JPH0617986B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention a. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inner core consisting essentially of silver bromide or silver iodobromide, and a plurality of inner cores provided outside the inner core and consisting essentially of silver bromide or silver iodobromide. The present invention relates to a silver halide photographic light-sensitive material containing negative type silver halide grains having an outer shell.

B. 2. Description of the Related Art In recent years, the demand for silver halide emulsions for photography has become more and more stringent, and higher levels of photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density and sufficiently wide exposure range have been achieved. There is a demand.

In response to these requirements, a silver iodobromide emulsion containing 0 to 10 mol% of iodine is well known as a high-sensitivity emulsion. The conventional methods for preparing these emulsions are pH conditions such as ammonia method, neutral method and acidic method, pA
As a method for controlling the g condition and a mixing method, a single jet method, a double jet method and the like are known.

On the basis of these known techniques, delicate technical means have been studied and put to practical use for the purpose of achieving higher sensitivity, improvement of graininess, high sharpness and low fog. In the silver iodobromide emulsion targeted by the present invention,
Emulsions in which not only the crystal habit and grain size distribution but also the iodine concentration distribution in each silver halide grain are controlled have been studied.

The most legitimate way to achieve photographic performance such as high sensitivity, excellent graininess, high sharpness, and low fog density as described above is to improve the quantum efficiency of silver halide. For this purpose, knowledge of solid state physics, etc. is being actively incorporated.

A study in which the quantum efficiency is theoretically calculated and the effect of particle size distribution is considered is described in, for example, the 1980 Tokyo Symposium's proceedings "Interactions Between Lights and Materials", page 91. Has been done. According to this research, it is predicted that narrowing the grain size distribution to produce a monodisperse emulsion is effective in improving quantum efficiency. In addition, in order to achieve the sensitization of the silver halide emulsion, in a process called chemical sensitization which will be described in detail later, in order to efficiently achieve high sensitivity while maintaining low fog, monodispersion The reasoning that emulsions would be advantageous would also be reasonable.

To industrially produce a monodisperse emulsion, JP-A-54-48521
Strict PAg and pH as described in the publication
Under the above control, it is necessary to control the theoretically determined supply rate of silver ions and halogen ions to the reaction system and sufficient stirring conditions. The silver halide emulsion produced under these conditions has a cubic, octahedral or tetradecahedral shape. That is, it is composed of so-called normal crystal grains having various ratios of the (100) plane and the (111) plane. It is known that such normal crystal grains can increase the sensitivity.

On the other hand, a silver iodobromide emulsion composed of polydispersed twin grains has been known as a silver halide emulsion suitable for a high speed photographic film.

Further, JP-A-58-113927 and others disclose silver iodobromide emulsions containing tabular twinned grains.

On the other hand, Japanese Laid-Open Patent Publication No. 53-22408 discloses that development activity is enhanced and sensitivity is enhanced by a laminated silver halide grain in which a plurality of outer shells (shells) are applied to the outside of the inner core. Kokoku 43-13162, J. Photo.Sci., 24 , 198 (197
6) etc.

Further, a silver halide grain having a coating layer provided by halogen substitution as the outermost layer of the silver halide grain is described in West German Patent 29
32650, JP-A-51-2417, JP-A-51-17436,
As described in JP-A No. 52-11927, these silver halide grains may accelerate the fixing speed, but on the contrary, they cause development inhibition and cannot provide sufficient sensitivity. It is not practical as a type emulsion.

Further, a positive type (internal latent image type) silver halide grain having a plurality of coating layers by halogen substitution on the outside of the inner core is known, and US Pat. Nos. 2,592,250 and 4,075,020 are known.
The details are described in Japanese Patent Publication No. 55-127549, etc. These silver halide grains are often used in an internal latent image type direct positive photosensitive material for diffusion transfer and the like, which naturally has too high an internal sensitivity.
It is not used at all in the negative emulsion targeted by the present invention.

On the other hand, JP 58-181037 A, JP 60-35726 A, JP 5
Each of the gazettes such as 9-116647 also discloses silver halide grains having an outer shell on the inner core as described above and considering various iodine contents of each layer.

In the field of silver halide photographic light materials, color sensitive materials having an ISO display sensitivity of more than 1000 have recently appeared due to various technological advances. However, as the sensitivity of these sensitive materials increases, the graininess and sharpness usually deteriorate, and the image quality is inferior to that of the conventional sensitive materials, so that it is very difficult for consumers to appreciate. At present, it is unsatisfactory, and a high-sensitivity negative photosensitive material having excellent graininess and sharpness is desired.

In astrophotography, indoor photography, sports photography and the like, negative photosensitive materials having higher sensitivity are required.

With regard to silver halide photographic light-sensitive materials in recent years, there is a demand for a light-sensitive material having photographic characteristics in which color reproducibility is not influenced by the type of light source used at the time of photography, and therefore blue light, green light and Many techniques have been developed for spectrally sensitizing a silver halide emulsion so that it can be appropriately exposed to red light, and it is known as a spectral sensitization method.

The purpose of such a spectral sensitization method is not only to increase the spectral sensitivity of the silver halide emulsion, but also to have an appropriate spectral sensitization wavelength range. Is not present, does not deteriorate the photographic characteristics,
It must satisfy various conditions such as excellent storage stability or no color contamination after development.

Among the above-described spectral sensitization methods, as a technique for spectrally sensitizing in the blue light region, for example, U.S. Pat. Nos. 3,480,434 and 3,752,670, West German Patent Application (OLS) 2,303,204
The use of sensitizing dyes described in Japanese Patent Publication No. 46-30023 and Japanese Patent Publication No. 46-30023 is known. It is also known that when a pure silver bromide emulsion further contains silver iodide, the long wavelength end of the intrinsic sensitivity region of silver halide shifts to the long wavelength side for spectral sensitization. On the other hand, halogen is one of the techniques for improving the image quality of a highly sensitive silver halide photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material), for example, a technique for improving image characteristics such as gradation, graininess or sharpness. It is a well-known technique to improve the image quality by incorporating silver iodide in a silver halide composition, particularly in a silver halide grain, and utilizing the development inhibiting effect of iodine ions released during development.

For example, a silver halide emulsion generally used for a black and white silver halide light-sensitive material contains 2 mol% or more of silver iodide, and the above technique can be used for adjusting the above-mentioned image quality. In particular, a silver halide light-sensitive material for color generally has a silver iodide content of 4 mol% or more,
Although the above technique can be used more effectively, although increasing the content of silver iodide as described above is preferable as a means for improving image quality, on the other hand, silver iodide increases sulfur content during chemical ripening. It has a drawback that it works suppressively to a sensitive reaction or a development reaction.

With regard to general photographing equipment, with the advent of cameras having high-speed shutters, photosensitive materials having high sensitivity and high illuminance reciprocity law failure characteristics have been demanded.

C. OBJECT OF THE INVENTION The object of the present invention is to provide a silver halide grain having a high sensitivity, an excellent sensitivity-fogging relationship, a wide exposure area, excellent graininess and sharpness, and particularly silver iodide as its silver halide composition. It is an object of the present invention to provide a silver halide photographic light-sensitive material having high blue light sensitivity when spectrally sensitized in the blue light region and excellent in high illuminance reciprocity law failure characteristics.

D. Structure of the Invention and Effects of the Invention That is, the present invention has an iodine content of 0 to 40 mol%,
Negative type having an inner core consisting essentially of silver bromide or silver iodobromide and a plurality of outer shells provided outside this inner core and consisting essentially of silver bromide or silver iodobromide In the silver halide photographic light-sensitive material containing silver halide grains, the silver halide grains have an iodine content of 2 to 12 mol%, and the outermost shell has an iodine content of 10 mol% or less. An iodine-rich shell having an iodine content higher than that of the outermost shell by 6 mol% or more is provided inside the outermost shell, and an intermediate shell between the outermost shell and the iodine-rich shell is provided between the outermost shell and the iodine-rich shell. An intermediate shell having an iodine content is provided, and the iodine content of the intermediate shell is 3 mol% or more higher than that of the outermost shell, and the iodine content of the high iodine shell is higher than that of the intermediate shell. Is also higher than 3 mol%, and the silver halide grains are A silver halide photographic material characterized by being sensitized with at least one sensitizing dye represented by the general formula (I).

General formula (I) (However, Y ₁ and Y ₂ are S, Se or O.

W ₁ , W ₂ , W ₃ , W ₄ , W ₅ , and W ₆ are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom,
An amino group, an acylamido group, an acyloxy group, an alkoxycarbonylamino group, an alkoxycarbonyl group or a hydroxy group, wherein W ₁ and W ₂ , W ₂ and W ₃ , W ₄ and W
₅ , W ₅ and W ₆ may be bonded to each other to form an aromatic carbocycle or an aromatic carbocycle.

