JPH1144923A - Production of silver halide photographic emulsion and silver halide photographic sensitive material containing that emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make obtainable the max. potential of high sensitivity-low fog by adding silver halide fine particles, the inner part and/or surfaces of which have been subjected to reduction sensitization, adding an oxidizing agent for silver nuclei when the fine particles are deposited on base particles, and selecting the oxidizing agent from specified compds. SOLUTION: Silver halide fine particles, the inner and/or surfaces of which are preliminarily subjected to reduction sensitization are added and deposited during or after silver halide base particles are produced so as to subject the base particles to reduction sensitization. This method includes a process to add an oxidizing agent for silver nuclei, and the oxidizing agent used is selected from compds. expressed by formula I or R-SO2 S-M or formula II of R-SO2 S-R1 . In the formulae, R, R1 , R2 each may be the same or different and are an aliphatic group, aromatic group or heterocyclic group, M is a cation, L is a bivalent connecting group, and m is 0 or 1. Thereby, the max. potential of high sensitivity-low fog of reduction sensitization can be obtd.

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 an emulsion having high sensitivity and less occurrence of fog, and a silver halide photosensitive material using the emulsion.

[0002]

2. Description of the Related Art Attempts for reduction sensitization have been studied for a long time. Carroll discloses in US Patent No. 2,487,850 a tin compound, and Lowe et al. In US Patent No. 2,512,9.
No. 25 disclosed a polyamine compound, and Fallens et al. Disclosed in British Patent No. 789,823 that thiourea dioxide-based compounds were useful as reduction sensitizers. In addition, Collier is a Photograph
hic scienceand engineerin
g Volume 23, page 113 (1979) compares the properties of silver nuclei made by various reduction sensitization methods.
She has, for example, dimethylaminoborane, stannous chloride,
A method using hydrazine, high pH aging, and low pAg aging was employed. The method of reduction sensitization is further described in U.S. Pat.
Nos. 8,698, 3,201,254, 3,4
No. 11,917, No. 3,779,777, No. 3,
No. 930,867. Regarding the method of using the reducing agent as well as the selection of the reduction sensitizer,
Nos. 33572 and 58-1410, JP-A-57-17
No. 9835. Further, a technique for improving the storage stability of the reduction-sensitized emulsion is disclosed in JP-A-57-8283.
Nos. 1 and 60-178445.

[0003] Reduction sensitization is described in James (THJ).
ames), The Photographic Process, 4th Edition, Macmillan, 1977, <T. H. Jam
es, The Theory of the Photo
graphical Process, 4th, Ma
As described on page 152, the silver nucleus formed by the two atoms generated by reduction sensitization captures holes, whereby the silver nuclei are decomposed into silver ions and unstable silver atoms. A mechanism has also been considered in which unstable silver atoms are decomposed into silver ions and conductor electrons, and the electrons contribute to latent image formation. According to this mechanism, the sensitivity is up to 2
It is possible to increase by a factor of two.

[0004]

The problem to be solved by the present invention is disclosed in Japanese Patent Laid-Open No. 2-19 / 1990.
Nos. 1938 and 3-168632 describe reduction sensitization techniques. When reduction sensitization is performed on grains by these methods, spectral sensitization is obtained in minus blue recording (green-sensitive layer and red-sensitive layer). Since the level of hole injection of the sensitizing dye is low, the sensitizing effect is still insufficient as compared with the blue recording (blue-sensitive layer), and there is a problem that fog is particularly high. Therefore, fog is low, high sensitivity, especially in minus blue recording,
There has been a strong demand for a reduction sensitization technique having low fog.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method of reduction sensitization that maximizes high sensitivity and low fog.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide, during and / or after the formation of silver halide base grains, silver halide fine grains of which the inside and / or the surface are reduction-sensitized, are added. A method for producing a silver halide photographic emulsion in which fine grains are deposited on the base grains, a step of adding an oxidizing agent for silver nuclei, wherein the oxidizing agent has the following general formula (1):
Selected from the compounds represented by (2) or (3), general formula (1) R-SO ₂ S-M general formula (2) R-SO ₂ S-R ₁ general formula (3) R-SO _{2 S-L m -SSO 2 -R} 2 and the silver halide photographic material containing silver halide photographic emulsion prepared by the above method is accomplished by. still,
The compounds represented by the general formulas (1) to (3) may be a polymer containing a divalent group derived from the structure represented by the general formula as a repeating unit.

Hereinafter, the present invention will be described in detail.

According to the present invention, the reduction sensitization is previously carried out inside the grains and / or
Alternatively, silver halide fine grains (hereinafter, also referred to as fine grains) applied to the surface are added during and / or after formation of silver halide base grains (hereinafter, also referred to as base grains), and are deposited to cause reduction to increase. It is characterized by giving a feeling.

The surprising effect of the method of adding the reduction sensitizing fine particles is that the control of the reduction sensitization nucleus in the base particles is easy and that the amount of unreacted reduction sensitizer is small, so that the reduction sensitizing effect is reduced. High sensitivity-To maximize the potential of low fog.

To perform reduction sensitization on fine grains, reduction sensitization may be performed during physical ripening of silver halide fine grains, or reduction sensitization may be performed during addition of a water-soluble silver salt and a water-soluble alkali halide. Or a method in which reduction sensitization is performed in a state where these additions are temporarily stopped, and then a further precipitation step is performed. Alternatively, reduction sensitization may be performed after the formation of the fine particles to form reduction sensitized silver nuclei on the surfaces of the fine particles. Examples of the reduction sensitization include a method of adding a reduction sensitizer to silver halide, a method of growing or ripening silver halide grains under a low pAg atmosphere of pAg 1 to 7, which is called silver ripening, and a method of high pH ripening. High pH of pH 8-11
Any of the methods of growing or ripening in the above atmosphere can be selected. Also, two or more of these methods can be used in combination. In particular, the method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

The reduction sensitizer that can be used in the present invention includes stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like. Can also be used in combination. The addition amount of the reduction sensitizer depends on the emulsion production conditions and must be appropriately selected. However, the addition amount is suitably in the range of 1 × 10 ⁻⁷ mol to 1 × 10 ⁻² mol per mol of silver halide. It is preferably in the range of 1 × 10 ⁻⁶ mol to 1 × 10 ⁻³ mol. These reduction sensitizers are added after being dissolved in water or a solvent such as alcohols, glycols, ketones, esters, and amides. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during the particle growth. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. In addition, a method in which the solution of the reduction sensitizer is added in several portions as the grains grow, or a method in which the solution is continuously added for a long time are also preferable methods.

