled to 5 ° C. While maintaining the same temperature, 54.0 g of chlorosulfuric acid was slowly added dropwise. After stirring for 2 hours, the mixture was heated to room temperature and poured into 500 ml of a saturated saline solution. After stirring for a while while heating, the mixture was filtered. The residue was washed with acetone and dried to obtain 62 g of β-chloroethylthiobenzene-4-sulfonic acid.

[0075] β- chloroethyl thio benzene-4-sulfonic acid 57g was dissolved in water 200ml, Na ₂ WO ₄ · ₂
0.74 g of H ₂ O was added and cooled to 10 ° C. While maintaining the same temperature, 79 g of hydrogen peroxide solution was added dropwise. After the reaction,
Water was distilled off under reduced pressure, and the residue was washed with acetone and dried to obtain 52 g of the desired product. The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis. Synthesis Example 7 (Synthesis of Compound BR-8) After 27.5 g of 5-aminoisophthalic acid and 40.5 g of sodium hydrogen carbonate were dissolved in 330 ml of water, 32.8 g of bromoacetyl chloride was slowly added dropwise under ice cooling.
After completion of the dropwise addition, the reaction was allowed to proceed for 30 minutes.
ml was slowly added dropwise. The precipitated crystals were collected by filtration and dried to obtain the desired product (yield: 45 g). The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis. Synthesis Example 8 (Synthesis of Compound BR-20) After dissolving 33 g of 2-aminoethane-1-sulfonic acid and 44.3 g of sodium hydrogen carbonate in 390 ml of water, 68 g of p-bromomethylbenzoyl chloride was slowly added dropwise at room temperature. After the dropwise addition, the mixture was reacted for 5 hours, filtered, and 40 g of sodium chloride was added to the filtrate. The precipitated crystals were collected by filtration and recrystallized from water to obtain the desired product (yield 4).
8g). Chemical structure: NMR spectrum, MS spectrum, IR spectrum and elemental analysis Synthesis Example 9 (Synthesis of Compound BR-61) 130 g of phenolsulfonic acid was dissolved in 1000 ml of water, and 140 g of sodium hydrogen carbonate was added little by little. 10 after addition
After cooling to ℃, 134 g of bromopropionic chloride was slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. After adding 30 g of activated carbon and further stirring, the activated carbon was filtered, the filtrate was distilled off under reduced pressure, and the residue was recrystallized from water to obtain 153 g of the desired product. Chemical structure is NMR spectrum, M
It was confirmed by S spectrum, IR spectrum and elemental analysis. Synthesis Example 10 (Synthesis of Compound BR-91) 131.8 g of sulfanilic acid was dissolved in 1000 ml of water, and 143.2 g of sodium hydrogencarbonate was added little by little. After completion of the addition, the mixture was cooled to 10 ° C., and 139 g of bromopropionic chloride was slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. After adding 30 g of activated carbon and further stirring, the activated carbon was filtered, the filtrate was distilled off under reduced pressure, and the residue was recrystallized from water to obtain 158 g of the desired product. The chemical structure was confirmed by NMR spectrum, MS spectrum, IR spectrum and elemental analysis.

The silver halide grains contained in the silver halide photographic emulsion of the present invention may have a regular crystal structure such as cubic, octahedral or tetradecahedral, or may have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, the ratio between the (100) plane and the (111) plane can be arbitrarily used. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed. Twin silver halide grains having two opposing parallel twin planes can be used, but in this case, tabular silver halide grains are preferred.

The twin is a silver halide crystal having one or more twin planes in one grain, and the form of the twin is classified according to Klein and Moiser. Spondents (Photographi)
she Korrespondentz) Volume 99
Page 100, p. 57.

When tabular silver halide grains are used,
Preferably, 50% or more of the total projected area of the silver halide grains contained in the silver halide photographic emulsion is tabular silver halide grains, more preferably 60% or more, and still more preferably 80% or more.

When tabular silver halide grains are used, the proportion of tabular silver halide grains having two twin planes parallel to the main plane may be 60% or more in terms of the number of silver halide grains. It is preferably at least 70%, more preferably at least 80%.

In the present invention, tabular silver halide grains mean silver halide grains having an aspect ratio (ratio of diameter to thickness of silver halide grains) of 1.3 or more. The aspect ratio is preferably 3.0 or more, and more preferably 5.0 or more.

To determine the aspect ratio, first, the silver halide grain diameter and thickness are determined by the following method.

A latex ball having a known particle size as an internal standard and a sample coated so that the principal plane is oriented parallel to the support were prepared on a support, and shadowing was performed by a carbon vapor deposition method from a certain direction. After that, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area diameter and thickness of each silver halide grain are determined using an image processing device or the like. In this case, the thickness of the silver halide grains can be calculated from the internal standard and the length of the shadow of the silver halide grains.

The twin plane of the silver halide grains can be observed with a transmission electron microscope. The specific method is as follows.

First, a sample is prepared by coating a silver halide emulsion on a support so that the main plane of the tabular silver halide grains is oriented substantially parallel to the support. This is cut using a diamond cutter to a thickness of 0.1 μm
Obtain approximately thin sections. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

In the present invention, the average grain size of the silver halide grains is preferably from 0.2 to 10 μm, more preferably from 0.3 to 7.0 μm.
m is more preferred, and 0.4 to 5.0 μm is most preferred.

Here, the average particle size is defined as the particle size ri at which ni × ri ³ of the frequencies ni and ri ³ of the particles having the particle size ri becomes maximum (three significant figures, the minimum figure) Is rounded off, and the number of measured particles is indiscriminately 1,000 or more.)

In the case of tabular silver halide grains, the particle size ri is a diameter obtained by converting a projected image viewed from a direction perpendicular to the main plane into a circular image having the same area. Yes,
In the case of silver halide grains having a shape other than tabular silver halide grains, the diameter is obtained by converting a projected image of the silver halide grains into a circular image having the same area. The particle size ri is obtained by magnifying a silver halide particle with an electron microscope at a magnification of 10,000 to 70,000 times,
It can be obtained by actually measuring the particle diameter or the area at the time of projection on the print.

In the present invention, any silver halide photographic emulsion such as a polydisperse emulsion having a wide particle size distribution and a monodisperse emulsion having a narrow particle size distribution is used, but a monodisperse emulsion is preferable.

The monodisperse emulsion is defined as having a particle size distribution of 20% or less when the particle size distribution is defined by the following formula: particle size distribution (%) = (standard deviation / average particle size) × 100. 16% or less. The average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

In the silver halide photographic emulsion of the present invention, any silver halide such as silver iodobromide, silver iodochlorobromide and silver iodochloride can be used. Is preferably silver iodobromide or silver iodochlorobromide.

