JPH0212142A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain high sensitivity and low fogging density by providing internal nuclei consisting of silver chloroiodobromide, silver iodobromide or silver bromide, the outermost shell having the iodine content higher than the iodine content than internal nuclei and intermediate shell consisting of silver halide particles to the silver halide particles to be incorporated into the emulsion in an emulsion layer. CONSTITUTION:The silver halide particles to be incorporated into one emulsion in the emulsion layer have the internal nuclei consisting of the silver chloroiodobromide, silver iodobromide or silver bromide and the outermost shell having the iodine content higher than the iodine content of the internal nuclei. The iodine content of the outermost shell is >=6mol% and further at least one intermediate shell are provided between the internal nuclei and the outermost shell. The average aspect ratio of the silver halide particles is specified to <8:1. The high sensitivity is obtd. and the fogging by pressure and stress is decreased in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material. In particular, it relates to negative-working silver halide sensitive materials for imaging.

[Prior art]

The properties required in a photographic silver halide emulsion are that it exhibits high sensitivity and low fog density, excellent graininess, high development activity, and excellent color sensitization. Furthermore, since various pressures and stresses are applied to photographic materials coated with silver halide emulsions during the manufacturing and use processes, it is also required that the photographic performance is not impaired by these pressures and stresses.

Silver halides used in photographic emulsions include silver iodide, silver bromide, silver chloride, and fine crystal grains of composites thereof. In general, these fine grains absorb only a portion of visible light, and therefore it is not possible to obtain a color photographic emulsion only by utilizing the light absorption inherent to silver halide. Therefore, when used in a color photographic emulsion, When performing so-called color sensitization by adsorbing dyes (even when used in black-and-white photographic emulsions at present), dye adsorption becomes stronger in the order of silver chloride, silver bromide, and silver iodide. Most of the silver halide fine grains currently commercialized for negative use have a concentration of 0 to several no.1% in order to achieve sufficient adsorption for zero-color sensitization.
However, on the other hand, the photoresponse sensitivity of silver halide fine grains is significantly reduced when a dye is adsorbed (dye desensitization). Therefore, in order to obtain excellent color sensitized emulsions, a technique that does not cause dye desensitization is essential and highly desired.

As will be detailed later, improvement in dye desensitization has been achieved by the present invention, and one of the fundamentals of this technique is that the surface silver iodide content is as high as 6111o1% or more.

It is conventionally known that particles with a high iodine content on the surface are undesirable as negative photographic materials because the progress of development is significantly delayed. For example, J, Photo
, Sci, + 2 Soil, 198 (1976) describes core/shell type particles with iodine contents of 18 and 36 mol % in the shell portion.

Furthermore, JP-A-62-19843 describes a color reversal photographic light-sensitive material of core/shell type in which the silver iodide content of the shell is higher than that of the core; The purpose of this method is to take advantage of the slow progress of development to increase the rate of increase in sensitivity and contrast during aggravated development, and it is unsuitable for use in negative applications. Further, in JP-A-49-90920 and JP-A-49-90921, there are examples in which the core is silver bromide and the shell is silver iodobromide, and the silver iodide content of the shell is 5.10 or 15 mo1%. However, it is used directly in positive emulsions and is not suitable for negative emulsions. JP-A-56-18831 discloses an example of monodisperse grains having a surface silver iodide content of 6 to 8-01%; It is described that it is effective only when used together with particles having a content of 3 so 1% or less, and that the former alone has low sensitivity.

Furthermore, JP-A-60-147727 discloses a multilayer structure grain in which the difference in average silver iodide content between two adjacent layers is 10 + to 1% or more, and the silver iodide content in the outermost layer is 40 mo 1% or less. As described in the claims, the preferred silver iodide content of the outermost layer is described as 0 to 10 mol%. Further, the silver iodide content in the outermost layer of the grains described in the Examples is all 3 mo1% or less.

An example of grains with a high silver iodide content in the outermost layer is JP-A-58-
No. 113,927, the grains were tabular grains with an average aspect ratio greater than 8:1. The aspect ratio referred to here is the ratio of the projected area to the circular phase diameter (hereinafter referred to as D circle) to the particle thickness. Particles with a high aspect ratio deteriorate graininess and are not preferred as photographic materials. and the tabular grains have two opposing parallel major faces and a central region extending between the two major faces, and the iodide content in the central region also has at least one central region extending between the two major faces. The iodide content was lower than that in the two laterally displaced regions.

An example of particles with a clear double structure is disclosed in JP-A-60-143.
No. 31, but the grains in this patent were conventionally made with surface iodine, such as 0 or more, which specifies that the outermost layer is silver halide microcrystals containing 5 mo1% or less of silver iodide. A technique for using grains with a silver oxide content of 5 mo1% or more in a practical negative emulsion had not been established.

Regarding multi-structure particles, for example, JP-A-61-24
No. 5151 and No. 62-131247, both of which have a lower silver iodide content in the outermost layer than in the inner part of the outermost layer. Moreover, there is no example in which the silver iodide content of the outermost layer is 5 mo1% or more.

Additionally, photographic materials coated with silver halide emulsions generally have
Various mechanical stresses are applied. For example, general photographic negative film is folded or pulled when it is rolled into a cartridge or loaded into a camera, or pulled for frame-by-frame advance.

On the other hand, sheet films such as photosensitive materials for printing and X-ray photosensitive materials for direct medical use are frequently handled by humans, so they often break or bend.

Furthermore, all types of sensitive materials are subjected to great stress during cutting and processing.

As described above, when various stresses are applied to a photographic material, stress is applied to the silver halide grains through gelatin, which is a holder (binder) for the silver halide grains, and a plastic film, which is a support, as a medium.

It is known that when stress is applied to silver halide grains, the photographic properties of the photographic material change.

Among these changes in photographic properties, a phenomenon called "stress fog" significantly impairs the image quality of photographs. For example, in the case of X-ray sensitive materials, this may lead to misdiagnosis.

Therefore, it is strongly desired to provide a photographic material that does not cause stress fog even under these stresses.

As such a solution, the following several methods are conventionally known.

For example, as a means to improve the pressure characteristics, there are methods such as adding a plasticizer such as a polymer or emulsion, or reducing the silver halide/gelatin ratio of a silver halide emulsion.
It is known to prevent pressure from reaching the particles.

However, since the method of adding a plasticizer reduces the mechanical strength of the emulsion layer, there is a limit to the amount of plasticizer that can be used, and increasing the amount of gelatin causes drawbacks such as slowing down the processing speed. However, it is difficult to achieve a sufficient effect, and therefore, it is most desirable that the particles themselves are hard to cause stress brittleness.

Regarding silver halide grains themselves having a multilayer structure, J.
, Photo, Sci, 24. 198 (
(1976) describes silver halide grains with a three-layer structure consisting of AgBr/AgBr I (1 = 18 or 32 mol%)/AgBr. Since the particles used in this paper were not even chemically sensitized, there was no description or discussion regarding stress fog.

Furthermore, U.S. Patent No. 4,210,450 proposes multilayer structure particles using an iodine substitution method, but since iodine substitution is always performed in the final step, the iodine content of the outermost layer is 95 mol. Because it has a high iodine layer of over %,
This is not preferable in terms of stress fog.

Furthermore, JP-A-58-181037 describes a high-sensitivity photographic emulsion containing silver halide grains consisting of at least three phases of silver iodobromide having different iodine contents and having an iodo mole % of at least 12%, and a method for producing the same. However, in the manufacturing method of this patent, the iodine distribution in each phase is not homogeneous, and there is no mention of stress fog.

On the other hand, it was reported in JP-A-53-2240 that development activity could be increased and sensitivity could be increased by using laminated type silver halide grains in which multiple shells were attached to the outside of an inner core.
Publication No. 8, Japanese Patent Publication No. 43-13162, J, Ph
oto, Sci, +2 Sat., 198 (1976), etc.