R ₁ and R ₂ are an alkyl group, an alkyl group having a carboxyl group, an alkyl group having a sulfo group (provided that n is 0
In the case of, at least one of R ₁ and R ₂ is an alkyl group having a carboxyl group or an alkyl group having a sulfo group).

X is an ion necessary to neutralize the charge.

n is 0 or 1, and when forming an intramolecular salt, n =
0. ) In the silver halide composition of the silver halide grain according to the present invention, the above-mentioned “consisting essentially of” means a halogen other than silver bromide or silver iodobromide within a range that does not impair the effects of the present invention. This means that silver chloride, for example, silver chloride may be contained. Specifically, in the case of silver chloride, the ratio is preferably 1 mol% or less.

Summarizing the features of the photographic light-sensitive material according to the present invention,
It is like (1) to (8) below.

(1). By using an emulsion containing a core / shell type silver halide grain having a high iodine shell inside, high sensitivity (compared to a non-core / shell emulsion), a wide exposure range and excellent graininess can be obtained.

(2). Higher sensitivity can be obtained by providing an intermediate shell having an intermediate iodine content between the high iodine shell and the low iodine shell (outermost shell layer) on the surface.

(3). The iodine content of the high-iodity shell is preferably 6 to 40 mol% and is higher than the outermost shell layer by 6 mol% or more, but if this content is less than 6 mol% (or 6 mol% from the outermost shell layer). If it is less than 40% by weight), the sensitivity decreases, and if it exceeds 40% by mole, polydispersion occurs, and from the viewpoint of sensitivity and sharpness, it is preferable not to exceed 40% by mole.

(Four). The difference in iodine content between the middle shell and the outermost shell or high iodine shell should be 3 mol% or more, respectively, because the effect of the middle shell decreases if this difference is too small. . (Sensitivity decreases.) Also, it is said that the upper limit of the difference in iodine content is 35 mol% to effectively bring out the effect of the intermediate shell (sensitivity, monodispersity, fog-sensitivity relationship, sharpness). Desirable from a point of view.

(Five). If the iodine content in the entire silver halide grains is too high, the developability will be poor and the sensitivity will be lowered. If it is too low, the gradation will be too hard and the exposure area will be narrow, and the graininess will be deteriorated. Therefore, it is preferable to select a specific range.

(6). Monodisperse emulsions are superior to polydisperse emulsions in sensitivity, sharpness, and fog-sensitivity relationship. That is, in polydispersion, the reaction to form shells is non-uniform, so it is difficult to form an ideal core / shell structure, there are fine particles that deteriorate sharpness, and chemical sensitization after particle formation is Since the optimum conditions differ depending on the grains, the sensitivity is low and the fog-sensitivity relationship tends to be poor, and a monodisperse emulsion is preferably used.

(7). In a multi-layer color light-sensitive material, a phenomenon in which the sensitivity is deteriorated due to multi-layering is called as compared with the case of a single layer (referred to as a multi-layer desensitizing effect). This multilayer desensitization effect is less likely to occur, and it can be used more effectively in a multilayer color light-sensitive material.

(8). Since the silver halide grains have been spectrally sensitized by using at least one kind of the sensitizing dye represented by the general formula (I), it is possible to obtain an effective high sensitivity in a blue light region, and The light-sensitive material spectrally sensitized by the present invention can have excellent graininess and sharpness, has a wide exposure area, and can improve the reciprocity law failure property of high illuminance.

In order to further improve the above-mentioned excellent effects, Ih: iodine content of high-iodity shell (mol%) Im: iodine content of middle shell (mol%) Il: iodine content of outermost shell (mol%) ), ΔI = Ih-Il ≧ 8 mol%, ΔIh = Ih-Im ≧ 4 mol%, ΔIl = Im-Il ≧ 4 mol%, and ΔI>
More preferably, 10 mol%, ΔIh> 4 mol%, and ΔIl> 4 mol%. (Above) where Il = 0 to 5 mol%
Is preferably 0 to 2 mol%, more preferably 0 to 1 mol%. Ih is preferably 6 to 40 mol%, more preferably 10 to 40 mol%. (Above) Further, the volume of the outermost shell is preferably 4 to 70% of the whole particle, and 10 to
50% is more preferable. The volume of high-iodity shell is 10 ~
80% is preferable, 20 to 50%, and further 20 to 45% is preferable. The volume of the intermediate shell is preferably 5 to 60%, more preferably 20 to 50% of the whole particles. The high-iodity shell may be at least a part of the inner nucleus, but it is preferable that the inner core exists separately inside the high-iodity shell.

The iodine content of the inner core is preferably 0 to 40 mol%, preferably 0 to 10 mol%, more preferably 0 to 6 mol%. The particle size of the inner core is preferably 0.05 to 0.8 μm, more preferably 0.05 to 0.4 μm.

Further, in the above-mentioned characteristic point, the iodine content in the whole grain is preferably 1 to 20 mol%, preferably 1 to 15 mol%,
Further, it is desirable that the amount is 2 to 12 mol%.

Regarding the particle size distribution of the grains at the above-mentioned characteristic points, either polydisperse or monodisperse may be used, but the variation coefficient of the particle size distribution is preferably a monodisperse emulsion of 20% or less. It should be 15% or less. This coefficient of variation is Is a measure of monodispersity.

A blue-sensitive layer as a multilayer color light-sensitive material having the above-mentioned characteristic points,
A multilayer is constituted by three or more emulsion layers consisting of three light-sensitive layers, a red-sensitive layer and a green-sensitive layer, and at least one of the blue-sensitive layers is a halogen according to the present invention (or the above-mentioned desirable). It is desirable to include a silver halide grain and a sensitizing dye.

The grain size of silver halide grains (defined as the length of one side of both grains having the same volume as the silver halide grains) is preferably 0.1 to 3.0 μm. The shape may be any of octahedron, cube, sphere, flat plate, etc., but octahedron is preferable.

The layer structure of the silver halide grain of the present invention will be further described. The inner core and the high-iodity shell may be the same as described above, or a separate inner core is provided inside the high-iodity shell. Is also good. The inner core and the high-iodity shell, the high-iodity shell and the intermediate shell, the intermediate shell and the outermost shell may be adjacent to each other, or at least one layer of another shell having an arbitrary composition between the shells. May be included (this is referred to as an arbitrary shell).

These arbitrary shells may be single shells of uniform composition,
It may be a group of shells composed of a plurality of shells having a uniform composition, the composition of which changes in a stepwise manner, or a continuous shell whose composition continuously changes among arbitrary shells. It may be a combination. Further, there may be a plurality of high-iodity shells and intermediate shells, or only one set.

Next, an example of the layer structure of silver halide grains according to the present invention will be described. The iodine content is indicated by I.

1. Inner core = 3-layer structure with high iodine shell 2. 6-layer structure containing fourth and fifth shells of arbitrary composition between the inner core and the high iodine shell 3. Seven-layer structure having optional fifth and sixth shells between the inner core and the high iodine shell and two intermediate shells between the outermost shell and the high iodine shell 4. Any 6th and 7th shell between the inner core and the high-iodity shell, and 1 layer of arbitrary shell (4th shell) between the high-iodity shell (5th shell) and the intermediate shell (3rd shell) , And an 8-layer structure having an arbitrary shell (second shell) between the middle shell (third shell) and the outermost shell 5. Structure with multiple high iodine shells The inner nucleus of the silver halide grain of the present invention is produced by P. Glafkides by Chimie et Physique Photohraphique (Pol.
Published by Paul Montel, 1967, by GFDuffin, Photohraphic Emulsion Chimis
try) (The Focal Press)
Ed., 1966), Vl Zelikman (VLZelikma
n) Others Making and Coating Photo Imaging
hraphic Emulsion (The Focal Press
cal Press), 1964) and the like. That is, the acidic method, the neutral method,
Any of the ammonia method and the like may be used, and as the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used.

It is also possible to use a method in which grains are formed in the presence of excess silver ions (so-called reverse mixing method). PA in the liquid phase where silver halide is produced as one of the simultaneous mixing methods
It is also possible to use a method of keeping g constant, that is, a so-called controlled double jet method. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used, but it is preferable to use the double jet method or the control double jet method.

The pAg at the time of preparing the internal core varies depending on the reaction temperature and the kind of the silver halide solvent, but it is preferably 2 to 11. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, a commonly known silver halide solvent such as ammonia or thioether can be used.

The shape of the inner core may be a plate, a sphere, a twin system, or may be an octahedron, a cube, a tetradecahedron, or a mixed system.

In addition, in order to make the particle size uniform, British Patent 1,535,01
No. 6, JP-B-48-36890, No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the grain growth rate, U.S. Pat.
As described in JP-A No. 242,445 and JP-A No. 55-158124, it is preferable to grow rapidly within a range not exceeding the critical saturation by using a method of changing the concentration of the aqueous solution. These methods are preferably used even when introducing arbitrary shells, high-iodity shells, intermediate shells, and outermost shells, because each silver halide grain is uniformly coated without re-nucleation.