The silver halide grains contained in the silver halide photographic emulsion of the present invention have an average silver iodide content of 1 to 40 mol%.
And more preferably 2 to 20 mol%
It is.

The average silver iodide content of silver halide grains is as follows:
EPMA method (Electron Probe Micror)
o Analyzer method). In particular,
A sample in which silver halide grains are well dispersed so as not to be in contact with each other is prepared. The sample is irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen. By determining the characteristic X-ray intensity, the silver iodide content of each silver halide grain can be determined, and this is measured for at least 50 silver halide grains, and the average thereof is determined.

In the present invention, core / shell type grains can also be preferably used as silver halide grains.
Core / shell type particles are particles composed of a core and a shell covering the core, and the shell is formed by one or more layers. The silver iodide content of the core and the shell is preferably different from each other.

For producing a silver halide photographic emulsion, various methods well known in the art can be used. That is, a single jet method, a double jet method, a triple jet method, a silver halide fine particle supply method, or the like can be used in any combination.
Further, a method of controlling the pH and pAg in the liquid phase in which silver halide is formed in accordance with the growth rate of silver halide can also be used.

For the production of a silver halide photographic emulsion, a seed emulsion can also be used. When a seed emulsion is used, the silver halide grains in the seed emulsion may have a regular crystal structure such as cubic, octahedral, or tetrahedral, or may have an irregular shape such as spherical or plate-like. It may have a crystal form. In these particles, the ratio between the (100) plane and the (111) plane can be arbitrarily used. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed.

In the present invention, when tabular silver halide grains are used, the silver halide grains in the seed emulsion to be used are preferably twinned silver halide grains having twin planes. Particularly preferred are twin silver halide grains having parallel twin planes.

Regardless of whether a seed emulsion is used or no seed emulsion is used, the conditions for silver halide nucleation and ripening may be those known in the art.

For the production of a silver halide photographic emulsion, a silver halide solvent known in the art can be used. Examples of silver halide solvents include (a) U.S. Pat. Nos. 3,271,157, 3,531,289, 3,574,628, JP-A-54-1019, and JP-A-5-1019.
Organic thioethers described in JP-A-4-158917 and JP-B-58-30571;
Nos. 82408, 55-29829 and 57-77
No. 736, etc .; (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319, etc .; ) Imidazoles described in JP-A-54-100717, (e) sulfites, (f) thiocyanates, (g) ammonia, (h) JP-A-57
Ethylenediamines substituted with hydroxylalkyl described in JP-A-196228, etc .;
Substituted mercaptotetrazoles described in JP-A-02531, etc., (j) water-soluble bromide, (k) JP-A-58-543.
No. 33 and the like.

For producing a silver halide photographic emulsion, any of an acidic method, a neutral method and an ammonia method can be used.

In the production of the silver halide photographic emulsion of the present invention, a halide ion and a silver ion may be mixed at the same time, or one may be mixed in the presence of one.
In consideration of the critical growth rate of silver halide crystals, halide ions and silver ions can be added sequentially or simultaneously while controlling the pAg and pH in the mixing vessel. In any step of silver halide formation, the halogen composition of the silver halide grains may be changed by using a conversion method.

In the process of forming and / or growing silver halide grains, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt), iron A metal ion is added using at least one selected from salts of other Group VIII metals (including complex salts) and the like, and these metals can be contained inside silver halide grains and / or on the surface of the grains.

In the production of a silver halide photographic emulsion, a substance capable of constituting a protective colloid can be used as a dispersion medium, but gelatin is preferably used.

When gelatin is used as the dispersion medium, lime-treated gelatin, acid-treated gelatin, ion-exchanged gelatin and the like can be used. The details of the gelatin production method are described in Arthur Weiss, "The Macromolecular Chemistry of Gelatin" (Academic Press, 1964) and the like.
Examples of the substance capable of forming a protective colloid other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate. , Sodium alginate, sugar derivatives such as starch derivatives,
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylimidazole, etc. Functional polymer substances.

In the production of a silver halide photographic emulsion, reduction sensitization can be carried out using a method known in the art. Reduction sensitization may be performed during or after silver halide grain formation. As a more specific method of reduction sensitization, ripening at a low pAg by supplying silver ions to silver halide grains, which is called silver ripening in the art.
Any method, such as a method of growing, a method of ripening and growing by raising the pH using an alkaline compound, or the addition of a reducing agent, or a combination thereof can be used.

In the present invention, when a reducing agent is used, for example, thiourea dioxide, ascorbic acid and its derivatives,
Stannous salts, borane compounds, hydrazine derivatives, formamidine sulfinic acid, silane compounds, amines and polyamines and sulfites can be used, preferably thiourea dioxide or ascorbic acid and its derivatives,
Stannous salts are used.

In the production of a silver halide photographic emulsion,
Oxidizing agents known in the art can also be used. As an oxidizing agent
For example, hydrogen peroxide (water) and its adduct: H
_TwoO_Two, NaBO_Two, H_TwoO_Two-3H_TwoO, 2Na_TwoCO_Three-3
H_TwoO_Two, Na_FourP_TwoO₇-2H_TwoO_Two, 2Na_TwoSO_Four-H_TwoO
_Two-2H_TwoO etc. Peroxy acid salt: K_TwoS_TwoO_Three, K_TwoC_Two
O _Three, K_FourP_TwoO_Three, K_Two[Ti (O)_TwoC_TwoO_Four] -3H
_TwoO, peracetic acid, ozone, thiosulfonic acid compounds, etc.
Can be

In the production of the silver halide photographic emulsion of the present invention, it is preferable that the silver halide grains in the silver halide photographic emulsion of the present invention having a reduction sensitization and an oxidizing agent have dislocation lines therein. . There is no particular limitation on the position where the dislocation line exists, but it is preferable that it exists near the outer peripheral portion, near the ridge line, or near the vertex of the silver halide grain.
The introduction position of dislocation lines in the silver halide grains is preferably 50% or more, more preferably 60% to less than 85%, based on the total silver amount of the silver halide grains. The number of dislocation lines is preferably 30% or more (number) of silver halide grains having 5 or more dislocation lines, more preferably 50% or more, and further preferably 80% or more. preferable. In each case, the number of dislocation lines in one grain is preferably 10 or more, more preferably 20 or more, and further preferably 30 or more.

The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton; Photo. Sci.
Eng. 11 (1967) 57 and T.I. Shiozaw
a; Soc. Photo. Sci. Japan35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out from the emulsion without paying enough pressure to generate new dislocation lines on the grains are placed on a mesh of an electron microscope to prevent damage (printout, etc.) by the electron beam. The specimen is observed by a transmission method in a cooled state. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass therethrough. Therefore, a clearer observation can be obtained by using a high-pressure electron microscope. From the grain photograph obtained by such a method, the position and number of dislocation lines in each silver halide grain can be determined.