However, the silver halide grains obtained for these purposes do not necessarily improve the stress properties and cause the problem of fogging due to stress.
In the bulletin, Purification 1! (inner core)/silver iodobromide emulsion (iodine content 1 mol%)/pure silver bromide laminated type silver halide grains are described, but fogging due to pressure occurs strongly, and from the viewpoint of pressure characteristics. There are the same problems as with conventional completely uniform silver iodobromide emulsions.

In the present invention, fog caused by pressure appears as fog in negative-working silver halide emulsions, and internal fog occurs in positive-working silver halide photographs, resulting in a decrease in optical density. This is what appears.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material which has high sensitivity, has little inherent desensitization caused by dyes, and also has little fogging caused by pressure and stress.

[Disclosure of the invention]

The above object of the present invention is to provide a photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which silver halide grains contained in one emulsion in the emulsion layer are silver chloride iodobromide, silver iodobromide, silver iodine, etc. has an inner core made of silver bromide or silver bromide, has an outermost shell with a higher iodine content than the inner core, and has a silver iodide content of 6 mo1% or more, and A silver halide photographic light-sensitive material characterized in that it has at least one intermediate shell between the inner core and the outermost shell, and the average aspect ratio of the silver halide grains is less than 8:1. achieved.

The characteristics of the photographic material according to the present invention will be described below.

(1) The silver iodide content of the outermost shell is as high as 6s+o1% or more. This makes it possible to significantly reduce the inherent desensitization caused by dyes. The preferred silver iodide content of the outermost shell is 8 to 30 mo1%, particularly preferably 10 to 20 mo1%.
It is 1101%.

(2) If the silver iodide content of the silver halide grains as a whole is too high, developability and fixability will deteriorate.

In the silver halide grains according to the present invention, the inner core has a lower silver iodide content than the outermost shell, and therefore the inner core has a lower silver iodide content than the outermost shell. It can be adjusted by the ratio of the outermost shell to the entire grain and the silver iodide content of the inner shell and the outermost shell. The preferred silver iodide content of the entire grain is 20 mo1% or less.

In addition, the proportion of the outermost shell in the entire particle is preferably 33%.
It is as follows.

(3) Since the aspect ratio is 8 or less, the graininess is excellent. The improvement in graininess due to a low aspect ratio is particularly remarkable for grains with a high surface silver iodide content.

(4) Higher sensitivity can be obtained by providing at least one intermediate shell between the outermost shell and the inner core.

(5) Capri generation due to pressure can be suppressed by providing at least one intermediate shell between the outermost shell and the inner shell.

The difference in iodine content between the outermost shell and the intermediate shell in contact with the outermost shell and the difference in the iodine content in the inner shell and the intermediate shell in contact with the inner shell are set at 3 mo1 in order to effectively suppress capri generation.
% or more.

In addition, the difference in silver iodide content was set at 30 m in order to obtain excellent sensitivity capri characteristics and to improve the monodispersity of the grains.
It is preferable that it is 1% or less. Further, it is preferable that the ratio of the intermediate shell to the entire particle is 33% or less.

In grains having a plurality of intermediate shells, the difference in silver iodide content between adjacent intermediate shells is preferably 30+wo1% or less.

The above are the essential characteristics of the particles according to the present invention, and the performance of the particles according to the present invention can be effectively utilized by taking the following measures.

Preferred halogen compositions of the silver halide grains having a layered structure of the present invention are as follows.

The inner shell is preferably made of silver iodobromide containing θ~5 mo1% of silver iodide, and the outermost shell is more concentrated than the inner shell.
It is preferably made of silver iodobromide or silver chloroiodobromide having a high silver coride content of 1% or more.

In the emulsion of the present invention, it is preferable that the iodine content between the grains is more uniform.0 It is preferable to judge whether the iodine content between the grains is uniform or not using the EPMA method (elect).
ron-Probe Micro Analyze
This becomes possible by using the r method).

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and then an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each particle.

When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is 50% or less, further 35% or less,
In particular, it is preferably 20% or less.

The size of the silver halide grains having a layered structure of the present invention is not particularly limited, but is preferably 0.2 μm or more, particularly 0.3 μm or more.
~2.0 μm is preferred.

The silver halide grains having a clear layered structure according to the present invention may have regular crystal shapes (normal crystal grains) such as hexahedron, octahedron, dodecahedron, or dodecahedron, or may have a spherical shape. ,
Irregular crystal shapes such as potato-like ones may also be used.
Further, tabular twin grains having an aspect ratio of 8:1 or less or twin grains having irregular multiple surfaces may be used.

Although the emulsions of the present invention can have a wide grain size distribution, emulsions with a narrow grain size distribution are preferred. In particular, in the case of normal crystal grains, the size of the grains that account for 90% of the total weight or number of silver halide grains in each emulsion is within ±40%, and further within ±30%, of the average grain size. Dispersed emulsions are preferred.

An example of the layer structure of the silver halide grains according to the present invention is shown in Table 1. The zero layer means an inner shell, an intermediate shell, and an outermost shell. The silver iodide content of each layer is defined as follows.

I i i Silver iodide content of inner shell (mol%) ■″
; Silver iodide content (mol %) of the intermediate shell (n is a natural number indicating the order from the inside of the intermediate shell) IO; Silver iodide content (mol %) of the outermost shell Clear layered structure of the present invention An emulsion having the above formula can be prepared by selecting and combining various methods known in the field of silver halide photographic materials.

First, to prepare the inner core, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting soluble root salts with soluble halogen salts include one-sided mixing method, simultaneous mixing method, and combinations thereof. . When the inner shell is a mixed crystal, it is preferable to add silver halide fine particles having the same halogen composition as the inner shell to be formed. In this case, the size of the fine particles is preferably 0.1 μm or less, and sometimes 0.03 μm or less.

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. As another type of simultaneous mixing method, a triple jet method in which soluble halogen salts of different compositions are added independently (for example, soluble root salt and soluble iodide salt) can also be used.

It is also possible to use the method of accelerating the addition rate over time as disclosed in Japanese Patent Publication No. 48-36890, or the method of increasing the addition concentration over time as disclosed in US Pat. No. 4,242,445. These two methods are effective for improving the monodispersity of particles.

Preparation of the inner core requires ammonia, rhodan salt, thioureas,
It is possible to carry out the process in the presence of a silver halide solvent such as a thioether or an amine, or it can also be carried out without a solvent.

It is desirable that the internal core be monodisperse, and therefore the pBr at the time of nucleation is preferably 1.70 or more, particularly preferably 2.00 to 4,00. Further, pBr during growth is preferably 1.20 or more, particularly preferably 1.20 or more.
40 to 3.50.

Furthermore, various gelatins or synthetic polymers can be used as a dispersion medium during internal nucleation.

The temperature during particle formation may be any temperature as long as the dispersion medium can be dissolved, but it is preferably from 40°C to 80°C.

The inner core has a silver iodide content of 50% to speed up the development process.
+*o1% or less is preferable, and 3e+o1% or less is particularly preferable.

The formation of the intermediate shell and the outermost shell can be performed successively after the completion of the internal nucleation. Alternatively, after forming the internal nucleus, it can be washed with water by a conventional flocculation method, gelatin is added thereto, and the mixture is used as a seed crystal. In this case, the size of the final particles can be easily controlled by adjusting the amount of seed crystals.

The final pH and pAg of the seed crystal are determined by Agz on the inner core surface.
40℃ to avoid introducing electron traps such as nuclei as much as possible
It is preferable to adjust the pH to 7.0 or lower and the pAg to 8.0 or higher, particularly the pH to 6.0 or lower and the pAg to 8.0.
It is preferable to adjust it to 6 or more.

Next, a method for forming the intermediate shell and the outermost shell will be described.