In the present invention, the silver halide fine grains preliminarily reduced and sensitized are deposited on silver halide base grains. The term “depositing” means that the fine grains are not aggregated as they are on the base grains but once. By reducing the reduction-sensitized silver halide fine particles and controlling the grain growth environment (temperature, pH, etc.), the entire surface or the side of the base grain,
It means that a reduction sensitized silver nucleus is incorporated into a localized site such as a vertex and is regenerated as silver halide.

The temperature, pH and time for depositing the reduction sensitized silver halide fine grains may be freely selected within a range where the fine grains are deposited on the base grains, but the physical ripening temperature is 30 ° C.
The temperature is preferably from 80 ° C to 80 ° C, more preferably from 40 ° C to 70 ° C. The pH is preferably 2 or more and 10 or less, and 3
More preferably, it is 7 or less.

The reduction sensitized silver halide fine grains may be deposited on the base grains at any time during the formation of the base grains, immediately after nucleation of the base grains, during the grain formation or immediately before the desalting step. good. Also, it may be after the formation of the particles, immediately after the start of chemical ripening, or after. It may be before or after the addition of the spectral sensitizing dye. The addition of the spectral sensitizing dye may be performed at any time after grain formation. The spectral sensitizing dye is 1 × 10 ⁻⁷ mol or more per mol of silver and 1 × 10 ⁷ mol or more.
It is preferable to add an amount of ^-1 mol or less, and more preferably an amount of 1 × 10 ^-5 mol or more and 1 × 10 ^-2 mol or less. The amount of the dye added depends on the size of the base particles, and the coverage is preferably 30 to 90% (surface area ratio). The base particles may be previously subjected to reduction sensitization.

The reduction sensitized silver halide fine particles to be added are:
1 × 10 ⁻⁷ mol or more and 5 × 10 per mol of silver of base particles
It is preferable to add the silver in an amount of ¹ mol or less, more preferably 1 x 10 ^-6 mol or more and 1 x 10 ^-1 mol or less.

The reduction sensitized silver halide fine grains used in the present invention can be prepared by a known method. That is, any method such as an acid method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide salt is a one-side mixing method,
Any of the simultaneous mixing method, a combination thereof, and the like may be used. As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a controlled double jet method can be used. However, this method has a narrow grain size distribution, It is preferable as a method for preparing an emulsion containing the reduction-sensitized halogenated fine particles of the present invention.

The reduction sensitized halogenated fine grain emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid in order to remove unreacted reduction sensitizer. The washing temperature can be selected according to the purpose,
It is preferable to select in the range of 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10, and more preferably from 3 to 8. PA at the time of washing
g can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

The reduction sensitized silver halide fine particles of the present invention are:
It may have a regular crystal form such as a cube, an octahedron, or a tetradecahedron, or may have a crystal form such as a sphere or a plate. The inside and the surface of the emulsion grains may have different halogen compositions, or may have a uniform halogen composition.

The average grain size of the reduction-sensitized silver halide fine grains is preferably from 0.01 to 0.1 μm, more preferably from 0.01 to 0.1 μm.
0.07 μm is more preferred.

The composition of the reduction-sensitized silver halide fine grains may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodobromide and silver iodobromide. The halogen composition may be the same as or different from that of the base particles.

In the present invention, the reduction sensitized silver nuclei are locally and selectively incorporated into the grains. That is, when the reduction sensitized silver halide fine grains are added to the base grains, the growth environment of the base grains (p
By controlling (H, temperature, silver potential), the substrate particles can be deposited on the entire surface, or on localized parts such as sides and vertices. As a result, a predetermined amount of the reduction sensitized silver nucleus can be locally and selectively present at a predetermined position of the base grain. Such a reduction-sensitized silver halide emulsion has not been known until now and is a completely new emulsion.

Next, the silver halide base grains used in the present invention will be described.

The base grains of the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, and silver chloroiodobromide. Other silver salts, for example, silver rhodanate, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are desired, silver halide grains having a high silver chloride content are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material. For example, the preferred range is 0.1 to 15 mol% for X-ray photographic materials and 0.1 to 5 mol% for graphic arts and micro photographic materials.
In the case of a photographic light-sensitive material represented by a color negative, a silver halide containing 1 to 30% of silver iodide is preferable, more preferably 5 to 20% by mole, and particularly preferably 8 to 15%.
Mol%. It is preferable that silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The base particles of the present invention preferably have a distribution or a structure with respect to the halogen composition in the particles. Typical examples are JP-B-43-13162, JP-A-61-215540, and JP-A-60-222845.
These are core-shell type or double structure type particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions as disclosed in JP-A-60-143331 and JP-A-61-75337. In addition, it is not a simple double structure.
It can be a triple structure as disclosed in No. 44 or a multilayer structure thereof or more, or a silver halide having a different composition can be thinly applied to the surface of a core-shell double structure grain. .

In the case of a base grain in which two or more silver halides are present as a mixed crystal or with a structure, it is important to control the halogen composition distribution between grains. Regarding a method for measuring the halogen composition distribution between grains, see JP-A-60-25.
No. 4032. Uniform halogen distribution between grains is a desirable property. Especially coefficient of variation 2
Emulsions having a high uniformity of 0% or less are preferred. Another preferred embodiment is an emulsion having a correlation between the grain size and the halogen composition, for example, a case in which the larger grains have a higher iodine content, while the smaller grains have a lower iodine content.
Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the base particles. Increasing the silver iodide content near the surface or increasing the silver chloride content can be selected according to the purpose because the dye adsorbability and the developing speed are changed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, this is a case where the halogen composition is changed only on one side of the tetrahedral grain composed of the (100) plane and the (111) plane, or one of the main plane and the side face of the tabular grain is changed.