There is no particular limitation on the method of introducing dislocation lines. For example, a method of adding an aqueous solution of an iodide ion such as potassium iodide and a solution of a water-soluble silver salt by double jet, a method of adding silver iodide fine particles, a method of adding iodine ion A known method such as a method of adding only a solution, a method using an iodide ion releasing compound described in JP-A-6-11781, or a compound according to the present invention, or a compound according to the present invention is used to prepare desired silver halide grains. Position and amount of dislocation lines can be introduced.

In the present invention, the silver halide grains according to the present invention can be formed by supplying fine silver halide grains.

The fine silver halide grains may be prepared before the preparation of the silver halide grains according to the present invention, or may be prepared in parallel with the preparation of the silver halide grains. When the latter is prepared in parallel, JP-A No. 1-18
3417, 2-44335, etc.
Silver halide fine particles can be produced by using a mixer separately provided outside the reaction vessel in which the formation of the silver halide grains according to the present invention is performed, but a preparation vessel is provided separately from the mixer, The silver halide fine particles once prepared in the mixer are arbitrarily prepared so as to be suitable for the growth environment in the reaction vessel in which the silver halide grains according to the present invention are prepared, and then supplied to the reaction vessel. Is preferred.

The method for preparing the silver halide fine grains is preferably an acidic to neutral environment (pH ≦ 7).

To produce the silver halide fine grains, a water-soluble silver salt containing silver ions and an aqueous solution containing halide ions may be mixed while appropriately controlling the supersaturation factor.
Regarding control of the supersaturation factor, see JP-A-63-92942.
And JP-A-63-31244 can be referred to.

The pAg for producing silver halide fine particles is:
In order to suppress the generation of reduced silver nuclei in the silver halide fine grains themselves, it is preferably 3.0 or more, more preferably 5.0 or more, and further preferably 8.
0 or more.

The temperature for producing fine silver halide grains is 50.
° C. or less, more preferably 40 ° C. or less,
Most preferably, it is 35 ° C. or lower.

Further, as the protective colloid used for producing silver halide fine particles, the above-mentioned protective colloid-forming substance used for producing silver halide particles according to the present invention can be used.

When the silver halide fine particles are formed at a low temperature, coarsening of the particle size due to Ostwald ripening after the formation of the silver halide fine particles can be suppressed. However, at a low temperature, gelatin is easily coagulated. 2-166422
It is preferable to use low molecular weight gelatin described in JP-A No. 6-131, a synthetic molecular compound having a protective colloid action on silver halide grains, or a natural high molecular compound other than gelatin. The concentration of the protective colloid is preferably at least 1% by weight, more preferably at least 2% by weight, further preferably at least 3% by weight.

The particle size of the silver halide fine particles is preferably 0.1 μm or less, more preferably 0.05 μm or less.

The silver halide fine grains can contain the above-described reduction sensitization and optionally metal ions, if necessary.

In the production of the silver halide photographic emulsion of the present invention, desalting can be carried out during or after the formation of silver halide grains for the purpose of suppressing the progress of physical ripening or removing unnecessary salts. Desalination can be performed, for example, by Research Disclosure (Research Disclosure).
e, hereinafter abbreviated as RD) 17643 No. II. More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a Nudel washing method performed by gelatinizing gelatin may be used, and inorganic salts, anionic surfactant A precipitation method using an agent, an anionic polymer (such as polystyrenesulfonic acid), or a gelatin derivative (such as acylated gelatin or carbamoylated gelatin) can be used.

In addition, desalination utilizing membrane separation described in Chemical Engineering Handbook, Revised 5th Edition (edited by the Society of Chemical Engineers, Maruzen), pages 924 to 954 can also be used.

Regarding the method of membrane separation, RD 102 vol.
0208 and 131, 13122;
-43727 and 62-27008, JP-A-62-207
No. 113137, No. 57-209823, No. 59-4
Nos. 3727, 62-113137 and 61-219
No. 948, No. 62-23035, No. 63-40137
No. 63-40039, JP-A-3-140946
And the methods described in JP-A Nos. 2-172816, 2-172817 and 4-22942 can also be referred to.

In the production of the silver halide photographic emulsion of the present invention, conditions other than those described above are described in JP-A-61-66.
No. 43, No. 61-14630, No. 61-112142
No. 62-157024, No. 62-18556,
63-92942, 63-151618, 6
Nos. 3-163451, 63-220238, 63
No. -311244, RD 365: 36544, 367: 36736, 391: 39121, etc., and appropriate conditions can be selected.

When a color light-sensitive material is constituted by using the silver halide photographic emulsion of the present invention, the silver halide emulsion is
Use those that have been subjected to physical ripening, chemical ripening and spectral sensitization. The compound used in such a process is RD176
43, page 23, section III to page 24, section VI-M, RD187
16,648-649 and RD308119,996
It is described in page III-A to page 1000, section VI-M.

Known photographic compounds that can be used in the present invention are also described in RD17643, page 25, Sections VIII-A to 2
Page 7, section XIII, RD 18716, pages 650 to 651,
RD308119, page 1003, paragraphs VIII-A to 101
Those described in page 2, section XXI-E can be used.

Various couplers can be used in the color light-sensitive material. Specific examples thereof are RD17643, 25
Pages VII-C-G, RD308119, page 1001 V
It is described in the section II-CG.

The compound used in the present invention is RD3081
19, page 1007, section XIV.

In the present invention, the aforementioned RD17643,
The supports described in page 28, section XVII, RD18716, pages 647-8 and RD308119, page 1009, section XVII can be used.

The light-sensitive material includes RD308119, 1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The photosensitive material is the same as that of RD308119, VI
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section I-K can be adopted.

The silver halide photographic emulsion of the present invention can be used for various color light-sensitive materials typified by color negative films for general use or motion pictures, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. Can be preferably applied.

The light-sensitive material according to the present invention uses the RD17
643, pages 28-29, section XIX, RD 18716,65
1 page and RD308119, 1010 to 1011 pages XI
The development can be carried out by the usual method described in section X.

