JPH1195347A - Manufacture of silver halide photographic emulsion, silver halide photographic sensitive material and additive for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To permit manufacture of the silver halide photographic emulsion enhanced in precise control of a halogen proportion in the surfaces of silver halide crystals and its stability and superior in sensitivity and fog resistance and storage stability by using a compound having a group adsorbable to silver halide and a substituent capable of releasing halide ions in the molecule. SOLUTION: This silver halide emulsion contains the compound having a group adsorbable to silver halide and a substituent capable of releasing halide ions in the molecule, and this compound can be used in an optical process in manufacture of the silver halide emulsion, but it is preferable that it is used after the silver halide grains near the outermost surfaces have been formed and this compound is represented by the formula:[A]- [L]m -[Z]n }r in which A is a group adsorbable to silver halide; L is a direct- or tri-valent bonding group; Z is a substituent capable of releasing halide ions; (m) is 0 or 1; (n) is 1 or 2; and (r) is 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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 have been increasing. Demands for higher sensitivity and higher image quality are increasing.

One of the dominant factors in increasing the sensitivity and image quality of silver halide photographic light-sensitive materials is silver halide grains. Silver halide grains aiming at higher sensitivity and higher image quality. Particle development has traditionally been pursued in the art.

However, the sensitivity tends to decrease as the size of silver halide grains is reduced to improve image quality, as is generally practiced. To achieve both high sensitivity and high image quality. Had limitations.

Techniques for improving the sensitivity / grain size ratio per silver halide grain have been studied in order to achieve higher sensitivity and higher image quality. As one of them, a technique using tabular silver halide grains is disclosed in JP-A-58-11.
No. 1935, No. 58-111936, No. 58-111
No. 937, No. 58-113927, No. 59-9943
No. 3 and the like. When these tabular silver halide grains are compared with so-called normal silver halide grains such as octahedral, tetrahedral, or hexahedral grains, when the silver halide grains have the same volume, the surface area increases, and thus Many sensitizing dyes can be adsorbed on the silver particle surface, and there is an advantage that the sensitivity can be further increased.

JP-A-6-230491, JP-A-6-235
988, 6-258745, 6-289516
And the like have also studied using tabular silver halide grains having a higher aspect ratio than before.

Further, Japanese Patent Application Laid-Open No. 63-92942 discloses a technique for providing a core having a high silver iodide content inside tabular silver halide grains, and Japanese Patent Application Laid-Open No. 63-163541 discloses a technique for 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, and shows effects on sensitivity and graininess, respectively.

Further, Japanese Patent Application Laid-Open No. 63-106746 discloses that
Tabular silver halide grains having a substantially layered structure in a direction parallel to two opposite main planes are disclosed in
No. 279237 has a layered structure separated by a plane substantially parallel to two opposite main planes, and the average silver iodide content of the outermost layer is the average silver iodide of the whole silver halide grains. It describes a technique using tabular silver halide grains at least 1 mol% higher than the content.

In addition, Japanese Patent Application Laid-Open No. 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 emulsion produced in the presence of an oxidizing agent for silver, and the effect on sensitivity and fog when a silver halide photographic material using the same is used.

Further, for example, see JP-A-63-220238.
In Japanese Patent Application Laid-Open No. Hei 3-175440, a technique using a silver halide emulsion containing tabular silver halide grains in which the positions of dislocation lines are defined is disclosed in JP-A-3-175440. A technique using a silver halide emulsion containing silver halide grains is disclosed in Japanese Patent Publication No. 3-186.
No. 95 discusses a technique using silver halide grains having a clear core / shell structure, and Japanese Patent Publication No. 3-31245 discusses a technique relating to silver halide grains having a core / shell three-layer structure. It has been studied as a sensitivity enhancement technique.

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 limitations in achieving both high sensitivity and high image quality, and are insufficient to satisfy recent demands on photosensitive materials. Was rare.

In order to improve the photographic performance, silver halide grains are subjected to more effective chemical sensitization and color sensitization to obtain more precise photosensitive nucleus sites and halogens on the surface of the silver halide grains. It was necessary to develop a technology that could control the composition.

[0016]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for adsorbing a compound on the surface of a silver halide grain and supplying halide ions from the compound to an arbitrary surface of the silver halide grain. By making finer control of the halogen composition on the crystal surface and improving the stability, a method for producing a silver halide photographic emulsion excellent in sensitivity, fogging and storage stability, and a silver halide photographic material using the same, To provide.

[0017]

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

(1) A method for producing a silver halide photographic emulsion, characterized in that a compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing halide ions is used.

(2) A silver halide characterized in that a compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing a halide ion is used for forming the vicinity of the outermost surface of silver halide grains. Manufacturing method of photographic emulsion.

(3) The method for producing a silver halide photographic emulsion as described in (1) or (2) above, wherein the adsorptive group has a selective adsorptivity to the main surface of the silver halide grains.

(4) The method for producing a silver halide photographic emulsion as described in any one of (1) to (3) above, wherein the halide ion is an iodide ion.

(5) The compound having, in the molecule, an adsorbing group to silver halide and a substituent capable of releasing halide ions is a compound represented by the following general formula (1): 5. The method for producing a silver halide photographic emulsion according to any one of items 1 to 4.

General formula (1) [A]-{[L] m- [Z] n} r wherein A represents an adsorbing group to silver halide, and L represents a divalent or trivalent linking group. And Z represents a substituent capable of releasing a halide ion, m represents 0 or 1, n represents 1 or 2, and r represents an integer of 1 to 3. (6) A silver halide photographic emulsion produced by the method for producing a silver halide photographic emulsion according to any one of the above 1 to 5, which is contained in at least one silver halide emulsion layer on a support. A silver halide photographic light-sensitive material comprising:

(7) An additive for a silver halide photographic light-sensitive material, which has, in the molecule, an adsorbing group to silver halide and a substituent capable of releasing halide ions.

(8) The additive for a silver halide photographic material as described in (7) above, wherein the adsorptive group has a selective adsorptivity to the main surface of the silver halide grains.

(9) The additive for a silver halide photographic material as described in the above item (7) or (8), wherein the halide ion is an iodide ion.

(10) The compound having, in the molecule, a group capable of releasing an adsorbable group to silver halide and a group capable of releasing a halide ion is a compound represented by the above general formula (1). 10. The additive for a silver halide photographic light-sensitive material according to any one of 7 to 9 above.

Hereinafter, the present invention will be described specifically.
The production process of a silver halide photographic emulsion and a silver halide photographic light-sensitive material is composed of steps such as silver halide grain formation, desalting, color sensitization, chemical sensitization, coating solution preparation, coating, and drying. In the present invention, the compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing halide ions is used in each step from the start of silver halide grain formation to before the coating step, that is, halogenation. It is used in one or a plurality of steps such as crystal growth of silver particles, physical ripening, desalting, color sensitization, chemical sensitization, and coating liquid preparation step.

In the present invention, silver halide grain formation means that after the nuclei of the silver halide grains in the silver halide photographic emulsion according to the present invention are formed, the crystal growth and physical ripening of the silver halide grains are completed. Up to the process. In the present invention, the silver halide emulsion grains are desalted, if necessary, before coating.
Although color sensitization and chemical sensitization can be performed, the coating solution preparation step referred to in the present invention uses the silver halide photographic emulsion according to the present invention after the completion of the last step among the necessary steps. Before the application of the silver halide photographic light-sensitive material is started.