The base particles of the present invention can be made of normal crystals containing no twin planes. 163, such as a single twin with one twin plane, a parallel multiple twin with two or more parallel twin planes, a non-parallel with two or more non-parallel twin planes It can be selected from multiple twins or the like depending on the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of normal crystals (1
(00) plane, octahedron (111) plane, JP-B-55-42737, JP-A-60-2228.
No. 42, dodecahedral particles having a (110) plane can be used. In addition, Journal o
f Imaging Science, Vol. 30, No. 247
Page, (hll) plane particles represented by (211) and (331) represented by (h) as reported in 1986.
The (hl) plane particles, the (hk0) plane particles represented by the (210) plane, and the (hkl) plane particles represented by the (321) plane also require some devising in the preparation method, but may be selected and used according to the purpose. it can. Depending on the purpose, particles having two or many planes, such as tetradecahedral particles in which (100) plane and (111) plane coexist in one particle, and particles in which (100) plane and (110) plane coexist, may also be used. You can select and use it. The value obtained by dividing the circle equivalent diameter of the photographing area of the particle by the particle thickness is called an aspect ratio, and defines the shape of the tabular particle. Tabular grains having an aspect ratio of greater than 1 can be used as the base grains of the present invention. Tabular grains are described in Cleeve, "Theory and Practice of Photography" (Cleve, Photography T
heavy and Practice (193
0)), p. 131; Gatov, Photographic Science and Engineering (Gutoff, P.
photographicc Science and
Engineering), Vol. 14, 248-257
P. (1970); U.S. Patent No. 4,434,226;
Nos. 4,414,310 and 4,433,048
No. 4,439,520 and British Patent No. 2,11.
2,157 and the like. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye,
This is described in detail in U.S. Pat. No. 4,434,226, cited above. The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and 100 or less. It is more preferably 2 or more and 20 or less, particularly preferably 3 or more.
It is not less than l0. If the aspect ratio is too high, a pressure drop or the like occurs, which is not preferable. The shape of the tabular grains can be selected from triangles, hexagons, circles and the like.
A regular hexagon whose six sides are almost equal in length as described in U.S. Pat. No. 4,797,354 is a preferred form.

The equivalent circle diameter of the projected area of the grains is often used as the grain size of the tabular grains, but grains having an average diameter of 0.6 μm or less as described in US Pat. No. 4,748,106 are generally used. Is preferable for high image quality. In addition, the thickness of the tabular grains is 0.5 μm or less,
It is more preferable to limit the thickness to 0.3 μm or less in order to increase sharpness. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable.

When monodisperse tabular grains having a narrow grain size distribution are used, more preferable results may be obtained. U.S. Pat. No. 4,797,354 and JP-A-2-8
No. 38 describes a method for producing monodisperse hexagonal tabular grains having a high tabularization ratio. Also, European Patent No. 514,742
The article describes a method for producing tabular grains having a coefficient of variation of the grain size distribution of less than 10% using a polyalkylene oxide block copolymer. It is preferable to use these tabular grains in the present invention. Further, a particle having a high uniformity of thickness having a variation coefficient of the particle thickness of 30% or less is also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select dislocations or dislocations that are introduced linearly with respect to a specific direction of the crystal orientation of the grains, or to introduce them all over the grains, or to introduce them only into specific portions of the grains,
For example, dislocations can be introduced only in the fringe portion of the particle, and the like can be selected. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle.

The base particles of the present invention are described in European Patent No. 96,72.
No. 7B1, No. 64,412B1 and the like, for example, a treatment for imparting roundness to particles, or West German Patent No. 2
The surface may be modified as disclosed in JP-A No. 306,447C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532 and JP-A-60-221320 disclose a method of forming a hole in a part of a crystal, for example, a vertex or a center of a plane, or U.S. Pat.
Raffle particles described in No. 966 are examples.

The particle size of the base particles of the present invention and the particles finally obtained can be determined by a circle equivalent diameter of a projected area using an electron microscope, a sphere equivalent diameter of a particle volume calculated from the projected area and the particle thickness, or a Coulter counter method. It can be evaluated by the sphere equivalent diameter of the volume. 0.05 as ball equivalent diameter
It can be used by selecting from ultrafine particles of not more than μm or coarse particles exceeding 10 μm. Preferably, particles having a size of 0.1 μm or more and 3 μm or less are used as photosensitive halogenated particles.

The base particles or finally obtained particles of the present invention may be a so-called polydisperse emulsion having a wide particle size distribution.
A monodisperse emulsion having a narrow size distribution can be selected and used according to the purpose. In some cases, the coefficient of variation of the diameter equivalent to the projected area of a particle is used as a scale representing the size distribution. When a monodispersed emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% or less, more preferably 20% or less, and still more preferably 15% or less.

The monodisperse emulsion may be defined as having a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size in terms of the number or weight of grains. In order to satisfy the target gradation of the light-sensitive material, two or more monodisperse silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The base particles of the present invention can be prepared by the method described in Graffide, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafk).
ides, Chimie et Physique P
hotgraphique Paul Monte
1, 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Photog).
raphic Emulsion Chemistry,
Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions" by Zeligman et al., Published by Focal Press (VL Zelikman et al, Makin).
g and Coating Photographi
c Emulsion, Focal Press, 19
64) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any of a one-side mixing method, a double-mixing method, a combination thereof and the like. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, base particles having a regular crystal form and a nearly uniform particle size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, US Pat. No. 4,33
No. 4,012, No. 4,301,241, No. 4-1
No. 50,994 is more preferred in some cases, and these can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from the method of adding the whole amount at once, adding a plurality of times, or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface.

A method of converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,14.
No. 2,900, European Patent Nos. 273,429 and 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a more insoluble silver salt. It can be selected from methods such as conversion at a time, conversion into a plurality of times, or continuous conversion.

In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1
469,480; U.S. Pat. No. 3,650,757;
The particle forming method in which the concentration is changed or the flow rate is changed as described in US Pat. No. 4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605 and No. 3,415,65
No. 0, No. 3,785,777, West German Patent No. 2,
556,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, or can be added together with the halide salts, silver salts or peptizers, and added to the reactor. Can also be introduced. As another variant, the ripening agent can be introduced independently during the silver halide and silver salt addition steps.