[0133]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. Embodiments of the present invention Example 1 (Preparation of seed emulsion T-1) Two parallel twin planes are prepared by the following method. Seed emulsion T-1 was prepared. (A-1 solution) Ossein gelatin 38. 0 g Potassium bromide 11.7 g 34.0 l with water (solution B-1) 810.0 g silver nitrate 3815 ml with water (solution C-1) 567.3 g potassium bromide 3815 ml with water (solution D-1) Ossein gelatin 163 0.4 g 10% methanol solution of surfactant (EO-1) 5.5 ml 3961 ml with water (E-1 solution) Sulfuric acid (10%) 91.1 ml (F-1 solution) 56% acetic acid aqueous solution Required amount (G- 1 solution) aqueous ammonia (28%) 105.7ml (H- 1 solution) aqueous potassium hydroxide (10%) necessary amount _{EO-1: HO (CH 2} CH 2 O) m [CH (CH 3) CH
₂ O] 19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.7
7) Using a stirring device described in JP-A-62-160128, 3
Solution E-1 was added to solution A-1 which was vigorously stirred at 0 ° C., and then solution B-1 and solution C-1 were added at a constant rate of 279 ml for 1 minute each by a double jet method to obtain silver halide nuclei. Was generated. Thereafter, solution D-1 was added, the temperature was raised to 60 ° C. over 31 minutes, solution G-1 was further added, and solution H-1 was added.
The pH was adjusted to 9.3 with the liquid, and aging was performed for 6.5 minutes.
After that, the pH was adjusted to 5.8 with the F-1 solution, and the remaining B-1 solution and the C-1 solution were further added to the solution 37 by the double jet method.
Min, and desalted immediately by a conventional method.

When this seed emulsion was observed with an electron microscope, a monodisperse flat plate having an average grain size (projected area circle-equivalent grain size) of 0.72 μm having two twin planes parallel to each other and a grain size distribution of 16% was obtained. It was a seed emulsion. (Preparation of Comparative Emulsion Em-1) A comparative emulsion Em-1 was prepared using the following solution. (A-2 solution) Ossein gelatin 519.9 g 10% methanol solution of surfactant (EO-1) 4.5 ml Seed emulsion T-1 5.3 mol equivalent 18.0 liters with water (B-2 solution) 3.5N aqueous silver nitrate solution 2787 ml (C-2 solution) Potassium bromide 1020 g Potassium iodide 29.1 g Water 2500 ml (D-2 solution) Potassium bromide 618.5 g Potassium iodide 8.7 g Water 1500 ml (E-2 Solution) 208.3 g of potassium bromide 1000 ml with water (F-2 solution) 56% acetic acid aqueous solution Required amount (H-2 solution) From 3.0% by weight of gelatin and silver iodide fine particles (average particle size: 0.05 μm) A fine grain emulsion equivalent to 0.672 mol is prepared in the following manner.

4. containing 0.254 mol of potassium iodide
An aqueous solution containing 10.59 mol of silver nitrate and 10.59 mol of potassium iodide in 9942 ml of 0% gelatin solution,
3092 ml of each was added at a constant speed over 35 minutes to form fine particles. The temperature during the formation of fine particles was controlled at 40 ° C.
H and EAg were successful. (K-2 solution) 10% Potassium hydroxide aqueous solution required amount Add solution A-2 into the reaction vessel and, while stirring vigorously at 75 ° C, remove solution B-2, solution C-2 and solution D-2. According to the combination shown in Table 1, addition was carried out by a double-jet method, a seed crystal was grown, and a comparative emulsion Em-1 was prepared.

Here, the addition rates of the B-2 solution, C-2 solution and D-2 solution are changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate, and the addition rates of the seed particles other than the growing seed particles are changed. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

The first growth was carried out by controlling the solution temperature in the reaction vessel to 75 ° C., the pAg to 8.9, and the pH to 5.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution temperature was increased to 6 for 15 minutes.
The temperature was lowered to 0 ° C., the whole amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel at 60 ° C., the pAg at 9.4, and the pH at 5.0, and all the remaining solution B-2 was added. pA
For control of g and pH, if necessary, E-2
Liquid, F-2 liquid and K-2 liquid were added.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, a hexagonal flat plate having an average grain size (grain size in terms of projected area circle) of 1.65 μm and a grain size distribution of 16% and an average aspect ratio of 8.5 was used. Monodispersed silver halide grains.
The state of dislocation lines formed in the silver halide grains was examined using a transmission electron microscope.
Grains having 5 or more dislocation lines were present in 90% or more of the total number. Many dislocation lines were formed in the fringe portions of the tabular silver halide grains.

[0140]

[Table 1]

(Preparation of Emulsion Em-2 of the Present Invention) In the preparation of the comparative emulsion Em-1, the following solution X was added immediately before the addition of the solutions B-2 and C-2, and immediately before the addition of the solution D-2. The following Y
The liquid was added. (Solution X) 100 mL of an aqueous solution containing 1.57 × 10 ⁻⁴ mol of thiourea dioxide (Solution Y) 100 mL of an aqueous solution containing 3.14 × 10 ⁻³ mol of sodium ethylthiosulfonate Also, before the start of addition of the H-2 solution The compound CL- of the present invention
After adding 3.0 mol% to the total silver halide in a 10% aqueous solution, the pH was raised to 9.5 and maintained for 5 minutes, and then the pH was returned to 5.0. Similarly, an emulsion Em-2 of the present invention was prepared. (Preparation of Emulsion Em-3 of the Present Invention) In the preparation of comparative emulsion Em-1, the following solution X was added immediately before the addition of solutions B-2 and C-2, and the following Y immediately before the addition of solution D-2: The liquid was added. (Solution X) 100 mL of an aqueous solution containing 1.57 × 10 ⁻⁴ mol of thiourea dioxide (Solution Y) 100 mL of an aqueous solution containing 3.14 × 10 ⁻³ mol of sodium ethylthiosulfonate Also, before the start of addition of the H-2 solution The compound CL- of the present invention
94 was added as a 10% aqueous solution of 3.0 mol% with respect to the total silver halide, then the pH was raised to 9.5, maintained for 5 minutes, and then returned to 5.0. Similarly, Emulsion Em-3 of the present invention was prepared. (Preparation of Emulsion Em-4 of the Present Invention) In the preparation of comparative emulsion Em-1, the following solution X was added immediately before the addition of solutions B-2 and C-2, and the following Y immediately before the addition of solution D-2: The liquid was added. (Solution X) 100 mL of an aqueous solution containing 1.57 × 10 ⁻⁴ mol of thiourea dioxide (Solution Y) 100 mL of an aqueous solution containing 3.14 × 10 ⁻³ mol of sodium ethylthiosulfonate Also, before the start of addition of the H-2 solution The compound CL- of the present invention
After adding 3.0 mol% with respect to the total silver halide in a 10% aqueous solution, the pH was raised to 9.5 and maintained for 5 minutes, and then the pH was returned to 5.0. Similarly, an emulsion Em-4 of the invention was prepared. (Preparation of Emulsion Em-5 of the Present Invention) In the preparation of comparative emulsion Em-1, the following solution X was added immediately before the addition of solutions B-2 and C-2, and the following Y immediately before the addition of solution D-2: The liquid was added. (Solution X) 100 mL of an aqueous solution containing 1.57 × 10 ⁻⁴ mol of thiourea dioxide (Solution Y) 100 mL of an aqueous solution containing 3.14 × 10 ⁻³ mol of sodium ethylthiosulfonate Also, before the start of addition of the H-2 solution The compound CL- of the present invention
109 to 3.0% by mole based on the total silver halide
Emulsion Em-5 of the invention was prepared in the same manner except that the pH was raised to 9.5 and maintained for 5 minutes after the addition of the aqueous solution, and then the operation was returned to pH 5.0.