If desired, a single shell or a plurality of shells may be provided between the high iodine shell and the inner core of the silver halide grain of the present invention. This high iodine shell can be provided by a conventional halogen substitution method, a method of coating with a silver halide or the like after subjecting the formed internal core or the internal core provided with an arbitrary shell to a desalting step, if necessary.

The halogen substitution method can be carried out, for example, by adding an aqueous solution mainly containing an iodo compound (preferably iodine potassium) after the inner core is formed, preferably an aqueous solution having a concentration of 10% or less. Specifically, it can be carried out by the method described in US Pat. No. 2,592,250, US Pat. No. 4,075,020, JP-A-55-127549 and the like. At this time, in order to reduce the difference in iodine distribution between the grains of the high iodine shell, it is desirable that the concentration of the aqueous iodine compound solution be 10 ⁻² mol% or less and the addition be performed over 10 minutes.

As a method for newly coating the inner core with silver halide, for example, simultaneous addition of a halide aqueous solution and a silver nitrate aqueous solution, that is, a simultaneous mixing method or a control double jet method can be performed. For details, JP-A-53-22408, JP-B-43-13162,
It can be carried out by the method described in JP-A-58-14829, J Photo Science (J. Photo.Sci.), 24 , 198 (1976) and the like.

The pAg at the time of forming the high-iodine shell is the reaction temperature,
Although it varies depending on the kind and amount of the silver halide solvent, those described above are preferably used in the same manner. When ammonia is used as the solvent, it is preferably 7-11.

As a method of forming a high-iodity shell, a simultaneous mixing method or
The control double jet method is more preferable.

The intermediate shell of the silver halide grain of the present invention has a high-iodity shell on the surface or, if necessary, a single or a plurality of arbitrary shells on the high-iodity shell, an internal core. Can be further provided on the outside of the grains containing silver by a method of coating a silver halide having a halogen composition different from the halogen composition of the high iodine shell by a simultaneous mixing method or a control double jet method.

As for these methods, the above-mentioned method of providing the high-iodity shell is similarly used.

The outermost shell of the silver halide grain of the present invention has an intermediate shell on the surface thereof, or optionally has one or more arbitrary shells on the intermediate shell, a high iodine shell, an internal shell. It can be provided outside the grains containing nuclei by a method of coating a silver halide having a halogen composition different from the halogen composition of the high iodine shell by a simultaneous mixing method or a controlled double jet method.

As for these methods, the method of providing the above-mentioned high-iodity shell is similarly used. If desired, one or more layers may be provided between the inner core and the high-iodity shell, between the high-iodity shell and the intermediate shell, and between the intermediate shell and the outermost shell. good. As for these arbitrary shells, the method of providing the above-mentioned high-iodity shell is similarly used. Inner core, high-iodity shell, middle shell,
With respect to the outermost shell and arbitrary shells at each position, a desalting step may be carried out in accordance with a conventional method, if necessary, when an adjacent shell is provided, or shells may be continuously formed without performing the desalting step. May be done.

The iodine content of the core-coated shell of the silver halide grain of the present invention is described, for example, in J. I. Goldst
eln), D.I. B. Williams “TEM /
X-ray analysis in ATEM "Scanning Electron Microscopy (1977), Volume 1 (IIT Research Institute, p. 651, March 1977).

The silver halide grain as the final product after forming the outermost shell of the present invention is an excess halogen compound produced at the time of preparation, or salts of by-produced or unnecessary nitrates, ammonia and the like, compounds are a dispersion medium of the grain. May be removed from.
The removal method is a Nudel washing method, a dialysis method or an inorganic salt, an anionic surfactant, which is commonly used in general emulsions.
A precipitation method using an anionic polymer (eg polystyrene sulfonic acid) or a gelatin derivative (eg acylated gelatin, carbamoylated gelatin, etc.),
A flocculation method or the like can be appropriately used.

The silver halide grains in other layers including the silver halide grains other than the core / shell type of the present invention can be optically sensitized to a desired wavelength range. There is no particular limitation on the optical sensitizing method, and for example, it is possible to perform optical sensitization by using, alone or in combination, an optical sensitizer such as a cyanine dye such as a cellomethine dye, a monomethine dye, a dimethine dye, and a trimethine dye, or a merocyanine dye. You can Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. For these technologies, U.S. Patents 2,688,545, 2,912,329, 3,397,
No. 060, No. 3,615,635, No. 3,628,964, U.S. Patent 1,19
5,302, 1,242,588, 1,293,862, West German Patent (OLS) 2,030,326, 2,121,780, Japanese Patent Publication No. 43-493
No. 6, No. 44-14030, Research Disclosure (Res
earch Disclosure) Volume 176 17643 (issued in December 1978) No. 23
It is also described in item J etc. on page IV. The selection can be arbitrarily determined depending on the wavelength region to be sensitized, sensitivity, etc., according to the purpose and application of the light-sensitive material.

Next, the core / shell type halogenated particles of the present invention are
Sensitized by the dye of the general formula (I),
Where R₁And R_TwoAt least one of the
Alkyl group having a silyl group or alkyl group having a sulfo group
Represents a kill group, and R₁Or R_TwoRepresents the above group
If the other is an alkyl group,
Is preferably a lower alkyl group such as methyl,
Examples thereof include ethyl, propyl and butyl. Well
The ion represented by X is, for example, H , Na ,
K , HN (CH_Three)_Three, HN (C_TwoH₅)_Three,salt
Iodide ion, bromide ion, iodide ion, thiocyanate
Salt, sulfamate, methylsulfate, ethylsa
Luffate, berchlorate, p-toluenesulfonate
There are In the same formula, Y₁And Y_TwoAre the same
May also be different, sulfur atom, oxygen atom, selenium
Represents an atom, W₁~ W₆Are hydrogen atom and halo, respectively.
Gen atom (eg chlorine, bromine, iodine, fluorine), hydro
A xyl group, an alkoxy group (eg, methoxy, ethoxy,
Propoxy, butoxy, etc.), amino groups (eg amino,
Methylamino, dimethylamino, diethylamino, etc.),
Acyl amide group (eg acetamide, propionamide
Etc.), acyloxy etc. (eg acetoxy, propionki)
Etc.), an alkoxycarbonyl group (eg ethoxycarl)
Bonyl, propoxycarbonyl, etc.), alkoxycarbo
Nylamino groups (eg ethoxycarbonylamino, pron
Poxycarbonylamino, butoxycarbonylamino
Etc.), alkyl groups (eg methyl, ethyl, propyl)
Etc.), an aryl group (eg phenyl, tolyl, etc.)
You

W ₁ and W ₂ , W ₂ and W ₃ , W ₄ and W ₅ , and W ₅ and W ₆ may be connected to each other to form, for example, a benzene ring.
This benzene ring may have a substituent.

Hereinafter, typical specific examples of the blue-sensitive dye that can be used in the present invention are described, but the present invention is not limited to these compounds.

Exemplified dye (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) The sensitizing dye represented by the general formula (I) as exemplified above is a known compound and is disclosed in, for example, US Pat.
No. 9,105, No. 2,238,231, British Patent No. 742,112 or F. M. Hama's "The Cyanine Soybean and Retained Compound" (InterScience Publishes, NY 1964), page 55, hereafter. Then, those not described can be easily synthesized by those skilled in the art by a similar method.

The sensitizing dyes according to the present invention may be used alone or in combination of two or more kinds. (See, for example, JP-A-59-116645). Further, the sensitizing dye according to the present invention can be used together with a sensitizing dye other than the sensitizing dye represented by the general formula (I) or a substantially colorless compound known as a supersensitizer. For example, U.S. Pat. Nos. 2,933,390 and 3,511,664
No. 3,615,613, No. 3,615,632, No. 3,615,64
Compounds having a pyrimidinylamino group or a triazinylamino group described in No. 1 and the like, British Patent No. 1,137,58
The aromatic organic acid-formaldehyde condensate or cadmium salt described in No. 0 may be included.

As a method for adding the sensitizing dye according to the present invention to the above photographic emulsion, various conventionally proposed methods can be applied. For example, as described in US Pat. No. 3,469,987, the sensitizing dye may be dissolved in a volatile organic solvent, the solution may be dispersed in a hydrophilic colloid, and the dispersion may be added to an emulsion. Furthermore, the sensitizing dyes according to the present invention are individually dissolved in the same or different solvents,
These solutions can be mixed or added separately prior to addition to the emulsion.

When the sensitizing dye according to the present invention is added to a silver halide emulsion, the solvent for the dye is, for example, methyl alcohol,
Water-miscible organic solvents such as ethyl alcohol and acetone are preferably used.