In the present invention, the compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing a halide ion can be used in any step of the production of a silver halide emulsion as described above. Is preferably used after the formation near the outermost surface of the silver halide grains. That is, the amount of silver used up to the formation of silver halide grains is 90%.
It is used after the% is added and before the coating liquid preparation step.

In the present invention, in order to add a compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing a halide ion in the step of producing a silver halide photographic emulsion, these compounds are added directly to the emulsion. May be added, or a solution of a single or mixed solvent of water, methanol, ethanol or the like may be added, and a method of adding an additive to a silver halide emulsion generally in the art is applied. be able to.

In the present invention, the amount of the compound having in the molecule an adsorbing group to silver halide and a substituent capable of releasing a halide ion is 1 × 1 to silver halide.
It is preferably 0 ^-7 to 30 mol%, more preferably 1 × 10 ^{-6 to} 5 mol%. Further, it is preferable to use a compound having a group capable of releasing a halide ion and a group capable of releasing a halide ion in a molecule according to the present invention. Furthermore, when a compound having an adsorbable group to silver halide and a substituent capable of releasing a halide ion is used in the molecule of the present invention, the distribution of the halogen composition between the obtained silver halide grains is narrowed.

In the present invention, the compound having an adsorptive group to silver halide and a substituent capable of releasing a halide ion in the molecule has a structure in which the adsorptive group to silver halide has a relative to the main surface of the silver halide grain. Preferably, it has selective adsorption.

In the present invention, having the selective adsorption property to the main surface of the silver halide grain means that the main surface of the silver halide grain is more adsorbed than other crystal planes when an adsorption isotherm curve to the silver halide grain is examined. It means that the adsorptivity to the constituting crystal plane is large.

Regarding these adsorption characteristics, see T.S. H. Ja
mes, The Theory of the Pho
graphical Process, Fourth
Edition, Macmillan, New York
k, 1977, Chap. 9, Chap. 1, Chap
13. A. Herz and J.M. Helling,
J. Colloid Interface Sci. ,
22, 391 (1966); L. Scruto
n, J. et al. Photo. Sci. , 22, 69 (1974)
Etc. can be referred to.

In the present invention, the aforementioned crystal plane is crystallographically indicated by the Miller index. For example, in the prior art in the art, cubic silver halide grains mainly consist of (100) planes, The tabular silver halide grains are mainly composed of (111) planes, and the tabular silver halide grains are mainly composed of (100) planes, or are mainly composed of (111) planes.
Each consisting of faces has been arbitrarily manufactured.

In the present invention, the main surface means a silver halide grain surface which is constituted by a crystal plane which occupies the largest area among the silver halide grain surfaces. The crystal planes constituting the main surface can be identified by observing the silver halide grains at a magnification of 10,000 to 50,000 times using an electron microscope. When it is desired to know in detail, for example, a measuring method using a sensitizing dye having a crystal plane dependence of adsorption on a silver halide surface can be used. For example, the area ratio between the (100) plane and the (111) plane constituting the surface of the silver halide grain is described in T.I. Tani, Journal of Image
ng Science, 29, 165 (1985). That is, various amounts of the dye (anhydro-3,3'-bis (4-sulfobutyl)-
The reaction spectrum of a thick liquid emulsion layer to which 9-methylthiacarbocyanine hydroxide (pyridinium salt) was added was measured, and it was noted that the above dyes gave significantly different spectra on the (100) plane and the (111) plane. Ku
By dealing with the Belka-Munk equation, (1
The ratio between the (00) plane and the (111) plane can be obtained.

In the present invention, the compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing a halide ion is added to a silver halide emulsion by a method generally used in the art. And after adding
A halide ion can be released and used by reaction with a base or / and a nucleophile.

Examples of the nucleophile that can be used in the present invention include hydroxide ion, sulfite ion, hydroxylamine, hydroxamic acid, metabisulfite ion,
Thiosulfate ions, oximes, mercaptans, sulfinates, carboxylates, ammonium compounds, amine compounds, phenols, alcohols, thioureas, ureas, hydrazines, sulfides, phosphines, and the like, Alkali hydroxide compounds are preferred.

In the present invention, the timing and rate of halide ion release can be controlled by the method, concentration, and reaction temperature of the nucleophile or base. In the present invention, a nucleophile and a base can be used in combination.

In the present invention, the concentration of the base and / or the nucleophile is preferably 1 × 10 ^{−7 to} 50 M, and preferably 1 × 10 ^−5.
-10 M is more preferable, and 1 x 10 ^{-3 to 5} M is particularly preferable. As for temperature, 20-90 ° C is preferred, 30-85 ° C is more preferred, and 35-80 ° C is still more preferred. In the present invention, when a base is used for releasing halide ions, the pH may be controlled. The pH at this time is preferably 2 to 12, and more preferably 3 to 11.

The amount of halide ions released is preferably from 0.001 to 30 mol% of the total silver halide amount,
1-10 mol% is more preferable.

In the present invention, the compound having an adsorbing group to silver halide and a substituent capable of releasing a halide ion in the molecule may release all of the halogen atoms in the compound, or a part of the compound may be decomposed. It may remain without being carried out.

In the present invention, the halide ion released from the compound having a substituent capable of releasing a halide ion and a group capable of releasing a halide ion in the molecule is preferably a chloride ion, a bromine ion or an iodide ion. And more preferably bromide ion and iodine ion, and still more preferably iodide ion.

In the present invention, the compound having an adsorbing group to silver halide and a substituent capable of releasing halide ions in the molecule may be used alone or in combination of two or more.

In the present invention, the compound having a substituent capable of releasing a halide ion and an adsorbing group to silver halide in the molecule is preferably a compound represented by the above general formula (1).

In the general formula (1), the adsorbing group to silver halide represented by A is specifically an atomic group having a mercapto group (for example, mercaptooxadiazole, mercaptotetrazole, mercaptotriazole, mercaptodiazole , Mercaptothiazole, mercaptothiadiazole, mercaptooxazole, mercaptoimidazole, mercaptobenzothiazole, mercaptobenzoxazole, mercaptobenzimidazole, mercaptotetrazaindene, mercaptopyridyl, mercaptoquinolyl, 2-mercaptopyridyl, mercaptophenyl, mercaptonaphthyl, etc. Group), an atom group having a thione group (for example, thiazoline-2-thione, oxazoline-2-thione, imidazoline-2-thione, benzothiazoline- - thione, benzimidazoline -2
-Thione, thiazolidine-2-thione, etc.), an atom group forming imino silver (for example, triazole, tetrazole, benzotriazole, hydroxyazaindene, benzimidazole, indazole, etc.), an atom having an ethynyl group Group (eg, each group such as 2- [N- (2-propynyl) amino] benzothiazole, N- (2-propynyl) carbazole), and atom group including mesoionic compounds (eg, W. Baker and WD Olli).
s is a quarterly review (Quart. Rev.)
11, 15 (1957), Advances in heterocyclic chemistry (Advances i)
n Heterocyclic Chemistry)
19, 1 (1976), which is a "5- or 6-membered heterocyclic compound, which cannot be satisfactorily represented by one covalent structural formula or polar structural formula, and forms a ring. A compound having a pi-electron hexaploid associated with every atom that bears a partially positive charge and is balanced with an equal negative charge on the exocyclic atom or group. " Examples of the mesoionic ring of the mesoionic compound include an imidazolium ring, a pyrazolium ring, an oxazolium ring, a thiazolium ring, a triazolium ring, a tetrazolium ring, a thiadiazolium ring, an oxadiazolium ring, a thiatriazorim ring, and an oxatriazolium ring. . ) And the like.