As is clear from Table 1, the middle shell and the outermost shell have a high silver iodide content. It is preferable to form a silver halide layer using a silver halide solvent such as ammonia, rhodan salt, thioureas, thioethers, amines, etc. in a state where silver halide has high solubility. Therefore, when using rhodan salt, it is necessary to conduct the treatment at a pBr of 2.3 or higher at 75°C, preferably a pBr of 2.5 or higher, and particularly preferably a pBr of 2.8 or higher.
pBr2.3 even when using thiourea or thioether
It is preferable to form the intermediate shell and the outermost shell in the above manner.

The temperature during the formation of the intermediate shell and the outermost shell is desirably high in order to increase the solubility of silver halide, preferably 40°C or higher, particularly preferably 60°C or higher.

There are various methods for supplying iodine, bromine, chlorine, and silver necessary to form the intermediate shell and the outermost shell, similar to those shown in the inner shell formation method, but they can be added as silver chloroiodobromide fine particles. A method of doing so is particularly preferred. In this case, the silver chloroiodobromide fine grains have a silver iodide content equal to or higher than the intermediate shell and outermost shell of the target grain, and the grain size is 0.1 μm or less, preferably 0.1 μm or less. It is 0.06 μm or less, particularly preferably 0.03 μm or less.

Further, the addition rate of the fine particles is preferably close to the dissolution rate of the added fine particles.

The aspect ratio of the particles obtained as described above is preferably 5 or less from the viewpoint of granularity. Improvement in granularity due to a decrease in aspect ratio is outside the scope of the present invention in the surface-high iodine type multi-structure particles according to the present invention. This is especially remarkable compared to the surface-low iodine type particles. The term "surface-low iodide type grains" as used herein refers to grains in which the outermost shell has a lower silver iodide content than the interior, and the surface silver iodide content is 61Ilo1% or less.

The silver halide grains of the present invention preferably account for 50% or more (in terms of projected area) of all silver halide grains in the emulsion,
Furthermore, it is preferably 70% or more, particularly 90% or more.

The emulsions of this invention are typically spectrally sensitized.

Methine dyes are usually used as the spectral sensitizing dyes used in the present invention, and these include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Dyes are included. Any of the basic heterocyclic nuclei commonly used for cyanine dyes can be applied to these dyes. Namely, viroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole), selenazole, imidazole, tetrazole, pyridine, etc.; alicyclic hydrocarbon rings are fused to these). nucleus;
and in addition to these, a nucleus in which aromatic hydrocarbon rings are fused, i.e., an indolenine nucleus, a benzindolenine nucleus, an indo-)
Ltj, benzoxadole I, naphthoxadol, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, quinoline, etc. can be used. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazolin-5-one, thiohydantoin, 2-thioxazolidine-2 as a core with a ketomethylene structure.
, 4-dione, thiazolidine-2,4-dione, rhodanine, and thiobarbic acid nuclei can be used.

The amount of enhancing dye added during silver halide emulsion preparation is
Although it cannot be stated unambiguously depending on the type of additive or the amount of silver halide, it can be used in an amount approximately equivalent to that added in a conventional method.

In other words, the preferred amount of aggravating dye added is silver halide 1
It is 0.001 to 100 mmol per mole, more preferably 0.01 to 101 + 11101.i
The sensitizing dye is added after or before chemical ripening.For the halogenated particles of the present invention, the sensitizing dye is most preferably added during or before chemical ripening (e.g. during particle formation, physical µmm is added at the time of waiting.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not subtly absorb visible light and exhibits supersensitization.For example, a nitrogen-containing Aminostyl compounds substituted with heterocyclic groups (
For example, U.S. Patent Nos. 2,933.390 and 3,635
．． No. 721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743.510), cadmium salts, azaindene compounds, etc., U.S. Pat. No. 3,615.613. , same 3
, 615.641, 3,617.295, 3,
The combinations described in No. 635.721 are particularly useful.

Silver halide emulsions are usually chemically enhanced.

For chemical exacerbations, eg I+, Frisel (1).

Fr1eser)lW, De-Grundlager der Fotografisien Prozesse Mint Zilberhalogenidene (mouth is Grundla(and d
erPMLographish@n Prozessa
＋＊it Silberhalogentden)(
Akademische Ferlagsgesellschacht 196B
) The method described on pages 675 to 734 can be used.

namely, sulfur-enhanced methods using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing agents (e.g., stannous salts, In addition to noble metal compounds (e.g., total complex salts,
A noble metal compound using complex salts of metals of group 1 of the periodic table such as pt, Ir, and Pd can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazole L
j [(especially nitro- or halogen ff3); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) , mercaptopyrimidine neck; the above-mentioned heterocyclic mercapto compound H having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compound such as oxazolinthione; , 3a, 7)
Tetraazaindene R); Benzenethiosulfonic acids;
Compounds known as anti-capri agents or stabilizers can be added, such as benzenesulfinic acid; and the like.

These anti-capri agents or stabilizers are usually added after chemical ripening, but more preferably during chemical ripening or during chemical ripening. ! Ff3 before the start of the first generation! I
You can choose from l. That is, in the process of forming silver halide emulsion grains, during the addition of the silver salt solution, after the addition until the start of chemical ripening, and during the chemical ripening (during the chemical ripening time, preferably within 50''A from the start). , more preferably within up to 20% of the time).

The emulsion of the present invention can be used in any photographic material having an N structure, regardless of whether the emulsion layer is IN or has two or more layers.

A halogenated mixed multilayer color photographic optical material using the emulsion of the present invention is a binder for recording blue, green and red light separately and a halogenated! ! It has a multilayer structure in which emulsion layers containing grains are superimposed, and each emulsion layer has a small number of layers (consisting of two layers, a high-speed layer and a low-speed layer.Especially in practical FF
As for the configuration, a II configuration such as the following /RL/S is also preferable.

Here, CL is a multilayer effect imparting layer, and the others are as described above.

Further, the high-sensitivity layer and the low-sensitivity layer having the same color sensitivity may be arranged in reverse order.

The halogenated S emulsion of the present invention can be used for color photosensitive materials as described above, but it can also be used for other photosensitive materials, whether the emulsion layer is single or multilayer, such as X-ray photosensitive materials, black and white photography. It can be similarly applied to photosensitive materials for printing, photolithographic materials for plate making, photographic paper, etc.

Various additives for the silver halide emulsion of the present invention, such as binders, °-5 chemical thickeners, spectral enhancers, stabilizers, gelatin hardeners, surfactants, antistatic agents, polymer latexes, matting agents, color couplers. Supports for photosensitive materials using ultraviolet absorbers, anti-fading agents, dyes and emulsions of these,
There are no particular restrictions on coating methods, exposure methods, development processing methods, etc.
611-things are mentioned.

(1) BH/BL10H/CL/RH/RL/S(ri BH/B'M/BL/GH/GM/CLRH/RM/
+3) described in the N configuration of RL/S and U.S. Patent No. 4,184,876)
BH/BL/GH/RH/GL/RL/5RD-22
534, JP 59-177551, JP 59-1775
52 etc. (4+ BH/'GH/RH/BL/GL/RL/S
This is an N configuration.

Here, B is a blue sensitive layer, G is a green sensitive layer, R is a red malignant layer, H is the highest iE5 degree layer, M is a medium aperture of 1, L is a low sensitivity layer, and S is a support. , a protective layer, a filter layer, an intermediate layer, an antihalation layer, a subbing layer, and other non-photosensitive layers are omitted.

Among these, the preferred layer configuration is +11, (2) or (4).

In addition, +51 B described in JP-A No. 61-34541
H/BL/CL10H10L/RH/RL/5 (61BH/BL/GH/GL/CL/RH Item 1
7643 (RD-17643), Volume 187, Item 18716 (RD-48716) and Volume 225
The description in Vol., Item 22534 (RD-22534) can be referred to.