Each of the above emulsions Em-1 to Em-5 was used in the following sample formulation, in the tenth layer, denoted as silver iodobromide g. These emulsions Em-1 to Em-5 were used after being optimally subjected to color sensitization and chemical sensitization by the method described in the following sample formulation. (Preparation of color photographic material) On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic material sample 1.
01 to 105 were produced.

In the following examples, unless otherwise specified, the amount of each material added is shown in grams per 1 m ² of the light-sensitive material.
However, silver halide and colloidal silver were converted to the amount of silver, and the sensitizing dye was indicated by the number of moles per mole of silver in the same layer. First layer (antihalation layer) Black colloidal silver 0.16 UV absorber UV-1 0.3 Colored magenta coupler CM-1 0.123 Colored cyan coupler CC-1 0.044 High boiling solvent OIL-1 0.167 Gelatin 1.33 Second layer (intermediate layer) Antifouling agent AS-1 0.16 High boiling point solvent OIL-1 0.20 Gelatin 0.69 Third layer (Low sensitivity red-sensitive layer) Silver iodobromide a 0.12 silver iodobromide b 0.29 sensitizing dye SD-1 2.37 × 10 ^-5 sensitizing dye SD-2 1.2 × 10 ^-4 sensitizing dye SD-3 2.4 × 10 ^-4 Sensitizing dye SD-4 2.4 × 10 ^-6 Cyan coupler C-1 0.32 Colored cyan coupler CC-1 0.038 High boiling solvent OIL-2 0.28 Stain inhibitor AS-2 0.002 Gelatin 0 .73 4th layer (medium speed red sensitive color Silver iodobromide c 0.10 Silver iodobromide d 0.86 Sensitizing dye SD-1 4.5 × 10 ^-5 Sensitizing dye SD-2 2.3 × 10 ^-4 Sensitizing dye SD- 3 4.5 × 10 ^-4 Cyan coupler C-2 0.52 Colored cyan coupler CC-1 0.06 DIR compound DI-1 0.047 High boiling point solvent OIL-2 0.46 Stain inhibitor AS-2 0.0. 004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 Sensitizing dye SD-1 3.0 × 10 ^-5 Sensitizing dye SD -1.5 × 10 ^-4 sensitizing dye SD-3 3.0 × 10 ^-4 Cyan coupler C-2 0.047 Cyan coupler C-3 0.09 Colored cyan coupler CC-1 0.036 DIR compound DI -1 0.024 High boiling point solvent OIL-2 0.27 Antifouling agent AS-2 0.0 6 Gelatin 1.28 6th layer (intermediate layer) High boiling point solvent OIL-1 0.29 Stain inhibitor AS-1 0.23 Gelatin 1.00 7th layer (Low sensitivity green color sensitive layer) Silver iodobromide a 0.19 silver iodobromide b 0.062 sensitizing dye SD-4 3.6 × 10 ^-4 sensitizing dye SD-5 3.6 × 10 ^-4 magenta coupler M-1 0.18 colored magenta coupler CM -1 0.033 High boiling point solvent OIL-1 0.22 Stain inhibitor AS-2 0.002 Stain inhibitor AS-3 0.05 Gelatin 0.61 Eighth layer (middle layer) High boiling solvent OIL-10 .26 Antifouling agent AS-1 0.054 Gelatin 0.80 Ninth layer (Medium sensitivity green color-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 Sensitizing dye SD-6 3 0.7 × 10 ^-4 sensitizing dye SD-7 7.4 × 10 ^-5 sensitizing dye SD-8 5.0 × 10 ^-5 Magenta coupler M-1 0.17 Magenta coupler M-2 0.33 Colored magenta coupler CM-1 0.024 Colored magenta coupler CM-2 0.029 DIR compound DI-2 0.024 DIR compound DI- 3 0.005 High boiling point solvent OIL-1 0.73 Antifouling agent AS-2 0.003 Antifouling agent AS-3 0.035 Gelatin 1.80 10th layer (highly sensitive green color-sensitive layer) Silver g 1.19 Sensitizing dye SD-6 4.0 × 10 ^-4 Sensitizing dye SD-7 8.0 × 10 ^-5 Sensitizing dye SD-8 5.0 × 10 ^-5 Magenta coupler M-10 0.065 colored magenta coupler CM-1 0.022 colored magenta coupler CM-2 0.026 DIR compound DI-2 0.003 DIR compound DI-3 0.003 high boiling point solvent OIL-1 0.19 High boiling solvent OIL-2 0.43 Stain inhibitor AS-2 0.014 Stain inhibitor AS-3 0.017 Gelatin 1.23 11th layer (yellow filter layer) Yellow colloidal silver 05 High boiling point solvent OIL-1 0.18 Stain inhibitor AS-1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide a 0.08 Silver iodobromide b 22 Sensitizing dye SD-9 6.5 × 10 ^-4 Sensitizing dye SD-10 2.5 × 10 ^-4 Yellow coupler Y-1 0.77 DIR compound DI-4 0.017 High boiling point solvent OIL-10 0.31 antifouling agent AS-2 0.002 gelatin 1.29 thirteenth layer (high-sensitivity blue-sensitive layer) silver iodobromide h 0.41 silver iodobromide i 0.61 sensitizing dye SD-94 .4 × 10 ^-4 sensitizing dye SD-10 1.5 × 10 ^-4 Ye -Coupler Y-1 0.23 High boiling point solvent OIL-1 0.10 Stain inhibitor AS-2 0.004 Gelatin 1.20 14th layer (First protective layer) Silver iodobromide j 0.30 UV absorber UV -1 0.055 Ultraviolet absorber UV-2 0.110 High boiling point solvent OIL-2 0.30 Gelatin 1.32 15th layer (second protective layer) Polymer PM-1 0.15 Polymer PM-2 0.04 Slip agent WAX-1 0.02 Dye D-1 0.001 Gelatin 0.55 The characteristics of the above silver iodobromide are shown below (the average particle size is
It refers to the length of one side of a cube of the same volume).

Emulsion No. Average grain size (μm) Average AgI content (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 Silver iodobromide b 0.40 8.0 1.4 Silver iodobromide c 0.60 7.0 3.1 Silver iodobromide d 0.74 7.0 5.0 Silver iodobromide e 0.60 7.0 4,1 Silver iodobromide f 0.65 8.7 6. 5 Silver iodobromide h 0.65 8.0 1.4 Silver iodobromide i 1.00 8.0 2.0 2.0 Silver iodobromide j 0.05 2.0 1.0 The preferred halogen of the present invention Production examples of silver iodobromide d and f will be described below as examples of forming silver iodide grains. Regarding silver iodobromide j, JP-A-1-183417 and 1-1.
No. 83644, No. 1-183645, No. 2-1664
It was prepared with reference to the description relating to No. 42.