Preferred specific examples of the substituent capable of releasing a halide ion represented by Z in the general formula (1) are shown below.

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The divalent or trivalent linking group represented by L in the general formula (1) includes a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom,
A group composed of a sulfur atom is preferable, and specifically, an alkylene group having 1 to 20 carbon atoms (for example, each group such as methylene, ethylene, propylene, and hexylene) and an arylene group (for example, each group such as phenylene and naphthylene) Group), -C
ONR _1- , -SO ₂ NR _2- , -O-, -S-, -NR _{3
-, - NR 4 CO -,} - NR 5 SO 2 -, - NR 6 CONR
_{7 -, - CO-O -} , - O-CO -, - CO- , etc., and groups that are combinations of these.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group represented by R _{1 to} R ₇ has 1 to 2 carbon atoms.
0 linear, branched or cyclic alkyl groups (e.g., methyl, ethyl, isopropyl, 2-ethyl-hexyl, cyclopentyl, cyclohexyl, etc.), alkenyl groups (e.g., propenyl, 3-pentenyl, 2-butenyl, Examples thereof include a cyclohexenyl group and the like, an alkynyl group (eg, propargyl and 3-pentynyl and the like), and aralkyl (eg, benzyl and phenethyl and the like). The aromatic group is a monocyclic or condensed ring group having 6 to 10 carbon atoms, and specific examples include a phenyl group and a naphthyl group. Examples of the heterocyclic group include an oxygen atom, a sulfur atom, and a nitrogen atom. It is a 5- to 7-membered monocyclic or condensed ring group, and specific examples include furyl, thienyl, benzofuryl, pyrrolyl, indolyl, thiazolyl, imidazoyl, morpholyl, piperazyl, pyrazyl and the like. Each of the groups represented by R _{1 to} R ₇ can be substituted with an arbitrary group at an arbitrary position. Examples of the substituent include a hydroxy group,
Halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, amino group (for example, methylamino, anilino, diethylamino, 2-hydroxyethylamino, etc.), acyl group (for example, acetyl) ,
Benzoyl, propanoyl, etc.), carbamoyl group (for example, carbamoyl, N-methylcarbamoyl,
Groups such as N, N-tetramethylenecarbamoyl, N-methanesulfonylcarbamoyl, N-acetylcarbamoyl), alkoxy groups (for example, methoxy, ethoxy,
-Hydroxyethoxy, 2-methoxyethoxy, etc.), alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, etc.), sulfonyl group (eg, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl) , P-toluenesulfonyl, etc.), a sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, N-ethylsulfamoyl, etc.), an acylamino group (eg,
Groups such as acetamide, trifluoroacetamide, benzamide, thienocarbonylamino, benzenesulfonamide, and the like; and alkoxycarbonylamino groups (for example, groups such as methoxycarbonylamino, N-methyl-ethoxycarbonylamino). .

The specific examples of the compounds of the present invention are shown below.
The compound of the present invention is not limited to this.

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[0059]

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The compound of the present invention can be synthesized by utilizing a known substitution reaction. For example, a method represented by the following equation is used.

[A] -COOH + Z-NH ₂ → condensing agent → [A] -CONH-Z + H ₂ O: Formula 1 [A] -NH ₂ + Z-COOH → condensing agent → [A] -NHCO-Z + H ₂ O: Formula 2 [A] -COCl + Z-NH ₂ → Base → [A] -CONH-Z + HCl: Formula 3 [A] -NH ₂ + Z-COCl → Base → [A] -NHCO-Z + HCl: Formula 4 [A] -X + Z -NRH → base → [A] -N (R) -Z + HX: formula 5 [A] -NRH + ZX → base → [A] -N (R) -Z + HX: formula 6 [A] -X + Z-OH → base → [A] —O—Z + HX: Formula 7 [A] —OH + Z—X → Base → [A] —O—Z + HX: Formula 8 In Formulas 5, 6, 7, and 8, X is a group that leaves after the reaction. Yes, for example, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), sulfo Ester group (e.g., p- toluenesulfonate, trifluoromethanesulfonate, m- each group such as chlorobenzene sulfonate) and the like.

[A] —CHO + Z—H ₂ → Base → [A] —CH ＝ Z + H ₂ O: Formula 9 [A] —H ₂ + Z—CHO → Base → [A] = CH—Z + H ₂ O: Formula 10 Hereinafter, specific synthesis examples of typical compounds of the present invention will be described.

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Synthesis Example (Synthesis of Compound Example 4) 20 g of the compound (A) is suspended in 100 ml of acetonitrile, and 20 ml of DMF is added to completely dissolve the suspension. Cool to -5 ° C and slowly add 12.9 g of thionyl chloride dropwise. Next, while maintaining the same temperature, iodine ethanol 16.
3 g are added dropwise. After reacting for 2 hours at the same temperature,
The mixture was concentrated under reduced pressure, and the residue was recrystallized from methanol to obtain 30.5 g of Exemplified Compound 4. (Yield 90%) The structure was identified by proton NMR and mass spectrum.

Synthesis Example (Synthesis of Compound Example 16) 22.2 g of the compound (C) was suspended in 150 ml of ethyl acetate, and 25 g of iodopropionyl chloride was slowly added dropwise at room temperature. After the dropwise addition, the mixture was heated under reflux for 3 hours, and after cooling, the precipitated crystals were separated by filtration. Recrystallization from methanol affords 35.7 g of Exemplified Compound 16 (88% yield). The structure was identified by proton NMR and mass spectrum.

In the present invention, in a compound having an adsorbing group to silver halide and a substituent capable of releasing a halide ion in the molecule, the adsorbing group to silver halide is adsorbed to silver halide to form a halogen. After some or all of the halide ions have been released, they may be desorbed from the silver halide.

The desorption includes, for example, the method described in JP-A-5-26511.
No. 1, No. 6-161005, etc., a method utilizing protonation can be used, and an adsorbing group to silver halide and a halide ion can be released in a molecule according to the present invention. Can be exchange-adsorbed using a sensitizing dye or other compound having an adsorptive group having a strong adsorptivity to silver halide rather than an adsorptive group to silver halide in a compound having a suitable substituent. Can also be used in combination.

The silver halide grains contained in the silver halide photographic emulsion according to 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 such 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, or particles of various crystal forms may be mixed.

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.
Is more preferable, and 0.4 to 5.0 μm is most preferable.
In the present invention, the average particle size is defined as an arithmetic mean of particles having a particle size ri (three significant figures, the least significant figure is rounded off, and the number of measured particles is indiscriminately 1,000 or more. Do).

In the case of tabular silver halide grains, the grain 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. 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 diameter ri can be obtained by photographing a silver halide particle with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter on the print or the area at the time of projection.

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.

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

In the present invention, the silver halide photographic emulsion may be any silver halide such as silver iodobromide, silver iodochlorobromide, silver iodochloride and the like. However, silver iodobromide and silver iodochlorobromide are particularly preferred.

In the present invention, the average silver iodide content of the silver halide grains contained in the silver halide photographic emulsion is from 1 to 4
0 mol%, more preferably 2 to 2 mol%.
0 mol%.

In the present invention, the average silver iodide content of silver halide grains is determined by an EPMA method (Electron Pro).
be Micro Analyzer). Specifically, a sample in which silver halide grains were well dispersed so as not to contact each other was prepared, and -1 was prepared with liquid nitrogen.
By irradiating an electron beam while cooling to below 00 ° C. and determining the characteristic X-ray intensities of silver and iodine emitted from the individual silver halide grains, the silver iodide content of each of the silver halide grains is reduced. This can be determined and measured for at least 50 silver halide grains and their average determined.