The description of these research disclosures is shown in the table below.

Additive type 1 Chemical sensitizer 2 Anger increasing agent Brightening agent Pigment @ Image stabilizer Hardening agent Binder Plasticizer, lubricant Color coupler R [1L7643 RD18716 RD22S34 Page 23, 648, right column Same as above, page 24, page 24, page 25 Page 26, page 26, page 27, page 651, left column, same as above, page 650, right column, page 32, page 28, page 25, page 649, page 31. A two-equivalent coupler in which the coupling active position is substituted with a coupling-off group is preferable than an equivalent coupler in which the coupling active position is a hydrogen atom because the amount of coating can be reduced. Colorless couplers or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
7.210, 2,875.057 and 3
, US Pat. No. 3,408.194, US Pat. No. 3,447.928;
Same No. 3.933.501 and No. 4,022゜62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401.752, IJiE4, 326.024, R
D18053 (April 1979), British Patent Nos. 1 and 4
No. 25.020, West German Application No. 2,219.917, West German Application No. 2. 261. No. 361, No. 2,329.5
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 87 and No. 2 433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat. Same No. 2゜3
No. 43.703, No. L 600.788, No. 2
．． No. 908.573, same No. 3. 062. No. 653,
3,152.196 and 3゜936.01
It is stated in issue 5 etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Patent No. 4.310.61
No. 9 or the nitrogen atom leaving group described in U.S. Patent No. 4.
Particularly preferred are the arylthio groups described in No. 351.897.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
061,432, preferably pyrazolo(5,1-C)(1,2,4)) liazoles described in U.S. Pat. (1
June 1984) and pyrazolotetrazole neck described in JP-A-60-33552 and Research Disclosure-24230 (June 1984) and JP-A-60-33552.
The imidazo(1,2-b) described in U.S. Pat. ) pyrazoles are preferred, including pyrazolo (1,5-
b) (1,2°4) triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, preferably the naphthol-based couplers described in U.S. Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom separation type described in No. 8.233 and No. 4,296.200. Specific examples of phenolic couplers include U.S. Patent Nos. 2.369.929 and 2.8.
No. 01.171, No. 2.772. No. 162, No. 2
．． No. 895,826, etc. Cyan couplers that are temperature and temperature robust are preferably used in the present invention, exemplified by U.S. Pat.
Phenolic cyan coupler having an alkyl group on an ethyl substrate at the meta-position of phenol 1ffi, which was published in U.S. Patent No. 2.002, U.S. Pat. No. 4,126.396,
No. 4.334.011 1. Same No. 4.327゜173
2,5-diacylamino ItA phenolic couplers described in German Patent Publication No. 3,329,729 and European Patent No. 121,355, and US Pat. No. 333.999, same No. 4. 451.559 and 4,427,76
These include phenolic couplers that have a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 7. Patent Application No. 59-93605, No. 59
Cyan couplers in which naphthol is substituted with a sulfonamide group, amide 51i, etc. at the 5-position described in No. 264277 and No. 59-268135 also have excellent fastness of colored images and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in conjunction with color negative phases for photography, as disclosed in U.S. Pat. Kosho 5
7-39413, or U.S. Pat. No. 4.0.04,929, U.S. Pat.
Typical examples include the magenta-colored cyan coupler described in No. 68.

Granularity can be improved by using a coupler in which the coloring dye exhibits appropriate diffusivity. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 4,366.237 and British Patent No. 2,125,570.
Also, European Patent No. 96゜570 and West German Application No. 3
．． 234. No. 533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and specialty couplers described above may form dimers or more polymers; typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,82.
No. 0 and No. 344. No. 080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. No. 173, U.S. Patent No. 4.367
．． No. 282, Japanese Patent Application No. 60-75041, and No. 60
-113596.

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called DIR coupler.

As a DIR coupler, for example, U.S. Pat. No. 3.227
．． Those that release heterocyclic mercapto type development inhibitors as described in Japanese Patent Publication No. 554, etc.; Those that release benzotriazole derivatives as development inhibitors as described in Japanese Patent Publication No. 5B-9942, etc.; those described in Japanese Patent Publication No. 51-16141, etc. A so-called colorless DIR coupler described in JP-A No. 52-90932, which releases a heterocyclic development inhibitor containing a heterocyclic compound after separation with decomposition of methylol; US Pat. No. 4,248.
962 and JP-A-57-56837, which release a development inhibitor with an intramolecular water removal reaction after separation; JP-A-56-114946 and JP-A-57-154234.
No. 57-188035, No. 5B-98728,
Those that release a development inhibitor by electron transfer via a conjugated system after separation as described in No. 58-209736, No. 5B-209737, No. 5B-209738, No. 58-209739, No. 5 B-209740, etc. Those that release a diffusible development inhibitor whose development inhibitor is deactivated in the developer described in Japanese Patent Application Laid-open Nos. 57-151944 and 58-217932; Japanese Patent Application No. 59-38263 and 58-217932;
Releases the reactive compound described in No. 9-39653 No. 1, etc.
Among the DIR couplers mentioned above, those that generate a development inhibitor or deactivate a development inhibitor by reaction in the film during development, etc., are more preferable in combination with the present invention. , JP-A-57-IS19
Developer deactivated type represented by No. 44; U.S. Patent No. 4゜24
8.962 and JP-A No. 57-154234; reaction type as typified by Japanese Patent Application No. 59-39653; particularly preferred among these are:
JP 57-151944, JP 58-217932, JP 59-75474, JP 59-82214,
These are the IJIJL liquid deactivation type DIR coupler described in Japanese Patent Application No. 59-82214 and No. 59-90438, and the reactive DIR coupler described in Japanese Patent Application No. 59-39653.

In the light-sensitive material of the present invention, a compound that releases an anti-forming agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator etc.") in an image form during development can be used. A typical example of such a compound is British Patent No. 2.0
97.140 and 2.131.188, and is a coupler that releases a development accelerator etc. by a coupling reaction with an oxidized product of an aromatic primary amine developer, that is, a DAR coupler. be.

The TjL image promoter released from the DAR coupler, etc.
It is preferable that the material has adsorption properties to silver halide.
A specific example of such an AR coupler is JP-A No. 59-1
No. 57638 and No. 59-170840. Particularly preferred are DAR couplers that produce N-acyl-substituted hydrazines having monocyclic or condensed heterocycles as adsorption groups, which are detached from the coupling active site of photographic couplers with sulfur or nitrogen atoms. A specific example of the coupler is JP-A-60-128446.
It is stated in the number.

Specific examples of high-boiling disintegrants used to disperse color couplers include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid or phosphonic acid. esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoxyethyl phosphate,
trichloropropyl phosphate, di-2-ethylhexyl phenine phosphonate, etc.), benzoic acid ester 1
i (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecaneamide, N-
(tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-L@r L-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, etc.) , trioctyl citrate, etc.), aniline derivatives (N,N-diptyl-2-butoxy-5-Lert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 5°C.
A organic solvent having a temperature of 0° C. or more and about 160° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxyethyl acetate/dimethylformamide.

Suitable supports that can be used in the silver halide photographic emulsion of the present invention are described, for example, in RD, No. 17643, page 28, and in 1hlB716, page 647, right-hand corner to page 648, left-hand corner.

The binder used in the halogenated emulsion to which the present invention is applied is preferably gelatin, but in addition to gelatin, derivative gelatin such as phthalated gelatin, dextran, cellulose M4, polyvinyl acetate, polyacrylamide, polyvinyl alcohol, etc. is used.

Examples of gelatin hardening agents include active halogen compounds 11
1(2,4-dichloro-6-hydroxy-1゜3.5-
triazine and its sodium salt, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propatol, 1,2-bis(vinylsulfonylacetamido)ethane, or vinyl polymers having vinylsulfonyl groups in their side chains, etc.) is preferable because it quickly hardens hydrophilic colloids such as gelatin and provides stable photographic properties.