When the sensitizing dye according to the present invention is added to a silver halide emulsion, the addition amount is 2 × 10 ^-6 mol to 1 × 10 ^-3 mol per mol of silver halide.

The silver halide grains used in the present invention can be subjected to various commonly used chemical sensitization methods. That is, active gelatin; water-soluble metals, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts and other precious metal sensitizers; sulfur sensitizers; selenium sensitizers; polyamines and stannous chloride. Such as a chemical sensitizer of a reduction sensitizer such as
Alternatively, they can be used in combination for chemical sensitization.

Known sulfur sensitizers can be used. Examples thereof include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine.
Other U.S. Patents 1,574,944, 2,410,689, and
No. 2,278,947, No. 2,728,668, No. 3,501,313, No. 3,656,955, German Patent No. 1,422,869, Japanese Patent Publication No. 56-24937, and sulfur increase described in JP-A-55-45010. Sensitizers can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is about 10 ^-7 mol to 1 mol of silver halide.
About 10 ^-1 mol is preferable.

Instead of sulfur sensitization, or selenium sensitization can be used in combination with sulfur sensitization, the selenium sensitizer is an aliphatic isoselenocyanate such as allyl isoselenocyanate, selenoureas, selenoketones, Selenoamides,
Selenocarboxylic acids and esters, selenophosphates, diethyl selenide, and selenides such as diethyl selenide can be used, and specific examples thereof include U.S. Pat.Nos. 1,574,944, 1,602,592, and
No. 1,623,499.

The addition amount varies over a wide range similarly to the sulfur sensitizer, but as a guide, it is preferably about 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide.

As the gold sensitizer, various kinds of gold compounds may be used, in which the oxidation number of gold may be +1 or +3. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, and viridyl trichlorogold.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably in the range of about 10 ^-7 to 10 ^-1 mol per mol of silver halide.

For the sensitization method of silver halide grains, a sensitization method using another noble metal, for example, a metal such as platinum, palladium, iridium or rhodium, or a salt thereof can be used together.

In the present invention, reduction sensitization can also be used in combination. The reducing agent is not particularly limited, but examples thereof include known stannous chloride, thiourea dioxide, hydrazine derivatives, and silane compounds.

The reduction sensitization is preferably performed during the growth of silver halide grains or after the completion of sulfur sensitization and gold sensitization.

Further, in the present invention, the silver halide grains according to the present invention can be remarkably enhanced in sensitivity by being chemically ripened in the presence of a silver halide solvent.

Examples of the silver halide solvent used in the present invention include U.S. Patent Nos. 3,271,157, 3,531,289, and 3,574,628.
Nos. 54-1019 and 54-158917.
(a) Organic thioethers, JP-A Nos. 53-82408 and 55-7773
No. 7, the same 55-2982 (b) thiourea derivative,
(C) A silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319, described in JP-A-54-100717. )
Examples thereof include imidazoles, (e) sulfite, (f) thiocyanate and the like.

These specific compounds are shown below.

(a) (d) (e) K ₂ SO ₃ (f) NH ₄ SCN KSCN Particularly preferred solvents are thiocyanate and tetramethylthiourea. The amount of solvent used also varies depending on the type, for example, in the case of thiocyanate,
A preferred amount is in the range of 5 mg to 1 g per mol of silver halide.

When forming each shell of the core / shell type emulsion of the present invention, various dopants can be doped. Examples of the internal dopant include silver, sulfur, iridium, gold,
Platinum, osmium, rhodium, tellurium, selenium, cadmium, zinc, lead, thallium, iron, antimony, bismuth, arsenic and the like are included. Since these dopants are doped, each water-soluble salt or complex salt can coexist when forming each shell.

As the binder of the silver halide grains according to the present invention or the dispersion medium used for producing them, a hydrophilic colloid usually used in silver halide emulsions is used. As the hydrophilic colloid, not only gelatin (either lime treatment or acid treatment may be used) but also gelatin derivatives such as gelatin and aromatic sulfonyl chloride, acid chloride, acid anhydride as described in US Pat. No. 2,614,928. , Isocyanate, gelatin derivatives made by reaction with 1,4-diketones, gelatin derivatives made by reaction of gelatin with trimellitic anhydride described in US Pat. No. 3,118,766, Japanese Patent Publication No. 39-5514. Gelatin derivatives by the reaction of an organic acid having an active halogen described with gelatin, gelatin derivatives by the reaction of an aromatic glycidyl ether with gelatin described in JP-B-42-26845, and maleimides described in US Pat. No. 3,186,846. ,
Gelatin derivatives by reaction of maleamic acid, unsaturated aliphatic diamide and the like with gelatin, sulfoalkylated gelatin described in British Patent 1,033,189, US Pat.
Polyoxyalkylene derivatives of gelatin as described in 553; polymeric graft products of gelatin, such as acrylic acid, methacrylic acid, esters thereof with mono- or polyhydric alcohols, also amides, acrylics (or methacrylics) Grafting of ethryl, styrene and other vinyl monomers alone or in combination with gelatin; synthetic hydrophilic polymer substances such as vinyl alcohol, N-vinylpyrrolidone, hydroxyalkyl (meth) acrylate, (meth) acrylamide, N Homopolymers containing monomers such as substituted (meth) acrylamides or copolymers thereof, copolymers of these with (meth) acrylic acid esters, vinyl acetate, styrene, etc., any of the above and maleic anhydride Acid, maleic acid, etc. ; Natural hydrophilic polymeric substance other than gelatin, such as casein, agar, alginic acid polysaccharides can be used alone or in combination.

The silver halide photographic emulsion containing the silver halide grains according to the present invention can contain various additives usually used depending on the purpose.

Examples of these additives include azoles or imidazoles, such as benzothiazolium salts, nitroinsoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles; triazoles such as aminotriazoles, benzotriazoles, nitrobenzotriazoles; tetrazoles such as mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; Mercaptotriazines, for example thioketo compounds such as oxazolithion; azaindenes, for example triazaindenes, tetraazaindenes (special 4-hydroxy substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes, etc .; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, imidazolium salt,
Stabilizers such as tetrazolium salts and polyhydroxy compounds, and antifoggants can be included.

The photographic light-sensitive material using the core / shell type emulsion of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chrome alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), An active vinyl compound (1,3,5-triacryloyl-hexahydro-S-
Triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-)
Hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.). Etc. can be used alone or in combination.

A photographic light-sensitive material using the core / shell type emulsion of the present invention contains a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. be able to. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination with methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalk (meth) acrylate, sulfaalkyl (meth) acrylate, styrenesulfonic acid, etc. can be used.

The silver halide photographic light-sensitive material according to the present invention comprises a development accelerator such as benzyl alcohol or polyoxyethylene-based compound, if necessary; a chroman-based, Claman-based, bisphenol-based, phosphite-based image stabilizer; wax. , Glycerides of higher fatty acids, lubricants such as higher alcohol esters of higher fatty acids, development regulators, developing agents, plasticizers,
It may contain a bleaching agent. As a surfactant that may be contained, a coating aid, an agent for improving the permeability to a processing solution, a defoaming agent, or a material for controlling various physical properties of a light-sensitive material, anionic, cationic, nonionic A variety of types or both sexes can be used. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl sodium sodium maleate copolymer, styrene-
Alkaline salts of a reaction product of a maleic anhydride copolymer and p-aminobenzenesulfonic acid are effective. Examples of matting agents include methyl polymethacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Examples of the latex added to improve the physical properties of the film include copolymers of acrylic acid ester, vinyl ester and the like with other monomers having an ethylene group. Examples of the gelatin plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer.

The emulsion having silver halide grains of the present invention can have a rich latitude by mixing at least two types of emulsions having different average grain sizes and different sensitivities, or by performing multi-layer coating.

The mixed silver salt crystal according to the present invention is used for general black and white, X ray,
Effectively applied to photographic light-sensitive materials for various purposes such as color, infrared, micro, silver dye bleaching, reversal, diffusion transfer, high contrast, photothermography, and photothermographic material. However, it is particularly suitable for a color sensitive material having high sensitivity.

In order to apply the core / shell type silver halide emulsion according to the present invention to a photographic light-sensitive material for color, at least one blue-sensitive layer contains the silver halide grains according to the present invention and a sensitizing dye (I). The techniques and materials used for a color light-sensitive material may be applied, for example, a combination of cyan, magenta and yellow couplers may be incorporated into an emulsion adjusted to have a red, green, and blue sensitivity. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloyl And acetanilides), and cyan couplers include naphthol couplers, phenol couplers, and ureido couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, a colored coupler having a color correction effect or a coupler releasing a development inhibitor with development (so-called D
IR coupler). In addition to the DIR coupler, the product of the coupling reaction may be colorless and may include a color-free DIR coupling which releases a development inhibitor.