Ammonia, thiocyanates (eg, rhodacali, rhodamonium), and organic thioether compounds (eg, US Pat. Nos. 3,574,628, 3,021,215, and 3,057,724) No. 3,038,805, No. 4,276,374,
Nos. 4,297,439 and 3,704,130
No. 4,782,013, JP-A-57-1049.
No. 26, etc.), thione compounds (for example, tetrasubstituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. Compounds described in JP-A-53-144319, meltcapto compounds capable of promoting the growth of silver halide grains described in JP-A-57-202531, and amine compounds (for example, JP-A-54-1).
00717). Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate and starch derivatives Sugar derivative; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various kinds of synthetic hydrophilic high molecular substances such as homopolymers or copolymers such as polyvinylimidazole and polyvinylpyrazole can be used.

As gelatin, lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. P30 (1966)
Enzyme-treated gelatin as described in may be used,
In addition, a hydrolyzate or enzymatic hydrolyzate of gelatin can also be used.

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

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

The base grains of the present invention can be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization and noble metal sensitization in any step of the production process of a silver halide emulsion. . It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitization nucleus is embedded in the inside of a grain, a type in which a chemical sensitization nucleus is embedded in a position shallow from the particle surface, and a type in which a chemical sensitization nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, it is preferable to form at least one type of chemical sensitization nucleus near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization alone or in combination, and is described by TH James in The Photographic Process, No. 4. Edition, Macmillan, 1977, (TH James, The Th
eory of the PhotographicP
process, 4thed, Makmi11an, 19
77) can be performed using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure 120, April 1974, 12008; Research Disclosure 34, June 1975,
13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,773,031, 3,857,711, 3,901,714,
Nos. 4,226,018 and 3,904,41
5, pAg 5-10, pH 5-8 and temperature 30-35 as described in GB 1,315,755.
At 80 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium or a combination of a plurality of these sensitizers. In the noble metal sensitization, for example, a noble metal salt of gold, platinum, or palladium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, for example, known compounds of chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent salt or a tetravalent salt of palladium.
Preferred palladium compounds are P ₂ PdX ₆ or R ₂ P
represented by dX _4. Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, for example, K ₂ PdCl ₄ ,
(NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (N
H ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdC
₁₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,7
No. 11, No. 4,226,018 and No. 4,05
Sulfur-containing compounds described in US Pat. No. 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitizer. Useful chemical sensitization aids include compounds known to suppress fog during chemical sensitization and increase sensitivity, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aids and modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757, JP-A-58-126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

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

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

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, for example, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.),
Selenium compounds such as selenoketones and selenamides can be used. Selenium sensitization may be preferably used in combination with sulfur sensitization or noble metal sensitization or both.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts very fine silver particles by-produced in the process of forming silver halide grains and in the course of chemical sensitization into silver ions is effective. The silver ion generated here may form a silver salt that is hardly soluble in water, such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water, such as silver nitrate. May be formed. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide, and adducts thereof (eg, NaBO ₂ .H ₂ O ₂ .3).
_{H 2 O, 2Na 2 CO 3} · 3H 2 O 2, Na 4 P 2 O 7
_{· 2H 2 O 2, 2Na 2} SO 4 · H 2 0 2 · 2H 2 O
H), peroxyacid salts (eg, K ₂ S ₂ O ₈ , K ₂ C
₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3H ₂ O, 4K ₂
SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O, Na _{3
[VO (O 2) (C} 2 H 4) 2 6H 2 O], permanganate (e.g., KMnO _4), chromate (eg, K
Oxygen acid salts such as ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and salts of high valent metals (eg, potassium hexacyanoferric acid) is there.

Examples of the organic oxidizing agent include thiosulfonic acid compounds, quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen ( Examples include N-promsuccinimide, chloramine T, chloramine B).

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, inorganic oxidizing agents for halogen elements, thiosulfonic acid compounds and organic oxidizing agents for quinones. A particularly preferred oxidizing agent is a thiosulfonic acid-based compound, and the outermost nucleus is coated in the presence of at least one compound selected from the compounds represented by formulas (1) to (3).

General formula (1) R-SO ₂ SM General formula (2) R-SO ₂ SR ₁ General formula (3) R-SO ₂ SL _m -SSO ₂ -R ₂ General formula ( In the thiosulfonic acid-based compound represented by 1), (2) or (3), when R, R ₁ and R ₂ are an aliphatic group, a saturated or unsaturated, straight-chain, branched or cyclic,
An aliphatic hydrocarbon group, preferably having 1 to 22 carbon atoms
An alkenyl group having 2 to 22 carbon atoms, or an alkynyl group, which may have a substituent. Examples of the alkyl group include a methyl group, an ethyl group,
Examples include a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, an isopropyl group and a t-butyl group. Examples of the alkenyl group include an allyl group and a butenyl group. Examples of the alkynyl group include a propargyl group and a butynyl group. The aromatic group represented by R, R ₁ and R ₂ includes a monocyclic or condensed ring aromatic group, and preferably has 6 to 20 carbon atoms, such as a phenyl group and a naphthyl group. Can be These may be substituted. The heterocyclic group represented by R, R ₁ and R ₂ preferably has at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium, and 3 to 15 carbon atoms having at least one carbon atom. A 3- to 6-membered ring is more preferable, for example, a pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring , Benzimidazole ring, selenazole ring,
Examples include a benzoselenazole ring, a tellurazole ring, a triazole ring, a benzotriazole ring, a tetrazole ring, an oxadiazole ring, and a thiadiazole ring.

Examples of the substituent for R, R ₁ and R ₂ include an alkyl group (methyl group, ethyl group, hexyl group, etc.),
Alkoxy group (methoxy group, ethoxy group, octyloxy group, etc.), aryl group (phenyl group, naphthyl group, tolyl group, etc.), hydroxy group, halogen atom, aryloxy group (phenoxy group, etc.), alkylthio group (methylthio group, Butylthio group, etc.), arylthio group (phenylphenyl group, etc.), acyl group (acetyl group, propionyl group, butyryl group, valeryl group, etc.), sulfonyl group (methylsulfonyl group, phenylsulfonyl group, etc.), acylamino group (acylamino group, benzoyl) amino group etc.), a sulfonylamino group (methanesulfonylamino group, etc. benzenesulfonylamino group), an acyloxy group (acetoxy, benzoxy group), a carboxyl group, a cyano group, a sulfo group, an amino group, -SO ₂ SM group ( M is a monovalent cation), -. SO ₂ R group R represents an alkyl group.) Can be mentioned.