N-carbamoylpyridinium salts [(1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.)
and haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium 2-naphthalenesulfonate, etc.) also have a fast (excellent) curing speed.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be developed by the usual method described in RD, 17643, pages 28-29, and 651 left column to right column of 1B716. I can do it.

A color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, clean fixing or fixing treatment.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step.

The color developing solution used in the development of the S optical material of the present invention is preferably an alkaline aqueous solution containing as a main component a aromatic primary amine color developing agent. Aminophenol compounds are also useful as color developing agents, but p-phinidine diamine compounds are preferably used, and a typical example is 3-methyl-4-amino-N,N-diethylaniline. , 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-7minor N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides or P-)luenesulfonates.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It is typical to include development inhibitors or antifoggants such as benzimidazoles, benzothiazole compounds or mercapto compounds. Also, if necessary, hydroxylamine, diethylhydroxylamine,! ! !
Sulfate hydrazine neck, phenyl semicarbazide neck, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo [2゜2.2]
Various preservatives such as octane), ethylene glycol,
Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers such as sodium boron hydride, couplers such as jFII, 1-phenyl-3-pyrazolidone. auxiliary developing agents, viscosity-imparting agents, aminopolycarboxylic acids,
Ring chelating agents such as aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nido-1-norotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, and hydroxyethyliminodi5H2 , 1-hydroxyethylidene-1,1 diphosphonic acid, nitrilo-N, N, N
-trimethylenephosphonic acid, ethylenediamine-N,
N.

Representative examples include N',N''-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or 7-minophenols such as N-methyl-p-aminophenol. It can be used in conjunction with the original.

The pH of these color developing agents and black and white developer is 9 to 12.
It is common that The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 31 or less per square meter of light-sensitive material, and the bromide ion concentration in the replenisher is reduced (by 50
It can also be set to 0- or less. When reducing the amount of replenishment, it is preferable to reduce the contact area with the air in the processing tank (by doing so to prevent evaporation of the solution and air oxidation), and to use means to suppress the accumulation of bromide ions in the developer. By doing so, the replenishment amount can also be increased by iK.

After color development a, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process), or separately (bleach-fixing process), or in order to speed up the process, it may be possible to perform a bleach-fixing process after the bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or cleaning treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■), Kobal) (I
Compounds of polyvalent metals such as II), chromium (VI), and li (II), perHM, quinone, nitro compounds, and the like are used.

Felicia is a typical bleaching agent? 9 Iex chromate; palliative complex salt of iron (I[[) or cobalt (m);
For example, 7-minopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, t,3-diaminopropanetetraacetic acid, glycol etheraminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; Excessive weight
Acid salts; bromates; permanganates; nitrobenzenes, etc. can be used; among these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron CI [[) complex salts and persulfuric acid salts; Salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution, and aminopolycarboxylic acid iron(I[[) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (f[[) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. You can also do it.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290.812, JP-A-53-95.630, Research Disclosure Maru 17.129 (197
Compounds having a mercapto group or a disulfide bond as described in JP-A-50-140129; U.S. Pat.
Thiourea derivatives described in No. 561; JP-A-58-16
Iodide salt described in No. 235; German Patent No. 2.748.
Polyoxyethylene compounds described in Japanese Patent Publication No. 430, polyamine compounds described in Japanese Patent Publication No. 45-8836, bromide ions, etc. can be used. Among these, compounds having mercapto-5 or disulfide groups are preferred from the viewpoint of a large promoting effect, and are particularly described in U.S. Pat. Preference is given to the compounds described in U.S. Pat. No. 4,552.
The compounds described in No. 834 are also preferred. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for exposure.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. It can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urna lor the 5ociety o
f Motion Picture and
Television Engineers No. 64 @, P
, 24B-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131.632/1988 can be used very effectively. Also, JP-A-57-8. 54
Isothiazolone compounds and cyabendazoles described in No. 2, chlorinated disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents," Hygiene Technology Association, "Microorganisms. It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" by Akebono, Japanese Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
C at 15-45°C for 20 seconds-10 minutes, preferably 2
A range of 30 seconds to 5 minutes at 5-40°C is selected. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8.543 and 58-14.83
All known methods described in No. 4, jO-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, and an example of this is a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color optical materials for photography. can.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may incorporate a color developing agent for the purpose of simplifying and speeding up the processing.In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent6. U.S. Patent No. 3.342.59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64,339 and JP-A-57-144,547.
No. 58-115.438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to reduce the limitations on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

Example 1 Emulsion 1 (Pure silver bromide matrix grains) A solution of 30 g of inert gelatin, 0.76 g of potassium bromide and 5 cc of a 25% ammonia aqueous solution dissolved in 11 parts of distilled water was stirred at 60°C, and then 600 cc of .98M silver nitrate aqueous solution was added over 50 minutes. 5' after the start of addition of the silver nitrate aqueous solution, a 0.98M potassium bromide aqueous solution was added to control the pBr to be 1.8.

Thereafter, the emulsion was cooled to 35°C, washed by a conventional flocculation method, 50 g of inert gelatin was added, and the emulsion was adjusted to pH 6.5 and pAg 8.6 at 40°C.

Emulsion 1 consisted of octahedral grains with a normal diameter of 0.73 μm and a coefficient of variation of 15%. Data regarding this particle size was obtained using the Coulter counter method (The Theo
ry of Photographic Processes
s4th, ed, P, 101).

Emulsion 2-5 The following solutions were used to prepare emulsions 2-5.

Emulsion 2 (pure silver bromide grains for comparison) To 556 g of Emulsion 1 (which contains 75 g of AgBr grains) was added distilled water 11 and potassium thiocyanate aqueous solution (2
N) 15cc was added. Add 441g of liquid A to this mixed aqueous solution.
and Solution B were added in 50 minutes using a controlled double jet method.

The flow rate of liquid B was controlled so that the pBr of the mixed liquid was 2.5. Further, the temperature of the liquid mixture was maintained at 75°C.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAg to 8.6 at 0°C. The obtained particles were octahedral particles with a spherical diameter of 0.92 μm.

Emulsion 3 To 444 g of Emulsion 1 were added 11 cc of distilled water and 15 cc of an aqueous solution of potassium thiocyanate (2N). While maintaining the temperature of this mixed aqueous solution at 75°C, 265 g of liquid A and liquid D were added over 25 minutes using a controlled double jet method. During this time, the flow rate of the mixed liquid is such that the pBr of the mixed liquid is 3.0.
It was controlled to be 0. Thereafter, 265 g of liquid A and liquid F were added over a period of 25 minutes using a controlled double jet method. During this time, the flow rate of the F liquid is set to p of the mixed liquid.
The Br was controlled to be 3.00.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
It was adjusted to have pi-16.5 and PAg 8.6 at 0°C. The obtained particles were octahedral particles with a spherical diameter of 0.99 μm.

Emulsion 4 To 556 g of Emulsion 1 were added 11 distilled water and 15 cc of potassium thiocyanate aqueous solution (2N). While maintaining the temperature of this mixed aqueous solution at 75°C, 8Bg of liquid A and liquid G were added over a period of 10 minutes using a controlled double jet method. Next, 88g of liquid A and liquid D were added using a controlled double jet method. Added over 10 minutes 6 Next, 88 g of Solution A and Solution E were added over 10 minutes using a controlled double jet method. Furthermore, A liquid 176
g and G liquid using a controlled double jet method.
Added over 0 minutes. During the addition of liquid A, CB,
The flow rates of liquid D, liquid E, and liquid G are determined when the pBr in the mixed aqueous solution is 3.
It was controlled so that it became 00.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAg to 8.6 at 0°C. The obtained particles were octahedral particles with a spherical diameter of 0.91 μm.