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

For producing the silver halide photographic emulsion of the present invention, 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. Also, the pH in the liquid phase in which silver halide is produced,
A method of controlling pAg according to the growth rate of silver halide can also be used.

For the production of the silver halide photographic emulsion of the present invention, a seed emulsion may 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 tetradecahedral, or may have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, the (100) plane and the (11) plane
1) Any ratio of planes can be used. Further, a composite of these crystal forms may be used, or 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 used are preferably twinned silver halide grains having twin planes, and two opposite parallel silver halide grains are used. Particularly preferred are twinned silver halide grains having a twinned plane.

In the present invention, whether a seed emulsion is used or a seed emulsion is not used, the conditions for silver halide nucleation and ripening are those known in the art. Can be.

For the production of the silver halide photographic emulsion of the present invention, 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 and 3,531,
Nos. 289 and 3,574,628, JP-A-54-10
No. 19, 54-158917, and JP-B-58-3
Organic thioethers described in No. 0571 and the like, (b)
Thiourea derivatives described in JP-A-53-82408, JP-A-55-29829 and JP-A-57-77736;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in JP-A-53-144319, and (d) JP-A-54-10
No. 0717, etc., (e) sulfite, (f) thiocyanate, (g) ammonia,
(H) ethylenediamines substituted with hydroxylalkyl described in JP-A-57-196228 and the like;
(I) substituted mercaptotetrazoles described in JP-A-57-202531, etc., (j) water-soluble bromide,
(K) Benzoimidazole derivatives described in JP-A-58-54333 and the like.

For the production of the silver halide photographic emulsion of the present invention, 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 simultaneously, or one of them may be mixed in the presence of the other. Also, considering the critical growth rate of silver halide crystals,
PAg and pH in a mixing vessel containing halide ions and silver ions
And can be added sequentially or simultaneously. 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 production of the silver halide photographic emulsion of the present invention, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt may be used in the process of nucleating silver halide grains and / or growing the nuclei formed. (Including complex salts), rhodium salts (including complex salts), iron or other salts of Group VIII metals (including complex salts) and the like, and adding a metal ion to the inside of the silver halide grains and These metals can be contained on the particle surface.

In the present invention, twin silver halide grains having two opposing parallel twin planes can be used, but in this case, tabular silver halide grains are preferred. The twins are silver halide crystals having one or more twin planes in one grain, and the classification of the twins is based on the report by Klein and Moiser, Photographic Correspondents ( Photographi
she Korrespondentz) Volume 99
Page 100, p. 57.

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

When tabular silver halide grains are used in the present invention, the ratio of tabular silver halide grains having two twin planes parallel to the main plane is 60% or more in terms of the number of silver halide grains. And more preferably 70
%, More preferably 80% or more.

In the present invention, the 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 diameter and thickness of the silver halide grains are determined by the following method. A latex ball having a known particle size as an internal standard and a sample coated such that the main plane was oriented parallel to the support were prepared on the support, and shadowing was performed by a carbon deposition method from a certain direction. Thereafter, 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 0.1μ.
Obtain a thin section of about m. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The silver halide grains in the silver halide photographic emulsion of the present invention preferably 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 the dislocation lines in the silver halide grains is preferably 50% or less, more preferably 60% or less, of the total silver content of the silver halide grains.
More preferably, it is introduced in an amount of at least 85%. 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 3 or more.
More preferably, the number is zero 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 through, so that 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.

The method for introducing dislocation lines into silver halide grains is not particularly limited. For example, a method in which an aqueous solution of an iodide ion such as potassium iodide and a solution of a water-soluble silver salt are added by a double jet, silver iodide A method of adding fine particles, a method of adding only an iodine ion solution, and JP-A-6-11781.
A known method such as a method using an iodide ion releasing compound described in No.

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

In the present invention, when gelatin is used as the dispersion medium, lime-treated gelatin, acid-treated gelatin, ion-exchanged gelatin and the like can be used. For details on the gelatin production method, see Arthur Weiss, "The Macromolecular Chemistry of
Gelatin "(Academic Press, 1964)
And so on.

Examples of substances that can form protective colloids other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethylcellulose, carboxymethylcellulose, and cellulose sulfate. Cellulose derivatives such as sodium alginate, starch derivatives, etc., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, etc. Examples include various types of synthetic or semi-synthetic hydrophilic high-molecular substances such as mono- or copolymers.

In the production of the silver halide photographic emulsion of the present invention, 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.

More specific methods of reduction sensitization include a method called silver ripening in the art, a method of ripening and growing at a low pAg by supplying silver ions to silver halide grains, and an alkaline compound. Any method or a combination of these methods can be used, for example, a method of ripening and growing by increasing the pH and adding a reducing agent.

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, formamidinesulfinic acid, silane compounds, amines and polyamines and sulfurous acid Although salts and the like can be used, thiourea dioxide, ascorbic acid and its derivatives, and stannous salts are preferably used.

In the production of the silver halide photographic emulsion of the present invention, an oxidizing agent known in the art can be used.
Examples of the oxidizing agent include hydrogen peroxide (water) and an adduct _{thereof: H 2 O 2, NaBO 2} , H 2 O 2 -3H 2 O, 2NaC
_{O 3 -3H 2 O 2, Na} 4 P 2 O 7 -2H 2 O 2, 2Na 2 SO 4
Such as -H ₂ O ₂ -2H ₂ O. Peroxy acid salt: K ₂ S ₂ O ₃ ,
_{K 2 C 2 O 3, K} 4 P 2 O 3, K 2 [Ti (O) 2 C 2 O 4] -3
H ₂ O, peracetic acid, ozone, thiosulfonic acid compounds and the like can be mentioned.

In the production of the silver halide photographic emulsion of the present invention, the above reduction sensitization and the addition of an oxidizing agent can be carried out in combination.

In the present invention, silver halide grains according to the present invention can be formed by supplying silver halide fine particles. The silver halide fine grains may be prepared in advance before preparing the silver halide grains according to the present invention, or may be prepared in parallel with the preparation of the silver halide grains. In the case of preparing the latter in parallel, see JP-A-1-1-1.
As described in JP-A-83417, JP-A-2-44335, etc., silver halide fine particles can be produced by using a mixer separately provided outside a reaction vessel in which silver halide grains according to the present invention are formed. Although it is possible to provide a preparation container separately from the mixer, the silver halide fine particles once prepared in the mixer can be arbitrarily selected so as to be suitable for a growth environment in a reaction container in which the preparation of the silver halide particles concerned is performed. It is preferable to supply the mixture to the reaction vessel after the preparation.

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

To produce the silver halide fine particles, 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.

PAg for producing the silver halide fine particles
Is preferably at least 3.0, more preferably at least 5.0, even more preferably at least 8.0 in order to suppress the generation of reduced silver nuclei in the silver halide fine grains themselves. .

The temperature for producing the silver halide fine particles is as follows:
The temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and most preferably 35 ° C. or lower.

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

When 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. 2-16642
It is preferable to use low molecular weight gelatin described in No. 2, etc., a synthetic molecular compound having a protective colloidal 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, even more preferably at least 3% by weight.

The particle size of the silver halide fine particles is 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. Desalting is performed, for example, by Research Disclosure (Research Disc).
Hereafter, it is abbreviated as RD. ) No. 17643, section II.