In carrying out the present invention, the following known anti-fading agents can be used in combination, and the color image stabilizers used in the present invention can be used alone or in combination of two or more kinds. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and bisphenols.

The light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used. These UV absorbers may be fixed in the hydrophilic colloid layer.

The light-sensitive material of the present invention may have a so-called forward layer structure as the structure of its light-sensitive emulsion layer, but a so-called reverse layer structure (particularly Japanese Patent Application Nos. 59-193609 and 59-202065 by the present applicant). Etc.), and a remarkable effect is obtained especially in the reverse layer structure.

The photosensitive silver halide emulsion layer of the present invention may be separated into two or more layers having different sensitivities. That is, for example, a blue-sensitive silver halide emulsion layer having a high sensitivity layer (BH) and a blue-sensitive silver halide emulsion layer having a low sensitivity layer (B
L), a high-sensitivity layer (GH) of a green-sensitive silver halide emulsion layer,
Low sensitivity layer (GL) of green-sensitive silver halide emulsion layer, high sensitivity layer (RH) of red-sensitive silver halide emulsion layer, low sensitivity layer (RL) of red-sensitive silver halide emulsion layer, or blue High sensitivity layer (BH) of sensitive silver halide emulsion layer, high sensitivity layer (GH) of green sensitive silver halide emulsion layer, high sensitivity layer (RH) of red sensitive silver halide emulsion layer, blue sensitive silver halide emulsion Such as the low-sensitivity layer (BL), the low-sensitivity layer of the green-sensitive silver halide emulsion layer (GL), the low-sensitivity layer of the red-sensitive silver halide emulsion layer (RL). For example, in the high sensitivity layer of the blue-sensitive silver halide emulsion layer
H), a high-sensitivity layer (GH) of a green-sensitive silver halide emulsion layer,
The silver halide contained in the high-sensitivity layer (RH) of the red-sensitive silver halide emulsion layer has an average grain size (average grain size) of 0.40 to
3.00 μm is preferable, and 0.50 to 2.50 μm is more preferable.

In the present invention, for example, in particular, a low-sensitivity layer (BL) of a blue-sensitive silver halide emulsion layer, a low-sensitivity layer of a green-sensitive silver halide emulsion layer (GL), and a low-sensitivity layer of a red-sensitive silver halide emulsion layer ( The average grain size (average grain size) of the silver halide contained in RL) is preferably 0.20 to 1.50 μm,
More preferably, it is 0.20 to 1.0 μm. Further, the low-sensitivity layer (BL) of the blue-sensitive silver halide emulsion layer, the low-sensitivity layer (GL) of the green-sensitive silver halide emulsion layer, and the low-sensitivity layer (RL) of the red-sensitive silver halide emulsion layer are intermediate-sensitivity layers. When separated into a low-sensitivity layer, the former is 0.30 to 1.50 μm and the latter is 0.15
It is preferable that the thickness is ˜1.00 μm.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

The light-sensitive material of the present invention includes a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative as an antifoggant,
You may contain an ascorbic acid derivative etc.

It is usual to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods, such as tape coating method, roller coating method and curtain coating method. A coating method, an extrusion coating method, or the like can be used. U.S. Patents 2,681,294 and 2,7
The methods described in 61,791 and 3,526,528 are advantageous methods. As the support for the photographic light-sensitive material, for example, a barite paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester film such as polyethylene terephthalate, or a commonly used one is used. Can be appropriately selected depending on the intended use of each photographic light-sensitive material.

These supports are subjected to a subbing process, if necessary.

The photographic light-sensitive material having the core / shell type silver halide emulsion according to the present invention can be developed after exposure by a known method usually used.

The black-and-white developing solution is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols, aminobenzenes, and other alkali metal sulfites, carbonates,
It may contain bisulfite, bromide, iodide and the like. When the photographic light-sensitive material is used for color, color development can be carried out by a commonly used color development method. In the reversal method, first, development is carried out with a black-and-white negative developing solution, then white exposure is carried out or processing is carried out in a bath containing a fogging agent, and then color development is carried out with an alkaline developing solution containing a color developing agent.
There is no particular limitation on the treatment method, and any treatment method can be applied, for example, as a typical one,
After color development, apply bleach-fixing treatment, and then wash and stabilize treatment if necessary, or after color development, apply bleaching and fixing treatment separately, and then wash and stabilize treatment as needed. You can

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N). -Ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfoamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, Photographic Processing Chemistry (Phot) by LFA Mason
ographic Processing Chemistry) Focal Press, 1966), pages 226-229, US patents.
Those described in 2,193,015, 2,592,364 and JP-A-48-64933 may be used.

The color developing solution may further contain a pH buffering agent, a development inhibitor or an anti-caprying agent. Further, if necessary, a water softener, a preservative, an organic solvent, a development accelerator, a dye forming coupler, a competitive coupler, a fogging agent, an auxiliary developing agent, a viscosity imparting agent, a polycarboxylic acid type chelating agent, an antioxidant. May be included.

The photographic emulsion layer after color development is usually bleached. The bleaching treatment may be carried out at the same time as the fixing treatment, or as a bleaching agent which may be carried out individually, iron (III), cobalt (I
V), chromium (VI), polyvalent metal compounds such as copper (II), peracids, quinones, nitroso compounds, etc. are used.

For bleaching or bleach-fixing solutions, U.S. Pat.
Various additives can be added in addition to the bleaching accelerators described in 3,241,966, JP-B-45-8506, JP-B-45-8836, and the thiol compounds described in JP-A-53-65732.

In addition, a production example of silver halide grains according to the present invention will be specifically described.

Production Example 1 (1-1) Production of Inner Core: A silver iodobromide emulsion EM-1 containing 4 mol% of silver iodide was produced using the following 6 kinds of solutions.

(Solution A-1) Ocein gelatin 39.7 g Distilled water 3936 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 35.4 ml Magnesium sulfate 3.6 g 6% nitric acid 75.6 ml Potassium bromide 2.06 g (solution B -1) Ocein gelatin 35.4 g Potassium bromide 807 g Potassium iodide 47 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 35.4 ml Distilled water 1432 ml (Solution E-1) Silver nitrate 1200 g 6 % Nitric acid 62 ml Distilled water 1467 ml (solution F-1) 25% KBr aqueous solution pAg adjustment required amount (solution H-1) 6% nitric acid pH adjustment required amount (solution I-1) 7% sodium carbonate aqueous solution pH adjustment required amount At 40 ° C., the solution A-1 was mixed with the solutions E-1 and B- using a mixing stirrer disclosed in JP-A Nos.
1 and 1 were added by the double jet method. PA during simultaneous mixing
The g, pH and addition rates of solutions E-1 and B-1 were controlled as shown in Table-1. The pAg and pH are controlled by a roller tube pump with a variable flow rate, and solution F-1 and solution H-1 are used.
Was carried out by changing the flow rate of. The pH was adjusted to 5.5 with Solution I-1 3 minutes after the addition of Solution E-1.

Next, deionized water is washed by a conventional method, and ossein gelatin is used.
Disperse in an aqueous solution containing 125 g, and then add distilled water to bring the total volume to 4
Adjusted to 800 ml.

This emulsion has an average grain size of 0.09 μm as observed by electron microscopy.
It was found to be a monodisperse emulsion of.

The particle size here is the side length when the volume of the particles is converted into a cube having the same volume, and the same applies to the following description.

(1-2) Addition of Fifth Shell: Using the following five types of solutions, EM-1 was used as a seed emulsion, and a shell of silver iodobromide having a silver iodide content of mol% was added thereto. Emulsion EM-2 was prepared.

(Solution A-2) Ocein gelatin 34.54 g Distilled water 8642 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 20 ml 4-hydroxy-6-methyl-1,3,3a, 7-tetra Azaindene 181.32 mg 28% Ammonia water 117.4 ml 56% Acetic acid aqueous solution 154 ml Magnesium sulfate 16 g Emulsion (EM-1) 0.329 mol equivalent (Solution B-2) Ocein gelatin 18.72 g KBr 763.8 g KI 21.8 g 4- Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 2.17 g Magnesium sulfate 7.4 g Distilled water 1578 ml (Solution E-2) AgNO ₃ 1142.4 g 28% ammonia water 931.4 ml Distilled water to make 1921 ml.

(Solution F-2) 50% KBr aqueous solution pAg adjustment required amount (Solution G-2) 56% acetic acid aqueous solution pH adjustment required amount At 40 ° C., mixing and stirring shown in JP-A-57-92523 and 57-92524. Solution A-2 to solution E-2 and B
-2 and -2 were added by the simultaneous mixing method for a minimum time of 32.5 minutes without the generation of small particles on the way. PAg during co-mixing,
The pH and the addition rates of the solutions E-2 and B-2 were continuously controlled as shown in Table-2. For controlling pAg and pH, solution F-2 and solution G- are controlled by a roller tube pump with variable flow rate.
2 and the solution B-2 were changed in flow rate. Two minutes after the addition of the solution E-2, pAg was changed by the solution G-2.
The pH was adjusted to 10.4 and after a further 2 minutes the pH was adjusted to 6.0 with solution F-2.