First, seed crystal emulsion-1 was prepared. (Preparation of Seed Emulsion-1) Using a mixing stirrer disclosed in JP-B-58-58288 and JP-B-58-58289, 3
A silver nitrate aqueous solution (1.16) was added to the following solution A1 adjusted to 5 ° C.
1 mol), a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide), and a silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode).
While maintaining V at 2 minutes by the simultaneous mixing method,
Nucleation was performed. Subsequently, the liquid temperature was raised to 60 ° C. over a period of 60 minutes, and the pH was adjusted to 5.0 with an aqueous sodium carbonate solution.
After adjusting to 0, an aqueous solution of silver nitrate (5.902 mol) was added,
A mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) was added over 42 minutes by a simultaneous mixing method while keeping the silver potential at 9 mV. 40 ° C after completion of addition
While the temperature was lowered, desalting and washing with water were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio (maximum side ratio of each grain) of 90% or more of the total projected area of silver halide grains. The emulsion was composed of hexagonal tabular grains having a ratio of a side length to a minimum side length of 1.0 to 2.0. This emulsion is referred to as seed emulsion-1. (Solution A1) Ossein gelatin 24.2 g Potassium bromide 10.8 g 10% ethanol solution of surfactant (EO-1) 6.78 ml 10% nitric acid 114 ml Water 9657 ml (Preparation of silver iodide fine grain emulsion SMC-1) While vigorously stirring 5 liters of a 6.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide, 2 liters of a 7.06 mol aqueous solution of silver nitrate and 2 liters of a 7.06 mol aqueous solution of potassium iodide were added for 10 minutes. Was added. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1. (Preparation of silver iodobromide d) Seed crystal emulsion equivalent to 0.178 mol
700 ml of a 4.5% by weight inert gelatin aqueous solution containing 0.5 ml of a 10% ethanol solution of 1 and surfactant (SU-1) was maintained at 75 ° C., the pAg was 8.4, and the pH was 5.0. After adjustment, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure. 1) An aqueous solution of 3.093 mol of silver nitrate and an aqueous solution of 0.287 mol of SMC-1 and potassium bromide were added to obtain pAg of 8.
4. It was added while maintaining the pH at 5.0. 2) Subsequently, the temperature of the solution was lowered to 60 ° C., and the pAg was adjusted to 9.8. Thereafter, 0.071 mol of SMC-1 was added and aging was performed for 2 minutes (introduction of dislocation lines). 3) 0.959 mol of silver nitrate aqueous solution and 0.03 mol of S
MC-1 and an aqueous potassium bromide solution with a pAg of 9.8,
It was added while maintaining the pH at 5.0.

Throughout the formation of the particles, each solution was added at an optimum rate so that the formation of new nuclei and the Ostwald ripening between particles did not proceed.

After completion of the addition, the mixture was washed with water at 40 ° C. using a usual flocculation method, and then gelatin was added to redisperse the mixture. The pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.75 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 6.7 mol%. (Preparation of silver iodobromide f) In the preparation of silver iodobromide d, 1)
The pAg was 8.8 and the amount of silver nitrate added was 2.
077 mol, the amount of SMC-1 was 0.218 mol,
The amount of silver nitrate added in the step 3) is 0.91 mol, SMC
Silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount of -1 was changed to 0.079 mol.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.65 μm, an average aspect ratio of 6.5, and a silver iodide content of 2 / 9.5 / X / 8 mol% (where X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes have been added to each of the above emulsions and ripened, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate are added to optimize the fog-sensitivity relationship. Chemical sensitization was applied.

Silver bromoiodides a, b, c, e, g, h and i were also subjected to spectral sensitization and chemical sensitization in accordance with the above-mentioned silver bromoiodides d and f.

In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1 (polyvinylpyrrolidone, weight average molecular weight: 1)
000), AF-2 (polyvinyl pyrrolidone, weight average molecular weight: 1,100,000), inhibitor AF-3,
AF-4, AF-5, hardeners H-1, H-2 and preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.
You. SU-1: C₈F₁₇SO_TwoN (C_ThreeH₇) CH_TwoCOOK SU-2: C₈F₁₇SO_TwoNH (CH_Two)_ThreeN⁺(CH_Three)_Three
Br^- SU-3: di (2-ethylhexyl) nato sulfosuccinate
Lithium SU-4: Tri-i-propylnaphthalenesulfonic acid sodium
Thorium ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ST-2: adenine AF-3: 1-phenyl-5-mercaptotetrazole AF-4: 1- (4-carboxyphenyl) -5-mer
Captotetrazole AF-5: 1- (3-acetamidophenyl) -5-meth
Lcaptotetrazole H-1: [(CH_Two= CHSO_TwoCH_Two)_ThreeCCH_TwoSO_TwoC
H_TwoCH_Two]_TwoNCH_TwoCH _TwoSO_ThreeKH-2: 2,4-dichloro-6-hydroxy-s-tri
Azine sodium OIL-1: Tricresyl phosphate OIL-2: Di (2-ethylhexyl) phthalate AS-1: 2,5-bis (1,1-dimethyl-4-hexyl)
Siloxycarbonylbutyl) hydroquinone AS-2: dodecyl gallate AS-3: 1,4-bis (2-tetradecyloxycal
Bonylethyl) piperazine

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The following color development processing was performed on the obtained photosensitive material samples 101 to 105. (Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishment amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used. Color developing solution and color developing replenisher Developer replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium bicarbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 2 mg-hydroxylamine sulfate 2.5 g 3.1 g sodium chloride 0.6 g-4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g 6.3 g diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and add potassium hydroxide or 20%
The color developing solution is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid. Bleaching solution and replenisher for bleaching solution Replenishing solution for bleaching solution Water 700 ml 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g Adjust to 1 liter, and adjust the pH of the bleaching solution to 4.4 and the pH of the replenisher to 4.0 using ammonia water or glacial acetic acid. Fixer and Fixer Replenisher Fixer Replenisher Water 800ml 800ml Ammonium thiocyanate 120g 150g Ammonium thiosulfate 150g 180g Sodium sulfite 15g 20g Ethylenediaminetetraacetic acid 2g 2g Aqueous fixer pH 6.2 using aqueous ammonia or glacial acetic acid
Then, the pH of the replenisher is adjusted to 6.5, and then water is added to make 1 liter. Stabilizing solution and stabilizing replenisher Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylol urea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC L- 77) 0.1 g ammonia water 0.5 ml After adding water to make 1 liter, add ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid. << Evaluation of Sensitivity and Granularity >> Samples 101 to 105 were subjected to a step wedge exposure using white light for 1/200 second and 3.2 CMS, and then immediately subjected to the above color development processing to obtain characteristic curves. .