The divalent linking group represented by L includes
An atom or atomic group containing at least one selected from C, N, S and O is preferable. Specifically, an alkylene group, alkenylene group, alkynylene group, arylene group, -O
-, - S -, - NH -, - CO -, - SO 2 - made from a single or combination of the like are preferable. L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group include-(CH ₂ ) _n- (n is 1 to
_{12), - CH 2 -CH =} CH-CH 2 -, - CH 2 C
≡CCH ₂ —, —CH ₂ -1,4-cyclohexylene—
CH ₂ —, a xylylene group, and the like. Examples of the divalent aromatic group include a phenylene group and a naphthylene group. These substituents may be further substituted with the substituents described above.

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

When the compounds represented by formulas (1) to (3) are polymers, examples of the repeating unit include the following.

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These polymers may be homopolymers or copolymers with other copolymerized monomers. Specific examples of the compound represented by the general formula (1), (2) or (3) are shown below, but are not limited thereto.

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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The compound represented by the general formula (1), (2) or (3) is disclosed in JP-A-54-109; UK Patent No. 97
2,211; Journal of Organic Chemi
Stry) 53, 396 (1988) or a method analogous thereto.

The formula (1) per mole of silver of the present invention,
The addition amount of the compound represented by (2) or (3) is 10 ^-7 to
It is desirable to select from the range of 10 ^-1 mol. Preferably 1
0 ^-6 to 10 ^-2 mol, more preferably 10 ^-5.
The range is from 10 to ³ mol. The compound represented by the general formula (1), (2) or (3) may be added at any stage during the grain formation of the silver halide emulsion, before or after chemical sensitization.
Preferably, it is added before chemical sensitization, and more preferably during grain formation. These compounds may be added at any stage before or after the start of reduction sensitization, but are preferably added after the start of reduction sensitization. In order to add the compounds represented by the general formulas (1) to (3) during the production process, a method usually used for adding an additive to a photographic emulsion can be applied. For example,
The water-soluble compound is an aqueous solution having a suitable concentration, and the water-insoluble or hardly-soluble compound is a water-miscible suitable organic solvent such as alcohols, glycols, ketones, esters, amides and the like. It can be dissolved in a solvent that does not adversely affect photographic properties and added as a solution.

It is a preferred embodiment to use the above-mentioned addition of the reduction sensitizing fine particles and the oxidizing agent for silver in combination. The method can be selected from a method in which an oxidizing agent is used and then reduction sensitization is performed with reduction sensitized fine particles, a method reverse thereto, or a method in which both coexist simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, Mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines;
Thioketo compounds such as oxazolinethione; azaindenes such as, for example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes) and pentaazaindenes; Many compounds known as antifoggants or stabilizers can be added, for example, US Pat. No. 3,954,47.
No. 4, No. 3,982,947, Japanese Patent Publication No. 52-286
No. 60 can be mentioned. One of the preferred compounds is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effect by adding during emulsion preparation, control the crystal wall of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The spectral sensitizing dyes adsorbed on the base particles of the present invention include methine dyes. Therefore, the effect of the present invention is that the photographic emulsion finally obtained is also spectrally sensitized by methine dyes and the like. It is preferable to exert. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are
It is a dye belonging to a cyanine dye, a merocyanine dye, and a complex merocyanine color cord. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, for example, an indolenine nucleus, a benzindolenine nucleus , An indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus. These nuclei may be substituted on carbon atoms.

The merocyanine dye or composite merocyanine dye includes, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidin-2,4-dione nucleus, thiazolidine-
5- to 6-membered heterocyclic nuclei such as 2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.
These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,977,229.
No. 3,397,060, No. 3,522,052
No. 3,527,641, No. 3,617,29
No. 3, No. 3,628,964, No. 3,666,4
No. 80, No. 3,672,898, No. 3,679,
No. 428, No. 3,703,377, No. 3,76
9,30l, 3,814,609, 3,8
37,862 and 4,026,707, British Patents 1,344,281 and 1,507,803,
These are described in JP-B-43-4936 and JP-B-53-12375, and JP-A-52-110618 and JP-A-52-109925.

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

The preferred spectral sensitizing dye of the present invention is added after the formation of the base grains and before the addition of fine grains. Usually, it is carried out after completion of chemical sensitization and before coating, but US Pat. Nos. 3,628,969 and 4,225,66.
As described in JP-A-58-158, the spectral sensitization can be carried out simultaneously with the chemical sensitization by adding the same at the same time as the chemical sensitizer.
It can be carried out prior to chemical sensitization as described in JP-A-113928, or it can be added before completion of precipitation of silver halide grains to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,255,666, i.e., some of these compounds may be added prior to chemical sensitization, and the remainder may be chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 × / mol of silver halide.
It can be used in an amount of from 10 ^-6 to 8 × 10 ^-3 mol. In the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective. It is.

When the emulsion obtained in the present invention is used as a light-sensitive material, the above-mentioned various additives are used. In addition, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (1978).
December 18), Item 18716 (November 1979)
Monday) and Item 308119 (December 1989)
Month).

The silver halide emulsion of the present invention can be used for various photographic materials by any conventional method. As one important aspect, the silver halide emulsion of the present invention is suitable for use in a multilayer photographic material having at least two silver halide emulsion layers.
For example, in the case of a multilayer photographic light-sensitive material such as a color negative film or a color reversal film, the silver halide emulsion of the present invention may be used on either the upper layer side or the lower layer side, or may be used together.

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EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. The invention can be better understood by reference to the following examples of emulsion preparation, emulsion and photographic elements that satisfy the requirements of the invention. Sensitivity is the exposure amount E that gives fog + 0.2 density
(E is expressed in units of lux / second.) It is expressed as the relative value of the logarithm of the reciprocal.

Example 1 << Preparation of silver halide fine grain emulsion (emulsion A) >> An aqueous solution containing 240 g of silver nitrate and an aqueous potassium bromide solution were simultaneously added over 10 minutes while stirring 2000 ml of a 3% aqueous gelatin solution at 50 ° C. while stirring. did. Meanwhile, the pAg was kept at 8.9. Thereafter, ultrafiltration and desalting were carried out to obtain a silver halide fine grain emulsion A containing silver halide fine grains having an average grain size of 0.05 μm.