Next, deionized water is washed by a conventional method, and ossein gelatin is used.
After being dispersed in an aqueous solution containing 128.6 g, the total amount was adjusted to 3000 ml with distilled water.

This emulsion has an average grain size of 0.27μ as observed by electron microscopy.
It was found to be a highly monodisperse emulsion with a coefficient of variation of m and a grain size distribution of 12%.

(1-3) Addition of Fourth Shell: Using the following five types of solutions, the above EM-2 was used as a seed emulsion, and a shell of silver iodobromide having a silver iodide content of 2.6 mol% was provided. Emulsion EM-3 was prepared.

(Solution A-3) Ocein gelatin 34.0 g Distilled water 7779 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 20 ml 4-hydroxy-6-methyl-1,3,3a, 7-tetra Azaindene 405 mg 28% Ammonia water 117.3 ml 56% Acetic acid aqueous solution 72 ml Seed emulsion (EM-2) 0.303 mol equivalent (Solution B-3) Ocein gelatin 18.74 g KBr 760.2 g KI 28.4 g 4-hydroxy-6- methyl-1,3,3a, 7- tetrazaindene 1.35g distilled water 1574 ml (solution E-3) to 1930ml with AgNO ₃ 1148 g 28% aqueous ammonia 937 ml distilled water.

(Solution F-3) 50% KBr aqueous solution pAg adjustment required amount (Solution G-3) 56% acetic acid aqueous solution pH adjustment required amount At 40 ° C, mixing and stirring shown in JP-A-57-92523 and 57-92524. Solution A-3 to solution E-3 and B
-3 and -3 were added by the simultaneous mixing method for a minimum time of 56.5 minutes without the generation of small particles on the way. PAg during co-mixing,
The pH and the addition rates of solutions E-3 and B-3 were controlled as shown in Table-3. The pAg and pH were controlled by changing the flow rates of the solution F-3, the solution G-3, and the solution B-3 by a roller tube pump having a variable flow rate. Solution E-3
2 minutes after the completion of the addition of p.
And after a further 2 minutes the pH was adjusted to 6.0 with solution F-3.

Next, deionized water is washed by a conventional method, and ossein gelatin is used.
After being dispersed in an aqueous solution containing 128.1 g, the total amount was adjusted to 3000 ml with distilled water.

By observation with an electron microscope, this emulsion has an average grain size of 0.80μ.
It was found that this was a highly monodisperse emulsion with a coefficient of variation of m and a grain size distribution of 10%.

(1-4) Addition of high-iodity shell, intermediate shell, and outermost shell of the present invention: The above-mentioned EM-3 was used as a seed emulsion by using the following seven kinds of solutions, and the high-iodity shell of the present invention, An emulsion EM-4 having an intermediate shell and an outermost shell was prepared.

(Solution A-4) Ocein gelatin 22.5 g Distilled water 6884 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol solution 20 ml 4-hydroxy-6-methyl-1,3,3a, 7-tetra Azaindene Amount shown in Table-4 28% Ammonia water 469 ml 56% Aqueous acetic acid solution 258 ml Emulsion 0.8828 mol equivalent (Solution B-4) Ocein gelatin 24 g KBr Amount shown in Table-5 Amount shown in KI Table-5 Amount 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene Amount shown in Table-5 Distilled water 1978 ml (Solution C-4) Ocein gelatin 24 g KBr Amount shown in Table-6 KI table Amount described in -6 4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene Amount described in Table-6 Distilled water 1978 ml (Solution D-4) Ocein gelatin 40 g KBr Described in Table-7 Amount of KI 4-hydroxy-6-methyl-1,3,3a, 7- amount of distilled water 3296 ml of tetraazaindene table -7 described (solution E-4) to 1866ml with AgNO ₃ 1109 g 28% aqueous ammonia 904 ml distilled water To do.

(Solution F-4) 50% KBr aqueous solution pAg adjustment required amount (Solution G-4) 56% acetic acid aqueous solution pH adjustment required amount At 50 ° C, mixing and stirring shown in JP-A-57-92523 and 57-92524. Solution A-4 into solution E-4 and B
-4 and 4-4 minutes by the simultaneous mixing method, C-4 is added at the same time as the addition of B-4 is completed, D-4 is added at the same time as the addition of C-4 is completed after 35.9 minutes, and 25.5 minutes later. finished. PAg, pH and solution E-4, B during co-mixing
The addition rates of C-4, C-4 and D-4 were controlled as shown in Table-8. The pAg and pH were controlled by changing the flow rates of the solution F-4 and the solution G-4 with a roller tube pump having a variable flow rate. Completion of addition of Solution E-4 2
After a few minutes, the pAg was adjusted to 10.4 with solution F-4 and after a further 2 minutes the pH was adjusted to 6.0 with solution G-4.

Next, deionized water is washed by a conventional method, and ossein gelatin is used.
Dispersed in an aqueous solution containing 127 g, then distilled water for a total volume of 3000 m
Adjusted to l.

By observation with an electron microscope, this emulsion has an average grain size of 1.60 μm.
It was found that this was a highly monodisperse emulsion with a coefficient of variation of m and a grain size distribution of 11%.

EM-4 is 15 mol%, 5 mol% and
Core / shell type silver iodobromide emulsion having a silver iodide content of 0.3 mol% (that is, I = 0.3, Ih = 15, Im
= 5).

Production Example 2 Using 7 kinds of solutions shown in (1-4) of Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,3a,
EM-5, EM-6, EM-7 in the same manner as in (1-4) of Production Example 1 except that the amount of 7-tetraazaindene added was changed to the amounts described in Tables 4, 5, 6, and 7. , EM-8, EM-
9 was produced. These are monodisperse emulsions with an average grain size of 1.60 μm, and the variation coefficient of grain size distribution is 17%, 15%,
It was 12%, 16% and 16%.

Production Example 3 Using 7 types of solutions shown in (1-4) of Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,3a,
EM-10 to EM-26 were produced in the same manner as in (1-4) of Production Example 1 except that the amount of 7-tetraazaindene prepared was changed to the amounts shown in Tables 4, 5, 6, and 7. These are average particle sizes
It is a monodisperse emulsion of 1.60 μm, and the coefficient of variation of grain size distribution is 10%, 10%, 11%, 12%, 13%, 18%, 19%,
35%, 39%, 10%, 11%, 11%, 11%, 12%, 12%, 12
% And 13%.

Production Example 4 Using 7 kinds of solutions shown in (1-4) of Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,3a,
EM-28, 29 was produced in the same manner as in (1-4) of Production Example 1 except that the amount of 7-tetraazaindene prepared was changed to the amounts shown in Tables 4, 5, 6, and 7. In addition, pA during mixing
g, pH and E-4, B-4, C-4, and D-4 were changed in control rate as shown in Table-9, and EM-27 was produced, as shown in Table-10. To produce EM-30,31.
These are monodisperse emulsions with an average grain size of 1.60 μm, and the variation coefficients of grain size distribution are 9%, 18%, 19%, 32% and 34%, respectively.
%Met.

Production Example 5 Using 7 kinds of solutions shown in (1-4) of Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,3a,
The amount of 7-tetraazaindene prepared was set to the amount described in Tables 4, 5, 6, and 7, and pAg, pH and E-4 during mixing were further adjusted.
The control of the addition rates of B-4, C-4, and D-4 is shown in Table-11, EM-32 is shown in Table-12, EM-33 is shown in Table-13. To produce EM-34.
These were monodisperse emulsions having an average grain size of 1.60 μm, and the variation coefficients of grain size distribution were 10%, 10%, and 12%, respectively.

Production Example 6 Using 7 kinds of solutions shown in (1-4) of Production Example 1, K
Br, KI and 4-hydroxy-6-methyl-1,3,3a,
EM-35, 36 and 37 were produced in the same manner as in (1-4) of Production Example 1 except that the amount of 7-tetraazaindene prepared was changed to those described in Tables 4, 5, 6 and 7. In addition, pA during mixing
EM-38 and 39 were produced by changing the control of g, pH and addition rate of E-4, B-4, C-4 and D-4 as shown in Table-12. These are monodisperse emulsions with an average grain size of 1.60 μm, and the variation coefficients of grain size distribution are 12%, 14% and 13%, respectively.
%, 9% and 11%.

E. EXAMPLES Next, the present invention will be described in more detail with reference to examples.

<Example 1> EM-5, EM-7, EM-4, EM-9 and dye NO.
3, No. 11, comparative dyes A and B are used to show the effect of the dye and the emulsion.