More specifically, in order to remove unnecessary soluble salts from a precipitate product or an emulsion after physical ripening,
A Noudel water washing method in which gelatin is gelled may be used, and inorganic salts, anionic surfactants, anionic polymers (eg, polystyrene sulfonic acid), or gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin) may be used. The precipitation method used can be used.

In addition, desalination using 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 No. 102, 10208 and 131, 13122, JP-B-59-43727 and JP-B-6-27008, and JP-A-6-27008
2-113137, 57-209823, 59
-43727, 62-11137, 61-2
No. 19948, No. 62-23035, No. 63-401
No. 37, No. 63-40039, JP-A-3-14094
6, No. 2-172816, No. 2-172817,
The method described in JP-A-4-22942 and the like 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
-311244, RD 365, 36544, 367
Appropriate conditions can be selected with reference to Vol. 36736, Vol.

In constructing a color photographic light-sensitive material using the silver halide emulsion of the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. The additive used in such a process is RD1764
3, 18716 and 308119. Table 1 shows relevant descriptions.

[0120]

[Table 1]

Known photographic additives which can be used in forming a color photographic light-sensitive material using the silver halide emulsion of the present invention are also described in the above RD. Table 2 shows relevant descriptions.

[0122]

[Table 2]

In constructing a color photographic light-sensitive material using the silver halide emulsion of the present invention, various couplers can be used, and specific examples are described in the above RD. Table 3 shows relevant descriptions.

[0124]

[Table 3]

The additive used for forming a color light-sensitive material using the silver halide emulsion of the present invention is RD308
It can be added by the dispersion method described in 119XIV. When a color light-sensitive material is formed using the silver halide emulsion of the present invention, the above-mentioned RD17643 is used.
Page 28, RD18716 pages 647 to 648, and RD3
The support described in XIX of 08119 can be used.

A color photographic light-sensitive material using the silver halide emulsion of the present invention can be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119VII-K.

The color photographic light-sensitive material using the silver halide emulsion of the present invention can have various layer constitutions such as a forward layer, a reverse layer and a unit constitution described in the aforementioned RD308119VII-K. .

The silver halide emulsion of the present invention is preferably used for various color light-sensitive materials represented by general or movie color negative films, slide or television color reversal films, color papers, color positive films and color reversal papers. Can be applied.

The color photographic light-sensitive materials used in the silver halide emulsion of the present invention are the same as those described in RD17643 28-29.
Page, RD18716 page 615 and RD308119
Development can be carried out by the usual method described in XIX.

[0130]

The present invention will be specifically described below with reference to examples.
The present invention is not limited to these examples.

Example 1 (Preparation of Seed Emulsion T-1) A seed emulsion having two parallel twin planes was prepared by the following method.

(E-1 solution) Deionized alkali-treated gelatin (average molecular weight 15,000) 244.0 g Potassium bromide 156.6 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _{19.8 (CH 2 CH 2 O) n} H (m + n = 9.77) 10% methanol solution 0.48mL water at 34.0L (F-1 solution) 3716ML silver nitrate 1200g water (G-1 solution) deionized alkali treatment Gelatin (average molecular weight 15,000) 31.6 g Potassium bromide 906.0 g With water 4.0 L (H-1 solution) Ammonia water (28%) 299 mL (I-1 solution) Water 8.0 L (J-1 solution) ) Ossein gelatin 400.0 g 4832 mL with water (K-1 solution) 69.2 g of potassium bromide 386 mL with water (L-1 solution) 56 wt% acetic acid aqueous solution 1000 mL 1000 mL Using a stirrer described in JP 2-160128, 3
Solution I-1 was added to solution E-1 which was vigorously stirred at 0 ° C., and then solution F-1 and solution G-1 were mixed by double jet method.
Per minute to produce silver halide nuclei.

Thereafter, the solution J-1 was added, the temperature was raised to 68 ° C. over 41 minutes, the solution H-1 was added, and the mixture was aged for 5 minutes. Thereafter, the K-1 solution was further added, and one minute later, the pH was adjusted to 4.7 using the L-1 solution, and immediately desalting was performed by a conventional method. When this seed emulsion was observed with an electron microscope, the average grain size (grain size in terms of projected area circle) having two twin planes parallel to each other was 0.31 μm, and the grain size distribution was 16%.
Was obtained.

(Preparation of Comparative Emulsion Em-1) Seed emulsion (T-
Comparative emulsion (Em-1) was prepared using 1) and the following solution.

(H-2 solution) Ossein gelatin 223.6 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) Of 10% methanol solution 3.6 mL Emulsion (T-1) 0.774 mol equivalent 5904 mL with water (I-2 solution) 3.5N silver nitrate aqueous solution 6490 mL (J-2 solution) 3.5N potassium bromide aqueous solution 7500 mL ( K-2 solution) Fine grain emulsion composed of 3.0% by weight of gelatin and silver iodide fine grains (average grain size: 0.05 μm) (Preparation method is shown below) Required amount <Preparation method of fine grain emulsion> 7.06 in 5000 mL of a 6.0% by weight gelatin solution containing potassium iodide
2000 mL of an aqueous solution containing moles of silver nitrate and 7.06 moles of potassium bromide was added at a constant rate over 10 minutes. During the fine particle formation, the pH was adjusted to 2.0 using nitric acid, and the temperature was adjusted to 40.
C. was controlled. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. Finished weight is 12.
It was 53 kg.

(Liquid L-2) 1.75N Potassium bromide aqueous solution required amount (M-2 liquid) 56% by weight acetic acid aqueous solution Required amount (N-2 liquid) 3.5N Potassium bromide aqueous solution 500mL H in the reaction vessel -2 solution is added and with vigorous stirring,
Solution I-2, Solution J-2 and Solution K-2 were added by the simultaneous mixing method according to the combination shown in Table 4 to grow a seed crystal to prepare a core / shell type silver halide emulsion.

Here, the addition speed of the solution I-2, solution J-2 and solution K-2 is 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.

In the crystal growth, first, the first addition was performed while controlling the solution temperature in the reaction vessel to 75 ° C. and the pAg to 8.8, and then the solution temperature in the reaction vessel was reduced to 60 ° C. in 15 minutes. Solution 2 was added over 4 minutes, and solution K-2 was added in an amount equivalent to 2% of the total silver used, followed by a second addition. Second
The addition was performed by setting the solution temperature in the reaction vessel to 60 ° C. and the pAg to 9.
8. The pH was controlled at 5.8. For control of pAg and pH, if necessary, L-2 solution,
Solution M-2 was added.

After the particles are formed, desalting treatment is carried out 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, they were hexagonal tabular monodispersed silver halide grains having an average particle size of 1.30 μm and a particle size distribution of 17% and an average aspect ratio of 8.0. The main surface is a (111) plane, and 95% or more of all silver halide grain surfaces are (111) planes.
Was composed of planes. The tabular silver halide grains had dislocation lines.

[0141]

[Table 4]

(Preparation of Comparative Emulsion Em-2)
Comparative emulsion (Em-2) was prepared in the same manner as in the preparation of m-1) except that K-2 solution was added in an amount of 1.5 × 10 ^-4 mol% based on the total silver halide before desalting. did.

(Preparation of Comparative Emulsion Em-3)
In the preparation of m-1), a comparative emulsion (Em-) was prepared in the same manner except that a 1.5 N aqueous solution of potassium iodide was added in an amount of 1.5 × 10 ⁻⁴ mol% based on the total silver halide before desalting.
3) was prepared.