As for the sensitivity, the green sensitivity (the reciprocal of the exposure amount giving a density of fog density + 0.10) was determined by setting the value of sample 101 to 100.
The relative values are shown below.

The granularity was determined by the RMS granularity (fog density +
The density of 0.30 was measured with a microdensitometer having an opening scanning area of 250 μm 2 and the change in density value (1000 times as large as the fluctuation of the density value) was measured.

Table 2 shows the evaluation results of the samples 101 to 105.

[0166]

[Table 2]

As is clear from Table 2, the emulsion E of the present invention
Samples 102 to 105 using m-2 to Em-5 were superior in sensitivity to Sample 101 using Comparative Emulsion Em-1,
Granular Example 2 (Preparation of Comparative Emulsion Em-11) Example 1
In the preparation of Comparative Emulsion Em-1 in Solution A-2,
Comparative emulsion Em-11 was prepared in the same manner except that the following solutions A-3 and C-3 were used instead of solution C-2. (A-3 solution) Ossein gelatin 519.9 g 10% methanol solution of surfactant (EO-1) 1.5 ml Seed emulsion T-1 5.3 mol equivalent 18.0 liters with water (C-3 solution) Potassium bromide 979 g Potassium iodide 87.2 g 2500 ml with water (Preparation of emulsions Em-12 to Em-17 of the present invention) In the preparation of comparative emulsion Em-11, reduction sensitization was performed in the same manner as Em-2 to Em-5. And before desalting, the compound CL-6 of the present invention.
1, CL-94, CL-91, CL-109, BR-6
1. After adding BR-109 in a 10% aqueous solution containing 4.0 mol% of the total silver halide, the pH was adjusted to 9.
5 and hold for 5 minutes, after which the pH was returned to 4.0,
Emulsion E of the present invention was prepared in the same manner except that it was aged for 10 minutes.
m-12 to Em-17 were prepared.

Using the emulsions Em-11 to Em-17, multi-layer color photographic material samples 111 to 11 in the same manner as in Example 1.
7 was produced and evaluated in the same manner. Table 3 shows the results.

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[Table 3]

As is clear from Table 3, the emulsion E of the present invention
Samples 112 to 117 using m-12 to Em-17 are:
As compared with the sample 111 using the comparative emulsion Em-11, the sample exhibited excellent sensitivity and granularity. Example 3 (Preparation of multilayer color light-sensitive material) In the preparation of Sample 101 using Comparative Emulsion Em-1 in Example 1, compounds CL-61 and CL-1 of the present invention were subjected to color sensitization and chemical sensitization.
09 in an amount of 1.0 mol% based on the total silver halide.
Of the multilayer color photographic material of the present invention 122 and 12 in the same manner as in the sample 101 except that is added as a 10% aqueous solution.
3 was produced. In the preparation of Sample 101, compounds BR-61 and BR-1 of the present invention after color sensitization and chemical sensitization.
09 in an amount of 2.0 mol% with respect to the total silver halide, respectively.
Were prepared in the same manner except that was added as a 10% aqueous solution.

The samples 101 and 122 to 125 were subjected to light wedge exposure and color development in the same manner as in Example 1, and the sensitivity and graininess were evaluated. Table 4 shows the results.

[0172]

[Table 4]

As is clear from Table 4, Sample 1 of the present invention
22 to 125 are superior in sensitivity to the comparative sample 101;
It showed granularity. Example 4 (Preparation of spherical seed emulsion T-2)
A monodisperse spherical seed emulsion T-2 was prepared. (A-4 solution) Ossein gelatin 80 g Potassium bromide 47.4 g 10% methanol solution of surfactant (EO-1) 20 ml Water 8.0 liter (B-4 solution) Silver nitrate 1200 g Water 1.6 liter (C-4 solution) Ossein gelatin 32.2 g Potassium bromide 840 g 1.6 liters with water (D-4 solution) Ammonia water (28%) 470 ml A-4 solution stirred vigorously at 40 ° C and B-4 Liquid and C-4
The solution was added by a double jet method in 11 minutes to generate silver halide nuclei. During this time, pBr was kept at 1.6.

After that, the temperature was lowered to 30 ° C. over 12 minutes,
Aging was performed for another 18 minutes. Then, add D-4 solution for 1 more.
Min, followed by aging for 5 minutes.

Thereafter, the pH was adjusted to 6.0 and immediately desalted. When this seed emulsion was observed with an electron microscope, it was found to be a monodisperse spherical emulsion having an average grain size (projected area circle equivalent grain size) of 0.43 μm having two twin planes parallel to each other and a grain size distribution of 20%. there were. (Preparation of Comparative Emulsion Em-31)
Comparative emulsion Em-31 was prepared. (A-5 solution) Ossein gelatin 268.2 g 10% methanol solution of surfactant (EO-1) 1.5 ml Seed emulsion (T-2) 0.341 mol equivalent 28% by weight aqueous ammonia solution 528 ml 56% by weight acetic acid Aqueous solution 795 ml 5930 ml with water (solution B-5) 3.5N aqueous ammoniacal silver nitrate solution 2675 ml (pH adjusted to 9.0 with ammonium nitrate) (solution C-5) 3.5 N odor containing 4.0% by weight of gelatin 2675 ml of potassium iodide aqueous solution (D-5 solution) Fine grain emulsion composed of 3.0% by weight of gelatin and silver iodide fine grains (average grain size: 0.05 μm) 0.844 mol The preparation method of the fine grain emulsion is as follows.

6.0 containing 0.06 mol of potassium iodide
To 5000 ml of a weight% gelatin solution, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added at a constant speed over 10 minutes. During the formation of fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. 12.53k finished weight
g. (E-5 solution) 1.75N potassium bromide aqueous solution required amount (F-5 solution) 56% by weight acetic acid aqueous solution required amount A-5 solution kept at 70 ° C in a reaction vessel, B-5 solution, C
Solution -5 and Solution D-5 were added by the simultaneous mixing method.

Here, the addition rates of the B-5 solution, C-5 solution and D-5 solution were changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

The supply of solution D-5 was carried out by changing the molar ratio with solution B-5 with respect to the particle size (addition time) as shown in Table 5.
Core / shell type silver halide grains having a multiple structure were prepared.

The pH and pAg during the crystal growth were controlled as shown in Table 5 using the E-5 solution and the F-5 solution. still,
The measurement of pH and pAg was performed using a silver sulfide electrode and a glass electrode according to a conventional method.