However, the comparative dye; A: B The effects were examined with respect to sensitivity, fog, granularity, width of exposed area, sharpness, multi-layer sensitivity, and high illuminance reciprocity law failure characteristics.

Sensitivity, fog, granularity, width of exposure area, sharpness, and reciprocity failure characteristics under high illuminance were measured by preparing a single-layer sample.

Regarding the multi-layer sensitivity, a multi-layer color light-sensitive material having light-sensitive layers of three colors of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer was prepared and its effect was examined.

Next, a method of preparing each sample and a method of measuring each performance will be described.

Preparation of Single Color Sensitive Coating Sample (Single Layer): Here, the case where the present invention is applied to a sample composed of a light-sensitive material having one emulsion layer containing a coupler will be described.

In this example, a yellow color coupler was used. That is,
Specifically, in this embodiment, α is used as a yellow color forming coupler.
-Pivaloyl-α- (1-benzyl-2-phenyl-
3,5-Dioxoimidazolidin-4-yl) -2'-chloro-5 '-[α-dodecyloxycarbonyl) ethoxycarbonyl] acetanilide (Y-1) was used.
As a solvent for dissolving the coupler, tricresyl phosphate (TCP) was adopted. The coupler was oil protected and dispersed according to a conventional method.

The silver iodobromide emulsions (EM-4 to EM- shown in the above Production Example)
9) was subjected to chemical sensitization according to a conventional method, and during the chemical sensitization, blue sensitization was carried out by a conventional method with a blue sensitizing dye-dyes NO.3, NO.11, A and B-. Each dye was used at a ratio of 1.7 × 10 ⁻⁴ mol per mol of silver halide grains.

In addition, a sample using the dyes No. 3, 11, A and B in combination was used. The dyes were used in a ratio of 8 × 10 ^-5 mol.

The emulsion layer of this example was prepared as follows.

Emulsion layer: A high-sensitivity blue-sensitive emulsion layer containing 1.5 g of gelatin and 0.65 g of TCP in which 1.30 g of yellow coupler (Y-1) was dissolved.

Each sample was subjected to wedge exposure according to a conventional method for measuring sensitometric performance (sensitivity, width of exposure area, fog) and graininess, and subjected to rectangular wave frequency wedge exposure for measuring sharpness, and then subjected to the next treatment. Processed in process.

Treatment process Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Shown below.

[Color developer]

 4-Amine-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / nitrate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g nitrilotri Acetic acid / trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

[Bleaching solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water is added to adjust the pH to 1 using ammonia water.

[Fixer]

 Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water is added to make 1 and pH is adjusted to 6.0 with acetic acid.

[Stabilizing liquid]

 Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

The developed sample was subjected to sensitometry measurement, granularity measurement, and sharpness measurement using blue light.

Fog: lowest optical density of so-called characteristic curve obtained by sensitometry (higher value means higher fog and not preferable.) Sensitivity: Optical density of fog +0.1 is given on the characteristic curve. The reciprocal of the exposure dose (exact value) (in the table of the results of the examples, relative sensitivity is set as 100. The larger the value, the faster the sensitivity.) The exposure is 1/50 second and 10 ^{− Four}
Two types of seconds were performed.

In each exposure, the exposure amount is constant, and the higher the illuminance reciprocity failure characteristic is, the better the sensitivity of 10 ⁻⁴ second exposure is smaller than that of 1/50 second exposure. The 1/50 second exposure is called low illuminance sensitivity, and the 10 ⁻⁴ second exposure is called high illuminance sensitivity.

Sharpness: MTF is used to detect the effect of improving image sharpness.
(Modulation Transfer Function) was determined, and the MTF values were compared at spatial frequencies of 30 mm and 10 lines / mm. The larger the value, the better.

Graininess ... RMS: Standard deviation of density variation of 10 when a dye image having a dye image density of Dmin + 0.8 is scanned with a microtensitometer having a circular scanning aperture of 25 μ.
The 00-fold value is shown as a relative value with the control sample being 100. The larger the value, the coarser the grain is, which is not preferable.

Extent of exposure area: The difference between the exposure amount (logarithmic value) giving an optical density of fogging +0.1 and the exposure amount (logarithmic value) giving a maximum optical density of -0.1 on the characteristic curve. The higher the value,
A wide exposure area is preferable.

Preparation of multi-layer color light-sensitive material (referred to as multi-layer sample): Silver iodobromide emulsion (EM-4, 5 to 7, shown in the above Production Example)
EM-9) was chemically sensitized according to a conventional method to prepare a color light-sensitive material consisting of 10 layers having three types of light-sensitive layers of a blue light-sensitive layer, a green light-sensitive layer and a red light-sensitive layer as follows.
The chemically sensitized emulsions EM-4 to EM-9 were changed only in the blue-sensitive high-sensitivity layer (the ninth layer). The other light-sensitive layers used emulsions of uniform composition which were quite common in each sample.

Layer 1 ... consisting of an undercoated cellulose triacetate film, and an antihalation layer (black colloidal silver)
It contains 0.40 g and 3.0 g gelatin. A sample was prepared by sequentially coating the following layers on a transparent support having In all of the following examples, the amount added to the light-sensitive material is shown per 1 m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver.

Layer 2 ... 1.4 g of low-sensitivity red-sensitive silver iodobromide (containing 7 mol% of silver iodide) emulsion sensitized red-sensitively, 1.2 g of gelatin and 0.8 g of 2- (4-n-). Butylsulfonylphenylureido) -5- {α- (2,4-di-t-amylphenoxy) -butane-amido} -phenol [hereinafter C
-1. ], 0.075 g of 1-hydroxy-4-
[4- (1-hydroxy-δ-acetamido-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ-
(2,4-di-t-amylphenoxy) butyl-2-naphthamide disodium [hereinafter referred to as colored cyan coupler (CC-1). ] And 0.015 g of 1-hydroxy-2- [δ- (2,4-di-t-amylphenoxy)]
n-butyl] naphthamide, 0.07 g of 4-octadecylsuccinimide-2- (1-phenyl-5-tetrazolylthio) -1-indanone [hereinafter referred to as DIR compound (D-
1). ] A low-sensitivity red-sensitive emulsion layer (hereinafter referred to as RL layer) containing 0.65 g of di-t-nonyl-phenol (DNP).

Layer 3 ... 1.3 g of high-sensitivity red-sensitive silver iodobromide emulsion (containing 6 mol% of silver iodide), 1.2 g of gelatin and 0.21 g of cyan coupler (C-1) and 0.02 g of colored cyan coupler. A high-sensitivity red-sensitive emulsion layer (hereinafter referred to as RH layer) containing 0.23 g of DNP in which (CC-1) is dissolved.

Layer 4 ... 0.07 g of 2,5-di-t-octylhydroquinone [hereinafter referred to as antifouling agent (HQ-1). ] N-dibutyl phthalate [hereinafter referred to as DBP
Called. ] And an intermediate layer containing 0.8 g of gelatin (hereinafter referred to as IL).

Layer 5: 0.80 g of low-sensitivity silver iodobromide (containing 6 mol% silver iodide) emulsion sensitized to green and 2.2 g of gelatin and 0.8 g of 7-chloro, 6-methyl-3,3 -{Δ- [P
-Dodecyloxybenzenesulfonamide) phenyl] propyl} -1H-pyrazolo [5,1-C] -1,2,4-
Triazole (hereinafter referred to as magenta coupler (M-1)), 0.15 g of 1- (2,4,6-trichlorofer) -4
-(1-Naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone [hereinafter referred to as colored magenta coupler (CM-1). ], 0.016 g of DIR compound (D-1) was dissolved
A low-speed green sensitive emulsion layer (hereinafter referred to as GL) containing 0.95 g of DNP.

Layer 6: 1.8 g of high-sensitivity green-sensitive silver iodobromide (containing 6 mol% silver iodide) emulsion sensitized to green, 1.9 g of gelatin and 0.20 g of magenta coupler (M-1) , And 0.
A high-sensitivity green-sensitive emulsion layer (hereinafter referred to as GH) containing 0.25 g of DNP in which colored magenta coupler (CM-1) was dissolved.

Layer 7: A yellow filter layer (hereinafter referred to as YC) containing 0.15 g of yellow colloidal silver, 0.1 g of DBP in which 0.2 g of antifouling agent (HQ-1) was dissolved, and 1.5 g of gelatin.

Layer 8: 0.2 g of low-sensitivity silver iodobromide sensitized blue-sensitive (containing 4 mol% of silver iodide (emulsion and 1.9 g of gelatin and 1.5 g of α-bivaloyl-α- (1- Benzyl-2
-Phenyl-3,5-dioxoimidazolidin-4-yl) -2'-chloro-5 '-[α-dodecyloxycarbonyl) ethoxycarbonyl] acetanilide [hereinafter referred to as Y-1. ] A low-sensitivity blue-sensitive emulsion layer (hereinafter referred to as BL) containing 0.6 g of TCP.