<< Preparation of silver halide fine grain emulsion (emulsion B) >> Average grain size was prepared in the same manner as in the preparation of emulsion A, except that 5 × 10 ⁻⁵ mol / mol Ag of thiourea dioxide was added to a 3% aqueous solution of gelatin. A 0.05 μm reduction-sensitized fine grain emulsion B was prepared.

<< Preparation of Seed Emulsion-1 >> A seed crystal emulsion was prepared as follows.

Using a mixing stirrer described in JP-B-58-58288, an aqueous solution of silver nitrate (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (iodine) were added to the following solution A1 adjusted to 35 ° C. 2 mol% of potassium chloride) was added in 2 minutes by the simultaneous mixing method while keeping the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) to form nuclei. Was. Subsequently, the liquid temperature was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution, and then an aqueous silver nitrate solution (5.
902 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) were added over 42 minutes by a simultaneous mixing method while keeping the silver potential at 9 mV.
After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The obtained 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 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% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml << Preparation of silver iodide fine grain emulsion SMC-1 >> 6.0% by weight containing 0.06 mol of potassium iodide 5l of gelatin aqueous solution
While stirring vigorously, 2 L of a 7.06 mol aqueous solution of silver nitrate and 2 L of a 7.06 mol aqueous solution of potassium iodide were added over 10 minutes. During this time, the pH was adjusted to 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 was 0.05 μm. This emulsion is designated as SMC-1.

<< Base Grain Emulsion (Emulsion C) >> 0.178 mol of seed crystal emulsion-1 and 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% ethanol solution 0.
4.5% by weight of an inert gelatin aqueous solution containing 5 ml 7
The solution was kept at 75 ° C., the pAg was 8.4, and the pH was 6.
After adjusting to 0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

1) 2.077 mol of silver nitrate aqueous solution and 0.1 mol
218 mol of SMC-1 and aqueous potassium bromide solution
The pAg was added while keeping the pH at 8.8 and the pH at 6.0.

2) Subsequently, the solution was cooled to 60 ° C.
Was adjusted to 9.8. Then, 0.71 mol of SMC-
1 and aged for 2 minutes. (Introduction of dislocation lines).

3) 0.91 mol of silver nitrate aqueous solution and 0.0
79 mol of SMC-1 and an aqueous potassium bromide solution were added to p
Ag was added at 9.8 and the pH was maintained at 5.0.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Edge length) 0.65 μm, average aspect ratio 6.5, silver iodide content 2 / 9.5 / X / 8.0 mol% from the inside of the grain
The emulsion was composed of tabular grains having a halogen composition of (X is a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

<< Preparation of Comparative Emulsion D >> In the step of preparing Emulsion C, Seed Emulsion-1 was added, and after adjusting pAg and pH, 1 × 10 ⁻⁵ mol / mol Ag of thiourea dioxide was added.
This emulsion is referred to as Emulsion D. << Preparation of Comparative Emulsion E >> In step 1) of the preparation of Emulsion C, 1 × 10 ⁻⁵ mol / mol Ag of thiourea dioxide was added when 50% of the added silver was consumed. This emulsion is referred to as Emulsion E. << Preparation of Comparative Emulsion F >> In the step of preparing Emulsion C, Seed Emulsion-1 was added, pAg and pH were adjusted, and 5 × 10 ⁻² mol / mol Ag of silver halide fine grain emulsion A was added and ripened. An emulsion was prepared so that the total amount of silver was the same. This emulsion was designated as emulsion F.

<< Preparation of Comparative Emulsion G >> Preparation of Emulsion C 1)
At the stage when 50% of the added silver amount is consumed in the process, 5 × 10 ^-2 mol / mol Ag of silver halide fine grain emulsion A is added and ripened, and then a combined emulsion is prepared so that the total silver amount is the same. did. This emulsion was used as emulsion G.

<< Preparation of Emulsion H of the Present Invention >> In the step of preparing Emulsion C, seed crystal emulsion-1 was charged, and after adjusting pAg and pH, silver halide fine grain emulsion B 5 × 10 ^-2 mol / mol Ag Was added and ripened, and a combined emulsion was prepared so that the total silver amount would be the same. This emulsion is designated as emulsion H.

<< Preparation of Emulsion I of the Present Invention >> In step 1) of the preparation of Emulsion C, at the stage when 50% of the added silver amount was consumed, 5 × 10 ⁻² mol / mol Ag of silver halide fine grain emulsion B was added. After the addition and ripening, a combined emulsion was prepared so that the total silver amount would be the same. This emulsion is designated as emulsion I.

<< Preparation of Emulsion J of the Present Invention >> In the step of preparing Emulsion C, seed crystal Emulsion-1 was introduced, pAg and pH were adjusted, and silver halide fine grain emulsion B was 10 × 10 ^-2 mol / mol.
After the addition of molar Ag and ripening, a combined emulsion was prepared so that the total silver amount would be the same. This emulsion is designated as emulsion J. << Sensitization >> Next, each of the emulsions C to J was subjected to the following sensitization.

0.5 mol of an emulsion sample was melted at 40 ° C., and the spectral sensitizing dyes SD-1 and SD-2 had a total coverage of about 70%.
% Was added at a ratio of 1: 1. Thereafter, triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added, and after optimal chemical sensitization according to a conventional method, 4-hydroxy-6-methyl-
1,3,3a, 7-tetraazaindene (TAI), 1
-Phenyl-5-mercaptotetrazole (PMT) was added.

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<< Preparation of Photosensitive Material Sample >> Each of the sensitized emulsions C to J was applied to a cellulose acetate film support coated with a gray silver antihalation layer, and the emulsion layer was coated with a surfactant and bismuth. It was overcoated with a 4.3 g / m ² gelatin layer containing (vinylsulfonyl) methane hardener (1.75% by weight based on total weight of gelatin). The amount of emulsion coating is 0.646 gAg / m
^2, this layer, the coupler 1, surfactant and gelatin amount 1.08 g / m ² was also be included. In this manner, single-layer samples 101 to 10 were prepared for emulsions C to J, respectively.
8 was obtained.

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<< Evaluation >> Sample 101 thus obtained
After exposure to wedges with white light for 0.01 second and color development according to the following processing steps, sensitivity and fog were measured using an optical densitometer (model PDA-65 manufactured by Konica). Table 1 shows the relative sensitivity and fog density when the sensitivity of the sample 101 was set to 100.