(Preparation of Comparative Emulsion Em-4)
In the preparation of m-1), compound (A) (1-
0.1% methanol solution of phenyl-5-mercaptotetrazole) was 1.5 × 10 ^{−4 based} on the total silver halide.
A comparative emulsion (Em-
4) was prepared.

(Preparation of Comparative Emulsion Em-5)
In the preparation of m-1), before desalting, 2-iodoethanol was added at 1.5 × 10 ⁻⁴ mol% based on the total silver halide, and the pH was raised to 9.5 and maintained for 5 minutes. Then p
In the same manner except that H was returned to 5.8, the comparative emulsion (Em
-5) was prepared.

(Preparation of Emulsion Em-6 of the Present Invention) In the preparation of the comparative emulsion (Em-1), before desalting, the compound 4 of the present invention was added to the total silver halide in an amount of 1.5 × 10 ^−4. After the addition of mol%, the pH was raised to 9.5 and maintained for 5 minutes, and then the emulsion (Em-6) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-7 of the Present Invention) In the preparation of the comparative emulsion (Em-1), the compound 16 of the present invention was added to the total silver halide at 1.5 × 10 ^-4 before desalting. After the mole% addition, the pH was raised to 9.5 and held for 5 minutes,
Thereafter, an emulsion (Em-7) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-8 of the Present Invention) In the preparation of the comparative emulsion (Em-1), the compound 15 of the present invention was added to the total silver halide at 1.5 × 10 ^-4 before desalting. After the mole% addition, the pH was raised to 9.5 and held for 5 minutes,
Thereafter, an emulsion (Em-8) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-9 of the Present Invention) In the preparation of the comparative emulsion (Em-1), before desalting, the compound 3 of the present invention was added to the total silver halide at 1.5 × 10 ^-4. After the addition of mol%, the pH was raised to 9.5 and maintained for 5 minutes, and thereafter, the emulsion (Em-9) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-10 of the Present Invention) In the preparation of the comparative emulsion (Em-1), the compound 12 of the present invention was added to the total silver halide at 1.5 × 10 ^-4 before desalting.
After the addition of mol%, the pH of the emulsion was raised to 9.5 and maintained for 5 minutes, and thereafter, the emulsion (Em-10) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-11 of the Present Invention) In the preparation of the comparative emulsion (Em-1), the compound 24 of the present invention was added to the total silver halide at 1.5 × 10 ^-4 before desalting.
After adding mol%, the pH was raised to 9.5 and maintained for 5 minutes, and then the emulsion (Em-11) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-12 of the Present Invention) In the preparation of the comparative emulsion (Em-1), before desalting, the compound 61 of the present invention was added to the total silver halide at 1.5 × 10 ^-4.
After adding mol%, the pH was raised to 9.5 and maintained for 5 minutes, and thereafter, the emulsion (Em-12) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

These emulsions Em-1 to Em-12 were used after being optimally subjected to color sensitization and chemical sensitization.

On a triacetylcellulose 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 light-sensitive material sample 10.
1 was produced. Samples 102 to 112 were prepared by changing Em-1 of the tenth layer as shown in Table 5 in the following sample formulation.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second Layer (Intermediate) Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-12 37 × 10 ^-5 SD-2 1.2 × 10 ^-4 SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 C-1 0.32 CC-1 0.038 OIL- 2 0.28 AS-2 0.002 Gelatin 0.73 Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 SD-1 4.5 × 10 ^-5 SD-2 2.3 × 10 ^-4 SD-3 4.5 × 10 ^-4 C-2 0.52 CC-1 0.06 DI-1 0.04 7 OIL-2 0.46 AS-2 0.004 Gelatin 1.30.

Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^{− 4} SD-3 3.0 × 10 ^-4 C-2 0.047 C-3 0.09 CC-1 0.036 DI-1 0.024 OIL-2 0.27 AS-2 0.006 Gelatin 1. 28 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.19 Silver iodobromide b0 0.062 SD-4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^-4 M-1 0.18 CM-1 0.033 OIL-1 0.22 AS-2 0.002 AS-30 0.05 gelatin 0.61 8th layer (intermediate layer) OIL-1 0.26 AS-1 0.054 gelatin 0.80.

Ninth layer (medium-sensitive green color-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 SD-6 3.7 × 10 ^-4 SD-7 7.4 × 10 ^{− 5} SD-8 5.0 × 10 ^-5 M-1 0.17 M-2 0.33 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL-1 0.73 AS-3 0.035 AS-2 0.003 Gelatin 1.80 10th layer (high-sensitivity green color-sensitive layer) Em-1 1.19 SD-6 4.0 × 10 ^-4 SD-7 8.0 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.065 CM-2 0.026 CM-1 0.022 DI-3 0.003 DI-2 0.003 OIL-1 0.19 OIL-2 0.43 AS-3 0.017 AS-2 0.014 Gelatin 1.23 11th layer (yellow filter layer) Color colloidal silver 0.05 OIL-1 0.18 AS-1 0.16 Gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide b 0.22 Silver iodobromide a 0.08 Silver iodobromide h 0.09 SD-9 6.5 × 10 ^-4 SD-10 2.5 × 10 ^-4 Y-1 0.77 DI-4 0.017 OIL-1 0.31 AS-20 .002 gelatin 1.29.

Thirteenth layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.61 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^{− 4} Y-1 0.23 OIL-1 0.10 AS-2 0.004 Gelatin 1.20 Fourteenth layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-20 .110 OIL-2 0.30 gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 gelatin 0.55 The characteristics of silver iodobromide are shown below (the average grain size here is the average of the length of one side of a cube having the same volume). The method for producing the emulsion conforms to the above-described Em-1.

Emulsion No. Average grain size (μm) Average AgI amount (mol%) Average diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3 0.1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 h 0.65 8.0 1.4 i 1.00 8.0 2 0.0 j 0.05 2.0 1.0 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizers ST-1, ST-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 1,
100,000 two types of polyvinylpyrrolidone (AF-
2), inhibitors AF-3, AF-4, AF-5, hardener H
-1, H-2 and the preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.

[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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Each sample was subjected to the following color development processing.

<< Reference Color Development Processing >> Processing Step Processing Time Processing Temperature Replenishment * Color Development 3 min 15 sec 38 ± 0.3 ° C. 780 cc Bleaching 45 sec 38 ± 2.0 ° C. 150 cc Fixed 1 min 30 sec 38 ± 2.0 ° C. 830 cc Stability 60 seconds 38 ± 5.0 ° C. 830 cc Drying 1 minute 55 ± 5.0 ° C. * The replenishing 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 developer water 800 cc Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20% sulfuric acid. Adjust pH to 0.06 using

Color developing replenisher water 800 cc Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make up to 1 liter, and the pH was adjusted to 10 using potassium hydroxide or 20%. Adjust to 18.

Bleaching solution water 700 cc 1,3-diaminopropanetetraacetic acid ammonium iron (III) salt 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. Adjust the pH to 4.4.

Bleach replenisher water 700 cc 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g After adjusting the pH to 4.4 using aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution water 800 cc Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher water 800 cc Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizing solution and stabilizing replenishing solution water 900 cc para-octylphenyl polyoxyethylene ether (n = 10) 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 cc Add water to make 1 liter, and adjust to pH 8.5 with ammonia water or 50% sulfuric acid.

Each of the samples 101 to 112 was prepared using white light.
/ 200 sec, after step exposure with 3.2 CMS, immediately apply the above-mentioned color development processing to obtain a characteristic curve, and determine the green sensitivity (the reciprocal of the exposure amount which gives a density of fog density +0.10, the value of sample 101) (Indicated by a relative value of 100).