Emulsion 5 To 667 g of Emulsion 1 were added 11 cc of distilled water and 1'5 cc of potassium thiocyanate aqueous solution (2N). While maintaining the temperature of this mixed aqueous solution at 75° C., 176 g of liquid A and liquid H were added over 20 minutes using a controlled double jet method. Furthermore, 176 g of liquid A and liquid F were added over a period of 20 minutes using a controlled double jet method. During the addition of A solution, the flow rates of F solution and H solution were controlled so that the pBr in the mixed aqueous solution was 3.00.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
It was adjusted to have p)(Ei, 5, pAg 8.6 at 0°C. The obtained particles were octahedral particles with a spherical diameter of 0.87 μm.

Emulsion 6 (pure silver bromide matrix grains) A 3% by weight gelatin solution 11 containing 0.05M potassium bromide was added to a 3% by weight gelatin solution 11 while stirring, using a double jet method, and the same as a 0.39M silver nitrate solution. .39M potassium bromide solution, 15cc.

Add for 15 seconds. During this time, the gelatin solution was kept at 50°C. After the addition, the temperature was raised to 75°C.

After completing the above-mentioned stage addition, 0.47M silver nitrate solution was added to 29
9Qcc was added over a period of minutes.

After a further 10 minutes, 150 g of silver nitrate was added at an accelerated flow rate (the flow rate at the end was 19 times the flow rate at the beginning) over a period of 60 minutes. The pBr was maintained at 3°00 during this 60 minute period.

After this, the emulsion was cooled to 35°C, washed by the conventional flocculage method, and at 40°C, the pH was adjusted to 6.5, and the pAg
After adjusting to 8.6 and storing it in a cool dark place, 87% of the tabular grains are tabular grains, and the average D
The circle is 1. The average thickness was 0°24 μm (coefficient of variation 16%). Data regarding particle size were determined from electron micrographs.

Emulsion 7-1O To prepare Emulsion 7-10, the same solutions A and B used to prepare Emulsion 2-5 were used.

Emulsion 7 (pure silver bromide grains for comparison) 625 g of emulsion 6 (which contains 75 g of AgBr grains) was mixed with 1z of distilled water and an aqueous solution of potassium thiocyanate (2N
) 15cc was added.

441 g of liquid A and liquid B were added to this mixed aqueous solution over a period of 50 minutes using a controlled double jet method.

The flow rate of liquid B was controlled so that the pBr of the mixed liquid was 2°9. Further, the temperature of the liquid mixture was maintained at 75°C.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAg to 8.6 at 0°C. 90% of the obtained grains were tabular grains, with an average D circle of 1.24 μm (coefficient of variation 15%) and an average thickness of 0.47 μm.

Emulsion 8 To 500 g of Emulsion 6 were added distilled water IIl and 15 cc of potassium thiocyanate aqueous solution (2N). While maintaining the temperature of this mixed aqueous solution at 75° C., 265 g of liquid A and liquid D were added over 25 minutes using a controlled double jet method. During this time, the pBr of the mixed liquid is 3.
．． It was controlled so that it became 00. Furthermore, after this, A liquid 265
g and F liquid by a controlled double jet method.
Added over 5 minutes. During this time, the flow rate of the F solution was controlled so that the pBr of the mixed solution was 3.00.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
It was adjusted to have pi (Ei, 5, pAg 8.6 at 0°C. 92% of the obtained grains were tabular grains, and the average D circle was 1.23 μm (coefficient of variation 12%). ), and the average thickness was 0.59 μm.

Emulsion 9 Distilled water IIl and 15 cc of potassium thiocyanate aqueous solution (2N) were added to 625 g of Emulsion 6. While maintaining the temperature of this mixed aqueous solution at 75°C, 88 g of liquid A and liquid E were added over 10 minutes using a controlled double jet method. Added over a period of minutes. Next, 8 Bg of liquid A and liquid E were added over 10 minutes using a controlled double jet method. Furthermore A1176
g and G liquid using a controlled double jet method.
Added over 0 minutes. During addition of A liquid, E liquid,
The flow rates of liquid D, liquid E, and liquid G are determined when the pBr in the mixed aqueous solution is 3.
It was controlled so that it became 00.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAg to 8.6 at 0°C. 90% of the obtained grains are tabular grains, and the average D circle is 1.25 μm (coefficient of variation 1
6%), and the average thickness was 0,646 μm.

Emulsion 10 Distilled water 11 and 15 cc of potassium thiocyanate aqueous solution (2N) were added to 6.750 g of emulsion. While maintaining the temperature of this mixed aqueous solution at 75° C., 176 g of liquid A and liquid H were added over 20 minutes using a controlled double jet method. Furthermore, 176 g of liquid A and liquid F were added over a period of 20 minutes using a controlled double jet method. During the addition of A solution, the flow rates of F solution and H solution are determined when the pBr in the mixed aqueous solution is 3. It was controlled to be OO.

After the addition was completed, the resulting emulsion was washed by the usual 70° curing method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAgs to 6 at 0°C. 90% of the obtained grains are tabular grains, and the average D circle is 1.25 μm (coefficient of variation 18
%), and the average thickness was 0.34 #m.

Table 1 shows the structure and photographic properties of emulsions 2 to 5 and 6 to 10.
Shown in (a) and (b).

This is the prescription value. When attempting to form a layer with a silver iodide content of 20 mo1% or more in the presence of silver halide, the silver iodide content of the high iodide layer may decrease slightly due to conversion with the lower iodide layer, but this invention This does not deviate from the scope of the above.

Photographic properties were determined as follows. That is, emulsions 2-5 and 6 to 1O were mixed with sodium thiosulfate, triethylthiourea,
After optimal chemical sensitization using potassium chloroaurate and potassium chloroaurate, the film was coated and processed according to the method described above.

(b) In the case of black and white development processing After the above chemical sensitization, 1° each of emulsions 2 to 5 and 6 to 1°
00g was dissolved at 40°C, and the following steps 1 to 2 were sequentially added while stirring to prepare a solution.

■ 4-Hydroxy-6-methyl-1,33a,7-chitrazaindene 3% 2cc ■ C+, Hss O (CHz CHO) ts
The surface protective layer coating solution was prepared by sequentially adding Φ to ⑦ with stirring at 40° C. according to the following procedure.

■ 14% gelatin aqueous solution 56.8 g ■ Polymethyl methacrylate fine particles (average particle size 3.0 μm) 3.9 g ■ Emulsion gelatin 10% 4.24 g Cl1zCO
OCHzCHCCtHs)CJqNa0sS-CHCO
OCHtCH (ctHs) cJ910, 6 ■ ■ H,.

68.8 cc ■ The emulsion coating solution and the surface protective layer coating solution obtained as above were coated on a cellulose triacetate film support by co-extrusion at a volume ratio of 103=
It was applied so that it became 45.

The amount of silver coated was 3.1 g/rd. 200ZUχ,1 with a light source of 2854”K color temperature for these samples.
/ After applying wedge exposure for 10 seconds, apply the following developer D-7.
6 for 7 minutes at 20° C., then fixed with fixer F-1, washed with water and dried.

[Developer D-76] Metol 2g Sodium sulfite 100g Hydroquinone
5g Borax・5H201
, 53g Add water 1a [Fixer F-1] Ammonium thiosulfate 200.0g Sodium sulfite (anhydrous) 20.0g Boric acid
8.0g Ethylenediaminetetraacetic acid disodium 0.1g Aluminum sulfate 15.0g Sulfuric acid
2.0g glacial acetic acid
Add 22.0g water and make 17! shall be. (The pH was adjusted to 4.2.) (b) In the case of color development processing, the emulsion and protective layer were coated on a triacetyl cellulose film support, which was provided with an undercoat layer.