<< Processing >> Processing Step Processing Time Processing Temperature Color Development 3 minutes 15 seconds 38 ± 0.3 ° C. Bleaching 45 seconds 38 ± 2.0 ° C. Fixing 1 minute 30 seconds 38 ± 2.0 ° C. Stability 60 seconds 38 ± 5.0 ° C. Dry for 1 minute 55 ± 5.0 ° C. The following color developing solution, bleaching solution, fixing solution and stabilizing solution 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 Water was added to make 1 liter, and potassium hydroxide or 20% sulfuric acid was added. PH 10. Adjust to 06.

Bleaching solution water 700 cc 1,3-diaminopropanetetraacetic acid iron (III) ammonium 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 pH to 4.4.

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.

Stabilized water 900 cc Paraoctylphenyl 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 (manufactured by UCC) L-77) 0.1 g ammonia water 0.5 cc Water was added to make up to 1 liter, and the pH was adjusted to 8.0 using ammonia water or 50% sulfuric acid. Adjust to 5.

[0110]

[Table 1]

From Table 1, it can be seen that Samples 106 to 108 using the emulsions (Emulsions H to J) to which the reduction sensitized fine particles were added have remarkably improved sensitivity and fogging, and have high sensitivity and unprecedented sensitivity. A low fog photographic emulsion could be obtained.

Example 2 << Preparation of Comparative Emulsion K >> In the step of preparing Emulsion C, seed crystal Emulsion-1 was charged, and after adjusting pAg and pH, 1 × 10 ⁻⁵ mol / mol Ag of thiourea dioxide was added. At the stage when 90% of the added silver was consumed, 1 × 10 ⁻⁴ mol / mol Ag of 2Na ₂ CO ₃ .3H ₂ O ₂ was added. Emulsion K
And

<< Preparation of Comparative Emulsion L >> In the step of preparing Emulsion C, seed crystal Emulsion-1 was charged, pAg and pH were adjusted, and 1 × 10 ⁻⁵ mol / mol Ag of thiourea dioxide was added. At the stage when 90% of the added silver was consumed, 3 × 10 ⁻⁵ mol / mol Ag of sodium ethylthiosulfonate was added. This emulsion was designated as emulsion L.

<< Preparation of Emulsion M of the Present Invention >> In the step of preparing Emulsion C, seed crystal emulsion-1 was charged, and after adjusting pAg and pH, silver halide fine grain emulsion B 5 × 10 ⁻² mol / mol Ag Was added and ripened, and at the stage when 90% of the added silver was consumed, 2Na ₂ CO ₃ .3H ₂ O ₂ was added at 1 × 10 ^-4 mol / mol.
A mole emulsion was added, and a combined emulsion was prepared so that the total silver amount would be the same. This emulsion was designated as emulsion M.

<< Preparation of Emulsion N of the Present Invention >> In the step of preparing Emulsion C, seed crystal emulsion-1 was added, pAg and pH were adjusted, and silver halide fine grain emulsion B 5 × 10 ⁻² mol / mol Ag Was added and ripened, and when 90% of the added silver was consumed, sodium ethylthiosulfonate was added at 3 × 10 ^-5 mol / mol Ag, and a combined emulsion was prepared so that the total silver was the same. did. This emulsion is designated as emulsion N.

The emulsions K to N were sensitized in the same manner as in Example 1 to prepare single-layer light-sensitive material samples.
4 was obtained. The sensitivity and fog of the obtained samples 201 to 204 were measured in the same manner as in Example 1. Table 2 shows the relative sensitivity and fog when the sensitivity of the sample 106 prepared in Example 1 was set to 100.

[0117]

[Table 2]

From Table 2, it can be seen that the emulsion using the oxidizing agent in combination with the reduction sensitization of the fine particles of the present invention has a further reduced fog without deteriorating the sensitivity. Could be obtained.

Embodiment 3 Next, an embodiment in which the present invention is applied to minus blue recording will be described. In the sensitization of Example 1, the spectral sensitizing dye was changed to SD-
3, the total coverage was about 70 instead of SD-4 and SD-5.
%, And the monolayer photosensitive material samples 301 to 308 were prepared using the emulsion of Example 1 except that the coupler was changed to coupler 2 in the preparation of the sample. Evaluation was performed in the same manner except that the development time was set to 2 minutes and 50 seconds.

Table 3 shows the results.

[0121]

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[0122]

[Table 3]

Thus, when the emulsion of the present invention was applied to minus blue recording, the same improvement effect as in the case of blue recording was confirmed.

Example 4 A sensitizing dye SD-
3, a single layer photosensitive material was added in the same manner as in Example 1 except that SD-4 and SD-5 were added at a ratio of 1: 1: 1 so that the total coverage was about 70%, and coupler 2 was used. Sample 401-
404 was produced. Sample 3 prepared in Example 3 was evaluated in the same manner except that the color development time was set to 2 minutes and 50 seconds.
Each relative sensitivity when the sensitivity of 07 is set to 100,
The fog is shown in Table 4.

<< Preparation of Comparative Emulsion O >> Preparation of Emulsion C 1)
In the process, 1 × 10 ⁻⁵ mol / mol Ag of thiourea dioxide was added when 50% of the added silver was consumed, and 2Na ₂ CO ₃ .3H was added when 90% of the added silver was consumed.
₂ O ₂ was added at 1 × 10 ^-4 mol / mol Ag. This emulsion is designated as emulsion O.

<< Preparation of Comparative Emulsion P >> 1) of Preparation of Emulsion C
In the process, 1 × 10 ⁻⁵ mol / mol Ag of thiourea dioxide was added when 50% of the added silver was consumed, and sodium ethylthiosulfonate was added at a stage where 90% of the added silver was consumed. × 10 ^-5 mol / mol Ag was added. This emulsion is designated as emulsion P.

<< Preparation of Emulsion Q of the Present Invention >> In step 1) of the preparation of Emulsion C, at the stage when 50% of the added silver amount was consumed, 5 × 10 ⁻² mol / mol Ag of silver halide fine grain emulsion B was added. At the stage when 90% of the added silver is consumed.
Na ₂ CO ₃ .3H ₂ O ₂ at 1 × 10 ^-4 mol / mol Ag
A silver halide emulsion was prepared so that the total amount of silver was the same. This emulsion is designated as emulsion Q.