After the particles are formed, desalting treatment is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

The silver halide grains in Comparative Emulsion Em-31 were observed with an electron microscope to find that the average grain size was 1.38 μm.
m, the grain size distribution was 13%, and octahedral twin silver halide grains in which the surface of the silver halide grains were almost composed of (111) faces, accounting for 97% of the total number of grains. (Preparation of Emulsions Em-32 to Em-37 of the Present Invention) In the preparation of the comparative emulsion Em-31, the addition time 17 in Table 5 was used.
At 4.6 minutes, the addition of Solution B-5 and Solution C-5 was suspended, and the compounds CL-61, CL-94, CL of the present invention were suspended.
-91, CL-109, BR-61, BR-109,
4.0 mol% to 10% of total silver halide
Emulsions Em-32 to Em-37 of the present invention were prepared in the same manner except that the pH was raised to 9.5, the pH was maintained for 5 minutes, and then the pH was returned to 6.5. did.

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[Table 5]

Comparative Emulsion Em-31 and Emulsion Em of the invention
Using -32 to 37, photosensitive material samples 131 to 137 were produced in the same manner as in Example 1, and evaluated in the same manner. Table 6 shows the results
Shown in

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[Table 6]

As is clear from Table 6, the emulsion E of the present invention
Samples 132 to 137 using m-32 to Em-37 are:
Example 5 (Preparation of Comparative Emulsion Em-41) Compared to Sample 131 using Comparative Emulsion Em-31, Example 5 (Preparation of Comparative Emulsion Em-41) In 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C., the following (solution A) and (B) Liquid) was simultaneously added by the double jet method over 30 minutes while controlling to pAg 6.6 and pH 2.0, and the following (Solution C) and (Solution D) were further added to pAg 7.3,
The mixture was simultaneously added by the double jet method over 180 minutes while controlling the pH at 5.8.

At this time, the control of pAg is described in JP-A-59-4559.
The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. (Solution A) Sodium chloride 1.03 g Potassium bromide 0.006 g Water 50 ml (Solution B) Silver nitrate 3.00 g Water 50 ml (Solution C) Sodium chloride 103.0 g Potassium bromide 0.63 g Water 600 ml (Solution D 300 g of silver nitrate, 600 ml of water, and after completion of addition, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.70 μm.
m, monodisperse cubic emulsion Em having a variation coefficient of particle size distribution of 7%
-41 was obtained. (Preparation of Emulsions Em-42 to Em-47 of the Invention) In the preparation of Comparative Emulsion Em-41, the addition of Solution C and Solution D was temporarily interrupted at a silver content of Solution D of 70%, and the compound BR of the invention was prepared. -61, BR-94, BR-91, BR-10
9, CL-61 and CL-109 were each added with a 10% aqueous solution of 4.0 mol% with respect to the total silver halide, and then the pH was raised to 9.5 and maintained for 5 minutes. Emulsions Em-42 to Em-47 of the present invention were prepared in the same manner except that the operation was returned to 0.8.

In each of the above emulsions Em-41 to Em-47,
After optimally performing chemical sensitization according to a conventional method, the above-mentioned sensitizing dyes SD-6, SD-7, and SD-8 were each added to 1.1 × 10 ⁻⁴ mol, 2.0 × 10 ^-4 mol, 0.3
An emulsion to which × 10 ^-4 mol was added was prepared.

Using these emulsions as shown in Table 7,
Single-layer light-sensitive material samples 141 to 1 each comprising a layer having the following composition on a triacetyl cellulose film support
47 were produced. First layer (emulsion layer) 1.8 g of the chemically and spectrally sensitized emulsion was added to 1.9 g of gelatin and 0.2 g of magenta coupler {1- (2,4,6-trichlorophenyl)- Green photosensitive emulsion layer containing 0.06 g of DNP (di-t-nonylphenol) dispersion in which 3- [3- (2,4-di-t-amylphenoxyacetamide) benzamide] -5-pyrazolone is dissolved . 0.2 g of a second layer (protective layer) in which 0.2 g of a stain inhibitor was dissolved.
11 g of DBP (dibutyl phthalate) dispersion and
Layer containing 5 g of gelatin.

To each of the above layers, an appropriate amount of a gelatin hardener or a surfactant was added.

Each of the samples 141 to 147 was subjected to light wedge exposure for sensitometry using green light, and evaluated in the same manner as in Example 1. Table 7 shows the results.

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[Table 7]

From Table 7, it can be seen that the emulsions Em-42 to Em- of the present invention were obtained.
Samples 142 to 147 using No. 47 were prepared using Comparative Emulsion Em
Excellent sensitivity compared to the coated sample 141 using −41,
It showed granularity.

[0193]

By using the compound for a silver halide photographic light-sensitive material of the present invention, a method for producing a silver halide photographic emulsion excellent in sensitivity and granularity and a silver halide photographic light-sensitive material using the same are provided. did it.

Claims (5)

[Claims] 1. A compound for a silver halide photographic light-sensitive material, having a substituent capable of releasing a bromine ion or a chloride ion in the molecule. 2. The compound for a silver halide photographic light-sensitive material according to claim 1, which is a compound represented by the following general formula (I). General formula _{(I) {X- (L 1} ) n1} n2 -L 2 - (SOL)
_{m wherein} X represents a chlorine atom or a bromine atom. L ₁ and L ₂
Represents a divalent linking group, and SOL represents a water-soluble group.
n ₁ represents 0 or 1, and m and n ₂ each represent an integer of 1 to 4. ] 3. L in the general formula (I)₁Is the following general formula (I
3. A structure represented by I).
A compound for a silver halide photographic light-sensitive material described above. Formula (II) -C (R₁) (R_Two) -CH (R_Three)-
EWG- [wherein, R₁, R_TwoAnd R_ThreeIs a hydrogen atom or a substituent
EWG represents -COO-, -OCO-, -SO
_Two−, −SO_TwoO-, -CON (R_Four)-, -N (R_Four) C
O-, -CSN (R_Four)-, -N (R_Four) CS-,-N
(R_Four)-, -O-, -S-, -CO-, -CS-,-
COCO-, -SO_TwoN (R_Four)-Or -N (R _Four) SO_Two
-Represents R_FourIs a hydrogen atom, an alkyl group or an aryl group
Represents ] 4. The silver halide photographic light-sensitive material compound according to claim 1, which is converted into a silver amount in silver halide grain formation in a step of producing a silver halide photographic emulsion. At least 40% by weight. 5. The method according to claim 1, wherein the compound for a silver halide photographic light-sensitive material is from 40% in terms of silver amount in the formation of silver halide grains in the production process of a silver halide photographic emulsion, until the silver halide grain formation is completed. 5. The method for producing a silver halide photographic emulsion according to claim 4, wherein