The structure of each layer is as follows.

+11 Emulsion layer/Emulsion 1 to 11 (coated silver amount 2.2 x 10-”s
ol/-) ・Coupler (1,5X10-"mol/n?)l Fist tricresyl phosphate (1,10g/rrr) Q gelatin (2,30g/rrr) (2
) Protective layer φ2.4-dichlorotriazine-6-hydroxy-5-) lyazine sodium salt (0.08g10f)/gelatin (1.80g/n?) After drying, blue exposure for sensitometry was applied to 1/10 give seconds, then F
uji CN16 treatment was performed.

[Fuji Photo Film - Standard Processing CN-16 Processing] The development process used here was carried out at 38°C under the following conditions.

1. Color development...2 minutes 45 seconds 2. Drifting
White...6 minutes 30 seconds 3, wash...
...3 minutes 15 seconds 4, established...
・6 minutes 30 seconds 5, washing with water...3 minutes 15
6 seconds, stable...3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g hydroxylamine sulfate 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate Add bleach solution ammonium bromide aqueous ammonia (28%) Ethylenediamine-tetraacetic acid sodium iron salt Add glacial acetic acid water to fix fixing solution Sodium tetrapolyphosphate Sodium sulfite Ammonium thiosulfate (70%) 2,4g 4,5g 160.0g 25,0d 30g 4tf 2,0g 4,0g Add sodium bisulfite water to 175.0aZ Add 4.6g stabilized formalin 8.0 water resistant lj! These sensitometry results are shown in Table 1. Table 1 (a) shows the relative blue sensitivity of emulsion 2 as 100, and Table 1 (b) shows the relative blue sensitivity of emulsion 7 as 100. As is clear, the grains according to the present invention had high sensitivity equivalent to or higher than that of pure silver bromide grains, despite the high silver iodide content in the shell portion.

Example 2 Emulsion 11 (silver iodobromide matrix grains) A solution of 30 g of inert gelatin, 0.76 g of potassium bromide and 5 cc of a 25% aqueous ammonia solution dissolved in distilled water 11 was stirred at 60°C. 600 cc of a 0.98 M silver nitrate aqueous solution was added over 50 minutes. 5' after the start of addition of the silver nitrate aqueous solution, an aqueous solution containing 13.1 g of potassium bromide and 4.9 g of potassium iodide was added to 11 to control the pBr to 2.3.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAg to 8.6 at 0°C. The obtained particles consisted of octahedral particles with a normal diameter of 0.74 μm, and the coefficient of variation was 14%.

Emulsion 12 (uniformly structured grains with a silver iodide content of 3 mo1% (for comparison)) Emulsion 11 550g (This is 75g of AgBr1 grains)
) containing distilled water 11 and 3,6-dithia-1,8
15 cc of octanediol (5%) was added. While keeping this mixed aqueous solution at 75°C,
g and G solution were added in 50 minutes by controlled double jet method. The flow rate of the G liquid is the pBr of the mixed liquid.
was controlled to be 2.5.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAg to 8.6 at 0°C. The obtained particles were octahedral particles with a spherical diameter of 0.95 μm.

Emulsion 13 Distilled water 11 and 1 sec of 3,6-cythia 1,8 octanediol (5%) were added to 550 g of emulsion 11.

While maintaining this mixed aqueous solution at 75° C., 176 g of liquid A and liquid E described in Example 1 were added over 20 minutes by a controlled double jet method. Next, 2G of A liquid
5 g and Part D were added over 30 minutes using a controlled double jet method. During the addition of solution A, the flow rates of solutions E and D are such that the pBr of the mixed aqueous solution is 3.00.
controlled to become.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAg to 8.6 at 0°C. The obtained particles were octahedral particles with a spherical diameter of 0.93 μm.

Emulsion 14 Distilled water 11 and 3,6-cythia 1.8 octanediol (5%) 15a were added to 550 g of emulsion 11. While keeping this mixed aqueous solution at 75°C,
132 g of liquid A and 132 g of liquid D were added over 15 minutes using a controlled double jet method.
g and E were added over 15 minutes using a controlled double jet method. Next, 265 g of Part A and Part G were added over 20 minutes using a controlled double jet method. While adding Solution A, the flow rates of Solutions D, E, and G were controlled so that the pBr of the mixed aqueous solution was 3.00.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
The pH was adjusted to 6.5 and pAg to 8.6 at 0°C. The obtained particles were octahedral particles with a spherical diameter of 0.96 μm.

Emulsion 12.13.14 was optimally chemically sensitized using 3-ethyl-5-benzylidene rhodanine, dimethylselenourea and potassium chloroaurate.

4-hydroxy-6-methyl-1,3゜3a after chemical sensitization
, 7-titrazaindene was added and coated onto a polyethylene terephthalate support to give a silver content of 3 g/rrl. Next, these samples were exposed to blue light for 1710 seconds using a tungsten light source at 2854 @ with a 419 nm interference filter, and then developed with the following developer D-1 (20°C for 4 minutes), followed by fixer F-1. After fixing in step 1, it was washed with water and dried.

[Developer D-1] 1-Phenyl-3-pyrazolidone 0.5g Hydroquinone 20.0g Ethylenediaminetetraacetic acid disodium 2.0g Potassium sulfite 60.0g Boric acid
4.0g potassium carbonate
20.0g sodium bromide
5.0g diethylene glycol
Add 30.0g water to make 11. (pH is 10.0
Adjust to. ) Table 2 shows the structure and photographic properties of emulsions 12, 13, and 14. Emulsion 13.14, which has the sensitivity of Emulsion 12 as 100, has a high silver iodide content in the outermost layer, but compared to Comparative Emulsion 12.
A high window density equivalent to or higher than that of the previous one was obtained.

Table 2 Example 3 Emulsion 15 (fine grain emulsion for intermediate shell formation) 19 g of inert gelatin and KBr (10%) were added to 11.
5 cc was dissolved in distilled water 11 to obtain liquid A.

A 1.176M silver nitrate aqueous solution was prepared and designated as Solution B.

Furthermore, 94.5 g of KBr and 114.7 g of K were added to 7 g of distilled water.
The solution dissolved in 13 cc was designated as Solution C. While keeping the A solution at 35° C., the B solution and the C solution were added by a double jet method in which the pBr of the A solution was controlled to be 2.8.

The amount of B liquid added was 500 cc.

After washing this emulsion using the conventional flocculation method,
Add 59g of inert gelatin, pH 6.4 at 40℃,
pAg8. Emulsion 15 was obtained. Emulsion 15 had a spherical shape according to an electron micrograph, and its average diameter was 0.05 μm.

Emulsion 16 (Fine grain emulsion for forming outermost shell) 19 g of inert gelatin and 11.5 ee of KBr (10%) were dissolved in distilled water IIl to prepare a solution A.

A 1.176M silver nitrate aqueous solution was prepared and designated as Solution B.

Furthermore, KBr84. Og and KI29.3g in distilled water 7
The solution dissolved in 13 cc was designated as Solution C. While keeping liquid A at 35°C, liquid B and liquid C were heated to A? It was added by a double jet method in which the pBr of & was controlled to be 268. The amount of B liquid added was 500 cc.

After washing this emulsion using the conventional flocculation method,
Add 59g of inert gelatin, pH 6.4 at 40℃,
pAg8. Emulsion 16 was obtained. According to an electron micrograph, Emulsion 16 had a spherical shape with an average diameter of 0.05 μm.