<< Preparation of Emulsion R of the Present Invention >> In step 1) of the preparation of Emulsion C, at the stage when 50% of the added silver amount was consumed, 5 × 10 ⁻² mol / mol Ag of silver halide fine grain emulsion B was added. At the stage when 90% of the added silver was consumed, sodium ethylthiosulfonate was added at 3 × 10 ⁻⁵ mol / mol Ag, and a combined emulsion was prepared so that the total silver was the same. This emulsion is designated as emulsion R.

[0129]

[Table 4]

As a result, when the emulsion of the present invention in which an oxidizing agent was used in combination was applied to minus blue recording, the same improvement effect as in the case of blue recording was confirmed.

Example 5 A multilayer color photographic light-sensitive material sample 501 was prepared by sequentially forming layers having the following compositions on a triacetyl cellulose film support provided with an undercoat layer from the support side.

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-6 2.37 × ^10-5 SD-7 1.2 x ^10-4 SD-8 2.4 x ^10-4 SD-9 2.4 x ^10-6 C-1 0.32 CC-1 0.038 OIL-20. 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-6 4.5 × 10 ^-5 SD ^{-7 2.3 × 10 -4 SD-8} 4.5 × 10 -4 C-2 0.52 CC-1 0.06 DI-1 0.047 OIL-2 0. 6 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-6 3.0 × 10 -5 SD -7 1.5 × 10 ^-4 SD-8 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 b 0.062 SD-9 3.6 × 10 ^-4 SD-10 3.6 × 10 ^-4 Coupler 2 0.18 CM-1 0.033 OIL-1 0.22 AS-2 0.002 AS-3 0.05 gelatin 0.61 8th layer (intermediate layer) OIL-1 0.26 AS-1 0.054 gelatin 0. 0 ninth layer (medium sensitivity green-sensitive layer) Silver iodobromide e 0.54 iodobromide f 0.54 SD-11 3.7 × 10 -4 SD-12 7.4 × 10 -5 SD -13 5.0 × 10 ^-5 Coupler 2 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) Silver iodobromide f 1.19 SD-11 4.0 × 10 ^-4 SD- ¹²⁸ 0.0 × 10 ^-5 SD-13 5.0 × 10 ^-5 Coupler 2 0.065 CM-2 0.026 CM-1 0.022 DI-3 0.003 DI-2 0.003 OIL-1 19 OIL-2 0.43 AS-3 0.017 AS-2 0.014 Gelatin 1.23 11th layer (yellow filter Yellow layer 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-14 6.5 × 10 ^-4 SD-15 2.5 × 10 ^-4 Coupler 1 0.77 DI-4 0.017 OIL-1 0.31 AS- 2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.61 SD-14 4.4 × 10 ^-4 SD-15 1 0.5 × 10 ^-4 coupler 1 0.23 OIL-1 0.10 AS-2 0.004 gelatin 1.20 14th layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.30 Gelatin 1.32 15th layer (second protective layer) PM-10 The 15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55 characteristic of the silver iodobromide is displayed below (one side length of a cube having the same volume as the average particle diameter).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) 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 As a typical example of forming silver halide grains of the present invention, a production example of silver iodobromide d and f is shown below. Further, silver iodobromide j (hereinafter also referred to as emulsion j) is disclosed in
Nos. 183417, 1-183644, 1-183
Nos. 645 and 2-166442.

<< Preparation of silver iodobromide d >> 0.178 mol of seed crystal emulsion-1 and HO (CH ₂ CH ₂ O) _m (CH
(CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m
700 ml of a 4.5% by weight aqueous solution of inert gelatin containing 0.5 ml of a 10% ethanol solution of + n = 9.77)
Was maintained at 75 ° C., the pAg was adjusted to 8.4, and the pH was adjusted to 5.0, and then 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, 0.287 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 8.4 and the pH at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
g was adjusted to 9.8. Thereafter, 0.071 mol of SM
C-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) An aqueous solution of 0.959 mol of silver nitrate, 0.03 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 9.8 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH 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 0.74 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 both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Preparation of silver iodobromide f In the preparation of silver iodobromide d, pAg was adjusted to 8.8 in step 1).
8 and the amount of silver nitrate to be added was 2.077 mol SMC-1.
And the amount of silver nitrate added in step 3) was 0.91 mol and the amount of SMC-1 was 0.079 mol in the same manner as for silver iodobromide d. Silver fide f was prepared.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Edge length) 0.65 μm, average aspect ratio 6.5, silver iodide content 2 / 9.5 / X / 8.0 mol% from the inside of the grain
The emulsion was composed of tabular grains having a halogen composition of (X is a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and the fogging and sensitivity were optimized according to a conventional method. Chemical sensitization was applied to obtain.

Silver iodobromide a, b, c, e, h and i were also prepared according to the above silver iodobromide d and f and subjected to spectral sensitization and chemical sensitization.

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, two types of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, inhibitors AF-3, AF-4 and 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.

[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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In the above multilayer sample, the same evaluation as in Example 1 was performed by replacing the silver iodobromide f of the tenth layer with Emulsion I. The effect of the present invention was also obtained in the multilayer color photosensitive material of Example 3, It was confirmed to be remarkable as in No. 4.

[0156]

As apparent from the above examples, the present invention can provide an emulsion having high sensitivity and low fog even in minus blue recording.

Claims (4)

[Claims] 1. During and / or after the formation of silver halide base grains, silver halide fine grains whose inside and / or surface are reduction-sensitized are added, and the fine grains are deposited on the base grains. A method for producing a silver halide photographic emulsion. 2. The method for producing a silver halide photographic emulsion according to claim 1, further comprising a step of adding an oxidizing agent for silver nuclei. 3. The method according to claim 1, wherein the oxidizing agent is represented by the following general formula (1):
3. The method for producing a silver halide photographic emulsion according to claim 2, wherein the method is selected from the compounds represented by (2) or (3). Formula _{(1) R-SO 2 S} -M Formula _{(2) R-SO 2 S} -R 1 Formula _{(3) R-SO 2 S} -L m -SSO 2 -R 2 wherein, R, R ₁ and R ₂ may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. R, R ₁ , R ₂ and L may combine with each other to form a ring. ] 4. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion produced by the method according to claim 1.