Layer 9: 1.0 g of high-sensitivity silver iodobromide (EM4, 5, 7, 9) sensitized to blue with dye Nos. 3, 11, A and B
The amounts of emulsion and dye used were the same as those for the single-layer sample. A high-sensitivity blue-sensitive emulsion layer (hereinafter referred to as BH) containing 0.65 g of TCP in which 1.5 g of gelatin and 1.30 g of yellow coupler (Y-1) were dissolved. ).

Layer 10 ... a protective layer having 2.3 g of gelatin (hereinafter R
That).

Measurement of Multilayer Sensitivity: The multilayer color light-sensitive material thus prepared was subjected to white wedge exposure according to a conventional method and processed in the above-mentioned processing step, and blue light sensitivity was obtained by sensitometric measurement (sensitivity definition: The same as in the case of the single color-sensitive coated sample).

Results of Example 1 (Effects of Emulsion and Dye): Fog, sensitivity (low illuminance, high illuminance), graininess, wideness of exposed area, sharpness, and sensitivity of multi-layered sample of a single color-sensitive coated sample are shown. -14 and 15 are shown.

Only the samples using the dyes (NO.3, 11) of the present invention and the emulsions (EM-4, 7) showed significantly less desensitization due to high illuminance, and the dyes other than the present invention using EM-4, 7 were used. The sensitivity (low, high illuminance) and the multi-layer sensitivity are better than those of the samples using A and B. Further, a dye (NO.3, 11) and an emulsion (E
M-5, 9) compared with the sample using
It can be seen that the fog and the multi-layer sensitivity are remarkably improved.

Further, it can be seen that the above-mentioned combination according to the present invention has improved graininess and exposure area as compared with the combinations other than the present invention.

Also, EM-7A was prepared in the same manner except that pure silver iodide (AgI) was used as the inner nucleus of EM-7, and a sample to which Dy-3 was applied was prepared in the same manner as in Example 1, and the same procedure was performed. As a result of evaluation, the sensitivity and fog were the same as those of EM-7, but the graininess was 41 and the exposure area was 1.13.
It was not possible to obtain excellent characteristics as in the present invention.

<Example 2> EM-4, EM-5, EM-9 to EM-18 of the above Production Example.
Table 16 shows the effect of iodine content in the high iodine shell in the same manner as in Example 1 using. The halogenated grains were used only in layer 9. In Example 2 and below, dye N
O.11 was used. The amount used is 1.7 × 10 ^-4 per mol of each emulsion.
It is a mole. EM-10 to EM-15 are examples in which the middle shell and the outermost shell are made the same and the iodine content of the high iodine shell is changed, but the higher the iodine content of the high iodine shell, the higher the iodine content. You can see that it becomes sensitive.

Emulsions with a high iodine content of 40 mol% or 50 mol% (E
In M-15 and EM-17), the sensitizing effect tends to be small, which is considered to be due to the broad grain size distribution, and an emulsion (EM) having the same high iodine shell (EM) other than the present invention. -16,
It can be seen that the emulsion of the present invention has a sufficient sensitizing effect as compared with EM-18).

Results of Example 2 (effect of intermediate shell): Table 16 shows the results of fog, sensitivity, graininess, width of exposed area, sharpness, and sensitivity of multilayer samples of the single color-sensitive coated sample.

From the above results, between the outermost shell (low iodine shell) and high iodine shell,
Conventional core / shell emulsions (EM-5, EM-9) having no intermediate shell having an intermediate iodine content, or those having an intermediate shell but having a high iodine shell and an intermediate shell having no sufficient difference in iodine content In comparison with the core / shell emulsion (EM-6) and the core / shell emulsion (EM-8) which does not have a sufficient difference in iodine content between the outermost shell and the intermediate shell, a high iodine shell based on the present invention, The core / shell emulsions having the middle shell and the outermost shell (EM-4, EM-7) have very high sensitivity.

Further, this effect is more remarkable in the multi-layer sensitivity, and the core / shell emulsion of the present invention is
It turns out that it is more effective.

Further, core / shell emulsions other than those of the present invention tend to have a broad grain size distribution and tend to have high fog, which is also not preferable.

<Example 3> EM-4, EM-5, EM-9 to EM-18 of the above Production Example.
Table 17 shows the effect of the iodine content of the high iodine shell in the same manner as in Example 3 using. EM-10 to EM-15
Is an example in which the middle shell and the outermost shell are made the same, and the iodine content of the high iodine shell is changed. It can be seen that the sensitivity becomes higher as the iodine content of the high iodine shell becomes higher.

Emulsions with a high iodine content of 40 mol% or 50 mol% (E
In M-15 and EM-17), the sensitizing effect tends to be small, which is considered to be due to the broad grain size distribution, and an emulsion (EM) having the same high iodine shell (EM) other than the present invention. -16,
It can be seen that a sufficient sensitizing effect is obtained in the emulsion of the present invention as compared with EM-18).

<Example 4> Similarly, the effect of iodine content in the low-iodity shell and intermediate shell is shown in Table-18.
Shown in. The lower the iodine content of the outermost shell, the greater the sensitizing effect of the present invention.

In particular, the lower the iodide content of the outermost shell, the greater the effect on the layer sensitivity. High iodine content of low-iodity shell (10 mol%
Above ... EM-26) Emulsion has lower sensitivity than comparative emulsion.

<Example 5> Similarly, the effect of the particle size distribution is shown in Table-19. The sensitizing effect of the present invention is more effectively obtained in a monodisperse emulsion having a narrow grain size distribution. The emulsion having a wide distribution is inferior to the emulsion having a narrow distribution in terms of fog and sharpness. The monodisperse emulsion of the present invention is more preferable as the emulsion having excellent sensitivity, fog and sharpness.

<Example 6> Similarly, the effect of the volume of the high-iodine shell is shown in Table-20. As for the sensitizing effect of the present invention, when the volume of the high iodine shell is as small as 5% (EM-33), the sensitizing effect is small, but the effect is small and it is 12% (EM-3).
2), 22% (EM-33), 41% (EM-34), a more preferable effect is obtained in an emulsion having a relatively large volume of high iodine shell.

<Example 7> Similarly, the effect of the total iodine content of the entire silver iodobromide is shown in Table-21.

In the present invention, emulsions having a relatively high total iodine content have a small sensitizing effect (EM-35, EM-36), and emulsions having a low total iodine content (EM-38) have graininess, sharpness and exposure. It is understood that it is preferable to use the emulsion of the present invention having an iodine content in an appropriate range in order to obtain high sensitivity, excellent graininess, sharpness, and a wide exposed area. .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Matsuzaka No. 1 Sakuramachi, Hino-shi, Tokyo Photograph by Konishi Roku Photo Industry Co., Ltd. (56) Reference JP-A-58-181037 (JP, A) JP-A-59-116645 (JP, A)

Claims (1)

[Claims] 1. An inner nucleus having an iodine content of 0 to 40 mol%, which is substantially composed of silver bromide or silver iodobromide, and which is provided outside the inner nucleus and is substantially brominated. In a silver halide photographic light-sensitive material containing negative type silver halide grains having a plurality of outer shells made of silver or silver iodobromide, the silver halide grains have an iodine content of 2 to 12 mol%. Further, the iodine content of the outermost shell is 10 mol% or less, and the iodine-rich shell having an iodine content of 6 mol% or more higher than that of the outermost shell is provided inside the outermost shell, An intermediate shell having an iodine content intermediate between those shells is provided between the shell and the iodine-rich shell, and the iodine content of the intermediate shell is 3 mol% or more higher than that of the outermost shell. And the iodine content of the high-iodine shell is higher than that of the intermediate shell by 3 mol% or more. A silver halide photographic light-sensitive material, wherein the silver halide grains are sensitized with at least one sensitizing dye represented by the following general formula (I). General formula (I) (However, Y ₁ , Y ₂ is S, Se or O. W ₁ , W ₂ , W ₃ , W ₄ , W ₅ , W ₆ are hydrogen atom, alkyl group, alkoxy group, aryl group, halogen atom,
An amino group, an acylamido group, an acyloxy group, an alkoxycarbonylamino group, an alkoxycarbonyl group or a hydroxy group, wherein W ₁ and W ₂ , W ₂ and W ₃ , W ₄ and W
₅ , W ₅ and W ₆ may be bonded to each other to form an aromatic carbocycle or an aromatic carbocycle. R ₁ and R ₂ are an alkyl group, an alkyl group having a carboxyl group, an alkyl group having a sulfo group (provided that n is 0
In the case of, at least one of R ₁ and R ₂ is an alkyl group having a carboxyl group or an alkyl group having a sulfo group). X is an ion necessary to neutralize the charge. n is 0 or 1, and when forming an intramolecular salt, n =
0. )