Emulsion 17 After adding distilled water 12 to 556 g of Emulsion 1, 20 cc of potassium thiocyanate aqueous solution (2N) was added. This solution was adjusted to have a pBr of 3.13 at 75°C using a silver nitrate aqueous solution, and was used as Solution I. Also emulsion 15 2
62g (containing 2 moles of ilo) was dissolved in 238g of distilled water to prepare liquid (2). Additionally, 16.278g of emulsion
(containing 0.2 mol of silver) was dissolved in 222 g of distilled water to prepare liquid (2). While keeping the solution (2) at 50°C, it was added to the solution I over 25 minutes. Next, Solution (2) was added to Solution I over 35 minutes while being kept at 50°C. Solution I was stirred at 75°C while solutions 1 and 2 were added.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
Emulsion 17 was obtained by adjusting the pH to 6.5 and pAg to 8.6 at 0°C. The obtained particles were octahedral particles with a normal diameter of 1.02 μm.

'JtJJ17t-13-ethyl-5benzylidene rhodanine Optimal chemical sensitization was performed using potassium chloroaurate.

After completion of chemical sensitization, coating and processing were carried out in accordance with the case of (a) black and white development described in Example 1.

For comparison, Emulsion 2 was optimally chemically sensitized using potassium 3-ethyl-5-benzylidene rhodanine chloraurate and then coated and processed according to the above recipe.

As a result of sensitometry, the sensitivity of Emulsion 17 was 165 when the sensitivity of Emulsion 2 was 100.

Also, the fog density is 0.10 for emulsion 1 and 0 for emulsion 12.
．． It was 09.

As described above, the grains according to the present invention achieved high sensitivity and low fog despite the high silver iodide content in the shell part, but another surprising effect is that dye desensitization is completely (or is not) possible. Or very rarely.An example is shown below.

Example 4 Emulsion 18 (comparative internal high iodine type multi-structure grains) 1,
Inert gelatin aqueous solution (H2098(la)
7. Gelatin 40g 5KBrO, Ig.

pH2,0 (Redox potential +210mV vs,
Ag/AgC1 electrode)) was added, the temperature was raised to 75°C, and the AgNOs aqueous solution and silver halide main solution (K
AgN
Os o, 07 g/min followed by AgNOs o, 0
Simultaneous addition of 28 g/min for 10 min followed by 7AgNO*
Simultaneous additions were made for 7 minutes at 0.168 g/min. During this time,
The pBr of the solution was 3.0. This was followed by a 14.3-fold concentration (A g N Os 0 ).

The initial flow rate was 3.0 using AgNCh (168 g/J) and silver halide main solution (halogen composition is the same as above).
aZ/min, 50 by linear flow increasing method with increase rate 0.3 @Z/min
C, D, J with a silver potential of 30 mV per minute.

Added. The obtained emulsion was washed with water and redispersed.

A replica image of the obtained octahedral particles was observed using a transmission electron microscope. As a result, the average particle diameter was 0.51/μm, and the coefficient of variation was 5.0%.

2. Production of intermediate shell ■ Emulsion containing 50 g of particles produced in H! 0600a
Z, add 10g of inert gelatin to the reaction container and adjust the pH to 2.
．． While keeping the temperature at 75℃, A g
N Ox aqueous solution (0.8M) and halide aqueous solution (K
In Br+KI, the content of Kl to KBr is 10 mo1
%) were added by a controlled double jet method. The amount of AgNO3 added was 0.266 mol. During this time, pBr was maintained at 2.3.

3. Manufacturing the outermost shell A g No. at 75° C. following the formation of an intermediate shell.

Aqueous solution (0.8M) and halide aqueous solution (KBr+K
In I, the content of Kl to KBr is 0. 3 go1%)
were added by a controlled double jet method. The amount of AgN0i added was 0.532 mol.

During this time, pBr was maintained at 2.0. After this, it was washed with water using the usual flocculation method, then redispersed, heated to 40°C, adjusted to pH 6.5pAg 8.6, and emulsion 18
I got it. The particles were octahedral particles with an average particle size of 0.81 μm (coefficient of variation 4°8%).

4. Preparation of samples for sensitivity measurement and performance evaluation Emulsions 2.3.4.7.8.9.12.14.18 were optimally chemically sensitized using sodium thiosulfate and potassium chloroaurate. However, the following sensitizing dye I was added immediately before or after chemical sensitization, or was not added at all.

The amount of dye added was the saturated adsorption amount to the grains in each emulsion, and the saturated adsorption amount was determined by Kubelkamunk's method.

After the chemical sensitization was completed, an emulsion layer and a surface protective layer were prepared and coated by the method described in Example 3.

For these samples, light from a light source with a color temperature of 2854 was passed through an interference filter that transmits light at 419 nm (15 nm at half maximum) and an SC52 Fuji filter that transmits light at wavelengths longer than 520 nm for 1/10 seconds. Each had a blue and minus blue exposure. This was followed by Kodak D76 treatment as described in Example 1.

The results of sensitometry are shown in Table 3 Ca) and (b). The alpha vent after the emulsion number in Table 3 indicates the case where A has no dye added, and the case B where dye is added before chemical sensitization. Table 3(a) shows the relative values when the blue depth of sample 1-A and the minus blue sensitivity of sample 2-B are taken as 100. Table 3(b) also shows the blue sensitivity of test $421-A and 22-B.
0, which is the relative value when the negative blue sensitivity of is set to 100.
In the present invention, loss of inherent sensitivity due to dyes is significantly improved. At this time, the negative blue sensitivity was significantly higher than that of the comparative emulsion.

Table 3 (a) Table 3 (b) Table 3 (a) Continued Example 5 (Stress property evaluation) Emulsion 19 (Comparative surface-high iodine double structure grains) Emulsion 1
1β of distilled water and 15 cc of potassium thiocyanate aqueous solution (2N) were added to 556 g. Example 1
441 g of liquid A and liquid F described in 1 were added using a controlled double jet method. The flow rate of Bi is p1 of the mixed liquid
Control was performed so that 3r was 3.00. Further, the temperature of the liquid mixture was maintained at 75°C.

After the addition was completed, the resulting emulsion was washed by the usual flocculation method, and 50 g of inert gelatin was added.
Emulsion 19 was obtained by adjusting the pHEi to 5 and pAg to 8.6 at 0°C. Emulsion 19 consisted of octahedral grains with a normal diameter of 0.91 μm.

After optimally chemically sensitizing the emulsion obtained as described above using sodium thiosulfate and potassium chloroaurate, Example 3
Sample 31 was obtained by preparing and coating an emulsion layer and a surface protective layer using the method described in .

A method for evaluating stress characteristics of particles according to the present invention will be described below.

Coated sample of Example 4 (sample 1.4.7, l01 in Table 3)
13.16 and 17) and coating sample 31 of Example 5.
It is bent under conditions where the relative humidity is controlled to 40% at 5°C. This bend is 180' along a 6mm diameter iron bar.
Bent. This operation was immediately followed by a wedge exposure at 10-'' sec.

The exposed sample was developed using the surface developer shown below for 10 minutes while maintaining the humidity of the developer at 20°C. This was fixed and washed with water.

Surface developer Monomethyl para-aminophenol sulfate Table 4 5g L-ascorbic acid 20g Sodium meborate 70g Potassium bromide
Add 2g of water to 11.

Ratio of change in fog due to bending to maximum density,
ΔFog/Dm is shown in Table 4 for each sample.

Example-6 Emulsion-17 prepared in Example-2 was prepared in JP-A-62-215.
When the emulsion was used as the fourth layer emulsion of sample 104 of Example-1 of Japanese Patent No. 271 and processed in the same manner as in Example-1, it showed good performance in both sensitivity and fog.

Claims (1)

[Claims] In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the emulsion in the emulsion layer are selected from silver chloroiodobromide, silver iodobromide, or silver bromide. an outermost shell having a higher iodine content than the inner core, the outermost shell has a silver iodide content of 6 mol% or more, and the inner core and the outermost shell has at least one intermediate shell in the middle, and has an average aspect ratio of 8:
A silver halide photographic light-sensitive material characterized by having silver halide grains having a particle size of less than 1.