Each sample was stored under the conditions of 40 ° C. and 80% RH for one week, and then exposed and treated in the same manner, and the sensitivity of the sample 101 immediately after the preparation was evaluated as 100.

Table 5 shows the evaluation results of the relative sensitivities of the coated samples 101 to 112 using the emulsions Em-1 to Em-12.

[0184]

[Table 5]

Table 5 shows that the emulsions Em-6 to Em-1 of the present invention
Coating Samples 106 to 112 using No. 2 are comparative emulsions Em-
Excellent sensitivity was exhibited for coating samples 101 to 105 using 1 to Em-5.

Example 2 (Preparation of Comparative Emulsion Em-23) In Comparative Emulsion Em-1 of Example 1, after color sensitization, Solution K-2 was used in an amount of 1.0 × 10 ^-4 mol based on total silver halide. % Of the comparative emulsion (Em-23)
Was prepared.

(Preparation of Comparative Emulsion Em-24) In Comparative Emulsion Em-1 of Example 1, a 0.1% methanol solution of the above compound (A) was added to the total silver halide after color sensitization. A comparative emulsion (Em-24) was prepared in the same manner except that chemical sensitization was performed after adding 0.0 × 10 ⁻⁴ mol%.

(Preparation of Comparative Emulsion Em-25) In Comparative Emulsion Em-1 of Example 1, 2-iodoethanol was added to the total silver halide at 1.2 × 10 ^-4 after color sensitization.
A comparative emulsion (Em-25) was prepared in the same manner except that chemical sensitization was performed after the addition of mol%.

(Preparation of Emulsion Em-26 of the Present Invention) In Comparative Emulsion Em-1 of Example 1, compound 4 according to the present invention after color sensitization was added 1.0 × to total silver halide.
An emulsion (Em-26) of the present invention was prepared in the same manner except that chemical sensitization was performed after adding 10 ^-4 mol%.

(Preparation of Emulsion Em-27 of the Present Invention) In Comparative Emulsion Em-1 of Example 1, after color sensitization, Compound 4 relating to the present invention was 1.6 × with respect to the total silver halide.
An emulsion (Em-27) of the present invention was prepared in the same manner except that chemical sensitization was performed after adding 10 ^-4 mol%.

The Em-1 of the tenth layer in Example 1 was replaced with the Em
Multilayer color photographic light-sensitive material samples 123 to 127 were prepared and evaluated in the same manner as in Sample 101, except that Samples were changed to -23 to Em-27. Table 6 shows the results.

[0192]

[Table 6]

Table 6 shows that the emulsions Em-26 and Em of the present invention were obtained.
The coated samples 126 and 127 using -27 exhibited excellent sensitivity to the coated samples 101 and 123 to 125 using the comparative emulsions Em-1 and Em-23 to Em-25.

Example 3 (Preparation of Comparative Emulsion Em-33) In Comparative Emulsion Em-1 of Example 1, after the color sensitization and the chemical sensitization, the K-2 solution was mixed with the total silver halide 1.5 ×. A comparative emulsion (Em-33) was prepared in the same manner except that ^10-4 mol% was added.

(Preparation of Comparative Emulsion Em-34) In Comparative Emulsion Em-1 of Example 1, after a color sensitization and a chemical sensitization, a 0.1% methanol solution of the compound (A) was added to a total silver halide. Comparative emulsion (Em-34) was prepared in the same manner except that 1.5 × 10 ^-4 mol% was added.

(Preparation of Comparative Emulsion Em-35) In Comparative Emulsion Em-1 of Example 1, 2-iodoethanol was added to total silver halide at 1.8 × 10 ^-4 after color sensitization and chemical sensitization. A comparative emulsion (Em-35) was prepared in the same manner except that mol% was added.

(Preparation of Emulsion Em-36 of the Present Invention) In Comparative Emulsion Em-1 of Example 1, compound 4 according to the present invention, after color sensitization and chemical sensitization, was 1.4 to the total silver halide. An emulsion (Em-36) of the present invention was prepared in the same manner except that × 10 ^-4 mol% was added.

(Preparation of Emulsion Em-37 of the Present Invention) In Comparative Emulsion Em-1 of Example 1, compound 4 according to the present invention was used after color sensitization and chemical sensitization in an amount of 2.0 to the total silver halide. An emulsion (Em-37) of the present invention was prepared in the same manner except that × 10 ^-4 mol% was added.

The Em-1 of the tenth layer in Example 1 was replaced with the Em
Multilayer color photographic light-sensitive material samples 133 to 137 were prepared and evaluated in the same manner as in Sample 101 except that the values were changed from -33 to Em-37. Note that the fog value of the sample 101 was 100
The relative values are shown below. Table 7 shows the results.

[0200]

[Table 7]

From Table 7, it can be seen that the emulsions Em-36 and Em of the present invention were obtained.
The coated samples 136 and 137 using -37 exhibited excellent sensitivity to the coated samples 101 and 133 to 135 using the comparative emulsions Em-1 and Em-33 to Em-35. Also, it can be seen that fog is low.

Example 4 (Preparation of spherical seed emulsion T-2)
A monodisperse spherical seed emulsion T-2 was prepared.

(A-3 solution) Ossein gelatin 80 g Potassium bromide 47.4 g Polyisopropylene-polyethyleneoxy-succinate sodium salt 10% methanol solution 20 mL Water 8.0 L (B-3 solution) Silver nitrate 1200 g 1.6L with water (C-3 solution) Ossein gelatin 32.2g Potassium bromide 840g 1.6L with water (D-3 solution) Ammonia water (28%) 470mL To A-3 solution vigorously stirred at 40 ° C , B-3 and C-3
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.

Thereafter, the temperature was lowered to 30 ° C. over 12 minutes,
Aging was performed for another 18 minutes. Thereafter, D-3 solution was further added for 1 minute, and aging was continued 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-41) A comparative emulsion (Em-41) was prepared using the spherical seed emulsion (T-2) and the following solution.
41) was prepared.

(A-4 solution) Ossein gelatin 268.2 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) 10% methanol solution 1.5 mL Seed emulsion (T-2) 0.341 mol equivalent 28 wt% ammonia aqueous solution 528 mL 56 wt% acetic acid aqueous solution 795 mL 5930 mL with water (B-4 solution) 3.5N ammoniacal silver nitrate aqueous solution 2046 mL (PH was adjusted to 9.0 with ammonium nitrate) (C-4 solution) 2046 mL of 3.5N potassium bromide aqueous solution containing 4.0% by weight of gelatin (D-4 solution) 3.0% by weight of gelatin and iodine Fine grain emulsion composed of silver iodide fine grains (average grain size: 0.05 μm) (Preparation method is shown below) 0.844 mol 0.06 mol containing 0.06 mol of potassium iodide The gelatin solution 5000 mL 7.06 M silver nitrate and 7.0
2000 mL of an aqueous solution containing 6 mol of potassium iodide was added at a constant speed over 10 minutes. During the fine particle formation, 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. The finished weight was 12.53 kg.

(E-4 solution) 3.0% by weight of gelatin and 1
5. Fine grain emulsion (preparation method is shown below) consisting of silver iodobromide fine grains (average grain diameter: 0.05 μm) containing silver iodide in an amount of 2.20 mol 0.06 mol of potassium bromide 2000 mL of an aqueous solution containing 7.06 mol of silver nitrate and 2,000 mL of an aqueous solution containing 6.99 mol of potassium bromide and 0.07 mol of potassium iodide were added at a constant rate over 5000 minutes to 5000 mL of a 0% by weight gelatin solution. . During the formation of fine particles, the pH was adjusted to 3.0 using nitric acid, and the temperature was set to 30 ° C.
Was controlled. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

(Solution F-4) 1.75N Potassium bromide aqueous solution required amount (G-4 solution) 56% by weight acetic acid aqueous solution required amount A-4 solution kept at 70 ° C. in a reaction vessel, B-4 solution , C
Solution -4 and solution D-4 were added over 163 minutes by the simultaneous mixing method, and then solution E-4 was independently added over 12 minutes.

Here, the addition rates of the B-4 liquid, C-4 liquid and D-4 liquid 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. Supply of D-4 solution is B
The core / shell type silver halide grains having a multiple structure were prepared by changing the speed ratio (molar ratio) to the liquid No.-4 with respect to the particle size (addition time) as shown in Table 8.

The pH and pAg during crystal growth were controlled as shown in Table 8 using the F-4 solution and the G-4 solution. The pH and pAg were measured according to a conventional method, using a silver sulfide electrode,
This was performed using a glass electrode.

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

When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size was 1.35 μm and the grain size distribution was 11%. The silver halide grains had (111) and (100) faces. And the major surface thereof was the (111) plane, occupying 80% of the total silver halide grain surface.

[0214]

[Table 8]

(Preparation of Comparative Emulsion Em-42) In the preparation of Comparative Emulsion (Em-41), before desalting, Solution K-2 was added in an amount of 2.0 × 10 ^-4 mol% based on the total silver halide. Except for this, a comparative emulsion (Em-42) was prepared in the same manner.

(Preparation of Comparative Emulsion Em-43) In the preparation of Comparative Emulsion (Em-41), before desalting, a 1.5 N aqueous solution of potassium iodide was added to the total silver halide in an amount of 2.0 × 1.
A comparative emulsion (E) was prepared in the same manner except that ^0-4 mol% was added.
m-43) was prepared.

(Preparation of Comparative Emulsion Em-44) In the preparation of Comparative Emulsion (Em-41), a 0.1% methanol solution of the above compound (A) was added to the total silver halide before desalting. A comparative emulsion (Em-44) was prepared in the same manner except that 0 × 10 ^-4 mol% was added.

(Preparation of Comparative Emulsion Em-45) In the preparation of Comparative Emulsion (Em-41), 2.5 × 10 ^-4 mol% of 2-iodoethanol was added to the total silver halide before desalting. Thereafter, a comparative emulsion (Em-45) was prepared in the same manner except that the pH was raised to 9.5 and maintained for 5 minutes, and thereafter, the pH was returned to 5.8.

(Preparation of Emulsion Em-46 of the Present Invention) In the preparation of the comparative emulsion (Em-41), the compound 4 of the present invention was added to the total silver halide in an amount of 2.5 × 10 ^-4 before desalting.
After adding mol%, the pH of the emulsion was raised to 9.5 and maintained for 5 minutes, and then the emulsion (Em-46) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-47 of the Present Invention) In the preparation of the comparative emulsion (Em-41), before desalting, the compound 16 of the present invention was added to the total silver halide in an amount of 2.5 × 10
After adding ^-4 mol%, the pH was raised to 9.5 and maintained for 5 minutes, and then the emulsion (Em-47) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-48 of the Present Invention) In the preparation of the comparative emulsion (Em-41), the compound 15 of the present invention was added to the total silver halide in an amount of 2.5 × 10
After adding ^-4 mol%, the pH was raised to 9.5 and maintained for 5 minutes, and then the emulsion (Em-48) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-49 of the Present Invention) In the preparation of the comparative emulsion (Em-41), before desalting, the compound 3 according to the present invention was added to the total silver halide in an amount of 2.5 × 10 ^-4.
After the mole% addition, the pH of the emulsion was raised to 9.5 and maintained for 5 minutes, and thereafter the emulsion (Em-49) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-50 of the Present Invention) In the preparation of the comparative emulsion (Em-41), before desalting, the compound 12 of the present invention was added to the total silver halide in an amount of 2.5 × 10 5
After adding ^-4 mol%, the pH was raised to 9.5 and maintained for 5 minutes, and then the emulsion (Em-50) of the present invention was prepared in the same manner except that the pH was returned to 5.8.

(Preparation of Emulsion Em-51 of the Present Invention) In the preparation of the comparative emulsion (Em-41), before desalting, the compound 24 of the present invention was added to the total silver halide in an amount of 2.5 × 10 5
After adding ^-4 mol%, the pH of the emulsion was raised to 9.5, maintained for 5 minutes, and then returned to 5.8 to prepare an emulsion (Em-51) of the present invention in the same manner.

(Preparation of Emulsion Em-52 of the Present Invention) In the preparation of the comparative emulsion (Em-41), before desalting, the compound 61 of the present invention was added to the total silver halide in an amount of 2.5 × 10 5
After adding ^-4 mol%, the pH of the emulsion was raised to 9.5, maintained for 5 minutes, and then returned to 5.8 to prepare an emulsion of the present invention (Em-52).

Using the emulsions Em-41 to Em-52, multilayer color photographic light-sensitive materials 141 to 152 were prepared in the same manner as in Example 1 and evaluated. Table 9 shows the results.

[0227]

[Table 9]

From Table 9, it can be seen that the emulsions Em-46 to Em- of the present invention were obtained.
Samples 146 to 152 using No. 52 were prepared as Comparative Emulsion Em
Excellent sensitivity was exhibited with respect to coating samples 141 to 145 using -41 to Em-45.

[0229]

According to the present invention, a method for producing a silver halide photographic emulsion having excellent sensitivity, fogging and storage stability, and a silver halide photographic material using the same can be provided.

Claims (10)

[Claims] 1. A method for producing a silver halide photographic emulsion, comprising using a compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing a halide ion. 2. A silver halide photograph characterized in that a compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing a halide ion is used for forming the vicinity of the outermost surface of silver halide grains. Emulsion manufacturing method. 3. The method for producing a silver halide photographic emulsion according to claim 1, wherein the adsorptive group has a selective adsorptivity to the main surface of the silver halide grains. 4. The method for producing a silver halide photographic emulsion according to claim 1, wherein said halide ions are iodide ions. 5. A compound having in its molecule an adsorbing group to silver halide and a substituent capable of releasing halide ions,
The method for producing a silver halide photographic emulsion according to any one of claims 1 to 4, wherein the compound is a compound represented by the following general formula (1). General formula (1) [A]-{[L] m- [Z] n} r wherein A represents an adsorptive group to silver halide, L represents a divalent or trivalent linking group, Represents a substituent capable of releasing a halide ion, m represents 0 or 1, n represents 1 or 2, and r represents an integer of 1 to 3. ] 6. A silver halide photographic emulsion produced by the method for producing a silver halide photographic emulsion according to claim 1 is contained in at least one silver halide emulsion layer on a support. A silver halide photographic material. 7. An additive for a silver halide photographic light-sensitive material, characterized in that the molecule has an adsorbing group to silver halide and a substituent capable of releasing a halide ion. 8. The additive for a silver halide photographic light-sensitive material according to claim 7, wherein said adsorptive group has a selective adsorptivity to a main surface of silver halide grains. 9. The additive for a silver halide photographic material according to claim 7, wherein the halide ion is an iodide ion. 10. A compound having in its molecule a group capable of releasing an adsorbable group to silver halide and a group capable of releasing a halide ion, which is a compound represented by the above general formula (1). 10. The additive for a silver halide photographic light-sensitive material according to any one of 7 to 9 above.